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    • 专利摘要:
    FUNCTIONED POLYMER, RUBBER COMPOSITION CONTAINING THE SAME AND PNEUMATIC. A functionalized elastomer is disclosed comprising the reaction product of a live anionic elastomeric polymer; and a polymerization terminator of formula I: where R ^ 1 ^, R ^ 2 ^ and R ^ 3 ^ are, independently, C ~ 1 ~ to C ~ 8 ~ alkyl or C ~ 1 ~ to C ~ 8 ~ alkoxy, provided that at least two of R ^ 1 ^, R ^ 2 ^ and R ^ 3 ^ are C ~ 1 ~ to C ~ 8 ~ alkoxy; R ^ 4 ^ C is C ~ 1 ~ to C ~ 8 ~ alkyl; Si is silicon; S is sulfur, and Z is R ^ 5 ^ or of formula II: where R ^ 5 ^ is alkyl, aryl, alkylaryl or arylalkyl. Also disclosed is a rubber composition comprising the functionalized elastomer and a tire comprising the rubber composition.
    公开号:BR102012029723B1
    申请号:R102012029723-0
    申请日:2012-11-22
    公开日:2020-10-20
    发明作者:Leena Nebhani；Michael Joseph Rachita
    申请人:The Goodyear Tire & Rubber Company；
    IPC主号:
    专利说明:

    Background of the Invention
    Metals from Groups I and II of the periodic table are commonly used to initiate the polymerization of monomers into polymers. For example, lithium, barium, magnesium, sodium and potassium are metals that are often used in such polymerizations. Primer systems of this type are of great commercial importance because they can be used to produce regulated stereo polymers. For example, lithium initiators can be used to initiate the anionic polymerization of isoprene in synthetic polyisoprene rubber or to initiate the polymerization of 1,3-butadiene in polybutadiene rubber having the desired microstructure.
    The polymers formed in such polymerizations present the metal used to initiate polymerization at the increasing end of their polymer chains and are often referred to as live polymers. They are referred to as live polymers because their polymer chains containing the terminal metal primer continue to grow or live until all available monomer is depleted. Polymers that are prepared using such metal initiators usually have structures that are essentially linear and normally do not contain appreciable amounts of branching.
    Rubberized polymers obtained by live polymerization techniques are usually composed of sulfur, accelerators, anti-degraders, a filler, such as carbon black, silica or starch and other desired rubber chemicals, and are subsequently cured or cured in the form useful article, such as a tire or an energy transmission belt. It has been shown that the physical properties of such cured rubbers depend on the degree to which the load is evenly dispersed throughout the rubber. This in turn is related to the level of affinity that the charge has with the specific rubberized polymer. This may be of practical importance in improving the physical characteristics of rubber articles that are obtained using such rubber compositions. For example, the rolling resistance and traction characteristics of tires can be improved by improving the affinity of carbon black and / or silica, for the rubberized polymer used in it. Therefore, it would be highly desirable to improve the affinity of a given rubberized polymer for fillers, such as carbon black and silica.
    In tire tread formulations, a better interaction between the load and the results of the rubberized polymer in low hysteresis and, consequently, tires manufactured with these rubber formulations have less rolling resistance. Low values of delta tangent at 60 ° C are indicative of low hysteresis and, consequently, rubber tires manufactured using formulations of this type with low values of delta tangent at 60 ° C, usually have less rolling resistance. The better interaction between the load and the rubberized polymer in tire tread formulations also typically results in tangent delta values greater than 0 ° C, which is indicative of better traction characteristics.
    The interaction between rubber and carbon black has been attributed to a combination of physical absorption (van der Waals strength) and chemosorption between oxygen containing functional groups on the surface of carbon black and rubber (see D. Rivin, J. Aron, and A. Medalia, Rubber Chem. & Technol. 41, 330 (1968) and A. Gessler, W. Hess, and A Medalia, Plast. Rubber Process, 3, 141 (1968)). Several other chemical modification techniques, especially for styrene-butadiene rubber obtained by solution polymerization (S-SBR), have also been described to reduce the loss of hysteresis, improving polymer-load interactions. In one of these techniques, the final solution of the rubber chain is modified with aminobenzophenone. This greatly improves the interaction between the polymer and the oxygen-containing groups on the carbon black surface (see N. Nagata, Nippon Kyokaishi Gomu, 62, 630 (1989)). Tin coupling of the polymers in the anionic solution is another commonly used chain end modification method that assists the polymer-charge interaction, presumably through the increased reaction with the quinone groups on the carbon black surface. The effect of this interaction is to reduce the aggregation between the carbon black particles, which in turn improves dispersion and ultimately reduces hysteresis. Summary of the Invention
    The present invention provides a low cost device for the functionalization of rubberized control polymers to improve its affinity with fillers, such as carbon black and / or silica. Such functionalized polymers can be beneficially used in the manufacture of tires and other rubber products, where the improved polymer / load interaction is desirable. In tread compounds this can result in lower polymer hysteresis which in turn provides a lower level of rolling resistance for the tire.
    The present invention, more specifically, is directed to a functionalized elastomer comprising the reaction product of a live anionic elastomeric polymer; and a polymerization terminator of formula I:
    where R1, R2 and R3 are independently C1 to C8 alkyl or C1 to Cs alkoxy, provided that at least two of R1, Rs and Rs are C1 to Ca alkoxy; R4 is C1 to C8 alkyl; Si is silicon; S is sulfur; and Z is Rs or formula II:
    where Rs is alkyl, aryl, alkylaryl or arylalkyl.
    The invention is further directed to a rubber composition comprising the functionalized elasomer and a tire comprising the rubber composition. Brief Description of Drawings
    Figure 1 shows G 'and tangent delta versus deformation for non-productive samples with silane coupling agent.
    Figure 2 shows G 'and tangent delta versus deformation for non-productive samples without silane.
    Figure 3 shows curing curves obtained in 7% deformation for productive batches with silane coupling agent.
    Figure 4 shows G 'and tangent delta versus deformation for productive samples with silane coupling agent.
    Figure 5 shows curing curves obtained in 7% deformation for productive batches without silane coupling agent.
    Figure 6 shows G 'and tangent delta versus deformation for productive samples without silane coupling agent. Detailed Description of the Invention
    A functionalized elastomer is described which comprises the reaction product of a live anionic elastomeric polymer and a polymerization terminator of formula I:
    where R1, R2 and R3 are, independently, C1 to C8 alkyl or C1 to C8 alkoxy, with the proviso that at least two of R1, R2 and R3 are C1 to C8 alkoxy, R4 is C1 to C8 alkyl; If it is silicon; S is sulfur; and Z is R5 or formula II:
    where R5 is alkyl, aryl, alkylaryl or arylalkyl.
    In addition, a rubber composition comprising the functionalized elastomer and a tire comprising the rubber composition is disclosed.
    The present invention provides a means for the functionalization of the terminal group of rubberized live polymers to improve its affinity with charges, such as carbon black and / or silica. The process of the present invention can be used to functionalize any living polymer that is terminated with a group I or II metal from the periodic table. These polymers can be produced using techniques that are well known to those skilled in the art. Metal-terminated rubber polymers that can be functionalized with a terminator of formula I according to the present invention can be made using monofunctional primers having the general structural formula PM, where P represents a polymer chain and where M represents a metal group I or II. The metal initiators used in the synthesis of such metal-terminated polymers can also be multifunctional organometallic compounds. For example, bifunctional organo-metallic compounds can be used to initiate such polymerization. The use of such bifunctional organometallic compounds as initiators generally results in the formation of polymers having the general structural formula M-P-M, where P represents a polymeric chain and where M represents a group I or II metal. Such polymers, which are terminated at both ends of their chain by a group I or II metal, can also be reacted with the terminator of formula I to functionalize both of their chain ends. It is believed that the use of bifunctional primers so that both ends of the polymer chains can be functionalized with the terminator of formula I can further improve the interaction with the charges, such as carbon black and silica.
    The initiator used to initiate the polymerization that is employed in the synthesis of the live rubberized polymer that is functionalized according to the present invention is typically selected from the group consisting of barium, lithium, magnesium, sodium and potassium. Lithium and magnesium are the metals that are most often used in the synthesis of such metal-terminated polymers (live polymers). Typically, lithium initiators are more preferred.
    Organolithium compounds are the preferred initiators for use in polymerizations of this type. Organolithium compounds, which are used as initiators, are usually organo monolithic compounds. Organolithium compounds, which are preferred as initiators, are monofunctional compounds, which can be represented by the general formula: R-Li, where R represents a hydrocarbyl radical containing from 1 to about 20 carbon atoms. Generally, such monofunctional organolithium compounds may contain from 1 to about 10 carbon atoms. Some preferred representative examples are buhilithium, sec-butylithium, n-hexylithium, n-octylithium, tertoctylithium, n-decylithium, phenyl-lithium, 1-naphthylithium, 4-butylphenylithium, p-tolylithium, 4-phenylbutylithium, cyclohexylithium, 4-butylcyclohexylite , and 4-cyclohexylbutylithium. Secondary butyllithium is a highly preferred organolithium initiator. Very finely divided lithium, with an average particle diameter of less than 2 microns, can also be used as the initiator for the synthesis of live rubber polymers that can be functionalized with a terminator of formula I according to the present invention. US Patent 4,048,420 which is hereby incorporated by reference in its entirety, describes the synthesis of live polymers terminated in lithium using finely divided lithium as the initiator. Lithium amides can also be used as an initiator for the synthesis of live polydiene rubbers (see US Patent No. 4,935,471 whose teachings are incorporated herein as a reference with respect to lithium amides that can be used as initiators for the synthesis of live rubber polymers).
    The amount of organolithium initiator used will vary depending on the molecular weight that is desired for the rubberized polymer to be synthesized, as well as the precise polymerization temperature that will be employed. The exact amount of organolithium compound required to produce a polymer with a desired molecular weight can be easily determined by those skilled in the art. However, as a general rule, we can employ 0.01 to 1 phm (parts per 100 parts by weight of monomer) of an organolithium initiator. In most cases, 0.01 to 1 phm of an organolithium initiator is used, it is preferable to use 0.025 to 0.07 phm of the organolithium initiator.
    Many types of unsaturated monomers that contain carbon-carbon double bonds can be polymerized into polymers using such metal catalysts. Elastomeric or rubber polymers can be synthesized by polymerizing dienic monomers that use this type of metal initiator system. The dienic monomers that can be polymerized into synthetic rubber polymers can be conjugated or non-conjugated diolymers. Conjugated diolefin monomers containing 4 to 8 carbon atoms are generally preferred. Aromatic monomers substituted with vinyl can also be copolymerized with one or more dienic monomers in rubber polymers, for example butadiene-styrene rubber (SBR). Some representative examples of conjugated dienic monomers that can be polymerized to rubber polymers include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 2-methyl-1,3-pentadiene , 2,3-dimethyl-1-3-pentadiene, 2-phenyl-1,3-butadiene, and 4,5-diethyl-1,3-octadiene. Some representative examples of aromatic vinyl-substituted monomers that can be used in the synthesis of rubber polymers include styrene, 1-vinylnaphthalene, 3-methylstyrene, 3,5-diethylstyrene, 4-propylstyrene-, 2,4,6-trimethylstyrene, 4- dodecylstyrene, 3-methyl-5-normal-hexylstyrene, 4-enylstyrene, 2-ethyl-4-benzylstyrene, 3,5-diphenylstyrene, 2,3,4,5-tetraethylstyrene-, 3-ethyl-1-vinylnaphthalene, 6 -isopropyl- 1-vinylnaphthalene, 6-cyclohexyl-1-vinylnaphthalene, 7-dodecyl-2-vinylnaphthalene, α-methylstyrene and the like.
    The metal-terminated rubber polymers that are functionalized with a terminator of formula I according to the present invention are generally prepared by polymerizing solutions using inert organic solvents, such as saturated aliphatic hydrocarbons, aromatic hydrocarbons, or ethers. Solvents used in solution polymerizations will normally contain between about 4 to about 10 carbon atoms per molecule and will be liquid under the conditions of polymerization. Some representative examples of suitable organic solvents include pentane, isoctane, cyclohexane, normal-hexane, benzene, toluene, xylene, ethylbenzene, tetrahydrofuran and the like, alone or in admixture. For example, the solvent can be a mixture of different hexane isomers. Such solution polymerizations result from the formation of a polymeric cement (a highly viscous solution of the polymer).
    The metal-terminated live rubber polymers used in the practice of the present invention can be of virtually any molecular weight. However, the numerical average molecular weight of the rubberized living polymer will typically be within the range of about 50,000 to about 500,000. It is more typical that such live rubber polymers have numerical average molecular weights in the range of 100,000 to 250,000.
    The metal-terminated live rubber polymer can be functionalized by simply adding a stoichiometric amount of a formula I terminator to a rubber polymer solution (a rubber polymer of the live polymer). In other words, about one mole of the terminator of formula I is added per mole of terminating metal groups in the live rubberized polymer. The number of moles of the metal terminating groups in such polymers is assumed to be the number of moles of the metal used in the initiator. Of course, it is possible to add more than a stoichiometric amount of the formula I terminator. However, the use of larger amounts is not beneficial for the final properties of the polymer. Even so, in many cases, it will be desirable to use a slight excess of the formula I terminator to ensure that at least a stoichiometric amount is actually employed or to control the stoichiometry of the functionalization reaction. In most cases, from about 0.8 to about 1.1 moles of the terminator of formula I will be used per mole of the metal terminating groups in the live polymer to be treated. In case it is not desirable to functionalize all ends of the metal-terminated chain into a rubberized polymer, then, obviously, smaller amounts of the terminator of formula I can be used.
    The formula I terminator will react with the live rubberized polymer terminated in metal over a very wide temperature range. For practical reasons, the functionalization of such live rubber polymers will normally be carried out at a temperature within the range of 0 ° C to 150 ° C. In order to increase reaction rates, in most cases, it will be preferable to use a temperature within the range of 20 ° C to 100 ° C, with temperatures in the range of 50 ° C to 80 ° C being more preferred. The leveling reaction is very fast and only very short reaction times within the range of 0.5 to 4 hours are normally required. However, in some cases, reaction times of up to about 24 hours can be employed to ensure maximum conversions.
    After the functionalization reaction is complete, it will normally be desirable to "exterminate" any remaining living polydiene chains. This can be achieved by adding an alcohol, such as methanol or ethanol, to the polymeric cement, after the functionalization reaction is complete, in order to eliminate any living polymer that has not been consumed by the reaction with the formula I terminator. The terminal group functionalized polydiene rubber can then be recovered from the solution using standard conventional techniques.
    The functionalized polymer can be combined into a rubber composition.
    The rubber composition may optionally include, in addition to the functionalized polymer, one or more rubbers or elastomers containing olefinic unsaturation. The phrases "rubber or elastomer containing olefinic unsaturation" or "diene-based elastomer" are intended to include both natural rubber and its various raw and retreaded forms, as well as several synthetic rubbers. In describing this invention, the terms "rubber" and "elastomer" may be interchangeable, unless otherwise stated. The terms "rubber composition", "mixed rubber" and "rubber compound" are used interchangeably to refer to rubber that has been combined or mixed with various ingredients and materials and such terms are well known to those skilled in the art. rubber mixture or rubber compost. Representative synthetic polymers are the homopolymerization products of butadiene and its homologues and derivatives, for example, methylbutadiene, dimethylbutadiene and pentadiene, as well as copolymers, such as those formed from butadiene or their homologues or derivatives with other unsaturated monomers. Among the latter are acetylenes, for example, vinyl acetylene; olefins, for example, isobutylene, which copolymerize with isoprene to form butyl rubber; vinyl compounds, for example, acrylic acid, acrylonitrile (which polymerize with butadiene to form NBR), methacrylic acid and styrene, the latter compound polymerizing with butadiene to form SBR, as well as vinyl esters and various unsaturated aldehydes, ketones and ethers, for example , acrolein, methyl isopropenyl ketone and vinyl ethyl ether. Specific examples of synthetic rubbers include neoprene (polychloroprene), polybutadiene (including cis-1,4-polybutadiene), polyisoprene (including cis-1,4-polyisoprene), butyl rubber, halobutyl rubber, such as chlorobutyl rubber or bromobutyl rubber, styrene rubber / isoprene / butadiene, copolymers of 1,3-butadiene or isoprene with monomers such as styrene, acrylonitrile and methyl methacrylate, as well as ethylene / propylene terpolymers, also known as ethylene / propylene monomer / diene (EPDM) and, specifically, ethylene / propylene / dicyclopentadiene terpolymers. Additional examples of rubbers that can be used include polymerized polymers of functionalized alkoxy-silyl solution (SBR, PBR, IBR and SIBR), polymers coupled to silicon and star branched polymers coupled to tin. The preferred rubber or elastomers are polyisoprene (natural or synthetic), polybutadiene and SBR.
    In one aspect, at least one additional rubber is preferably at least two of the diene-based rubbers. For example, a combination of two or more rubbers is preferred, such as 1,4-polyisoprene cis rubber (natural or synthetic, although natural is preferred), 3,4-polyisoprene rubber, stretch rubber / isoprene / butadiene, solution polymerization and emulsion derived from styrene / butadiene rubbers, cis 1,4-polybutadiene rubbers and emulsion polymerization prepared from butadiene / acrylonitrile copolymers.
    In one aspect of this invention, a styrene / butadiene derived from emulsion polymerization (E-SBR) can be used, having a relatively conventional styrene content of about 20 to about 28% by weight of bonded styrene or, for some applications , an E-SBR having a medium to relatively high bound styrene content; namely, a bound styrene content of about 30 to about 45%.
    E-SBR prepared by emulsion polymerization means that styrene and 1,3-butadiene are copolymerized as an aqueous emulsion. These are well known to those skilled in the art. The content of bound styrene can vary, for example, from about 5 to about 50%. In one aspect, E-SBR may also contain acrylonitrile to form a terpolymer rubber, such as E-SBAR, in amounts, for example, from about 2 to about 30% by weight of acrylonitrile bound in the terpolymer.
    Styrene / butadiene / acrylonitrile copolymer rubbers prepared by emulsion polymerization containing about 2 to about 40% by weight of acrylonitrile bound in the copolymer are also contemplated as diene based rubbers for use in this invention.
    SBR (S-SBR) prepared by solution polymerization typically has a bound styrene content in the range of about 5 to about 50, preferably about 9 to about 36%. S-SBR can be conveniently prepared, for example, by catalyzing organo-lithium, in the presence of an organic hydrocarbon solvent.
    In one embodiment, cis 1,4-polybutadiene (BR) rubber can be used. Such a BR can be prepared, for example, by polymerizing an organic solution of 1,3-butadiene. BR can be conveniently characterized, for example, by having at least a content of 90% cis 1,4.
    Cis 1,4-polyisoprene rubber and cis 1,4-polyisoprene natural rubber are well known to those skilled in the art of rubber.
    The term "phr" as used in this document and according to conventional practice refers to "parts by weight of a respective material per 100 parts by weight of rubber or elastomer".
    The rubber composition can also include up to 70 phr of processing oil. Process oil can be included in the rubber composition as an extension oil typically used to extend elastomers. Process oil can also be included in the rubber composition by adding the oil directly during the composting of the rubber. The processing oil used can include both the extension oil present in the elastomers and the processing oil added during composting. Suitable processing oils include various oils as are known in the art, including aromatic, paraffinic, naphthenic, vegetable oils and oils with low PCA content, such as, MES, ADHD, SRAE and heavy naphthenic oils. Suitable oils containing low PCA content include those having polycyclic aromatic content of less than 3% by weight, as determined by the IP346 method. The procedures for the IP346 method can be found in Standard Methods for Analysis & Testing of Petroleum and Related Products and British Standard 2000 Parts, 2003, 62- edition, published by the Institute of Petroleum, United Kingdom.
    The rubber composition can include about 10 to about 150 phr of silica.
    In another embodiment, 20 to 80 phr of silica can be used.
    The silicon pigments generally used that can be used in the rubber compound include conventional precipitated and pyrogenic silicon pigments (silica). In one embodiment, precipitated silica is used. The conventional silicon pigments in that invention are precipitated silicas, such as, for example, those obtained by acidification of a soluble silicate, for example, sodium silicate.
    Such conventional silicas can be characterized, for example, by having a BET surface area, as measured using nitrogen gas. In one embodiment, the BET surface area can vary in the range of about 40 to about 600 square meters per gram. In another embodiment, the BET surface area can be in the range of about 80 to about 300 square meters per gram. The BET method for measuring the surface area is described in the Journal of the American Chemical Society, volume 60, page 304 (1930).
    Conventional silica can also be characterized by having an absorption value of dibutyl phthalate (DBP) in a range of about 100 to about 400, alternatively, about 150 to about 300.
    Conventional silica is expected to have an average final particle size, for example, in the range of 0.01 to 0.05 microns, as determined by electron microscopy, although the silica particles may be even smaller, or possibly larger in size.
    Various commercially available silicas can be used, such as, for example only and without limitation, silicas commercially available from PPG Industries, under the trademark Hi-Sil with designations 210, 243, etc .; silicas available in Rhodia, for example, with designations Z1165MP and Z165GR and silicas available in Degussa GmbH with, for example, designations VN2 and VN3 etc.
    Carbon blacks generally used can be used as conventional fillers in an amount ranging from 10 to 150 phr. In another embodiment, 20 to 80 phr carbon black can be used. Representative examples of such carbon blacks include N110, N121, N134, N220, N231, N234, N242, N293, N299, N315, N326, N330, N332, N339, N343, N347, N351, N358, N375, N539, N550, N582, N630, N642, N650, N683, N754, N762, N765, N774, N787, N907, N908, N990 and N991. These carbon blacks have iodine absorptions ranging from 9 to 145 g / kg and DBP number ranging from 34 to 150 cm3 / 100 g.
    Other fillers may be used in the rubber composition including, but not limited to particulate fillers including ultra-high molecular weight polyethylene (UHMWPE), particulate polymer gels including, but not limited to, US Patent numbers 6,242,534; 6,207,757; 6,133,364; 6,372,857; 5,395,891 or 6,127,488 and cargo comprised of plasticized starch, but not limited to that disclosed in US Patent number 5,672,639. Other fillers can be employed in an amount ranging from 1 to 30 phr.
    In one embodiment, the rubber composition may contain an organo-silicon compound containing conventional sulfur. In one embodiment, the sulfur-containing organosilicon compounds are the 3,3'-bis polysulfides (trimethoxy or triethoxy silylpropyl). In one embodiment, the sulfur-containing organosilicon compounds are 3,3'-bis disulfide (triethoxy silylpropyl) and / or 3,3'-bis tetrasulfide (silyl propyl triethoxy).
    In another embodiment, the appropriate sulfur-containing organosilicon compounds include compounds disclosed in US Patent No. 6,608,125. In one embodiment, sulfur-containing organosilicon compounds include 3- (octaneylthio) -1-propyltriethoxysilane,
    which is commercially available as NXT ™ from Momentive Performance Materials.
    In another embodiment, the appropriate sulfur-containing organosilicon compounds include those disclosed in US Patent Publication number 2003/0130535. In one embodiment, the organosilicon compound containing sulfur is Si-363 from Degussa.
    The amount of sulfur-containing organosilicon compound in a rubber composition will vary depending on the level of other additives that are used. In general, the amount of the compound will vary from 0.5 to 20 phr. In one embodiment, the amount will vary from 1 to 10 phr.
    It is readily understood by those skilled in the art that the rubber composition can be composted by processes generally known in the rubber composting technique, such as mixing various sulfur vulcanizable constituent rubbers with various commonly used additive materials, such as, for example, sulfur donors, curing aids, such as activators and retardants and processing additives, such as oils, resins including taching and plasticizing resins, fillers, pigments, fatty acid, zinc oxide, waxes, antioxidants and anti-zoning agents and peptizing agents . As known to those skilled in the art, depending on the intended use of the sulfur vulcanizable and sulfur vulcanized material (rubbers), the additives mentioned above are selected and generally used in conventional amounts. Representative examples of sulfur donors include elemental sulfur (free sulfur), an amine disulfide, polymeric polysulfide and sulfur olefin adducts. In one embodiment, the sulfur vulcanizing agent is elemental sulfur. The sulfur curing agent can be used in an amount ranging from 0.5 to 8 phr, alternatively with a range of 1.5 to 6 phr. Typical amounts of tachyting resins, when used, comprise about 0.5 to about 10 phr, generally about 1 to about 5 phr. Typical amounts of processing aids comprise about 1 to about 50 phr. Typical amounts of antioxidants comprise about 1 to about 5 phr. Representative antioxidants can be, for example, diphenyl-p-phenylenediamine and others, such as, for example, those disclosed in The Vanderbilt Rubber Handbook (1978), pages 344-346. Typical amounts of anti-zonants comprise about 1 to 5 phr. Typical amounts of fatty acids, when used, which may include stearic acid comprise about 0.5 to about 3 phr. Typical amounts of zinc oxide comprise about 2 to about 5 phr. Typical amounts of waxes comprise about 1 to about 5 phr. Microcrystalline waxes are often used. Typical amounts of peptizers comprise about 0.1 to about 1 phr. Typical peptides can be, for example, pentachlorothiophenol and dibenzamidodiphenyl disulfide.
    Accelerators are used to control the time and / or temperature required for vulcanization and to improve the properties of the vulcanized product. In one embodiment, a simple accelerator system can be used; that is, primary accelerator. The primary accelerator (s) can be used in total amounts ranging from about 0.5 to about 4, preferably about 0.8 to about 1.5 phr. In another embodiment, the combinations of a primary and secondary accelerator can be used with a secondary accelerator being used in smaller amounts, such as from about 0.05 to about 3 phr, in order to activate and improve the properties of the vulcanized product. The combinations of these accelerators can produce a synergistic effect on the final properties and are slightly better than those produced by using each accelerator alone. In addition, delayed-action accelerators can be used, which are unaffected by normal processing temperatures, but produce satisfactory curing at common vulcanization temperatures. Vulcanization retardants can also be used. Suitable types of accelerators that can be used in the present invention are amines, disulfides, guanidines, thiourea, thiazoles, thiomas, sulfenamides, dithiocarbamates and xanthates. In one embodiment, the primary accelerator is a sulfenamide. If a second accelerator is used, the secondary accelerator is preferably a guanidine, dithiocarbamate or thiurama compound.
    The mixing of the rubber composition can be carried out by methods known to those skilled in the rubber mixing technique. For example, ingredients are typically mixed in at least two stages; namely, at least one non-productive stage followed by a productive mixing stage. Final dressings including sulfur vulcanizing agents are typically mixed in the final stage which is conventionally referred to as the “productive” mixing stage, in which mixing typically takes place at a temperature, or final temperature, below (s) temperature (s) mixing in relation to the preceding non-productive mixing stage (s). The terms "non-productive" and "productive" mixing stages are well known to those skilled in the rubber mixing technique. The rubber composition can be subjected to a thermomechanical mixing step. The thermomechanical mixing step generally comprises mechanical work in a mixer or extruder for an appropriate period of time, in order to produce a rubber temperature between 140 ° C and 190 ° C. The appropriate duration of thermomechanical work varies as a function of operating conditions and the volume and nature of the components. For example, thermodynamic work can be 1 to 20 minutes.
    The rubber composition can be incorporated into a variety of rubber tire components. For example, the rubber component may be a tread (including the upper part of the tread and the base of the tread), side, filling, nylon fabric, side reinforcement, wire coating, inner lining. In one embodiment, the component is a tread.
    The tire of the present invention can be tire for racing cars, tire for passenger car, tire for aircraft, for agriculture, earthmoving, for vehicles traveling off-road, tire for trucks and the like. In one embodiment, the tire is intended for use in a passenger vehicle or truck. The tire can also be radial or oblique.
    The vulcanization of the tire of the present invention is generally carried out at conventional temperatures ranging from about 100 to 200 ° C. In one embodiment, vulcanization is carried out at temperatures ranging from 110 ° C to 180 ° C. Any common vulcanization process can be employed, such as heating in a press or mold, heating with superheated steam or hot air. Such tires can be built, shaped, molded, cured by various methods that are known and will be readily clear to those skilled in the art.
    The invention is illustrated by the following examples which are merely illustrative and are not intended to limit the scope of the invention or the way in which it can be practiced. Unless specifically stated, parts and percentages are given by weight. Example 1
    Synthesis of S-benzyl S'-trimethoxysilylpropyltrithiocarbonate:

    To a stirred solution of 3- (mercaptopropyl) trimethoxysilane (30 mmol) in 50 ml of anhydrous methanol was added dropwise a solution of sodium methoxide in methanol (25% by weight in methanol, 30 mmol) under nitrogen. After stirring for 30 minutes, carbon disulfide (40 mmol) was added dropwise to the solution and the mixture was stirred at room temperature for 3 hours. Benzyl bromide (30 mmol) was added to the yellow solution and the mixture was stirred for 3½ hours under a nitrogen atmosphere. The mixture was concentrated, diluted with dichloromethane, filtered, concentrated under reduced pressure and dried overnight in the Schlenk tube. The purity of the synthesized compound was characterized by means of 1H-NMR (400 MHz). Example 2
    Synthesis of S-benzyl S'-triethoxysilylpropyltrithocrabonate:

    To a stirred solution of 3- (mercaptopropyl) triethoxysilane (30 mmol) in 50 ml of anhydrous ethanol was added dropwise a solution of sodium ethoxide in ethanol (21% by weight in ethanol, 30 mmol) under nitrogen. After stirring for 30 minutes, carbon disulfide (40 mmol) was added dropwise to the solution, and the mixture was stirred at room temperature for 3 hours. Benzyl bromide (30 mmol) was added to the yellow solution and the mixture was stirred for 3 ½ hours under nitrogen. The mixture was concentrated, diluted with dichloromethane, filtered, concentrated under reduced pressure and dried overnight in the Schlenk tube. The purity of the synthesized compound was characterized by means of 1H-NMR (400 MHz). Example 3
    Synthesis of Silane, trimethoxy [3- (phenylmethyl) thio] propyl]:

    To a stirred solution of 3- (mercaptopropyl) trimethoxysilane (30 mmol) in 50 ml of anhydrous methanol was added dropwise a solution of sodium methoxide in methanol (25% by weight in methanol, 30 mmol) under nitrogen. After stirring for 30 minutes, benzyl bromide (30 mmol) was added dropwise to the solution, and the mixture was stirred at room temperature overnight. The mixture was concentrated, diluted with dichloromethane, filtered, concentrated under reduced pressure and dried overnight in the Schlenck tube. The synthesized compound was characterized by means of 1H-NMR (400 MHz). Example 4
    Synthesis of Silane, triethoxy [3- (phenylmethyl) thio] propyl]:

    To a stirred solution of 3- (mercaptopropyl) triethoxysilane (30 mmol) in 50 ml of anhydrous ethanol was added dropwise a solution of sodium ethoxide in methanol (21% by weight of ethanol, 30 mmol) under a nitrogen. After stirring for 30 minutes, benzyl bromide (30 mmol) was added dropwise to the solution, and the mixture was stirred at room temperature overnight. The mixture was concentrated, diluted with dichloromethane, filtered, concentrated under reduced pressure and dried overnight in the Schlenck tube. The synthesized compound was characterized by means of 1H-NMR (400 MHz). Example 5 Copolymerization of styrene and butadiene
    Polymerizations were carried out in a 3.78 L reactor at 65 ° C. A pre-mixture of styrene and butadiene monomer was loaded into a reactor, followed by the addition of a modifier (TMEDA, 5.7 mmol) and initiator (n-butyl lithium, 1.6 mmol). When the conversion was above 98%, the polymerization was terminated with isopropanol or with functional terminator (S-benzyl S'-triethoxysilylpropyltrithiocarbonate and silane, triethoxy [3- (phenylmethyl) -thio] -propyl]).
    The polymer obtained was characterized (results shown in Table 1), using different techniques, for example, SEC, for determining molecular weight, DSC for determining Tg, IV for determining cis, trans, styrene and vinyl content and Mooney viscosity. Table 1
    1Styrene-butadiene rubber polymerized in a functionalized solution with sul fanylsilane, as commercially available from Styron. 2Styrene-butadiene rubber polymerized in solution. 3 Styrene-butadiene rubber polymerized in solution terminated with S-benzyl S'-triethoxysilylpropyltrithiocarbonate from Example 2. 4Ethylene-butadiene rubber polymerized in solution terminated with silane, triethoxy [3- (phenylmethyl) -thio] -propyl]) from Example 4 . Example 6 Mixing studies and compound testing:
    The functionalized SBRs in Example 3, as well as the control (non-functionalized SBR) and comparative thiol functionalized with silane and silane were mixed with silica and oil in a 75 ml_ three-piece mixer, CW Brabender® equipped with Banbury rotors ®.
    The SBR samples were mixed with additives in a three-stage mixing procedure, as shown in Table 2, with all quantities supplied in parts by weight, per 100 parts by weight of elastomer (phr). All ingredients were mixed on silica. In the first stage of non-productive mixing, the compounds were mixed for 4 minutes at 60 rpm, using 140 ° C as the starting temperature. All compounds were pressed in a compression molding machine for 1 minute before the second stage of non-productive mixing. In the second stage of non-productive mixing the conditions were the same as those of the first stage of non-productive mixing, with the mixing time of 3 minutes. Productive mixtures were performed using a starting temperature of 60 ° C and 60 rpm with a mixing time of 3 minutes. Table 2 Variable (addition, as indicated in Examples 7-10) Silane1 5.2 First Non-Production Stage SBR 100 Silica 65 Oil 30 Stearic Acid 2 Zinc Oxide 3.5 Second Non-Production Stage Remoating Sulfur Production Mix Stage 1, 7 Sulfenamide 1.6 Diphenylguanidine 1.5 Anti-degradant 0.75 1 Bis (triethoxysilyl) disulfide
    The compounds were tested for silica interaction, using an Alpha Technology® RPA 2000®. Green (uncured) compounds were first heated to 160 ° C and the increase in torque was monitored as a function of time using a deformation of 1 Hz and 0.48%, in order to determine the "flocculation" charge rate. Subsequently, the compounds were cooled to 40 ° C and an oscilloscope voltage scan was performed using 1 Hz, in order to determine the Payne effect, that is, the voltage dependence of G ', G "and tangent delta. The cure was performed at 160 ° C using 7% deformation The dynamic properties of the cured compounds were initially measured by curing the sample at 160 ° C for 30 minutes in the lowest possible deformation to mimic a static cure, after which these samples were cooled and tested in the manner determined for green compounds. Example 7
    In this example, the addition of silane in a first non-productive mixing step is illustrated. The mixing of the compound was carried out according to Example 6, with the addition of the silane coupling agent in the first non-productive mixing stage followed by the second non-productive stage. No production mixing steps were performed in this example.
    Figure 1 shows the results of the strain scan conducted at 40 ° C on non-productive compounds after 30 minutes of heat treatment in low strain at 160 ° C in RPA. As shown in figure 1, G 'and tangent delta of Control Sample 2 non-functionalized and Sample 4 of thioester-functionalized polymer show higher strain dependence. Comparative polymer Sample 1 and trithiocarbonate functionalized Sample 3 show reduced strain dependence which indicates less load-load interaction and more load-polymer interaction.
    The ratio of low amplitude (0.48% deformation) modulus (LAM) and high amplitude (100% deformation) modulus (HAM) is a measure of the Payne effect and is provided in Table 3 for the various samples. The higher the LAM / HAM ratio, the lower the polymer-charge interaction. As can be seen in Table 3, Sample 2 of the non-functionalized control polymer shows a higher LAM / HAM value indicating minimal polymer-charge interaction, while Sample 1 and Sample 3 of polymer functionalized with trithiocarbonate show a LAM / Lower HAM. Table 3
    Example 8
    In this example, the non-productive mixture with the addition of silane is illustrated. The mixing of the compound was carried out according to Example 6, with the first stage of non-productive mixing followed by the second stage of non-production. No production mixing steps were performed in this example.
    Figure 2 shows the results of the strain scan conducted at 40 ° C on non-productive compounds after 30 minutes of heat treatment of the samples in low strain at 160 ° C in RPA. In this case, no coupling agent was added to evaluate only the interaction between the ends of the polymeric chain and the charge. In this case, similar to the results obtained when the coupling agent was used in Example 7, G 'and delta tangent of Control Sample 2 and Sample 4 of thioester-functionalized polymer show greater strain dependence. Comparative sample 1 and Sample 3 of trithiocarbonate functionalized polymer show reduced strain dependence.
    The ratio of the low amplitude (0.48% deformation) and high amplitude (100% deformation) modules is shown in Table 4. Without the use of the silane coupling agent, the Payne effect is improved when compared to Payne effect observed with the use of the silane coupling agent in Example 7. Control Sample 2 and Sample 4 of thioester-functionalized polymer show a very high LAM / HAM value, i.e., relatively high Payne effect. Comparative Sample 1 and Sample 3 of trithiocarbonate functionalized polymer show the lowest Payne effect indicating good interaction between polymer and charge. As a result of the good interaction of the polymer and the charge, the values of tangent delta for the polymers functionalized with tritiocarbonate and comparative are inferior to the non-functionalized control and polymers functionalized with thioester. Table 4
    Example 9
    In this example, the addition of silane to a batch of production is illustrated. The mixing of the compound was carried out according to Example 6, with the first stage of non-productive mixing followed by the second stage of non-productive and finally a stage of productive mixing. The addition of silane coupling agent was carried out in the first stage of non-productive mixing.
    The curing curves obtained with silane coupling agent at 7% strain are shown in figure 3. The curing parameters Max torque S'max and change in delta torque S are provided in Table 5. Table 5

    Deformation sweeps were conducted in separate RPA operations. In these operations, the samples were cured at 160 ° C for 30 minutes using the least possible deformation (0.28%) in order to imitate the static cure and not to change the load-load or load-polymer interaction. The deformation sweep cures were obtained at 40 ° C as shown in figure 4.
    The ratio of the low amplitude (0.48% deformation) and high amplitude (100% deformation) modules is shown in Table 6. The deformation scan conducted on the cured compounds indicates that Comparative Sample 1 and Polymer Sample 3 functionalized with trithiocarbonate have a reduced Payne effect, thus improving the interaction of polymer and charge in relation to Sample 2 of non-functionalized polymer control. Table 6
    Example 10
    In this example the mixture of the production compound is illustrated, without the addition of silane. The mixing of the compound was carried out according to Example 6, with the first non-productive mixing stage followed by the second non-productive stage and the productive stage. No silane coupling agent was added.
    The curing curve obtained for the productive sample without 7% deformation silane coupling agent is shown in figure 5. The curing parameters max torque S'max and change in delta torque S are provided in Table 7. Table 7

    Deformation sweeps were conducted in separate RPA operations. In these operations, the samples were cured at 160 ° C for 30 minutes using the least possible deformation (0.28%) in order to imitate the static cure and not to change the load-load or load-polymer interaction. The ratio of the low amplitude (0.48% deformation) and high amplitude (100% deformation) modules is shown in table 8. The deformation sweep curves were obtained at 40 ° C as shown in figure 6. Table 8

    Deformation sweeps conducted on cured compounds indicate that Sample 3 of functionalized polymer with trithiocarbonate shows reduced Payne effect thus improved polymer interaction and loading compared to Sample 2 of non-functionalized polymer control. In addition, the delta tangent values for Comparative Sample 1 and Sample 3 of trithiocarbonate polymer are lower compared to Sample 2 of non-functionalized control and Sample 4 of polymer functionalized with thioether. Discussion
    As shown above, both Comparative Sample 1 and Sample 3 of trithiocarbonate-functionalized polymer reduced the Payne effect, as well as the delta tangent values compared to the non-functionalized Control Sample 2 and Thioether-functionalized Polymer Sample 4. Although it is not intended to be limited to any theory, this can be explained by the difference in the terminal groups that are present in such polymers, as in the discussion that follows.
    In Comparative Example 1, the polymer is terminated using an end terminating agent based on the siloxy and sulfur-silane groups, as described in US 2008/0287601. In the polymeric chain that carries both siloxide and sulfur-silane groups, siloxide groups assist in providing covalent interaction with the silica surface and silane-protected sulfur helps in providing interaction between polymer chains. The sulfur-silane group has potential for cleavage during mixing and, therefore, results in the generation of active thiol groups that can help in crosslinking. Comparative Sample 1 is coupled using additional coupling agents that can assist in achieving better processability.
    Sample 3 of trithiocarbonate-functionalized polymer is terminated using end terminating agent based on the siloxy and trithiocarbonate groups. Similar to Comparative Sample 1 of the polymer, the siloxy groups help in providing covalent interaction with silica and the trithiocarbonate groups help in obtaining a good interaction between the polymer chains. When siloxy-functionalized trithiocarbonates are used as an end-terminating agent, there is a possibility that the active polymer chain can be attached to the end-terminating group via nucleophilic displacement of the alkoxy group, as well as the polymeric chain can be attached to the bond of thiocarbonyl. The polymeric chain attached to the siloxide group helps to obtain the good interaction between the polymeric chain and the charge, although the second functional group in the end terminating agent, which in this case is the thiol (generated from the trithiocarbonate) helps in the interactions of the chains polymeric through crosslinking. The trithiocarbonate group can potentially cleave to the thiol group during mixing and the thiol groups thus generated help to improve crosslinking of polymer chains. With the use of the siloxy trithiocarbonate end terminating agent, it is also possible to obtain coupling between the polymer chains without adding any additional coupling agent, since the end terminating agent based on the siloxy and trithiocarbonate group can interact with the anionic polymer chain lives in two different ways. One way is the replacement of the ethoxy group present in the siloxy tritiocarbonate with a polymeric chain and the second way is the reaction of the anionic polymeric chain with a thiocarbonyl group.
    Sample 4 of thioester-functionalized polymer was synthesized to observe the advantage of having thiol group generated during mixing in reducing the Payne effect. The thioester group is stable and is not capable of generating active thiol group. The thioester-functionalized polymer carries the siloxy group that can interact with silica in covalent mode. However, there are no additional interactions present other than Sample 3 of polymer functionalized with trithiocarbonate. Therefore, thioether-functionalized polymers have a greater Payne effect than polymers functionalized with trithiocarbonate and comparative polymers.
    Sample 2 of non-functionalized polymer was synthesized as a control to observe the difference in functionalized versus non-functionalized behavior in its interaction with silica. Sample 2 of non-functionalized polymer showed a greater Payne effect in all cases, which means less interaction with silica, since there is no functional group that can interact with silica. However, the reduction of the Payne effect is observed when the coupling agent is used, but it is even greater compared to the reduction observed with the trithiocarbonate functionalized polymer with silane coupling agent.
    Although certain representative embodiments and details have been shown for purposes of illustrating the present invention, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the scope of the present invention.
    权利要求:
    Claims (13)
    [0001]
    1. Functionalized elastomer CHARACTERIZED by the fact that it comprises the reaction product of a live anionic elastomeric polymer; and a polymerization terminator of formula I:
    [0002]
    2. Functionalized elastomer, according to claim 1, CHARACTERIZED by the fact that R1, R2 and R3 are each selected from a Ci to Cs alkoxy.
    [0003]
    3. Functionalized elastomer, according to claim 1 or 2, CHARACTERIZED by the fact that Z is of formula II.
    [0004]
    4. Functionalized elastomer according to claim 1 or 2, CHARACTERIZED by the fact that Z is an alkyl, an aryl, an alkylaryl or an arylalkyl.
    [0005]
    5. Functionalized elastomer, according to any of the preceding claims, CHARACTERIZED by the fact that the live anionic elastomer is derived from at least one diene monomer.
    [0006]
    6. Functionalized elastomer, according to any of the preceding claims, CHARACTERIZED by the fact that the live anionic elastomer is derived from at least one diene monomer and at least one aromatic vinyl monomer.
    [0007]
    7. Functionalized elastomer, according to any of the preceding claims, CHARACTERIZED by the fact that the live anionic elastomer is derived from at least one of isoprene and butadiene.
    [0008]
    8. Functionalized elastomer, according to any of the preceding claims, CHARACTERIZED by the fact that the live anionic elastomer is derived from at least one among isoprene and butadiene, and styrene.
    [0009]
    9. Functionalized elastomer, according to any of the preceding claims, CHARACTERIZED by the fact that the live anionic elastomer is derived from butadiene and styrene
    [0010]
    10. Functionalized elastomer, according to any of the preceding claims, CHARACTERIZED by the fact that the polymerization terminator of formula I has the structure:
    [0011]
    11. Rubber composition CHARACTERIZED by the fact that it comprises the functionalized elastomer, as defined in any of the preceding claims.
    [0012]
    12. Rubber composition according to claim 11, CHARACTERIZED by the fact that it additionally comprises silica.
    [0013]
    13. Pneumatic CHARACTERIZED by the fact that it has the rubber composition, as defined in claim 11 or 12.
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    同族专利:
    公开号 | 公开日
    US20130131263A1|2013-05-23|
    EP2596963B1|2014-07-02|
    JP6161264B2|2017-07-12|
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    法律状态:
    2015-01-06| B03A| Publication of an application: publication of a patent application or of a certificate of addition of invention|
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-08-27| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2020-03-17| B07A| Technical examination (opinion): publication of technical examination (opinion)|
    2020-08-25| B09A| Decision: intention to grant|
    2020-10-20| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 22/11/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US13/302,066|2011-11-22|
    US13/302,066|US8865829B2|2011-11-22|2011-11-22|Functionalized polymer, rubber composition and pneumatic tire|
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