double cure sealants

专利摘要:
Compositions that are curable by free radical redox reactions are disclosed. Free radical healing reactions between polythiols and polyalkenyls are initiated by the reaction of metal complexes and organic peroxides. The compositions are useful as sealants.
公开号:BR112019025977A2
申请号:R112019025977-5
申请日:2018-06-08
公开日:2020-07-07
发明作者:Jiancheng Liu；Srikant Pathak；Bruce Virnelson
申请人:Prc-Desoto International, Inc.；
IPC主号:

专利说明:

[001] [001] This application claims the benefit under 35 U.S.C. § 119 (e) of US Provisional Application No. 62 / 517,648 filed on June 9, 2017, which is incorporated by reference in its entirety. FIELD
[002] [002] Disclosure refers to compositions that are curable by free radical redox reactions are disclosed. Free radical curing reactions between polythiols and polyalkenyls are initiated by the reaction of metal complexes and organic peroxides. The compositions are useful as sealants. FUNDAMENTALS
[003] [003] Sealants that are curable using ultraviolet (UV) radiation are useful in various applications. UV-curable coatings and sealants can be stored as a single component and can have an extended application time. Although capable of providing highly reliable seals in certain applications, the thickness or geometry of a seal can prevent the ultraviolet light necessary to initiate the free radical cure reaction from reaching all portions of the applied sealant. Incomplete, insufficient and / or inhomogeneous exposure to ultraviolet light can result in a sealant that is not completely cured or that will only cure after an unacceptably long period of time. In addition, on some seals it is not possible to completely irradiate the uncured sealant.
[004] [004] Double curing systems that combine a UV-initiated free radical curing reaction and a redox-initiated free radical reaction can be combined to provide a sealant that will at least partially cure after exposure to UV radiation and subsequently continue to cure through a free radical reaction initiated by redox. Such combined double cure sealants are disclosed, for example, in International PCT Application No. WO 2016/106352, which discloses free radical reactions initiated by UV radiation and by a peroxide-amine redox reaction.
[005] [005] Alternative curing and dark curing sealants that at least partially cure during exposure to UV radiation and continue to cure for an extended period of time are desired. SUMMARY
[006] [006] According to the present invention, compositions comprise a polythiol, wherein the polythiol comprises a thiol-terminated prepolymer; a polyalkenyl, wherein the polyalkenyl comprises an alkenyl-terminated prepolymer, a polyalkenyl monomer or a combination thereof; a metallic complex; and an organic peroxide.
[007] [007] According to the present invention, cured sealants are prepared from a composition according to the present invention.
[008] [008] In accordance with the present invention, the parts are sealed with a cured sealant according to the present invention.
[009] [009] In accordance with the present invention, vehicles comprise a cured sealant according to the present invention.
[010] [010] In accordance with the present invention, aerospace vehicles comprise a cured sealant according to the present invention.
[011] [011] According to the present invention, methods of sealing a part comprise applying the composition according to the present invention to a part; and allow the applied composition to cure, to seal the part.
[012] [012] According to the present invention, sealant systems comprise a first part, wherein the first part comprises a polyalkenyl; and a second part, wherein the second part comprises a polythiol; wherein the first part comprises a metal complex and the second part comprises an organic peroxide; or wherein the first part comprises an organic peroxide and the second part comprises a metal complex.
[013] [013] According to the present invention, sealants are prepared from a sealant system according to the present invention, in which the first part and the second part are combined.
[014] [014] In accordance with the present invention, parts are sealed with a sealant system in accordance with the present invention.
[015] [015] In accordance with the present invention, vehicles comprise a cured sealant according to the present invention.
[016] [016] According to the present invention, aerospace vehicles comprise a cured sealant according to the present invention.
[017] [017] According to the present invention, methods of sealing a part, comprise combining the first part and the second part of the sealant system according to the present invention to provide a sealant; apply the sealant to a part; and allow the applied sealant to cure, to seal the part. BRIEF DESCRIPTION OF THE DRAWINGS
[018] [018] The drawings described here are for illustration purposes only.
[019] [019] FIG. 1 shows a reaction scheme for a UV-initiated free radical reaction between a thiol and an alkenyl.
[020] [020] FIG. 2 shows a reaction scheme for the generation of free radicals using the reaction between an organic peroxide and a metal complex.
[021] [021] FIG. 3 is a graph showing the hardness of sealants provided by the present disclosure under different curing conditions.
[022] [022] FIG. 4 is a graph showing the depth of cure for sealants provided by the present disclosure following UV radiation.
[023] [023] FIG. 5 is a graph showing the physical properties of sealants provided by the present disclosure under different curing conditions.
[024] [024] FIG. 6 is a graph showing the hardness of sealants provided by the present disclosure having different amounts of metal complex and organic peroxide.
[025] [025] FIG. 7 is a graph showing the depth of cure of sealants provided by the present disclosure having different amounts of metal complex and organic peroxide.
[026] [026] FIG. 8 is a graph showing the extrusion rate of sealants provided by the present disclosure after combining the polyol component and the polyalkenyl component.
[027] [027] FIG. 9 is a graph showing the hardness and depth of cure of sealants provided by the present disclosure having different amounts of metal complex and organic peroxide.
[028] [028] FIG. 10 is a graph showing the hardness and depth of cure of sealants provided by the present disclosure having different amounts of organic anion.
[029] [029] FIG. 11 is a graph showing the hardness of sealants provided by the present disclosure under different curing conditions.
[030] [030] FIG. 12 is a graph showing physical properties of sealants provided by the present disclosure under different curing conditions.
[031] [031] FIG. 13 is a graph showing application time and adherence-free time for various short cure sealant formulations.
[032] [032] FIG. 14 is a graph showing the Shore A hardness of short-curing sealants cured under UV and dark conditions.
[033] [033] FIG. 15 is a graph showing Shore A hardness of sealants measured within a few minutes of UV exposure.
[034] [034] FIG. 16A is a graph showing the application time for certain of the double cure, short cure sealant formulations shown in table 13.
[035] [035] FIG. 16B is a graph showing the open time for certain of the short cure, double cure sealant formulations shown in table 13.
[036] [036] FIG. 17 is a graph showing the Shore A hardness of fully cured sealants, cured under UV and dark curing conditions.
[037] [037] FIG. 18 is a graph showing Shore A hardness of sealants measured within a few minutes following exposure to UV curing conditions. DETAILED DESCRIPTION
[038] [038] For the purposes of the following detailed description, it should be understood that the modalities provided by the present disclosure may assume several variations and alternative step sequences, except where expressly specified to the contrary. In addition, except in any operational examples or where otherwise indicated, all figures that express, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all examples by the term "about".
[039] [039] Despite the fact that the numerical ranges and parameters presented in the broad scope of the invention are approximations, the numerical values presented in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard variation found in their respective test measurements.
[040] [040] Also, it should be understood that any numerical range reported here is intended to include all sub-ranges included in this. For example, a range of
[041] [041] A dash (“-”) that is not between two letters or symbols is used to indicate a point of attachment for a substituent or between two atoms. For example, -CONH2 is linked via the carbon atom.
[042] [042] "Alcanodiíla" refers to a diradical of a saturated or unsaturated, branched or straight chain acyclic hydrocarbon group, having, for example, from 1 to 18 carbon atoms (C1-18), from 1 to 14 atoms carbon (C1-14), from 1 to 6 carbon atoms (C1-6), from 1 to 4 carbon atoms (C1-4) or from 1 to 3 hydrocarbon atoms (C1-3). It will be assessed that a branched alkanediyl has a minimum of three carbon atoms. An alkanediyl may be C2-14 alkanediyl, C2-10 alkanediyl, C2-8 alkanediyl, C2-6 alkanediyl, C2-4 alkanediyl or C2-3 alkanediyl.
[043] [043] "Alcanocycloalkane" refers to a saturated hydrocarbon group having one or more cycloalkyl and / or cycloalkanodiyl groups and one or more alkyl and / or alkanodiyl groups, where cycloalkyl, cycloalkanodiyl, alkyl and alkanodiyl are defined here.
[044] [044] "Alcanocycloalkane diary" refers to a diradical of an alkanocycloalkane group. An alkanocycloalkanediyl group may be alkanocycloalkanodiyl C4-18, alkanocycloalkanodiyl C4-12, alkanocycloalkanodiyl C4-8, alkanocycloalkanodiyl C6-12, alkanocycloalkylalkyl or alkanocycloalkyl 6 -alkyl-6-alkanocycloalkyl 6 -alkylalkyl 6 -alkylalkyl 6 -alkylalkyl 6 -alkylalkyl 6 -alkyl 6 -alkylalkyl 6 -alkyl. Examples of alkanocycloalkanediyl groups include 1,1,3,3-tetramethylcyclohexane-1,5-diyl and cyclohexylmethane-4,4'-diyl.
[045] [045] "Alcanoarene" refers to a hydrocarbon group having one or more aryl and / or arenodiyl groups and one or more alkyl and / or alkanodiyl groups, where aryl, arenodiyl, alkyl and alkanodiyl are defined here. Each aryl and / or arenodiyl group can be C6-12, C6-10, phenyl or benzene diyl. Each alkyl and / or alkanediyl group can be C1-6, C1-4, C1-3, methyl, methanodiyl, ethyl or ethane-1,2-diyl. An alkanoarene group can be C4-18 alkanoarene, C4-16 alkanoarene, C4-12 alkanoarene, C4-8 alkanoarene, C6-12 alkanoarene, C6-10 alkanoarene or C6-9 alkanoarene.
[046] [046] "Alcanoarenodiíla" refers to a diradical of an alkanoarene group.
[047] [047] "Alkenyl" group refers to the structure -CR = C (R) 2 where the alkenyl group is a terminal group and is attached to a larger molecule. In such embodiments, each R can independently comprise, for example, hydrogen and C1-3 alkyl. Each R can be hydrogen and an alkenyl group can have the structure -CH = CH2.
[048] [048] "Aloxy" refers to an -OR group where R is alkyl as defined here.
[049] [049] "Alkyl" refers to a monoradical of a saturated or unsaturated, branched or straight chain acyclic hydrocarbon group having, for example, from 1 to 20 carbon atoms, from 1 to 10 carbon atoms, from 1 to 6 carbon atoms, from 1 to 4 carbon atoms or from 1 to 3 carbon atoms. It will be assessed that a branched alkyl has a minimum of three carbon atoms. An alkyl group can be C1-6 alkyl, C1-4 alkyl or C1-3 alkyl. Examples of alkyl groups include methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-hexyl, n-decyl and tetradecyl. An alkyl group is C1-6 alkyl, C1-4 alkyl and C1-3 alkyl.
[050] [050] “Arenodiíla” refers to the monocyclic or polycyclic aromatic group of diradical. Examples of arenodiyl groups include benzene-diyl and naphthalene-diyl. A sandstone group may be C6-12 sandstone, C6-10 sandstone, C6-9 sandstone or benzene-diamine.
[051] [051] "Cycloalkane diary" refers to a monocyclic or polycyclic hydrocarbon group saturated with diradical. A cycloalkanodiyl group may be C3-12 cycloalkanodiyl, C3-8 cycloalkanodiyl, C3-6 cycloalkanodiyl or C5-6 cycloalkanodiyl. Examples of cycloalkanediyl groups include cyclohexane-1,4-diyl, cyclohexane-1,3-diyl and cyclohexane-1,2-diyl.
[052] [052] "Cycloalkyl" refers to a group of saturated monocyclic or polycyclic monoradical hydrocarbons. A cycloalkyl group can be C3-12 cycloalkyl, C3-8 cycloalkyl, C3-6 cycloalkyl or C5-6 cycloalkyl.
[053] [053] "Heteroalkanediyl" refers to an alkanediyl group in which one or more of the carbon atoms are replaced with a heteroatom, such as N, O, S or P.
[054] [054] "Heterocycloalkanediyl" refers to a cycloalkanodiyl group in which one or more of the carbon atoms are replaced with a heteroatom, such as N,
[055] [055] "Heteroarenodiíla" refers to a arenodiíla group in which one or more of the carbon atoms are replaced with a heteroatom, such as N, O, S or P.
[056] [056] A "polyalkenyl" refers to a compound having at least two alkenyl groups. The at least two alkenyl groups can be terminal alkenyl groups and such polyalkenyls can be referred to as alkenyl-terminated compounds. Alkenyl groups can also be pendent alkenyl groups. A polyalkenyl can be a dialkenyl, having two alkenyl groups. A polyalkenyl may have more than two alkenyl groups such as three to six alkenyl groups.
[057] [057] A "polyalkenyl prepolymer" refers to a polyalkenyl having at least one repeating unit in the polyalkenyl backbone. A polyalkenyl prepolymer generally has a molecular weight in the range of 500 Dalton to 6,000 Dalton, such as from 500 Dalton to 4,000 Dalton or from 500 Dalton to 2,000 Dalton.
[058] [058] A "monomeric polyalkenyl" refers to a polyalkenyl that does not include repeating units in the polyalkenyl backbone. A monomeric polyalkenyl generally has a molecular weight that is less than that of a polyalkenyl prepolymer. Monomeric polyalkenyls can be bifunctional or have an alkenyl functionality greater than two.
[059] [059] "Formed from" or "prepared from" denotes open language, for example, comprising, claim language. As such, it is intended that a composition "formed from" or "prepared from" a list of reported components is a composition comprising at least the reported components or the reaction product of at least the reported components and may further comprise unreported, additional components used to form or prepare the composition.
[060] [060] "Reaction product" means a chemical reaction product of at least the reported reagents and may include partial reaction products as well as fully reacted products and other reaction products that are present in a smaller amount. For example, a "prepolymer comprising the reagent reaction product" refers to a prepolymer or combination of prepolymers that are the reaction product of at least the reported reagents. The reagents may further comprise additional reagents.
[061] [061] A compound having a thiol or alkenyl functionality refers to a compound that has reactive thiol or alkenyl groups, respectively. The reactive thiol or alkenyl groups can be terminal groups attached to the ends of the molecule, they can be attached to the main chain of the molecule or the compound can contain thiol or alkenyl groups which are terminal groups or are attached to the main chain.
[062] [062] As used here, the term "cure" or "cured" as used in connection with a composition, for example, "composition when cured" or a "cured composition", means that any curable or crosslinkable components of the composition are at least least partially reacted or cross-linked.
[063] [063] The term “equivalent” refers to the number of functional reactive groups in the substance. "Equivalent weight" is effectively equal to the molecular weight of a substance, divided by the valence or number of functional reactive groups of the substance.
[064] [064] A "main chain" of a prepolymer refers to the segment between the reactive terminal groups. A prepolymer backbone typically includes repeating subunits. For example, the main chain of an HS- [R] n-SH polythiol is - [R] n-.
[065] [065] A "core" of a polyfunctionalizing agent B (-V) z refers to portion B.
[066] [066] A "core" of a compound or polymer refers to the segment between the terminal reactive groups. For example, the core of an HS-R-SH polythiol will be -R-. A compound or prepolymer core can also be referred to as a compound backbone or a prepolymer backbone. A core of a polyfunctionalizing agent can be an atom or a structure such as a cycloalkane, a substituted cycloalkane, heterocycloalkane, substituted heterocycloalkane, arene, substituted arene, heteroarene or substituted heteroarene from which the portions having a reactive functional are bonded.
[067] [067] "Nucleus of a diisocyanate" refers to the portion that forms the diisocyanate without the isocyanate groups. For example, the core of a diisocyanate having the structure O = C = N-R4-N = C = O is represented by -R4-. For example, a nucleus of the 4,4'-methylene dicyclohexyl aliphatic diisocyanate has the structure:
[068] [068] "Prepolymer" refers to oligomers, homopolymers and copolymers.
[069] [069] A prepolymer includes multiple repeating subunits linked together that can be the same or different. The multiple repeating subunits make up the prepolymer backbone.
[070] [070] A "curable composition" refers to a composition that comprises at least two reagents capable of reacting to form a cured composition. For example, a curable composition may comprise an isocyanate-terminated extended polythioether prepolymer and a polyamine capable of reacting to form a cured polymer. A curable composition can include a catalyst for the curing reaction and other components such as, for example, fillers, pigments and adhesion promoters. A curable composition may be curable at room temperature or may require exposure to elevated temperature such as a temperature above room temperature or other condition (s) to initiate and / or to accelerate the curing reaction. A curable composition can initially be provided as a two-part composition including, for example, a separate base component and an accelerator component. The base composition can contain one of the reactants participating in the curing reaction such as an isocyanate-terminated extended polythioether prepolymer and the accelerator component can contain the other reagent such as a polyamine. The two components can be mixed immediately before use to provide a curable composition. A curable composition can exhibit a viscosity suitable for a particular application method. For example, a Class A sealant composition, which is suitable for brush applications, can be characterized by a viscosity of 1 poise to 500 poise (0.1 Pa-s to 50 Pa). A Class B sealant composition, which is suitable for fillet seal applications, can be characterized by a viscosity of 4,500 poise to 20,000 poise (450 Pa-s to 2,000 Pa-s). A Class C sealant composition, which is suitable for contact seal applications, can be characterized by a viscosity of 500 poise to 4,500 poise (50 Pa-s to 450 Pa-s). The viscosity of the compositions is measured as described here. After the two components of a sealant system are combined and mixed, the curing reaction can proceed and the viscosity of the curable composition can increase and at some point, it will no longer be viable, as described here. The duration between when the two components are mixed to form the curable composition and when the curable composition can no longer be reasonably or practically applied to a surface for its intended purpose can be referred to as the working time. As can be assessed, the working time can depend on several factors including, for example, the curing chemical, the catalyst used, the method of application and the temperature. Once a curable composition is applied to a surface (and during application), the curing reaction can proceed to provide a cured composition. A cured composition develops an adhesive-free surface, cures and then completely cures over a period of time. A curable composition can be considered to be cured when the surface hardness is at least 30 Shore A for a Class B seal or a Class C sealant. After a sealer has cured to a 30 Shore A hardness it can last for several days several weeks for a curable composition to completely cure. A composition is considered completely cured when the hardness no longer increases.
[071] [071] "Substituted" refers to a group in which one or more hydrogen atoms are all independently substituted with the same or different substituent (s). A substituent can comprise halogen, - S (O2) OH, -S (O) 2, -SH, -SR where R is C1-6 alkyl, -COOH, -NO2, -NR2 where each R independently comprises hydrogen and C1 alkyl -3, -CN, = O, C1-6 alkyl, - CF3, -OH, phenyl, C2-6 heteroalkyl, C5-6 heteroaryl, C1-6 alkoxy or -COR where R is C1-6 alkyl. A substituent can be -OH, -NH2 or C1-3 alkyl.
[072] [072] "Derived from" as in "a portion derived from a compound" refers to a portion that is generated during the reaction of a precursor compound with a reagent. For example, a bis (alkenyl) compound CH2 = CH-R-CH = CH2 can react with another compound such as two compounds having thiol groups to produce the derivative - (CH2) 2-R- (CH2) 2- portion reaction of alkenyl groups with thiol groups. For example, for a precursor diisocyanate having the structure O = C = N-R-N = C = O, a portion derived from the diisocyanate has the structure -C (O) -NH-R-NH-C (O) -. As another example, for a precursor non-linear short chain diol having the HO-R-OH structure, a portion derived from the non-linear short chain diol has the -O- R-O- structure.
[073] [073] "Derived from the reaction of -V with a thiol" refers to a -V'- moiety that results from the reaction of a thiol group with a moiety comprising a terminal group reactive with a thiol group. For example, a group V- may comprise CH2 = CH-CH-O-, where the alkenyl terminal group CH2 = CH- is reactive with a thiol group -SH. During the reaction with a thiol group, the -V'- moiety is -CH2-CH2-CH2-O-.
[074] [074] "Dark cure" refers to healing mechanisms that do not require exposure to actinic radiation such as UV radiation to initiate the reaction. Actinic radiation can be applied to a curing system in darkness to accelerate the curing of all or part of a composition, but exposing the composition to actinic radiation is not necessary to cure the sample. A dark curing composition can cure completely under dark conditions without exposure to actinic radiation.
[075] [075] The glass transition temperature Tg is determined by dynamic mechanical analysis (DMA) using a TA Instruments Q800 device with a frequency of 1 Hz, an amplitude of 20 microns and a temperature ramp of -80 ° C to 25 ° C, with Tg identified as the peak of the tan δ curve.
[076] [076] When reference is made to a chemical group defined, for example, by several carbon atoms, the chemical group is intended to include all sub-bands of carbon atoms as well as a specific number of carbon atoms. For example, a C2-10 alkanediyl includes a C2-4 alkanediyl, C5-7 alkanediyl and other sub-bands, a C2 alkanediyl, a C6 alkanediyl and alkanodiyls having other specific number (s) of carbon atoms of 2 to 10.
[077] [077] A polyfunctionalizing agent can have the structure of Formula (1): B1 (-V) z (1) where B1 is the nucleus of the polyfunctionalizing agent, each V is a portion terminated in a reactive functional group such as a thiol group , an alkenyl group, an epoxy group, an isocyanate group or a Michael ez accepting group is an integer from 3 to 6, such as 3, 4, 5 or 6. In polyfunctionalizing agents of Formula (1), each -V it can have the structure, for example, -R-SH or -R-CH = CH2, where R can be, for example, C2-10 alkanediyl, C2-10 heteroalkanyi, substituted C2-10 alkanediyl or substituted C2-10 heteroalkanediyl.
[078] [078] When the V portion is reacted with another compound the -V1- portion results and is said to have been derived from the reaction with the other compound. For example, when V is -R-CH = CH2 and is reacted, for example, with a thiol group, the V1 portion is - R-CH2-CH2- is derived from the reaction.
[079] [079] In polyfunctionalizing agents of Formula (1), B1 can be, for example, C2-8 alkane-triyl, C2-8 heteroalkane-triyl, C5-8 cycloalkane-triyl, C5-8 heterocycloalkane-C5-8 cycloalkane-triyl -8 substituted, C5-8 heterocycloalkane-triyl, C6-arene-triyl, C4-5-heteroaryl-triyl, C6-substituted-aryl-trilyl or C4-5-substituted hetero-aryl-triyl.
[080] [080] In polyfunctionalizing agents of Formula (1), B1 can be, for example, C2-8 alkanetetrail, C2-8 heteroalkanetetrail, C5-10 cycloalkanetetrail, C5-10 heterocycloalkanetetrail C6-10, C4-8 heteroarene-tetrayl, substituted C2-8-alkane-tetrayla, C2-8-substituted heteroalkane-tetrail, C5-10-substituted cycloalkanetetrail, C5-10-substituted heterocycloalkane-tetrail, C6-10-substituted heteroaryl and heteroarylene -tetrail C4-10 substituted.
[081] [081] Examples of suitable alkenyl-terminated polyfunctionalizing agents include trialyl cyanurate (TAC), trialyl isocyanurate (TAIC), 1,3,5-trialyl-1,3,5-triazinane-2,4,6-trione, 1,3-bis (2-methylalyl) -6-methylene-5- (2-oxopropyl) -1,3,5-triazinone-2,4-dione, tris (allyoxy) methane, pentaerythritol trialyl ether, 1- (allyloxy) -2,2-bis ((allyoxy) methyl) butane, 2-prop-2-ethoxy-1,3,5-tris (prop-2-enyl) benzene, 1,3,5-tris (prop - 2-enyl) -1,3,5-triazinane-2,4-dione and 1,3,5-tris (2-methylalyl) -1,3,5-triazinane-2,4,6-trione, 1 , 2,4-trivinylcyclohexane and combinations of any of the foregoing.
[082] [082] A polyfunctionalizing agent of Formula (1) can be terminated in thiol.
[083] [083] Examples of suitable trifunctional thiol-terminated polyfunctionalizing agents include, for example, 1,2,3-propanotrityiol, 1,2,3-benzenotrityiol, 1,1,1-butanotrityiol, heptane-1,3-7-trityiol , 1,3,5-triazine-2,4-6-trityl, isocyanurate-containing tritols and combinations thereof, as disclosed in US Application Publication No. 2010/0010133 and the polythiols described in U.S. Patents Nos.
[084] [084] Examples of suitable polyol polyfunctionalizing agents include pentaerythritol tetra (3-mercapto-propionate) (PETMP), trimethylol-propane tri (3-mercaptopropionate) (TMPMP), glycol di (3-mercaptopropionate) (GDMP) , tris [2- (3-mercapto-propionyloxy) ethyl] isocyanurate (TEMPIC), hexa (3-mercaptopropionate) di-pentaerythritol (di-PETMP), tri (3-mercaptopropionate) pentaerythritol, tri- (3- mercaptopropionate ) of triethylolethane and combinations of any of the foregoing.
[085] [085] Examples of suitable polyfunctionalizing agents of mercaptoacetate polythiol include pentaerythritol tetramercaptoacetate (PRTMA), trimethylolpropane trimercaptoacetate (TMPMA), glycol dimercaptoacetate (GDMA), ethyl etherol glycol dimercaptoacetate, and any trimethyl ethanol glycol dimercaptoacetate. precedent.
[086] [086] Examples of suitable polyol polyfunctionalizing agents include pentaerythritol tetraacrylate, tris [2- (3-mercaptopropionyloxy) ethyl] isocyanurate, 2,3-di (2-mercaptoethylthio) -1-propane-thiol, dimercaptodiethylsulfide (2 , 2'-thiodiethanethiol), dimercaptodioxaoctane (2,2 '- (ethylenedioxy) dietanethiol, 1,8-dimercapto-3,6-dioxaoctane and combinations of any of the foregoing.
[087] [087] Other examples of polythifunctional polythiolating agents and polythiol monomers include pentaerythritol tetra (3-mercaptopropionate) (PETMP), pentaerythritol tetramercaptoacetate (PETMA), dipentaerythritol tetrahydrate, tetrahydrate, tetrahydrate (tetrahydrate), pentaerythritol, tetramercapto, tetramercapto, tetramercapto, tetramercapto. dipentaerythritol-mercaptopropionate), dipentaerythritol pentamercaptoacetate, dipentaerythritol hexa (3-mercaptopropionate), dipentaerythritol hexamercaptoacetate, tetra (3-mercaptopropionate) ditrimethylolpropane, tetramethyl ethoxy, ethoxy, ethoxy and ethoxylate as ethoxylates of these compounds. Examples include, pentaerythritol tetra (3-mercaptopropionate) (PETMP), dipentaerythritol tetra (3-mercaptopropionate) tetra (3-mercaptopropionate) dipentaerythritol, penta (3-mercaptopropionate) dipentaerythritol tetramercaptoacetate, penta (3-mercaptopropionate)
[088] [088] Suitable polyfunctional polythiolating agents are commercially available, for example, from Bruno Bock Tiochemicals under the trade name Thiocure®.
[089] [089] "Derived from a polyfunctionalizing agent" refers to a portion that results from the reaction of a polyfunctionalizing agent with a functional reactive group.
[090] [090] "Polyol polyfunctionalizing agent" refers to a polyol having, for example, 3 to 6 terminal hydroxyl groups. A polyol polyfunctionalizing agent can have a molecular weight, for example, less than 1,400 Dalton, less than
[091] [091] "Polythiol polyfunctionalizing agent" refers to a polythiol having, for example, 3 to 6 terminal thiol groups. A polyfunctionalizing agent of polythiol may have a molecular weight, for example, less than 1,400 Dalton, less than 1,200 Dalton, less than 1,000 Dalton, less than 800 Dalton, less than 700 Dalton, less than 600 Dalton, less than 500 Dalton, less than 400 Dalton, less than 300 Dalton, less than 200 Dalton or less than 100 Dalton. Polyfunctionalizing agents of polythiol can be represented by the formula B4 (-V) z, where B4 represents a core of a z-valiant polyfunctionalizing agent B4 (-V) z, z is an integer from 3 to 6; and each -V is a moiety comprising a terminal thiol (- SH) group.
[092] [092] A polythiol or a polyalkenyl may be a polyfunctionalizing agent of polythiol or a polyfunctionalizing agent of polyalkenyl, respectively.
[093] [093] “Composition” is intended to cover a product comprising specific components in specific quantities, as well as any product that results, directly or indirectly, from the combination of specific ingredients in specific quantities.
[094] [094] "Molecular weight" refers to a theoretical molecular weight estimated from the chemical structure of a compound such as a monomeric compound or a numerical average molecular weight as appropriate for a given prepolymer, for example, using chromatography of gel permeation using polystyrene standards.
[095] [095] "Application time" refers to the duration that a curable composition can be applied to a surface. The application time can be, for example, at least 2 hours, at least 4 hours, at least 6 hours, at least 12 hours, at least 16 hours, at least 20 hours or at least 24 hours. The application time may depend on the application method such as, for example, by extrusion, rotation, brushing or diffusion. The application time of a curable composition can be determined by measuring the extrusion rate of a composition as described in the Examples. For example, the application time of a curable composition provided by the present disclosure can be defined as the duration until the curable composition exhibits an extrusion rate, as determined by extrusion through a No 440 nozzle (Semco, 0.125 inches in diameter) and 4 inches long, available from PPG Aerospace) at a pressure of 90 psi (620 KPa) greater than 15 g / min, greater than 30 g / min or greater than 50 g / min. An appropriate application time may depend, for example, on the specific application method, temperature, humidity, thickness, surface area and volume.
[096] [096] “Adhesion free time” refers to the length of time when co-reactive components are first combined and mixed to form a curable sealant until a coating prepared from the curable sealant exhibits freedom of adherence as determined by applying it. a polyethylene sheet to the surface of the sealant with manual pressure and observing if the sealant adheres to the surface of the polyethylene sheet.
[097] [097] “Full cure” refers to the length of time when co-reactive components are first combined and mixed to form a curable sealant until a coating prepared from the curable sealant exhibits a hardness of at least Shore 40A at 25 ° C and 50% RH. A time to complete healing can be, for example, 1 week to 2 weeks, 1 week to 6 weeks, 2 weeks to 5 weeks or 3 weeks to 5 weeks.
[098] [098] "Curing time" refers to the length of time when the co-reactive components are first combined and mixed to form a curable sealant until a coating prepared from the curable sealant exhibits Shore 30A hardness under conditions of 25 ° C and 50% RH.
[099] [099] Specific gravity is determined according to ASTM D1475.
[0100] [0100] Shore A hardness is measured using a Type A durometer in accordance with ASTM D2240.
[0101] [0101] Tensile strength and elongation are measured according to AMS
[0102] [0102] Reference is now made to certain compounds, compositions and methods of the present invention. The compounds, compositions and methods disclosed are not intended to be limiting of the claims. On the contrary, the claims are intended to cover all alternatives, modifications and equivalents.
[0103] [0103] Combinations of metal complexes and organic peroxides can be used as free radical catalysts to cure compositions such as sealants. Combinations of metal complexes and organic peroxides can also communicate useful double curing properties to radiation-curable sealants such as UV-curable sealants. The curing dynamics may depend on the combination of metal complexes and organic peroxides. Using different mixtures of solvents to disperse the metal complexes it is also possible with controlling the gel time of the sealant and controlling the time to completely cure the sealant under dark conditions. Physical properties and adhesion of sealants cured using a radial redox initiated dark cure reaction are comparable to those of sealants cured using actinic radiation only (in the absence of the dark curing catalyst system) such as UV radiation. Such double cure sealants have several advantages. For example, the surface of a sealant can be quickly cured by exposure to radiation allowing the part to be manipulated and handled while the unexposed portion of the sealant completely heals. Using a double curing mechanism the surface of a sealant can be quickly cured without exposing the total depth of the sealant to radiation and subsequently the unexposed sealant can completely cure. Also, in geometries and configurations where it is not possible to directly expose a radiation-curable sealant, a portion of the sealant can be exposed to radiation thereby initiating dark cure redox curing mechanisms that can propagate through unexposed areas of the sealant. Dual curing mechanisms can also provide opportunities to control the cure rate of a sealant, which can lead to improved properties such as improved tensile strength,% elongation, solvent resistance and adhesion.
[0104] [0104] As illustrated in FIG. 1, unmodified UV-curable compositions based on thiol-ene chemistry react by generating free radicals when exposed to actinic radiation such as UV radiation in the presence of a photoinitiator (I). An unmodified UV-curable composition refers to a UV-curable composition that does not include an organic peroxide metal complex / free radical initiator. The free radical generated by the photoinitiator subtracts a hydrogen from a thiol group creating a thienyl radical that can be added to an alkylene group, creating a sulfur-carbon bond and a β-carbon radical, which initiates chain propagation.
[0105] [0105] In dark cure mode, that is, when actinic radiation such as UV radiation is not used to generate free radicals, the disclosure provides an alternating radical initiation mechanism that occurs in the absence of actinic radiation. In the disclosed dark curing mechanism, thiol-ene polymerization proceeds through a controlled generation of free radicals using a combination of an organic peroxide and a metal complex in the absence of actinic radiation. FIG. 2 illustrates the decomposition of an organic peroxide, tert-butyl peroxybenzoate, in the presence of a metal complex to generate free radicals.
[0106] [0106] After free radicals are generated as shown in FIG. 2, the polymerization of the polyol and polyalkenyl components can continue in the manner as shown in FIG. 1. The use of organic peroxides and metal complexes as free radical curing catalysts in darkness can provide cured compositions with properties similar to those of UV cured compositions (without a dark curing catalyst).
[0107] [0107] The compositions provided by the present disclosure comprise a polythiol, a polyalkenyl, a metal complex and an organic peroxide. Compositions provided by the present disclosure comprise a thiol-containing sulfur-containing prepolymer, a polyalkenyl, a metal complex and an organic peroxide.
[0108] [0108] Sealant compositions and formulations provided by the present disclosure may comprise a thiol-terminated sulfur-containing prepolymer such as a thiol-terminated polythiopolymer prepolymer, a thiol-terminated polysulfide prepolymer, a thiol-terminated polysulfide prepolymer. polyform containing thiol-terminated sulfur, a thiol-terminated monosulfide prepolymer or a combination of any of the foregoing. A sulfur-containing prepolymer refers to a prepolymer that has one or more thioether groups -S- and / or sulfide -S-S- in the prepolymer backbone. Prepolymers containing only thiol or other sulfur-containing groups, as end groups or as pendant groups on the prepolymer backbone are not covered by sulfur-containing prepolymers. Thus, a prepolymer having the structure HS-RR (-CH2-SH) -R- (CH2) 2-S (O) 2- (CH2) 2-S (O) 2-CH = CH2 where each R is a portion that does not contain a sulfur atom is not covered by a sulfur-containing prepolymer; however, the prepolymer comprises two terminal thiol groups. A prepolymer having the structure HS-RR (-CH2-SH) -R- (CH2) 2-S (O) 2- (CH2) 2-S (O) 2-CH = CH2 where at least one R is a portion containing a sulfur atom, such as a thioether or sulfide group, is comprised of a sulfur-containing prepolymer. The prepolymer described in the preceding paragraph comprises a terminal thiol group and at least one sulfur atom in the prepolymer backbone. In sulfur-containing prepolymers provided by the present disclosure, the sulfur content of the prepolymer backbone (and not including terminal thiol groups) can be, for example, from 0.1% by weight to 20% by weight, from 0 , 1% by weight to 10% by weight, from 0.1% by weight to 5% by weight or from 0.1% by weight to 2% by weight, where% by weight refers to the total weight of the pre- sulfur-containing polymer.
[0109] [0109] A thiol-terminated sulfur-containing prepolymer may comprise a thiol-terminated polythioether or a thiol-terminated sulfur-containing prepolymer may comprise a thiol-terminated polysulfide prepolymer. A thiol-terminated sulfur-containing prepolymer may comprise a combination of different thiol-terminated polythiopolymer prepolymers and / or thiol-terminated polysulfide prepolymers and the thiol-terminated polythiopolymer prepolymers and / or prepolymers thiol-terminated polysulfide compounds may have the same or different functionality. A thiol-terminated sulfur-containing prepolymer may have an average thiol functionality of 2 to 6, 2 to 4, 2 to 3, 2.3 to 2.8 or 2.05 to 2.5. For example, a thiol-terminated sulfur-containing prepolymer may comprise a difunctional thiol-terminated sulfur-containing prepolymer, a tri-functional thiol-terminated sulfur-containing prepolymer or a combination thereof. A sulfur-containing prepolymer may comprise a thiol-terminated sulfur-containing polypolymer prepolymer. A sulfur-containing prepolymer may comprise a thiol-terminated monosulfide prepolymer.
[0110] [0110] Compositions and sealants provided by the present disclosure may comprise, for example, from 30% by weight to 70% by weight, from 40% by weight to 60% by weight, from 43% by weight to 57% by weight, from 46 wt% to 54 wt% or 48 wt% to 52 wt% of a thiol-containing sulfur-containing prepolymer or combination of thiol-terminated sulfur-containing prepolymers, such as a polyether ether prepolymer thiol-terminated, a thiol-terminated polysulfide prepolymer, a thiol-terminated sulfur-containing polymorph prepolymer, a thiol-terminated monosulfide prepolymer, or a combination of any of the foregoing, where% by weight is based on the total weight of the curable composition.
[0111] [0111] A sulfur-containing prepolymer may comprise a thiol-terminated polythiopolymer prepolymer. Examples of suitable thiol-terminated polythiopolymer prepolymers are disclosed, for example, in U.S. Patent No. 6,172,179, which is incorporated by reference in its entirety. A thiol-terminated polythiopolymer prepolymer may comprise Permapol® P3.1E, Permapol® P3.1E-2.8, Permapol® L56086 or a combination of any of the foregoing, each of which is available from PRC-DeSoto International Inc. Permapol® P3.1E, Permapol® P3.1E-2.8, Permapol® L56086 are covered by U.S. Patent No. 6,172,179.
[0112] [0112] A thiol-terminated polythiopolymer prepolymer may comprise a thiol-terminated polythiopolymer prepolymer comprising at least a portion having the structure of Formula (2): -R1- [S- (CH2) 2-O- (R2-O-) m (CH2) 2-S-R1] n- (2) where,
[0113] [0113] In portions of Formula (2), R1 can be - [(CHR3) pX-] q (CHR3) r-, where each X can be independently selected from O and S. In portions of Formula (2), R1 can be - [(CHR3) pX-] q (CHR3) r-, each X can be O or each X can be S.
[0114] [0114] In portions of Formula (2), R1 can be - [(CH2) pX-] q (CH2) r-, where each X can be independently selected from O and S. In portions of Formula (2), R1 can be - [(CH2) pX-] q (CH2) r-, each X can be O or each X can be S.
[0115] [0115] In portions of Formula (2), R1 can be - [(CH2) pX-] q (CH2) r-, where p can be 2, X can be O, q can be 2, r can be 2, R2 can be ethanediyl, m can be 2 and n can be 9.
[0116] [0116] In portions of Formula (2), each R1 can be derived from 1,8dimercapto-3,6-dioxaoctane (DMDO), each R1 can be derived from dimercaptodiethylsulfide (DMDS) or a combination of these.
[0117] [0117] In portions of Formula (2), each m can independently be an integer from 1 to 3. Each m can be the same and can be 1, 2 or 3.
[0118] [0118] In portions of Formula (2), n can be an integer from 1 to 30, an integer from 1 to 20, an integer from 1 to 10 or an integer from 1 to 5. In addition, n can be any integer from 1 to 60.
[0119] [0119] In portions of Formula (2), each p can be independently 2, 3, 4, 5 and 6. Each p can be the same and can be 2, 3, 4, 5 or 6.
[0120] [0120] In portions of Formula (2), each q can be independently 1, 2, 3, 4 or 5. Each q can be the same and can be 1, 2, 3, 4 or 5.
[0121] [0121] In portions of Formula (2), each r can be independently 2, 3, 4, 5, 6, 7, 8, 9 or 10.
[0122] [0122] In portions of Formula (2), each r can be the same and can be 2, 3, 4, 5, 6, 7, 8, 9 or 10.
[0123] [0123] In portions of Formula (2), each r can independently be an integer from 2 to 4, from 2 to 6 or from 2 to 8.
[0124] [0124] In portions of Formula (2), each R2 may independently be a C2-10 n-alkanediyl group, a C3-6 branched alkanediyl group or a - [(CH2) p-X-] q (CH2) r- group.
[0125] [0125] In portions of Formula (2), each R2 can independently comprise a C2-10 n-alkanediyl group.
[0126] [0126] In portions of Formula (2), each R2 can independently be a group - [(CH2) p-X-] q (CH2) r-, where each X can be O or S.
[0127] [0127] A thiol-terminated polythiopolymer prepolymer may comprise a thiol-terminated polythiopolymer prepolymer of Formula (2a), a thiol-terminated polythiopolymer prepolymer of Formula (2b) or a combination of these: HS- R1- [S- (CH2) 2-O- (R2-O) m (CH2) 2-S-R1-] nSH (2a) {HS-R1- [S- (CH2) 2-O- (R2- O-) m (CH2) 2-S-R1-] nS-V '-} zB (2b)
[0128] [0128] In prepolymers of Formula (2a) and Formula (2b), R1 can be - [(CH2- X-] q (CH2) r-, where p can be 2, X can be O, q can be 2, r can be 2, R2 can be ethanediyl, m can be 2 and n can be 9.
[0129] [0129] In prepolymers of Formula (2a) and Formula (2b), R1 may comprise C2-6 alkanodiyl or - [(CHR3) p-X-] q (CHR3) r-.
[0130] [0130] In prepolymers of Formula (2a) and Formula (2b), R1 can be -
[0131] [0131] In prepolymers of Formula (2a) and Formula (2b), where R1 can be - [(CHR3) pX-] q (CHR3) r-, p can be 2, r can be 2, q can be 1 and X can be S; or where p can be 2, q can be 2, r can be 2 and X can be O; or p can be 2, r can be 2, q can be 1 and X can be O.
[0132] [0132] In prepolymers of Formula (2a) and Formula (2b), R1 can be - [(CHR3) p-X-] q (CHR3) r- and each R3 can be hydrogen or at least one R3 can be methyl.
[0133] [0133] In prepolymers of Formula (2a) and Formula (2b), each R1 can be the same or at least one R1 can be different.
[0134] [0134] In prepolymers of Formula (2a) and Formula (2b), each m can be independently an integer from 1 to 3. Each m can be the same and can be 1, 2 or 3.
[0135] [0135] In prepolymers of Formula (2a) and Formula (2b), n can be an integer from 1 to 30, an integer from 1 to 20, an integer from 1 to 10 or an integer from 1 to 5. The variable n can be any integer from 1 to
[0136] [0136] In prepolymers of Formula (2a) and Formula (2b), each p can be independently 2, 3, 4, 5 and 6. Each p can be the same and can be 2, 3, 4, 5 or
[0137] [0137] In prepolymers of Formula (2a) and Formula (2b), each q can be independently 1, 2, 3, 4 or 5. Each q can be the same and can be 1, 2, 3, 4 or
[0138] [0138] In prepolymers of Formula (2a) and Formula (2b), each r can be independently 2, 3, 4, 5, 6, 7, 8, 9 or 10.
[0139] [0139] In prepolymers of Formula (2a) and Formula (2b), each r can be the same and can be 2, 3, 4, 5, 6, 7, 8, 9 or 10.
[0140] [0140] In prepolymers of Formula (2a) and Formula (2b), each r can be independently an integer from 2 to 4, from 2 to 6 or from 2 to 8.
[0141] [0141] A thiol-terminated polythiopolymer prepolymer may comprise a portion having the structure of Formula (2c): -S-R1- [SAS-R1-] nS- (2c) where, n is an integer of 1 to 60; each R1 is independently selected from C2-10 alkanediyl, C6-8 cycloalkanediyl, C6-14 alkanocycloalkanediyl, C5-8 heterocycloalkanediyl and - [(CHR3) pX-] q (CHR3) r-, where, p is an integer of 2 to 6; q is an integer from 1 to 5; r is an integer from 2 to 10; each R3 is independently selected from hydrogen and methyl; and each X is independently selected from O, S and NR, where R is selected from hydrogen and methyl; and each A is independently a portion derived from a polyvinyl ether of Formula (3) and a polyalkenyl polyfunctionalizing agent of Formula (4): CH2 = CH-O- (R2-O) m-CH = CH2 (3) B ( -R70-CH = CH2) z (4) where, m is an integer from 0 to 50; each R2 is independently selected from C1-10 alkanediyl, C6-8 cycloalkanediyl, C6-14 alkanocycloalkanediyl and - [(CHR3) pX-] q (CHR3) r-, where p, q, r, R3 and X are as defined as for R1; B represents a core of a polyfunctionalizing agent, polyalkenyl z-valent B (-R70-CH = CH2) z where,
[0142] [0142] In portions of Formula (2c), R1 can be alkanodiyl C2-10.
[0143] [0143] In portions of Formula (2c), R1 can be - [(CHR3) p-X-] q (CHR3) r-.
[0144] [0144] In portions of Formula (2c), X can be selected from O and S and so - [(CHR3) pX-] q (CHR3) r- in Formula (2c) can be - [(CHR3) pO-] q (CHR3) r- or - [(CHR3) p- S-] q (CHR3) r-. P and r can be equal, just as where p and r can be both, two.
[0145] [0145] In portions of Formula (2c), R1 can be selected from C2-6 alkanodiyl and - [(CHR3) p-X-] q (CHR3) r-.
[0146] [0146] In portions of Formula (2c), R1 can be - [(CHR3) p-X-] q (CHR3) r- and X can be O or X can be S.
[0147] [0147] In portions of Formula (2c) where R1 can be - [(CHR3) p-X-] q (CHR3) r-, p can be 2, r can be 2, q can be 1 and X can be S; or p can be 2, q can be 2, r can be 2 and X can be O; or p can be 2, r can be 2, q can be 1 and X can be O.
[0148] [0148] In portions of Formula (2c) where R1 can be - [(CHR3) p-X-] q (CHR3) r-, each R3 can be hydrogen or at least one R3 can be methyl.
[0149] [0149] In portions of Formula (2c), R1 can be - [(CH2) pX-] q (CH2) r- where each X can be independently selected from O and S. In portions of Formula (2c), R1 can be - [(CH2) pX-] q (CH2) r- each X can be O or each X can be S.
[0150] [0150] In portions of Formula (2c), R1 can be - [(CH2) pX-] q (CH2) r-, where p can be 2, X can be O, q can be 2, r can be 2, R2 can be ethanediyl, m can be 2 and n can be 9.
[0151] [0151] In portions of Formula (2c), each R1 can be derived from 1,8-dimercapto-3,6-dioxaoctane (DMDO; 2,2- (ethane-1,2-diylbis (sulfanyl)) bis (ethan -1-thiol)) or each R1 can be derived from dimercaptodiethylsulfide (DMDS; 2,2'-thiobis (ethan-1-thiol)) and combinations thereof.
[0152] [0152] In portions of Formula (2c), each p can be independently selected from 2, 3, 4, 5 and 6. Each p can be the same and can be 2, 3, 4, 5 or 6.
[0153] [0153] In portions of Formula (2c) each q can be independently 1, 2, 3, 4 or 5. Each q can be the same and can be 1, 2, 3, 4 or 5.
[0154] [0154] In portions of Formula (2c), each r can be independently 2, 3, 4, 5, 6, 7, 8, 9 or 10. Each r can be the same and can be 2, 3, 4, 5 , 6, 7, 8, 9 or 10.
[0155] [0155] In portions of Formula (2c), each r can independently be an integer from 2 to 4, from 2 to 6 or from 2 to 8.
[0156] [0156] In portions of Formula (2c), each A can be derived from a polyvinyl ether such as a divinyl ether. A divinyl ether can comprise a divinyl ether having the structure of Formula (3). Divinyl ethers are also referred to as bis (alkenyl) ethers.
[0157] [0157] In divinyl ethers of Formula (3), m can be an integer from 0 to 50, such as from 0 to 40, from 0 to 20, from 0 to 10, from 1 to 50, from 1 to 40, from 1 to 20, from 1 to 10, from 2 to 50, from 2 to 40, from 2 to 20 or from 2 to 10.
[0158] [0158] In divinyl ethers of Formula (3), each R2 can be independently selected from a C2-10 n-alkanediyl group, a branched C3-6 alkanediyl group and a - [(CH2) pX-] q (CH2) group r-.
[0159] [0159] In divinyl ethers of Formula (3), each R2 may independently be a C2-10 n-alkanediyl group, such as methanediyl, ethanediyl, n-propanediyl or n-butanediyl.
[0160] [0160] In divinyl ethers of Formula (3), each R2 can independently comprise a group - [(CH2) p-X-] q (CH2) r-, where each X can be O or S.
[0161] [0161] In divinyl ethers of Formula (3), each R2 can independently comprise a group - [(CH2) p-X-] q (CH2) r-.
[0162] [0162] In divinyl ethers of Formula (3), each m can independently be an integer from 1 to 3. Each m can be the same and can be 1, 2 or 3.
[0163] [0163] In divinyl ethers of Formula (3), each R2 can be independently selected from a C2-10 n-alkanediyl group, a C3-6 branched alkanediyl group and a - [(CH2) pX-] q (CH2) group r-.
[0164] [0164] In divinyl ethers of Formula (3), each R2 can independently be a C2-10 n-alkanediyl group.
[0165] [0165] In divinyl ethers of Formula (3), each R2 can independently be a group - [(CH2) p-X-] q (CH2) r-, where each X can be O or S.
[0166] [0166] In divinyl ethers of Formula (3), each R2 can be independently a group - [(CH2) pX-] q (CH2) r-, where each X can be O or S and each p can be independently 2, 3, 4, 5 and 6.
[0167] [0167] In divinyl ethers of Formula (3), each p can be the same and can be 2, 3, 4, 5 or 6.
[0168] [0168] In divinyl ethers of Formula (3), each R2 can be independently a group - [(CH2) pX-] q (CH2) r-, where each X can be O or S and each q can be independently 1, 2, 3, 4 or 5.
[0169] [0169] In divinyl ethers of Formula (3), each q can be the same and can be 1, 2, 3, 4 or 5.
[0170] [0170] In divinyl ethers of Formula (3), each R2 can be independently a group - [(CH2) pX-] q (CH2) r-, where each X can be O or S and each r can be independently 2, 3, 4, 5, 6, 7, 8, 9 or 10. In divinyl ethers of Formula (3), each r can be the same and can be 2, 3, 4, 5, 6, 7, 8, 9 or 10. In divinyl ethers of Formula (3), each r can independently be an integer from 2 to 4, from 2 to 6 or from 2 to 8.
[0171] [0171] In divinyl ethers of Formula (3), each R2 can be independently a group - [(CH2) pX-] q (CH2) r-, where each X can be O or S and each r can be independently 2, 3, 4, 5, 6, 7, 8, 9 or 10. In divinyl ethers of Formula (3), each r can be the same and can be 2, 3, 4, 5, 6, 7, 8, 9 or 10. In divinyl ethers of Formula (3), each r can independently be an integer from 2 to 4, from 2 to 6 or from 2 to 8.
[0172] [0172] Examples of suitable divinyl ethers include ethylene glycol divinyl ether (EG-DVE) butanediol divinyl ether (BD-DVE) hexanediol divinyl ether (HD-DVE), diethylene glycol divinyl ether (DEG-DVE), ether triethylene glycol divinyl ether tetraethylene glycol divinyl ether cyclohexanedimethanol ether, polytetrahydrofuryl divinyl ether; and combinations of any of the foregoing.
[0173] [0173] A divinyl ether may comprise a divinyl ether containing sulfur. Examples of suitable sulfur-containing divinyl ethers are disclosed, for example, in International PCT Publication No. WO 2018/085650, which is incorporated by reference in its entirety.
[0174] [0174] In portions of Formula (2c) each A can be independently derived from a polyalkenyl polyfunctionalizing agent. A polyalkenyl polyfunctionalizing agent can have the structure of Formula (4), where z can be 3, 4, 5 or 6.
[0175] [0175] In polyfunctionalizing polyalkenyl agents of Formula (4), each R70 can be independently selected from C1-10 alkanediyl, each A can be independently selected from C1-10 heteroalkanediyl, each A can be independently selected from substituted C1-10 alkanediyl or each A can be independently selected from substituted C1-10 heteroalkanediyl. The one or more substituent groups can be selected from, for example, -OH, = O, C1-4 alkyl and C1-4 alkoxy. The one or more heteroatoms can be selected from, for example, O, S and a combination of these.
[0176] [0176] Examples of suitable polyalkenyl polyfunctionalizing agents include trialyl cyanurate (TAC), trialyl isocyanurate (TAIC), 1,3,5-trialyl-1,3,5-triazinane-2,4,6-trione), 1,3-bis (2-methylalyl) -6-methylene-5- (2-oxopropyl) -1,3,5-triazinone-2,4-dione, tris (allyoxy) methane, pentaerythritol trialyl ether, 1- (allyloxy) -2,2-bis ((allyoxy) methyl) butane, 2-prop-2-ethoxy-1,3,5-tris (prop-2-enyl) benzene, 1,3,5-tris (prop - 2-enyl) -1,3,5-triazinane-2,4-dione and 1,3,5-tris (2-methylalyl) -1,3,5-triazinane-2,4,6-trione, 1 , 2,4-trivinylcyclohexane and combinations of any of the foregoing.
[0177] [0177] In portions of Formula (2c) the molar ratio of portions derived from a divinyl ether to portions derived from a polyalkenyl polyfunctionalizing agent can be, for example, from 0.9 mol% to 0.9999 mol%, from 0 , 95 mol% to 0.99 mol% or 0.96 mol% to 0.99 mol%.
[0178] [0178] In portions of Formula (2c), each R1 can be - (CH2) 2-O- (CH2) 2-O- (CH2) 2-; each R2 can be - (CH2) 2-; and m can be an integer from 1 to 4.
[0179] [0179] In portions of Formula (2c), R2 can be derived from a divinyl ether such as diethylene glycol divinyl ether, a polyalkylene polyfunctionalizing agent such as trialyl cyanurate or a combination thereof.
[0180] [0180] In polythioether prepolymers of Formula (2c), each A can be independently selected from a portion of Formula (3a) and a portion of Formula (4a): - (CH2) 2-O- (R2-O ) m- (CH2) 2- (3a) B {-R70- (CH2) 2-} 2 {-R70- (CH2) 2-S - [- R1-SAS-Su-R1-SH} z-2 ( 4a) where m, R1, R2, R70, A, n and n are defined as in Formula (2c), Formula (3) and Formula (4).
[0181] [0181] In portions of Formula (2c), each R1 can be - (CH2) 2-O- (CH2) 2-O- (CH2) 2-; each R2 can be - (CH2) 2-; m can be an integer from 1 to 4; and the polyfunctionalizing agent B (-R70-CH = CH2) z comprises trialyl cyanurate where z is 3 and each R70 is -O-CH2-CH = CH2.
[0182] [0182] Polythioether prepolymers comprising a portion of Formula (2c) can be terminated in thiol.
[0183] [0183] A thiol-terminated polythiopolymer prepolymer may comprise a thiol-terminated polythiopolymer prepolymer of Formula (2d): HS-R1- [SAS-R1-] n-SH (2d) where, n is an integer from 1 to 60; each R1 is independently selected from C2-10 alkanediyl, C6-8 cycloalkanediyl, C6-14 alkanocycloalkanediyl, C5-8 heterocycloalkanediyl and - [(CHR3) pX-] q (CHR3) r-, where, p is an integer of 2 to 6; q is an integer from 1 to 5; r is an integer from 2 to 10; each R3 is independently selected from hydrogen and methyl; and each X is independently selected from O, S and NR, where R is selected from hydrogen and methyl; and each A is independently selected from a portion derived from a polyvinyl ether of Formula (3) and a portion derived from a polyalkenyl polyfunctionalizing agent of Formula (4): CH2 = CH-O- (R2-O) m-CH = CH2 (3) B (-R70-CH = CH2) z (4) where, each R2 is independently selected from C1-10 alkanediyl, C6-8 cycloalkanediyl, C6-14 alkanocycloalkanediyl and - [(CHR3) pX-] q (CHR3) r-, where p, q, r, R3 and X are as defined as for R1;
[0184] [0184] In thiol-terminated polythiopolymer prepolymers of Formula (2d), R1 can be alkanodiyl C2-10.
[0185] [0185] In thiol-terminated polythiopolymer prepolymers of Formula (2d), R1 can be - [(CHR3) p-X-] q (CHR3) r-.
[0186] [0186] In thiol-terminated polythiopolymer prepolymers of Formula (2d), X can be selected from O and S and so - [(CHR3) pX-] q (CHR3) r- in Formula (2d) can be - [(CHR3) pO-] q (CHR3) r- or - [(CHR3) pS-] q (CHR3) r-. P and r can be equal, just as where p and r can be both, two.
[0187] [0187] In thiol-terminated polythiopolymer prepolymers of Formula (2d), R1 can be selected from C2-6 alkanodiyl and - [(CHR3) p-X-] q (CHR3) r-.
[0188] [0188] In thiol-terminated polythiopolymer prepolymers of Formula (2d), R1 can be - [(CHR3) p-X-] q (CHR3) r- and X can be O or X can be S.
[0189] [0189] In thiol-terminated polythiopolymer prepolymers of Formula (2d), where R1 can be - [(CHR3) pX-] q (CHR3) r-, p can be 2, r can be 2, q can be 1 and X can be S; or p can be 2, q can be 2, r can be 2 and X can be O; or p can be 2, r can be 2, q can be 1 and X can be O.
[0190] [0190] In thiol-terminated polythiopolymer prepolymers of Formula (2d), where R1 can be - [(CHR3) pX-] q (CHR3) r-, each R3 can be hydrogen or at least one R3 can be methyl .
[0191] [0191] In thiol-terminated polythiopolymer prepolymers of Formula (2d), R1 can be - [(CH2) pX-] q (CH2) r- where each X can be independently selected from O and S. In pre -thiol-terminated polythiopolymer polymers of Formula (2d), R1 can be - [(CH2) pX-] q (CH2) r-, each X can be O or each X can be S.
[0192] [0192] In thiol-terminated polythiopolymer prepolymers of Formula (2d), R1 can be - [(CH2) pX-] q (CH2) r-, where p can be 2, X can be O, q can be 2, r can be 2, R2 can be ethanediyl, m can be 2 and n can be 9.
[0193] [0193] In thiol-terminated polythiopolymer prepolymers of Formula (2d), each R1 can be derived from 1,8-dimercapto-3,6-dioxaoctane (DMDO; 2,2- (ethane-1,2-diylbis) (sulfanyl)) bis (ethan-1-thiol)) or each R1 can be derived from dimercaptodiethylsulfide (DMDS; 2,2'-thiobis (ethan-1-thiol)) and combinations thereof.
[0194] [0194] In thiol-terminated polythiopolymer prepolymers of Formula (2d), each p can be independently selected from 2, 3, 4, 5 and 6. Each p can be the same and can be 2, 3, 4, 5 or 6.
[0195] [0195] In thiol-terminated polythiopolymer prepolymers of Formula (2d), each q can be independently 1, 2, 3, 4 or 5. Each q can be the same and can be 1, 2, 3, 4 or 5.
[0196] [0196] In thiol-terminated polythiopolymer prepolymers of Formula (2d), each r can be independently 2, 3, 4, 5, 6, 7, 8, 9 or 10. Each r can be the same and can be 2, 3, 4, 5, 6, 7, 8, 9 or 10.
[0197] [0197] In thiol-terminated polythiopolymer prepolymers of Formula (2d), each r can independently be an integer from 2 to 4, from 2 to 6 or from 2 to 8.
[0198] [0198] In thiol-terminated polythiopolymer prepolymers of Formula (2d), each A can be independently selected from a portion of Formula (3a) and a portion of Formula (4a): - (CH2) 2-O- ( R2-O) m- (CH2) 2- (3a) B {-R70- (CH2) 2-} 2 {-R70- (CH2) 2-S - [- R1-SAS-] n1-R1-SH} z-2 (4a) where m, R1, R2, R70, A, n1 and z are defined as in Formula (3) and Formula
[0199] [0199] In thiol-terminated polythiopolymer prepolymers of Formula (2d) the molar ratio of portions derived from a divinyl ether to portions derived from a polyalkenyl polyfunctionalizing agent can be, for example, 200: 1, 150: 1 , 100: 1, 50: 1 or 25: 1.
[0200] [0200] Polyethers comprising a portion of Formula (2) or Formula (2c) can be terminated in alkenyl.
[0201] [0201] A thiol-terminated polythiopolymer prepolymer may comprise, for example, a thiol-terminated polythiopolymer prepolymer of Formula (2e): CH2 = CH-A1- (CH2) 2-S-R1- [SAS -R1-] nS- (CH2) 2-A1-CH = CH2 (2e) where, n is an integer from 1 to 60; each R1 is independently selected from C2-10 alkanediyl, C6-8 cycloalkanediyl, C6-14 alkanocycloalkanediyl, C5-8 heterocycloalkanediyl and - [(CHR3) pX-] q (CHR3) r-, where, p is an integer of 2 to 6; q is an integer from 1 to 5; r is an integer from 2 to 10; each R3 is independently selected from hydrogen and methyl; and each X is independently selected from O, S and NR, where R is selected from hydrogen and methyl; and each A is independently selected from a portion derived from a polyvinyl ether of Formula (3) and a portion derived from a polyalkenyl polyfunctionalizing agent of Formula (4): CH2 = CH-O- (R2-O) m-CH = CH2 (3) B (-R70-CH = CH2) z (4) where,
[0202] [0202] In alkenyl-terminated polyether ether prepolymers of Formula (2e), R1 can be C2-10 alkanodiyl.
[0203] [0203] In alkenyl-terminated polythether prepolymers of Formula (2e), R1 can be - [(CHR3) p-X-] q (CHR3) r-.
[0204] [0204] In alkenyl-terminated polyethylene prepolymers of Formula (2e), X can be selected from O and S and so - [(CHR3) pX-] q (CHR3) r- in Formula (2e) can be - [(CHR3) pO-] q (CHR3) r- or - [(CHR3) pS-] q (CHR3) r-. P and r can be equal, just as where p and r can be both, two.
[0205] [0205] In alkenyl-terminated polythiopolymer prepolymers of Formula (2e), R1 can be selected from C2-6 alkanediyl and - [(CHR3) p-X-] q (CHR3) r-.
[0206] [0206] In alkenyl-terminated polyethylene prepolymers of Formula (2e), R1 can be - [(CHR3) p-X-] q (CHR3) r- and X can be O or X can be S.
[0207] [0207] In alkenyl-terminated polyethylene prepolymers of Formula (2e), where R1 can be - [(CHR3) p-X-] q (CHR3) r-, p can be 2, r can be 2, q can be
[0208] [0208] In alkenyl-terminated polythiopolymer prepolymers of Formula (2e), where R1 can be - [(CHR3) pX-] q (CHR3) r-, each R3 can be hydrogen or at least one R3 can be methyl .
[0209] [0209] In alkenyl-terminated polythiopolymer prepolymers of Formula (2e), R1 can be - [(CH2) pX-] q (CH2) r- where each X can be independently selected from O and S. In pre -alkenyl-terminated polythioether polymers of Formula (2e), R1 can be - [(CH2) pX-] q (CH2) r- each X can be O or each X can be S.
[0210] [0210] In alkenyl-terminated polythiopolymer prepolymers of Formula (2e), R1 can be - [(CH2) pX-] q (CH2) r-, where p can be 2, X can be O, q can be 2, r can be 2, R2 can be ethanediyl, m can be 2 and n can be 9.
[0211] [0211] In alkenyl-terminated polyethylene prepolymers of Formula (2e), each R1 can be derived from 1,8-dimercapto-3,6-dioxaoctane (DMDO; 2,2- (ethane-1,2-diylbis (sulfanyl)) bis (ethan-1-thiol)) or each R1 can be derived from dimercaptodiethylsulfide (DMDS; 2,2'-thiobis (ethan-1-thiol)) and combinations thereof.
[0212] [0212] In alkenyl-terminated polyethylene prepolymers of Formula (2e), each p can be independently selected from 2, 3, 4, 5 and 6. Each p can be the same and can be 2, 3, 4, 5 or 6.
[0213] [0213] In alkenyl-terminated polyethylene prepolymers of Formula (2e), each q can be independently 1, 2, 3, 4 or 5. Each q can be the same and can be 1, 2, 3, 4 or 5.
[0214] [0214] In alkenyl-terminated polyethylene prepolymers of Formula (2e), each r can be independently 2, 3, 4, 5, 6, 7, 8, 9 or 10. Each r can be the same and can be 2, 3, 4, 5, 6, 7, 8, 9 or 10.
[0215] [0215] In alkenyl-terminated polythiopolymer prepolymers of Formula
[0216] [0216] In alkenyl-terminated polyethylene prepolymers of Formula (2e), each A can be independently selected from a portion of Formula (3a) and a portion of Formula (4b): - (CH2) 2-O- ( R2-O) m- (CH2) 2- (3a) B {-R70- (CH2) 2-} 2 {-R70- (CH2) 2-S - [- R1-SAS-] n1-R1-S ( CH2) 2-A1-CH = CH2} z-2 (4b) where m, R1, R2, R70, A, n1 and z are defined as in Formula (3) and Formula (4).
[0217] [0217] In alkenyl-terminated polyethylene prepolymers of Formula (2e) the molar ratio of portions derived from a divinyl ether to portions derived from a polyalkylene polyfunctionalizing agent can be, for example, 200: 1, 150: 1 , 100: 1, 50: 1 or 25: 1.
[0218] [0218] Various methods can be used to prepare thiol-terminated polythiopolymer prepolymers of Formula (2a) and Formula (2b). Examples of suitable thiol-terminated polythether prepolymers and methods for their production are described in U.S. Patent No. 6,172,179. Such thiol-terminated polythiopolymer prepolymers can be difunctional, that is, linear prepolymers having two terminal thiol groups, or they can be polyfunctional, i.e., branched prepolymers having three or more terminal thiol groups. In practice, thiol-terminated polythiopolymer prepolymers are a combination of prepolymers having complex structures having average thiol functionality, for example, from 2.1 to 2.9.
[0219] [0219] A thiol-terminated polythiopolymer prepolymer may comprise a combination of different thiol-terminated polythiopolymer prepolymers and the thiol-terminated polythiopolymer prepolymers may have the same or different functionality. A thiol-terminated polythiopolymer prepolymer or combination of thiol-terminated polythiopolymer prepolymers may have an average functionality, for example, from 2 to 6, from 2 to 4, from 2 to 3, from 2.05 to 2 , 8 or from 2.05 to 2.5. For example, a thiol-terminated polythiopolymer prepolymer may comprise a difunctional thiol-terminated polythiopolymer, a tri-functional thiol-terminated polythiopolymer or a combination thereof.
[0220] [0220] A thiol-terminated polythiopolymer prepolymer can be prepared by reacting a polythiol and a diene such as a divinyl ether and the respective amounts of reagents used to prepare polythiopolymer prepolymers can be chosen to produce thiol groups terminals. Thus, in some cases, (n or> n, such as n + 1) mol of a polythiol, such as a dithiol or a mixture of at least two different dithiols and 0.05 mol to 1 mol, such as 0, 1 mol to 0.8 mol, of a thiol-terminated polyfunctionalizing agent and / or an alkenyl-terminated polyfunctionalizing agent can be reacted with (n) mol of a diene, such as a divinyl ether or a combination of at least two different dienes , such as a combination of two different divinyl ethers. A thiol-terminated polyfunctionalizing agent may be present in the reaction mixture in an amount sufficient to provide a thiol-terminated polythiopolymer prepolymer having an average thiol functionality, for example, 2.05 to 3, such as 2.1 to 2.8 or from 2.1 to 2.6.
[0221] [0221] A reaction used to prepare a thiol-terminated polythiopolymer prepolymer can be catalyzed by a free radical catalyst. Suitable free radical catalysts include azo compounds, for example, azobisnitrile compounds such as azo (bis) isobutyronitrile (AIBN); organic peroxides, such as benzoyl peroxide and tert-butyl peroxide; and inorganic peroxides, such as hydrogen peroxide. The reaction can also be carried out by irradiation with ultraviolet light with or without a radical initiator / photosensitizer. Ion catalysis methods, using inorganic or organic bases, for example, triethylamine, can also be used.
[0222] [0222] Suitable thiol-terminated polythiopolymer prepolymers can be produced by reacting a divinyl ether or combination of divinyl ethers with an excess of dithiol or combination of dithiol.
[0223] [0223] A thiol-terminated polythiopolymer prepolymer can comprise the reaction product of reagents comprising: (a) a dithiol of Formula (5): HS-R1-SH (5) in which, R1 is selected from C2 alkanodylyl -6, C6-8 cycloalkanodiyl, C6-10 alkanocycloalkodiyl, C5-8 heterocycloalkanodiyl and - [(CHR3) pX-] q (CHR3) r-; where, each R3 is independently selected from hydrogen and methyl; each X is independently selected from -O-, -S-, -S-S- and -NR- where R is selected from hydrogen and methyl; p is an integer from 2 to 6; q is an integer from 1 to 5; and r is an integer from 2 to 10; and (b) a bis (alkenyl) ether of the Formula (3): CH2 = CH-O- (R2-O-) mCH = CH2 (3) in which, each R2 is independently selected from C1-10 alkanediyl, C6 cycloalkanediyl -8, C6-14 alkanocycloalkanediyl and - [(CHR3) pX-] q (CHR3) r-, where p, q, r, R3 and X are as defined above; and m is an integer from 0 to 50.
[0224] [0224] The reagents may further comprise (c) a polyfunctional compound such as a polyalkylene polyfunctionalizing agent such as a polyfunctional compound B (-V) z, where B, -V and z are defined as for Formula (2b).
[0225] [0225] In dithols of Formula (5), R1 can be - [(CHR3) p-X-] q (CHR3) r-.
[0226] [0226] In dithols of Formula (5), R1 can be - [(CHR3) pX-] q (CHR3) r- and X can be selected from O and S and so - [(CHR3) pX-] q (CHR3 ) r- in Formula (5) can be - [(CHR3) pO-] q (CHR3) r- or - [(CHR3) pS-] q (CHR3) r-. P and r can be equal, just as where p and r can be both, two.
[0227] [0227] In dithols of Formula (5), R1 may comprise C2-6 alkanodiyl and - [(CHR3) p-X-] q (CHR3) r-.
[0228] [0228] In dithols of Formula (5), R1 can be - [(CHR3) p-X-] q (CHR3) r- and X can be O or X can be S.
[0229] [0229] In dithols of Formula (5) where R1 can be - [(CHR3) p-X-] q (CHR3) r-, p can be 2, r can be 2, q can be 1 and X can be S; or p can be 2, q can be 2, r can be 2 and X can be O; or p can be 2, r can be 2, q can be 1 and X can be O.
[0230] [0230] In dithols of Formula (5) where R1 can be - [(CHR3) p-X-] q (CHR3) r-, each R3 can be hydrogen or at least one R3 can be methyl.
[0231] [0231] In dithols of Formula (5), each R1 can be derived from 1,8-dimercapto-3,6-dioxaoctane (DMDO; 2,2- (ethane-1,2-diylbis (sulfanyl)) bis (ethan -1-thiol)) or each R1 can be derived from dimercaptodiethylsulfide (DMDS; 2,2'-thiobis (ethan-1-thiol)) and combinations thereof.
[0232] [0232] In dithols of Formula (5), where R1 can be - [(CHR3) pX-] q (CHR3) r-, each p can independently comprise 2, 3, 4, 5 and 6. Each p can be the same and can be 2, 3, 4, 5 or 6.
[0233] [0233] In dithols of Formula (5), where R1 can be - [(CHR3) pX-] q (CHR3) r-, each q can be independently 1, 2, 3, 4 or 5. Each q can be the same and can be 1, 2, 3, 4 or 5.
[0234] [0234] In dithols of Formula (5), where R1 can be - [(CHR3) pX-] q (CHR3) r-, each r can be independently 2, 3, 4, 5, 6, 7, 8, 9 or 10. Each r can be the same and can be 2, 3, 4, 5, 6, 7, 8, 9 or 10.
[0235] [0235] In dithols of Formula (5), where R1 can be - [(CHR3) pX-] q (CHR3) r-, each r can be independently an integer from 2 to 4, from 2 to 6 or from 2 to 8.
[0236] [0236] In bis (alkenyl) ethers of Formula (3), each m can independently be an integer from 1 to 3. Each m can be the same and can be 1, 2 or 3.
[0237] [0237] In bis (alkenyl) ethers of Formula (3), each R2 can independently comprise a C2-10 n-alkanediyl group, a C3-6 branched alkanediyl group or a - [(CH2) pX-] q (CH2 ) r-.
[0238] [0238] In bis (alkenyl) ethers of Formula (3), each R2 can independently comprise a C2-10 n-alkanediyl group.
[0239] [0239] In bis (alkenyl) ethers of Formula (3), each R2 can independently comprise a group - [(CH2) p-X-] q (CH2) r-, where each X can be O or S.
[0240] [0240] In bis (alkenyl) ethers of Formula (3), each R2 can independently comprise a group - [(CH2) pX-] q (CH2) r-, where each X can be O or S and each p can be independently 2, 3, 4, 5 and 6.
[0241] [0241] In bis (alkenyl) ethers of Formula (3), each R2 can independently comprise a group - [(CH2) pX-] q (CH2) r-, where each p can be the same and can be 2, 3 , 4, 5 or 6.
[0242] [0242] In bis (alkenyl) ethers of Formula (3), each R2 can independently comprise a group - [(CH2) pX-] q (CH2) r-, where each X can be O or S and each q can be independently 1, 2, 3, 4 or 5.
[0243] [0243] In bis (alkenyl) ethers of Formula (3), each R2 can independently comprise a group - [(CH2) pX-] q (CH2) r-, where each q can be the same and can be 1, 2 , 3, 4 or 5.
[0244] [0244] In bis (alkenyl) ethers of Formula (3), each R2 can independently comprise a group - [(CH2) pX-] q (CH2) r-, where each X can be O or S and each r can be independently 2, 3, 4, 5, 6, 7, 8, 9 or 10,
[0245] [0245] In bis (alkenyl) ethers of Formula (3), each r can be the same and can be 2, 3, 4, 5, 6, 7, 8, 9 or 10. In bis (alkenyl) ethers of Formula (3), each r can independently be an integer from 2 to 4, from 2 to 6 or from 2 to 8.
[0246] [0246] Dithols suitable for use in preparing thiol-terminated polythiopolymer prepolymers include those having the structure of Formula (5): HS-R1-SH (5) wherein, R1 can be C2-6 alkanodiyl, C6 cycloalkanediyl -8, C6-10 alkanocycloalkanediyl, C5-8 heterocycloalkanediyl or - [(CHR3) pX-] q (CHR3) r-; wherein, each R3 can be independently hydrogen or methyl; each X can be independently O, S, -S-S- or NR where R can be hydrogen or methyl; p is an integer from 2 to 6; q is an integer from 1 to 5; and r is an integer from 2 to 10.
[0247] [0247] Examples of suitable dithols include 1,2-ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 1,3-butanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,3-pentanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,3-dimercapto-3-methylbutane, dipentenodimercaptan, ethylcyclohexyldithiol (ECHDT), dimercaptodiethylsulfide, methyl substituted dimercapodiethylsulfide, dimercapodane, dimercapodine, dimercapodine -oxapentan and a combination of any of the foregoing.
[0248] [0248] A dithiol may have one or more pendant groups comprising a lower alkyl group (e.g., C1-6), a lower alkoxy group or a hydroxyl group. Suitable alkyl pendant groups include, for example, C1-6 linear alkyl, C3-6 branched alkyl, cyclopentyl and cyclohexyl.
[0249] [0249] Other examples of suitable dithiols include dimercaptodiethylsulfide (DMDS) (in Formula (5), R1 is - [(CH2) pX-] q (CH2) r-, where p is 2, r is 2, q is 1 and X is S); dimercaptodioxaoctane (DMDO) (in Formula (5), R1 is - [(CH2) p-X-] q (CH2) r-, where p is 2, q is 2, r is 2 and X is O); and 1,5-dimercapto-3-oxapentane (in Formula (5), R1 is - [(CH2) p- X-] q (CH2) r-, where p is 2, r is 2, q is 1 and X is O). It is also possible to use dithiols that include both hetero atoms in the main carbon chain and pendant alkyl groups, such as methyl groups. Such dithiols include, for example, methyl-substituted DMDS, such as HS-CH2CH (CH3) -S-CH2CH2-SH, HS-CH (CH3) CH2-S-CH2CH2-SH and dimethyl-substituted DMDS, such as HS- CH2CH (CH3) -S-CH (CH3) CH2-SH and HS-CH (CH3) CH-S-CH2CH (CH3) -SH.
[0250] [0250] Bis (alkenyl) ethers suitable for preparing thiol-terminated polythiopolymer prepolymers include, for example, Formula (3) bis (alkenyl) ethers: CH2 = CH-O- (R2-O-) mCH = CH2 (3) where each R2 can be independently C1-10 alkanediyl, C6-8 cycloalkanediyl, C6-14 alkanocycloalkanediyl or - [(CHR3) pX-] q (CHR3) r-, where each R3 can independently comprise hydrogen or methyl; each X can independently comprise O, S, -S-S- or NR where R can be hydrogen or methyl; p can be an integer from 2 to 6; q can be an integer from 1 to 5; and r can be an integer from 2 to 10.
[0251] Suitable bis (alkenyl) ethers include, for example, compounds having at least one oxyalkanediyl group -R2-O-, such as from 1 to 4 oxyalkanediyl groups, i.e. compounds where m in Formula (3) is a integer ranging from 1 to 4. The variable m in Formula (3) can be an integer ranging from 2 to 4. It is also possible to use commercially available divinyl ether mixtures that are characterized by a non-integral mean value for the number of oxyalkane diary units per molecule. Thus, m in Formula (3) can also assume rational numerical values ranging from 0 to 10.0, such as from 1.0 to 10.0, from 1.0 to 4.0 or from 2.0 to 4.0 .
[0252] [0252] Examples of suitable bis (alkenyl) ethers include ethylene glycol divinyl ether (EG-DVE) (R2 in Formula (3) is ethanediyl in is 1), butanediol divinyl ether (BD-DVE) (R2 in Formula ( 3) is butanediyl and is 1), hexanediol divinyl ether (HD-DVE) (R2 in Formula (3) is hexanediyl in é 1), diethylene glycol divinyl ether (DEG-DVE) (R2 in Formula (3) is ethanediyl in é 2), triethylene glycol divinyl ether (R2 in Formula (3) is ethanodiyl in é 3), tetraethylene glycol divinyl ether (R2 in Formula (3) is ethanediyl in é 4), cyclohexanodimethanol divinyl ether, ether polytetrahydrofuryl divinyl; trivinyl ether monomers, such as trimethylolpropane trivinyl ether; tetrafunctional ether monomers, such as pentaerythritol tetravinyl ether; and combinations of two or more such polyvinyl ether monomers. A polyvinyl ether can have one or more pendant groups which can comprise alkyl groups, hydroxyl groups, alkoxy groups or amine groups.
[0253] [0253] Bis (alkenyl) ethers in which R2 in Formula (3) is branched C3-6 alkanediyl can be prepared by reacting a polyhydroxyl compound with acetylene. Examples of such divinyl ethers include compounds in which R2 in Formula (3) is an alkyl substituted methanodiyl group such as CH (-CH3) or an alkyl substituted ethanediyl.
[0254] [0254] Two or more types of bis (alkenyl) ethers of Formula (3) may be used. Thus, two dithiols of Formula (5) and one divinyl ether of Formula (3), one dithiol of Formula (5) and two divinyl ethers of Formula (3), two dithiols of Formula (5) and two divinyl ethers of Formula ( 3) and more than two compounds of one or both of Formula (5) and Formula (3), can be used to produce a variety of thiol-terminated polythiopolymer prepolymers.
[0255] [0255] Bis (alkenyl) ethers can comprise, for example, from 20 mol% to less than 50 mol% of the reagents used to prepare a thiol-terminated polythiopolymer prepolymer or 30 mol% less than 50 mol percent.
[0256] [0256] Relative amounts of dithols and bis (alkenyl) ethers can be selected to produce polythioether prepolymers having terminal thiol groups.
[0257] [0257] The reaction between bis (alkenyl) dithols and ethers and / or bis (alkenyl) polyethols and ethers can be catalyzed by a free radical catalyst, an ion catalyst or ultraviolet radiation. Suitable free radical catalysts include, for example, azo compounds, for example azobisnitriles such as azo (bis) isobutyronitrile (AIBN); organic peroxides such as benzoyl peroxide and tert-butyl peroxide; and inorganic peroxides such as hydrogen peroxide. In certain reactions, the catalyst does not comprise acidic or basic compounds and does not produce acidic or basic compounds during decomposition. Examples of suitable free radical catalysts include azo-type catalysts, such as Vazo®-57 (Du Pont), Vazo®-64 (Du Pont), Vazo®-67 (Du Pont), V-70® (Wako Specialty Chemicals ) and V-65B® (Wako Specialty Chemicals). Examples of other suitable free radical catalysts include alkyl peroxides, such as tert-butyl peroxide. The reaction can also be carried out by irradiation with ultraviolet light with or without a portion of cationic photoinitiation.
[0258] [0258] Thiol-terminated polythiopolymer prepolymers provided by the present disclosure can be prepared by combining at least one dithiol of Formula (5) and at least one bis (alkenyl) ether of Formula (3) followed by the addition of a catalyst appropriate and carrying out the reaction at a temperature, for example, within a range of 30 ° C to 120 ° C, such as 70 ° C to 90 ° C, for a duration, for example, within a range of 2 hours to 24 hours, such as 2 hours to 6 hours.
[0259] [0259] Thiol-terminated polythiopolymer prepolymers may comprise a polyfunctional polythioether prepolymer, i.e., they may have an average thiol functionality greater than 2.0. Suitable polyfunctional thiol polythioether prepolymers include, for example, those having the structure of Formula (2b): {HS-R1- [S- (CH2) 2-O- (R2-O) m- (CH2) 2-S-R1-] nS-V '-} zB (2b) where z has an average value greater than 2.0, such as a value within the range of 2.1 and 3, a value within a range of 2.1 and 4, a value within a range of 3 and 6, or it can be an integer from 3 to 6.
[0260] [0260] Polyfunctionalizing agents suitable for use in preparing such polyfunctional thiol-terminated polythiopolymer prepolymers include trifunctionalizing agents, i.e., compounds where z is 3. Suitable trifunctionalizing agents include, for example, trialyl cyanurate (TAC), 1 , 2,3-propanotrityiol, tritols containing isocyanurate and combinations thereof, as disclosed in US Order Publication No. 2010/0010133, which is incorporated by reference in its entirety; and isocyanurates as disclosed, for example, in U.S. Patent No.
[0261] [0261] Thiol-terminated polythiopolymer prepolymers provided by the present disclosure are liquid at room temperature (20 ° C to 25 ° C) and may have a glass transition temperature Tg, for example, less than -20 ° C, less than -30 ° C or less than -40 ° C. The glass transition temperature Tg is determined by Dynamic Mass Analysis (DMA) using a TA Instruments Q800 apparatus with a frequency of 1 Hz, an amplitude of 20 microns and a temperature ramp of -80 ° C to 25 ° C, with Tg identified as the peak of the tan δ curve.
[0262] [0262] Thiol-terminated polythiopolymer prepolymers may exhibit a viscosity, for example, within a range of 20 poise to 500 poise (2 Pa-s to 50 Pa-s), 20 poise to 200 poise (2 Pa -s to 20 Pa-s) or 40 poise to 120 poise (4 Pa-s to 12 Pa-s), measured using a Brookfield CAP 2000 viscometer, with a No 6 axis, at a speed of 300 rpm and a temperature 25 ° C.
[0263] [0263] Thiol-terminated polythiopolymer prepolymers provided by the present disclosure can be characterized by a numerical average molecular weight and / or a molecular weight distribution. Polythioether prepolymers can exhibit a numerical average molecular weight, for example, from 500 Dalton to 20,000 Dalton, from
[0264] [0264] The main chain of a thiol-terminated polythiopolymer prepolymer provided by the present disclosure can be modified to improve properties such as adhesion, tensile strength, elongation, UV resistance, hardness and / or flexibility of prepared sealants and coatings using polyether ethers. For example, adhesion promoting groups, antioxidants, metal binders and / or urethane bonds can be incorporated into the backbone of a polyether ether prepolymer to improve one or more performance attributes.
[0265] [0265] Permapol® P3.1E, Permapol® P3.1E-2.8 and Permapol® L56086 are thiol-terminated polythiopolymer prepolymers covered by the Formula (2) portion and the Formula (2c) portion and the prepolymers thiol-terminated polythioether compounds of Formula (2a), (2b) and Formula (2d).
[0266] [0266] Sulfur-containing polythether prepolymers prepared by the present disclosure can also be prepared using sulfur-containing poly (alkenyl) ethers and / or may contain polyurethane and / or polyurea segments in the prepolymer backbone. Sulfur-containing poly (alkenyl) ethers and sulfur-containing polyether ethers prepolymers prepared using sulfur-containing poly (alkenyl) ethers are disclosed in PCT International Application No. WO 2018/085650, which is incorporated by reference in its entirety. Bis (alkenyl) ethers containing urethane / urea and sulfur-containing polythioether prepolymers containing bis (alkenyl) ethers containing urethane / urea are disclosed in U.S. Order Publication No. 2017/0368737, which is incorporated by reference in its entirety.
[0267] [0267] Polyether ethers prepolymers provided by the present disclosure may comprise a main chain of Formula (2c): -S-R1 - [- SAS-R1-] sS- (2c) where, s is an integer of 1 at 60;
[0268] [0268] In portions of Formula (2c), s can be an integer, for example, from 1 to 40, from 1 to 30, from 1 to 20 or from 1 to 10.
[0269] [0269] In portions of Formula (2c), R1 can be n-alkanediyl C2-6, such as ethane-diyl, n-propane-diyl, n-butane-diyl, n-pentane-diyl or n-hexane-diyl .
[0270] [0270] In portions of Formula (2c), R1 can be - [(- CHR-) p-X-] q - (- CHR-) r-.
[0271] [0271] In portions of Formula (2c), R1 can be - [(- CHR-) p-X-] q - (- CHR-) r-, where at least one R can be -CH3.
[0272] [0272] In portions of Formula (2c), R1 can be - [(- CH2-) p-X-] q - (- CH2-) r-.
[0273] [0273] In portions of Formula (2c), R1 can be - [(- CH2-) p-X-] q - (- CH2-) r- and each X can be -O-.
[0274] [0274] In portions of Formula (2c), R1 can be - [(- CH2-) pX-] q - (- CH2-) r- and each X can be -S- at least one X can be -S- , each X can be -SS- or at least one X can be -SS-.
[0275] [0275] In portions of Formula (2c), R1 can be - [(- CH2-) p-X-] q - (- CH2-) r- and each p can be 2 and r can be 2.
[0276] [0276] In portions of Formula (2c), R1 can be - [(- CH2-) p-X-] q - (- CH2-) r-, where p can be 1, 2, 3, 4 or 5.
[0277] [0277] In portions of Formula (2c), R1 can be - [(- CH2-) p-X-] q - (- CH2-) r-, where q can be 1, 2, 3, 4 or 5.
[0278] [0278] In portions of Formula (2c), R1 can be - [(- CH2-) p-X-] q - (- CH2-) r-, where r can be 1, 2, 3, 4 or 5.
[0279] [0279] In portions of Formula (2c), R1 can be - [(- CH2-) p-X-] q - (- CH2-) r-, where each p can be 2 and r can be 2; and q can be 1, 2, 3, 4 or 5.
[0280] [0280] In portions of Formula (2c), R1 can be - [(- CH2-) pX-] q - (- CH2-) r-, where each X can be -S- or at least one X can be - S-; each p can be 2 and r can be 2; and q can be 1, 2, 3, 4 or 5.
[0281] [0281] In portions of Formula (2c), R1 can be - [(- CH2-) pX-] q - (- CH2-) r-, where each X can be -O- or at least one X can be - O-; each p can be 2 and r can be 2; and q can be 1, 2, 3, 4 or 5.
[0282] [0282] In portions of Formula (2c), R1 can be - [(- CH2-) pX-] q- (CH2) r-, where p is 2, r is 2, q is 1 and X is -S- ; R1 can be - [(- CH2-) p-X-] q- (CH2) r-, where p is 2, q is 2, r is 2 and X is -O-; or R1 can be - [(- CH2-) p-X-] q- (CH2) -, where p is 2, r is 2, q is 1 and X is -O-.
[0283] [0283] In portions of Formula (7), each n can be 1, 2, 3 or 4.
[0284] [0284] In portions of Formula (7), each Y 'can be -O- or each Y' can be -S-.
[0285] [0285] In portions of Formula (7), R4 can be n-alkanediyl C2-6, such as ethane-diyl, n-propane-diyl, n-butane-diyl, n-pentane-diyl or n-hexane-diyl .
[0286] [0286] In portions of Formula (7), R4 can be C2-6 n-alkanediyl; both Y 'can be -S- and one Y' can be -S- and the other Y 'can be -O-.
[0287] [0287] In portions of Formula (7), R4 can be - [(- CH2-) p-X-] q - (- CH2-) r-.
[0288] [0288] In portions of Formula (7), R4 can be - [(- CH2-) pX-] q - (- CH2-) r-, where each X can be -O- or each X can be -SS- or at least one X can be -O- or at least one X can be -SS-.
[0289] [0289] In portions of Formula (7), R4 can be - [(- CH2-) pX-] q - (- CH2-) r-, where each X can be -S- or at least one X can be - S-.
[0290] [0290] In portions of Formula (7), R4 can be - [(- CH2-) p-X-] q - (- CH2-) r-, where each p can be 2 and r can be 2.
[0291] [0291] In portions of Formula (7), R4 can be - [(- CH2-) p-X-] q - (- CH2-) r-, where q can be 1, 2, 3, 4 or 5.
[0292] [0292] In portions of Formula (7), R4 can be - [(- CH2-) p-X-] q - (- CH2-) r-, where each p can be 2 and r can be 2; and q can be 1, 2, 3, 4 or 5.
[0293] [0293] In portions of Formula (7), R4 can be - [(- CH2-) p-X-] q - (- CH2-) r-, where each X can be -S-; each p can be 2 and r can be 2; and q can be 1, 2, 3, 4 or 5.
[0294] [0294] In portions of Formula (7), R4 can be - [(- CH2-) p-X-] q - (- CH2-) r-, where each X can be -O-; each p can be 2 and r can be 2; and q can be 1, 2, 3, 4 or 5.
[0295] [0295] In portions of Formula (7), R4 can be - [(- CH2-) p-X-] q - (- CH2-) r-, where each X can be -O-; and each Y 'can be -S-.
[0296] [0296] In portions of Formula (7), R4 can be - [(- CH2-) p-X-] q - (- CH2-) r-, where each X can be -S-; and each Y 'can be -O-.
[0297] [0297] In portions of Formula (7), each n can be 2, each Y- can be independently selected from -O- and -S- and R4 can be - [(- CH2-) pX-] q - (- CH2-) r-, where each X is independently selected from -O-, -S- and -SS-, p is 2, q is selected from 1 and 2 and r is 2.
[0298] [0298] In portions of Formula (7), each n can be 2, each Y- can be independently selected from -O- and -S- and R4 can be C2-4 alkanediyl, such as ethanediyl, n-propanedyl or n -butanodiíla.
[0299] [0299] In portions of Formula (3a), m can be an integer, for example, from 1 to 20, from 2 to 20, from 2 to 10, from 2 to 6 or from 2 to 4. In portions of Formula (3a), m can be, for example, 1, 2, 3, 4, 5 or 6.
[0300] [0300] In portions of Formula (3a), each R2 can be independently n-alkanediyl C2-6 such as 1,2-ethane-diyl, 1,3-propane-diyl, 1,4-butane-diyl, 1, 5- pentane-diyl or 1,6-hexane-diyl. In portions of Formula (3a), each R2 can be n-alkanediyl C2-6 such as 1,2-ethane-diyl, 1,3-propane-diyl, 1,4-butane-diyl, 1,5-pentane- diyl or 1,6-hexane-diyl.
[0301] [0301] In portions of Formula (3a), m can be 1, 2, 3 or 4; and R2 can be n-C2-6 alkanediyl such as 1,2-ethane-dialy, 1,3-propane-dialy, 1,4-butane-dialy, 1,5-pentane-dialy or 1,6-hexane- diíla.
[0302] [0302] A portion of Formula (7) can be derived from a sulfur-containing bis (alkenyl) ether, such as a sulfur-containing bis (alkenyl) ether of Formula (7a): CH2 = CH-O- (CH2) n- Y'-R4-Y '- (CH2) nO-CH = CH2 (7a) where n, Y' and R4 are defined as in Formula (2a).
[0303] [0303] A portion of Formula (3a) can be derived from a divinyl ether, such as a divinyl ether of Formula (3): CH2 = CH-O - (- R2-O-) m-CH = CH2 (3) where me and R2 are defined as in Formula (7)
[0304] [0304] In polythiopolymer prepolymers comprising a Formula (2c) backbone, each A may be a portion of Formula (3a).
[0305] [0305] In polythiopolymer prepolymers comprising a Formula (2c) backbone, each A can be independently a portion of Formula (7a) or a portion of Formula (3a), where at least one A is a portion of Formula (7a).
[0306] [0306] In polythioether prepolymers comprising a main chain of Formula (2c), from 20 mol% to 80 mol%, 30 mol% to 70 mol% or 40 mol% to 60% mol mol of the portions of A may comprise portions of Formula (3a) and the remaining portions of A may be portions of Formula (7).
[0307] [0307] In polyether ethers prepolymers comprising a main chain of Formula (2c), s can be, for example, an integer from 1 to 40, from 1 to 20, from 2 to 60, from 2 to 40, from 2 to 20, from 5 to 60, from 5 to 40, from 5 to 20, from 10 to 40 or an integer from 10 to 30. Polythioether prepolymers having a main chain of Formula (2c) can also comprise a combination of polyether ether prepolymers having an average value of s from 1 to 40, from 1 to 20, from 2 to 60, from 2 to 40, from 2 to 20, from 5 to 60, from 5 to 40, from 5 to 20, 10 to 40, or 10 to 30, including values other than integers.
[0308] [0308] Polyether ethers prepolymers provided by the present disclosure may comprise bis (alkenyl) ethers containing urethane / urea incorporated in the prepolymer backbone. Segments of bis (alkenyl) ethers containing urethane / urea and polyether ether prepolymers containing urethane / urea in the prepolymer backbone are disclosed in U.S. Order Publication No. 2017/0368737, which is incorporated by reference in its entirety.
[0309] [0309] Polyether ethers prepolymers provided by the present disclosure can be prepared, for example, by reacting a polythiol or combination of polythioles with a bis (alkenyl) ether containing urethane / urea or a combination of bis (alkenyl) ethers containing urethane / urea.
[0310] [0310] Polythioether prepolymers provided by the present disclosure can be prepared by reacting a polythiol or combination of polythiols, a bis (alkenyl) ether containing urethane / urea or a combination of bis (alkenyl) ethers containing urethane / urea and an ether divinyl or combination of divinyl ethers.
[0311] [0311] Polythether prepolymers provided by the present disclosure may comprise a main chain of Formula (2c): -S-R1 - [- SAS-R1-] sS- (2c) where, s is an integer of 1 at 60; each R1 is selected from C2-10 alkanediyl, C6-8 cycloalkanediyl, C6-10 alkanocycloalkanediyl and - [(- CHR-) pX-] q- (CHR) r-, where each R is independently selected from hydrogen and methyl, where each X is independently selected from -O- and -S- each p is independently an integer from 2 to 6;
[0312] [0312] In portions of Formula (2c), each R1 can be - [- (CHR) p-X-] q- (CHR) r-.
[0313] [0313] In portions of Formula (2c), X can be selected from -O- and -S- and so - [- (CHR) pX-] q- (CHR) r- can be - [(- CHR-) pO-] q- (CHR) r-, - [(- CHR) 2-) pS-] q- (CHR) r-, - [(- CH2-) 2-O-] q- (CH2) 2- or - [(- CH2) 2-S-] q- (CH2) 2-. P and r can be the same, just as both p and r can be 2, 3 or 4.
[0314] [0314] In portions of Formula (2c), each R1 can be selected from C2-6 alkanodiyl and - [- (CHR) p-X-] q- (CHR) r-.
[0315] [0315] In portions of Formula (2c), each R1 can be - [- (CHR) p-X-] q- (CHR) r- and X can be -O- or X can be -S-.
[0316] [0316] In portions of Formula (2c), each R1 can be - [- (CHR) pX-] q- (CHR) r-, p can be 2, r can be 2, q can be 1 and X can be -S-; or p can be 2, q can be 2, r can be 2 and X can be-O-; or p can be 2, r can be 2, q can be 1 and X can be -O-.
[0317] [0317] In portions of Formula (2c), each R1 can be - [- (CHR) p-X-] q- (CHR) r-, each R can be hydrogen or at least one R can be methyl.
[0318] [0318] In portions of Formula (2c), each R1 can be derived from dimercaptodioxaoctane (DMDO) or each R1 is derived from dimercaptodiethylsulfide (DMDS).
[0319] [0319] In portions of Formula (2c), each R1 can be - [(CH2) 2-O-] 2- (CH2) 2-.
[0320] [0320] In portions of Formula (2c), each R1 can be - [- (CHR) p-X-] q- (CHR) r-, each p can be independently selected from 2, 3, 4, 5 and 6; or each p can be the same and can be 2, 3, 4, 5 or 6.
[0321] [0321] In portions of Formula (2c), each R1 can be - [- (CHR) pX-] q- (CHR) r-, each r can be selected from 2, 3, 4, 5, 6, 7 and 8.
[0322] [0322] In portions of Formula (2c), each R1 can be - [- (CHR) p-X-] q- (CHR) r-, each q can be selected from 1, 2, 3, 4 and 5.
[0323] [0323] In portions of Formula (2c), each R1 can be - [- (CHR) pX-] q- (CHR) r-, each m can be independently an integer from 1 to 3. Each m can be the same as 0, 1, 2 or 3.
[0324] [0324] In polythioether prepolymers of Formula (2c), s can be an integer from 0 to 30, an integer from 0 to 20, an integer from 0 to 10 or an integer from 0 to 5.
[0325] [0325] In polythioether prepolymers of Formula (2c), s can be 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.
[0326] [0326] In polythioether prepolymers of Formula (2c), R1 is - [(- CH2-) pX-] q- (CH2) r-, where p is 2, X is -O-, q is 2, r is 2, R2 is ethanediyl, m is 2 and n is 9.
[0327] [0327] In polythioether prepolymers of Formula (2c), R1 is selected from C2-6 alkanodiyl and - [- (CHR) p-X-] q- (CHR) r-.
[0328] [0328] In portions of Formula (2c), R1 is - [- (CHR) p-X-] q- (CHR) r- and X is -O- or X is -S-.
[0329] [0329] In portions of Formula (2c), where R1 is - [- (CHR) p-X-] q- (CHR) r-, p is 2, r is 2, q is 1 and X is -S-; or where p is 2, q is 2, r is 2 and X is -O-; or p is 2, r is 2, q is 1 and X is - O-.
[0330] [0330] In portions of Formula (2c), where R1 is - [- (CHR) p-X-] q- (CHR) r-, each R is hydrogen or at least one R is methyl.
[0331] [0331] In portions of Formula (2c), each R1 is the same or at least one R1 is different.
[0332] [0332] In portions of Formula (2c), s can be an integer from 1 to 20 or an integer from 1 to 10, such as 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.
[0333] [0333] In portions of Formula (2c), each R1 can be C2-4 alkanediyl, n-ethane-diyl, n-propane-diyl, n-butane-diyl, n-pentane-diyl or n-hexane-diyl.
[0334] [0334] A portion of Formula (2c) can be derived from a bis (alkenyl) ether containing urethane / urea, such as a bis (alkenyl) ether containing urethane / urea from Formula (8a): CH2 = CH-O-R5 -Y'-C (= O) -NH-R4-NH-C (= O) -Y'-R5-O-CH = CH2 (8a) where Y ', R4 and R5 are defined as in Formula (8) .
[0335] [0335] A portion of Formula (3a) can be derived from a divinyl ether, such as a divinyl ether of Formula (3): CH2 = CH-O - (- R2-O-) m-CH = CH2 (3) where m and R2 are defined as in Formula (3a).
[0336] [0336] In polyether ethers prepolymers comprising a Formula (2c) backbone, each A may be a portion of Formula (8).
[0337] [0337] In polyether ether prepolymers comprising a Formula (2c) backbone, each A can be independently a portion of Formula (8) or a portion of Formula (3a), where at least one A is a portion of Formula (8).
[0338] [0338] In polythioether prepolymers comprising a main chain of Formula (2c), from 1 mol% to 20 mol%, from 1 mol% to 15 mol%, from 1 mol% to 10% in mol or 2 mol% to 8 mol% of portions of A can comprise portions of Formula (8) and the remaining A portions can be portions of Formula (3a), where mol% is based on the total mol of - A- in the main chain of Formula (2c). For example, in a polythioether prepolymer of Formula (2c), 5 mol% of portions of A may comprise a portion of Formula (8) and 95 mol% of portions of A may comprise a portion of Formula (3a ), where the mol% is based on the total mol portions of Formula (8) and portions of Formula (3a) forming the polythioether prepolymer comprising a main chain of Formula (2c).
[0339] [0339] In polyether ether prepolymers comprising a main chain of Formula (2c), m can be, for example, an integer from 1 to 40, from 1 to 20, from 2 to 60, from 2 to 40, from 2 to 20, 5 to 60, 5 to 40, 5 to 20, 10 to 40 or an integer from 10 to 30.
[0340] [0340] In polythioether prepolymers of Formula (2c) the polyether ether prepolymer may comprise a thiol-terminated polythether prepolymer of Formula (2d), a thiol-terminated polythether prepolymer of Formula (2e ) or a combination of these: HS-R1 - [- SAS-R1-] s-SH (2d) {HS-R1 - [- SAS-R1-] sS-V '-} zB (2e) where s, R1, A, B, z and V 'are defined as for Formula (2c) and Formula (8); and at least one A comprises a portion of Formula (3a).
[0341] [0341] A thiol-terminated sulfur-containing prepolymer may comprise a thiol-terminated sulfur-containing polypolymer.
[0342] [0342] Sulfur-containing polyform prepolymers useful in sealant applications are disclosed, for example, in U.S. Patent No. 8,729,216 and U.S. Patent No. 8,541,513, each of which is incorporated by reference in its entirety .
[0343] [0343] A thiol-terminated sulfur-containing polyform prepolymer may have the structure of Formula (9): R3-R1- (S) p-R1- [OC (R2) 2-O-R1- (S) p -R1-] n-R3 (9) where n is an integer selected from 1 to 50; each p is independently selected from 1 and 2; each R1 comprises C2-6 alkanediyl; each R2 independently comprises hydrogen, C1-6 alkyl, C7-12 phenylalkyl, substituted C7-12 phenylalkyl, C6-12 cycloalkylalkyl, substituted C6-12 cycloalkylalkyl, C3-12 cycloalkyl, substituted C3-12 cycloalkyl, C6-12 aryl and aryl Substituted C6-12; and each R3 is -OR3 'where R3' comprises a thiol-terminated group.
[0344] [0344] In sulfur-containing polyformal prepolymers of Formula (9), each R1 can be independently C2-6 alkanediyl, C2-4 alkanediyl, C2-3 alkanediyl or ethane-1,2-diyl. In sulfur-containing poliform prepolymers of Formula (9), each R1 can be ethane-1,2-diyl.
[0345] [0345] In sulfur-containing polyform prepolymers of Formula (9), each R2 can be independently hydrogen, C1-6 alkyl, C1-4 alkyl, C1-3 alkyl or C1-2 alkyl. In sulfur-containing poliform prepolymers of Formula (9), each R2 can be hydrogen, methyl or ethyl.
[0346] [0346] In sulfur-containing polyform prepolymers of Formula (9), each R1 can be the same and can be C2-3 alkanediyl such as ethane-1,2-diyl or propane-1,3-diyl; and each R2 can be the same and can be hydrogen or C1-3 alkyl such as methyl, ethyl or propyl. In sulfur-containing poliform prepolymers of Formula (9), each R1 can be ethane-1,2-diyl. In sulfur-containing polyformal prepolymers of Formula (9), each R2 can be hydrogen. In sulfur-containing poliform prepolymers of Formula (9), each R1 can be ethane-1,2-diyl and each R2 can be hydrogen.
[0347] [0347] In sulfur-containing poliform prepolymers of Formula (9), n can be an integer selected from 1 to 50, an integer from 2 to 40, an integer from 4 to 30 or n can be a number integer from 7 to 30.
[0348] [0348] In sulfur-containing polyform prepolymers of Formula (9), each p is the same and can be 1 and each p is the same and can be 2.
[0349] [0349] In sulfur-containing polymorphic prepolymers of Formula (9) may have a numerical average molecular weight of 200 Dalton to 6,000 Dalton, 500 Dalton to 5,000 Dalton, 1,000 Dalton to 5,000 Dalton, 1,500 Dalton to 4000 Dalton or from 2,000 Dalton to 3,600 Dalton, where the numerical average molecular weight is determined by gel permeation chromatography using a polystyrene standard.
[0350] [0350] In sulfur-containing polyform prepolymers of Formula (9), each R3 may be a thiol-terminated group and may comprise a group of Formula (a), Formula (b), Formula (c), Formula (d ), Formula (e), Formula (f), Formula (g) or Formula (h): HS-R7-R6-O- (a) HS-R7-O- (b) HS-R7-S- (c ) HS- (d) HS-R7-NH-C (= O) -O- (e) HS-R7-C (= O) -O-R9-NH-C (= O) -O- (f) HS-R7-C (= O) -NH-R9-NH-C (= O) -O- (g) HS-R7-C (= O) -O- (h) where each R6 can be a derived portion a diisocyanate or a portion derived from an ethylenically unsaturated monoisocyanate; each R7 can be C2-14 alkanediyl or C2-14 heteroalkanediyl; and each R9 can be C2-6 alkanediyl, C2-6 heteroalkanediyl, C6-12 arenodiyl, substituted C6-12 arenodiyl, C6-12 heteroarenodiyl, substituted C6-12 heteroarenodiyl, C3-12 cycloalkanidiyl, C3-12 cycloalkylodiyl, C3- -12, substituted C3-12 heterocycloalkanediyl, C7-18 alkanoarenediyl, substituted C7-18 heteroalkanediyl, C4-18 alkanocycloalkanediyl or substituted C4-18 alkanocycloalkanediyl.
[0351] [0351] Sulfur-containing polyform prepolymers provided by the present disclosure may have the structure of Formula (10): {R6-R1- (S) p-R1- [OC (R3) 2-O-R1- (S) p-R1-] nOC (R3) 2-O-} mZ (10) where each n is an integer selected from 1 to 50; m is an integer selected from 3 to 6; p is independently comprised of 1 or 2; each R1 independently comprises C2-6 alkanediyl; each R3 independently comprises hydrogen, C1-6 alkyl, C7-12 phenylalkyl, substituted C7-12 phenylalkyl, C6-12 cycloalkylalkyl, substituted C6-12 cycloalkylalkyl, C3-12 cycloalkyl, substituted C3-12 cycloalkyl, C6-12 aryl or aryl C6-12 replaced; each R5 is -OR5 'where R5' can be a thiol-terminated group; and Z represents the core of a m-valent precursor polyol Z (OH) m.
[0352] [0352] In sulfur-containing polyform prepolymers of Formula (10), each R1 can be independently C2-6 alkanediyl, C2-4 alkanediyl, C2-3 alkanediyl or ethane-1,2-diyl. In sulfur-containing polyform prepolymers of Formula (10), each R1 can be ethane-1,2-diyl.
[0353] [0353] In sulfur-containing polyform prepolymers of Formula (10), each R3 can be independently hydrogen, C1-6 alkyl, C1-4 alkyl, C1-3 alkyl or C1-2 alkyl. In sulfur-containing polyformal prepolymers of Formula (10), each R3 can be hydrogen, methyl or ethyl.
[0354] [0354] In sulfur-containing polyform prepolymers of Formula (10), each
[0355] [0355] In sulfur-containing polyform prepolymers of Formula (10), m may be 1, m may be 2, m may be 3, m may be 4, m may be 5 or m may be 6.
[0356] [0356] In sulfur-containing polyform prepolymers of Formula (10) where m is 3, the precursor polyol Z (OH) m can be a triol of Formula (11): (11) where each R2 is independently C1- alkanediyl. 6 or a triol of Formula (12): (12) where each R2 is independently C1-6 alkanediyl. Consequently, in these modalities Z can have the structure:
[0357] [0357] In sulfur-containing polymorph prepolymers of Formula (10), each n can be a selected integer from 1 to 50, a selected integer from 2 to 40, a selected integer from 4 to 30 or a number selected integer from 7 to 30.
[0358] [0358] In sulfur-containing polyform prepolymers of Formula (10), each p can be the same and is 1 and each p is the same and is 2.
[0359] [0359] In sulfur-containing polyformal prepolymers of Formula (10) it has a numerical average molecular weight of 200 Dalton to 6,000 Dalton, from 500 Dalton to
[0360] [0360] In sulfur-containing polyform prepolymers of Formula (10), R6 is -OR5 ', where each R5 can be the same.
[0361] [0361] In sulfur-containing polyform prepolymers of Formula (10), each R5 can be a thiol-terminated group of Formula (a), Formula (b), Formula (c), Formula (d), Formula (and ), Formula (f), Formula (g) or Formula (h): HS-R7-R6-O- (a) HS-R7-O- (b) HS-R7-S- (c) HS- (d ) HS-R7-NH-C (= O) -O- (e)
[0362] [0362] A thiol-terminated sulfur-containing prepolymer may comprise a thiol-terminated polysulfide prepolymer.
[0363] [0363] A polysulfide prepolymer refers to a prepolymer that contains one or more polysulfide bonds, that is, -Sx- bonds, where x is 2 to 4, in the prepolymer main chain and / or pending positions in the prepolymer chain. A polysulfide prepolymer can have two or more sulfur-sulfur bonds. Suitable polysulfides are commercially available, for example, from AkzoNobel and Toray Industries, Inc. under the names Tioplast® and Tiokol-LP®, respectively.
[0364] [0364] Examples of suitable polysulfide prepolymers are disclosed, for example, in U.S. Patent Nos. 4,623,711; 6,172,179; 6,509,418; 7,009,032; and 7,879,955, each of which is incorporated by reference in its entirety.
[0365] [0365] Examples of suitable thiol-terminated polysulfides include Tioplast ™ G polysulfides such as Tioplast ™ G1, Tioplast ™ G4, Tioplast ™ G10, Tioplast ™ G12, Tioplast ™ G21, Tioplast ™ G22, Tioplast ™ G44, Tioplast ™ G122 and
[0366] [0366] Examples of suitable thiol-terminated polysulfide prepolymers also include Tiokol ™ LP polysulfides available from Toray Industries, Inc. such as Tiokol ™ LP2, Tiokol ™ LP3, Tiokol ™ LP12, Tiokol ™ LP23, Tiokol ™ LP33 and Tiokol ™ LP55. Tiokol ™ LP polysulfides have an average molecular weight of
[0367] [0367] A thiol-terminated sulfur-containing prepolymer can comprise a Tiokol-LP® polysulfide, a Tioplast® G polysulfide or a combination thereof.
[0368] [0368] A thiol-terminated sulfur-containing prepolymer may comprise a thiol-terminated monosulfide.
[0369] [0369] A thiol-terminated monosulfide may comprise a thiol-terminated monosulfide of Formula (15a), a thiol-terminated monosulfide of Formula (15b) or a combination of these:
[0370] [0370] In thiol-terminated monosulfides of Formula (15a) and (15b), each X can be independently S or O, each X can be S or each X can be O.
[0371] [0371] In thiol-terminated monosulfides of Formula (15a) and (15b), p can be an integer from 2 to 6 or p can be 1, 2, 3, 4, 5 or 6.
[0372] [0372] In thiol-terminated monosulfides of Formula (15a) and (15b), q can be an integer from 1 to 5, q can be an integer from 2 to 5 or q can be
[0373] [0373] In thiol-terminated monosulfides of Formula (15a) and (15b), n can be an integer from 2 to 60, from 3 to 60 or from 25 to 35.
[0374] [0374] In thiol-terminated monosulfides of Formula (15a) and (15b), each R can be independently C2-10 alkanediyl or C6-8 cycloalkanodiyl, each R can be C2-10 alkanediyl or each R can be C6-8 cycloalkanediyl .
[0375] [0375] In thiol-terminated monosulfides of Formula (15a) and (15b), each R can be alkanodiyl C2-6, alkanodiyl C2-4, alkanodiyl C3-10 or alkanodiyl C3-6.
[0376] [0376] In thiol-terminated monosulfides of Formula (15a) and (15b), each R can be ethanediyl, 1,3-propanediyl, 1,2-propanediyl, 1,4-butanediyl or 1,3-butanediyl.
[0377] [0377] In thiol-terminated monosulfides of Formula (15a) and (15b), each R1 can be independently C1-10 alkanediyl or C6-8 cycloalkanodiyl, each R can comprise C1-10 alkanediyl or each R1 can comprise C6-8 cycloalkanediyl .
[0378] [0378] In thiol-terminated monosulfides of Formula (15a) and (15b), each R1 can be C1-6 alkanediyl, C1-4 alkanediyl, C2-10 alkanediyl or C2-6 alkanediyl.
[0379] [0379] In thiol-terminated monosulfides of Formula (15a) and (15b), each R1 can be methanediyl, ethanediyl, 1,3-propanediyl, 1,2-propanediyl, 1,4-butanediyl or 1,3-butanediyl.
[0380] [0380] In thiol-terminated monosulfides of Formula (15a) and (15b), each R2 can be independently C2-10 alkanediyl or C6-8 cycloalkanodiyl, each R2 can comprise C2-10 alkanodiyl or each R2 can be C6-8 cycloalkanediyl .
[0381] [0381] In the thiol-terminated monosulfides of Formula (15a) and (15b), each R2 may be C2-6 alkanediyl, C2-4 alkanediyl, C3-10 alkanediyl or C3-6 alkanediyl.
[0382] [0382] In thiol-terminated monosulfides of Formula (15a) and (15b), each R2 can be ethanediyl, 1,3-propanediyl, 1,2-propanediyl, 1,4-butanediyl or 1,3-
[0383] [0383] In thiol-terminated monosulfides of Formula (15a) and (15b), p can be 1 or 2, q can be 1 or 2, n can be an integer from 1 to 60 or an integer from 25 to 35 , each X can be O or S, each R can be C2-4 alkanediyl, each R1 can be C1-4 alkanediyl and each R2 can be C2-4 alkanediyl.
[0384] [0384] In thiol-terminated monosulfides of Formula (15a) and (15b), p can be 1 or 2, q can be 1 or 2, n can be an integer from 1 to 60 or an integer from 25 to 35 , each X can be O or S, each R can be alkanodiyl C2, each R1 can be alkanodiyl C1 and each R2 can be alkanodiyl C2.
[0385] [0385] In thiol-terminated monosulfides of Formula (15a) and (15b), p can be 1 or 2, q can be 1 or 2, n can be an integer from 1 to 60 or an integer from 25 to 35 , each X can be O, each R can be alkanodiyl C2, each R1 can be alkanodiyl C1 and each R2 can be alkanodiyl C2.
[0386] [0386] In thiol-terminated monosulfides of Formula (15a) and (15b), B represents a core of a z-valent polyfunctionalizing agent B (-V) z and B (-V) z can be 1,2,3-trichloropropane , 1,1,1-tris (chloromethyl) propane, 1,1,1-tris (chloromethyl) ethane and 1,3,5-tris (chloromethyl) benzene or a combination of any of the foregoing.
[0387] [0387] Thiol-terminated monosulfides of Formula (15a) and (15b) can be prepared by reacting an organic α, ω-dialo compound, a metal hydrosulfide, a metal hydroxide and an optional polyfunctionalizing agent. Examples of suitable organic α, ω-dialo compounds include bis (2-chloroethyl) formal.
[0388] [0388] A thiol-terminated monosulfide may comprise a thiol-terminated monosulfide of Formula (16a), a thiol-terminated monosulfide of Formula (16b) or a combination of these: H - [- S- (RX) pC (R1) 2 - (XR) q-] n-SH (16a) (H - [- S- (RX) pC (R1) 2- (XR) q-] nS-V '-} zB (16b) where, each X can independently be S or O; p is an integer from 1 to 5; q is an integer from 1 to 5; n is an integer from 1 to 60; each R can be independently alkanodiyl C2-10; each R1 can be independently hydrogen or C1-10 alkanediyl; B represents a core of a z-valiant polyfunctionalizing agent B (-V) z where: z is an integer from 3 to 6; and each V is a portion comprising a reactive terminal group with a thiol group, and each -V'- is derived from the reaction of -V with a thiol.
[0389] [0389] In thiol-terminated monosulfides of Formula (16a) and (16b), each X can be S or each X can be O.
[0390] [0390] In thiol-terminated monosulfides of Formula (16a) and (16b), p can be an integer from 2 to 5 or q can be 1, 2, 3, 4 or 5.
[0391] [0391] In thiol-terminated monosulfides of Formula (16a) and (16b), n can be an integer from 2 to 60, from 3 to 60 or from 25 to 35.
[0392] [0392] In thiol-terminated monosulfides of Formula (16a) and (16b), each R can be independently C2-6 alkanediyl or C2-4 alkanediyl.
[0393] [0393] In thiol-terminated monosulfides of Formula (16a) and (16b), each R can be ethanediyl, 1,3-propanediyl, 1,2-propanediyl, 1,4-butanediyl or 1,3-butanediyl.
[0394] [0394] In thiol-terminated monosulfides of Formula (16a) and (16b), each R can be n-alkanediyl C2-10, branched C2-10 alkanediyl or a combination thereof.
[0395] [0395] In thiol-terminated monosulfides of Formula (16a) and (16b), each R1 can independently be hydrogen or C2-6 alkanediyl.
[0396] [0396] In thiol-terminated monosulfides of Formula (16a) and (16b), each R1 can independently be hydrogen, ethanediyl, 1,3-propanediyl, 1,2-propanediyl, 1,4-butanediyl or 1,3-butanediyl .
[0397] [0397] In thiol-terminated monosulfides of Formula (16a) and (16b), each R1 can be C1-10 n-alkanediyl, branched C1-10 alkanediyl or a combination thereof.
[0398] [0398] In the thiol-terminated monosulfides of Formula (16a) and (16b), each X is O, p is 1 or 2, q is 1 or 2, n is 1 to 60 such as 2 to 60, each R is alkanediyl C2-4 such as ethanediyl and each R1 is hydrogen.
[0399] [0399] In thiol-terminated monosulfides of Formula (16a) and (16b), each X is O, p is 1, q is 1, n is 1 to 60 such as 2 to 60, each R is C2-4 alkanediyl such as ethanediyl and each R1 is hydrogen.
[0400] [0400] In thiol-terminated monosulfides of Formula (16a) and (16b), each X is O, p is 2, q is 2, n is 1 to 60 such as 2 to 60, each R is C2-4 alkanediyl such as ethanediyl and each R1 is hydrogen.
[0401] [0401] In thiol-terminated monosulfides of Formula (16a) and (16b), B represents a core of a z-valent polyfunctionalizing agent B (-V) z and B (-V) z can be 1,2,3-trichloropropane , 1,1,1-tris (chloromethyl) propane, 1,1,1-tris (chloromethyl) ethane and 1,3,5-tris (chloromethyl) benzene or a combination of any of the foregoing.
[0402] [0402] Thiol-terminated monosulfides of Formula (16a) and (16b) can be prepared by reacting an α, ω-dialo organic compound, a metal hydrosulfide, a metal hydroxide and an optional polyfunctionalizing agent. Examples of suitable organic α, ω-dialo compounds include bis (2-chloroethyl) formal. Examples of suitable metal hydrosulfides and metal hydroxides include sodium hydrosulfide and sodium hydroxide. Examples of suitable polyfunctionalizing agents include 1,2,3-trichloropropane, 1,1,1-tris (chloromethyl) propane, 1,1,1-tris (chloromethyl) ethane and 1,3,5-tris (chloromethyl) benzene. Methods of synthesizing thiol-terminated monosulfides of Formula (16a) and (16b) are disclosed, for example, in U.S. Patent No.
[0403] [0403] A thiol-terminated monosulfide may comprise a thiol-terminated monosulfide of Formula (17a), a thiol-terminated monosulfide of Formula (17b) or a combination of these: HS-R- (Sy-R) t-SH (17a ) {HS-R- (Sy-R) tS-V '-} zB (17b) where, t is an integer from 1 to 60; y has an average value within the range of 1.0 to 1.5; each R can be independently branched alkanediyl, branched sandstone or a portion having the structure - (CH2) p-O- (CH2) q-O- (CH2) r-; where, q is an integer from 1 to 8; p is an integer from 1 to 10; and r is an integer from 1 to 10; B represents a core of a z-valiant polyfunctionalizing agent B (-V) z where: z is an integer from 3 to 6; and each V is a portion comprising a terminal group reactive with a thiol group; and each -V'- is derived from the reaction of -V with a thiol.
[0404] [0404] In thiol-terminated monosulfides of Formula (17a) and Formula (17b), t can be, for example, an integer from 2 to 60, from 1 to 40 or from 1 to 20.
[0405] [0405] In thiol-terminated monosulfides of Formula (17a) and Formula (17b), where R is - (CH2) pO- (CH2) qO- (CH2) r-, q can be, for example, an integer of 1 to 6 or an integer from 1 to 4. For example, q can be 1, 2, 3, 4, 5 or 6.
[0406] [0406] In thiol-terminated monosulfides of Formula (17a) and Formula (17b), where R is - (CH2) pO- (CH2) qO- (CH2) r-, each p can be, for example, an integer 1 to 6 or 1 to 4. For example, each p can be 1, 2, 3, 4, 5, 6, 7, 8, 9 or
[0407] [0407] In thiol-terminated monosulfides of Formula (17a) and Formula (17b), where R is - (CH2) pO- (CH2) qO- (CH2) r-, each r can be, for example, an integer 1 to 6 or 1 to 4. For example, each p can be 1, 2, 3, 4, 5, 6, 7, 8, 9 or
[0408] [0408] In thiol-terminated monosulfides of Formula (17a) and Formula (17b), y can have a value of 1.
[0409] [0409] In thiol-terminated monosulfides of Formula (17a) and Formula (17b), R can be - (CH2) p-O- (CH2) q-O- (CH2) r-.
[0410] [0410] In thiol-terminated monosulfides of Formula (17a) and Formula (17b), R can be - (CH2) pO- (CH2) qO- (CH2) r-, each q can be 1, 2, 3 or 4 and each per can be 1 or 2.
[0411] [0411] In the thiol-terminated monosulfides of Formula (17a) and Formula (17b), 0 mol% to 20 mol% of the R groups can comprise branched alkanodiyl or branched sandstone and 80 mol% to 100 mol% of the groups R can comprise - (CH2) pO- (CH2) qO- (CH2) r-, where mol% is based on the total mol of groups R.
[0412] [0412] In thiol-terminated monosulfides of Formula (17a) and Formula (17b), B represents a core of a z-valent polyfunctionalizing agent B (-V) z and B (- V) z can comprise, for example, 1, 2,3-trichloropropane, 1,1,1-tris (chloromethyl) propane, 1,1,1-tris (chloromethyl) ethane and 1,3,5-tris (chloromethyl) benzene or a combination of any of the foregoing.
[0413] [0413] Thiol-terminated monosulfides of Formula (17a) and Formula (17b) can be prepared by reacting an α, ω-dialo organic compound, a metal hydrosulfide, a metal hydroxide and an optional polyfunctionalizing agent. Examples of suitable organic α, ω-dialo compounds include bis (2-chloroethyl) formal.
[0414] [0414] Examples of thiol-terminated monosulfides of Formula (17a) and Formula (17b) are disclosed, for and in U.S. Publication No. 2016/0152775 and in U.S. Patent No. 9,079,833.
[0415] [0415] A thiol-terminated monosulfide may comprise a thiol-terminated monosulfide of Formula (18): HS- (RO-CH2-OR-Sm-) n-1-RO-CH2-OR-SH (18) where R is alkanodiyl C2-4, m is 1 to 8 and n is an integer from 2 to 370
[0416] [0416] In thiol-terminated monosulfides of Formula (18), m can be, for example, an integer from 1 to 6 and an integer from 1 to 4 or the integer 1, 2, 3, 4, 5, 6 , 7 or 8.
[0417] [0417] In thiol-terminated monosulfides of Formula (18), n can be, for example, an integer from 1 to 200 or an integer from 2 to 100,
[0418] [0418] In thiol-terminated monosulfides of Formula (18), each R can be independently ethanediyl, 1,3-propanediyl, 1,1-propanediyl, 1,2-propanediyl, 1,4-butanediyl, 1,1-butanediyl , 1,2-butanediyl or 1,3-butanediyl.
[0419] [0419] Examples of the thiol-terminated monosulfides of Formula (18) are disclosed, for example, in JP 62-53354.
[0420] [0420] Thiol-terminated monosulfides can be liquid at room temperature. Thiol-terminated monosulfides can have a viscosity, in 100% solids, of no more than 1,500 poise (150 Pa-s), such as 40 poise to 500 poise (4 Pa-s to 50 Pa-s), in a temperature of about 25 ° C and a pressure of about 760 mm Hg (101 kPa) determined according to ASTM D-2849 § 79-90 using a Brookfield CAP 2000 viscometer.
[0421] [0421] Thiol-terminated monosulfides can have a numerical average molecular weight within the range of 300 Dalton to 10,000 Dalton, such as within the range of 1,000 Dalton to 8,000 Dalton, the molecular weight being determined by gel permeation chromatography using a polystyrene pattern. Thiol-terminated monosulfides may have a glass transition temperature Tg less than - 40 ° C, less than - 55 ° C or less than -60 ° C.
[0422] [0422] Thiol-terminated sulfur-containing prepolymers can be modified to include terminal alkenyl groups by reacting the thiol-terminated sulfur-containing prepolymer with a polyalkenyl ether, such as a bis (alkenyl) ether under suitable reaction conditions.
[0423] [0423] Compositions provided by the present disclosure may comprise a polyalkenyl or combination of polyalkenyls. A polyalkenyl may be difunctional or may have an alkenyl functionality greater than two (2) such as 3 to 6, including an alkenyl functionality of 3, 4, 5 or 6. A polyalkenyl may comprise a polyalyl compound, a bis ether (alkenyl), a bis (alkenyl) ether containing sulfur or a combination of any of the foregoing.
[0424] [0424] The curable compositions provided by the present disclosure may comprise, for example, from 1% by weight to 10% by weight of a polyalkenyl or combination of polyalkenyls, from 2% by weight to 9% by weight, 3% by weight to 8% by weight or from 4% by weight to 7% by weight of a polyalkenyl or polyalkenyl combination, where the% by weight is based on the total weight of the curable composition.
[0425] [0425] A polyalkenyl can comprise any suitable compound comprising two or more alkenyl groups. A polyalkenyl may comprise an alkenyl-terminated prepolymer, such as an alkenyl-terminated sulfur-containing prepolymer. A polyalkenyl may comprise a polyalkenyl monomer, having a low molecular weight such as, for example, a molecular weight less than 1,000 Dalton, less than 800 Dalton, less than 600 Dalton or less than 400 Dalton. A polyalkenyl may comprise a polyalkenyl-terminated prepolymer, a polyalkenyl monomer or a combination thereof. A polyalkenyl may have, for example, 2, 3, 4, 5 or 6 terminal alkenyl groups. A polyalkenyl may comprise a bis (alkenyl) ether, a poly (alkenyl) ether, a sulfur-containing bis (alkenyl) ether, a sulfur-containing poly (alkenyl) ether, a bis (alkenyl) ether containing urethane / urea, a poly ether (alkenyl) containing urethane / urea or a combination of any of the foregoing. A poly (alkenyl) ether refers to an alkenyl having more than two terminal alkenyl groups such as 3 to 6 terminal alkenyl groups.
[0426] [0426] A polyalkenyl may have the structure of Formula (19): CH2 = CH-R-CH = CH2 (19) where R is selected from C1-10 alkanediyl, C5-10 cycloalkanodiyl, C6-20 alkanocycloalkanidiyl C1-20 10, heterocycloalkanodiyl C5-10,
[0427] [0427] A polyalkenyl may have more than two terminal alkenyl groups and may, for example, be any of the alkenyl-terminated polyfunctionalizing agents disclosed herein.
[0428] [0428] A polyalkenyl may comprise a bis (alkenyl) ether. The compositions provided by the present disclosure can comprise a bis (alkenyl) ether or a combination of bis (alkenyl) ethers.
[0429] [0429] A bis (alkenyl) ether can have the structure of Formula (3): CH2 = CH-O - (- R2-O-) m-CH = CH2 (3) where, m is 0 to 50; and each R2 can be independently C2-6 n-alkanediyl, C3-6 branched alkanediyl, C6-8 cycloalkanediyl, C6-10 alkanocycloalkanediyl or - [(- CH2-) pO-] q - (- CH2-) r-, em whereas, each p is independently an integer ranging from 2 to 6; q is an integer from 1 to 5; and r is an integer from 2 to 10.
[0430] [0430] In bis (alkenyl) ethers of Formula (3), m can be an integer from 0 to 50, such as an integer from 1 to 6, from 1 to 4 or from 1 to 3.
[0431] [0431] In bis (alkenyl) ethers of Formula (3), m can be 1, 2, 3, 4, 5 or
[0432] [0432] In bis (alkenyl) ethers of Formula (3), each R2 can be independently C2-6 alkanediyl such as 1,2-ethane-diyl, 1,3-propane-diyl, 1,4-butane-diyl, 1,5-pentane-diyl or 1,6-hexane-diyl.
[0433] [0433] In bis (alkenyl) ethers of Formula (3), each R2 can be - [(- CH2-) p-O-] q - (- CH2-) r-.
[0434] [0434] In bis (alkenyl) ethers of Formula (3), each R2 can be - [(- CH2-) pO-] q - (- CH2-) r-, where each p can be 2, each r can be 2 eq can be 1, 2, 3, 4 or
[0435] [0435] Examples of suitable bis (alkenyl) ethers include divinyl ether, ethylene glycol divinyl ether (EG-DVE), butanediol divinyl ether (BD-DVE), hexanediol divinyl ether (HD-DVE), diethylene divinyl ether glycol (DEG-DVE), triethylene glycol divinyl ether (TEG-DVE), tetraethylene glycol divinyl ether and cyclohexanedimethanol divinyl ether.
[0436] [0436] Suitable bis (alkenyl) ethers include, for example, compounds having at least one oxyalkanediyl group, such as from 1 to 4 oxyalkanediyl groups, i.e. compounds where m in Formula (3) is an integer from 1 to 4. In Formula (3), m can be an integer ranging from 2 to 4. It is also possible to use commercially available divinyl ether mixtures that are characterized by a non-integer average value for the number of oxyalkanediol units per molecule . Thus, m in Formula (3) can also assume rational numerical values, for example, ranging from 0 to 10.0, such as from 1.0 to 10.0, from 1.0 to 4.0, from 2.0 to 4.0 or from 2.1 to 3.9.
[0437] [0437] Examples of suitable bis (alkenyl) ethers include, divinyl ether, ethylene glycol divinyl ether (EG-DVE) (R2 in Formula (3) is ethanediyl in is 1), butanediol divinyl ether (BD-DVE) ( R2 in Formula (3) is butanediyl in is 1), hexanediol divinyl ether (HD-DVE) (R2 in Formula (3) is hexanediyl in is 1), diethylene glycol divinyl ether (DEG-DVE) (R2 in Formula (3) is ethanediyl in is 2), divinyl ether of triethylene glycol (R2 in Formula (3) is ethanediyl in is 3), divinyl ether in tetraethylene glycol (TEG-DVE) (R2 in Formula (3) is ethanediyl in is 4), cyclohexanodimethanol divinyl ether, cyclohexanodimethanol divinyl ether, polytetrahydrofuryl divinyl ether; trivinyl ether monomers, such as trimethylolpropane trivinyl ether; tetrafunctional ether monomers, such as pentaerythritol tetravinyl ether; and combinations of two or more such divinyl ether monomers.
[0438] [0438] Bis (alkenyl) ethers in which R2 in Formula (3) is branched C3-6 alkanediyl can be prepared by reacting a polyhydroxyl compound with acetylene. Examples of bis (alkenyl) ethers of this type include compounds in which R2 in Formula (3) is an alkyl substituted methanediyl group such as -CH (CH3) - (for example Pluriol® combinations such as Pluriol®E- divinyl ether 200 (BASF Corporation), for which R2 in Formula (3) is ethanediyl and is 3.8) or an alkyl substituted ethanediyl (for example -CH2CH (CH3) - such as polymeric combinations of DPE including DPE-2 and DPE -3, International Specialty Products).
[0439] [0439] Other useful bis (alkenyl) ethers include compounds in which R2 in Formula (3) is polytetrahydrofuryl (poly-THF) or polyoxyalkanodiyl, such as those having an average of about 3 monomer units.
[0440] [0440] A polyalkenyl may comprise a sulfur-containing bis (alkenyl) ether or a combination of sulfur-containing bis (alkenyl) ethers. Bis (alkenyl) ethers containing sulfur are disclosed in PCT International Application No. WO 2018/085650, which is incorporated by reference in its entirety. A bis (alkenyl) ether containing sulfur may have the structure of Formula (7a): CH2 = CH-O- (CH2) n-Y'-R4-Y '- (CH2) nO-CH = CH2 (7a) where , each n is independently an integer from 1 to 4; each Y 'independently comprises -O- or -S-; and R4 can be C2-6 n-alkanediyl, C3-6 branched alkanediyl, C6-8 cycloalkanediyl, C6-10 alkanocycloalkanidiyl or - [(- CH2-) p-X-] q - (- CH2-) r-,
[0441] [0441] In sulfur-containing bis (alkenyl) ethers of Formula (7a), each n can be 1, 2, 3 or 4.
[0442] [0442] In sulfur-containing bis (alkenyl) ethers of Formula (7a), each Y 'may be -O- or each Y' may be -S-.
[0443] [0443] In sulfur-containing bis (alkenyl) ethers of Formula (7a), R4 can be n-alkanediyl C2-6, such as ethane-diyl, n-propane-diyl, n-butane-diyl, n-pentane-diyl or n-hexane-dialy.
[0444] [0444] In sulfur-containing bis (alkenyl) ethers of Formula (7a), R4 can be C2-6 n-alkanediyl; both Y 'can be -S- and one Y' can be -S- and the other Y 'can be -O-.
[0445] [0445] In sulfur-containing bis (alkenyl) ethers of Formula (7a), R4 can be - [(- CH2-) p-X-] q - (- CH2-) r-.
[0446] [0446] In bis (alkenyl) ethers containing sulfur of Formula (7a), R4 can be - [(- CH2-) pX-] q - (- CH2-) r-, where each X can be -O- or each X can be -SS- or at least one X can be -O- or at least one X can be -SS-.
[0447] [0447] In sulfur-containing bis (alkenyl) ethers of Formula (7a), R4 can be - [(- CH2-) pX-] q - (- CH2-) r-, where each X can be -S- or at least minus one X can be - S-.
[0448] [0448] In sulfur-containing bis (alkenyl) ethers of Formula (7a), R4 can be - [(- CH2-) pX-] q - (- CH2-) r-, where each p can be 2 and r can be 2 .
[0449] [0449] In sulfur-containing bis (alkenyl) ethers of Formula (7a), R4 can be - [(- CH2-) pX-] q - (- CH2-) r-, where q can be 1, 2, 3, 4 or 5.
[0450] [0450] In sulfur-containing bis (alkenyl) ethers of Formula (7a), R4 can be - [(- CH2-) pX-] q - (- CH2-) r-, where each p can be 2, r can be 2 eq can be 1, 2, 3, 4 or 5.
[0451] [0451] In sulfur-containing bis (alkenyl) ethers of Formula (7a), R4 can be - [(- CH2-) p-X-] q - (- CH2-) r-, where each X can be -S-; each p can be 2, r can be 2 and q can be 1, 2, 3, 4 or 5.
[0452] [0452] In sulfur-containing bis (alkenyl) ethers of Formula (7a), R4 can be - [(- CH2-) p-X-] q - (- CH2-) r-, where each X can be -O-; each p can be 2, r can be 2 and q can be 1, 2, 3, 4 or 5.
[0453] [0453] In sulfur-containing bis (alkenyl) ethers of Formula (7a), R4 can be - [(- CH2-) p-X-] q - (- CH2-) r-, where each X can be -O-; and each Y 'can be -S-.
[0454] [0454] In sulfur-containing bis (alkenyl) ethers of Formula (7a), R4 can be - [(- CH2-) p-X-] q - (- CH2-) r-, where each X can be -S-; and each Y 'can be -O-.
[0455] [0455] In sulfur-containing bis (alkenyl) ethers of Formula (7a), each n can be 2, each Y 'can be independently selected from -O- and -S- and R4 can be - [(- CH2-) pX -] q - (- CH2-) r-, where each X is independently selected from -O-, - S- and -SS-, p can be 2, q can be selected from 1 and 2 and r can be 2.
[0456] [0456] In sulfur-containing bis (alkenyl) ethers of Formula (7a), each n can be 2, each Y 'can be independently selected from -O- and -S- and R4 can be C2-4 alkanediyl, such as ethanediyl , n-propanediyl or n-butanediyl.
[0457] [0457] Sulfur-containing bis (alkenyl) ethers may comprise sulfur-containing bis (alkenyl) ethers of Formula (7b), Formula (7c), Formula (7d), Formula (7e), Formula (7f), Formula (7g), Formula (7h), Formula (7i) or a combination of any of the foregoing: CH2 = CH-O- (CH2) 2-S - (- (CH2) 2-O-) 2- (CH2) 2-S- (CH2) 2-O-CH = CH2 (7b) CH2 = CH-O- (CH2) 2-S- (CH2) 2-S- (CH2) 2-S- (CH2) 2-O-CH = CH2 (7c)
[0458] [0458] Examples of suitable sulfur-containing bis (alkenyl) ethers include 3,9,12,18-tetraoxa-6,15-dithiaicosa-1,19-diene, 3,6,15,18-tetraoxa-9,12- dithiaicosa-1,19-diene, 3,15-dioxa-6,9,12-tritiaeptadeca-1,16-diene, 3,9,15-trioxa-6,12-dithiaeptadeca-1,16-diene, 3, 6,12,15-tetraoxa-9-thiaeptadeca-1,16-diene, 3,12-dioxa- 6,9-ditiatetradeca-1,13-diene, 3,6,12-trioxa-9-tiatetradeca-1, 13-diene, 3,6,13,16-tetraoxa-9,10-dithiaoctadeca-1,17-diene and combinations of any of the foregoing.
[0459] [0459] A sulfur-containing bis (alkenyl) ether provided by the present disclosure can be liquid at room temperature. A bis (alkenyl) ether containing sulfur may have a numerical average molecular weight of 200 Dalton to 2,000 Dalton, 200 Dalton to 1,500 Dalton, 200 Dalton to 1,000 Dalton, 200 Dalton to 800 Dalton or 300 Dalton to 500 Dalton, where the numerical average molecular weight is based on the molecular structure.
[0460] [0460] The synthesis of sulfur-containing bis (alkenyl) ethers is disclosed, for example, in PCT Order Publication No. 2018/085650, which is incorporated by reference in its entirety.
[0461] [0461] Sulfur-containing bis (alkenyl) ethers of Formula (7a) are difunctional. Sulfur-containing alkenyl ethers provided by the present disclosure may also include sulfur-containing polyalkenyl ethers having a functionality greater than two, such as a functionality of 3 to 6. Also, poly (alkenyl) ethers provided by the present disclosure may also include poly (alkenyl ethers) ) having a functionality greater than two, such as a functionality from 3 to 6.
[0462] [0462] For example, a sulfur-containing poly (alkenyl) ether or poly (alkenyl) ether may have the structure of Formula (7j): B (-V'-R10) z (7j) where, B comprises a nucleus of a z-valent B (-V) z polyfunctionalizing agent; z is an integer from 3 to 6; and each -V'- is an organic portion; and each R10 is a moiety comprising a terminal sulfur-containing alkenyl ether group, a terminal alkenyl ether group or a combination thereof.
[0463] [0463] A multifunctional sulfur-containing alkenyl ether can be derived from a sulfur-containing bis (alkenyl) ether of Formula (7a) by reacting a sulfur-containing bis (alkenyl) ether of Formula (7a) with a polyfunctionalizing agent, where the Polyfunctionalizing agent comprises terminal groups reactive with alkenyl groups such as thiol groups. For example, a multifunctional alkenyl ether can be derived from a bis (alkenyl) ether of Formula (3) by reacting a bis (alkenyl) ether of Formula (3) with a polyfunctionalizing agent, where the polyfunctionalizing agent comprises reactive end groups with alkenyl groups such as thiol groups.
[0464] [0464] For example, a poly (alkenyl) ether containing polyfunctional sulfur may have the structure of Formula (7k): {CH2 = CH-O- (CH2) n-Y'-R4-Y '- (CH2) nO- (CH2) 2-V '-} zB (7k) where n, Y' and R4 are defined as in Formula (7a), z and B are defined as in Formula (2b) and -V'- can be derived from the reaction of -V with an alkenyl group.
[0465] [0465] In poly (alkenyl) ethers containing multifunctional sulfur of Formula (7k), B (-V) z can be a polythiol just like any of the one disclosed here,
[0466] [0466] Multifunctional sulfur-containing poly (alkenyl) ethers of the Formula (7k) can be prepared by reacting a sulfur-containing bis (alkenyl) ether of the Formula (7a) with a thiol B (-V) z terminated polyfunctional agent in the presence of of a suitable catalyst such as an amine catalyst.
[0467] [0467] Similarly, multifunctional polyalkylene ethers can have the structure of Formula (20): {CH2 = CH-O - (- R2-O-) m- (CH2) 2-V '-} zB (20) where m, z, R2, V 'and B are defined as in Formula (3) and Formula (2b). A polyalkenyl may have an alkenyl functionality greater than 2, such as an alkenyl functionality of 3, 4, 5 or 6. Examples of suitable polyalkenyls include 1,3,5-trialyl-1,3,5-triazine-2,4 , 6 (1H, 3H, 5H) -trione and trialyl cyanurate (2,4,6-trialyloxy-1,3,5-triazine).
[0468] [0468] Multifunctional sulfur-containing poly (alkenyl) ethers can be used to prepare polythioether prepolymers containing sulfur-containing bis (alkenyl) ether provided by the present disclosure. For example, reagents may include poly (alkenyl) ethers containing multifunctional sulfur as part of the alkenyl component. Multifunctional sulfur-containing poly (alkenyl) ethers may be the only polyfunctional reagent having a functionality greater than 2 or may be used in combination with an alkenyl-terminated polyfunctionalizing agent such as trialyl cyanurate or trialyl isocyanurate.
[0469] [0469] A polyalkenyl may comprise a bis (alkenyl) ether containing urethane / urea or a combination of bis (alkenyl) ethers containing urethane / urea.
[0470] [0470] A bis (alkenyl) ether containing urethane / urea may have the structure of
[0471] [0471] In bis (alkenyl) ethers containing urethane / urea of Formula (21), each Y 'can be -O-, each Y' can be -NH- or a Y 'can be -O- and a Y' can be -NH-.
[0472] [0472] In bis (alkenyl) ethers containing urethane / urea of Formula (21), R5 can be n-alkanediyl C2-6, such as ethane-diyl, n-propane-diyl, n-butane-diyl, n-pentane -diíla or n-hexane-diaíla.
[0473] [0473] In bis (alkenyl) ethers containing urethane / urea of Formula (21), R5 can be n C2-6 n-alkanediyl; either Y 'may be -O- or Y' may be -NH- or one Y 'may be -NH- and the other Y' may be -O-.
[0474] [0474] A bis (alkenyl) ether containing urethane / urea provided by the present disclosure can be liquid at room temperature. A bis (alkenyl) ether containing urethane / urea can have a numerical average molecular weight of 200 Dalton a
[0475] [0475] Bis (alkenyl) ethers containing urethane / urea can be prepared by reacting a diisocyanate with a hydroxyl vinyl ether, an amino vinyl ether or a combination of a hydroxyl vinyl ether and an amino vinyl ether.
[0476] [0476] For example, a bis (alkenyl) ether containing urethane / urea can comprise reagent reaction products comprising: (a) a diisocyanate having the structure of Formula (22):
[0477] [0477] In compounds of Formula (23), Y can be -NH2 or Y can be -OH.
[0478] [0478] In compounds of Formula (23), R4 may comprise the nucleus of an aliphatic isocyanate.
[0479] [0479] In compounds of Formula (23), R5 can be methane-dialy, ethane-dialy, butane-dialy or pentane-dialy.
[0480] [0480] In compounds of Formula (23), R5 can be cyclopentane-diyl or cyclohexane-diyl.
[0481] [0481] Bis (alkenyl) ethers containing urethane / urea can be prepared by reacting a diisocyanate with a hydroxyl vinyl ether of Formula (22) where Y is - OH, an amino vinyl ether of Formula (23) where Y is -NH2 or a combination of a hydroxyl vinyl ether of Formula (22) and an amino vinyl ether of Formula (23).
[0482] [0482] Bis (alkenyl) ethers containing urethane / urea can be prepared by reacting a diisocyanate with a hydroxyl vinyl ether and / or amino vinyl ether in the presence of a tin catalyst such as dibutyl tin dilaurate.
[0483] [0483] Bis (alkenyl) ethers containing urethane / urea of Formula (21) are difunctional. Bis (alkenyl) ethers containing urethane / urea provided by the present disclosure also include bis (alkenyl) ethers containing urethane / urea multifunctional having an alkenyl functionality greater than two, such as an alkenyl functionality of 3 to 6.
[0484] [0484] For example, a bis (alkenyl) ether containing urethane / urea may have the structure of Formula (26): B (-V'-R6) z (26) where, B comprises a core of a polyalkenyl ether z -valent; z is an integer from 3 to 6; each -V'- is an organic portion; and each R6 comprises a bis (alkenyl) ether group containing urethane / terminal urea.
[0485] [0485] In a polyalkenyl ether of Formula (26), -V'- can be derived from the reaction of a polyfunctionalizing agent B (-V) z where V comprises a terminal group reactive with an alkenyl group such as a thiol group.
[0486] [0486] In polyalkylene ethers of Formula (26), each R6 can independently comprise a portion of Formula (27): CH2 = CH-O-R5-Y'-C (= O) -NH-R4-NH-C ( = O) -Y'-R5-O- (CH2) 2- (27) where Y ', R4 and R5, are defined as for Formula (8a).
[0487] [0487] A bis (alkenyl) ether containing urethane / multifunctional urea can be derived from a bis (alkenyl) ether containing urethane / urea of Formula (8), for example, by reacting a bis (alkenyl) ether containing urethane / urea of Formula (8a) with a polyfunctionalizing agent of Formula (1): B (-V) z (1)
[0488] [0488] For example, a bis (alkenyl) ether containing polyfunctional urethane / urea may have the structure of Formula (28): {CH2 = CH-O-R5-Y'-C (= O) -NH-R4-NH -C (= O) -Y'-R5-O- (CH2) 2-V '-} zB (28) where Y', R4 and R5 are defined as in Formula (28), z and B are defined as in Formula (1) and V 'can be derived from the reaction of V with an alkenyl group -CH = CH2.
[0489] [0489] In bis (alkenyl) ethers containing the multifunctional urethane / urea of Formula (28), B (-V) z can be a polythiol such as any of that disclosed here, such as 1,2,3-propane trityl and tritols containing isocyanurate.
[0490] [0490] Bis (alkenyl) ethers containing urethane / urea of Formula (28) may be prepared by reacting a bis (alkenyl) ether containing urethane / urea of Formula (21) with a thiol B (-V) terminated polyfunctionalizing agent ) z in the presence of a suitable catalyst such as an amine catalyst.
[0491] [0491] A bis (alkenyl) ether containing polyfunctional urethane / urea can also have the structure of Formula (28a), Formula (28b) or a combination of these: {CH2 = CH-O-R5-Y'-C (= O ) -NH-R4-NH-C (= O) -Y'-R5-O- (CH2) 2-V '-} z-wB {-V} w (28a) {CH2 = CH-O-R5- Y'-C (= O) -NH-R4-NH-C (= O) -Y'-R5-O- (CH2) 2-V '-} z-wB {-V' - (CH2) 2- O - (- R2-O-) m-CH = CH2} w (28b) where Y ', R4, R5, V, V', R2 and m are defined as for Formula (21) and Formula (1) and w is an integer from 1 to z-1.
[0492] [0492] Compositions provided by the present disclosure may comprise a metal complex or combination of metal complexes capable of generating free radicals.
[0493] [0493] Suitable metal complexes are able to react with organic peroxides at temperatures of 20 ° C to 25 ° C to generate free radicals.
[0494] [0494] Suitable metal complexes include metal (II) (M2 +) and metal (III) (M3 +) complexes. Anions can be compatible with the other components of a curable composition. For example, suitable anions include organic anions.
[0495] [0495] In the presence of a suitable organic peroxide, suitable metal complexes can provide a completely cured composition, for example, within 7 days, within 10 days, within 14 days, within 21 days or within 28 days.
[0496] [0496] Suitable metal complexes include metal complexes of cobalt, copper, manganese, iron, vanadium, potassium, cerium and aluminum. Suitable binders include organic binders.
[0497] [0497] Examples of suitable metal (II) complexes include manganese (II) bis (tetramethylcyclopentadienyl), manganese (II) 2,4-pentanedioant, manganese acetylacetonate (II), iron (II) acetylacetonate, iron trifluoromethanesulfonate ( II), iron (II) fumarate, cobalt (II) acetylacetonate, copper (II) acetylacetonate and combinations of any of the foregoing.
[0498] [0498] Examples of suitable metal (III) complexes include manganese 2,4-pentanedionate (III), manganese acetylacetonate (III), manganese methanesulfonate (III), iron acetylacetonate (III) and combinations of any of the precedent.
[0499] [0499] Examples of suitable metal complexes include Mn (III) (acac) 3, Mn (III) (2,2'-bipyridyl) 2 (acac) 3, Mn (II) (acac) 2, V (acac) 3 (2,2'-bipyridyl), Fe (III) acac) 3 and combinations of any of the foregoing.
[0500] [0500] Suitable Mn complexes can be formed with linkers including, for example, 2,2'-bipyridine, 1,10-phenanthroline, 1,4,7-trimethyl-4,7-triazacyclononane, 1,2-bis ( 4,7-dimethyl-1,4,7-triazacyclononan-1-yl) -ethane, N, N, N ', N ”, N'”, N '”- hexamethyltriethylenetetraamine, acetylacetonate (acac), N, N' - bis (alicylidene) cyclohexylenediamine, 5,10,15,20-tetracisphenylporphyrin, 5,10,15,20-tetracis (4'-methoxyphenyl) porphyrin, porphyrin, 6-amino-1,4,6-trimethyl-1, 4-diazacycloeptane, 6-dimethylamino-1,4-bis (pyridine-2-ylmethyl) -6-methyl-1,4-diazacycloeptane, 1,4,6-trimethyl-6 [N-pyridin-2-ylmethyl) - N-methylamino] -1,4-dizazcycloeptane, 4,11-dimethyl-1,4,8,11- tetraazabicyclo [6,6,2] hexadecane and combinations of any of the foregoing.
[0501] [0501] Suitable Fe complexes can be formed with linkers including, for example, 1,4-deazacycloeptane-based binders such as 6-amino-1,4,6-trimethyl-1,4-diazacycloeptane, 6-dimethylamino- 1,4-bis (pyridine-2-ylmethyl) -6-methyl-1,4-diazacycloeptane, 1,4,6-trimethyl-6 [N- (pyrinin-2-ylmethyl) -N-methylamino] -1, 4-
[0502] [0502] Suitable metal complexes can be trivalent or tetravalent.
[0503] [0503] The metal complex binder can be selected to improve the storage stability of a formulation containing the metal complex.
[0504] [0504] Curable compositions provided by the present disclosure may comprise, for example, from 0.01% by weight to 3% by weight, of metal complex, from 0.05% by weight to 2.5% by weight, from 0, 1% by weight to 2% by weight or 0.5% by weight to 1.5% by weight, where% by weight is based on the total weight of the curable composition.
[0505] [0505] Curable compositions provided by the present disclosure may comprise an organic peroxide or combination of organic peroxides.
[0506] [0506] Examples of suitable organic peroxides include ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxycetals, alkyl peresters and percarbonates.
[0507] [0507] Suitable organic peroxides include tert-butyl peroxide, cumene hydroperoxide, p-menthane hydroperoxide, di-tert-butyl peroxide, tert-butylcumyl peroxide, acetyl peroxide, isobutyryl peroxide, octaneyl peroxide, peroxide dibenzoyl, 3,5,5-trimethylhexanoyl peroxide and tert-butyl peroxyisobutyrate. Additional examples of suitable organic peroxides include benzoyl peroxide, tert-butyl perbenzoate, o-methylbenzoyl peroxide, p-methylbenzoyl peroxide, di-tert-butyl peroxide, dicumyl peroxide, 1,1-bis (tert-butylperoxy ) -3,3,5-trimethyl cyclohexane, 1,1-di (tert-butylperoxy) cyclohexane, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-dimethyl-2,5 - di (tert-butylperoxy) hexane, 1,6-bis (p-toluoylperoxy carbonyloxy) hexane, di (4-methylbenzoyl peroxy) hexamethylene bis-carbonate, tert-butylcumyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide , 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5-di (tert-butylperoxy ) hexane, 1,3-bis (t-butylperoxypropyl) benzene, di-tert-butylperoxy-diisopropylbenzene, tert-butylperoxybenzene, 2,4-dichlorobenzoyl peroxide, 1,1-dibutylperoxy-3,3,5-trimethylsiloxane, peroxivalerate of n-butyl-4,4-di-tert-butyl and combinations of any of the foregoing.
[0508] [0508] Examples of suitable organic peroxides include 3,3,5,7,7-pentamethyl-1,2,4-trioxepano, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexino-3, peroxide di-tert-butyl, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, tert-butyl cumyl peroxide, di (tert-butylperoxyisopropyl) benzene, dicumyl peroxide, 4,4-di ( butyl tert-butylperoxy) valerate, 2-ethylhexyl tert-butylperoxy carbonate, 1,1-di (tert-butylperoxy-3,3,5-trimethylcyclohexane, tert-butyl peroxybenzoate, di (4-methylbenzoyl peroxide), peroxide dibenzoyl and di (2,4-dichlorobenzoyl) peroxide, which are commercially available, for example, from AkzoNobel.
[0509] [0509] Compositions provided by the present disclosure may also contain a metal salt, such as, for example, Fe (II) sulfate heptahydrate or Mn (III) stearate.
[0510] [0510] Curable compositions provided by the present disclosure may comprise, for example, from 0.2% by weight to 3% by weight of an organic peroxide, from 0.5% by weight to 3% by weight, from 0.7% by weight to 2.5% by weight, from 0.1% by weight to 2% by weight, from 0.2% by weight to 2% by weight or from 0.2% by weight to 1% by weight, where the weight% is based on the total weight of the curable composition.
[0511] [0511] Metal complexes and organic peroxides can be supplied in diluted solutions of a solvent. For example the solutions may comprise from 1% by weight to 15% by weight or from 5% by weight to 15% by weight of the metal complex or organic peroxide. Examples of solvents include acetylacetone, HB-40® (combination of terphenyls), toluene, water, isopropanol, methyl propyl ketone, hexanes, methanol and cyclohexane.
[0512] [0512] The solvent can influence the application / gelation time and the curing time of a curable composition. For example in Fe (III) (acetylacetonate) 3 and Mn (III) (acetylacetonate) 3 systems, increasing the ratio of toluene to acetylacetonate in the solution can make the metal center more available for reaction by changing the balance in a direction where the binder (s) can spread out more easily. This mechanism should also be applicable with other ligand and metal ligand complexes such as 2-ethylhexanoic acid and cobalt (II) bis (2-ethylhexanoate). Thus, using different metals, organic anions and solvent compositions, the curing time and application time can be selected for double curing systems.
[0513] [0513] Suitable solvents can have, for example, a polarity similar to that of toluene. Suitable solvents include, for example, toluene, o-xylene, cyclohexane, diethyl ether, methyl tert-butyl ether, hexane and ethyl acetate.
[0514] [0514] Suitable organic peroxides include those commercially available under the brand name Trigonox®, Butanox® and Perkodox® from AkzoNobel, and under the brand name Cadox® from Summit Composites Pty, Ltd.
[0515] [0515] Curable compositions provided by the present disclosure may not include an amine catalyst. An amine catalyst can reduce adhesion-free time. An amine catalyst can be selected to reduce adherence free time without compromising or negatively modifying the curing profile in darkness. An amine cure modifier can include a primary amine, a secondary amine, a tertiary amine or a combination of any of the foregoing.
[0516] [0516] Examples of suitable amine cure modifiers include ditetiltoluenediamene, p-toluidine, N- (2-hydroxyethyl) -N-methyl-p-toluidine (MHPT), p-tolyldiethanolamine (TDEA), Ethacure® 300 (dimethyltiotoluenediamine and monomethyltiotoluenediamine), Ethacure® 100 (3,5-dimethylthio-2,4-toluenediamine, 3,5-dimethylthio-2,6-toluenediamine and dialkylated m-phenylenediamines), p-tolylethanol amine, triethanolamine, 4, N, N ' -trimethylaniline, NN-dimethyl-para-p-toluidine, N, N-diisopropylethylamine, N, N, N ', N ”, N'” - pentamethyl-diethylenetriamine, tris (2-pyridylmethyl) amine, N- (2- hydroxyethyl) -N-methyl-p-toluidine, dihydroxyethyl, N, N-diethyltoluene-2,5-diamine and combinations of any of the foregoing.
[0517] [0517] Examples of suitable primary amines include, for example, C3-10 aliphatic primary amines.
[0518] [0518] Examples of suitable secondary amines include, for example, cycloaliphatic diamines such as Jefflink® 754 and aliphatic diamines such as Clearlink® 1000.
[0519] [0519] Examples of suitable tertiary amines include aromatic tertiary amines such as toluene-based tertiary amines. Examples of suitable tertiary amines include, for example, N, N-dimethylethanolamine (DMEA), diaminobicyclooctane (DABCO), triethylene diamine (TEDA), bis (2-dimethylaminoethyl) ether (BDMAEE), N-ethylmorpholine, N ', N'- dimethylpiperazine, N, N, N ', N', N ”-pentamethyl-diethylene triamine (PMDETA), N, N'-dimethylcyclohexylamine (DMCHA), N, N-dimethylbenzylamine (DMBA), N, N-dimethylketylamine, N , N, N ', N ”, N” -pentamethyl-dipropylene-triamine (PMDPTA), triethylamine and 1- (2-hydroxypropyl) imidazole.
[0520] [0520] Examples of other amine cure modifiers include triethylamine (TEA), dimethylcyclohexylamine (DMCHA), tetramethylethylenediamine, tetramethylpropanediamine, tetramethylhexamethylenediamine,
[0521] [0521] An example of an amine synergist includes Ce (NH4) (NO3) 6.
[0522] [0522] Other cure modifiers can be used. For example, suitable cure modifiers include Butonox® P-50, ammonium persulfate, Borchi® OXY-coat 1310, potassium hex-cem®, Poly-cure® 503 and FirstCure® MHPT.
[0523] [0523] Fillers such as silica gel can also affect the curing profile of a sealant. Other fillers that are sensitive to actinic radiation and that can affect the curing profile include silica and alumina.
[0524] [0524] Curable compositions provided by the present disclosure may include one or more materials to modify the application time, the free time of adhesion and / or the surface adhesion of the composition. The application time, the adherence free time and / or the surface adhesion of the composition can be controlled or modified by incorporating, for example, a dark curing synergist, a dark curing co-catalyst, an oxygen decontaminant isolated particle, a hydrogen donor (subtraction), filler or a combination of any of the preceding. Compositions provided by the present disclosure may include, for example, from 0.01% by weight to 5% by weight, from 0.01% by weight to 3% by weight, from 0.01% by weight to 2% by weight, from 0.01% by weight to 1% by weight or from 0.05% by weight to 1% by weight of such curing profile modifiers.
[0525] [0525] Examples of suitable dark cure synergists include hydrogen donors such as primary and secondary amines.
[0526] [0526] Examples of compounds that can modify the adhesion-free time include stearic acid and -vinyl-2-norbornene and combinations of these.
[0527] [0527] Examples of suitable free radical decontaminants include 2,5-diphenylfuran.
[0528] [0528] Examples of suitable isolated particulate oxygen decontaminants include ascorbic acid and Fe (II).
[0529] [0529] Examples of suitable hydrogen donors include primary amines, secondary amines, alcohols, hydroxyl-containing compounds and combinations of any of the foregoing.
[0530] [0530] Curable compositions can comprise a solvent. The selection and amount of solvent in a double cure sealant composition provided by the present disclosure can influence the adhesion free time. As the solvent evaporates onto the surface of a sealant layer, the solvent that evaporates can suppress oxygen on the surface and therefore decrease the free time of adhesion. In general, the use of volatile solvents can reduce the free time of adhesion.
[0531] [0531] Curable compositions provided by the present disclosure may comprise a hydroxyl-functional vinyl ether or combination of hydroxyl-functional vinyl ethers.
[0532] [0532] A hydroxyl functional vinyl ether can have the structure of Formula (29): CH2 = CH-O- (CH2) t-OH (29) where t is an integer from 2 to 10. In functional vinyl ethers in hydroxyl of Formula (29), t can be 1, 2, 3, 4, 5 or t can be 6. Examples of suitable hydroxyl functional vinyl ethers include 1-methyl-3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether and a combination of these. A hydroxyl functional vinyl ether can be 4-hydroxybutyl vinyl ether.
[0533] [0533] Curable compositions provided by the present disclosure may comprise, for example, from 0.1% by weight to 10% by weight of a hydroxyl functional vinyl ether, from 0.2% by weight to 9% by weight, from 0 , 3% by weight to 0.7% by weight and from 0.4% by weight to 0.7% by weight, where% by weight is based on the total weight of the curable composition.
[0534] [0534] Curable compositions provided by the present disclosure may comprise an amino functional vinyl ether or combination of amino functional vinyl ethers.
[0535] [0535] An amino-functional vinyl ether can have the structure of Formula (30): CH2 = CH-O- (CH2) t-NH2 (30) where t is an integer from 2 to 10. In functional vinyl ethers in amino of Formula (30), t can be 1, 2, 3, 4, 5 or t can be 6. Examples of suitable amino functional vinyl ethers include 1-methyl-3-aminopropyl vinyl ether, 4-aminobutyl vinyl ether and a combination of any of the foregoing. An amino functional vinyl ether can be 4-aminobutyl vinyl ether.
[0536] [0536] Curable compositions provided by the present disclosure may comprise, for example, from 0.1% by weight to 10% by weight of an amino functional vinyl ether, from 0.2% by weight to 9% by weight, from 0 , 3% by weight to 0.7% by weight and from 0.4% by weight to 0.7% by weight, where% by weight is based on the total weight of the curable composition.
[0537] [0537] A curable composition can include a hydroxyl functional vinyl ether and an amino functional vinyl ether.
[0538] [0538] Compositions provided by the present disclosure may comprise a monomeric polyol. A monomeric dithiol can have, for example, the structure of Formula (5).
[0539] [0539] A polythiol may comprise a polythiol having a thiol functionality greater than 2 such as a thiol functionality of 3 to 6 or a combination of any of the foregoing. A polythiol may comprise a combination of polythioles having an average thiol functionality greater than 2 such as a 2.1 to 5.9 or 2.1 to 2.9 thiol functionality.
[0540] [0540] For example, a polythiol can be trifunctional, tetrafunctional, pentafunctional, hexafunctional or a combination of any of the foregoing.
[0541] [0541] Suitable thiol-terminated monomers include, for example, mercapto-propionates, mercapto-acetates, mercapto-acrylates and other polythioles.
[0542] [0542] Examples of suitable mercapto-propionates include pentaerythritol tetra (3-mercapto-propionate) (PETMP), trimethylol-propane tri (3-mercaptopropionate) (TMPMP), glycol di (3-mercaptopropionate) (GDMP), tris [2- (3-mercapto-propionyloxy) ethyl] isocyanurate (TEMPIC), hexa (3-mercaptopropionate) di-pentaerythritol (di-PETMP), tri (3-mercaptopropionate) pentaerythritol and tri- (3- mercaptopropionate) triethylolethane.
[0543] [0543] Examples of suitable thiol-terminated prepolymers include ethoxylated trimethylolpropane tri (3-mercaptopropionate) and polycaprolactone tetra-3-mercaptopropionate.
[0544] [0544] Examples of suitable mercaptoacetates include pentaerythritol tetramercaptoacetate (PRTMA), trimethylolpropane trimercaptoacetate (TMPMA), glycol dimercaptoacetate (GDMA), ethylene glycol dimercaptoacetate and trimethoxy acetate acetate.
[0545] [0545] Examples of suitable mercaptoacrylates include pentaerythritol tetraacrylate, tris [2- (3-mercaptopropionyloxy) ethyl] isocyanurate, 2,3-di (2-mercaptoethylthio) - 1-propane-thiol, dimercaptodiethylsulfide (2, 2'-thiodiethanethiol), dimercaptodioxaoctane (2,2 '- (ethylenedioxy) dietanethiol and 1,8-dimercapto-3,6-dioxaoctane.
[0546] [0546] Suitable thiol-terminated monomers are commercially available from Bruno Bock Tiochemicals under the trade name Thiocure®.
[0547] [0547] A polythiol may comprise a polythiol of Formula (31): B (-V) z (31) wherein, B comprises a core of a z-valent polyfunctionalizing agent B (-V) z; z is an integer from 3 to 6; and each -V is independently a moiety comprising a terminal thiol group.
[0548] [0548] In polythols of Formula (31), z can be, for example, 3, 4, 5 or 6.
[0549] [0549] In polythiols of Formula (31), z can be 3. Suitable trifunctional polythols include, for example, 1,2,3-propanotrityiol, tritols containing isocyanurate and combinations thereof, as disclosed in US Application Publication No 2010 / 0010133 and the polythiols described in U.S. Patent Nos. 4,366,307; 4,609,762; and 5,225,472. Combinations of polythiols of Formula (31) can also be used.
[0550] [0550] Other examples of suitable polythiol monomers include 1,2,3-propanotrityiol, isocyanurate-containing tritiols and combinations thereof, as disclosed, for example, in US Order Publication No. 2010/0010133, which is incorporated by reference in its wholeness and isocyanurates as disclosed, for example, in US Order Publication No. 2011/0319559, which is incorporated by reference in its entirety.
[0551] [0551] Suitable thiol-terminated monomers can be characterized, for example, by a molecular weight less than 2,000 Dalton, less than 1,500 Dalton, less than 1,000 Dalton, less than 500 Dalton or less than 250 Dalton. Suitable thiol-terminated monomers can be characterized, for example, by a weighted average molecular weight of 200 Dalton to 2,000 Dalton, 200 Dalton to 1,500 Dalton, 200 Dalton to 1000, Dalton, 500 Dalton to 2,000 Dalton or 500, Dalton to 1,500 Dalton. Compositions provided by the present disclosure may comprise, for example, from 0.1% by weight to 5% by weight of a polythiol, from 0.2% by weight to 3.5% by weight, from 0.5% by weight to 3% by weight or 1% by weight to 3% by weight of a polythiol, where% by weight is based on the total weight of the composition.
[0552] [0552] Compositions provided by the present disclosure may comprise a plasticizer or combination of plasticizers.
[0553] [0553] Compositions may comprise a polybutadiene plasticizer.
[0554] [0554] Compositions provided by the present disclosure may include a photoinitiator or combination of photoinitiators. The radiation can be actinic radiation that can apply energy that can generate a kind of initiation of a photopolymerization initiator during irradiation with it and broadly includes α raises, γ rays, X rays, ultraviolet (UV) light including UVA, UVA spectra and UVC), visible light, blue light, infrared, near infrared or an electron beam. For example, the photoinitiator can be a UV photoinitiator.
[0555] [0555] Examples of suitable UV photoinitiators include α-hydroxy ketones, benzophenone, α, α-diethoxyacetophenone, 4,4-diethylaminobenzophenone, 2,2-dimethoxy-2-phenylacetophenone, 4-isopropylphenyl 2-hydroxy-2-propyl ketone, 1- hydroxycyclohexyl phenyl ketone, isoamyl p-dimethylaminobenzoate, methyl 4-dimethylaminobenzoate, methyl O-benzoylbenzoate, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2-hydroxy-2-methyl -phenylpropan-1-one, 2-isopropylthioxanthone, dibenzosuberone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bisacyclophosphine oxide.
[0556] [0556] Examples of suitable benzophenone photoinitiators include 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-hydroxy-1,4,4- (2-hydroxyethoxy) phenyl] -2-methyl-1- propanone, α-dimethoxy-α-phenylacetophenone, 2-benzyl-2- (dimethylamino) -1- [4- (4-
[0557] [0557] Examples of suitable oxime photoinitiators include (hydroxyimino) cyclohexane, 1- [4- (phenylthio) phenyl] -octane-1,2-dione-2- (O-benzoyloxime), 1- [9-ethyl-6 - (2-methylbenzoyl) -9H-carbazol-3-yl] -ethanone-1- (O-acetyloxime), trichloromethyl-triazine derivatives), 4- (4-methoxystyryl) -2,6-trichloromethyl-1,3 , 5-triazine), 4- (4-methoxyphenyl) -2,6-trichloromethyl-1,3,5-triazine and α-aminoketone (1- (4-morpholinophenyl) -2-dimethylamino-2-benzyl-butan- 1-one).
[0558] [0558] Examples of suitable phosphine oxide photoinitiators include diphenyl (2,4,6-trimethylbenzoyl) -phosphine oxide (TPO) and phenylbis (2,4,6-trimethyl benzoyl) phosphine oxide (BAPO).
[0559] [0559] Other examples of suitable UV photoinitiators include Irgacure ™ products from BASF, for example Irgacure ™ 184, Irgacure ™ 500, Irgacure ™ 1173, Irgacure ™ 2959, Irgacure ™ 745, Irgacure ™ 651, Irgacure ™ 369, Irgacure ™ 907, Irgacure ™ 1000, Irgacure ™ 1300, Irgacure ™ 819, Irgacure ™ 819DW, Irgacure ™ 2022, Irgacure ™ 2100, Irgacure ™ 784, Irgacure ™ 250; in addition, BASF's Irgacure ™ products are used, for example Irgacure ™ MBF, Darocur ™ 1173, Darocur ™ TPO, Darocur ™ 4265 products.
[0560] [0560] A UV photoinitiator may comprise, for example, 2,2-dimethoxy-1,2-diphenylethan-1-one (Irgacure® 651, Ciba Specialty Chemicals), 2,4,6-trimethylbenzoyl-diphenyl-phosphinooxide ( Darocur® TPO, Ciba Specialty Chemicals) or a combination thereof.
[0561] [0561] Other examples of suitable photoinitiators include Darocur® TPO (available from Ciba Specialty Chemicals), Lucirin® TPO (available from BASF), Speedcure® TPO (available from Lambson), Irgacure® TPO (available from Ciba Specialty Chemicals and Omnirad® (available from IGM Resins) and combinations of any of the foregoing.
[0562] [0562] Compositions provided by the present disclosure may comprise from 1% by weight to 5% by weight, from 1.5% by weight to 4.5% by weight, from 2% by weight to 4% by weight, from 2, 5% by weight to 3.5% by weight of a UV photoinitiator or combination of UV photoinitiators, where% by weight is based on the total weight of the curable composition.
[0563] [0563] Compositions provided by the present disclosure may comprise a filler or combination of fillers. Suitable fillers can comprise, inorganic fillers, organic fillers, lightweight fillers and combinations of any of the foregoing.
[0564] [0564] Curable compositions can comprise, for example, 15% by weight to 35% by weight of filler, 17% by weight to 33% by weight, 20% by weight to 30% by weight of filler or 22 % by weight to 28% by weight, where% by weight is based on the total weight of the curable composition. The compositions provided by the present disclosure may comprise, for example, silica gel, fumigated silica, calcium carbonate, micronized oxidized polyethylene homopolymer, lightweight microcapsules or a combination of any of the foregoing.
[0565] [0565] Compositions and sealants provided by the present disclosure may comprise an organic filler or a combination of organic fillers.
[0566] [0566] An organic filler can have a specific gravity, for example, less than 1.15, less than 1.1, less than 1.05, less than 1, less than 0.95, less than than 0.9, less than 0.8 or less than 0.7. Organic fillers can have a specific gravity, for example, within a range of
[0567] [0567] Organic fillers can comprise thermoplastics, thermosets or a combination of these. Examples of suitable thermoplastics and thermosets include epoxies, epoxy-amides, ETFE copolymers, nylon, polyethylenes, polypropylenes, polyethylene oxides, polypropylene oxides, polyvinylidene chlorides, polyvinylfluorides, TFE, polyamides, polyimide, fluoroethylene, propylene fluids, ethylene propylene fluids. polycarbonates, polyetheretherketones, polyethylene ketones, polyphenylene oxides, polyphenylene sulfides, polystyrenes, polyvinyl chlorides, melamines, polyesters, phenolics, epichlorohydrins, fluorinated hydrocarbons, polycyclics, polybutadiene, polyethylene, polyisoprene, polyisoprene, polyisoprene, polyisoprene , liquid crystal polymers and combinations of any of the foregoing.
[0568] [0568] Examples of suitable organic fillers include polyamides, polyimides, polyethylene, polyphenylene sulfides and combinations of any of the foregoing.
[0569] [0569] Examples of suitable polyamide 6 and polyamide 12 particles are available from Toray Plastics as grades SP-500, SP-10, TR-1 and TR-2. Suitable polyamide powders are also available from Arkema Group under the trade name Orgasol® and from Evonik Industries under the trade name Vestosin®.
[0570] [0570] Examples of suitable polyimide powders are available from Evonik Industries under the trade name P84®.
[0571] [0571] An organic filler can include a polyethylene powder, such as an oxidized polyethylene powder. Suitable polyethylene powders are available from Honeywell International, Inc. under the trade name ACumist®, from INEOS under the trade name Eltrex® and Mitsui Chemicals America, Inc. under the trade name Mipelon ™.
[0572] [0572] The use of organic fillers such as polyphenylene sulfide in aerospace sealants is disclosed in U.S. Patent No. 9,422,451, which is incorporated by reference in its entirety. Polyphenylene sulphide is a thermoplastic engineering resin that exhibits dimensional stability, chemical resistance and resistance to corrosive and high temperature environments. Polyphenylene sulfide engineering resins are commercially available, for example, under the trade names Ryton® (Chevron), Techtron® (Quadrant), Fortron® (Celanese) and Torelina® (Toray). Polyphenylene sulfide resins are generally characterized by a specific gravity of about 1.3 to about 1.4.
[0573] [0573] An organic filler can take any suitable shape. For example, an organic filler may comprise fractions of crushed polymer that have been filtered to select a desired size range. An organic filler can comprise substantially spherical particles. Particles can be solid or they can be porous.
[0574] [0574] An organic filler can have an average particle size, for example, within a range of 1 μm to 100 μm, 2 μm to 40 μm, 2 μm to 30 μm, 4 μm to 25 um, 4 μm to 20 μm, from 2 μm to 12 μm or from 5 μm to 15 μm. An organic filler can have an average particle size, for example, less than 100 μm, less than 75 μm, less than 50 μm, less than 40 μm or less than 20 μm. The particle size distribution can be determined using a Fischer Sub-Sieve Sizer or by optical inspection.
[0575] [0575] An organic filler can include a low density such as a modified expanded thermoplastic microcapsule. Suitable modified expanded thermoplastic microcapsules may include an outer coating of a melamine or urea / formaldehyde resin.
[0576] [0576] Compositions and sealants provided by the present disclosure may comprise an inorganic filler or combination of inorganic fillers. An inorganic filler can be included to provide mechanical reinforcement and to control the rheological properties of the composition. Inorganic fillers can be added to compositions to communicate desirable physical properties such as, for example, to increase impact resistance, to control viscosity or to modify the electrical properties of a cured composition.
[0577] [0577] An inorganic filler can be coated or uncoated. For example, an inorganic filler can be coated with a hydrophobic coating, such as a polydimethylsiloxane coating.
[0578] [0578] Compositions provided by the present disclosure may comprise, for example, from 5% by weight to 25% by weight of an inorganic filler or combination of inorganic fillers, from 7% by weight to 23% by weight, 10% by weight at 20% by weight or from 12% by weight to 18% by weight, where% by weight is based on the total weight of the composition.
[0579] [0579] Compositions provided by the present disclosure may comprise silica gel or a combination of silica gel. Suitable silica gels include Gasil® silica gel available from PQ Corporation and Sylysia®, CariAct® and Sylomask® silica gel available from Fuji Silysia Chemical Ltd. The compositions provided by the present disclosure may comprise, for example, 5% by weight at 25% by weight, from 10% by weight to 20% by weight or 12% by weight at 18, of silica gel, where% by weight is based on the total weight of the curable composition.
[0580] [0580] Compositions provided by the present disclosure may comprise low density microcapsules. A low density microcapsule can comprise a thermally expandable microcapsule.
[0581] [0581] A thermally expandable microcapsule refers to a hollow shell comprising a volatile material that expands at a predetermined temperature. Thermally expandable thermoplastic microcapsules can have an average initial particle size of 5 μm to 70 μm, in some cases 10 μm to 24 μm or 10 μm to 17 μm. The term "average initial particle size" refers to the average particle size (numerical weighted average of the particle size distribution) of the microcapsules before any expansion. The particle size distribution can be determined using a Fischer Sub-Sieve Sizer or by optical inspection.
[0582] [0582] A thermally expandable thermoplastic microcapsule can comprise a volatile hydrocarbon within a thermoplastic resin wall. Examples of hydrocarbons suitable for use in such microcapsules include methyl chloride, methyl bromide, trichloroethane, dichloroethane, n-butane, n-heptane, n-propane, n-hexane, n-pentane, isobutane, isopentane, isooctane , neopentane, petroleum ether and fluorine-containing aliphatic hydrocarbons, such as Freon ™ and combinations of any of the foregoing.
[0583] [0583] Examples of materials suitable for forming the wall of a thermally expandable microcapsule include polymers of vinylidene chloride, acrylonitrile, styrene, polycarbonate, methyl methacrylate, ethyl acrylate and vinyl acetate, copolymers of these monomers and combinations of polymers and copolymers .
[0584] [0584] Examples of suitable thermoplastic microcapsules include Expancel ™ microcapsules such as Expancel ™ DE microspheres available from AkzoNobel. Examples of suitable Expancel ™ DE microspheres include
[0585] [0585] Suitable low density fillers such as low density microcapsules can have an average diameter (d0.5), for example, from 1 μm to 100 μm, from 10 μm to 80 μm or from 10 μm to 50 μm, as determined according to ASTM D1475.
[0586] [0586] Low density fillers such as low density microcapsules can be characterized by a specific gravity within a range of 0.01 to 0.09, from 0.04 to 0.09, within a range of 0.04 to 0.08, within a range of 0.01 to 0.07, within a range of 0.02 to 0.06, within a range of 0.03 to 0.05, within a range of 0 , 05 to 0.09, from 0.06 to 0.09 or within a range of 0.07 to 0.09, where specific gravity is determined according to ASTM D1475. Low density fillers such as low density microcapsules can be characterized by a specific gravity less than 0.1, less than 0.09, less than 0.08, less than 0.07, less than 0, 06, less than 0.05, less than 0.04, less than 0.03 or less than 0.02, where the specific gravity is determined according to ASTM D1475.
[0587] [0587] Low density fillers such as low microcapsules can be characterized by an average particle diameter from 1 μm to 100 μm and can be substantially spherical in shape. Low density fillers such as low density microcapsules can be characterized, for example, by an average particle diameter of 10 μm to 100 μm, 10 μm to 60 μm, 10 μm to 40 μm or 10 μm to 30 μm , as determined according to ASTM D1475.
[0588] [0588] Low density fillers may comprise uncoated microcapsules, coated microcapsules or combinations thereof.
[0589] [0589] Low density fillers such as low density microcapsules can comprise expanded microcapsules or microbalions having a coating of an aminoplastic resin such as a melamine resin.
[0590] [0590] Low density fillers such as low density microcapsules can comprise thermally expandable thermoplastic microcapsules having an outer coating of an aminoplastic resin, such as a melamine resin. The coated low density microcapsules may have an outer coating of a melamine resin, where the coating may have a thickness, for example, less than 2 μm, less than 1 μm or less than 0.5 μm. The melamine coating on the lightweight microcapsules is believed to make the microcapsules reactive with the thiol-terminated polythiopolymer prepolymer and / or the polyepoxide curing agent, which enhances fuel resistance and makes the microcapsules resistant to pressure .
[0591] [0591] The thin coating of an aminoplastic resin can have a film thickness of less than 25 μm, less than 20 μm, less than 15 μm or less than 5 μm. The thin coating of an aminoplastic resin can have a film thickness of at least 0.1 nanometers, such as at least 10 nanometers or at least 100 nanometers, or, in some cases, at least 500 nanometers.
[0592] [0592] Aminoplastic resins can be based on the condensation products of formaldehyde, with a substance bearing an amino group or starch. Condensation products can be obtained by reacting alcohols and formaldehyde with melamine, urea or benzoguanamine. Condensation products from other amines and amides can also be used, for example, triazine aldehyde condensates, diazines, triazoles, guanidines, guanamines and alkyl- and aryl-substituted derivatives of such compounds, including alkyl- and aryl-substituted ureas and alkyl- and aryl-substituted melamines. Examples of such compounds include N, N'-dimethyl urea, benzourea, diciandiamide, formaguanamine, acetoguanamine, glycoluryl, ameline, 2-chloro-4,6-diamino-1,3,5-triazine, 6-methyl-2,4 -diamino-1,3,5-triazine, 3,5-diaminotriazole, triaminopyrimidine, 2-mercapto-4,6-diaminopyrimidine and 3,4,6- tris (ethylamino) -1,3,5 triazine. Suitable aminoplastic resins can also be based on the condensation products of other aldehydes such as acetaldehyde, crotonaldehyde, acrolein, benzaldehyde, furfural and glyoxal.
[0593] [0593] An aminoplastic resin may comprise a low alkylated, highly alkylated aminoplast resin that has a degree of polymerization less than 3.75, such as less than 3.0 or less than 2.0. The average numerical degree of polymerization can be defined as the average number of structural units per polymeric chain. For example, a degree of polymerization of 1.0 indicates a completely monomeric triazine structure, while a degree of polymerization of 2.0 indicates two triazine rings joined by a methylene or methylene-oxy bridge. The degree of polymerization represents an average degree of polymerization value as determined by gel permeation chromatography using polystyrene standards.
[0594] [0594] An aminoplastic resin can contain methylol or other alkyl groups and at least a portion of the alkyl groups can be etherified by reaction with an alcohol. Examples of suitable monohydric alcohols include alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, benzyl alcohol, other aromatic alcohols, cyclic alcohols such as cyclohexanol, glycol monoethers and alcohols substituted by halogen or other substituted alcohols, such such as 3-chloropropanol and butoxyethanol. Aminoplastic resins can be substantially alkylated with methanol or butanol.
[0595] [0595] An aminoplastic resin can comprise a melamine resin.
[0596] [0596] A suitable aminoplastic resin may comprise a urea-formaldehyde resin.
[0597] [0597] Particles coated with aminoplastic resin are distinct from uncoated particles that are merely incorporated into a polymeric network, as is the case when uncoated low density particles are dispersed in a film-forming binder. For particles coated with aminoplastic resin, a thin film is deposited on the outer surface of separate separate particles such as thermally expanded microcapsules. These particles coated with aminoplastic resin can then be dispersed in a film-forming binder, thereby resulting in the dispersion of the coated particles throughout an entire polymeric network. The thin coating of an aminoplastic resin can cover, for example, 70% to 100%, 80% to 100% or 90% to 100% of the outer surface of a low density particle such as a thermally expanded microcapsule. The coating of an aminoplastic resin can form a substantially continuous coating on the outer surface of a low density particle.
[0598] [0598] Low density microcapsules can be prepared by any suitable technique, including, for example, as described in U.S. Patent Nos.
[0599] [0599] Before applying an aminoplastic resin coating, a thermally expanded thermoplastic microcapsule can be characterized by a specific gravity, for example, within a range of 0.01 to 0.05, within a range of 0.015 to 0.045 , within a range of 0.02 to 0.04 or within a range of 0.025 to 0.035, where specific gravity is determined according to ASTM D1475. For example, Expancel ™ 920 DE 40 and Expancel ™ 920 DE 80 can be characterized by a specific gravity of about 0.03, where the specific gravity is determined according to ASTM D1475.
[0600] [0600] After coating with an aminoplastic resin, an aminoplastic-coated microcapsule can be characterized by a specific gravity, for example, within a range of 0.02 to 0.08, within a range of 0.02 to 0.07, within a range of 0.02 to 0.06, within a range of 0.03 to 0.07, within a range of 0.03 to 0.065, within a range of 0.04 to 0.065, within a range of 0.045 to 0.06 or within a range of 0.05 to 0.06, where specific gravity is determined according to ASTM D1475.
[0601] [0601] Compositions and sealants provided by the present disclosure may include an adhesion promoter or combination of adhesion promoters.
[0602] [0602] Curable compositions provided by the present disclosure may comprise, for example, less than 0.1% by weight of an adhesion promoter, less than 0.2% by weight, less than 0.3% by weight or less than 0.4% by weight of an adhesion promoter, where% by weight is based on the total weight of the curable composition. A curable composition provided by the present disclosure may comprise, for example from 0.05% by weight to 0.4% by weight, from 0.05% by weight to 0.3% by weight, from 0.05% by weight to 0.2% by weight of an adhesion promoter.
[0603] [0603] Low density compositions provided by the present disclosure may comprise an adhesion promoter or combination of adhesion promoters. An adhesion promoter can include a phenolic adhesion promoter, a combination of phenolic adhesion promoters, an organo-functional silane, a combination of organo-functional silanes or a combination of any of the foregoing. An organosilane can be an amine-functional silane.
[0604] [0604] Compositions and sealants provided by the present disclosure may comprise a phenolic adhesion promoter, an organosilane or a combination thereof. A phenolic adhesion promoter can comprise a cooked phenolic resin, an uncooked phenolic resin or a combination thereof. Examples of suitable adhesion promoters include phenolic resins such as phenolic resin
[0605] [0605] Phenolic adhesion promoters may comprise the reaction product of a condensation reaction of a phenolic resin with one or more thiol-terminated polysulfides. Phenolic adhesion promoters can be terminated in thiol.
[0606] [0606] Examples of suitable phenolic resins include 2- (hydroxymethyl) phenol, (4-hydroxy-1,3-phenylene) dimethanol, (2-hydroxybenzene-1,3,4-triyl) trimethanol, 2-benzyl-6- (hydroxymethyl) phenol, (4-hydroxy-5 - ((2-hydroxy-5- (hydroxymethyl) cyclohexa-2,4-dien-1-yl) methyl) - 1,3-phenylene) dimethanol, (4-hydroxy -5 - ((2-hydroxy-3,5-bis (hydroxymethyl) cyclohexa-2,4-dien- 1-yl) methyl) -1,3-phenylene) dimethanol and a combination of any of the foregoing.
[0607] [0607] Suitable phenolic resins can be synthesized by the catalyzed reaction based on phenol with formaldehyde.
[0608] [0608] Phenolic adhesion promoters may comprise the reaction product of a condensation reaction of a Metilon® resin, a Varcum® resin or a Durez® resin available from Durez Corporation with a thiol-terminated polysulfide such as a Tioplast® resin.
[0609] [0609] Examples of Metilon® resins include Metilon® 75108 (methylol phenol allyl ether, see U.S. Patent No. 3,517,082) and Metilon® 75202.
[0610] [0610] Examples of Varcum® resins include Varcum® 29101, Varcum® 29108, Varcum® 29112, Varcum® 29116, Varcum® 29008, Varcum® 29202, Varcum® 29401, Varcum® 29159, Varcum® 29181, Varcum® 92600, Varcum® 92600, Varcum® 92600 ® 94635, Varcum® 94879 and Varcum® 94917.
[0611] [0611] An example of a Durez® resin is Durez® 34071.
[0612] [0612] Compositions provided by the present disclosure may comprise an organo-functional adhesion promoter such as an organo-functional silane. An organo-functional silane can comprise hydrolyzable groups attached to a silicon atom and at least one organofunctional group. An organofunctional silane can have the structure Ra- (CH2) n-Si (-OR) 3-nRbn, where Ra is an organofunctional group, n is 0, 1 or 2 and R and Rb is alkyl such as methyl or ethyl. Examples of organofunctional groups include epoxy, amino, methacryloxy or sulfide groups. An organofunctional silane can be a dipodal silane having two or more silane groups, a functional dipodal silane, a non-functional dipodal silane or a combination of any of the foregoing.
[0613] [0613] An amine functional silane can comprise a primary amine functional silane, a secondary amine functional silane or a combination thereof. A primary amine functional silane refers to a silane having a primary amino group. A secondary amine functional silane refers to a silane having a secondary amine group. An amine functional silane can comprise, for example, from 40% by weight to 60% by weight of a primary amine functional silane; and from 40% by weight to 60% by weight of a secondary amine functional silane; 45 wt% to 55 wt% of a primary amine functional silane and 45 wt% to 55% by weight of a secondary amine functional silane; or 47% by weight to 53% by weight of a primary amine functional silane and 47% by weight to 53% by weight of a secondary amine functional silane; where wt% is based on the total weight of the functional amine silane in a composition.
[0614] [0614] A secondary amine functional silane can be a sterically hindered amine functional silane. In a sterically hindered amine functional silane the secondary amine may be close to a large group or portion that limits or restricts the degrees of freedom of the secondary amine compared to the degrees of freedom for a non-sterically hindered secondary amine. For example, in a sterically hindered secondary amine, the secondary amine may be close to a phenyl group, a cyclohexyl group or a branched alkyl group.
[0615] [0615] Functional amine silanes can be monomeric amine functional silanes having a molecular weight, for example, from 100 Dalton to 1000 Dalton, from 100 Dalton to 800 Dalton, from 100 Dalton to 600 Dalton or from 200 Dalton to 500 Dalton.
[0616] [0616] Examples of suitable primary amine functional silanes include 4-aminobutyltriethoxysilane, 4-amino-3,3-dimethylbutyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, 3 (m-aminophenoxy) propyltrimethoxysilane, m-aminophenyl p-aminophenyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltris (methoxyethoxyethoxy) silane, 11-aminoundecyltriethoxysilane, 2- (4-pyridylethyl) triethoxysilane, 2- (2-pyridylethyl-methoxy-ethyl) -aminopropylsilanotriol, 4-amino-3,3-dimethylbutylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 1-amino- 2- (dimethylethoxylsilyl) propane, 3-aminopropylthiisopropylene ethoxysilane and 3-aminopropylmethylethoxysilane.
[0617] [0617] Examples of suitable amine functional disilanes include aminoethylaminomethyl) phenethyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropyltrimethoxysilane.
[0618] [0618] Examples of suitable secondary amine functional silanes include 3- (N-allylamino) propyltrimethoxysilane, n-butylaminopropyltrimethoxysilane, tert-butylaminopropyltrimethoxysilane, (N, N-cyclohexylaminomethyl) methyldiethoxysilane, (N-cyclohexylaminylmethyl) trimethoxysilane, (3- (n-ethylamino) isobutyl) methyldiethoxysilane, (3- (N-ethylamino) isobutyl) trimethoxysilane, N-methylaminopropylmethydimethoxysilane, N-methylaminopropyltrimethoxysilane, N-methylaminopropyltrimethoxyethylmethylmethyl-phenylmethylamine, N-methylamethoxy-methylene
[0619] [0619] Suitable amine functional silanes are commercially available, for example, from Gelest Inc. and Dow Corning Corporation.
[0620] [0620] Curable compositions provided by the present disclosure may comprise less than 3% by weight of an adhesion promoter, less than 2% by weight, less than 1% by weight or less than 0.5% by weight, where% by weight is based on the total weight of the curable composition.
[0621] [0621] Curable compositions provided by the present disclosure may comprise a pigment, an ink, a photochromatic agent or a combination of any of the foregoing. Because a curable composition can cure completely under dark conditions, an ink, pigment and / or photochromatic agent can be used. To cure with actinic radiation, the surface of an applied sealant can heal and the unexposed regions of the applied sealant can heal.
[0622] [0622] Any suitable paint, pigment and / or photochromatic agent can be used.
[0623] [0623] In certain applications it may be desirable that a photochromatic agent that is sensitive to the degree of cure is used. Such agents can provide a visual indication that the sealant has been exposed to a desired amount of actinic radiation or example, to cure the sealant. Certain photochromatic agents can be used as indicators of cure. A cure indicator can facilitate the ability to assess the extent of cure for a sealant by visual inspection.
[0624] [0624] A photochromic material can be a compound that is activated by absorbing radiation energy having a particular wavelength, such as UV radiation, which causes a characteristic change such as a color change. A characteristic change can be an identifiable change in a characteristic of the photochromic material that can be detected using an instrument or visually. Examples of characteristic changes include a change in color or depth of color and a change in structure or other interactions with energy in the visible portions of UV, infrared (IR), close to the IR or away from the IR of the electromagnetic spectrum such as absorption and / or reflectance. A color change at visible wavelengths refers to a color change at wavelengths within a range of 400 nm to 800 nm.
[0625] [0625] A sealant composition provided by the present disclosure can include at least one photochromatic material. A photochromic material can be activated by absorbing radiation energy (visible and non-visible light) having a particular wavelength, such as UV light, to undergo a characteristic change such as a color change. The characteristic change may be a change in characteristic of the photochromatic material alone or it may be a change in characteristic of the sealant composition. Examples of suitable photochromic materials include spiropyranes, spiropyrimidines, spirooxazins, diarylenes, photochromatic quinones, azobenzenes, other photochromatic inks and combinations thereof. These photochromic materials undergo a reversible color change when exposed to radiation where the first and second colored states are different colors or different depths of the same color.
[0626] [0626] Spiropyans are photochromic molecules that change color and / or fluoresce under light sources of different wavelength. Spiropyans typically have a 2H-pyran isomer in which the hydrogen atom at position two is replaced by a second ring system attached to the carbon atom at position two of the pyran molecule in a spiro mode resulting in a carbon atom that is common in both rings. The second ring is often, but not exclusively, heterocyclic. Examples of suitable spiropyranes include 1 ', 3'-dihydro-8-methoxy-1', 3 ', 3'-trimethyl-6-nitrospiro [2H-1-benzopyran-2-, 2' - (2H) -indole] ; 1 ', 3'-dihydro-1', 3 ', 3'-trimethyl-6-nitrospiro [2H-1-benzopyran-2,2' - (2H) -indol]; 1,3-dihydro-1,3,3-trimethylspirus [2H-indole-2,3 ’- [3H] naphth [2,1-b] [- 1,4] oxazine]; 6,8-dibromo-1 ', 3'-dihydro-1', 3 ', 3'-trimethylspirus [2H-1-benzopyran-2,2' - (2-H) -indole]; 5-chloro-1,3-dihydro-1,3,3-trimethylspirus [2H-indole-2,3 '- [3H] phenantr [9, -10-b] [1,4] oxazine]; 6-bromo-1 ', 3'-dihydro-1', 3 ', 3'-trimethyl-8-nitrospiro [2H-1-benzopyran-2,2-'- (2H) -indole]; 5-chloro-1,3-dihydro-
[0627] [0627] Azobenzenes are capable of photoisomerization between trans and cis isomers. Examples of suitable azobenzenes include azobenzene; 4- [bis (9,9-dimethylfluoren-2-yl) amino] azobenzene; 4- (N, N-dimethylamino) azobenzene-4'-isothiocyanate; 2,2'-dihydroxyazobenzene; 1,1'-dibenzyl-4,4'-bipyridinium dichloride; 1,1'-diheptyl-4,4'-bipyridinium dibromide; 2,2 ', 4'-trihydroxy-5-chloroazobenzene-3-sulfonic acid and combinations thereof.
[0628] [0628] Examples of suitable photochromatic spirooxazins include 1,3-dihydro-1,3,3-trimethylspirus [2H-indole-2,3 '- [3H] phenantr [9,10-b] (1,4-) oxazine ]; 1,3,3-trimethyl spiro (indoline-2,3 '- (3H) naphth (2,1-b) (1,4) oxazine); 3-ethyl-9'-methoxy-1,3-dimethylspir (indoline-2,3 '- (3H) naphth (2,1-b) (1,4) -oxazine); 1,3,3-trimethylspir (indoline-2,3 '- (3H) pyrido (3,2-f) - (1,4) benzox-azine); 1,3-dihydrospiro (indoline-2,3 '- (3H) pyrido (3,2-
[0629] [0629] Examples of suitable photochromatic spiropyrimidines include 2,3-dihydro-2-spiro-4 '- [8'-aminonaphthalen-1' (4'H) -one] pyrimidine; 2,3-dihydro-2-spiro-7 '- [8'-imino-7', 8'-dihydronaphthalen-1'-amine] pyrimidine and combinations thereof.
[0630] [0630] Examples of suitable photochromatic diaethylenes include 2,3-bis (2,4,5-trimethyl-3-thienyl) maleic anhydride; 2,3-bis (2,4,5-trimethyl-3-thienyl) maleimide; cis-1,2-dicyan-1,2-bis (2,4,5-trimethyl-3-thienyl) ethane; 1,2-bis [2-methylbenzo [b] thiophen-3-yl] - 3,3,4,4,5,5-hexafluoro-1-cyclopentene; 1,2-bis (2,4-dimethyl-5-phenyl-3-thienyl) -3,3,4,4,5,5-hexafluoro-1-cyclopentene; stilbene; dithienylethenes and combinations thereof.
[0631] [0631] Examples of suitable forochromatic quinones include 1-phenoxy-2,4-dioxianthraquinone; 6-phenoxy-5,12-naphthacenequinone; 6-phenoxy-5,12-pentacenequinone; 1,3-dichloro-6-phenoxy-7,12-phthaloylpyren and combinations thereof.
[0632] [0632] Examples of suitable photochromatic agents that can be used as a cure indicator include ethylviolet and Disperse Red 177.
[0633] [0633] A photochromic material can produce a reversible color change feature when irradiated. The reversible color change can be caused by a reversible transformation of the photochromatic material between two molecular forms having different absorption spectra as a result of the absorption of electromagnetic radiation. When the radiation source is removed or turned off, the photochromic material normally reverts to its first color state.
[0634] [0634] A photochromic material may exhibit an irreversible color change following exposure to radiation. For example, exposing the photochromic material to radiation can cause the photochromic material to change from a first state to a second state. When the radiation exposure is removed, the photochromic material is prevented from reverting to the initial state as a result of a physical and / or chemical interaction with one or more components of the sealant composition.
[0635] [0635] A composition provided by the present disclosure may include, for example, 0.1% by weight to 10% by weight of a photochromic material, such as 0.1% by weight to 5% by weight or 0, 1% by weight to 2% by weight, where% by weight is based on the total weight of the composition.
[0636] [0636] Compositions provided by the present disclosure can be formulated as sealants. As formulated it is meant that in addition to the reactive species that forms the cured polymer network, additional material can be added to a composition to communicate desired properties to the uncured sealant and / or the cured sealant. For uncured sealant these properties may include viscosity, pH and / or rheology. For cured sealants, these properties may include weight, adhesion, corrosion resistance, color, glass transition temperature, electrical conductivity, cohesion and / or physical properties such as tensile strength, elongation and hardness. The compositions provided by the present disclosure may comprise one or more additional components suitable for use in aerospace sealants and the selection may depend at least in part on the desired performance characteristics of the sealant cured under conditions of use.
[0637] [0637] Curable compositions provided by the present disclosure can be visually clear. A visually clear sealant can allow visual inspection of the seal quality. Curable compositions can be transmissive or partially transmissive to actinic radiation such as UV radiation. The materials that form a curable composition can be selected to provide a desired curing depth following exposure to actinic radiation. For example, the filler used can be selected to be transmissive or partially transmissive to actinic radiation such as UV radiation and / or the size and geometry of the filler can be selected to send incident scattering actinic radiation.
[0638] [0638] Curable compositions provided by the present disclosure may comprise, for example, from 3% by weight to 9% by weight of a poly (alkenyl) ether, from 55% by weight to 75% by weight of a sulfur-containing prepolymer. finished in thiol, 5% by weight to 15% by weight of an inorganic filler such as fumigated silica and 10% by weight to 20% by weight of silica gel, where% by weight is based on the total weight of the composition curable.
[0639] [0639] Curable compositions provided by the present disclosure may comprise, for example, from 4% by weight to 8% by weight of a polyalkenyl such as a poly (alkenyl) ether, from 60% by weight to 70% by weight of a polyol such as a thiol-containing sulfur-containing prepolymer, from 7% by weight to 13% by weight of an inorganic filler such as fumigated silica and from 12% by weight to 18% by weight of silica gel, where the% in weight is based on the total weight of the curable composition.
[0640] [0640] Curable compositions provided by the present disclosure may comprise, for example, from 5% by weight to 7% by weight of a poly (alkenyl) ether, from 63% by weight to 67% by weight of a sulfur-containing prepolymer. finished in thiol, from 8% by weight to 11% by weight of an inorganic filler such as fumigated silica and from 14% by weight to 16% by weight of silica gel, where% by weight is based on the total weight of the composition curable.
[0641] [0641] Curable compositions provided by the present disclosure may comprise, for example, from 3% by weight to 9% by weight of a poly (alkenyl) ether, from 55% by weight to 75% by weight of a sulfur-containing prepolymer. finished in thiol, from 1% by weight to 3.5% by weight of a polythiol having a thiol functionality greater than two, from 5% by weight to 15% by weight of an inorganic filler such as fumigated silica and 10% by weight to 20% by weight of a silica gel, where the% by weight is based on the total weight of the curable composition.
[0642] [0642] Curable compositions provided by the present disclosure may comprise, for example, from 4% by weight to 8% by weight of a poly (alkenyl) ether, from 60% by weight to 70% by weight of a sulfur-containing prepolymer finished in thiol, from 1.3% by weight to 3.1% by weight of a polythiol, from 7% by weight to 13% by weight of an inorganic filler such as fumigated silica and from 12% by weight to 18% in weight of silica gel, where% by weight is based on the total weight of the curable composition.
[0643] [0643] Curable compositions provided by the present disclosure may comprise, for example, from 5% by weight to 7% by weight of a poly (alkenyl) ether, from 63% by weight to 67% by weight of a sulfur-containing prepolymer. finished in thiol, from 1.6% by weight to 2.9% by weight of a polythiol, from 8% by weight to 11% by weight of an inorganic filler such as fumigated silica and from 14% by weight to 16% in weight of silica gel, where% by weight is based on the total weight of the curable composition.
[0644] [0644] Any of the foregoing curable compositions comprises a dark curing metal / organic peroxide complex catalyst. For example, a curable composition can comprise from 0.01% by weight to 3% by weight of a metal complex and from 0.2% by weight to 3% by weight of organic peroxide, where% by weight is based on weight total composition.
[0645] [0645] Curable compositions provided by the present disclosure may comprise, for example, from 1% by weight to 10% by weight of a polyalkenyl such as a divinyl ether, from 2% by weight to 9% by weight, 3% by weight to 8% by weight or from 4% by weight to 7% by weight of a polyalkenyl, where% by weight is based on the total weight of the curable composition.
[0646] [0646] Curable compositions provided by the present disclosure may comprise, for example, from 0.01% by weight to 3% by weight of a hydroxy vinyl ether, from 0.05% by weight to 2.5% by weight, from 0.1% by weight to 2% by weight or 0.2% by weight to 1.5% by weight of a hydroxy vinyl ether, where% by weight is based on the total weight of the curable composition.
[0647] [0647] Curable compositions provided by the present disclosure may comprise, for example, from 45% by weight to 85% by weight of a polythiol such as a thiol-terminated prepolymer such as a thiol-terminated polythiopolymer, of 50% by weight to 80% by weight or 60% by weight to 75% by weight of a polythiol such as a thiol-terminated prepolymer, where% by weight is based on the total weight of the curable composition.
[0648] [0648] Curable compositions provided by the present disclosure may comprise, for example, from 0.1% by weight to 10% by weight of a polythiol having a thiol functionality greater than 2, from 0.5% by weight to 8% in weight, from 1% by weight to 6% by weight or from 1% by weight to 4% by weight of a polythiol having a thiol functionality greater than two, where% by weight is based on the total weight of the curable composition.
[0649] [0649] Curable compositions provided by the present disclosure may comprise, for example, from 0.01% by weight to 2% by weight of a photoinitiator, from 0.05% by weight to 1.5% by weight of a photoinitiator or 0.05% by weight to 1% by weight of a photoinitiator, where% by weight is based on the total weight of the curable composition.
[0650] [0650] Curable compositions provided by the present disclosure may comprise, for example, 0.01% by weight to 4% by weight of a plasticizer, 0.05% by weight to 3% by weight or 0.1% by weight. weight at 2% by weight of a plasticizer, where% by weight is based on the total weight of the curable composition.
[0651] [0651] Curable compositions provided by the present disclosure may comprise, for example, from 1% by weight to 50% by weight of a filler, from 5% by weight to 40% by weight, from 10% by weight to 30% by weight or from 15% by weight to 25% by weight of a filler, where the% by weight is based on the total weight of the curable composition.
[0652] [0652] Curable compositions provided by the present disclosure may comprise, for example, from 0.01% by weight to 3% by weight of an adhesion promoter, from 0.05% by weight to 2.5% by weight or from 0 , 05% by weight to 1% by weight of an adhesion promoter, where% by weight is based on the total weight of the curable composition.
[0653] [0653] Curable compositions provided by the present disclosure may comprise, for example, from 0.01% by weight to 4% by weight, from 0.02% by weight to 3% by weight, from 0.05% by weight to 2 % by weight or 0.1% by weight to 1.5% by weight of an organic peroxide, where% by weight is based on the total weight of the curable composition.
[0654] [0654] Curable compositions provided by the present disclosure may comprise, for example, from 0.001% by weight to 3% by weight of a metal complex, from 0.001% by weight, to 2% by weight, from 0.01% by weight, to 2% by weight, from 0.01% by weight to 1% by weight or from 0.05% by weight to 0.5% by weight of a metal complex, where% by weight is based on the total weight of the composition curable.
[0655] [0655] Curable compositions provided by the present disclosure may comprise: from 1% by weight to 10% by weight of a divinyl ether; from 45% by weight to 85% by weight of a thiol-terminated polythether; from 0.1% by weight to 5% by weight of an organic peroxide; and from 0.01% by weight to 2% by weight of a metal complex, where% by weight is based on the total weight of the curable composition.
[0656] [0656] Curable compositions provided by the present disclosure may comprise: from 4% by weight to 6% by weight of a divinyl ether; from 50% by weight to 80% by weight of a thiol-terminated polythiopolymer prepolymer; from 0.2% by weight to 4% by weight of an organic peroxide; and from 0.02% by weight to 1% by weight of a metal complex, where% by weight is based on the total weight of the curable composition.
[0657] [0657] Curable compositions provided by the present disclosure may comprise: from 2% by weight to 8% by weight of a divinyl ether; from 60% by weight to 75% by weight of a thiol-terminated polythiopolymer prepolymer; from 0.5% by weight to 2% by weight of an organic peroxide; and from 0.05% by weight to 0.5% by weight of a metal complex, where% by weight is based on the total weight of the curable composition.
[0658] [0658] Curable compositions provided by the present disclosure may comprise: from 0.01% by weight to 2% by weight of a synergist such as a hydrogen donor such as a primary amine or a secondary amine; from 0.02% by weight to 1.5% by weight, from 0.05% by weight to 1% by weight or from 0.1% by weight to 0.5% by weight, where% by weight is justified in the total weight of the curable composition.
[0659] [0659] Curable compositions provided by the present disclosure may comprise: from 1% by weight to 10% by weight of a polyalkenyl monomer; from 45% by weight to 85% by weight of a thiol-terminated prepolymer; from 0.1% by weight to 5% by weight of an organic peroxide; and from 0.001% by weight to 2% by weight of a metal complex, where% by weight is based on the total weight of the curable composition.
[0660] [0660] Curable compositions provided by the present disclosure may comprise: from 4% by weight to 6% by weight of a polyalkenyl monomer; from 50% by weight to 80% by weight of a thiol-terminated prepolymer; from 0.2% by weight to 4% by weight of an organic peroxide; and from 0.002% by weight to 1% by weight of a metal complex, where% by weight is based on the total weight of the curable composition.
[0661] [0661] Curable compositions provided by the present disclosure may comprise: from 2% by weight to 8% by weight of a polyalkenyl monomer; from 60% by weight to 75% by weight of a thiol-terminated prepolymer; from 0.5% by weight to 2% by weight of an organic peroxide; and from 0.005% by weight to 0.5% by weight of a metal complex, where% by weight is based on the total weight of the curable composition.
[0662] [0662] Curable compositions provided by the present disclosure may comprise: from 1% by weight to 10% by weight of a polythiol monomer; from 45% by weight to 85% by weight of an alkenyl-terminated prepolymer; from 0.1% by weight to 5% by weight of an organic peroxide; and from 0.001% by weight to 2% by weight of a metal complex, where% by weight is based on the total weight of the curable composition.
[0663] [0663] Curable compositions provided by the present disclosure may comprise: from 4% by weight to 6% by weight of a polythiol monomer; from 50% by weight to 80% by weight of an alkenyl-terminated prepolymer; from 0.2% by weight to 4% by weight of an organic peroxide; and from 0.002% by weight to 1% by weight of a metal complex, where% by weight is based on the total weight of the curable composition.
[0664] [0664] Curable compositions provided by the present disclosure may comprise: from 2% by weight to 8% by weight of a polythiol monomer; from 60% by weight to 75% by weight of an alkenyl-terminated prepolymer; from 0.5% by weight to 2% by weight of an organic peroxide; and from 0.005% by weight to 0.5% by weight of a metal complex, where% by weight is based on the total weight of the curable composition.
[0665] [0665] Uncured sealants provided by the present disclosure can be provided as a two-part system comprising a first part and a second part that can be prepared and stored separately, combined and mixed at the time of use.
[0666] [0666] Curable sealant systems of the present disclosure can be provided as two-part sealant compositions. The two parts can be maintained separately and can be combined before use. A first part may comprise, for example, polyalkenyls, hydroxyl functional vinyl ethers, inorganic filler, organic filler and lightweight filler. A second part may comprise, for example, thiol-containing sulfur-containing prepolymers, polythioles, organic filler, inorganic filler, lightweight filler and adhesion promoters. Optional additives can include plasticizers, pigments, solvents, reactive diluents, surfactants, thixotropic agents, flame retardants and a combination of any of the foregoing. A metal complex can be added to the first part and an organic peroxide can be added to the second part. A metal complex can be added to the second part and an organic peroxide can be added to the first part.
[0667] [0667] The first part and the second part can be formulated to be made compatible when combined such that the constituents of the first and second parts can mix and be homogeneously dispersed to provide a sealant or coating composition for application to a substrate. Factors that affect the compatibility of the first and second parts include, for example, viscosity, pH, density and temperature.
[0668] [0668] A first part may comprise, for example, 70% by weight to 90% by weight, 72% by weight to 88% by weight or 76% by weight to 84% by weight, of a polyalkenyl such as a poly (alkenyl) ether, where% by weight is based on the total weight of the first part.
[0669] [0669] A first part can comprise, for example, 70% by weight to 90% by weight of a polyalkenyl such as a poly (alkenyl) ether, 3% by weight to 13% by weight of a plasticizer and 6 % by weight to 16% by weight of a filler, where% by weight is based on the total weight of the first part. A first part may comprise, for example, 72% by weight to 88% by weight of a poly (alkenyl) ether, from 5% by weight to 11% by weight of a plasticizer and of
[0670] [0670] A second part may comprise, for example, from 60% by weight to 80% by weight, from 62% by weight to 78% by weight or from 66% by weight to 74% by weight, of a prepolymer containing thiol-terminated sulfur, where% by weight is based on the total weight of the second part.
[0671] [0671] A second part may comprise from 60% by weight to 80% by weight of a thiol-containing sulfur-containing prepolymer, from 5% by weight to 15% by weight of a filler and from 11% by weight to 21 % by weight of a silica gel, where% by weight is based on the total weight of the second part. A second part may comprise from 62% by weight to 78% by weight of a thiol-containing sulfur prepolymer, from 7% by weight to 13% by weight of a filler and from 13% by weight to 19% by weight of a silica gel, where% by weight is based on the total weight of the second part. A second part may comprise from 66% by weight to 74% by weight of a thiol-containing sulfur prepolymer, from 9% by weight to 11% by weight of a filler and from 15% by weight to 17% by weight of a silica gel, where% by weight is based on the total weight of the second part.
[0672] [0672] The pH of each part of a sealant system can be selected to improve the storage stability of each part.
[0673] [0673] Curable compositions provided by the present disclosure can be used as aerospace sealants or coatings and in particular, as sealants or coatings where hydraulic fluid resistance is desired. A sealant
[0674] [0674] Compositions provided by the present disclosure can be applied directly to the surface of a substrate or to an sublayer such as a primer by any suitable coating process.
[0675] [0675] In addition, methods are provided to seal an opening using a composition provided by the present disclosure. These methods comprise, for example, applying the curable composition to at least one surface of a part; and curing the applied composition to provide a sealed part.
[0676] [0676] Compositions, including sealants, provided by the present disclosure can be applied to any of a variety of substrates. Examples of substrates to which a composition can be applied include metals such as titanium, stainless steel, steel alloy, aluminum and aluminum alloy, any of which can be anodized, prepared, coated with organic or coated with chromate; epoxy; urethane; graphite; fiberglass composite; Kevlar®; acrylics; and polycarbonates. Compositions provided by the present disclosure can be applied to a substrate such as aluminum and aluminum alloy.
[0677] [0677] Sealant compositions provided by the present disclosure can be formulated as Class A, Class B or Class C sealants. A Class A sealant refers to a brushable sealant having a viscosity of 1 poise to 500 poise and is designed for brush application. A Class B sealant refers to an extrusable sealant having a viscosity of 4,500 poise to 20,000 poise and is designed for extrusion application by means of a pneumatic gun. A Class B sealant can be used to form fillets and seal on vertical surfaces or edges where low slag / slag is required. A Class C sealant has a viscosity from 500 poise to 4,500 poise and is designed for application by a combed tooth spreader or cylinder. A Class C sealant can be used for sealing the contact surface. Viscosity can be measured according to Section 5.3 of the SAE Aerospace Standard AS5127 / 1C published by SAE International Group.
[0678] [0678] Compositions provided by the present disclosure can be applied directly to the surface of a substrate or to an sublayer by any suitable coating process known to those of ordinary skill in the art.
[0679] [0679] In addition, methods are provided to seal an opening using a composition provided by the present disclosure. These methods comprise, for example, providing the curable composition of the present disclosure; applying the curable composition to at least one surface of a part; and curing the applied composition to provide a sealed part.
[0680] [0680] Compositions, including sealants, provided by the present disclosure can be applied to any of a variety of substrates. Examples of substrates to which a composition can be applied include metals such as titanium, stainless steel, steel alloy, aluminum and aluminum alloy, any of which can be anodized, prepared, coated with organic or coated with chromate; epoxy; urethane; graphite; fiberglass composite; Kevlar®; acrylics; and polycarbonates.
[0681] [0681] A composition provided by the present disclosure can be cured under ambient conditions, where ambient conditions refer to a temperature of 20 ° C to 25 ° C and atmospheric humidity. A composition can be cured under conditions ranging from a temperature of 0 ° C to 100 ° C and a humidity of 0% relative humidity to 100% relative humidity. A composition can be cured at a higher temperature such as at least 30 ° C, at least 40 ° C or at least 50 ° C. A composition can be cured at room temperature, for example, 25 ° C. The methods can be used to seal openings in aerospace vehicles including aircraft and aerospace vehicles.
[0682] [0682] Openings, surfaces, joints, fillets, contact surfaces including openings, surfaces, fillets, joints and contact surfaces of aerospace vehicles, sealed with the compositions provided by the present disclosure are also disclosed. Compositions and sealants can also be used as seat fasteners.
[0683] [0683] Curable compositions provided by the present disclosure can be for sealing fasteners. Curable compositions provided by the present disclosure can be used as sealing caps. A sealing cap refers to a sealant molded to cover a fastener. Thus, aspects of the invention include sealing caps comprising a curable composition provided by the present disclosure. Sealing caps and thiol / ene formulations suitable for use in sealing caps are disclosed, for example, in U.S. Patent No. 9,533,798, U.S. Patent No. 8,932,685 and U.S. Patent No. 7,438,974, each of which it is incorporated by reference in its entirety. A sealing cap can be provided having the hull cured or partially cured and filled with an uncured portion. The sealing cap can be stored at a low temperature until use. The uncured portion can be at least partially cured using actinic radiation and / or can be cured without exposure to actinic radiation via the dark curing mechanism. As another example, a sealing cap comprising a composition provided by the present disclosure can be deposited on a fixative and at least partially cured by exposure to actinic radiation with development of full cure over time through the dark curing mechanism. .
[0684] [0684] The time to form a viable seal using the curable compositions of the present disclosure may depend on several factors as can be assessed by those skilled in the art and as defined by the requirements of applicable standards and specifications. In general, the curable compositions of the present disclosure develop resistance to adhesion within about 3 days to about 7 days after mixing and application to a surface. In general, the resistance to total adhesion as well as other properties of the cured compositions of the present disclosure becomes fully developed within 7 days after mixing and applying a curable composition to a surface.
[0685] [0685] A cured composition can have a thickness, for example, of 5 mils to 25 mils (127 μm to 635 μm) such as 10 mils to 20 mils (254 μm to 508 μm).
[0686] [0686] The free radical photopolymerization reaction can be initiated by exposing a composition provided by the present disclosure to actinic radiation such as UV radiation, for example, for less than 120 seconds, less than 90 seconds, less than 60 seconds or less than 30 seconds.
[0687] [0687] The free radical photopolymerization reaction can be initiated by exposing a composition provided by the present disclosure to actinic radiation such as UV radiation, for example, from 15 seconds to 120 seconds, from 15 seconds to 90 seconds, from 15 seconds to 60 seconds.
[0688] [0688] UV radiation may include irradiation at a wavelength of 394 nm.
[0689] [0689] The total power of the UV exposure can be, for example, from 50 mW / cm2 to 500 mW / cm2, from 50 mW / cm2 to 400 mW / cm2, from 50 mW / cm2 to 300 mW / cm2, from 100 mW / cm2 to 300 mW / cm2 or from 150 mW / cm2 to 250 mW / cm2.
[0690] [0690] Curable compositions provided by the present disclosure can be exposed to a UV dose of 1 J / cm2 to 4 J / cm2 to cure the sealant. The UV source is an 8W lamp with a UVA spectrum. Other doses and / or other sources of
[0691] [0691] Compositions provided by the present disclosure can also be cured with radiation in bands of blue wavelength such as an LED.
[0692] [0692] Compositions provided by the present disclosure are curable without exposure to actinic radiation such as UV radiation. The composition can be at least partially curable during exposure to actinic radiation and such compositions can include photoionization. Actinic radiation such as UV radiation can be applied to at least a portion of an applied sealant. The sealant can be accessible to actinic radiation and the portion of the sealant exposed to UV radiation can be a surface depth. For example, actinic radiation can initiate the light curing reaction to a depth, for example, of at least 4 mm, at least 6 mm, at least 8 mm or at least 10 mm. A portion of the sealant may not be accessible to actinic radiation because of the absorption or dispersion of actinic radiation from the sealant that prevents the actinic radiant from interacting with the full thickness of the sealant. A portion of the sealant can be obscured by the geometry of the part being sealed or it can be obscured by an overlapping structure.
[0693] [0693] Curable compositions provided by the present disclosure can be exposed to UV radiation to initiate double cure reactions. The compositions can be exposed to a UV dose of, for example, 1 J / cm2 to 4 J / cm2. The UV dose can be selected, for example, to provide a UV curing depth of 1 mm to 25 mm, 2 mm to 20 mm, 5 mm to 18 mm or 10 mm to 15 mm.
[0694] [0694] The curing reaction in darkness can extend beyond the region exposed to actinic radiation at a distance, for example, 1 cm or less, 2 cm or less, 4 cm or less, 6 cm or less, 10 cm or less or 20 cm or less. For example, the curing reaction in darkness may extend beyond the region exposed to actinic radiation at a distance of 0.1 cm to 20 cm, from 0.1 cm to 10 cm, from 0.1 cm to 6 cm, from 0.1 cm to 4 cm, from 0.1 cm to 2 cm or from 0.1 cm to 1 cm. The distance can refer to a depth within the curable composition, a distance within the plane of a coating or both. In other words, the distance can refer to a distance parallel and / or orthogonal to the direction of the actinic radiation.
[0695] [0695] Curable compositions provided by the present disclosure can be exposed to actinic radiation, for example, for 120 seconds or less, for 90 seconds or less, for 60 seconds or less, for 30 seconds or less or 15 seconds or less. Curable compositions provided by the present disclosure can be exposed to actinic radiation, for example, within a range of 10 seconds to 120 seconds, from 15 seconds to 120 seconds, for 30 seconds to 90 seconds or from 30 seconds to 60 seconds.
[0696] [0696] A curable composition can be applied to a surface. The curable composition can be exposed to actinic radiation. Actinic radiation can extend to a depth in the thickness of the applied sealant, such as, for example, to a depth of 0.25 inches, 0.5 inches, 0.75 inches, 1 inch, 1.25 inches or 1 , 5 inches. The portion of the sealant exposed to actinic radiation can cure by a free radical mechanism. The depth of exposure to actinic radiation may depend on a number of factors including, for example, absorption by the materials forming the sealant, dispersion or radiation by the materials forming the sealant such as by filler and / or the geometry of the applied sealant.
[0697] [0697] A portion of the applied composition may not be exposed to actinic radiation. For example, actinic radiation may not extend through the thickness of the sealant applied. The unexposed portion of the sealant underlying the portion exposed to actinic radiation can heal by free radicals generated by the organic peroxide / metal complex. Similarly, portions of the sealant applied adjacent to the portion exposed to actinic radiation can heal by the mechanism of organic peroxide / metal complex.
[0698] [0698] Curable compositions provided by the present disclosure, after application to a part, can be exposed to actinic radiation for a time sufficient to completely or partially cure the sealant surface. The total depth of the sealant can then cure over time through curing mechanisms in darkness. Providing a completely or partially cured surface can facilitate the handling of the part.
[0699] [0699] Actinic radiation can be applied to a curable composition at any time during the curing process. For example, actinic radiation can be applied to a sealant applied immediately after application or at any time while the sealant is curing. For example, it may be desirable to coat a large surface area with a sealant and then expose the entire surface to actinic radiation. Actinic radiation can be applied once or several times during the healing process. In general, exposing the sealant to actinic radiation will cure the sealant to a certain depth. The depth of cure induced by actinic radiation can depend on several factors such as, for example, the formulation of sealant, the filler content and the type and conditions of radiation.
[0700] [0700] Sealant compositions provided by the present disclosure can also cure during exposure to ambient lighting.
[0701] [0701] Curable compositions provided by the present disclosure do not require exposure to actinic radiation to cure. Cured compositions can cure under dark conditions through free radicals generated by the organic peroxide / metal complex mechanism. Cured compositions can cure at temperatures within a range of 20 ° C to 30 ° C, such as 22 ° C to 28 ° C. Thus, the curing reaction in darkness does not require the application of heat or generation of free radicals in an area of the sealant adjacent to the curing area in darkness.
[0702] [0702] Cured compositions provided by the present disclosure, such as cured sealants, exhibit acceptable properties for use in aerospace sealant applications. In general, it is desirable for sealants used in aviation and aerospace applications to exhibit the following properties: peel strength greater than 20 pounds per linear inch (pli) on Aerospace Material Specification (AMS) 3265B substrates determined under dry conditions, following the immersion in JRF Type I for 7 days and then immersion in a 3% NaCl solution according to the specifications of the AMS 3265B test; tensile strength between 300 pounds per square inch (psi) and 400 psi; shear strength greater than 50 pounds per linear inch (pli); elongation between 250% and 300%; and hardness greater than 40 Durometer A. These and other properties of the cured sealant suitable for aviation and aerospace applications are disclosed in AMS 3265B, which is incorporated by reference in its entirety. It is also desirable that, when cured, the compositions of the present disclosure used in aviation and aircraft applications exhibit a percentage volume of swelling not greater than 25% following immersion for one week at 60 ° C (140 ° F) at 760 torr (101 kPa) in Jet Reference Fluid (JRF) Type 1. Other properties, ranges and / or thresholds may be appropriate for other sealant applications.
[0703] [0703] The cured compositions provided by the present disclosure can be fuel resistant. The term “fuel resistant” means that a composition, when applied to a substrate and cured, can provide a cured product, such as a sealant, which exhibits a percentage volume of swelling of not more than 40%, in some cases not more than 25%, in some cases not more than 20% and in other cases not more than 10%, after immersion for one week at 140 ° F (60 ° C) and 760 torr (101 kPa) in JRF Type I according to methods similar to those described in ASTM D792 (American Society for Testing and Materials) or AMS 3269 (Aerospace Material Specification). Type I JRF, as used for determining fuel resistance, has the following composition: toluene: 28 ± 1% by volume; cyclohexane (technical): 34 ± 1% by volume; isooctane: 38 ± 1% by volume; and tertiary dibutyl disulfide: 1 ± 0.005% by volume (see AMS 2629, issued on July 1, 1989, § 3.1.1., available from SAE (Society of Automotive Engineers)).
[0704] [0704] Compositions provided by the present disclosure provide a cured product, such as a sealant, exhibiting a tensile elongation of at least 200% and a tensile strength of at least 200 psi when measured according to the procedure described in AMS 3279, § 3.3.17.1, test procedure AS5127 / 1, § 7.7. In general, for a Class A sealant there is no requirement for traction and elongation. For a Class B sealant, as a general requirement, the tensile strength is equal to or greater than 200 psi (1.38 MPa) and the elongation is equal to or greater than 200%. Acceptable elongation and tensile strength may differ depending on the application.
[0705] [0705] Compositions provide a cured product, such as a sealant, that exhibits a shear strength in the overlap joint of more than 200 psi (1.38 MPa), such as at least 220 psi (1.52 MPa), at least 250 psi (1.72 MPa), and, in some cases, at least 400 psi (2.76 MPa), when measured according to the procedure described in SAE AS5127 / 1 paragraph 7.8.
[0706] [0706] A cured sealant prepared from a composition provided by the present disclosure meets or exceeds the requirements for aerospace sealants as presented in AMS 3277.
[0707] [0707] Curable compositions provided by the present disclosure can be formulated to exhibit a desired curing profile. A curing profile can be characterized by an application time, an adhesion-free time, a curing time and a total curing time. Definitions of these durations are provided here. For example, a curable composition provided by the present disclosure can be formulated to exhibit an application time of 0.5 hours, an adhesion-free time of less than 2 hours and a curing time of 3 hours under conditions of 25 ° C and 50% RH. Other formulations may exhibit, for example, an application time of 2 hours, an adhesion-free time less than 8 hours and a curing time of 9 hours; or an application time of 4 hours, an adhesion-free time of less than 24 hours and a curing time of less than 24 hours. Other curing profiles can be designed for a particular application and based on considerations such as material volume, surface area, method of application, coating thickness, temperature and humidity.
[0708] [0708] Depending on the application, an acceptable extrusion rate can be at least 15 g / min, at least 20 g / min, at least 30 g / min, at least 40 g / min, at least 50 g / min or at least 60 g / min when extruded through a No 404 nozzle at a pressure of 90 psi (620 kPa).
[0709] [0709] For certain applications it may be desirable that the application time is, for example, at least 2 hours, at least 5 hours, at least 10 hours, at least 15 hours, at least 20 hours or at least 25 hours.
[0710] [0710] Curing time is defined as the duration after time when the components of the sealant composition are first combined until the time when the surface hardness of the sealant is Shore 30A. Shore A hardness can be measured using Type A durometer according to ASTM D2240.
[0711] [0711] Sealants provided by the present disclosure are intended to be cured at 25 ° C, however, sealants can be cured at higher temperatures, which will decrease the free time of adhesion and the curing time. Unless otherwise clear from the context, application, adhesion-free time and curing time refer to the characteristic times of a curing profile for a sealant cured at 25 ° C.
[0712] [0712] After the curing time, the hardness of the sealant will continue to increase until the sealant is completely cured. A fully cured sealant can have a hardness, for example from Shore 40A to Shore 80A, from Shore 45A to Shore 70A or from Shore 50A to Shore 60A. Following curing to Shore 30A hardness, the sealant can cure completely within, for example, 1 day to 6 weeks, 3 days to 5 weeks, 4 days to 4 weeks or 1 week to 3 weeks.
[0713] [0713] Double cure, short cure sealants provided by the present disclosure can be characterized, for example, from an adhesion free time of less than 1 day, less than 16 hours or less than 8 hours. Double cure, short cure sealants provided by the present disclosure can be characterized, for example, from an adhesion free time of 2 hours to 24 hours, from 4 hours to 20 hours or from 8 hours to 16 hours.
[0714] [0714] Double cure, long cure sealants provided by the present disclosure can be characterized, for example, from an adhesion-free time of more than 1 day, more than 3 days, more than 6 days or more than 9 days. Double cure, long cure sealants provided by the present disclosure can be characterized, for example, from an adhesion-free time of 1 day to 10 days, from 2 days to 8 days or from 4 days to 6 days.
[0715] [0715] A long curing sealant can have, for example, an open time of 1 hour to 5 hours and a curing time of 2 weeks to 4 weeks.
[0716] [0716] For example, using Mn (acac) 3 and the metal complex, a sealant provided by the present disclosure can exhibit an application time of 15 minutes to 2 hours, an adhesion-free time of 14 hours to 3 days and a time from 1 day to 3 days.
[0717] [0717] In general, the metal complex can provide coarse control of a sealant cure profile and an amine catalyst can provide fine control of the sealant cure profile.
[0718] [0718] In general, for certain applications it may be desirable that the application time is from 15 minutes to 2 hours and the curing time is from 3 hours to 36 hours.
[0719] [0719] Compositions provided by the present disclosure can be cured using radiation within the blue region of the electromagnetic spectrum. For example, compositions can be curable using radiation within a range, for example, from 365 nm to 395 nm.
[0720] [0720] Openings, surfaces, joints, fillets, contact surfaces including openings, surfaces, fillets, joints and contact surfaces of aerospace vehicles, sealed with compositions provided by the present disclosure are also disclosed. A composition provided by the present disclosure can be used to seal a part. A part can include multiple surfaces and joints.
[0721] [0721] Compositions provided by the present disclosure can be used to seal parts exposed or potentially exposed to fluids such as solvents, hydraulic fluids and / or fuel.
[0722] [0722] Compositions provided by the present disclosure can be used to seal a part including a vehicle surface.
[0723] [0723] The term "vehicle" is used in its broadest sense and includes all types of aircraft, spaceship, vessel and land vehicles. For example, a vehicle may include, aircraft such as airplanes including private aircraft and passenger, freight and military aircraft; helicopters, including private, commercial and military helicopters; aerospace vehicles including, rockets and other spacecraft. A vehicle may include a land vehicle such as, for example, trailers, cars, trucks, buses, vans, construction vehicles, golf carts, motorcycles, bicycles, trains and rail cars. A vehicle may also include a vessel such as, for example, ships, boats and a hydrofoil.
[0724] [0724] A composition provided by the present disclosure can be used in an F / A-18 jet or related aircraft such as the F / A-18E Super Hornet and F / A-18F (produced by McDonnell Douglas / Boeing and Northrop); on the passenger jet aircraft Boeing 787 Dreamliner, 737, 747, 717, a related aircraft (produced by Boeing Commercial Airplaines); on the V-22 Osprey; VH-92, S-92 and related aircraft (produced by NAVAIR and Sikorsky); on the G650, G600, G550, G500, G450 and related aircraft (produced by Gulfstream); and on the A350, A320, A330 and related aircraft (produced by Airbus). Compositions provided by this disclosure may be used on any suitable commercial, military or general aviation aircraft such as, for example, those produced by Bombardier Inc. and / or Bombardier Aerospace such as Canadair Regional Jet (CRJ) and related aircraft; produced by Lockheed Martin such as the F-22 Raptor, the F-35 Lightning and related aircraft; produced by Northrop Grumman such as the B-2 Spirit and related aircraft; produced by Pilatus Aircraft Ltd .; produced by Eclipse Aviation Corporation; or produced by Eclipse Aerospace (Kestrel Aircraft).
[0725] [0725] Compositions provided by the present disclosure can be used to seal vehicle parts and surfaces such as fuel tank surfaces and other surfaces exposed to or potentially exposed to aerospace solvents, aerospace hydraulic fluids and aerospace fuels.
[0726] [0726] The present invention includes parts sealed with a composition provided by the present disclosure and assemblies and apparatus comprising a part sealed with a composition provided by the present disclosure.
[0727] [0727] The present invention includes vehicles comprising a part such as a surface sealed with a composition provided by the present disclosure. For example, an aircraft comprising a fuel tank or portion of a fuel tank sealed with a sealant provided by the present disclosure is included within the scope of the invention.
[0728] [0728] Compositions can be as coatings or sealants and in particular sprayable coatings and sealants having a high filler content such as, for example, a filler content of 1% by weight to 90% by weight and / or a filler content from 1% by vol to 80% by vol. Coatings and sealants can be applied to any suitable surface including, for example, vehicle surfaces, architectural surfaces, consumer products, electronics, marine equipment and industrial equipment. ASPECTS OF THE INVENTION
[0729] [0729] Aspect 1. A composition comprising: a thiol-containing sulfur-containing prepolymer; a polyalkenyl; a metallic complex; and an organic peroxide.
[0730] [0730] Aspect 2. The composition of aspect 1, wherein the thiol-terminated sulfur-containing prepolymer comprises a thiol-terminated polythiopolymer prepolymer, a thiol-terminated polysulfide prepolymer, a polyform prepolymer containing thiol-terminated sulfur, a thiol-terminated monosulfide prepolymer or a combination of any of the foregoing.
[0731] [0731] Aspect 3. The composition of any one of aspects 1 to 2, wherein the thiol-terminated sulfur-containing prepolymer comprises a thiol-terminated polythiopolymer prepolymer.
[0732] [0732] Aspect 4. The composition of any one of aspects 1 to 3, wherein the thiol-terminated sulfur-containing prepolymer comprises a thiol-terminated polythiopolymer of Formula (2a), a polyether ether prepolymer thiol-terminated Formula (2b) or a combination of these: HS-R1- [S- (CH2) 2-O- (R2-O) m (CH2) 2-S-R1-] nSH (2a) {HS- R1- [S- (CH2) 2-O- (R2-O-) m (CH2) 2-S-R1-] nS-V '-} zB (2b) in which, each R1 independently comprises C2-10 alkanediyl , C6-8 cycloalkanodiyl, C6-14 alkanocycloalkanodiyl, C5-8 heterocycloalkanodiyl or - [(CHR3) pX-] q (CHR3) r-, where, p is an integer from 2 to 6; q is an integer from 1 to 5; r is an integer from 2 to 10; each R3 independently comprises hydrogen or methyl; and each X independently comprises O, S or NR, where R comprises hydrogen or methyl; each R2 is independently comprised of C1-10 alkanediyl, C6-8 cycloalkanediyl, C6-14 alkanocycloalkanediyl or - [(CHR3) pX-] q (CHR3) -, where p, q, r, R3 and X are as defined as for R1; m is an integer from 0 to 50; n is an integer from 1 to 60; B represents a nucleus of a polyfunctionalizing agent, z-valiant B (-V) z where, z is an integer from 3 to 6; and each V is a portion comprising a terminal group reactive with a thiol; and each -V'- is derived from the reaction of -V with a thiol.
[0373] [0373] Aspect 5. The composition of any one of aspects 1 to 4, wherein the polyalkenyl comprises a bis (alkenyl) ether.
[0374] [0374] Aspect 6. The composition of any one of aspects 1 to 5, wherein the polyalkenyl comprises divinyl ether of cyclohexanedimethanol.
[0375] [0375] Aspect 7. The composition of any one of aspects 1 to 6, in which the metal complex comprises cobalt (II) bis (2-ethyl hexanoate), manganese (III) (acetylacetonate) 3, iron (III) ( acetylacetonate) 3 or a combination of any of the foregoing.
[0376] [0376] Aspect 8. The composition of any one of aspects 1 to 7, wherein the organic peroxide comprises tert-butyl peroxybenzoate.
[0377] [0377] Aspect 9. The composition of any one of aspects 1 to 8, wherein the metal complex comprises a metallic complex of Co (II), Co (III), Mn (II), Mn (III), Fe (II ), Fe (III), Cu (II) or a combination of any of the foregoing.
[0378] [0378] Aspect 10. The composition of any one of aspects 1 to 9, further comprising a hydroxyl functional vinyl ether.
[0379] [0379] Aspect 11. The composition of any one of aspects 1 to 10, further comprising 4-hydroxybutyl vinyl ether.
[0380] [0380] Aspect 12. The composition of any one of aspects 1 to 11, wherein the composition comprises from 55% by weight to 75% by weight of the thiol-containing sulfur-containing prepolymer, on which% by weight is substantiated in the total weight of the composition.
[0381] [0381] Aspect 13. The composition of any one of aspects 1 to 12, wherein the composition comprises from 2% by weight to 10% by weight of the polyalkenyl, where% by weight is based on the total weight of the composition.
[0382] [0382] Aspect 14. The composition of any one of aspects 1 to 13, wherein the composition comprises from 0.01% by weight to 3% by weight of the metal complex, where% by weight is based on the total weight of the composition.
[0383] [0383] Aspect 15. The composition of any one of aspects 1 to 14, wherein the composition comprises from 0.2% by weight to 3% by weight of the organic peroxide, where the% by weight is based on the total weight of the composition.
[0384] [0384] Aspect 16. The composition of any one of aspects 1 to 15, wherein the composition comprises from 0.1% by weight to 2% by weight of a hydroxyl functional vinyl ether, on which the% by weight is based in the total weight of the composition.
[0385] [0385] Aspect 17. The composition of any one of aspects 1 to 16, wherein the composition comprises: from 55% by weight to 75% by weight of the thiol-containing sulfur-containing prepolymer; from 2% by weight to 10% by weight of the polyalkenyl; from 0.01% by weight to 3% by weight of the metal complex; from 0.2% by weight to 3% by weight of organic peroxide, from 0.1% by weight to 2% by weight of a hydroxyl functional vinyl ether, where% by weight is based on the total weight of the composition.
[0386] [0386] Aspect 18. The composition of any of aspects 1 to 17, wherein, the thiol-terminated sulfur-containing prepolymer comprises a thiol-terminated polythiopolymer prepolymer; the polyalkenyl comprises cyclohexanedimethanol divinyl ether; the metal complex comprises cobalt (II) bis (2-ethyl hexanoate), manganese (III) (acetylacetonate) 3, iron (III) (acetylacetonate) 3 or a combination of any of the foregoing; the organic peroxide comprises tert-butyl peroxybenzoate; and further comprising a hydroxyl functional vinyl ether, a plasticizer and a polythiol; wherein, the hydroxyl functional vinyl ether comprises 4-hydroxybutyl vinyl ether; the plasticizer comprises a polybutadiene; and the polyol has a thiol functionality of three, a thiol functionality of four, or a combination thereof.
[0387] [0387] Aspect 19. The composition of aspect 18, further comprising an organic filler, an inorganic filler, a lightweight filler or a combination of any of the foregoing.
[0388] [0388] Aspect 20. The composition of any one of aspects 1 to 19, in which, the metallic complex comprises a metallic cation and an anion; the metal cation has an oxidation number of 2, 3 or a combination thereof; and the anion comprises an organic anion.
[0389] [0389] Aspect 21. The composition of aspect 20, wherein the metallic cation comprises a metallic cation of Co, Mn, Fe, Cu, V, Cu, Al or a combination of any of the foregoing.
[0390] [0390] Aspect 22. The composition of any of aspects 20 to 21, in which the organic anion comprises acetylacetonate.
[0391] [0391] Aspect 23. The composition of any one of aspects 1 to 22, wherein the composition further comprises a polythiol, a photoinitiator, a plasticizer, a silica gel, a filler or a combination of any of the foregoing.
[0392] [0392] Aspect 24. The composition of any one of aspects 1 to 23, wherein the composition further comprises 0.1% by weight to 3% by weight of a plasticizer, where% by weight is based on the total weight composition.
[0393] [0393] Aspect 25. The composition of any one of aspects 1 to 24, wherein the composition further comprises from 15% by weight to 25% by weight of a filler, where the% by weight is based on the total weight of the composition .
[0394] [0394] Aspect 26. The composition of any one of aspects 1 to 25, wherein the composition further comprises a filler, wherein the filler comprises an organic filler, fumigated silica, silica gel, a lightweight filler or a combination any of the foregoing.
[0395] [0395] Aspect 27. The composition of any one of aspects 1 to 26, wherein the composition comprises from 10% by weight to 20% by weight of silica gel, where% by weight is based on the total weight of the composition .
[0396] [0396] Aspect 28. The composition of any one of aspects 1 to 27, wherein the composition comprises from 5% by weight to 15% by weight silica gel, where% by weight is based on the total weight of the composition.
[0397] [0397] Aspect 29. The composition of any one of aspects 1 to 28, where the composition is curable under dark conditions.
[0398] [0398] Aspect 30. The composition of any one of aspects 1 to 29, in which the composition has an application time equal to or greater than 30 minutes.
[0399] [0399] Aspect 31. The composition of any of aspects 1 to 30, wherein the composition completely cures under dark conditions within twelve (12) days.
[0400] [0400] Aspect 32. A cured sealant comprising the composition of any one of aspects 1 to 31.
[0401] [0401] Aspect 33. The cured sealant of aspect 32, where the cured sealant exhibits a tensile strength greater than 200 psi (1.3 MPa) and an elongation greater than 200% following exposure to the Jet Reference Fluid Type I according to AMS 3269, where the tensile strength and elongation are determined according to AMS 3279.
[0402] [0402] Aspect 34. A part sealed with sealant cured from any of aspects 32 to 33.
[0403] [0403] Aspect 35. A method of sealing a part comprising: applying the composition of any one of aspects 1 to 31 to a part; and allowing the applied composition to cure, to seal the part.
[0404] [0404] Aspect 36. The method of aspect 35, further comprising, after applying the composition, exposing at least a portion of the composition applied to actinic radiation.
[0405] [0405] Aspect 37. A sealant system, comprising: a first part, wherein the first part comprises a polyalkenyl; and a second part, wherein the second part comprises a thiol-containing sulfur-containing prepolymer, wherein the first part, the second or both the first and the second parts comprise a metal complex and an organic peroxide.
[0406] [0406] Aspect 38. The sealant system of aspect 37, wherein the first part, the second or both the first and second parts comprise a UV sensitive photoinitiator.
[0407] [0407] Aspect 39. A sealant comprising the sealant system of any of aspects 37 to 38, in which the first part and the second part are combined.
[0408] [0408] Aspect 40. A part sealed with the sealant system of any of the aspects 37 to 39.
[0409] [0409] Aspect 41. A method of sealing a part, comprising combining the first part and the second part of the sealant system of any of aspects 37 to 40 to provide a sealant; apply the sealant to a part; and allow the applied sealant to cure, to seal the part.
[0410] [0410] Aspect 42. Method of aspect 41, further comprising, after applying the sealant, exposing at least a portion of the sealant applied to actinic radiation.
[0411] [0411] Aspect 1A. A composition comprising: a polythiol, wherein the polythiol comprises a thiol-terminated prepolymer; a polyalkenyl, wherein the polyalkenyl comprises an alkenyl-terminated prepolymer, a polyalkenyl monomer or a combination thereof; a metallic complex; and an organic peroxide.
[0412] [0412] Aspect 1Aa. The composition of aspect 1A, wherein the polythiol comprises a thiol-terminated prepolymer.
[0413] [0413] Aspect 2A. The composition of aspect 1A, wherein the thiol-terminated prepolymer comprises a thiol-terminated sulfur-containing prepolymer.
[0414] [0414] Aspect 3A. The composition of aspect 2A, wherein the thiol-terminated sulfur-containing prepolymer comprises a thiol-terminated polythiopolymer prepolymer, a thiol-terminated polysulfide prepolymer, a thiol-terminated polysulfide prepolymer, a thiol-terminated monosulfide prepolymer or a combination of any of the foregoing.
[0415] [0415] Aspect 4A. The composition of aspect 3A, wherein the thiol-terminated sulfur-containing prepolymer comprises a thiol-terminated polythiopolymer prepolymer.
[0416] [0416] Aspect 5A. The composition of aspect 4A, wherein the thiol-terminated sulfur-containing prepolymer comprises a portion having the structure of Formula (2c): -S-R1- [SAS-R1-] nS- (2c) where, n is an integer from 1 to 60; each R1 is independently selected from C2-10 alkanediyl, C6-8 cycloalkanediyl, C6-14 alkanocycloalkanediyl, C5-8 heterocycloalkanediyl and - [(CHR3) pX-] q (CHR3) r-, where, p is an integer of 2 to 6; q is an integer from 1 to 5; r is an integer from 2 to 10; each R3 is independently selected from hydrogen and methyl; and each X is independently selected from O, S and NR, where R is selected from hydrogen and methyl; and each A is independently a portion derived from a polyvinyl ether of Formula (3) and a polyalkenyl polyfunctionalizing agent of Formula (4): CH2 = CH-O- (R2-O) m-CH = CH2 (3) where , m is an integer from 0 to 50; each R2 is independently selected from C1-10 alkanediyl, C6-8 cycloalkanediyl, C6-14 alkanocycloalkanediyl and - [(CHR3) pX-] q (CHR3) r-, where p, q, r, R3 and X are as defined as for R1; B represents a core of a polyfunctionalizing agent, polyalkenyl z-valent B (-R70-CH = CH2) z where, z is an integer from 3 to 6; and each R70 is independently selected from C1-10 alkanediyl,
[0417] [0417] Aspect 6A. The composition of aspect 4A, wherein the thiol-terminated sulfur-containing polythioether comprises a thiol-terminated polythiopolymer prepolymer of Formula (2a), a thiol-terminated polythiopolymer prepolymer of Formula (2b) or a combination of these: HS-R1- [S- (CH2) 2-O- (R2-O) m (CH2) 2-S-R1-] nSH (2a) (HS-R1- [S- (CH2) 2-O- ( R2-O-) m (CH2) 2-S-R1-] nS-V '-} zB (2b) in which, each R1 independently comprises C2-10 alkanediyl, C6-8 cycloalkanodiyl, C6-14 alkanocycloalkanidiyl C5-14 -8 or - [(CHR3) pX-] q (CHR3) r-, where, p is an integer from 2 to 6; q is an integer from 1 to 5; r is an integer from 2 to 10 ; each R3 independently comprises hydrogen or methyl; and each X independently comprises O, S or NR, where R comprises hydrogen or methyl; each R2 is independently comprised of C1-10 alkanediyl, C6-8 cycloalkanediyl, C6-14 alkanocycloalkanyl or - [ (CHR3) pX-] q (CHR3) r-, where p, q, r, R3 and X are as defined as for R1; m is an integer of 0 at 50; n is an integer from 1 to 60; B represents a nucleus of a polyfunctionalizing agent, z-valiant B (-V) z where, z is an integer from 3 to 6; and each V is a portion comprising a terminal group reactive with a thiol; and each -V'- is derived from the reaction of -V with a thiol.
[0418] [0418] Aspect 7A. The composition of any one of aspects 1A to 6A, wherein the alkenyl-terminated prepolymer comprises an alkenyl-terminated sulfur-containing prepolymer.
[0419] [0419] Aspect 7Aa. The composition of any of aspects 1A to 67A, wherein the polythiol comprises a polythiol monomer.
[0420] [0420] Aspect 8A. The composition of aspect 7Aa, wherein the polythiol monomer comprises a dithiol monomer, a polythiol monomer having a thiol functionality greater than two or a combination thereof.
[0421] [0421] Aspect 9A. The composition of any of aspects 7A to 8A, wherein the polythiol monomer comprises a sulfur-containing dithiol monomer, a sulfur-containing polythiol monomer having a thiol functionality greater than two or a combination thereof.
[0422] [0422] Aspect 10A. The composition of any one of aspects 1A to 9A, wherein the polyalkenyl monomer comprises a dialkenyl monomer, a polyalkenyl monomer having an alkenyl functionality greater than two or a combination thereof.
[0423] [0423] Aspect 11A. The composition of any one of aspects 1A to 10A, wherein the polyalkenyl monomer comprises a sulfur-containing dialkyl monomer, a sulfur-containing polyalkenyl monomer having an alkenyl functionality greater than two or a combination thereof.
[0424] [0424] Aspect 12A. The composition of any one of aspects 1A to 11A, wherein the polyalkenyl monomer comprises a bis (alkenyl) ether.
[0425] [0425] Aspect 13A. The composition of any one of aspects 1A to 12A, wherein the polythiol comprises a thiol-terminated polythiopolymer prepolymer; and the polyalkenyl comprises a bis (alkenyl) ether.
[0426] [0426] Aspect 14A. The composition of any of aspects 1A to 13A, wherein the polyalkenyl monomer comprises ethylene glycol divinyl ether (EG-DVE), butanediol divinyl ether (BD-DVE), hexanediol divinyl ether (HD-DVE),
[0427] [0427] Aspect 15A. The composition of any of aspects 1A to 14A, wherein the metal complex comprises cobalt (II) bis (2-ethyl hexanoate), manganese (III) (acetylacetonate) 3, iron (III) (acetylacetonate) 3 or a combination any of the foregoing.
[0428] [0428] Aspect 16A. The composition of any one of aspects 1A to 15A, wherein the organic peroxide comprises tert-butyl peroxybenzoate.
[0429] [0429] Aspect 17A. The composition of any one of aspects 1A to 16A, wherein the metal complex comprises a metallic complex of Co (II), Co (III), Mn (II), Mn (III), Fe (II), Fe (III) , Cu (II), V (III) or a combination of any of the foregoing.
[0430] [0430] Aspect 17Aa. The composition of any one of aspects 1A to 17A, wherein the metal complex comprises an organic binder, wherein the organic binder is acetylacetonate.
[0431] [0431] Aspect 18A. The composition of any one of aspects 1A to 17Aa, further comprising a hydroxyl functional vinyl ether.
[0432] [0432] Aspect 19A. The composition of aspect 18A, comprising 4-hydroxybutyl vinyl ether.
[0433] [0433] Aspect 20A. The composition of any one of aspects 1A to 19A, wherein the curable composition comprises a free radical photoinitiator.
[0434] [0434] Aspect 21A. The composition of any one of aspects 1A to 20A, wherein the curable composition comprises a hydrogen donor.
[0435] [0435] Aspect 22A. The composition of aspect 21A, wherein the hydrogen donor comprises a primary amine, a secondary amine or a combination thereof.
[0436] [0436] Aspect 23A. The composition of any of aspects 21A to 22A, wherein the composition comprises from 45% by weight to 85% by weight of the thiol-terminated sulfur-containing prepolymer, wherein the% by weight is based on the total weight of the composition.
[0437] [0437] Aspect 24A. The composition of any one of aspects 1A to 23A, wherein the composition comprises from 1% by weight to 10% by weight of the polyalkenyl, where the% by weight is based on the total weight of the composition.
[0438] [0438] Aspect 25A. The composition of any one of aspects 1A to 24A, wherein the composition comprises from 0.001% by weight to 2% by weight of the metal complex, where the% by weight is based on the total weight of the composition.
[0439] [0439] Aspect 26A. The composition of any one of aspects 1A to 25A, wherein the composition comprises from 0.1% by weight to 5% by weight of the organic peroxide, where the% by weight is based on the total weight of the composition.
[0440] [0440] Aspect 27A. The composition of any one of aspects 1A to 26A, wherein the composition further comprises from 0.01% by weight to 3% by weight of a hydroxyl functional vinyl ether, where the% by weight is based on the total weight of the composition .
[0441] [0441] Aspect 28A. The composition of any one of aspects 1A to 27A, wherein the composition further comprises from 0.01% by weight to 2% by weight of a photoinitiator, where% by weight is based on the total weight composition.
[0442] [0442] Aspect 29A. The composition of any one of aspects 1A to 28A, wherein the composition further comprises from 0.01% by weight to 2% by weight of a primary amine, a secondary amine, a tertiary amine or a combination thereof, where the% by weight is based on the total weight of the composition.
[0443] [0443] Aspect 30A. The composition of any one of aspects 1A to 29A, wherein the composition comprises from 45% by weight to 85% by weight of the thiol-terminated sulfur-containing prepolymer; from 1% by weight to 10% by weight of the polyalkenyl;
[0444] [0444] Aspect 31A. The composition of any of aspects 1A to 30A, wherein, the thiol-terminated sulfur-containing prepolymer comprises a thiol-terminated polythiopolymer prepolymer; the polyalkenyl comprises cyclohexanedimethanol divinyl ether, triethylene glycol divinyl ether or a combination thereof; the metal complex comprises cobalt (II) bis (2-ethyl hexanoate), manganese (III) (acetylacetonate) 3, iron (III) (acetylacetonate) 3 or a combination of any of the foregoing; the organic peroxide comprises tert-butyl peroxybenzoate; and further comprising a hydroxyl functional vinyl ether, a photoinitiator and a polythiol; wherein, the hydroxyl functional vinyl ether comprises 4-hydroxybutyl vinyl ether; and the polyol has a thiol functionality of three, a thiol functionality of four, or a combination thereof.
[0445] [0445] Aspect 32A. The composition of aspect 31A, further comprising an organic filler, an inorganic filler, a lightweight filler or a combination of any of the foregoing.
[0446] [0446] Aspect 33A. The composition of any one of aspects 1A to 32A, wherein, the metal complex comprises a metal cation and an anion; the metal cation has an oxidation number of 2, 3 or a combination thereof; and the anion comprises an organic anion.
[0447] [0447] Aspect 34A. The composition of aspect 33A, wherein the metallic cation comprises a metallic cation of Co, Mn, Fe, Cu, V, Cu, Al or a combination of any of the foregoing.
[0448] [0448] Aspect 35A. The composition of any of aspects 33A to 34A, wherein the organic anion comprises acetylacetonate.
[0449] [0449] Aspect 36A. The composition of any of aspects 1A to 35A,
[0450] [0450] Aspect 37A. The composition of any one of aspects 1 to 36A, wherein the composition further comprises from 0.01% by weight to 4% by weight of the plasticizer, wherein the% by weight is based on the total weight of the composition.
[0451] [0451] Aspect 38A. The composition of any of aspects 36A to 37A, wherein the composition comprises from 1% by weight to 50% by weight of the filler, wherein the% by weight is based on the total weight of the composition.
[0452] [0452] Aspect 39A. The composition of any of aspects 36A to 38A, wherein the filler comprises an organic filler, fumigated silica, silica gel, a lightweight filler or a combination of any of the foregoing.
[0453] [0453] Aspect 40A. The composition of any of aspects 36A to 39A, wherein the composition comprises from 10% by weight to 20% by weight of the silica gel, where the% by weight is based on the total weight of the composition.
[0454] [0454] Aspect 41A. The composition of any of aspects 36A to 39A, wherein the composition comprises from 5% by weight to 15% by weight of the silica gel, where the% by weight is based on the total weight of the composition.
[0455] [0455] Aspect 42A. The composition of any one of aspects 1A to 41A, wherein the composition is curable under dark conditions.
[0456] [0456] Aspect 43A. The composition of any one of aspects 1A to 42A, wherein the composition has an application time equal to or greater than 30 minutes.
[0457] [0457] Aspect 44A. The composition of any of aspects 1A to 43A, wherein the composition completely cures to Shore 30A hardness under dark conditions within 4 weeks.
[0458] [0458] Aspect 45A. The composition of any one of aspects 1A to 44A, wherein, the composition is both curable during exposure to actinic radiation; how much the composition is curable without exposure to actinic radiation.
[0459] [0459] Aspect 46A. The composition of any one of aspects 1A to 45A, wherein the composition is curable at a temperature of 20 ° C to 30 ° C.
[0460] [0460] Aspect 47A. The composition of any one of aspects 1A to 46A, wherein the composition is curable during exposure to a 1 J / cm2 to 4 J / cm2 of a UVA source.
[0461] [0461] Aspect 48A. The composition of any one of aspects 1A to 47A, wherein the composition is curable under dark conditions at a temperature of 25 ° C.
[0462] [0462] Aspect 49A. A cured sealant prepared from the composition of any of aspects 1A to 48A.
[0463] [0463] Aspect 50A. The cured sealant of aspect 49A, where the cured sealant exhibits a tensile strength greater than 200 psi (1.3 MPa) and an elongation greater than 200% following exposure to Jet Reference Fluid Type I according to AMS 3269, where tensile strength and elongation are determined according to AMS 3279.
[0464] [0464] Aspect 51A. A part sealed with sealant cured from any of the 49A to 50A aspects.
[0465] [0465] Aspect 52A. A vehicle comprising the sealant cured from any of the aspects 49A to 50A.
[0466] [0466] Aspect 53A. An aerospace vehicle comprising the sealant cured from any of the 49A to 50A aspects.
[0467] [0467] Aspect 54A. A method of sealing a part comprising: applying the composition of any of aspects 1A to 48A to a part; and allowing the applied composition to cure, to seal the part.
[0468] [0468] Aspect 55A. The method of aspect 54A, further comprising, after applying the composition, exposing at least a portion of the applied composition to actinic radiation.
[0469] [0469] Aspect 56A. A sealant system, comprising: a first part, wherein the first part comprises a polyalkenyl; and a second part, wherein the second part comprises a polythiol; wherein the first part comprises a metal complex and the second part comprises an organic peroxide; or wherein the first part comprises an organic peroxide and the second part comprises a metal complex.
[0470] [0470] Aspect 56Aa. The sealant system of aspect 56A, in which polyalkenyl, polythiol, metal complex and organic peroxide are defined as in any of aspects 1A to 19A, 31A and 33A to 35A.
[0471] [0471] Aspect 56Ab. The sealing system of any of aspects 56A or 56Aa, wherein the sealing system comprises any of aspects 21A, 22A, 32A, 36A to 48A or a combination of any of the foregoing.
[0472] [0472] Aspect 57A. The sealant system of aspect 56A, wherein the first part, the second or both the first and the second parts comprise a UV sensitive photoinitiator.
[0473] [0473] Aspect 58A. A sealer prepared from the sealant system of aspect 56A, in which the first part and the second part are combined.
[0474] [0474] Aspect 59A. A part sealed with the 56A aspect sealant system.
[0475] [0475] Aspect 60A. A vehicle comprising the cured sealant of aspect 56A.
[0476] [0476] Aspect 61A. An aerospace vehicle comprising the cured sealant of aspect 56A.
[0477] [0477] Aspect 62A. A method of sealing a part, comprising: combining the first part and the second part of the sealant system of aspect 56A to provide a sealant; apply the sealant to a part; and allow the applied sealant to cure, to seal the part.
[0478] [0478] Aspect 63A. The method of aspect 62A, further comprising, after applying the sealant, exposing at least a portion of the applied sealant to actinic radiation.
[0479] [0479] Aspect 64A. A seal cap comprising the cured sealant of aspect 56A.
[0480] [0480] Aspect 65A. A method of sealing a closure comprising applying a composition of any one of aspects 1A to 48A to a closure and curing the applied composition. EXAMPLES
[0481] [0481] The modalities provided by the present disclosure are further illustrated by reference to the following examples, which describe the compositions provided by the present disclosure and uses of such compositions. It will be evident to those skilled in the art that many modifications, both to materials and methods, can be practiced without departing from the scope of the disclosure.
[0482] [0482] A curable composition has been prepared by combining Part A and Part B.
[0483] [0483] Part A and Part B constituents are provided in Table 1 and Table 2, respectively.
[0484] [0484] Preparation of Part A: In a Black Max 200 JAR glass (Flack Tek Inc .; Landrum, SC), the composition of Part A was prepared by sequentially adding vinyl ethers, initiators, plasticizers and fillers (Table 1) followed by gentle mixing first using a spatula and then using a Speed Mixer (Hauschild, Model No DAC 600FVZ) at 2,000 rpm for 30 s. After adding the fumigated silica, the resulting mixture was mixed at 2,000 rpm for 60 s to produce a well dispersed mixture having a viscosity of about 280 poise (28 Pa-s) (Brookfield CAP 2000 viscometer; Axis H7, 10 rpm , 25 ° C). In addition, before adding Part A to a formulation, the cup was mixed at 2,000 rpm for 30 s to ensure homogeneity before transferring the material to a formulation cup.
[0485] [0485] Preparation of Part B: In a Hauschild Max 200 JAR, 57.34 g of Permapol® P-3.1 E prepolymer (PPG Aerospace, Sylmar, CA) (Thiol EW: 1625) was added followed by 13.53 g of a higher functionality Permapol® P3.1 E-2.8 (PPG Aerospace, Sylmar, CA) (Thiol EW: 1531) and 2.49 g of a polythiol (Table 2). The resulting mixture was first mixed manually using a spatula followed by mixing at 1,200 rpm for 1 min using a Hauschild Speed Mixer. To this mixture, 5.39 g of Acumist® A6, a micronized oxidized polyethylene homopolymer (Honeywell International, Morris Plains, NJ) was added, followed by Hauschild's mixture at 2,000 rpm for 1 min. To this mixture, fumigated silicas were added followed by mixing at 2,350 rpm for 2 min. This was followed by the addition of 16.37 g of silica gel (Gasil® IJ35, PQ Corporation, Valley Forge, PA) and mixing at 2,300 rpm for 2 min (twice) with an intermittent manual mixing to ensure that the entire filler into the glass to be incorporated. This was followed by the addition of a lightweight filler (Expancel® 920; AkzoNobel Inc.) and mixing at 1800 rpm for 1 min. This was followed by the addition of an adhesion promoter (mercaptopropyl trimethoxy silane) and mixed at 2,000 rpm for 1 min (twice) with an intermittent manual mixing. The final formulation had a viscosity of about 20,000 poise (2,000 Pa-s) (Brookfield CAP2000 viscometer; Axis H7, 10 rpm 25 ° C).
[0486] [0486] Part A and Part B were mixed in a weight ratio of 100 g of Part B to 8 g of Part A to provide UV curable compositions. The basic UV curable composition has been modified to communicate double curing capabilities as disclosed in the following examples.
[0487] [0487] In a Black 200 JAR Hauschild cup, 46.3 g of Part A was combined with 3.7 g of Part B (100: 8 weight ratio). The mixture was mixed at 2,000 rpm for 1 min after manual mixing with a spatula. To this mixture, using a dripper, 0.945 g of Trigonox® C (AkzoNobel Polymer Chemicals LLC; tert-butyl peroxybenzoate) was added to the drops. (Note: Organic peroxides are highly reactive species and all instructions regarding the manufacturer's safety, handling and storage must be strictly adhered to). The resulting mixture was carefully mixed manually with a stainless steel spatula followed by Hauschild's mixture at 1,600 rpm for 30 s. Care must be taken not to generate too much heat by over-mixing (longer time or higher rotation rate) to avoid reducing peroxide activity through premature decomposition.
[0488] [0488] To prepare the solution of Fe (III) (acac) 3, separately, in a 20 ml glass vial, a 10% solution by weight of Fe (III) (acetylacetonate) 3 was made in acetylacetone. The resulting solution was intensely colored. Both chemicals are commercially available from Sigma-Aldrich (St. Louis, MO).
[0489] [0489] To make the final composition of Example 2, 0.07 g of Fe (III) (acac) 3 solution was added to the mixture of Part A, Part B and Trigonox® C. The resulting sample was mixed manually, followed by by Hauschild mixture at 1,800 rpm for 30 s. The resulting composition was poured into a small aluminum cup 3/8 inches deep (1.9 inches in diameter) for hardness measurements. A flow sample was also manufactured to test traction and elongation by pouring 20 g to 30 g of the composition between two sheets of polyethylene separated by spacers 0.125 inches thick and pressing the layers between two steel plates to create a sample in disk shape to be further cured. The resulting samples were (a) immediately cured in UV; or (b) kept in a dark cabinet (exempt from illumination), to generate samples of light curing (a) and dark curing (b), respectively, for further testing.
[0490] [0490] As for the hardness test the thickness of the test samples was 0.25 inches and the thickness of the sealant for the flow samples was 0.125 inches.
[0491] [0491] In a Black 200 JAR Hauschild cup, 46.3 g of Part A, 3.7 g of Part B and 0.945 g of Trigonox® C were mixed sequentially and prepared as described in example 2.
[0492] [0492] To prepare the Mn (III) solution (acetylacetonate) 3, in a 20 mL glass vial a 10% solution of Mn (III) (acetylacetonate) 3 was made by combining 90 parts of toluene and 10 parts of acetylacetonate and Mn (III) (acetylacetonate) 3. The resulting solution was intensely colored. All reagents used are commercially available from Sigma-Aldrich (St. Louis, MO).
[0493] [0493] To manufacture a curable composition of Example 3 0.5 g of the Mn (III (acetylacetonate) 3) solution was added to the mixture of Part A, Part B and Trigonox® C, followed by manual mixing and Hauschild mixture at 1,800 rpm for 30 s Samples of hardness and flux for both light and dark curing were prepared using the methods described in example 2.
[0494] [0494] In a Black 200 JAR Hauschild glass, 46.3 g of Part A and 3.7 g of Part B were mixed and prepared as described in example 2. To this mixture, 0.47 g of a 50% solution 50 of Trigonox® C in Jayflex ™ DINP Plasticizer (Care must be taken when diluting and handling organic peroxides!) Was added to the drops followed by manual mixing using a stainless steel spatula. The mixture was further mixed in a Hauschild Mixer at 1,600 rpm for 30 s. To this mixture 0.23 g of Duroct® Cobalt 12% (Dura Chemicals; Emeryville, CA) was added, followed by manual mixing and Hauschild's mixture at 1,800 rpm for 30 s to prepare the final sealant composition. Hardness and flux samples for both light and dark curing were prepared according to the methods described in example 2.
[0495] [0495] To prepare cobalt catalysts, Duroct® Cobalt 12% was used as a commercially available source for cobalt (II) bis (2-ethylhexanoate) and is supplied as an 80% (w / w) solution in Stoddard Solvent and 2- acid
[0496] [0496] To understand the curing characteristics and transparency (at 395 nm) of cured compositions when modified with catalysts for curing in the dark / double, curing depth measurements were performed. These measurements were made by applying the sealant formulations to a notch in a 0.4 inch sample (length x width is 0.5 in x 0.5 in). The sample was exposed for 30 s in a flow of 224 mW / cm2 at 395 nm. The curing depth was obtained by determining the depth at which the sample was completely cured by exposure. Flow and shell samples were exposed to a dose for 60 s at a flow of 224 mW / cm2 at 395 nm.
[0497] [0497] The properties of the samples were tested under various conditions: unmodified, modified (cured in UV) and modified (cured in darkness) referred to in Examples 2 to 4 are summarized in Tables 3A to 3C.
[0498] [0498] Stripping resistance tests were performed on panels
[0499] [0499] The results are shown in Tables 4 to 7.
[0500] [0500] Peeling resistance was determined according to AS 5127 / 1C. The stripping results show favorable failure modes (100% cohesive failure) and the absolute stripping values are similar for samples cured in UV and cured in the dark.
[0501] [0501] The hardness of a polythioether / polyene based sealant using an Mn (III) (acetylacetonate) 3 / tert-butylperoxybenzoate catalyst as the dark cure catalyst is shown in FIG. 3. The applied sealant was exposed to UV radiation at 395 nm for 3 s (224 mW / cm3). The test sample consisted of a panel to which a layer of 0.25 inch (6.35 mm) thick sealant was applied.
[0502] [0502] The curing depth for a polythio / polyalkenyl based sealant using Mn (III) (acetylacetonate) 3 / tert-butylperoxybenzoate catalyst is shown in FIG. 4. FIG. 4 shows the hardness of the sealant with depth. The sealant was exposed to UV radiation at 395 nm for 30 s (224 mW / cm2) and Shore A hardness was measured at depths of 6 mm to 14 mm. The sealant cured to a depth of 8 mm immediately after exposure to UV radiation. The sealant cured (hardness greater than Shore 40A) to a depth of 12 mm to 14 mm within 24 hours. Within 4 days, samples exposed to UV and cured in the dark had an identical Shore 48A hardness.
[0503] [0503] Physical properties (tensile strength and elongation in traction)
[0504] [0504] Part A and Part B compositions were stable as determined by the fact that there was no change in the viscosity of the compositions when maintained at 120 ° F (49 ° C) for 14 days (test limit) or 140 ° F (60 ° C) for 7 days (test limit) in dark conditions. In other studies, the concentration of organic peroxide in Part A and the concentrations of Mn (III) (acetylacetonate) 3 were increased up to 3 times and 1.5 times, respectively. Again, after 14 days at 120 ° F (49 ° C) there was no change in viscosity indicating that the compositions were stable in storage.
[0505] [0505] FIG. 6 shows the effect of the composition of the dark curing catalyst Mn (III) (acetylacetonate) 3 / tert-butylperoxybenzoate on the cure rate as reflected in the hardness of the sample over time. Dark curing catalyst systems having different amounts of organic peroxide (tert-butylperoxybenzoate) and metallic catalyst (Mn (III) (acetylacetonate) 3) were prepared as in Table 8: Table 8. Dark curing catalyst compositions. Catalyst Sample Sample Sample Sample 6 (1) 6 (2) 6 (3) 6 (4) tert-Butylperoxybenzoate,% by weight 1 1 1 0.5 0.5 Mn (III) (acetylacetonate) 3,% by weight1 0 .5 0.25 0.5 0.25 Total catalyst,% by weight 1 1.5 1.25 1 1 Organic peroxide / metal complex, 2 4 1 2 percentage weight ratio 1 Based on the total weight of the composition.
[0506] [0506] The hardness of the sealants containing the various concentrations of curing catalyst in darkness was measured in three (3) days and in seven (7) days after application. The hardness of the samples exposed to ambient fluorescent lighting was also measured. The results are shown in FIG. 6. The curing depth has also been determined and the results are shown in FIG. 7.
[0507] [0507] The results shown in FIGS. 6 and 7 demonstrate that a concentration of organic peroxide as low as 0.75% by weight and a metal complex as low as 0.5% by weight can be used to provide a total cure in darkness within three (3) days. The application time of these compositions was 30 min, that is, B-1/2 (extrusion of 30 min, viable for 30 min). The physical properties including hardness, tensile / elongation and peeling resistance of dark cured sealants are comparable to those of UV cured sealants.
[0508] [0508] A Fe (III) dark curing catalyst (acetylacetonate) 3 / tert-butylperoxybenzoate was also evaluated. The application time as reflected in the extrusion rate (B-1/2; greater than 30 min) with the time after mixing the polyol (Part B) and polyalkenyl (Part A) components is shown in FIG. 8. The results show that the practical application time for this system is greater than 2 hours (extrusion rate is greater than 100 g / min).
[0509] [0509] FIG. 9 shows the effect of the composition of the Fe (III) dark curing catalyst (acetylacetonate) 3 / tert-butylperoxybenzoate on the curing rate as reflected in the hardness of the sample over time. Dark curing catalyst systems having different amounts of organic peroxide (tert-butylperoxybenzoate) and metallic catalyst (Fe (III) (acetylacetonate) 3) were prepared as in Table 9: Table 9. Dark curing catalyst compositions. Sample Sample Sample Sample 9 (1) 9 (2) 9 (3) 9 (4) tert-Butylperoxybenzoate,% by weight 1 1.89 1.89 1.89 Fe (III) (acetylacetonate) 3,% by weight 0 , 29 0.15 0.07 0.039 Total catalyst,% by weight 1.29 2.04 1.96 1.929 Percent weight ratio peroxide 3.4 12.6 27.0 48.5 organic / metal complex
[0510] [0510] The hardness and depth of cure of sealants containing the various concentrations of dark cure catalyst were measured (a) eight (8) days after UV exposure, (b) 3 days exposed to ambient fluorescent lighting (RL), (c) eight (8) days under dark conditions or (d) twelve (12) days under dark conditions. The results are shown in FIG. 9.
[0511] [0511] The metal complexes are supplied as solutions containing a solvent and anion. For example, Fe (III) (acetylacetonate) 3 can be supplied as a 10% solution of toluene and acetylacetonate. To assess the effects of the metal complex solvent composition on the properties of a sealant cured in the dark, Fe (III) (acetylacetonate) 3 solutions having different solvent compositions were prepared having the solvent compositions shown in Table 10: Table 10 Composition of metal complex solvent.
[0512] [0512] For these solutions, the% by weight represents the% by weight of the total solvent.
[0513] [0513] Sealants were prepared having 1.89% by weight of organic peroxide (tert-butylperoxybenzoate) and 0.10% by weight of the solutions of Fe (III) (acetylacetonate) 3 shown in Table 10. The hardness and depth of curing of cured sealants were measured 12 days after application and further exposed to (a) UV, (b) UV after twelve (12) days, (c) ambient fluorescent lighting (RL) after 12 days or dark conditions after twelve (12) days. Also, sealants with a solution of Fe (III) (acetylacetonate) 3 having 100% gelled toluene within 15 min.
[0514] [0514] The cure rate as reflected by the hardness of a sealant containing
[0515] [0515] Based on these results, for the Fe (III) catalyst (acetylacetonate) 3 / tert-butylperoxybenzoate, the concentration of the metal complex can be as low as 0.07% by weight and the concentration of organic peroxide can be as low as low as 1.5% by weight, where% by weight is based on the total weight of the curable composition. Under dark curing conditions the sealant completely cures within 8 days. The application time is longer than 2 h, that is, 30 min or longer. The physical properties including hardness, tensile / elongation and peeling resistance of dark cured sealants are comparable to those of UV cured sealant. The results suggest that the concentration of metal complex can be reduced within a range of 0.02% by weight to 0.05% by weight; however, at these concentrations the time to cure completely under dark conditions can be longer. Also, the results suggest that adjusting the solvent / anion ratio of the metal complex solution can be used to adjust the curing time in darkness.
[0516] [0516] The fuel resistance of compositions provided by the present disclosure has also been assessed. The results are shown in Table 12: Table 12. Fuel resistance of cured sealants. 12 (1) 12 (2) 12 (3) 12 (4) Curing in UV Curing 1 day / RL Curing in darkness darkness Complex Fe (III) (acac) 3 Fe (III) (acac) 3 Fe (III) (acac) 3 Mn (III) (acac) 3 metallic 0.1% by weight1 0.1% by weight 0.1% by weight 1.0% by weight 10% solution 10% solutions 10% solution a 10%% Resistance to 20 (8 days) 25 25 30 (3 days) peeling at 30 (11 days) dry, lb / in Failure mode 20% Cohesive 100% Cohesive 100% cohesive 100% cohesive peeling at (8 days ) Some dry 20% Cohesive adhesion (11 days) superficial JRF Type I lb / in> 20 30 30 20 Failure mode 20% cohesive 100% Cohesive 100% Cohesive 100% Cohesive JRF Type I 1 Based on weight% of curable composition; catalyst in 10% by weight acetyl acetone solution.
[0517] [0517] The sealants were applied to a prepared substrate 6111-44, by AMS 27725. Peeling resistance was determined according to AS 5127 / 1C.
[0518] [0518] In summary, based on the results for the UV curable composition (unmodified composition - control) the UV cured sealant exhibits 450 psi / 250% tensile / elongation, Shore 48A hardness and peeling resistance in various substrates greater than 25 lb / in (0.45 kg / mm). The same dark cured sealant exhibits comparable physical and adhesive properties in 3 days for the Mn (III) based sealant and in 8 days for the Fe (III) based sealant.
[0519] [0519] It has also been observed that standard ambient fluorescent lighting accelerates healing to a greater degree than curing in darkness alone. Sealants containing the Fe (III) based catalyst cure faster under fluorescent lighting than Mn (III) based systems and comparable unmodified UV curable compositions.
[0520] [0520] Short cure sealant formulations having the components as shown in Table 13. Trigonox® C, tert-butyl peroxybenzoate) in specific weight% have been added to Part A and Part B combined where the% by weight is based on total weight of Part A, Part B and Trigonox® C. The metallic catalyst and additive were added to the specific weight% where the weight% is based on the total weight of Part A, Part B and Trigonox® C. The samples were prepared in a total amount of about 50 g.
[0521] [0521] Note that the metal complexes were added to the sealant composition as a diluted solution. For example, Mn (acac) 3 was supplied as 10% by weight of Mn (acac) 3 in an acetylacetone solution. Adding 1% by weight of the 10 to 10% Mn (acac) solution to a composition effectively adds 0.1% by weight of the Mn (acac) 3 complex to the composition.
[0522] [0522] The adhesion of UV and dark cured Samples was determined for Short Curing Formulation 1 (see Table 13), which included Mn (acac) 3 as the metal complex and Ce (NH4) (NO3) 6 as a nitrogen synergist. Adhesion was tested on AMS 27725, AMS 4911, 2024-T3, AMS 2471 and AMS 5516 substrates.
[0523] [0523] The adhesion of samples cured in UV and darkness was determined for Short Curing Formulation 1 (see Table 13), which included Mn (acac) 3 as the metal complex and Ce (NH4) (NO3) 6 as a nitrogen synergist following immersion in Jet Reference Fluid (JRF) Type I or NaCl solution. Adhesion was tested on AMS 27725, AMS 4911, 2024-T3, AMS 2471 and AMS 5516 substrates. Test panels were treated with a surface preparer RW 6111-44 (available from PPG Aerospace). A 0.125 inch (3.175 mm) thick layer of the formulation was applied to the prepared substrate. The samples were exposed to 1 J / cm2 to 2 J / cm2 of UVA radiation or cured in the dark for about 40 hours. The samples were immersed in JRF Type I for 7 days at 60 ° C followed by 3 days at 25 ° C, according to AMS 2620, Rev. E or a 3% NaCl solution for 7 days at 60 ° C followed for 3 days at 25 ° C. The results are shown in Table 15 and Table 16, respectively.
[0524] [0524] The thermal resistance properties of samples cured in UV and in the dark were determined for short cure formulations 3 and 10 (see Table 13) according to AMS 3277J Section 3.6.21 (Heat Cycle Test). These formulations had an application time of 30 min to 45 min. Test panels were treated with a surface preparer RW 6111-44 (pre-hydrolyzed organosilane preparer available from PPG Aerospace). A 0.125 inch (3.175 mm) thick layer of Formula 3 or Formulation 10 was applied to the prepared substrate. The samples were exposed to 1 J / cm2 to 2 J / cm2 of UVA radiation or cured in the dark for about 72 hours. Following curing, the samples were immersed in JRF Type I for 7 days at 60 ° C (AMS 2629) followed by 3 air-dried days at 49 ° C and 7 days of thermal aging at 149 ° C (300 ° F) . The results for Formulation 3 and Formulation 10 are shown in Table 17 and Table 18, respectively.
[0525] [0525] The application time (AT) and the adhesion free time (TFT) for various short cure formulations containing cure profile modifiers were determined. Test samples were prepared by combining the components for various short cure formulations as shown in Table 13. The application time was determined as the length of time the components were combined at the time the sealer exhibited an extrusion rate of 15 g / min when extruded through a No 440 nozzle (Semco, 125 inches internal diameter and 4 inches long, available from PPG Aerospace) at a pressure of 90 psi (620 KPa). The open time was determined by applying a 0.125 inch thick coating of the sealant to a substrate and at intervals while the sealant is cured, applying a sheet of polyethylene to the surface of the sealant with manual pressure, removing the foil. polyethylene and observing if any sealant adhered to the polyethylene sheet. Adhesion free time was the length of time that the sealant components were first combined with the time when no sealant was observed on the polyethylene sheet.
[0526] [0526] The results shown in FIG. 13, demonstrate that a wide range of application times and adherence-free times can be obtained by selecting the metallic catalyst (s) and additive (s). The formulation number is shown in the table.
[0527] [0527] FIG. 14 shows the Shore A hardness of sealants fully cured under UV and dark curing conditions. The sealant components were combined according to Table 13 and the sealant formulations applied to a substrate at a thickness of 0.125 inches (3.175 mm). For samples cured in UV, the sealants were exposed to 1 J / cm2 to 2 J / cm2 of UVA radiation and kept at 25 ° C for 7 days. The initial Shore A hardness of the sealants within a few minutes of exposure to UV and the results are shown in FIG. 15. For samples cured in darkness, the sealants were stored under dark conditions at 25 ° C for 7 days. Shore A hardness was measured according to ASTM D2240 using a Type A durometer.
[0528] [0528] The application time, adhesion free time and Shore A hardness of the various short cure sealant formulations included in Table 13 are shown in Table 19. The application time was determined by extrusion as described here. Adhesion-free time by applying a sheet of polyethylene to the surface of the sealant with manual pressure and observing the adhesion of the sealant. The initial Shore A hardness was measured within a few minutes of exposure to UVA radiation. In general, for many applications it may be desirable for the application time to be at least 30 minutes, the adhesion free time to be at least 25 hours and the initial hardness following UV exposure to be at least Shore 35A. Formulations 11, 12, 26 and 28-R included an amine synergist. Sealant formulations 14 and 20 included a co-catalyst. Sealant formulation 73 included an oxygen decontaminant.
[0529] [0529] FIGS. 16A and 16B show the application time and open time, respectively, for some of the sealant formulations in Table 13, in a graphic format.
[0530] [0530] The physical properties of the various long-curing sealants shown in Table 20 were determined after curing in UV and darkness. The results are shown in Table 21 for sealants cured in the dark and in Table 22 for sealants cured in UV. Hardness was measured for fully cured samples used for tensile / elongation measurements. In general, for certain applications, it may be desirable for the tensile strength to be greater than 200 psi (1.38 MPa) and the% elongation to be greater than 300%.
[0531] [0531] The Shore A hardness of certain fully cured short cure sealants shown in Table 13 cured under UV or dark conditions is shown in FIG. 17.
[0532] [0532] The initial Shore A hardness of certain short cure sealants shown in Table 13 measured within a few minutes after exposure to UV is shown in FIG. 18.
[0533] [0533] The effects of certain solvents on the application time, adhesion-free time and initial hardness (UV curing) of various sealants shown in Table 13, are shown in Table 23.
[0534] [0534] Finally, it should be noted that there are alternative ways of implementing the modalities disclosed here. Consequently, these modalities should be considered as illustrative and not restrictive. Besides that,
the claims should not be limited to the details provided here and are entitled to their full scope and equivalents thereof.

权利要求:
Claims (23)
[1]
1. Composition, CHARACTERIZED by the fact that it comprises: a polythiol, in which the polythiol comprises a thiol-terminated prepolymer; a polyalkenyl, wherein the polyalkenyl comprises an alkenyl-terminated prepolymer, a polyalkenyl monomer or a combination thereof; a metallic complex; and an organic peroxide.
[2]
2. Composition according to claim 1, CHARACTERIZED by the fact that the thiol-terminated prepolymer comprises a thiol-terminated sulfur-containing prepolymer.
[3]
3. Composition according to claim 2, CHARACTERIZED by the fact that the thiol-terminated sulfur-containing prepolymer comprises a thiol-terminated polythioether prepolymer, a thiol-terminated polysulfide prepolymer, a prepolymer of thiol-terminated sulfur-containing poliform, a thiol-terminated monosulfide prepolymer or a combination of any of the foregoing.
[4]
4. Composition according to claim 3, CHARACTERIZED by the fact that the thiol-terminated sulfur-containing prepolymer comprises a thiol-terminated polythiopolymer prepolymer.
[5]
5. Composition according to claim 4, CHARACTERIZED by the fact that the thiol-terminated sulfur-containing prepolymer comprises a portion having the structure of Formula (2c): -S-R1- [SAS-R1-] nS- (2c) where, n is an integer from 1 to 60; each R1 is independently selected from C2-10 alkanediyl, C6-8 cycloalkanodiyl, C6-14 alkanocycloalkanodiyl, C5-8 heterocycloalkanidiyl and -
[(CHR3) p-X-] q (CHR3) r-, where, p is an integer from 2 to 6; q is an integer from 1 to 5; r is an integer from 2 to 10; each R3 is independently selected from hydrogen and methyl; and each X is independently selected from O, S and NR, where R is selected from hydrogen and methyl; and each A is independently a portion derived from a polyvinyl ether of Formula (3) and a polyalkenyl polyfunctionalizing agent of Formula (4): CH2 = CH-O- (R2-O) m-CH = CH2 (3) B ( -R70-CH = CH2) z (4) where, m is an integer from 0 to 50; each R2 is independently selected from C1-10 alkanediyl, C6-8 cycloalkanediyl, C6-14 alkanocycloalkanediyl and - [(CHR3) pX-] q (CHR3) r-, where p, q, r, R3 and X are as defined as for R1; B represents a core of a polyfunctionalizing agent, polyalkenyl z-valent B (-R70-CH = CH2) z where, z is an integer from 3 to 6; and each R70 is independently selected from C1-10 alkanediyl, C1-10 heteroalkanediyl, substituted C1-10 alkanediyl and substituted C1-10 heteroalkanediyl.
[6]
6. Composition, according to claim 1, CHARACTERIZED by the fact that the polythiol comprises a polyol monomer.
[7]
7. Composition according to claim 1, CHARACTERIZED by the fact that the polyalkenyl monomer comprises a bis (alkenyl) ether.
[8]
8. Composition according to claim 1, CHARACTERIZED by the fact that the metal complex comprises cobalt (II) bis (2-ethyl hexanoate), manganese (III) (acetylacetonate) 3, iron (III) (acetylacetonate) 3 or a combination of any of the foregoing.
[9]
9. Composition according to claim 1, CHARACTERIZED by the fact that the organic peroxide comprises tert-butyl peroxybenzoate.
[10]
10. Composition according to claim 1, CHARACTERIZED by the fact that the metal complex comprises a metallic complex of Co (II), Co (III), Mn (II), Mn (III), Fe (II), Fe (III), Cu (II), V (III) or a combination of any of the foregoing.
[11]
11. Composition according to claim 1, CHARACTERIZED by the fact that the curable composition comprises a free radical photoinitiator.
[12]
12. Composition according to claim 1, CHARACTERIZED by the fact that the curable composition comprises a hydrogen donor.
[13]
13. Composition according to claim 1, CHARACTERIZED by the fact that the hydrogen donor comprises a primary amine, a secondary amine or a combination thereof.
[14]
14. Composition according to claim 1, CHARACTERIZED by the fact that the composition comprises from 0.01% by weight to 2% by weight of a primary amine, a secondary amine, a tertiary amine or a combination of these, wherein the% by weight is based on the total weight of the composition.
[15]
15. Composition according to claim 1, CHARACTERIZED by the fact that the composition comprises: from 45% by weight to 85% by weight of the thiol-containing sulfur-containing prepolymer; from 1% by weight to 10% by weight of the polyalkenyl; from 0.001% by weight to 2% by weight of the metal complex; and 0.1% by weight to 5% by weight of organic peroxide,
wherein the weight% is based on the total weight of the composition.
[16]
16. Composition, according to claim 1, CHARACTERIZED by the fact that the composition is curable under dark conditions.
[17]
17. Composition, according to claim 1, CHARACTERIZED by the fact that, the composition is curable during exposure to actinic radiation; and the composition is curable without exposure to actinic radiation.
[18]
18. Composition, according to claim 1, CHARACTERIZED by the fact that the composition is curable at a temperature of 20 ° C to 30 ° C.
[19]
19. Cured sealant, CHARACTERIZED by the fact that it is prepared from the composition according to claim 1.
[20]
20. Part, CHARACTERIZED by the fact that it is sealed with the cured sealant according to claim 19.
[21]
21. Vehicle, CHARACTERIZED by the fact that it comprises the cured sealant according to claim 19.
[22]
22. Aerospace vehicle, CHARACTERIZED by the fact that it comprises the cured sealant according to claim 19.
[23]
23. Method of sealing a part, CHARACTERIZED by the fact that it comprises: applying the composition of claim 1 to a part; and allow the applied composition to cure, to seal the part.

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法律状态:
2021-11-03| B350| Update of information on the portal [chapter 15.35 patent gazette]|

优先权:

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申请号 | 申请日 | 专利标题

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US201762517648P| true| 2017-06-09|2017-06-09|

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US62/517,648|2017-06-09|

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PCT/US2018/036746|WO2018227149A1|2017-06-09|2018-06-08|Dual cure sealants|

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