Polymeric articles containing hindered amine light stabilizers based on multi-functional carbonyl co

专利摘要:
A polymeric article comprising a sufficient amount of at least one polymeric material and at least one novel hindered amine light stabilizer to inhibit at least one of photolysis or pyrolysis. The hindered amine light stabilizer may be a monomer or oligomeric hindered amine light stabilizer.
公开号:KR20030051771A
申请号:KR10-2003-7006081
申请日:2001-10-26
公开日:2003-06-25
发明作者:새시토마스패트릭
申请人:사이텍 테크놀러지 코포레이션；
IPC主号:

专利说明:

POLYMERIC ARTICLES CONTAINING HINDERED AMINE LIGHT STABILIZERS BASED ON MULTI-FUNCTIONAL CARBONYL COMPOUNDS}
[2] Ultraviolet ("UV") or radiation, in particular sunlight, can cause decomposition of various materials, in particular polymeric materials. This often makes the material yellow or brittle, which can be in the form of shaped articles, extruded articles, films, tapes, coatings, and the like. However, such degradation can be suppressed by adding light stabilizers in or on the polymeric article. The most commonly used stabilizers are UV absorbers, hindered amine light stabilizers ("HALS") and phenolic and nonphenolic antioxidants.
[3] HALS removes free radicals that form in a polymer material when it is exposed to UV light. The functional component of the HALS molecule is generally the 2,2,6,6-tetraalkylpiperidine moiety. Typically, 2,2,6,6-tetraalkylpiperidine moieties are attached to a carbonyl or melamine functional group (US Pat. Nos. 4,331,586; 3,840,494; Re.31,342; Re.30,385; 3,640,928; 4,086,204; 4,265,805). Attaching the 2,2,6,6-tetraalkylpiperidine moiety to a carbonyl or melamine functional group usually reduces the volatility and extractability of the stabilizer. Low volatility serves as an important feature of light stabilizers in high temperature applications that are commonly encountered in processing thermoplastics and curing thermosets and coatings. High temperatures are also present in the end use of stabilized materials. Low volatility helps prevent the loss of stabilizers during processing, curing and high temperature end use. Generally HALS molecules containing 2,2,6,6-tetraalkylpiperidine groups attached to a carbonyl group are 2,2,6,6-tetraalkylpiperidin-4-ols or 4-amino-2,2 Prepare by reacting 6,6-tetramethylpiperidine with carboxylic acid chlorides or esters.
[4] US Pat. Nos. 31,342, 4,021,432 and 4,049,647 disclose 1- and 4-substituted piperidines which are stabilizers of organic materials. This stabilizer is prepared by reacting the corresponding 1-substituted piperidinol with an acid chloride or reacting the 4-substituted piperidine with a compound which introduces a residue into the 1-position of this piperidine moiety.
[5] US Patent No. 3,840,494 discloses polymer compositions stabilized against such degradation by adding acid esters of 4-piperidinol derivatives in an amount sufficient to prevent light degradation and heat degradation. Acid esters of 4-piperidinol derivatives are prepared by reacting a 4-piperidinol derivative with a carboxylate ester in xylene together with sodium hydroxide. For example, the reaction of 4-hydroxy-2,2,6,6-tetramethylpiperidine with ethyl benzoate produces 4-benzoyloxy-2,2,6,6-tetramethylpiperidine do.
[6] Likewise, 2,2,6,6-tetramethylpiperidin-4-ol can be reacted with diesters or diacid chlorides to produce diester-HALS. In addition, 2,2,6,6-tetramethylpiperidin-4-ol can be reacted with diisocyanate to produce the polyurethane-HALS. However, diisocyanates are relatively expensive and are less practical than diesters when producing HALS.
[7] Compounds having an ester functional group at one end of the hydrocarbon chain and a urethane functional group at the other end of the hydrocarbon chain (alkoxycarbonylamino alkanoates) are known for various uses other than light stabilization and can be prepared according to various synthetic schemes. (E.g. Effenberger, F .; Drauz, K .; Foerster, S .; Mueller, W., Chem. Ber., 114 (1), 173-89; Dixit, A .; Tandel, S .; Rajappa 35; 33, 6133-4, Duong, et al., Aust. J. Chem., 29, 2651-61, 1976; Iwaka et al., J. Org. Chem. , 31, 142-46, 1966; Taub; Hino; J. Chem. Eng. Data, 9, 106, 1964; US Pat. No. 5,300,678 Merger et al.).
[8] US Pat. No. 5,574,162 discloses 1-hydrocarbyloxy substituted HALS further comprising a reactive functional group that chemically attaches by condensation reaction to a selected polymer substrate.
[9] Oligomeric HALS is also known. For example, TINUVIN 622 is an oligomeric HALS available from Ciba Specialty Chemicals Inc. (Hawthorne, NY). TINUVIN 622 can be produced by reacting N- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol with dimethyl succinate. US Pat. No. 4,223,412 discloses condensation and addition polymers containing polyalkylpiperidine radicals which are useful as light stabilizers for plastics in repeatable molecular units. In one embodiment this copolymer is prepared by copolymerizing or cocondensing a polyalkylpiperidine containing monomer with a polyalkylpiperidine free monomer such as caprolactam.
[10] US Pat. No. 6,271,377 discloses HALS in which N-atoms are substituted with N-alkyloxy moieties containing one to three hydroxyl groups.
[11] US Pat. No. 4,331,586 to Hardy discloses oligomers containing at least one piperidyl moiety in a repeating unit for use as a light stabilizer. Polymeric films containing the disclosed oligomeric HALS provide protection to polymeric materials such as polypropylene but become vulnerable after exposure to UV light for about 1,700 hours.
[12] HALS compounds can be used alone or in combination with other light stabilizers to inhibit photolysis of the polymer. Initially, UV light absorbers such as benzotriazole and benzophenone have been used to stabilize the polymer material and to prevent degradation of the material against UV light exposure. Subsequently, it has been found that HALS compounds have a better effect than UV light absorbers alone, and at least one HALS compound is currently used with UV light absorbers for most common applications (see, for example, US Pat. No. 4,740,542; 4,619,956; 5,461,151; 5,721,298). Likewise, HALS compounds are often used with other stabilizers such as antioxidants (see, eg, US Pat. No. 4,722,806). Mixtures of other stabilizers with HALS may provide polymer materials with better weatherability.
[13] US Pat. No. 4,619,956 discloses the incorporation of a HALS compound with a tris-aryl-s-triazine UV light absorber in a polymer to stabilize a polymer film, coating or molded article against the action of light, moisture and oxygen. In this case, the HALS compound is a 2,2,6,6-tetraalkylpiperidine compound, a salt or a metal complex, and the UV light absorber is preferably tris-aryl-2-triazine represented by the following formula:
[14]
[15] Wherein X, Y and Z are each aromatic carbocyclic groups, at least one of which has a hydroxyl group in the ortho direction relative to the triazine ring attachment point. R ¹ to R ⁹ are each hydrogen, hydroxy, alkyl, alkoxy, sulfone, carboxy, halo, haloalkyl or acylamino. UV light absorbers and HALS compounds are used in amounts of about 0.01 to 5% by weight, respectively, but only blends containing the same amount of UV light absorbers and HALS compounds are exemplified. The composition is effective to stabilize the polymeric material so that it does not lose gloss or yellow after exposure to UV light for about 1,000 to 2,400 hours.
[16] However, there is still a need for improved articles, compositions, and methods of using and manufacturing the same, which stabilize polymer materials for a long period of time and act as a barrier to UV exposure.
[1] The present invention relates generally to novel hindered amine light stabilizers (HALS) and their use as blockers against ultraviolet light or light ("UV light"). The present invention also relates to concentrates and articles containing this stabilizer and methods of making all of them.
[17] Summary of the Invention
[18] The present invention relates to a polymeric article comprising at least one polymeric material and at least one compound represented by formula (I), (II) or (III) below to inhibit at least one of photolysis or pyrolysis. The compound represented by the formula (I) is as follows:
[19] Formula I
[20] RZ-CO-CR ^a R ^b -(-CR ^c R ^d- ) _n -NH- (Y) _m -CO-A
[21] Wherein n is an integer from 1 to 15 and m is 0 or 1; R ^a , R ^b , R ^c and R ^d are each hydrogen or hydrocarbyl group; Y is CO-C (R ^e R ^f ) _p (where R ^e and R ^f are each hydrogen or hydrocarbyl groups and p is 0 or an integer from 1 to 20) or CO-C ₆ H ₄ − (where , The substitution pattern on the phenylene group is an ortho, meta or para substitution pattern and one or more hydrogens of the phenylene group may be substituted with a hydrocarbyl group or a functional group); Z is -O- or -NG-, wherein G is H, C ₁ to C ₁₂ alkyl or radical R; R is represented by the following formula; A is a ZR or hydrocarbyl group.
[22]
[23] In this expression,
[24] R ¹ is hydrogen, C ₁ to C ₁₈ alkyl, O, OH, CH ₂ CN, C ₁ to C ₁₈ alkoxy, C ₁ to C ₁₈ hydroxyalkoxy, C ₅ to C ₁₂ cycloalkoxy, C ₅ to C ₁₂ hydro cycloalkoxy, C ₃ to C ₆ alkenyl, C ₁ to C ₁₈ alkynyl group, one, two or three C ₁ a C ₇ to C ₉ to C ₄ substituted or unsubstituted phenyl-alkyl phenylalkyl, or Aliphatic C ₁ to C ₈ acyl; R ² is hydrogen, C ₁ to C ₈ alkyl or benzyl; R ³ , R ⁴ , R ⁵ and R ⁶ are each hydrogen, C ₁ to C ₈ alkyl, benzyl or phenethyl, or two in situ R additions together with the carbon to which they are attached form C ₅ to C ₁₀ cycloalkyl It is. Compounds of formula (II) are as follows:
[25] Formula II
[26]
[27] Wherein i, j, k and l are integers from about 0 to 300, the sum of i, j, k and l is greater than 2 and E-F is as follows;
[28]
[29] E-F 'is as follows;
[30]
[31] E'-F is as follows;
[32]
[33] E'-F 'is as follows;
[34]
[35] S is a hydrogen or piperidine-4-ol or 4-aminopiperidine floating unit having the structure
[36]
[37] T is a unit derived from hydrogen or a multifunctional carbonyl compound having the structure
[38]
[39] In which D is a hydrocarbyl group, n is an integer from 1 to 15, m is 0 or 1, and s is 0 or an integer from 1 to 10; R ^a , R ^b , R ^c and R ^d are each hydrogen or hydrocarbyl group; Y is CO-C (R ^e R ^f ) _p (where R ^e and R ^f are each hydrogen or hydrocarbyl groups and p is 0 or an integer from 1 to 20) or CO-C ₆ H ₄ − (where , The substitution pattern on the phenylene group is an ortho, meta or para substitution pattern and one or more hydrogens of the phenylene group may be substituted with a hydrocarbyl group or a functional group); R ² is hydrogen, C ₁ to C ₈ alkyl or benzyl; R ³ , R ⁴ , R ⁵ and R ⁶ are each hydrogen, C ₁ to C ₈ alkyl, benzyl or phenethyl, or two in situ R moieties together with the carbon to which they are attached form C ₅ to C ₁₀ cycloalkyl and; Z is -O- or NG, wherein G is H, C ₁ to C ₁₂ alkyl; when s is greater than 0, P is NH or O; When s is 0, P is O or OLO, where L is hydrocarbylene. Compounds of formula III are:
[40] Formula III
[41]
[42] Wherein i and j are integers from about 0 to 300 and the sum of i and j is greater than 2;
[43] M-F is as follows;
[44]
[45] M-F 'is as follows;
[46]
[47] T is a unit derived from hydrogen or a multifunctional carbonyl compound having the structure:
[48]
[49] Wherein D is a hydrocarbyl group, n is an integer from about 1 to 15, m is 0 or 1, and R ^a , R ^b , R ^c and R ^d are each hydrogen or hydrocarbyl group; Y is CO-C (R ^e R ^f ) _p (where R ^e and R ^f are each hydrogen or hydrocarbyl groups and p is an integer from about 0 to 20) or CO-C ₆ H ₄ − (where The substitution pattern on the phenylene group is an ortho, meta or para substitution pattern and one or more hydrogens of the phenylene group may be substituted with a hydrocarbyl group or a functional group); M is a moiety derived from one or more diamino or dihydroxy groups comprising a 4-aminopiperidine radical represented by the following formula, and is bonded to the multifunctional carbonyl compound by a hydroxy or amino group of M: :
[50]
[51] Wherein R ¹ is hydrogen, C ₁ to C ₁₈ alkyl, O, OH, C ₁ to C ₁₈ alkoxy, C ₁ to C ₁₈ hydroxyalkoxy, C ₅ to C ₁₂ cycloalkoxy, C ₅ to C ₁₂ hydroxy C ₇ to C ₉ which is phenyl unsubstituted or substituted with cycloalkoxy, CH ₂ CN, C ₃ to C ₆ alkenyl, C ₁ to C ₁₈ alkynyl, 1, 2 or 3 C ₁ to C ₄ alkyl Phenylalkyl, or aliphatic C ₁ to C ₈ acyl; R ² is hydrogen, C ₁ to C ₈ alkyl or benzyl; R ³ , R ⁴ , R ⁵ and R ⁶ are each hydrogen, C ₁ to C ₈ alkyl, benzyl or phenethyl, or two in situ R moieties together with the carbon to which they are attached form C ₅ to C ₁₀ cycloalkyl do.
[52] The amount of the compound represented by formula (I), (II) or (III) may range from about 0.01 to 10% by weight of the polymeric article. Polymeric materials include polyolefins; Polyester; Polyethers; Polyketones; Polyamides; Natural and synthetic rubbers; Polyurethane; polystyrene; High impact polystyrene; Polyacrylates; Polymethacrylates; Polyacetals; Polyacrylonitrile; Polybutadiene; polystyrene; ABS; SAN (styrene acrylonitrile); ASA (acrylate styrene acrylonitrile); Cellulose acetate butyrate; Cellulose polymers; Polyimide; Polyamideimide; Polyetherimide; Polyphenylsulfide; PPO; Polysulfones; Polyethersulfones; Polyvinyl chloride; Polycarbonate; Polyketones; Aliphatic polyketones; Thermoplastic TPO; Amino resin crosslinked polyacrylates and polyesters; Polyisocyanate crosslinked polyesters and polyacrylates; Phenol / formaldehyde, urea / formaldehyde and melamine / formaldehyde resins; Dry and undrying alkyd resins; Alkyd resins; Polyester resins; Acrylate resins crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, carbamates and epoxy resins; Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic and aromatic glycidyl compounds crosslinked with anhydrides or amines; Polysiloxanes; Michael addition polymers with activated unsaturated and methylene compounds of amines or blocked amines, Michael addition polymers with ketimines with activated unsaturated and methylene compounds, polyketimines and unsaturated acrylic resins in combination with unsaturated acrylic polyacetoacetate resins Combined polyketamine; Radiation curable compositions; Epoxy melamine resins; Organic dyes; Beauty products; Cellulosic paper compositions; Photographic film paper; ink; And combinations thereof. The polymeric material may be a copolymer or homopolymer of polyolefin. The polymeric material may comprise polyamide.
[53] Polymeric articles also include antioxidants, UV absorbers and light stabilizers, metal deactivators, phosphites and phosphonites, hydroxylamines, nitrons, thiosynergists, peroxide impurity removers, polyamide stabilizers, basic co-stabilizers, Nucleating agents, fillers and reinforcing agents, benzofuranone, indolinone, acid impurity removers, antistatic agents, blowing agents, catalysts, purifiers, emulsifiers, fillers, refractory materials, fluorescent bleaches, infrared absorbers, leveling aids, lubricants, metal deactivators, mold release agents And one or more additives selected from the group consisting of nucleating agents, optical brighteners, pigments, plasticizers, flow additives, and mixtures thereof. One or more additives may be provided in up to about 10% by weight content of the polymeric article.
[54] The present invention also provides a sufficient content of at least one of the polymer article having at least one surface and the compound represented by the formula (I), (II) or (III) to be applied to at least one surface of the polymer article and to inhibit at least one of photolysis or pyrolysis. The present invention relates to a multilayer polymer article comprising a thin film of polymer composition.
[55] The thin film can be applied to each surface of the polymeric article. The amount of the compound may range from about 0.1 to 20% by weight of the thin film. The thickness of the thin film may range from about 5 to 500 μm. The polymeric article is thermoplastic and the thin film may be thermoplastic. The thermoplastic article and the thin film can be made of the same thermoplastic resin.
[56] The invention also relates to a coating containing at least one of the compounds represented by formula (I), (II) or (III) in an amount sufficient to inhibit at least one of photolysis or thermal decomposition. The content of at least one of the compounds represented by Formula I, II, or III may range from about 0.01 to 20% by weight of the article.
[57] The present invention also relates to concentrates containing at least one of the compounds of formula (I), (II) or (III) in the range of about 15 to 95%.
[58] Detailed description of the invention
[59] The present invention has found an improved group of HALS compounds that provide substantially similar or better sun protection for longer periods of time as compared to conventional HALS compounds. HALS compounds of the present invention are based on the reaction of a carbonyl group with a lactam of a carbonyl compound. The HALS compound of the present invention has a piperidin-4-ol or 4-aminopiperidine group, which is a functional component of the HALS compound, attached to the end of the hydrocarbon chain by an ester functional group or an amide functional group, and the other end of the hydrocarbon chain. Includes compounds terminated by amide bonds that are not HALS functional groups. This compound may also be called "ester / amide HALS compound" and "amide / amide HALS compound". Alternatively, the end of the hydrocarbon chain can be terminated with a piperidin-4-ol or 4-aminopiperidine group. In this embodiment, the HALS molecules are attached by ester functionalities at one end of the hydrocarbon chain and by urethane functionalities at the other end. Thus, it may be referred to as "ester / urethane HALS compound". HALS molecules may also be attached by amide functionalities at one end of the hydrocarbon chain and urea functionalities at the other end. Thus, this compound may be referred to as an "amide / urea HALS compound". As another series of compounds, the piperidin-4-ol or 4-aminopiperidine group is bonded by an ester bond to one end of the hydrocarbon chain and by an oxamate bond to the other end of the hydrocarbon chain, leading to an "ester. / Oxamate HALS compound "or a piperidin-4-ol or 4-aminopiperidine group is bonded by an amide bond to one end of the hydrocarbon chain and an oxamide bond to the other end of the hydrocarbon chain Can be combined to provide an “amide / oxamide HALS compound”.
[60] Monomer HALS Compounds of the Invention
[61] This HALS compound is represented by the following formula (I):
[62] Formula I
[63] RZ-CO-CR ^a R ^b- (CR ^c R ^d ) _n -NH- (Y) _m -CO-A
[64] Wherein n is an integer between 1 and 15, preferably between 4 and 11, and m is 0 or 1; R ^a , R ^b , R ^c and R ^d are each hydrogen or hydrocarbyl group; Y is CO-C (R ^e R ^f ) _p (where R ^e and R ^f are each hydrogen or hydrocarbyl groups and p is 0 or an integer from 1 to 20) or CO-C ₆ H ₄ − (where , The substitution pattern on the phenylene group, i.e., -C ₆ H _4- , is an ortho, meta or para substitution pattern and one or more hydrogens of the phenylene group may be substituted with a hydrocarbyl group or other functional group commonly found in organic molecules. Can be); Z is -O- or -NG-, wherein G is H, C ₁ to C ₁₂ alkyl or radical R; The radical R is represented by the formula: A is a ZR or hydrocarbyl group.
[65]
[66] In this expression,
[67] R ¹ is hydrogen, C ₁ to C ₁₈ alkyl, O, OH, CH ₂ CN, C ₁ to C ₁₈ alkoxy, C ₁ to C ₁₈ hydroxyalkoxy, C ₅ to C ₁₂ cycloalkoxy, C ₅ to C ₁₂ hydroxy C ₇ to C ₉ phenylalkyl, which is phenyl unsubstituted or substituted with oxycycloalkoxy, C ₃ to C ₆ alkenyl, C ₁ to C ₁₈ alkynyl, 1, 2 or 3 C ₁ to C ₄ alkyl, Or aliphatic C ₁ to C ₈ acyl; R ² is hydrogen, C ₁ to C ₈ alkyl or benzyl; R ³ , R ⁴ , R ⁵ and R ⁶ are each hydrogen, C ₁ to C ₈ alkyl, benzyl or phenethyl, or two in situ R additions together with the carbon to which they are attached form C ₅ to C ₁₀ cycloalkyl It is.
[68] The term "hydrocarbyl" as used herein is a monovalent hydrocarbon group having a valence obtained by extracting hydrogen from carbon. Hydrocarbyl includes, for example, groups of aliphatic (straight and branched), cycloaliphatic, aromatic and complex properties such as aralkyl and alkalyl. Hydrocarbyl also includes internal unsaturated groups and activated unsaturated groups. More specifically, hydrocarbyl generally has alkyl, cycloalkyl, aryl, aralkyl, alkaryl, alkenyl, cycloalkenyl and alkynyl having about 1 to 24 carbon atoms, preferably about 1 to 12 carbon atoms. But is not limited to this. Hydrocarbyl may comprise one or more carbonyl groups (included in the number of carbon atoms) and / or heteroatoms (eg, at least one oxygen, nitrogen, sulfur or silicon) in the chain or ring. Hydrocarbyl may also comprise one or more hydrogens of a hydrocarbon group substituted with a functional group generally observed in organic molecules. The expression “functional group commonly observed in organic molecules” refers to nonhydrocarbyl groups generally observed in organic molecules, such as halides, cyano groups, amino groups, thiol groups, carboxylate groups, hydroxyl groups, sulfo Nate groups, nitroso groups, nitro groups and the like, but are not limited thereto.
[69] The term "hydrocarbylene" as used in the context of the present invention is a divalent hydrocarbon group in which both valences are derived by the loss of hydrogen from a carbon atom. The definition of hydrocarbylene includes, of course, groups equivalent to the aforementioned hydrocarbyl and functional hydrocarbyl having excess valence (eg, alkylene, alkenylene, arylene, etc.).
[70] In a preferred embodiment of the invention, R ¹ is H, C ₁ to C ₄ alkyl, C ₁ to C ₁₈ alkoxy, C ₅ to C ₁₂ cycloalkoxy, O or OH; R ₂ is H or C ₁ to C ₄ alkyl; R ³ , R ⁴ , R ⁵ and R ⁶ are H or C ₁ to C ₄ alkyl; R ^a , R ^b , R ^c and R ^d are each hydrogen, aromatic or C ₁ to C ₄ alkyl; n is about 2 to 10. In a more preferred embodiment, R is a 2,2,6,6-tetramethylpiperidine radical (ie R ³ , R ⁴ , R ⁵ , R ⁶ is methyl and R ² is hydrogen) or 1,2, 2,6,6-pentamethylpiperidine radical (ie, R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are methyl); R ^a , R ^b , R ^c and R ^d are each hydrogen; Z is -O-; m is 0 or 1; n is 4 to 10.
[71] Synthesis of Monomer HALS Compound
[72] HALS compounds represented by Formula I are generally prepared by reacting a polyfunctional carbonyl compound with 4-piperidine-ol or 4-aminopiperidine moiety. Multifunctional carbonyl compounds are represented by the formula:
[73] DO-CO-CR ^a R ^b -(-CR ^c R ^d- ) _n -NH- (Y) _m -CO-B
[74] [Wherein n is an integer of about 1 to 15, preferably 4 to 11, m is 0 or 1, and R ^a , R ^b , R ^c and R ^d are each hydrogen or hydrocarbyl group; Y is CO-C (R ^e R ^f ) _p (where R ^e and R ^f are each hydrogen or hydrocarbyl groups and p is 0 or an integer from about 1 to 20) or CO-C ₆ H ₄ − (where Wherein the substitution pattern on the phenylene group, ie —C ₆ H ₄ —, is an ortho, meta or para substitution pattern and one or more hydrogens of the phenylene group may be substituted with a functional group or hydrocarbyl group commonly observed in organic molecules. Present); D is a hydrocarbyl group; B is OD or D.]; Prepared by reacting a carbonyl compound with 1-substituted piperidin-4-ol or 4-aminopiperidine of the formula:
[75]
[76] In which Z is OH or NHG, wherein G is H or C ₁ to C ₁₂ alkyl or radical R (where R is as described above); R ¹ is hydrogen, C ₁ to C ₁₈ alkyl, O, OH, CH ₂ CN, C ₁ to C ₁₈ alkoxy, C ₁ to C ₁₈ hydroxyalkoxy, C ₅ to C ₁₂ cycloalkoxy, C ₅ to C ₁₂ hydro cycloalkoxy, C ₃ to C ₆ alkenyl, C ₁ to C ₁₈ alkynyl group, one, two or three C ₁ a C ₇ to C ₉ to C ₄ substituted or unsubstituted phenyl-alkyl phenylalkyl, or Aliphatic C ₁ to C ₈ acyl; R ² is hydrogen, C ₁ to C ₈ alkyl, or benzyl; R ³ , R ⁴ , R ⁵ and R ⁶ are each hydrogen, C ₁ to C ₈ alkyl, benzyl or phenethyl, or two in situ R additions together with the carbon to which they are attached form C ₅ to C ₁₀ cycloalkyl Doing.
[77] The reaction between the polyfunctional carbonyl compound and the 4-piperidine-ol or 4-aminopiperidine moiety is carried out for a time sufficient to form the compound represented by the formula (I). The expression "acting for a time sufficient to form a compound of (predetermined formula)" means combining the reactants and reacting for a time sufficient to produce a target compound, i.e., a compound of the formula, in a detectable amount. By "detectable amount" of a compound is meant the amount of the compound that can be detected by any means readily available to those skilled in the art. Means of detecting compound formation in the reaction mixture include thin layer chromatography (TLC), high performance liquid chromatography (HPLC), gas chromatography (GC), column chromatography, nuclear magnetic resonance spectroscopy (NMR), infrared (IR) Spectroscopy, ultraviolet (UV) or visible (VIS) spectroscopy, and wet chemical analysis. The time required for the production of the desired compound depends on various variables and therefore cannot be generalized. For example, the reaction time may vary depending on temperature, pressure, specific reactants (ie, polyfunctional carbonyl compounds and 1-substituted piperidin-4-ol or 4-aminopiperidine), solvent and catalyst if provided. Different. However, the parameters allowed to produce the desired product can be readily determined by one skilled in the art without undue experimentation.
[78] The reaction can be carried out in a solvent or in the absence of a solvent. When the reaction is carried out in the absence of a solvent, either a multifunctional carbonyl compound, 4-piperidine-ol or 4-aminopiperidine is provided in excess to be used as the reaction medium. Alternatively, the multifunctional carbonyl compound and 4-piperidine-ol or 4-aminopiperidine can be present in stoichiometric amounts. The multifunctional carbonyl compound and 4-piperidine-ol or 4-aminopiperidine can be present as a melt. The reaction is preferably carried out in the presence of an organic solvent. Any solvent compatible with the reagent may be used. Preferred solvents for use in the process of the invention include hydrocarbon solvents such as saturated alkanes; benzene; toluene; xylene; Halogenated hydrocarbons; Ethers such as ethyl ethers; Ring ethers such as tetrahydrofuran and dioxane; Amides such as dimethylformamide; Sulfoxides such as dimethyl sulfoxide; Ketones such as 2-butanone or methyl isobutyl ketone, and the like, or mixtures thereof, but are not limited thereto. More preferred solvents include toluene, benzene and xylene.
[79] When the reaction is carried out in a solvent, the concentration of the multifunctional carbonyl contained in the organic solvent is generally in the range of about 0.025M to 2.5M, preferably about 0.125M to 2M, more preferably about 0.25M to 1.35M. . The molar ratio of 1-substituted piperidin-4-ol or 4-aminopiperidine to the multifunctional carbonyl compound is between about 20: 1 and 1: 5, preferably about 10: 1 to 1: 3 , More preferably between about 5: 1 and 1: 5.
[80] The reaction of the polyfunctional carbonyl compound with 4-piperidine-ol or 4-aminopiperidine produces an alcohol represented by the structural formula DOH. This alcohol is preferably removed from the reaction mixture once formed to aid in the completion of the reaction. Removal of this alcohol can be carried out by all means available to those skilled in the art, such as distillation and / or azeotropic distillation.
[81] The reaction is preferably carried out in the presence of a catalyst. Selective catalysts can be basic or acidic catalysts. The term "base catalyst" means any compound capable of separating protons. Suitable base catalysts for the present invention include alkoxide ions; Hydroxide ions; Amide ions; And amines such as triethylamine, DBU (1,8-diazabicyclo [5.4.0] undec-7-ene) or DBN (1,5-diazabicyclo [4.3.0] non-5-ene) There is, but is not limited to this. When an amine is used as the base, the amine is preferably a tertiary amine.
[82] The term "acid catalyst" means any inorganic or organic acid having at least one acidic proton or Lewis acid. The organic acid comprises at least one acidic functional group, such as one or more of RCO ₂ H, RSO ₃ H, RSO ₂ H, RSH, ROH, RPO ₃ H, RPO ₂ H, wherein R is a hydrocarbyl group All organic compounds are included. Preferred positive assets include HCl, HBr, HI, HNO ₃ , HNO ₂ , H ₂ S, H ₂ SO ₄ , H ₃ PO ₄ , H ₂ CO ₃ , acetic acid, formic acid, propionic acid, butanoic acid, benzoic acid, phthalic acid, oxalic acid , Malonic acid, succinic acid, glutaric acid, adipic acid, methanesulfonic acid and p-toluenesulfonic acid or mixtures thereof. Lewis acids suitable for the process of the invention include aluminum halides, alkylaluminum halides, boron halides, dialkyl tin oxides and derivatives thereof, tin halides, titanium halides, lead halides, zinc halides, iron halides, gallium halides, arsenic halides, copper Halides, cadmium halides, mercury halides, antimony halides, and the like, but are not limited thereto. Preferred Lewis acids include aluminum trichloride, aluminum tribromide, 1,3-diacetoxy-1,1,3,3-tetrabutyldistannoic acid, trimethylaluminum, boron trifluoride, boron trichloride, zinc dichloride , Titanium tetrachloride, titanium (IV) isopropoxide, tin dichloride, tin tetrachloride, tetraalkoxy titanate or mixtures thereof, but is not limited thereto.
[83] The acid or base catalyst may also be a catalyst with a solid support, such as an Amberlyst catalyst.
[84] The catalyst is generally less than about 30 mole percent based on the molar amount of the multifunctional carbonyl compound, preferably less than about 20 mole percent based on the molar amount of the multifunctional carbonyl compound, more preferably multifunctional It is preferably added in an amount of less than about 10 mol% based on the molar amount of carbonyl compound, most preferably less than about 5 mol% based on the molar amount of the multifunctional carbonyl compound.
[85] Preferred base catalysts for use in the process of the invention are methoxide ions. Preferred acid catalysts are Lewis acids. Preferred Lewis acids are 1,3-diacetoxy-1,1,3,3-tetrabutyldistannoic acid.
[86] The reaction preferably proceeds for less than about 20 hours, more preferably less than about 10 hours. The reaction temperature is generally between about room temperature and 150 ° C., for example below the boiling point of the solvent. In addition, the reaction generally proceeds at atmospheric pressure. Representative reaction conditions for forming the compound of formula (I) are shown in the Examples.
[87] Once the compound of formula (I) is formed, it is then recovered from the reaction mixture by any means available to those skilled in the art. Methods for recovering the compound from the reaction mixture include, but are not limited to, chromatography, recrystallization, distillation, extraction, and the like. It is also possible to recover the compound from the reaction mixture using one or more methods.
[88] In a preferred embodiment, the substituted 4-piperidin-4-ol is 1,2,2,6,6-pentamethyl-4-piperidinol or 2,2,6,6-tetramethyl-4-pipe The lidinologo, polyfunctional carbonyl compound is methyl 6- (methoxycarbonylamino) hexanoate, butyl 6- (butoxycarbonylamino) undecanoate, methyl 6- (butoxycarbonylamino) ound Canoate, butyl 6- (methoxycarbonylamino) undecanoate or methyl 6- (methoxycarbonylamino) undecanoate.
[89] Multifunctional carbonyl compounds can be prepared by any method available to those skilled in the art. In one embodiment, the multifunctional carbonyl compound is prepared by reacting lactam with a carbonyl compound. For example, multifunctional carbonyl compounds can be prepared by the reaction of lactams with carbonyl compounds using base catalysts according to the methods disclosed in US Pat. No. 5,300,678, which is expressly incorporated herein by reference.
[90] All lactams can be used in the method of this invention. The size of the lactam ring is preferably between about 4 and 13 atoms. More preferably, the lactam is caprolactam or laurolactam.
[91] The carbonyl compound should include at least one reactive carbonyl group. "Reactive carbonyl group" means any carbonyl group attached to a good leaving group and activated in the nucleophilic acyl substitution direction. The reactive carbonyl group can be for example an ester or acid chloride. Preferably, the carbonyl compound is an ester. More preferred carbonyl compounds are dialkyl carbonates, dialkyl oxalates, dialkyl diesters or alkyl esters. The general structural formula of the carbonyl compound is as follows:
[92]
[93] Wherein m is 0 or 1 and Q is a good leaving group such as chloride or OD, where D is a hydrocarbyl group, preferably methyl, B is a Q or hydrocarbyl group, and Y is CO -C (R ^e R ^f ) _p (where R ^e and R ^f are each hydrogen or hydrocarbyl groups and p is 0 or an integer from about 1 to 20) or CO-C ₆ H _4- (where phenyl The substitution pattern on the rene group, i.e., -C ₆ H _4- , is an ortho, meta or para substitution pattern and one or more hydrogens of the phenylene group can be substituted with hydrocarbyl groups or other functional groups commonly found in organic molecules. ) to be.
[94] When the carbonyl compound is a dialkyl carbonate, the resulting polyfunctional carbonyl compound is a hydrocarbon chain whose one end terminates with an ester functional group and the other end terminates with a urethane functional group. When the carbonyl compound is a dialkyl oxalate, the resulting polyfunctional carbonyl compound is a hydrocarbon chain whose one end terminates with an ester functional group and the other end terminates with an oxamate functional group. When the carbonyl compound is a dialkyl ester, the resulting polyfunctional carbonyl compound is a hydrocarbon chain that contains an amide bond and each terminal terminates with an ester functional group. In the case where the carbonyl compound is an alkyl ester, the resulting polyfunctional carbonyl compound is a hydrocarbon chain whose one end terminates with an ester functional group and the other end terminates with an amide functional group.
[95] The reaction of the carbonyl compound with lactam can be carried out in a solvent or in the absence of a solvent. When the reaction is carried out in the absence of solvent, an excess carbonyl compound may be used as the reaction medium, so that the carbonyl compound is present in excess relative to the lactam. However, lactams may also be present in excess and used as reaction medium. Or the lactam and carbonyl compounds may be present in stoichiometric amounts. The lactams and carbonyl compounds may be present as melts. When the reaction is carried out in the absence of solvent, the excess carbonyl compound or lactam can be recovered and recycled, for example, by distillation. The advantage of not using a solvent is that the problems associated with the disposal of the waste solvent can be avoided.
[96] In other embodiments, one or more different lactams are reacted with one or more different carbonyl compounds. For example, two lactam molecules can be reacted with one molecule of carbonyl compound.
[97] Suitable solvents for the process of the invention include hydrocarbon solvents such as saturated alkanes; benzene; toluene; xylene; Halogenated hydrocarbons; Ethers such as ethyl ethers; Ring ethers such as tetrahydrofuran and dioxane; Amides such as dimethylformamide; Sulfoxides such as dimethyl sulfoxide; Ketones such as 2-butanone or methyl isobutyl ketone; Alcohols and mixtures thereof, but is not limited thereto. When the reaction is carried out in a solvent, the concentration of lactam contained in the solvent is in the range of about 0.025M to 10M, preferably about 0.375M to 6M, more preferably about 0.25M to 4M. The molar ratio of lactam to carbonyl compound is generally between about 1:10 and 5: 1, preferably between about 1: 5 and 2: 1, more preferably between about 1: 2.5 and 1.5: 1.
[98] The reaction proceeds for a time sufficient to form a detectable amount of the multifunctional carbonyl compound. In general, the reaction time is less than about 12 hours. The reaction temperature is generally from room temperature to 150 ° C., for example below the boiling point of the solvent when a solvent is used. The reaction is generally carried out at room temperature.
[99] The present invention also provides an improved method for preparing multifunctional carbonyl compounds. According to the process of the invention, the lactam and carbonyl compound are reacted in the presence of an acid catalyst, preferably a Lewis acid catalyst.
[100] All Lewis acid catalysts can be used according to the process of the invention. For example, any of the aforementioned Lewis acid catalysts can be used. The Lewis acid catalyst is preferably titanium (IV) isopropoxide. Lewis acids are preferred catalysts because they can be easily removed from the reaction mixture. For example, many Lewis acids, such as tetraorganitanate, are readily hydrolyzed by stoichiometric water to form highly insoluble titanium dioxide, which can be easily removed from the reaction mixture by filtration. Other Lewis acids, such as boron trifluoride etherate, are sufficiently volatile and can be easily removed from the reaction mixture by distillation. Thus, the use of Lewis acids is advantageous because it obviates the need to extract the reaction mixture with an aqueous solvent to remove the catalyst. Omission of the extraction step to remove the catalyst reduces the production of aqueous waste that ultimately must be disposed of by the process of the present invention.
[101] In another improved process of the invention, the lactam and carbonyl compound are reacted with an alkoxide anion, preferably a methoxide anion, as a base catalyst. However, this reaction is carried out at less than about 20 ° C, preferably less than about 19 ° C, more preferably less than about 15 ° C. The lactam and carbonyl compound are reacted for less than about 5 hours, preferably less than about 2 hours, more preferably less than about 1 hour.
[102] Reactions carried out at low temperatures are preferred because they can be kept below the flash point of the hot reagents and such low temperature reactions are quite safe. For example, dimethyl carbonate (a common carbonyl compound used in the process of the invention) has a flash point of 19 ° C. The present method of proceeding the reaction at temperatures below 19 ° C., ie below flash point, is much safer than the prior art methods which require higher temperatures.
[103] Once the multifunctional carbonyl compound is formed, the carbonyl compound is first recovered from the reaction mixture and then reacted with 1-substituted piperidin-4-ol or 4-aminopiperidine to form the HALS of the present invention. You can. Multifunctional carbonyl compounds can be recovered by any person skilled in the art. If desired, the polyfunctional carbonyl compound is not recovered from the reaction mixture, but instead a detectable amount of the multifunctional carbonyl compound is formed and then the 1-substituted piperidin-4-ol or 4- Aminopiperidine may also be added. The mono-substituted piperidin-4-ol or 4-aminopiperidine reacts with the multifunctional carbonyl compound to form the HALS of the present invention.
[104] In a preferred process, the compound of formula (I) is prepared by reacting lactam with a carbonyl compound and 1-substituted piperidin-4-ol or 4-aminopiperidine in one step. This method involves reacting the lactam with a carbonyl compound in a first step to form a multifunctional carbonyl compound, and then in the subsequent step, a 1-substituted piperidin-4-ol or 4-amino polyfunctional carbonyl compound. Rather than reacting with piperidine, the lactam and carbonyl compound and 1-substituted piperidin-4-ol or 4-aminopiperidine are combined and reacted simultaneously. The lactam and the carbonyl compound and 1-substituted piperidin-4-ol or 4-aminopiperidine are combined in one reaction vessel and allowed to react for a time sufficient to form a detectable amount of HALS of Formula (I).
[105] The ratio of lactam to carbonyl compound used in embodiments of such methods ranges from about 2: 1 to 1: 4, preferably from about 1: 1 to 1: 2, and lactam to 1-substituted piperidine The ratio of -4-ol or 4-aminopiperidine is about 1: 1 to 1: 6, preferably about 1: 2 to 1: 4.
[106] This one step reaction may be carried out in a solvent or in the absence of a solvent. If a solvent is used, any solvent compatible with the reagent may be used. Representative solvents include, but are not limited to, the solvents described above in the reaction of a polyfunctional carbonyl compound with 1-substituted piperidin-4-ol or 4-aminopiperidine. The reaction of this embodiment is preferably carried out in the presence of a solvent. When using a solvent, the concentration of lactam is generally between about 0.025M and 10M, preferably between about 0.325M and 6M, more preferably between about 0.75M and 4M.
[107] Preferably, the reaction is carried out in the presence of a catalyst. The catalyst may be the same as that used for the reaction of the polyfunctional carbonyl compound with 1-substituted piperidin-4-ol or 4-aminopiperidine. The catalyst is generally used in an amount of less than about 30 mole percent, preferably less than about 20 mole percent, more preferably less than about 10 mole percent, most preferably less than 5 mole percent, relative to the amount of carbonyl compound. .
[108] The carbonyl compound is preferably an ester, ie, Q is OD so that the reaction results in the formation of an alcohol of the structural formula HOD. Once this alcohol is formed, it is preferably removed from the reaction mixture to complete the reaction. The alcohol can be removed by any means available to one skilled in the art, such as distillation and / or azeotropic distillation.
[109] The reaction time is preferably less than about 20 hours, more preferably less than about 10 hours. In general, the reaction temperature is between about room temperature and 250 ° C. In general, the reaction proceeds at atmospheric pressure. Representative reaction conditions for forming HALS of Formula I in one step process are shown in the Examples. Once the HALS of Formula I is formed, this compound can be recovered from the reaction mixture by any means available to those skilled in the art.
[110] Oligomeric HALS Compounds of the Invention
[111] The present invention also provides oligomeric HALS represented by the following formula (II):
[112] Formula II
[113]
[114] In this formula, i, j, k and l are integers between about 0 and 300, preferably between about 0 and 200, more preferably between 0 and about 100. The sum of i, j, k and l is greater than 2, preferably the sum of i, j, k and l is greater than about 3, more preferably greater than about 6. Preferably, at least two of i, j, k and l are one or more or are of formula III:
[115] Formula III
[116]
[117] In this formula, i and j are integers between about 0 and 300, preferably between about 0 and 200, more preferably between 0 and about 100. The sum of i and j is greater than 2. The sum of i and j is preferably greater than about 3, more preferably greater than about 6. At least two of i, j, k and l are preferably one or more.
[118] E and E 'in formula (II) are piperidin-4-ol or 4-aminopiperidine moieties, and F and F' are each derived from a multifunctional carbonyl compound. T may be F, F 'or hydrogen and S may be E, E' or hydrogen.
[119] E-F includes the following:
[120]
[121] E-F 'includes:
[122]
[123] E'-F includes:
[124]
[125] E'-F 'includes:
[126]
[127] In formula (III), M is a diamino or dihydroxy group comprising a 4-aminopiperidine group which is an R group as described above. "Diamino or dihydroxy group" means a group derived from a compound comprising at least two hydroxy groups, at least two amino groups, or at least one amino group and at least one hydroxy group. The amino group can be a primary or secondary amino group.
[128] M-F includes the following:
[129]
[130] M-F 'includes:
[131]
[132] In the oligomer HALS represented by formula III, the diamino or dihydroxy group containing 4-aminopiperidine, ie M, is bound to the polyfunctional carbonyl compound by hydroxy or amino group.
[133] Formulas II and III may be block copolymers or random copolymers, ie EF, E-F ', E'-F and E'-F' units or MF and MF 'units are distributed irregularly through the polymer chain . In the oligomer HALS of the above-mentioned formula II or III, S is hydrogen or a unit derived from piperidin-4-ol or 4-aminopiperidine moiety, having the following structural formula:
[134]
[135] T is a unit derived from hydrogen or a polyfunctional carbonyl compound having the following structural formula:
[136]
[137] In which D is a hydrocarbyl group.
[138] N is an integer between 1 and 15, preferably between 4 and 11, m is 0 or 1 and s is 0 or an integer between about 1 and 10 in the oligomer HALS of Formulas II and III; R ^a , R ^b , R ^c and R ^d are each hydrogen or hydrocarbyl group; Y is CO-C (R ^e R ^f ) _p (where R ^e and R ^f are each hydrogen or hydrocarbyl groups and p is 0 or an integer from about 1 to 20) or CO-C ₆ H ₄ − (where Wherein the substitution pattern on the phenylene group is an ortho, meta or para substitution pattern and one or more hydrogens of the phenylene group may be substituted with a hydrocarbyl group or a functional group generally found in organic molecules); Z is -O- or -NG-, wherein G is H, C ₁ to C ₁₂ alkyl; R ² is hydrogen, C ₁ to C ₈ alkyl or benzyl; R ³ , R ⁴ , R ⁵ and R ⁶ are each hydrogen, C ₁ to C ₈ alkyl, benzyl or phenethyl, or two in situ R additions together with the carbon to which they are attached form C ₅ to C ₁₀ cycloalkyl To; When s is greater than 0, P is NH or O, and when s is 0, P is O or OLO, where L is hydrocarbylene.
[139] As noted above, in the HALS of Formula II, E, E 'and S are units derived from the piperidin-4-ol or 4-aminopiperidine moiety, and F, F' and T are multifunctional carbonyl compounds Units of origin, in the HALS of Formula III, F and F 'are units derived from a multifunctional carbonyl compound, and M is as described above. The molar percentage of units derived from the multifunctional carbonyl compound in the HALS of Formula II is preferably greater than the molar percentage of units derived from the piperidin-4-ol or 4-aminopiperidine moiety. It is preferred that the mole% of units derived from the multifunctional carbonyl compound in HALS of formula III is greater than the mole% of the diamino or dihydroxy group containing the 4-aminopiperidine group, ie M. This is advantageous because multifunctional carbonyl compounds are less expensive.
[140] In the oligomeric HALS of formula (II) R ² is H or C ₁ to C ₄ alkyl; R ³ , R ⁴ , R ⁵ and R ⁶ are each hydrogen or C ₁ to C ₄ alkyl; R ^a , R ^b , R ^c and R ^d are each hydrogen, aromatic or C ₁ to C ₄ alkyl; n is between about 4 and 11; s is preferably between about 2 and 5. In a more preferred embodiment, R ² is hydrogen; R ³ , R ⁴ , R ⁵ and R ⁶ are each methyl; R ^a , R ^b , R ^c and R ^d are each hydrogen, Z is O, n is between 4 and 11, s is 2, m is 0 and P is O.
[141] In another embodiment, R ² is hydrogen, R ³ , R ⁴ , R ⁵ and R ⁶ are methyl, R ^a , R ^b , R ^c and R ^d are each hydrogen, Z is O, n is Is between 4 and 11, and s is zero.
[142] Preferably, in oligomer HALS of formula III, M is N, N'-bis (2,2,6,6-tetramethyl-4-piperidinyl) -1.6-hexanediamine (BPIP) or N- (2, 2,6,6-tetramethylpiperidinol) diethanolamine and n is between about 4 and 11.
[143] Advantageously, the number average molecular weight of the oligomeric HALS compounds of formulas (II) and (III) is generally between about 400 and 20,000, preferably between about 1000 and 15000 and more preferably between about 2000 and 9000.
[144] Synthesis of Oligomeric HALS Compound
[145] The present invention also relates to a process for preparing oligomeric HALS represented by formula (II) and formula (III). Oligomeric HALS of Formula II is prepared by reacting a multifunctional carbonyl compound represented by Formula IV with 1-substituted piperidin-4-ol or 4-aminopiperidine represented by Formula IV-1 :
[146] Formula IV
[147] DO-CO-CR ^a R ^b -(-CR ^c R ^d- ) _n -NH- (Y) _m -CO-OD
[148] [Wherein n is an integer between about 1 to 15, preferably 4 to 11, m is 0 or 1, and R ^a , R ^b , R ^c and R ^d are each hydrogen or hydrocarbyl group; Y is CO-C (R ^e R ^f ) _p (where R ^e and R ^f are each hydrogen or hydrocarbyl groups and p is 0 or an integer from about 1 to 20) or CO-C ₆ H ₄ − (where Wherein the substitution pattern on the phenylene group is an ortho, meta or para substitution pattern and one or more hydrogens of the phenylene group can be substituted with functional groups or hydrocarbyl groups generally observed in organic molecules); D is hydrocarbyl]
[149] Formula IV-1
[150]
[151] In which Z is OH or NHG, wherein G is H or C ₁ to C ₁₂ alkyl; R ¹ is — (CH ₂ ) _s —OH, — (CH ₂ ) _s —NH ₂ , C ₁ to C ₁₈ hydroxyalkoxy or C ₅ to C ₁₂ hydroxycycloalkoxy, where s is from about 1 to An integer between 10, preferably between 2 and 8); R ² is hydrogen, C ₁ to C ₈ alkyl or benzyl; R ³ , R ⁴ , R ⁵ and R ⁶ are each hydrogen, C ₁ to C ₈ alkyl, benzyl or phenethyl or two in situ R additions together with the carbon to which they are attached form C ₅ to C ₁₀ cycloalkyl have.
[152] Oligomeric HALS of Formula III is prepared by reacting a polyfunctional carbonyl compound of Formula IV with a diamino or dihydroxy compound containing a 4-aminopiperidine group. Diamino or dihydroxy compounds are N, N'-bis (2,2,6,6-tetramethyl-4-piperidinyl) -1,6-hexanediamine (BPIP) or N- (2,2, It is preferred to include 6,6-tetramethylpiperidinol) diethanolamine.
[153] Multifunctional carbonyl compounds are prepared by any method available to those skilled in the art. The multifunctional carbonyl compound is preferably prepared by the process of the invention in which the carbonyl compound is reacted with lactam in the presence of Lewis acid or the carbonyl compound is reacted with lactam and alkoxide at low temperature, ie below 20 ° C. However, the carbonyl compound should be one having two reactive carbonyl groups or having one carbonyl group activated with two leaving groups (eg, phosgene or dialkyl carbonate). The leaving group is preferably an ester. Preferred carbonyl compounds include dialkyl carbonates, dialkyl oxalates and dialkyl esters.
[154] The reaction can be carried out in the absence of solvent or in the presence of an organic solvent. When the reaction is carried out without solvent, it contains a polyfunctional carbonyl compound or a 1-substituted piperidin-4-ol or 4-aminopiperidine (for compound II) or 4-aminopiperidine group Either the diamino or dihydroxy compound (in the case of compound III) is provided in excess and can be used as the reaction medium. Alternatively, the difunctional or dihydroxy compound containing a multifunctional carbonyl compound and a 1-substituted piperidin-4-ol or 4-aminopiperidine or 4-aminopiperidine group is provided in stoichiometric amounts. Can be. The reaction may also be carried out in a melt.
[155] It is preferable to perform reaction in an organic solvent. Any solvent may be used as long as it is compatible with the reagents. Preferred solvents for use in the process of the invention include hydrocarbon solvents such as saturated alkanes; benzene; toluene; xylene; Halogenated hydrocarbons; Ethers such as ethyl ethers; Ring ethers such as tetrahydrofuran and dioxane; Amides such as dimethylformamide; Sulfoxides such as dimethyl sulfoxide; Ketones such as 2-butanone or methyl isobutyl ketone, and the like, or mixtures thereof, but are not limited thereto. More preferred solvents include toluene, benzene and xylene or mixtures thereof.
[156] The concentration of the multifunctional carbonyl compound contained in the organic solvent is generally in the range of about 0.025M to 2.5M, preferably about 0.125M to 2M, more preferably about 0.25M to 1.35M. The molar ratio of the multifunctional carbonyl compound used to prepare the oligomer HALS of formula II to the 1-substituted piperidin-4-ol or 4-aminopiperidine or the multiples used to prepare the oligomer HALS of formula III The molar ratio of functional carbonyl compound to diamino or dihydroxy compound containing 4-aminopiperidine groups is between about 5: 1 and 1: 5, preferably between about 2: 1 and 1: 2, more Preferably between about 1.2: 1 and 1: 1.2.
[157] In a preferred embodiment of the process for preparing oligomeric HALS of Formula (II), the substituted piperidin-4-ol or 4-aminopiperidine is N- (2-hydroxyethyl) -2,2,6,6- Tetramethyl-4-piperidinol. In a preferred embodiment of the process for preparing oligomeric HALS of formula III, diamino or dihydroxy compounds containing 4-aminopiperidine groups include BPIP or N- (2,2,6,6-tetramethyl piperidi Nol) diethanolamine or mixtures thereof.
[158] If desired, but preferably the reaction is carried out in the presence of a catalyst. The catalyst can be a base catalyst or an acid catalyst. The base catalyst is preferably a methoxide ion. As the acid catalyst, Lewis acid is preferable. Preferred Lewis acids are 1,3-diacetoxy-1,1,3,3-tetrabutyldistannoic acid.
[159] The catalyst is generally less than about 30 mole percent by weight of the multifunctional carbonyl compound, preferably less than about 20 mole percent by weight of the multifunctional carbonyl compound, more preferably multifunctional carbonyl The amount is added in an amount of less than about 10 mole percent, most preferably less than about 5 mole percent, based on the weight of the multifunctional carbonyl compound.
[160] 1-substituted piperidin-4-ol or 4-aminopiperidine used to prepare oligomer HALS of formula II or diamino containing 4-aminopiperidine group used to prepare oligomer HALS of formula III Or the reaction of the multifunctional carbonyl compound to the dihydroxy compound is carried out for a time sufficient to form a detectable amount of oligomeric HALS of formula II or formula III. Reaction time, temperature and pressure can be readily determined by one skilled in the art without undue experimentation. The reaction time is generally less than about 20 hours, preferably less than about 15 hours, more preferably less than about 10 hours. The reaction temperature is generally from about room temperature to about 150 ° C., for example below the boiling point of the solvent. The reaction is preferably carried out at atmospheric pressure. Representative reaction conditions used to form compounds of Formula II or III are shown in the Examples.
[161] After the oligomeric HALS of formula (II) or (III) is formed, the HALS is recovered from the reaction mixture by any means available to those skilled in the art.
[162] In a preferred method, oligomeric HALS of formulas II and III are lactams and carbonyl compounds of formula II and 1-substituted piperidin-4-ol or 4-aminopiperidine in the preparation of oligomeric HALS of formula II, In preparing the oligomeric HALS of III, a diamino or dihydroxy compound is prepared by reacting in one step:
[163]
[164] Wherein m is 0 or 1 and Q is a good leaving group such as chloride or OD, where D is a hydrocarbyl group, preferably methyl, B is a Q or hydrocarbyl group, and Y is CO -C (R ^e R ^f ) _p (where R ^e and R ^f are each hydrogen or hydrocarbyl groups and p is 0 or an integer from about 1 to 20) or CO-C ₆ H _4- (where phenyl The substitution pattern on the rene group is an ortho, meta or para substitution pattern and one or more hydrogens of the phenylene group may be substituted with hydrocarbyl groups or other functional groups commonly found in organic molecules). Lactam, carbonyl compound and 1-substituted piperidin-4-ol or 4-aminopiperidine, or diamino or dihydroxy compounds containing 4-aminopiperidine groups are combined in one reaction vessel and formulated The reaction is carried out for a time sufficient to form a detectable amount of the compound represented by II or III. The ratio of lactam to carbonyl compound ranges from about 2: 1 to 1: 4, preferably about 1: 1 to 1: 2, with lactam to 1-substituted piperidin-4-ol or 4-aminopiperi The ratio of dine or diamino or dihydroxy compound is about 2: 1 to 1: 2, preferably about 1: 1.
[165] One-step reactions can be carried out in a solvent or in the absence of a solvent. The reaction is preferably carried out in the presence of a solvent. If a solvent is used, any solvent may be used as long as it is compatible with the reagent. Representative solvents include, but are not limited to, the solvents described above in the reaction of a polyfunctional carbonyl compound with 1-substituted piperidin-4-ol or 4-aminopiperidine. If a solvent is used, the concentration of lactam is generally between about 0.075M and 10M, preferably between about 0.375M and 6M and more preferably between about 0.75M and 4M.
[166] If desired, but preferably the reaction is carried out in the presence of a catalyst. It is also possible to use the same catalysts used for the reaction of the polyfunctional carbonyl compounds with the 1-substituted piperidin-4-ols or 4-aminopiperidine. The catalyst is generally used in an amount of less than about 30 mol%, preferably less than about 20 mol%, more preferably less than about 10 mol%, most preferably less than 5 mol% relative to the amount of carbonyl compound. .
[167] Generally, the reaction time is less than about 20 hours, preferably less than about 15 hours, more preferably less than about 10 hours. In general, the reaction temperature is between about room temperature and 250 ° C. Preferably the reaction is carried out at atmospheric pressure. Representative reaction conditions for forming oligomeric HALS in one step according to the method of the present invention can be readily determined by one skilled in the art, but are guided in the Examples.
[168] Once the oligomeric HALS of formula (II) or (III) is formed, the HALS can be recovered from the reaction mixture by any means available to those skilled in the art.
[169] Polymer articles comprising HALS and methods of making the same
[170] HALS of the present invention, ie HALS of formula (I), (II) or (III), is provided as a pure compound or is about 15 to 98% by weight, preferably about 20 to 95% by weight, more preferably about 25 to 90% by weight, more More preferably, it may be provided in the form of a concentrate comprising at least one of about 40 to 70% by weight of the HALS compound of Formula I, II or III and the polymer resin.
[171] HALS compounds of the present invention impart excellent weatherability and sulfur change to the polymer. In addition, HALS compounds of the invention generally exhibit low volatility. Accordingly, the present invention also provides a polymeric article stabilized by addition of a newly discovered effective amount of HALS compound that inhibits at least one of photolysis or pyrolysis, and a process for preparing the same. Any suitable polymer compatible with the HALS composition of the present invention may be combined with one or more HALS of the present invention to form a sunscreen polymeric article. The polymeric article comprises at least one polymeric material and at least one of the HALS of Formula I, II or III in an amount sufficient to inhibit at least one of photolysis or pyrolysis. The polymeric article is about 0.01 to 10% by weight, preferably about 0.03 to about 1% by weight, more preferably about 0.05% of the polymeric material used to form the article and at least one HALS represented by Formula I, II or III. To 0.5% by weight to stabilize. This article can be for example an extrudate, molding, tape, film, fiber or coating.
[172] The method of making the polymeric article is stabilized by combining the polymeric material with about 0.01 to 10% by weight, preferably about 0.03 to about 1% by weight, more preferably about 0.05 to 0.5% by weight of one or more HALS compounds of the present invention. Preparing the polymer composition and molding an article from the polymer composition. Polymer articles can be extrusion, sheet extrusion, injection molding, blow molding, injection blow molding, rotational molding, rolling, thermoforming, compression molding, vacuum molding, pressure molding, reaction injection molding, solvent casting, fiber spinning, and others available to those skilled in the art. It can be prepared by similar techniques. The HALS of the present invention may be added to the polymeric material by any means known in the art, and those skilled in the art will appreciate various methods of combining one or more HALS compounds and one or more polymeric materials to make a polymeric article according to the present invention. It will be easy to see.
[173] In addition, other conventional various additives may be added to the polymeric material, either alone or in combination. Examples of such additives include, but are not limited to, one or more of the following classes:
[174] a. Antioxidant
[175] (i) alkylated monophenols such as 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethyl Phenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- (α-methylcyclohexyl) -4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4 Methoxymethylphenol; Nonylphenols having linear or branched side chains, such as 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6- (1-methylundec-1-yl) phenol, 2,4-dimethyl -6- (1-methylheptadec-1-yl) phenol, 2,4-dimethyl-6- (1-methyltridec-1-yl) phenol, CYANOX® 1790, CYANOX® 2246 And CYANOX® 425 antioxidants (available from Scitech Industries, West Paterson, NJ), IRGANOX® 1010 Antioxidants and IRGANOX® 1076 Antioxidants (Shiba Special, Hothorn, NY) Commercially available in teas) and mixtures thereof;
[176] (ii) alkylthiomethylphenols such as 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6- Ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol and mixtures thereof;
[177] (iii) hydroquinones and alkylated hydroquinones such as 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydro Quinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di -tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate and bis (3,5-di-tert-butyl-4-hydroxyphenyl) adipate .
[178] (iv) tocopherols such as α-tocopherol (vitamin E), β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof;
[179] (v) hydroxylated thiodiphenyl ethers such as 2,2'-thiobis (6-tert-butyl-4-methylphenol), 2,2'-thiobis (4-octylphenol), 4,4 '-Thiobis (6-tert-butyl-3-methylphenol), 4,4'-thiobis (6-tert-butyl-2-methylphenol), 4,4'-thiobis (3,6-di -sec-amylphenol), 4,4'-bis (2,6-dimethyl-4-hydroxyphenyl) disulfide and mixtures thereof;
[180] (vi) alkylidenebisphenols such as 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 2, 2'-methylenebis [4-methyl-6- (α-methylcyclohexyl) phenol], 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-methylenebis (6 -Nonyl-4-methylphenol), 2,2'-methylenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (6-tert-butyl-4-isobutylphenol), 2,2'-methylidenebis [6-α-methylbenzyl) -4-nonylphenol], 2,2'- Methylenebis [6- (α, α-dimethylbenzyl) -4-nonylphenol], 4,4'-methylenebis (2,6-di-tert-butylphenol), 4,4'-methylenebis (6- tert-butyl-2-methylphenol), 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis (3-tert-butyl-5-methyl-2 -Hydroxybenzyl) -4-methylphenol, 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1,1-bis (5-tert-butyl-4- Hydroxy-2-methylphenyl) -3-n-dodecylmercap Butane, ethylene glycol bis [3,3-bis (3'-tert-butyl-4'-hydroxyphenyl) butyrate], bis (3-tert-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene , Bis [2- (3'-tert-butyl-2'-hydroxy-5'-methylbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate, 1,1-bis (3,5-dimethyl 2-hydroxyphenyl) butane, 2,2-bis (3,5-di-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (5-tert-butyl-4-hydroxy- 2-methylphenyl) -4-n-dodecylmercaptobutane, 1,1,5,5-tetra (5-tert-butyl-4-hydroxy-2-methylphenyl) pentane and mixtures thereof;
[181] (vii) O-, N- and S-benzyl compounds such as 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy -3,5-dimethylbenzyl mercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzyl mercaptoacetate, tris (3,5-di-tert-butyl-4-hydroxybenzyl ) Amine, bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl -3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate and mixtures thereof;
[182] (viii) hydroxybenzylate malonates, such as dioctadecyl-2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, dioctadecyl-2- (3-tert -Butyl-4-hydroxy-5-methylbenzyl) malonate, dododecylmercaptoethyl-2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, bis [4 -(1,1,3,3-tetramethylbutyl) phenyl] -2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate and mixtures thereof;
[183] (ix) aromatic hydroxybenzyl compounds such as 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis ( 3,5-di-tert-butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxy Oxybenzyl) phenol and mixtures thereof;
[184] (x) triazine compounds such as 2,4-bis (octylmercapto-6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2- Octylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3 , 5-di-tert-butyl-4-hydroxyphenoxy) -1,3,5-triazine, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenoxy ) -1,3,5-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4- tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenylethyl) -1,3 , 5-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -hexahydro-1,3,5-triazine, 1,3,5 -Tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate and mixtures thereof;
[185] (xi) benzylphosphonates such as dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphoate , Dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, 3, Calcium salts of monoethyl ester of 5-di-tert-butyl-4-hydroxybenzylphosphonic acid, and mixtures thereof;
[186] (xii) acylaminophenols such as 4-hydroxylauranilide, 4-hydroxysteaanylide and octyl N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate, and Mixtures thereof;
[187] (xiii) β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid ester; β- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid ester; β- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid ester; 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid and monohydric or polyhydric alcohols such as methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1 , 9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N , N'-bis (hydroxyethyl) oxamide, 3-thiaundanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7 Esters of trioxabicyclo [2.2.2] octane, and mixtures thereof;
[188] (xiv) Amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, such as N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropy Onyl) hexamethylenediamine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine, and mixtures thereof;
[189] (xv) ascorbic acid (vitamin C) or salts or esters thereof;
[190] (xvi) amine antioxidants such as N, N'-diisopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-bis (1, 4-dimethylpentyl) -p-phenylenediamine, N, N'-bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N'-bis (1-methylheptyl) -p- Phenylenediamine, N, N'-dicyclohexyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N'-bis (2-naphthyl) -p-phenylene Diamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N- (1-methylheptyl) -N '-Phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4- (p-toluenesulfonamoyl) diphenylamine, N, N'-dimethyl-N, N '-Di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N- (4-tert -Octylphenyl) -1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamines such as p, p'-di-tert-octyldiphenylamine, 4-n -Butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis (4-methoxyphenyl) amine, 2,6- Di-tert-butyl-4-dimethylaminomethylphenol, 2,4'-diaminophenylmethane, 4,4'-diaminodiphenylmethane, N, N, N ', N'-tetramethyl-4,4 '-Diaminodiphenylmethane, 1,2-bis [(2-methylphenyl) amino] ethane, 1,2-bis (phenylamino) propane, (o-tolyl) biguanide, bis [4- (1', 3'-dimethylbutyl) phenyl] amine, tert-octylated N-phenyl-1-naphthylamine, mixture of mono and dialkylated tert-butyl / tert-octyldiphenylamine, mono and dialkylated nonyldi Mixtures of phenylamines, mixtures of mono and dialkylated dodecyldiphenylamines, mixtures of mono and dialkylated isopropyl / isohexyldiphenylamines, mixtures of mono and dialkylated tert-butyldiphenylamines, 2,3 -Dihydro-3,3-dimethyl-4H-1,4-benzothiazine, pheno Azine, a mixture of mono and dialkylated tert-butyl / tert-octyl phenothiazine, a mixture of mono and dialkylated tert-octylphenothiazine, a mixture of mono and dialkylated tert-allylphenothiazine, N, N, N ', N'-tetraphenyl-1,4-diaminobut-2-ene, N, N-bis (2,2,6,6-tetramethylpiperid-4-yl) hexamethylenediamine, Bis (2,2,6,6-tetramethylpiperid-4-yl) sebacate, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethyl Piperidin-4-ol and mixtures thereof;
[191] b. Conventional UV Absorbers and Light Stabilizers
[192] (i) 2- (2'-hydroxyaryl) benzotriazoles such as 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl -2'-hydroxyphenyl) benzotriazole, 2- (5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5 '-(1,1, 3,3-tetramethylbutyl) phenyl) benzotriazole or 2- (2H-benzotriazol-2-yl) -4-tert-octyl-phenol [CYASORB (available from Cytec Industries, West Paterson, NJ) UV-5411 LightStabilizer], 2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2) '-Hydroxy-5'-methylphenyl) -5-chloro-benzotriazole, 2- (3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl) -benzotriazole, 2- (2'-hydroxy-4'-octoxyphenyl) benzotriazole, 2- (3 ', 5'-di-tert-amyl-2'-hydroxyphenyl) benzotriazole, 2- (3', 5'-bis (α, α-dimethylbenzyl) -2'-hydroxyphenyl) -benzotri Sol; 2- (3'-tert-butyl-2'-hydroxy-5 '-(2-octyloxycarbonylethyl) phenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-5 '-[2- (2-ethylhexyloxy) -carbonylethyl] -2'-hydroxyphenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy -5 '-(2-methoxycarbonylethyl) phenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonyl Ethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '-(2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert- Butyl-5 '-[2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'- Mixture of methylphenyl) benzotriazole and 2- (3'-tert-butyl-2'-hydroxy-5 '-(2-isooctyloxycarbonylethyl) phenylbenzotriazole, 2- [3'-tert- Butyl-5 '-(2-methoxycarbonylethyl) -2'-hydroxyphenyl] benzotriazole and polyethylene glycol 300 [R-CH ₂ CH-COO (CH ₂ ) ₃ ] _2- (where R is 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-yl phenyl) [TINUVIN, commercially available from Ciba Specialty 2,2-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-yl phenol], and mixtures thereof, transesterification products of 900 Light Stabilizer] ;
[193] (ii) 2-hydroxybenzophenones such as 4-hydroxy, 4-methoxy, 4-octoxy CYASORB® UV-531 Light Stabilizer, (commercially available from Cytec Industries), 4-decyloxy, 4 Dodecyloxy, 4-benzyloxy, 4,2 ', 4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy compounds, and mixtures thereof;
[194] (iii) esters of substituted and unsubstituted benzoic or salicylic acid compounds such as 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis (4-tert-butyl Benzoyl) resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl- 4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, and 2-methyl-4,6-di-tert-butylphenyl-3,5-di-tert- Butyl-4-hydroxybenzoate and mixtures thereof;
[195] (iv) acrylate or alkoxycinnamates such as ethyl α-cyano-β, β-diphenylacrylate, isooctyl α-cyano-β, β-diphenylacrylate, methyl α-carbomethoxycinnamate , Methyl α-cyano-β-methyl-p-methoxycinnamate, butyl α-cyano-β-methyl-p-methoxycinnamate, methyl α-carbomethoxy-p-methoxycinnamate, N -(β-carbomethoxy-β-cyanovinyl) -2-methylindolin, and mixtures thereof;
[196] (v) 1: 1 or with or without additional ligands such as nickel (II) complexes of nickel compounds such as amines and thio-bisphenols, for example n-butylamine, triethanolamine or N-cyclohexyldiethanolamine Nickel complex of 2,2'-thio-bis [4- (1,1,3,3-tetramethylbutyl) phenol] including 1: 2 complex, nickel dibutyldithiocarbamate, 4-hydroxy- Nickel salts of monoalkyl esters, including methyl or ethyl esters of 3,5-di-tert-butylbenzylphosphonic acid, nickel complexes of ketoxime including 2-hydroxy-4-methylphenyl undecyl ketoxime, with or without additional ligands Nickel complex of 1-phenyl-4-lauroyl-5-hydroxypyrazole, and mixtures thereof;
[197] (vi) steric hindered amines and their N compounds (eg, N-alkyl, N-hydroxy, N-alkoxy and N-acyl), such as bis (2,2,6,6-tetramethylpiperidine-4 -Yl) sebacate, bis (2,2,6,6-tetramethylpiperidin-4-yl) succinate, bis (1,2,2,6,6-pentamethylpiperidin-4-yl ) Sebacate, bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (1,2,2,6,6-pentamethylpiperidine- 4-yl) -n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4- Condensates of hydroxypiperidine and succinic acid, N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) hexamethylenediamine and 4-tert-octylamino-2,6 Condensates of dichloro-1,3,5-triazine, tris (2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate, tetrakis (2,2,6,6- Tetramethylpiperidin-4-yl) -1,2,3,4-butanetetracarboxylate, 1,1 '-(1,2-ethane Yl) bis (3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6 -Tetramethylpiperidine, bis (1,2,2,6,6-pentamethylpiperidyl) -2-n-butyl-2- (2-hydroxy-3,5-di-tert-butylbenzyl ) Malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, bis (1-octyloxy-2, 2,6,6-tetramethylpiperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate, N, N'-bis (2,2, 6,6-tetramethylpiperidin-4-yl) condensate of hexamethylenediamine with 4-morpholino-2,6-dichloro-1,3,5-triazine, 2-chloro-4,6- Condensates of bis (4-n-butylamino-2,2,6,6-tetramethylpiperidyl) -1,3,5-triazine with 1,2-bis (3-aminopropylamino) ethane, 2 -Chloro-4,6-bis (4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl) -1,3,5-triazine and 1,2-bis- (3- Condensates of aminopropylamino) ethane, 8-az Tyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, 3-dodecyl-1- (1-ethanoyl -2,2,6,6-tetramethylpiperidin-4-yl) pyrrolidine-2,5-dione, 3-dodecyl-1- (2,2,6,6-tetramethylpiperidine -4-yl) pyrrolidin-2,5-dione, 3-dodecyl-1- (1,2,2,6,6-pentamethylpiperidin-4-yl) pyrrolidine-2,5 A mixture of -dione, 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, N, N'-bis (2,2,6,6-tetramethyl Condensate of piperidin-4-yl) hexamethylenediamine with 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, 1,2-bis (3-aminopropylamino) ethane, Condensates of 2,4,6-trichloro-1,3,5-triazine and 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. [136504-96-6]), N- (2,2,6,6-tetramethyl piperidin-4-yl) -n-dodecylsuccinimide, N- (1,2,2,6, 6-pentamethylpiperidin-4-yl) -n-dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4- Oxoospiro [4.5] decane, oxo-piperazinyl-triazine or so-called PIP-T HALS, such as GOODRITE® 3034, 3150 and 3159, commercially available from BF Goodrich Chemical Company, Akron, Ohio Analogous materials disclosed in US Pat. No. 5,071,981, optically binding HALS, such as SANDUVOR® PR-31 and PR-32, commercially available from Clariant Corporation, Charlotte, NC, and similar materials disclosed in British Application No. 2269819, Reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospyro [4.5] decane and epichlorohydrin. Examples of tetramethylpiperidine-derived HALS include CYASORB® UV-3346 Light Stabilizer (commercially available from Cytec Industries), SANDUVOR® 3055 HALS, SANDUVOR® 3056 HALS and SANDUVOR® 3058 HALS (commercially available from Sandoz Corporation, Charlotte, NC), CHIMASORB® 944 Stabilizer, TINUVIN® 622 Stabilizer, and TINUVIN® 144 Stabilizer (commercially available from Shiva Specialties, respectively) and Mixtures thereof. Also, US Pat. Nos. 5,106,891, 4,740,542, 4,619,956, 4,426,471, 4,426,472, 4,356,307, 4,344,876, 4,314,933, which are incorporated herein by reference; See GB-A-2269819, EP-A-309400, EP-A-309401, EP-A-309402 and EP-A-0434608.
[198] (vii) oxamides, oxanilides, benzoxazinones, benzoxazoles or triazines such as 2,2 '-(1,4-methylene) bis [4H-3,1-benzoxazin-4-one] (CYASORB (Trademark) UV-3638 Light Stabilizer (commercially available from Cytec Industries), 4,4'-dioctyloxy oxanilide, 2,2'-diethoxy oxanilide, 2,2'-dioctyloxy-5, 5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butyloxanide, 2-ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) oxamide, 2-ethoxy-5-tert-butyl-2'-ethyloxanide, and 2-ethoxy-2'-ethyl-5,4'- A mixture of di-tert-butoxanilide, a mixture of o- and p-methoxy disubstituted oxanilides and a mixture of o- and p-ethoxy disubstituted octyloxyphenyl-1,3,5-triazine, 2 -(2-hydroxy-4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl)- 4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4, 6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, 2- (2-hydroxy-4-tridecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2 -Hydroxy-4- (2-hydroxy-3-butyloxypropyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2- Hydroxy-4- (2-hydroxy-3-octyloxypropyloxy) -phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4- Dodecyloxy / tridecyloxy-2-hydroxypropoxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [ 2-hydroxy-4- (2-hydroxy-3-dodecyloxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- ( 2-hydroxy-4-hexyloxy) phenyl-4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2,4,6-tris [2-hydroxy-4- (3-part Methoxy-2-hydroxypropoxy) phenyl] -1,3,5-triazine, 2- (2-hydroxyphenyl) -4- (4-methoxyphenyl) -6-phenyl-1,3,5 Triazine and CYAGARD® UV-1164L Light Stabilizer (commercially available from Cytec Industries) and mixtures thereof;
[199] (c) metal deactivators such as N, N'-diphenyloxamide, N-salicyl-N'-salicyloyl hydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis (benzylidene) oxalyl dihydrazide, oxa Nilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N, N'-diacetyladifoyl dihydrazide, N, N'-bis (salicyloyl) oxalyl dihydrazide , N, N'-bis (salicyloyl) thiopropionyl dihydrazide and mixtures thereof;
[200] (d) phosphites and phosphonites including peroxide degradants such as alkyl phosphites, aryl phosphites and aralkyl phosphites such as triphenyl phosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite, tris ( Nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite ULTRANOX® 618 Antioxidant, bis- (2,4-di-tert-butylphenyl) penta Erythritol diphosphite ULTRANOX (trademark) 626 Antioxidant (commercially available from GE Specialty Chemicals, Parkersburg, West Virginia, USA), Tris (2,4-di-tert-butylphenyl) phosphite, diisodecyl penta Erythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (isodecyloxy) pentaerythritol diphosphite, bis (2,4-di -tert- Tyl-6-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tris (tert-butyl) phenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4 -Di-tert-butylphenyl) -4,4'-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo [d, g] -1,3,2-dioxaphosphosine, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzo [d, g] -1,3,2-di Oxaphosphosine, bis (2,4-di-tert-butyl-6-methylphenyl) methylphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) ethylphosphite, and mixtures thereof;
[201] (e) hydroxylamines such as N, N-dibenzylhydroxylamine, N, N-diethylhydroxylamine, N, N-dioctylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-ditetradecylhydroxylamine, N, N-dihexadecylhydroxylamine, N, N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecyl-hydroxylamine, N-heptadecyl- N-octadecylhydroxylamine, N, N-dialkylhydroxylamine from hydrogenated tallow fatty acid amine and mixtures thereof;
[202] (f) nitrons such as N-benzyl-alpha-phenyl nitron, N-ethyl-alpha-methyl nitron, N-octyl-alpha-heptyl nitron, N-lauryl-alpha-undecyl nitron, N -Tetradecyl-alpha-tridecyl nitron, N-hexadecyl-alpha-pentadecyl nitron, N-octadecyl-alpha-heptadecyl nitron, N-hexadecyl-alpha-heptadecyl nitron, N-octa N, N-dialkylhydroxy made from decyl-alpha-pentadecyl nitron, N-heptadecyl-alpha = heptadecyl nitron, N-octadecyl-alpha-hexadecyl nitron, hydrogenated Uji fatty acid amine Nitrons derived from amines, and mixtures thereof;
[203] (g) thiosynergists, such as dilauryl thiodipropionate and distearyl thiodipropionate and mixtures thereof;
[204] (h) peroxide decontamination agents, such as esters of β-thiodipropionic acid, for example lauryl, stearyl, myristyl or tridecyl esters, zinc salts of mercaptobenzimidazole or 2-mercaptobenzimidazole, Zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis (β-dodecylmercapto) propionate and mixtures thereof;
[205] (i) copper salts, divalent manganese salts and mixtures thereof mixed with polyamide stabilizers such as iodides and / or phosphorus compounds;
[206] (j) basic co-stabilizers such as melamine, polyvinylpyrrolidone, dicyanamide, triallyl cyanurate, urea compound, hydrazine compounds, amines, polyamides, polyurethanes, alkali metal salts of alkaline fatty acids and alkaline earth metal salts Calcium stearate, zinc stearate, manganese behenate, manganese stearate, sodium lysoleate and potassium palmitate, antimony pyrocatecholate, tin pyrocatecholate, and mixtures thereof;
[207] (k) phosphates, carbonates and sulfates of nucleating agents such as inorganic materials such as talc and metal oxides (eg titanium oxide or magnesium oxide) and preferably alkaline earth metals; Organic compounds such as mono or polycarboxylic acids and salts thereof such as 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate and sodium benzoate; Polymeric compounds such as ionic copolymers (“ionomers”) and mixtures thereof;
[208] (l) fillers and reinforcing agents such as calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and other natural products, powders or fibers, and synthetic fibers And mixtures thereof;
[209] (m) Benzofuranone and indolinones such as US Pat. Nos. 4,325,863, 4,338,244, 5,175,312, 5,216,052 and 5,252,643 and DE-A-4316611, DE-A-4316622, DE-A-4316876 , EP-A-0589839 and EP-A-0591102; 3- [4- (2-acetoxy-ethoxy) phenyl] -5,7-di-tert-butyl-benzofuran-2-one, 5,7-di-tert-butyl-3- [4- ( 2-stearoyloxyethoxy) -phenyl] benzofuran-2-one, 3,3'-bis [5,7-di-tert-butyl-3- (4- [2-hydroxyethoxy] phenyl ) Benzofuran-2-one], 5,7-di-tert-butyl-3- (4-ethoxyphenyl) benzofuran-2-one, 3- (4-acetoxy-3,5-dimethylphenyl) -5,7-di-tert-butyl-benzofuran-2-one, 3- (3,5-dimethyl-4-pivaloyloxyphenyl) -5,7-di-tert-butyl-benzofuran-2 -One, and mixtures thereof;
[210] (n) sulfur-containing antioxidants such as organic sulfides and disulfides such as distearyl thiodipropionate CYANOX® STDP Antioxidant (commercially available from Cytec Industries), pentaerythritol tetrakis (beta- Laurylthiopropionate) SEENOX® 412 S Antioxidant (commercially available from Witco Chemical Corporation, Brooklyn, NY), and mixtures thereof. For example, one or more of these additives may be mixed. For example, CYANOX® 2777 Antioxidant, a commercial product of Cytec Industries, contains a phenolic antioxidant and a phosphite antioxidant. All of these compositions may comprise quenching agents such as CYASORB® UV-1084 Light Stabilizer, a commercial product from Cytec Industries, and CYASORB® UV-531 Light Stabilizer.
[211] (o) Other additives, such as acid impurity removers, antistatic agents, foaming agents, catalysts, purifiers, emulsifiers, fillers, refractory materials, fluorescent bleaches, infrared absorbers, leveling aids, lubricants, metal deactivators, mold release agents, nucleating agents, optical brighteners , Pigments, plasticizers, flow additives and mixtures thereof.
[212] The invention also relates to an additive composition comprising HALS represented by the formula (I), (II) or (III) and at least one additive described above. The amount of HALS to other additives is between about 500: 1 and 1: 500 (by weight).
[213] The total content of the additive may be between about 10% by weight or less, preferably between about 0.1 and about 5% by weight, more preferably between about 0.2 and 3% by weight, based on the weight of the polymer.
[214] Photostabilized polymeric articles can be prepared from polymeric materials that have been chemically or physically incorporated into the polymeric materials of the present invention. Non-limiting examples of polymer materials that can be stabilized as such include polyolefins; Polyester; Polyethers; Polyketones; Polyamides; Natural and synthetic rubbers; Polyurethane; polystyrene; High impact polystyrene; Polyacrylates; Polymethacrylates; Polyacetals; Polyacrylonitrile; Polybutadiene; polystyrene; ABS; SAN (styrene acrylonitrile); ASA (acrylate styrene acrylonitrile); Cellulose acetate butyrate; Cellulose polymers; Polyimide; Polyamideimide; Polyetherimide; Polyphenylsulfide; PPO; Polysulfones; Polyethersulfones; Polyvinyl chloride; Polycarbonate; Polyketones; Aliphatic polyketones; Thermoplastic TPO; Amino resin crosslinked polyacrylates and polyesters; Polyisocyanate crosslinked polyesters and polyacrylates; Phenol / formaldehyde, urea / formaldehyde and melamine / formaldehyde resins; Dry and undrying alkyd resins; Alkyd resins; Polyester resins; Acrylate resins crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, carbamates and epoxy resins; Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic and aromatic glycidyl compounds crosslinked with anhydrides or amines; Polysiloxanes; Activated unsaturation of amines or blocked amines and Michael addition polymers with methylene compounds, activated unsaturation of ketimines and michael addition polymers with methylene compounds, combinations with polyketimines and unsaturated acrylic resins in combination with unsaturated acrylic polyacetoacetate resins Polyketamine; Radiation curable compositions; Epoxy melamine resins; Organic dyes; Beauty products; Cellulosic paper compositions; Photographic film paper; ink; And combinations thereof.
[215] Degradable polymers can be any polymer that requires stabilization and include homopolymers and copolymers of various monomers. This polymer may be an additive polymer, a condensation polymer, a graft polymer, a thermoset polymer, a photopolymer, a polymer blend or a thermoplastic polymer. These include polymer films such as fibers and polypropylene films; It may be in the form of a thin film such as a solvent-based coating, an aqueous coating, a dry lacquer, a powder coating, a gel coat or the like or in the form of a molded article. Examples of degradable polymers that can be stabilized include, but are not limited to:
[216] 1. Monoolefins and diolefins such as but not limited to ethylene, propylene, isobutylene, butene, methylpentene, hexene, heptene, octene, isoprene, butadiene, hexadiene, dicyclopentadiene, ethylidene and cycloolefins, such as Homopolymers and copolymers of cyclopentene and norbornene; For example polyethylene (which may be crosslinked in some cases) such as high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultra high molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE) ), Low density polyethylene (LDPE), linear low density polyethylene (LLDPE), branched low density polyethylene (BLDPE) or polymers of polypropylene (PP) or ethylene propylene diene monomer (EPDM); And combinations thereof.
[217] 2. Carbon monoxide and / or other vinyl monomers such as acrylic acid and methacrylic acid, acrylates and methacrylates, acrylamides, acrylonitrile, styrene, vinyl acetates (such as ethylene / vinyl acetate copolymers (EVA)), vinyl halides Copolymers of one or more monoolefins and / or diolefins with vinylidene halides, maleic anhydride and allyl monomers such as allyl alcohol, allyl amine, allyl glycidyl ether and compounds thereof; And combinations thereof.
[218] 3. hydrocarbon resins (such as C ₅ to C ₉ ) and their hydrogenated variants and mixtures of polyalkylenes and starches; And combinations thereof.
[219] 4. Homopolymers and copolymers of styrenes such as styrene, p-methylstyrene and α-methylstyrene, such as polystyrene, polyalphamethylstyrene, high impact polystyrene (HIPS) and combinations thereof.
[220] 5. One or more styrene and other vinyl monomers such as olefins and diolefins (eg ethylene, isoprene and / or butadiene), acrylic acid and methacrylic acid, acrylates and methacrylates, acrylamides, acrylonitrile, Copolymers with vinyl acetate (such as ethylene / vinyl acetate copolymer), vinyl halides, vinylidene halides, maleic anhydride and allyl compounds such as allyl alcohol, allyl amine, allyl glycidyl ether; And combinations thereof.
[221] 6. Styrene graft copolymers on polybutadiene, polybutadiene / styrene copolymer and polybutadiene / acrylonitrile copolymer; Styrene (or α-methylstyrene) and acrylonitrile (or methacrylonitrile) graft copolymers on polybutadiene; Styrene and maleic anhydride graft copolymers on polybutadiene; Styrene, acrylonitrile and maleic anhydride or maleimide graft copolymers on polybutadiene; Acrylonitrile / styrene / acrylonitrile polymer (ASA), styrene and acrylonitrile graft copolymers on ethylene / propylene / diene copolymers; Styrene and acrylonitrile on polyalkyl acrylates or methacrylates; And styrene and acrylonitrile on acrylate / butadiene (ABS) copolymers; And combinations thereof.
[222] 7. halogen-containing polymers such as polyvinylchloride (PVC), chlorinated polyethylene (CPE), or polychloroprene; Chlorinated rubber; Chlorinated and brominated isobutylene / isoprene copolymers; Chlorinated or sulfochlorinated polyethylene; Copolymers of ethylene and chlorinated ethylene; Epichlorohydrin polymers and copolymers; And polymers and copolymers of halogen containing vinyl compounds such as vinyl chloride, vinylidene chloride, vinyl fluoride and / or vinylidene fluoride, other vinyl monomers or other polyvinyl halides; And combinations thereof.
[223] 8. homopolymers and copolymers derived from α, β-unsaturated acids and compounds thereof such as acrylic acid, methacrylic acid, acrylate, methacrylate, acrylamide and acrylonitrile; And combinations thereof.
[224] 9. Unsaturated monomers other than those described in (5), such as olefins and diolefins (e.g. butadiene), styrene, vinyl halides, maleic anhydride and allyl monomers such as allyl alcohol, allyl amine, allyl glycidyl ether Copolymers with; And combinations thereof.
[225] 10. Unsaturated alcohols and amines or acyl compounds or acetals thereof, such as vinyl alcohol (such as polyvinyl alcohol crosslinked polyvinyl alcohol), vinyl acetate, vinyl stearate, vinyl benzoate, vinyl maleate, vinyl butyral, allyl alcohol, Homopolymers and copolymers derived from allyl amine, allyl glycidyl ether, allyl phthalate and allyl melamine; And copolymers of these monomers with other ethylenically unsaturated monomers described above; And combinations thereof.
[226] 11. Homopolymers and copolymers of cyclic ethers such as alkylene glycols and alkylene oxides, and copolymers with bisglycidyl ethers; And combinations thereof.
[227] 12. polyacetals such as polyoxymethylene (POM) and polyoxymethylene containing ethylene oxide as comonomer; And polyoxymethylene modified with thermoplastic polyurethanes, acrylates and / or MBS; And combinations thereof.
[228] 13. polyphenylene oxide (PPO) and sulfides; And combinations thereof.
[229] 14. Hydroxy functional components such as polyurethanes (PUR) derived from polyhydric alcohols, polyethers, polyesters, polyacryl and / or polybutadienes on the one hand and aliphatic and / or aromatic isocyanates on the other hand; And precursors thereof, including isocyanate crosslinked polymers; And combinations thereof.
[230] 15. Polyamides (PA) and copolyamides derived from diamines, dicarboxylic acids and / or aminocarboxylic acids or the corresponding lactams, such as NYLON® plastics such as polyamide 4, polyamide 6, poly Amide 6/6 /, polyamide 6/10, polyamide 6/9, polyamide 6/12, polyamide 4/6, polyamide 12/12, polyamide 11 and polyamide 12; aromatic polyamides derived from m-xylene diamine and adipic acid; Polyamides prepared from hexamethylene diamine and isophthalic acid and / or terephthalic acid in the presence or absence of an elastomer as modifier, such as poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; Block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers, chemically bonded or grafted elastomers, or polyethers such as polyepoxides, polyethylene glycols, polypropylene glycols or polytetramethylene glycols; And polyamides condensed during processing (RIM polyamide systems); And combinations thereof.
[231] 16. polyurea, polyimide, polyamide-imide, polyetherimide, polyesterimide, polyhydantoin and polybenzimidazole; And combinations thereof.
[232] 17. Polyesters derived from dicarboxylic acids, diols and / or hydroxycarboxylic acids or the corresponding lactones such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), glycol modified polyethylene terephthalate ( PETG), polyethylene terephthalate (PCTG) modified with 1,4-cyclohexanedimethanol, poly-1,4-dimethylcyclohexane terephthalate and polyhydroxybenzoate, and block copolyethers from hydroxyl terminal ethers ester; Polyester modified with polycarbonate or MBS; PEN, PTT; And combinations thereof.
[233] 18. Polycarbonates (PC) such as resins and polyester carbonates include polycarbonates based on divalent phenols such as 2,2-bis- (4-hydroxyphenyl) propane (bisphenol A); 2,4-bis (4-hydroxyphenyl) -2-methylbutane; 1,1, -bis (4-hydroxyphenyl) -cyclohexane; 2,2-bis- (3-chloro-4-hydroxyphenyl) propane; 4,4'-sulfonyldiphenol; And 1,1-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane; And combinations thereof. In addition, polycarbonate copolymers comprising two or more phenols, branched polycarbonates obtained by reacting polyvalent aromatic compounds with divalent phenols and carbonate precursors, and polycarbonates comprise a significant portion of the formulation (ie, at least 20%, preferably Preferably at least 50%) polymer blends are preferred. Preferred resins for all layers are bisphenol A polycarbonates.
[234] US Pat. No. 5,288,788 discloses polycarbonates and polyester carbonates, in particular aromatic polycarbonates such as 2,2-bis (4-hydroxyphenyl) propane or 1,1-bis (4-hydroxyphenyl) cyclohexane Polycarbonate is described. Mixtures of each of these polymers (polycompounds) or mixtures of these polymers with other polymers, such as polyolefins, polyacrylates, polydienes or other elastomers in the form of impact strength modifiers (polycompounds) are also HALS compounds of the invention. Can be stabilized by
[235] Preferred among these compounds are polycarbonates, polyesters, polyamides, polyacetals, polyphenylene oxides and polyphenylene sulfides, with polycarbonate being particularly preferred. These compounds are to be understood in particular that the repeat units of the constituent form are polymers corresponding to the formula:
[236]
[237] In this formula, A is a divalent phenol radical. Suitable examples of A are given in US Pat. Nos. 4,960,863 and DE-A-3 922 496, which are incorporated herein by reference. “A” can be derived from hydroquinone, resorcinol, dihydroxybiphenylene or bisphenol in the generic sense, for example bis (hydroxyphenyl) alkane, cycloalkane, sulfide, ether, ketone, sulfone , Sulfoxide, α, α'-bis (hydroxyphenyl) -diisopropylbenzene, for example compound 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl 4-hydroxyphenyl) -propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, or represented by the formula It can be derived from the compound:
[238]
[239]
[240] 19. Polysulfones, polyether sulfones and polyether ketones.
[241] 20. aldehyde condensation resins such as crosslinked polymers derived from phenol / formaldehyde resins, urea / formaldehyde resins and melamine / formaldehyde resins; And combinations thereof.
[242] 21. dry and non-dry alkyd resins; Combinations thereof.
[243] 22. unsaturated polyester resins derived from copolyesters obtained by reaction of vinyl compounds with polyhydric alcohols and saturated and unsaturated dicarboxylic acids as crosslinking agents, and halogen-containing variants thereof; And combinations thereof.
[244] 23. Crosslinkable acrylic resins derived from substituted acrylates such as epoxy acrylate, hydroxy acrylate, isocyanato acrylate, urethane acrylate or polyester acrylate; And combinations thereof.
[245] 24. Acrylate resins, polyester resins and alkyd resins crosslinked by melamine resins, urea resins, isocyanates, isocyanurates, carbamates or epoxy resins; And combinations thereof.
[246] 25. Aliphatic, cycloaliphatic, heterocyclic and / or aromatic glycidyl compounds crosslinked by conventional curing agents such as anhydrides or amines, such as crosslinked epoxy resins derived from bisphenol A and bisphenol F; And combinations thereof.
[247] 26. Natural polymers such as cellulose, rubber, gelatin and chemically modified homogeneous compounds thereof, such as cellulose acetate, cellulose propionate and cellulose ethers such as cellulose butyrate, nitrocellulose or methyl cellulose, and rosin and compounds thereof; And combinations thereof.
[248] 27. polysiloxanes; And combinations thereof.
[249] 28. Michael addition polymers of acrylates and activated unsaturated and / or methylene compounds such as methacrylates, maleates and acetoacetates with amines or blocked amines (eg, ketimines); And combinations thereof.
[250] 29. Any mixture or combination of the foregoing compounds, such as PP / EPDM, polyamide / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBTP / ABS, PC / ASA, PC / PBT, PVC / CPE, PVC / acrylate, POM / thermoplastic PUR, PC / thermoplastic polyurethane, POM / acrylate, POM / MBS, PPO / HIPS, PPO / PA6.6 and copolymers, PA / HDPE, PP / HDPE, PP / LDPE, LDPE / HDPE, LDPE / EVA, LDPE / EAA, PA / PP, PA / PPO, PBT / PC / ABS, PBT / PET / PC etc.
[251] 30. Naturally occurring and synthetic organic materials, such as mineral oils, animal fats and vegetable fats, oils and waxes, or synthetic esters (eg phthalates, adipates, phosphates or trimellitates) based oils which may be mixtures of the following compounds: , Mixtures of fats or waxes and mineral oils with synthetic esters in any ratio.
[252] 31. An aqueous emulsion of natural or synthetic rubber, such as natural latex or latex of carboxylated styrene / butadiene copolymers; And combinations thereof.
[253] 32. Unsaturated acrylic polyacetoacetate resins or unsaturated acrylic resins such as urethane acrylates, polyether acrylates, polyketimines in combination with vinyl or acrylic copolymers with unsaturated side groups and acrylated melamine; And combinations thereof.
[254] 33. A radiation curable composition containing an ethylenically unsaturated monomer or oligomer and a polyunsaturated aliphatic oligomer; And combinations thereof.
[255] 34. Epoxymelamine resins, such as photostable epoxy resins crosslinked by co-etherified high solids melamine resins of epoxy functionality. The amino resin crosslinked polymer may be amino resin crosslinked thermosetting acrylic or amino resin crosslinked thermosetting polyester. Suitable amino resins include alkylated and nonalkylated melamine-formaldehyde resins, guanamine-formaldehyde resins, urea-formaldehyde resins, glycouril formaldehyde resins, and the like; And combinations thereof.
[256] 35. Organic dyes such as azo dyes (diazo, triazo and polyazo), anthraquinones, benzodifuranone, polycyclic aromatic carbonyl dyes, indigoid dyes, polymethines, styryl dyes, diaryls and tris Aryl carbonium dyes, phthalocyanines, quinophthalones, sulfur dyes, nitro and nitroso dyes, stilbene dyes, formazan dyes, quinacridones, carbazoles, and perylene tetracarboxylic acid diimides; And combinations thereof.
[257] 36. Cosmetic products such as synthetics such as antioxidants, preservatives, lipids, solvent surfactants, colorants, antiperspirants, skin conditioners, humectants, and the like; Skin lotions, collagen creams, sunscreens, facial makeup, and the like, including natural products such as collagen, protein, mink oil, olive oil, coconut oil, canova wax, beeswax, lanolin, cocoa butter, xanthan gum, aloe and the like; And combinations thereof.
[258] 37. For example, newspaper, card, poster, packaging, labels, stationery, books and magazines, sticky type paper, multipurpose and office paper, computer paper, copy paper, laser and inkjet printing paper, offset paper, money paper Cellulose-based paper composition for use in combination with them.
[259] 38. Photo film.
[260] 39. Ink.
[261] The term "copolymer" as used herein refers to a polymer of two or more different monomers. The photostabilized polymeric material is preferably made of polyolefin homopolymers or copolymers, more preferably of homopolymers or copolymers of polyethylene or polypropylene.
[262] The novel HALS of the present invention can also be used in multilayer systems. In such a system, the polymer composition containing the new HALS of the present invention in an amount of about 0.1 to 20% by weight, preferably a relatively high content, for example about 5 to 15% by weight, contains little or no UV stabilizer. To shaped articles made of polymers that do not have a thin film (typically about 5 to 500 μm, preferably about 10 to 100 μm thick). Such compositions may be applied simultaneously with the shaping of the base structure, for example by coextrusion. Alternatively, it may be applied to the preformed base structure by, for example, lamination of a film or coating of a solution. The surface layer of the final article has a UV filter function to protect the interior of the article from ultraviolet light. The surface layer preferably comprises at least one of the HALS of the present invention at about 0.1-20% by weight, preferably about 1-15% by weight, more preferably about 2-10% by weight of the surface layer composition.
[263] British Patent Application No. 2,290,745 discloses a number of methods developed for concentrating ultraviolet absorbers on or near the surface of polymeric materials. Examples include surface impregnation methods (US Pat. Nos. 3,309,220, 3,043,709, 4,481,664 and 4,937,026) and coating methods of plastic articles using solutions containing thermoplastic resins and ultraviolet absorbers (e.g., US Pat. No. 4,668,588). And 4,353,965). However, both techniques have disadvantages such as requiring additional processing steps (ie, application, drying or curing) and suffer from difficulties associated with the handling of many processed articles. Another disadvantage, in particular with regard to the production of polycarbonate sheets, is that the post-adding treatment has a detrimental effect on the surface of the polymer matrix.
[264] As described in US Pat. No. 5,445,872, application of the surface layer via coextrusion is carried out in a known manner using known coextrusion apparatus as taught in US Pat. Nos. 3,487,505 and 3,557,265, which are the present invention. It is a preferred method of incorporating HALS compounds into the surface of a polymeric article according to the invention. Coextrusion is a known method of co-extrusion of multiple layers forming a single composite material to produce a laminated thermoplastic. U.S. Patent 4,540,623 describes a coextruded material of at least 40 layers. Other methods known to those skilled in the art also produce as few as two or three different layers.
[265] In one embodiment, the present invention is about 0.1 to 10 mils (0.00254 to 0.254 mm) thick, preferably about 0.1 to 5 mils (0.00254 mm to 0.127) comprising at least one HALS of the invention in the range of about 0.1 to 20% by weight. Mm) thick thermoplastic layer coated. Preferred concentrations range from about 2 to 15 weight percent; The most preferred concentration is in the range of about 5 to 10% by weight.
[266] The HALS of the present invention can be incorporated into the thermoplastic of the surface layer by standard methods, such as by anhydrous mixing of the granular resin and additives prior to extrusion. The HALS layer can be applied to one or more sides of the thermoplastic article according to the invention.
[267] Laminated thermoplastic articles corresponding to the present invention that include additional layers such as waterproof layers as disclosed in US Pat. No. 4,992,322 are also within the scope of the present invention.
[268] The core layer and the coating layer may be the same thermoplastic resin or different. Examples of thermoplastics include thermoplastic polyesters, polyester carbonates, polyphenylene oxides, polyvinyl chlorides, polypropylenes, polypropylenes, polyethylenes, polyacrylates, polymethacrylates, and maleic anhydrides and styrene and polybutadiene Copolymers and combinations such as styrene and acrylonitrile on the phase; And combinations thereof.
[269] Polymers stabilized in this way have high weather resistance, in particular high resistance to ultraviolet radiation. Thus, it is possible to substantially maintain the mechanical properties, color and gloss of the polymer for a long time even under adverse conditions.
[270] Coating Stabilizers Containing HALS Compounds and Their Preparation
[271] In another embodiment of the invention, the novel mixtures containing one or more HALS of the invention can be used as a stabilizer for coatings, such as paints. In particular, they are useful as coatings and paints for the automotive industry. The term "coating" refers to a free flowing composition that can be applied in a thin film to the surface of an article, which is then cured to form a substantially solid surface on the article. In general, the coating forms an interface between the article and the environment.
[272] Such novel coating compositions comprise at least one HALS of the invention in the range of about 0.01 to 20% by weight, preferably about 0.01 to 10% by weight and more preferably about 0.02 to 5% by weight.
[273] The coating can be applied to the surface of the article in one or more layers to form a multilayer system. In multilayer systems, the concentration of novel HALS compounds provided to the surface layer may be relatively large, such as in the range of about 0.01 to 20% by weight, preferably about 0.01 to 10% by weight, more preferably about 0.02 to 5% by weight. have.
[274] The novel stabilizers used in coatings provide another advantage of preventing or preventing delamination, ie, delamination of the coating from the substrate. This advantage is particularly important in the case of metallic substrates, including multilayer systems on metallic substrates with a tendency to exfoliate.
[275] Coatings generally include a binder that suspends the pigment and other additives in the coating and attaches the coating to the substrate.
[276] This binder is in principle described in all binders customary in the art, such as Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A18, pp. 368-426, VCH, Weinheim, 1991, which is incorporated herein by reference. It may be. In general, the binder is a film-forming binder mainly composed of thermoplastic or thermosetting resins, in particular thermosetting resins. Examples are alkyds, acrylics, polyesters, phenols, melamines, epoxies and polyurethane resins and mixtures thereof.
[277] Such a binder may be a low temperature curable or high temperature curable binder. In addition, in some systems it may be advantageous to add a curable catalyst to the system. Suitable catalysts for accelerating curing of binders are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, Vol. A18, pp. 469, VCH Verlagsgesellschaft, Weinheim, 1991.
[278] Preferred binders include functional acrylate resins and crosslinkers.
[279] Various binders can be used in such coating systems. Examples of suitable coating compositions comprising specific binders include, but are not limited to:
[280] 1. Paints based on low or high temperature crosslinkable alkyds, acrylates, polyesters, epoxies or melamine resins or mixtures of such resins, to which a curable catalyst may be added, if necessary;
[281] 2. two-component polyurethane paints based on hydroxyl-containing acrylate, polyester or polyether resins and aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates; Or mixtures thereof;
[282] 3. one-component polyurethane paints based primarily on blocked isocyanates, isocyanurates or polyisocyanates which are stripped off during firing; Or mixtures thereof;
[283] 4. two-component paints based on (poly) ketimines and aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates; Or mixtures thereof;
[284] 5. two-component paints based on (poly) ketimines and unsaturated acrylate resins or polyacetoacetate resins or methacrylamidoglycolate methyl esters; Or mixtures thereof;
[285] 6. two-component paints based on carboxyl or amino containing polyacrylates and polyepoxides; Or mixtures thereof;
[286] 7. two-component paints based on acrylate resins containing anhydride groups and polyhydroxy or polyamino components; Or mixtures thereof;
[287] 8. two-component paints based on (poly) oxazolines and anhydride-containing acrylate resins or unsaturated acrylate resins or aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates; Or mixtures thereof;
[288] 9. two-component paints based on unsaturated polyacrylates and polymalonates; Or mixtures thereof;
[289] 10. Thermoplastic polyacrylate paints based on surface crosslinkable acrylate resins or thermoplastic acrylate resins in combination with etherified melamine resins; Or mixtures thereof;
[290] 11. Paint systems or mixtures thereof based on siloxane modified or fluorine modified acrylate resins.
[291] In addition to the novel HALS and binders of the present invention, the coating compositions presented herein may further comprise one or more additional additives such as antioxidants or additional ultraviolet absorbers or stabilizers. Additional additives include, but are not limited to, those specifically described above. Further additives are used in the coating composition in an amount of about 0.01 to 5% by weight, preferably about 0.02 to 2% by weight.
[292] Furthermore, additional components as are well known to those skilled in the art as suitable for the coating composition, such as, but not limited to solvents, pigments, dyes, plasticizers, stabilizers, thixotropes, anhydrous catalysts and / or leveling agents or combinations thereof It can be included in. Examples of possible ingredients are those described in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A18, pp. 429-471, VCH, Weinheim, 1991, which is incorporated herein by reference.
[293] Examples of anhydrous catalysts or curable catalysts are, for example, organometallic compounds, amines, amino-containing resins and / or phosphines. Examples of organometallic compounds are metal carboxylates, specifically carboxylates of metals Pb, Mn, Co, Zn, Zr or Cu, or metal chelates, specifically chelates of metals Al, Ti or Zr or organometallic compounds, such as Organotin compounds and mixtures thereof.
[294] Examples of metal carboxylates are stearates of Pb, Mn or Zn, octoates of Co, Zn or Cu, naphthenates of Mn and Co or corresponding linoleates, resinates or thalates, and mixtures thereof .
[295] Examples of metal chelates include aluminum, titanium or zirconium chelates of acetylacetone, ethyl acetylacetate, salicyaldehyde, salicylicoxime, o-hydroxyacetophenone, or ethyl trifluoroacetylacetate, and alkoxides of these metals and mixtures thereof to be.
[296] Examples of organotin compounds are dibutyltin oxide, dibutyltin dilaurate or dibutyltin dioctoate and mixtures thereof.
[297] Examples of amines specifically include tertiary amines such as tributylamine, triethanolamine, N-methyldiethanolamine, N-dimethylethanolamine, N-ethylmorpholine, N-methylmorpholine or diazabicyclooctane ( Triethylenediamine) and salts thereof, and mixtures thereof. Another example is quaternary ammonium salts such as trimethylbenzylammonium chloride. The amino containing resin is a binder and at the same time a curable catalyst. An example is an amino containing acrylate copolymer.
[298] The curable catalyst used may also be a phosphine, for example triphenylphosphine.
[299] The novel coating composition may also be a radiation curable coating composition. In such cases, the binder includes monomeric or oligomeric compounds comprising ethylenically unsaturated bonds which, after application, are cured by actinic radiation, ie converted to crosslinked high molecular weight forms. If the system is UV curable it usually also includes a photoinitiator. Such systems are described in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A18, pp. 451-453, which is incorporated herein by reference. In radiation curable coating compositions, novel stabilizers may also be used in the presence or absence of additional ultraviolet stabilizers, including steric hindered amines.
[300] The coating compositions presented herein can be applied to any preferred substrate, for example metal, wood, plastic or ceramic materials. In particular, it is preferable to be used as a top coat for surface finishing of automobiles. If the topcoat comprises two layers of a colored bottom layer and an uncolored top layer, the novel coating composition may be used in either or both of the top layers or the bottom layer, but is preferably used in the top layer.
[301] The novel coating compositions can be applied to the substrate by conventional methods available to those skilled in the art, for example by brushing, spraying, pouring, dipping or electrophoresis, etc. Ullmann's Encyclopedia of Industrial Chemistry , 5th Edition, Vol. A18, pp. 491-500.
[302] Depending on the binder system, the coating may be cured at room temperature or require heating. The coating is preferably cured at a temperature in the range of about 50 to 150 ° C., and for powder coatings the temperature should be higher.
[303] The coatings obtained according to the invention generally have good resistance to the damaging effects of light, oxygen and heat. In particular, the coated coatings claimed herein provide excellent light stability and weather resistance.
[304] Accordingly, the present invention includes coatings, specifically paints, in which a certain amount of one or more HALS of the present invention is incorporated into or on an article to stabilize it against the damaging effects of light, oxygen, and / or heat. This paint may be a colored monocoat comprising a film forming binder and an organic pigment or dye, an inorganic pigment, a metallic pigment or a mixture thereof. The paint also includes a primer adhered to a metal or plastic substrate; A colored base coat adhered to the primer and comprising a film forming binder and an organic pigment or dye, an inorganic pigment, a metallic pigment or a mixture thereof; And a transparent top coat adhered to the base coat and comprising a film forming binder and optionally a transparent pigment. This paint is preferred for automotive topcoats.
[305] The invention also provides a method of stabilizing an organic polymeric coating against damage by light, oxygen and / or heat, including mixing a mixture comprising at least one HALS of the invention with a coating composition, as well as light, oxygen and And / or the use of a mixture containing one or more HALS of the invention used in coating compositions as a stabilizer against thermal damage.
[306] The coating composition may comprise an organic solvent or solvent mixture in which the binder is dissolved. This coating composition, on the other hand, may be an aqueous solution or a dispersion. The carrier may be a mixture of organic solvent and water. The coating composition may be a high solids amount of paint or solvent-free (eg powder coating material).
[307] The pigment may be an inorganic, organic or metallic pigment. The novel coating composition preferably contains no pigment at all, so that it is preferably used as a clearcoat composition.
[308] Likewise, the coating composition is preferred for use as a topcoat in the automotive industry, in particular as a colored or colorless topcoat of paint surface finishes. However, it can also be used for the bottom coat.
[309] The following examples merely illustrate preferred embodiments of the invention and should not be construed as limiting the invention, the scope of the invention being limited only by the appended claims.
[310] Examples 1 to 9: Preparation of Multifunctional Carbonyl Compound HALS Compounds
[311] Eight HALS compounds of the formulas were synthesized according to the invention.
[312]
[313] Compound I (n = 5, R = Hydrogen)
[314] Compound II (n = 5, R = methyl)
[315] Compound III (n = 11, R = Hydrogen)
[316] Compound IV (n = 11, R = methyl)
[317]
[318] Compound V
[319]
[320] Compound VI
[321]
[322] In this equation, i, j, k and l are integers, and the sum of i, j, k and l is greater than two.
[323] Compound VII (Mn = about 2,000)
[324] Compound VIII (Mn = about 8,800)
[325] Compounds I and II were prepared from methyl 6- (methoxycarbonylamino) hexanoate (Compound A), compounds III and IV were prepared from butyl 6-butoxycarbonylaminoundecanoate (Compound B), Compound V was prepared from methyl 6-[(methoxyoxoacetyl) amino] -hexanoate (compound C), and compound VI was prepared from methyl 6- (octanoylamino) hexanoate (compound D). Compounds VII and VIII were prepared from compound A and N- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol.
[326]
[327] Compound A (n = 5, R = methyl)
[328] Compound B (n = 11, R = butyl)
[329]
[330] Compound C
[331]
[332] Compound d
[333] N- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol hydrolyzed TINUVIN 622 with aqueous sodium hydroxide / tetrahydrofuran and then removed tetrahydrofuran under reduced pressure. After the aqueous layer was extracted with chloroform, the chloroform layer was dried and filtered, and prepared by removing chloroform under reduced pressure. The obtained N- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol had a melting point of 179 to 183 ° C (melting point 182 ° C, DE 2,352,658 in the literature). The synthesis of compounds A, B, C and D was carried out as follows:
[334] Synthesis of Compound A:
[335] 10g (88mmol) of caprolactam, 10.5g (117mmol) of dimethyl carbonate, 5.23 sodium methoxide in a 300 ml round bottom three-necked flask equipped with a condenser and ground glass stopper with argon inlet and outlet, mechanical stirrer g (96.8 mmol) and 100 ml methanol were added. The mixture was heated to reflux for 24 hours and then cooled to room temperature. 7.3 g (121 mmol) of glacial acetic acid were added and methanol was removed by rotary evaporator. The residue was dissolved in 100 ml of methylene chloride and the organic layer was extracted with water to remove unreacted caprolactam. Removal of solvent by rotary evaporation followed by further removal of solvent under vacuum (<1 mm) at 95 ° C. yielded 5.23 g (29%) of compound A as an almost colorless oil. The structure of compound A was confirmed by NMR:
[336]
[337] Synthesis of Compound B:
[338] 13.96 g (0.070 mol) of laurolactam, 13.4 g (0.076 mol) of dibutyl carbonate, 4.16 g (0.077 mol) of sodium methoxide in a 250 ml three-necked reaction flask equipped with a magnetic stirrer, reflux condenser and thermometer adapter And 130 g of butanol were added. This mixture was heated at 110 ° C. for 64 hours. After cooling to room temperature 4.9 g (0.10 mol) of glacial acetic acid in 30 g of butanol were added and the mixture was stirred for 5 minutes. The resulting mixture was diluted with 500 ml of methylene chloride, washed with water and dried (MgSO ₄ ). After filtration and rotary evaporation 19.6 g of an oil phase solid was obtained. Flash chromatography with 200-400 mesh 60 cc silica gel (0.5% methanol / methylene chloride) afforded 7.2 g (25%) of the title compound as a white semisolid. The structure of compound B was confirmed by NMR:
[339]
[340] Synthesis of Compound C:
[341] To a 100 ml round bottom flask equipped with a stir bar was added 8.45 g (75 mmol) of caprolactam, 8.85 g (75 mmol) of dimethyl oxalate and 0.16 g (3 mmol) of sodium methoxide. The mixture was immersed in a 50 ° C. oil bath, heated for 30 minutes and then cooled to 35 ° C. for 1 hour. After stirring for several hours at this temperature, the mixture was cooled and left overnight at room temperature. The mixture was diluted with 125 ml of methylene chloride, washed with water and then with saturated sodium chloride solution. Drying on the molecular sieve, filtration and solvent removal under reduced pressure yielded 12.5 g (72% yield) of a light yellow liquid which crystallized to a low melting solid upon standing. The structure of this material was confirmed by ¹ H NMR analysis:
[342]
[343] Synthesis of Compound D:
[344] To a 100 ml round bottom flask equipped with a stir bar was added 16.9 g (150 mmol) of caprolactam, 23.7 g (150 mmol) of methyl caprylate and 0.32 g (6 mmol) of sodium methoxide. This mixture was immersed in an oil bath at 185-195 ° C. and heated for 58 hours. After cooling to 75 ° C. and adding 0.35 g (6 mmol) of acetic acid, the flask was further cooled and the remaining methyl caprylate (17 g) was distilled off at 48 to 67 ° C./0.8 mm and then caprolactam at 90 to 95 ° C./0.8 mm. (10 g) was removed. The residue was diluted with methylene chloride and washed with water to further remove caprolactam, dried (MgSO ₄ ), filtered and evaporated under reduced pressure to give Compound D (6.3 g, 38% yield based on unrecovered caprolactam). Obtained as a brown wax. The structure of this material was confirmed by ¹ H NMR analysis:
[345]
[346] Synthesis of Compounds E and F Mixtures:
[347] To a 50 ml thick film reaction vessel equipped with a Teflon screw cap and a magnetic stir bar, 10.6 g (53.7 mmol) of laurolactam, 9.83 g (56.4 mmol) of dibutyl carbonate and 0.58 g (10.7 mmol) of sodium methoxide were added. . The mixture was immersed in a 120 ° C. oil bath and heated for 2 hours. After cooling to room temperature the mixture was diluted with 100 ml of methylene chloride and 0.67 g (11.2 mmol) of acetic acid was added thereto. The product was obtained as off-white paste after filtration and removal of the solvent by rotary evaporation followed by further solvent removal at 95 ° C. under vacuum (<1 mm). ¹ H NMR (CDCl ₃ ) showed that both compounds E and F were mainly present in a molar ratio of about 80:20. Flash chromatography (3.5% methanol / methylene chloride) gave a pure sample of both components.
[348] Compound E:
[349] Compound F:
[350]
[351] Low temperature reaction of the reactants produced little or no compound F.
[352] Synthesis of Compound G and H Mixtures:
[353] To a 50 ml thick film reaction vessel equipped with a Teflon screw cap and a magnetic stir bar was added 6.06 g (53.7 mmol) of caprolactam, 9.83 g (56.4 mmol) of dibutyl carbonate and 0.58 g (10.7 mmol) of sodium methoxide. The mixture was immersed in a 129 ° C. oil bath and heated for 2 hours. After cooling to room temperature the mixture was diluted with 100 ml of methylene chloride and 0.67 g (11.2 mmol) of acetic acid was added thereto. The product was obtained as a yellow paste after filtration and removal of the solvent by rotary evaporation followed by further solvent removal at 95 ° C. under vacuum (<1 mm). ¹ H NMR (CDCl ₃ ) confirmed that both compounds G and H were mainly present in a molar ratio of about 80:20.
[354]
[355] Low temperature reaction of the reactants produced little or no compound H.
[356] Synthesis of Compounds I and J Mixture:
[357] To a 25 ml thick film reaction vessel equipped with a Teflon screw cap and a magnetic stir bar was added 2.26 g (20 mmol) of caprolactam, 1.89 g (21 mmol) of dimethyl carbonate and 54 mg (1.0 mmol) of sodium methoxide. The mixture was immersed in a 130 ° C. oil bath and heated for ½ hour. After cooling to room temperature the mixture was diluted with 100 ml of methylene chloride and 0.67 g (11.2 mmol) of acetic acid was added thereto. The product was obtained as a yellow paste after filtration and removal of the solvent by rotary evaporation followed by further solvent removal at 95 ° C. under vacuum (<1 mm). ¹ H NMR (CDCl ₃ ) confirmed that both Compounds I and J were present in a molar ratio of about 80:20.
[358]
[359] Low temperature reaction of these reactants produced little or no compound J.
[360] The synthesis of mixtures of compounds E and F, G and H, I and J forms intermediates, in particular by the nucleophilic acyl addition of lactam anions in the carbonyls of carbonates at high temperatures, and then the second in lactam carbonyls of these intermediates. It demonstrates that polyfunctional carbonyl compounds can be formed by the reaction of lactam anions. The resulting multifunctional carbonyl compound is reacted with a 4-aminopiperidine radical to give a HALS mixture which is an effective stabilizer. In general, the product produced in the low temperature reaction was poor in color.
[361] Example 1 2,2,6,6-tetramethylpiperidin-4-yl 6- (2,2,6,6-tetramethyl-4-piperidineoxycarbonyl amino) hexanoate (compound I) manufacture.
[362] 20 g (98.4 mmol) of Compound A, 2,2,6,6-tetramethyl-4-piperidinol 46.3 in a 500 ml three-necked flask equipped with a magnetic stirrer, a Dean Stark trap with a condenser, a thermometer and a glass stopper. g (0.295 mol) and 150 ml of toluene were added. Under slow nitrogen flow, 20 ml of toluene was distilled off and the trap was drained. The glass cap was removed and 1.0 g (1.67 mmol) of 1,3-diacetoxy-1,1,3,3-tetrabutyldistannoic acid was added. 75 ml of toluene was slowly distilled for an additional 8 hours. After 110 ml of toluene was further added, 80 ml of toluene was removed for an additional 2 hours. NMR analysis showed a conversion rate of> 98%. The mixture was cooled to rt and diluted with ether. The organic solution was washed with water to remove excess amino alcohol and dried over sodium carbonate. Filtration and removal of the solvent under reduced pressure followed by further removal of the solvent under vacuum (<1 mm) at 95 ° C. yielded 41.2 g (92%) of compound I as a white solid, mp 59-62 ° C. The structure of this material was confirmed by ¹ H NMR analysis.
[363]
[364] Example 2. 1,2,2,6,6-pentamethylpiperidin-4-yl 6- (1,2,2,6,6-pentamethyl-4-piperidineoxycarbonylamino) hexa Preparation of Noate (Compound II).
[365] In a 100 ml three-necked flask equipped with a magnetic stirrer, Dean Stark trap with condenser, thermometer and glass stopper, Compound A 4.85 g (23.9 mmol), 1,2,2,6,6-pentamethyl-4-pipe 12.2 g (71.6 mmol) of lidinol and 30 ml of toluene were added. Under slow argon, 17 ml of toluene was distilled off and the trap drained. The glass cap was removed and 0.26 g (0.43 mmol) of 1,3-diacetoxy-1,1,3,3-tetrabutyldistannoic acid was added. 22 ml of toluene was slowly distilled for 1 hour. A further 10 ml of toluene was added and then 11 ml of toluene was removed for an additional 3 hours. NMR analysis showed a conversion of> 97%. The mixture was cooled to rt and diluted with ethyl acetate. The organic solution was washed with water to remove excess amino alcohol and dried over magnesium sulfate. Filtration and removal of the solvent under reduced pressure followed by further removal of the solvent under vacuum (<1 mm) at 95 ° C. gave 10.23 g (89%) of compound II as an almost colorless viscous oil. The structure of this material was confirmed by ¹ H NMR analysis.
[366]
[367] The TGA T-10% value of compound II was 237 ° C.
[368] Example 3 2,2,6,6-tetramethylpiperidin-4-yl 6- (2,2,6,6-tetramethyl-4-piperidineoxycarbonylamino) undecanoate (compound III) Preparation.
[369] The 250 ml one-necked reaction flask was equipped with a magnetic stirrer and a distillation head equipped with a receiving flask with nitrogen inlet and outlet in the thermometer, condenser and foamer. This flask was charged with 4.3 g (11.57 mmol) of Compound B, 7.27 g (46.3 mmol) of 2,2,6,6-tetramethyl-4-piperidinol and 200 ml of xylene. Under slow nitrogen flow, 25 ml of xylene was distilled off and the trap was drained. After lowering the temperature of the heat source and cooling the mixture to 110 ° C, 0.17 g (0.28 mmol) of 1,3-diacetoxy-1,1,3,3-tetrabutyldistanoxane was added to raise the temperature of the heat source. . 290 mL of xylene was slowly distilled for 7 hours with addition of 100 mL of xylene at 3 hours. After further adding 240 ml of xylene, it was distilled again for 12 hours, during which time 175 ml was collected. NMR analysis showed a> 90% conversion. The mixture was cooled to rt and diluted with ether. The organic solution was washed with water to remove excess amino alcohol and dried over magnesium sulfate. Filtration and removal of the solvent under reduced pressure followed by further removal of the solvent under vacuum (<1 mm) at 95 ° C. yielded 5.5 g (83%) of compound III as a yellow oil. The structure of this material was confirmed by ¹ H NMR analysis.
[370]
[371] Example 4 1,2,2,6,6-pentamethylpiperidin-4-yl 6- (1,2,2,6,6-pentamethyl-4-piperidineoxycarbonylamino) ound Preparation of Decanoate (Compound IV).
[372] The 250 ml one-necked reaction flask was equipped with a magnetic stirrer and a distillation head equipped with a receiving flask with nitrogen inlet and outlet in the thermometer, condenser and foamer. The flask was charged with 4.5 g (12.1 mmol) of Compound B, 8.3 g (48.4 mmol) of 1,2,2,6,6-pentamethyl-4-piperidinol, and 200 ml of xylene. Under slow nitrogen flow, 25 ml of xylene was distilled off and the trap was drained. The mixture was cooled to 110 ° C. by lowering the temperature of the heat source, and then 0.19 g (0.31 mmol) of 1,3-diacetoxy-1,1,3,3-tetrabutyldistanoxane was added. At 5, 21, and 23 hours, 100 ml, 100 ml and 150 ml of xylene were distilled for 24 hours, respectively. The mixture was cooled to rt and diluted with ether. The organic solution was washed with water to remove excess amino alcohol, then washed with aqueous NaOH and then additional water and finally dried over magnesium sulfate. Filtration and removal of the solvent under reduced pressure followed by further removal of the solvent under vacuum (<1 mm) at 95 ° C. yielded 5.4 g (79%) of compound IV as an almost colorless oil. The structure of this material was confirmed by ¹ H NMR analysis.
[373]
[374] Example 5. 2,2,6,6-tetramethylpiperidin-4-yl 6-[(2,2,6,6-tetramethyl-4-piperidinyloxy) oxoacetyl] amino hexanoate Preparation of (Compound V).
[375] The 250 ml one-necked reaction flask was equipped with a magnetic stirrer, a Dean Stark trap equipped with a condenser and a nitrogen inlet and outlet. The flask was charged with 10.0 g (43.3 mmol) of Compound C, 20.4 g (130 mmol) of 2,2,6,6-tetramethyl-4-piperidinol and 150 ml of toluene. 15 ml of toluene was distilled off under a slow nitrogen stream and the trap was drained. After the temperature of the heat source was lowered and the mixture was cooled to 110 ° C, 0.46 g (0.76 mmol) of 1,3-diacetoxy-1,1,3,3-tetrabutyldistanoxane was added to increase the temperature of the heat source. . 110 ml of toluene was slowly distilled again for 9 hours, then 25 ml of xylene was added, and 20 ml of solvent was distilled again for 6 hours. The resulting mixture was cooled to room temperature and diluted with ethyl acetate. The organic solution was washed with water to remove excess amino alcohol and dried over molecular sieve. Filtration and removal of the solvent under reduced pressure followed by further removal of the solvent under vacuum (<1 mm) at 95 ° C. yielded 13.0 g (62%) of compound V as a yellow oil. The structure of this material was confirmed by ¹ H NMR analysis.
[376]
[377] Example 6. Preparation of 2,2,6,6-tetramethylpiperidin-4-yl 6- (octanoylamino) hexanoate (Compound VI).
[378] The 250 ml one-necked reaction flask was equipped with a magnetic stirrer, a Dean Stark trap equipped with a condenser and a nitrogen inlet and outlet. The flask was charged with 6.1 g (22.5 mmol) of Compound D, 5.29 g (33.7 mmol) of 2,2,6,6-tetramethyl-4-piperidinol, and 150 ml of toluene. 8 ml of toluene was distilled off under a slow nitrogen stream and the trap was drained. After lowering the temperature of the heat source and cooling the mixture to 110 ° C, 0.17 g (0.28 mmol) of 1,3-diacetoxy-1,1,3,3-tetrabutyldistanoxane was added to raise the temperature of the heat source. . 100 ml of toluene was slowly distilled again for 16 hours, and the resulting mixture was cooled to room temperature and diluted with methylene chloride. The organic solution was washed with water to remove excess amino alcohol and dried over anhydrous sodium carbonate. Filtration and removal of the solvent under reduced pressure followed by further removal of the solvent under vacuum (<1 mm) at 60 ° C. yielded 8.0 g (90%) of compound VI as light brown wax. The structure of this material was confirmed by ¹ H NMR analysis.
[379]
[380] Example 7. Synthesis of Oligomeric HALS Compounds (Compounds VII and VIII)
[381] 5.45g (26.8mmol) of Compound A, 27ml of toluene, 1,3-diacetoxy 163 mg (0.27 mmol) of -1,1,3,3-tetrabutyldistannoic acid and 5.4 g of N- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol Was charged. The mixture was heated to distill 13 ml of solvent for 3 hours. An amount of 12 ml was separated from the reaction mixture (fraction A) and examined as described below. The remaining reaction mixture was heated for another 2.5 hours to distill 8 ml of solvent. After addition of 10 ml of xylene, 15 ml of additional solvent was distilled off for 3 hours by increasing the temperature. The resulting reaction mixture (fraction B) was examined as described below.
[382] Overhaul of Fraction A: A 12 ml volume was diluted with methylene chloride, washed with water, dried (MgSO ₄ ), filtered and the solvent removed under reduced pressure. Further solvent removal under vacuum (<1 mm) at 50-60 ° C. afforded 4.4 g of compound VII as a clear colorless semisolid. High performance Exclusion Chromatography (HPSEC) using polystyrene as a standard showed that the number average molecular weight (Mn) of the material was 2,000. The structure of this material was confirmed by ¹ H NMR analysis.
[383]
[384] Overhaul of Fraction B: The remaining reaction mixture was diluted with methylene chloride, washed with water, dried (MgSO ₄ ), filtered and the solvent was removed under reduced pressure. Further solvent was removed under vacuum (<1 mm) at 80-90 ° C. to yield 4.6 g of compound VIII as a white foam. High performance size exclusion chromatography (HPSEC) using polystyrene as a standard showed that the number average molecular weight (Mn) of the material was 8,800. The structure of this material was confirmed by ¹ H NMR analysis.
[385]
[386] Example 8 2,2,6,6-tetramethyl-4-piperidine 6- (2,2,6,6-tetramethyl-4-piperidineoxycarbonyl amino) hexanoate (Compound I Base catalyzed one-step reaction to produce).
[387] 1.69 g (15 mmol) of caprolactam and 2.74 g (15.75) of dibutyl carbonate in a 100 ml three-necked round bottom flask equipped with a magnetic stirring rod, an anhydrous toluene addition funnel and a Dean Stark trap equipped with a condenser and nitrogen inlet / outlet mmol), 4.94 g (31.5 mmol) of 2,2,6,6-tetramethyl-4-piperidinol and 50 ml of toluene were added. The mixture was heated to a heating mantle temperature of 142 ° C. to distill 6 ml of solvent into a trap. The mixture was cooled and 75 mg (1.39 mmol) of sodium methoxide were added to this mixture. The mixture was reheated to the boiling point and 20 mL was distilled into the trap for 4 hours. The trap was drained and 25 ml of toluene was added to the mixture via an addition funnel. Again, 25 ml of solvent was distilled for 4 hours, 25 ml of anhydrous xylene was added, and 35 ml of solvent was removed for 6 hours. ¹ H NMR confirmed a> 95% conversion of the starting material. After cooling to room temperature, diluted with methylene chloride, washed with water, dried (molecular sieve), filtered and solvent removed under reduced pressure to give a yellow oil. After further removing the volatiles at 90 ° C./0.8 mm, 5.0 g of pale yellow semisolid was obtained (75% yield). ¹ H NMR confirmed that the desired hindered amine compound I was present in about 85% purity.
[388] Example 9. 2,2,6,6-tetramethyl-4-piperidine 6- (2,2,6,6-tetramethyl-4-piperidineoxycarbonyl amino) hexanoate (Compound I Lewis acid catalyzed one step reaction to produce.
[389] 16.9g (150mmol) of caprolactam, 39.2g (225mmol) of dibutyl carbonate, 2,2 in a 250 ml three-necked round bottom flask equipped with a stirrer rod, a Deanstark trap with condenser and nitrogen inlet / outlet 70.65 g (450 mmol) of 6,6-tetramethyl-4-piperidinol and 200 ml of toluene were added. The mixture was heated to a pot temperature of 120 ° C. to distill 12 ml of solvent into a trap. The mixture was cooled and 0.85 g (3 mmol) of titanium isopropoxylated (IV) was added to this mixture. The mixture was reheated to the boiling point and the solvent was distilled for 20 hours by slowly increasing the pot temperature from 120 ° C to 210 ° C. ¹ H NMR confirmed a> 95% conversion of the starting material. The trap was removed and the flask was mounted on a condenser with a vapor jacket and a distillation head. Solid impurities (28.0 g) were distilled at 75-120 ° C./0.8 mm. The flask residue was diluted with methylene chloride and 0.3 ml of water was added thereto. After stirring overnight at room temperature, it was filtered and the solvent removed to give 59.0 g of a dark pale yellow oil (89% yield). ¹ H NMR confirmed that the desired hindered amine compound I was present in about 90% purity. 30 g of hexane was added to this oil and the mixture was heated until homogeneous. One After cooling to 5 ℃ allowed to stand for 12 hours at the temperature and then filtered to give to afford the hindered amine I 36g of the desired white solid (53% yield, mp 51 to 54 ℃), ¹ H NMR results purity of about 95 Was%.
[390] Example 10 Preparation of Oligomeric HALS (Compound IX) from BPIP and Compound A.
[391] 5.0 g (24.6 mmol) compound A, 100 ml mixed xylene, and N, N ' 9.69 g (24.6 mmol) of bis (2,2,6,6-tetramethyl-4-piperidinyl) -1,6-hexanediamine (BPIP) were added. The mixture was heated to reflux for 1 hour, and then the temperature of this heat source was lowered, and 30 ml of xylene was collected by draining from the Dean Stark trap, and 1,3-diacetoxy-1,1,3,3-tetrabutyldi 0.22 g (0.37 mmol) stanoxane was added. The mixture was reheated to boiling point and again 50 ml of solvent was collected for several hours. An additional 100 ml part of anhydrous xylene was added and distilled for several hours. The mixture was cooled to room temperature, diluted with methylene chloride, washed with water, dried (molecular sieve), filtered and solvent removed under reduced pressure to give 12.1 g of compound IX as a tacky yellow solid.
[392] Compound IX
[393]
[394] In this equation, i and j are integers, and the sum of i and j is 2 or more. The structure of compound IX was confirmed by ¹ H NMR analysis.
[395]
[396] Example 11. One step reaction to produce oligomeric HALS from caprolactam, N-hydroxyethyl-2,2,6,6-tetramethyl-4-piperidinol and dibutyl carbonate.
[397] 1.0 g of N-hydroxyethyl-2,2,6,6-tetramethyl-4-piperidinol in a 50 ml three-necked reaction flask equipped with a magnetic stirrer and a Dean Stark trap with condenser and nitrogen inlet and outlet (4.97 mmol), 0.56 g (4.97 mmol) of caprolactam, 0.86 g (4.97 mmol) of dibutyl carbonate, 30 mL of toluene and 40 mg (0.75 mmol) of sodium methoxide were added. The flask was immersed in an oil bath and heated to distill the solvent for 4 hours. 20 mL of xylene was added to the reaction mixture, and 20 mL of the solvent was further distilled off for 4 hours. The resulting mixture was cooled to room temperature and diluted with dichloromethane. The organic solution was washed with water, dried (MgSO ₄ ) and filtered. The solvent was then removed using a rotary evaporator under reduced pressure and further removed under vacuum (<1 mmHg) at 95 ° C. to yield 1.5 g (88%) of compound VII. The structure of compound VII was confirmed by ¹ H NMR.
[398] Example 12. Low Temperature Synthesis of Compound A.
[399] 50.33 g (558 mmol) of dimethyl carbonate and 1.04 g (19.3 mmol) of sodium methoxide were added to a 250 ml three-necked round bottom flask equipped with a magnetic stirrer, ground glass stopper, condenser and nitrogen inlet and thermometer. The mixture was cooled to 15 ° C. and 21.8 g (193 mmol) of caprolactam were added. The mixture was stirred with intermittent cooling to maintain the reaction temperature between about 9-18 ° C. for 45 minutes, then 2.4 g (40 mmol) of glacial acetic acid were added at <19 ° C. The mixture was dissolved in 100 ml of methylene chloride, the organic layer was extracted with water, dried (MgSO ₄ ), filtered and the solvent was removed under reduced pressure, and further solvent was removed at 95 ° C. under vacuum (<1 mmHg) to obtain Compound A 39.0 g (99%). ) Was collected as a nearly colorless oil.
[400] Example 13. Preparation of HALS Mixture by Reaction of 2,2,6,6-Tetramethyl-4-piperidinol with Compound E and F Mixtures.
[401] The 250 ml three neck reaction flask was equipped with a magnetic stirrer, thermometer adapter, and a distillation head with a condenser, receiver and nitrogen inlet / outlet. To the flask was added 4.3 g (10.45 mmol) of the above obtained E / F mixture, 7.27 g (46.3 mmol) of 2,2,6,6-tetramethyl-4-piperidinol and 200 ml of xylene. Under slow nitrogen, 10 ml of xylene was distilled off and the trap was drained. After lowering the temperature of the heat source and cooling the mixture to 110 ° C., 0.17 g (0.28 mmol) of 1,3-diacetoxy-1,1,3,3-tetrabutyldistanoxane was added to increase the temperature of the heat source. I was. Again 172 ml of xylene was slowly distilled for 12 hours. The resulting mixture was cooled to room temperature and diluted with ethyl acetate. The organic solution was washed with water to remove excess amino alcohol and dried over molecular sieve. The solvent was further removed under vacuum (<1 mm) at 95 ° C. after solvent removal by filtration and rotary evaporation to yield 5.6 g (93%) of the composition MI as a yellow oil. The structure of the compound present in this mixture was confirmed by ¹ H NMR analysis.
[402]
[403]
[404] Example 13. Preparation of HALS Mixture by Reaction of 1,2,2,6,6-pentamethyl-4-piperidinol with Compound E and F Mixtures.
[405] The 500 ml three-necked reaction flask was equipped with a magnetic stirrer, thermometer adapter, and a distillation head with a condenser, receiver and nitrogen inlet / outlet. To this flask was added 7.9 g (19.2 mmol) of the E / F mixture obtained above, 14.5 g (85.04 mmol) of 1,2,2,6,6-pentamethyl-4-piperidinol and 300 ml of xylene. Under slow nitrogen flow, 100 ml of xylene was distilled off and the trap was drained. After the temperature of the heat source was lowered and the mixture was cooled to 100 ° C., 0.34 g (0.56 mmol) of 1,3-diacetoxy-1,1,3,3-tetrabutyldistanoxane was added to raise the temperature of the heat source. I was. Again 160 ml of xylene was slowly distilled for 10 hours. Again, 20 ml of xylene was added and heating was continued for 8 hours, during which 32 ml of xylene was collected. The resulting mixture was cooled to room temperature and diluted with methylene chloride. The organic solution was washed with water to remove excess amino alcohol and dried over MgSO ₄ . The solvent was further removed under vacuum (<1 mm) at 95 ° C. after solvent removal by filtration and rotary evaporation to yield 11.2 g (96%) of composition M-II as a yellow oil. The structure of the compound present in this mixture was confirmed by ¹ H NMR analysis.
[406]
[407]
[408] Performance of HALS Compounds According to the Invention
[409] Examples 15-21 1,2,2,6,6-pentamethyl-4-piperidine 6- (1,2,2,6,6-pentamethyl-4-piperidineoxycarbonylamino) Weather Resistance of 2k Acrylic Urethane Clear Coat Compositions Containing Hexanoate (Compound II)
[410] Compound II (1% by total resin solids) was predissolved in the solvent mixture (5-10% solids) and then added to the clear 2k acrylic urethane composition shown in Table I. 2k acrylic urethanes are two-component urethanes made by reacting a hydroxy functional acrylic polymer with an isocyanate crosslinker. Components I and II were mixed just before use. The clear coat was applied to a 4 "x 12" cold rolled steel panel (ACT Laboratories, Inc., Inc., Hill), precoated with an E-coat primer and a white base coat. In order to apply a transparent coat to the precoated panel, an inlay technique using WC-60 WIRE-CATORS ^™ , a commercial product of Renetta Corporation, Hohokus, NJ, was performed. The clear coat was flashed at room temperature for 10 minutes and cured at 120 ° C. for 30 minutes.
[411] Table I. Acrylic Urethane Transparent Coat Composition
[412] Raw materialcontent Component IJONCRYL ^R CDX-588 acrylic resin ^a 100 copies T-12 (2% solids in catalyst solution) ^b Part 5 Solvent mixturePart 45 Compound IIPart 1 ^cComponent IIDESMODUR ^R N-3390 (90% solids) ^d Part 33 Solvent mixturePart 17 Catalyst solutionT-12 (dibutyltin dilaurate) ^b chapter 1 Acetic acidPart 4 Propylene Glycol Methyl Ether AcetatePart 45 Solvent mixturexylenechapter 1 Propylene Glycol Methyl Ether Acetatechapter 1 Methyl amyl ketonechapter 1^a JONCRYL is ^a commercial product of SC Johnson & Sons Inc., Racine, Wisconsin. ^b T-12 is a commercial product of Air Products, located in Allentown, Pennsylvania. ^c 1% ^d DESMODUR, based on total resin solids content, is a commercial product of Bayer Corporation, Pittsburgh, Pennsylvania.
[413] Accelerated weathering tests include the Atlas Ci65 WeatherOmeter ("Xenon WOM") with xenon arc lamp (commercially available from Atlas Electronic Devices Corporation, Chicago, Illinois) and QUV with UVA-340 fluorescent bulbs in accordance with SAE J1960 automotive exterior test protocol. The coating was carried out using an accelerated weathering tester device (commercially available from Q Panel Laboratories Products, Cleveland, Ohio). Natural weathering tests were conducted using a 5 ° South Direct weather test in Southern Florida. Specular reflectivity (gloss and salience or DOI of the image), total color change rate (delta E) and yellow change rate (delta b) were measured as a function of weathering time. Specular reflectivity was measured as described in ASTM E284 and D253. Color change and yellow change were measured as described in ASTM D2244.
[414] The performance of Compound II under QUV weathering test is summarized in Examples 15-17. The effect of Compound II on gloss retention is shown in Example 15, the effect on DOI retention is shown in Example 16, and the effect on delta E is shown in Example 17.
[415] Example 15. QUV Weather Resistance (UVA-340 Bulb), Gloss Retention% Effect of 2k Acrylic Urethane Transparent Coat Stabilized with Compound II
[416] StabilizerImpressions (hours)15272500300635084014449550005500600265007011 No addition1028691.972.265.149.941.742.234.033.82.1 Compound II10296.898.799.799.698.910199.310099.996.2
[417] The 2k acrylic urethane clear coat stabilized with 1% of compound II showed excellent gloss retention% compared to the 2k urethane clear coat containing no stabilizer.
[418] Example 16. QUV Weather Resistance (UVA-340 Bulb), DOI Retention% Effect of 2k Acrylic Urethane Transparent Coat Stabilized with Compound II
[419] StabilizerImpressions (hours)15272500300635084014449550005500600265007011 No addition10197.483.745.326.11412.912.78.49.10.1 Compound II102101101102106106107107107107107
[420] The 2k acrylic urethane clear coat stabilized with 1% of compound II exhibited a better percent DOI retention compared to the 2k urethane clear coat containing no stabilizer.
[421] Example 17 Effect of 2k Acrylic Urethane Clear Coat Stabilized with Compound II on QUV Weather Resistance (UVA-340 Bulb), Delta E
[422] StabilizerImpressions (hours)47315273006401450006002 No addition1.191.993.293.514.014.41 Compound II0.390.631.221.221.361.73
[423] The 2k acrylic urethane clear coat stabilized with 1% of compound II showed an excellent effect on the total color change rate (delta E) compared to the 2k urethane clear coat containing no stabilizer. An increase in delta E indicates undesirable discoloration of the urethane coat.
[424] In addition to the above-described properties, visual evaluation of foaming was performed. After about 7011 hours, the unstabilized coating completely delaminated while the coating containing Compound II showed no signs of foaming.
[425] The performance of Compound II under Xenon WOM weathering test is summarized in Examples 18-20. The effect of Compound II on gloss retention is shown in Example 18, the effect of Compound II on DOI retention is shown in Example 19, and the effect on delta E is shown in Example 20. The effect of Compound II under natural weathering test (Florida) on gloss retention, yellow change (delta b) and total color change (delta E) is shown in Example 21.
[426] Example 18 Xenon Weather Resistance Test (SAE J1960 Automotive Exterior Test), 2% Gloss Retention Effect of 2k Polyurethane Acrylic Coating Stabilized with Compound II
[427] StabilizerImpressions (hours)485987151320112517294735394039 No addition97.394.595.990.676.464.247.334.5 Compound II96.595.095.496.092.784.773.162.4
[428] The 2k acrylic urethane clear coat stabilized with 1% of compound II showed excellent gloss retention% compared to the 2k urethane clear coat containing no stabilizer.
[429] Example 19. Xenon Weather Resistance (SAE J1960 Automotive Exterior Test), DOI Retention% Effect of 2k Polyurethane Acrylic Coating Stabilized with Compound II
[430] StabilizerImpressions (hours)48598715132011251729473539403944435003 No addition10410110196.486.576.754.236.624.116.6 Compound II10110210110110099.696.093.889.075.3
[431] The 2k acrylic urethane clear coat stabilized with 1% of compound II exhibited a better percent DOI retention compared to the 2k urethane clear coat containing no stabilizer.
[432] Example 20 Effect of 2k Polyurethane Acrylic Coating Stabilized with Compound II on Xenon Weather Resistance (SAE J1960 Automotive Exterior Test), Delta E
[433] StabilizerImpressions (hours)48598715132011251729473539403944435003 No addition0.901.081.422.102.423.313.303.683.784.28 Compound II0.420.540.511.061.082.292.242.442.412.45
[434] The 2k acrylic urethane clear coat stabilized with 1% of compound II showed an excellent effect on the total color change rate (delta E) compared to the 2k urethane clear coat containing no stabilizer. An increase in delta E indicates undesirable discoloration of the urethane coat.
[435] In addition to the above-described properties, visual evaluation of the degree of cracking was performed after 5003 hours. At grades 0 to 5, the top 0 and unstabilized coatings showed a grade of 5 (severe cracking) while the coating stabilized with 1% Compound II showed a grade of 1 (very weak cracking).
[436] Example 21 Effect of Compound 2 Stabilized 2k Acrylic Urethane Transparent Coat on Florida Weather Resistance (50 ° South, Direct, 18 Months), Gloss Retention%, Yellow Change (delta b) and Total Color Change (delta E)
[437] StabilizerGlossDelta bDelta E No addition930.610.73 Compound II (1%)960.130.25
[438] The 2k acrylic urethane clear coat stabilized with 1% Compound II under natural weathering test conditions showed superior performance in gloss retention, yellow change and total color change compared to 2k urethane clear coat containing no stabilizer. An increase in delta E indicates undesirable discoloration of the urethane coating. An increase in delta b represents an undesirable rate of yellowing of the urethane coating.
[439] Example 22. Comparison of Compound II to Conventional HALS Compounds in Polypropylene Articles
[440] 0.25 in PROFAX 6501 polypropylene powder containing 0.1% 2,4,6-tri-t-butylphenol (commercially available from Montel USA, Inc., Wilmington, Delaware, USA). Each anhydrous blended in the% loading concentration. The blend was ground for 4 minutes at 160-170 ° C. at 25 rpm with a steam double roller mill. This sample was then compression molded into a film at 200 ° C. for 3 minutes under a maximum pressure of 30 tons. The thickness of the sample used for the exposure test was in the range of 2.0 to 2.5 mils as measured for each film. The samples were exposed to an dry Xenon weatherometer and 120 ° C. oven. The increase in carbonyl absorption intensity after sample digestion was measured with a Perkin-Elmer 1310 infrared spectrometer (commercially available from Perkin-Elmer Corporation, Norwalk, Conn.). The percent carbonyl formation is shown according to the following relationship:
[441] % Carbonyl Formation = (A _x -A _o ) / a * l
[442] Where A _o is absorbance at 5.85 microns for unexposed film-absorbance at 5.35 microns
[443] A _x absorbance at 5.35 microns less than the absorbance at 5.85 microns for the exposed film
[444] a = 0.20 (absorption coefficient for "carbonyl" present in polypropylene)
[445] l = film thickness (mil)
[446] The end point of exposure was defined as the exposure time to reach 0.1% carbonyl formation. The data in Table II shows the comparison of various commercial HALS compounds with Compound II.
[447] Table II
[448] Performance of HALS Compounds Added to PROFAX 6501 Polypropylene
[449] Sample IDHALS compounds added to PROFAX 6501 polypropyleneAnhydrous XeWOM (time) ^a 120 ° C Oven (Sun) ^aACYASORB (registered trademark) UV-3346 ^b 132036 BCHIMASORB (registered trademark) 944 ^c 169051 CTINUVIN ^R 783 ^c 98751 DUVASORB ^R HA-88 ^d 190051 EUV-CHEK ^R AM-340 ^c > 200011 FTINUVIN ^R 770 ^c 1200-16007 GTINUVIN ^R 765 ^c 1200-160014 HCompound II> 200011 IN / A<4009^a Average of two samples, 2.5 mil ^{b Product from} Scitec Industries, Inc. West Paterson, Nc ^c Product from Ciba Specialty Chemicals Inc., Inc. (Hoston, NY) ^d 3 V Inc., Georgetown, SC Products of ^e Ferro Corporation (Cleveland, Ohio)
[450] The data presented in Table II demonstrate that Compound II outperforms unstabilized systems and shows equal or better performance than other HALS compounds tested after 2000 hours of exposure to XeWOM.
[451] Comparison of Conventional HALS and HALS Compounds of the Invention
[452] Example 23 Performance of Compounds I-IV, VII, and VIII Compared to Conventional HALS Added to PROFAX 6501 Polypropylene Articles
[453] Several commercially available HALS compounds, along with compounds I through IV, VII and VIII, were prepared with 0.07% calcium stearate (Witco Corporation, Greenwich, Connecticut) and Cyanox A-2777 (Cytech Industries, West Paterson, NJ). ), And anhydrously blended to a PROFAX 6501 polypropylene powder (commercially available from Montel USA Inc., Wilmington, Delaware) containing 0.07% at a concentration of 0.2%. The blended material is a brabender equipped with a single mixing screw extruder with one pass through five zones at 50 to 75 rpm, respectively, at temperatures of zones 1 to 5 at 210 ° C, 215 ° C, 220 ° C, 225 ° C and 230 ° C, respectively. Brabender) Melt mixed on a PL-2000 torque rheometer base (product of CW Brabender Inc., South Hekensec, NJ). The extrudate was cooled, dried and pelletized. The pellets were compression molded into sample plaques (2 × 2.5 × 0.100 inch) at 275 ° C. using a PHI press (available from Pasadena Hylaurics Inc., The City of Industry, Calif.). ASTM G using Test Method B with alternating exposure of sample plaques to light and dark conditions and intermittent exposure to a water spray that maintains an ambient temperature of 63 ± 3 ° C. and a relative humidity of 30 ± 5% (Miami, Florida). Exposed to xenon-arc weather resistance according to the -26 standard method. Color (ΔE) is the Macbeth Color Eye Colorimeter (Gretag-Macbeth L.C., New Windsor, NY) under laboratory conditions consisting of Illumination C, 2 ° observer, specular component exclusion, and UV component addition. Was measured. Specular reflectance was measured according to the ASTM D523 standard method using a Gardner black plate 60 ° glossmeter which measures deviation loss up to 50%. The pellets were also injection molded into tension bars using a hydraulic injection molding machine (Arburg "Allrounder" (commercially available from Arburg GmbH & Co., Rosburg, Germany). The temperature used was as follows: nozzle, 200 ° C .; Nozzle side, 220 ° C .; Central 225 ° C .; Inlet 210 ° C .; And molding machine 52 ° C. The blended material was made into a thin film. This thin film was prepared as described in Example 22.
[454] Compounds I-IV, VII, and VIII are described in Tinuvin 765 (bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, CAS # 41556-26-7) (Hoddon, NY) Commercially available from Ciba Specialty Corporation); Tinuvin 770 (bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, CAS # 52829-07-9) (commercially available from Ciba Specialty Corp., Hodon, NY); Tinuvin 622 (1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethyl piperidine-succinic acid, dimethyl ester, copolymer CAS # 65447-77-0) (New York Commercially available products of Ciba Specialty Corporation, Hawthorne); Chimasorb 944 (poly [6- (1,1,3,3-tetramethylbutyl) amino] -1,3,5-triazine-2,4-diyl]-[(2,2,6,6-tetra Methyl-4-piperidyl) imino], CAS # 71878-19-8) (commercially available from Ciba Specialty Corporation, Hodon, NY); Tinuvin 783 (a 1: 1 blend of Chimasorb 944 and Tinuvin 622) (commercially available from Ciba Specialty Corp., Hodon, NY).
[455] Table III shows a comparison of ΔE = 3 hours for HALS of the invention with several commercial HALS, 50% gloss retention time for polypropylene plaques, and time to break (measured via carbonyl in thin films). Table IV compares the time taken for 50% strength retention, 50% elongation retention and 50% toughness strength retention using PROFAX polypropylene tensile bars for HALS of the invention and various commercially available HALS compounds.
[456] TABLE III
[457] Performance of HALS of the Invention Relative to Conventional HALS in PROFAX 6501 Polypropylene Plaques and Polypropylene Thin Films
[458] additive△ E = 3 time required (plaque)50% gloss retention time (plaque)Time to break (thin film) ^*Compound VII208013331000 Compound VIII1267707600 Tinuvin 622 ^a 529895600 No addition180<100200 Compound II2300> 1600Compound IV> 3000> 1600800 Tinuvin 765 ^a 2740> 1600600 No addition180<100200 Compound I474> 1200600 Compound III600> 6001000 Tinuvin 770 ^a 581> 1200600 No addition180<100200^* Measured through an increase to a concentration of 0.1% of carbonyl uptake as described in Example 22. ^a Commercial item from Ciba Specialty Corporation in Hodon, New York.
[459] Table IV
[460] Performance of the HALS of the present invention, Florida weather resistance test and xenon weather resistance test relative to conventional HALS using PROFAX 6501 propylene tension bar
[461] additive50% strength retention period (month) (Florida weather resistance test)50% elongation retention period (month) (Florida weatherability test)50% tensile strength retention time (xenon weather resistance test) Compound VII> 125Compound VIII85Tinuvin 62275No addition<3<3Compound II 840 Compound IV 1100 Tinuvin 765 640 No addition 204 Compound I 384 Compound III 690 Tinuvin 770 1000 No addition 204
[462] The data in Tables III and IV demonstrate that the HALS of the present invention outperforms unstabilized systems and exhibits the same or better performance as compared to commercial HALS compounds.
[463] Example 24 Performance Comparison of Compounds I-IV, VII, and VIII Relative to Conventional HALS in Polyethylene Articles
[464] 0.01% zinc stearate (commercially available from Mallinklot Chemicals, St. Louis, MO) and 0.07% Cyanox A-2777 (New Jersey) with 0.1% loading of compounds I to IV, VII and VIII, respectively, with several commercially available HALS compounds It was added to LLDPE prills containing Cytec Industries, Inc., West Patterson, and anhydrous blended. The blended material is a brabender equipped with a single mixing screw extruder with one pass through five zones at 50 to 75 rpm, respectively, at temperatures of zones 1 to 5 at 170 ° C, 175 ° C, 180 ° C, 185 ° C and 190 ° C, respectively. Brabender) melt mixed on a PL-2000 torque rheometer base. The extrudate was cooled, dried and pelletized. The pellet was compression molded into sample plaques (2 × 2.5 × 0.100 inch) at 177 ° C. using a PHI press. ASTM G using Test Method B with alternating exposure of sample plaques to light and dark conditions and intermittent exposure to water spray maintaining an ambient temperature of 63 ± 3 ° C. and a relative humidity of 30 ± 5% (Miami, Florida). Exposed to a xenon-arc weather resistance meter according to the -26 standard method. Color (ΔE) was measured with a Macbeth Color Eye Colorimeter under laboratory conditions consisting of Illumina C, 2 ° observer, specular component exclusion, UV component addition. The blended material was also made into a thin film. This thin film was prepared as described in Example 22.
[465] Table V shows a comparison of ΔE = 3 hours, 50% gloss retention time, and time to break (measured via carbonyl) for HALS of the invention and various commercially available HALS compounds in LLDPE plaques and thin films.
[466] Table V
[467] Performance of HALS of the Invention Relative to Conventional HALS in LLDPE Plaques and Thin Films
[468] additive△ E = 3 hours (plaque)50% gloss retention time (plaque)Time to break (thin film) ^*Compound VII612257291000 Compound VIII683149001800 Tinuvin 622> 760062121000 No addition1802467200 Compound II> 7600> 76002200 Compound IV> 760068501000 Tinuvin 765> 7600> 76001000 No addition1802467200 Compound I> 76007492> 1800 Compound III> 76007446> 1800 Tinuvin 77060072521800 No addition1802467200^* Measured through an increase to a concentration of 0.1% of carbonyl uptake as described in Example 22.
[469] The data in Tables III and IV demonstrate that the HALS of the present invention outperforms unstabilized systems and exhibits the same or better performance when compared to commercial HALS compounds.
[470] Example 25 Performance Comparison of Compound VIII Relative to Conventional HALS in Polypropylene Articles
[471] 0.2% loading of compound VIII, Cyasorb ^R UV-3346 and compound VIII 1: 1 blend, Cyasorb ^R UV-3346 and several commercially available HALS compounds, respectively, with 0.07% calcium stearate (Witco Corporation, Greenwich, Connecticut). Commercially available) and 0.07% Cyanox A-2777 (commercially available from Cytec Industries, West Paterson, NJ) and added to PROFAX 6501 polypropylene flake (Montel USA Inc., Wilmington, Dela.). The blended material is a brabender equipped with a single mixing screw extruder with one pass through zone 5 at 50 to 75 rpm, respectively, at temperatures of zones 1 to 5 at 210 ° C, 215 ° C, 220 ° C, 225 ° C and 230 ° C, respectively. Brabender) Melt mixed on a PL-2000 torque rheometer base (product of CW Brabender Inc., South Hekensec, NJ). The extrudate was cooled, dried and pelletized. The pellets were compression molded into sample plaques (2 × 2.5 × 0.100 inch) at 275 ° C. using a PHI press (available from Pasadena Hylaurics Inc., The City of Industry, Calif.). ASTM G using Test Method B with alternating exposure of sample plaques to light and dark conditions and intermittent exposure to water spray maintaining an ambient temperature of 63 ± 3 ° C. and a relative humidity of 30 ± 5% (Miami, Florida). Exposed to a xenon-arc weather resistance meter according to the -26 standard method. Specular reflectance was measured according to the ASTM D523 standard method using a Gardner black plate 60 ° glossimeter measuring 50% deviation loss.
[472] Example 25 Performance Comparison of Compound VIII of the Invention Relative to Conventional HALS in PROFAX 6501 Polypropylene Plaques
[473] additive50% gloss retention time Compound VIII2450 Cyasorb UV-33462400 1: 1 Cyasorb UV-3346: Compound VIII (1: 1)> 2850 Tinuvin 7832283 Tinuvin 6222850
[474] The data of Example 25 demonstrates that the HALS of the present invention exhibits the same or better performance than commercial HALS compounds.
[475] Example 26 Performance Comparison of Compounds I and II Relative to Conventional HALS in Nylon 6 Plaques
[476] B85ZP Nylon 6 (Morris Town, Morristown, NJ) containing 0.075% Cyanox A-2777 (commercially available from Cytec Industries, West Paterson, NJ) at 0.3% loading of Compounds I and II and several commercially available HALS compounds Commercially available products of Well Ink), and anhydrous blended. The blended material was fitted with a 0.75 inch 25: 1 single mixing screw extruder with one pass through four zones at 70 rpm, each at a temperature of Zones 1 to 4 at 245 ° C., 260 ° C., 270 ° C. and 260 ° C., respectively. (Haake) SS (commercially available from Hoark Inc., Paramus, NJ) was melt mixed. The extrudate was cooled, dried and pelletized. The pellets were injected into an injection molding machine (Arburg Allrounder 320-210-750; commercially available from Arburg GmbH & Co., Rosburg, Germany) at a nozzle of 245 ° C, nozzle side 260 ° C, central part 270 ° C, inlet part 270 ° C and molding machine 82 ° C. Injection molded into sample plaques (2 × 2.5 × 0.100 inches). ASTM G using Test Method B with alternating exposure of sample plaques to light and dark conditions and intermittent exposure to water spray maintaining an ambient temperature of 63 ± 3 ° C. and a relative humidity of 30 ± 5% (Miami, Florida). Exposed to a xenon-arc weather resistance meter according to the -26 standard method. Colors measured by yellow change index (YI) and ΔE were measured by Macbeth color eye colorimeter under laboratory conditions consisting of Illuminate C, 2 ° observer, specular component exclusion, UV component addition.
[477] Example 26 Performance Comparison of Compounds I and II Relative to Conventional HALS in Nylon 6 Plaques
[478] additiveYI value after 4000 hours△ E value UV-334668.3 UV-35295.68 Nylostab S-EED ^a 3.36.8 Tinuvin 7703.48.3 Compound I2.37.8 Compound II2.47.3 No addition8.412.3^a Nylostab S-EED is a development of Clariant Corporation, Charlotte, NC; N, N'-bis (2,2,6,6-tetramethyl-4-piperidinyl) isophthalamide)
[479] The data in Example 26 demonstrates that the HALS of the present invention outperforms unstabilized systems and exhibits the same or better performance compared to other HALS compounds.
[480] The invention described and claimed herein is not to be limited in scope by the specific embodiments as the specific embodiments disclosed above are intended to illustrate various aspects of the invention. Accordingly, all equivalent embodiments are within the scope of the present invention. Various modifications of the invention in addition to those shown and described herein will be apparent to those skilled in the art from the foregoing detailed description. Such modifications are also within the scope of the appended claims.

权利要求:
Claims (13)
[1" claim-type="Currently amended] A polymeric article comprising at least one polymeric material and at least one compound represented by the following formula (I), (II) or (III) in an amount sufficient to inhibit at least one of photolysis or pyrolysis, wherein: Polymer articles wherein the compounds represented by:
Formula I
RZ-CO-CR ^a R ^b -(-CR ^c R ^d- ) _n -NH- (Y) _m -CO-A
[Wherein n is an integer from 1 to 15 and m is 0 or 1; R ^a , R ^b , R ^c and R ^d are each hydrogen or hydrocarbyl group; Y is CO-C (R ^e R ^f ) _p (where R ^e and R ^f are each hydrogen or hydrocarbyl groups and p is 0 or an integer from 1 to 20) or CO-C ₆ H ₄ − (where , The substitution pattern on the phenylene group is an ortho, meta or para substitution pattern and one or more hydrogens of the phenylene group may be substituted with a hydrocarbyl group or a functional group); Z is -O- or -NG-, wherein G is H, C ₁ to C ₁₂ alkyl or radical R; R is represented by the following formula; A is a ZR or hydrocarbyl group.

In this expression,
R ¹ is hydrogen, C ₁ to C ₁₈ alkyl, O, OH, CH ₂ CN, C ₁ to C ₁₈ alkoxy, C ₁ to C ₁₈ hydroxyalkoxy, C ₅ to C ₁₂ cycloalkoxy, C ₅ to C ₁₂ hydro cycloalkoxy, C ₃ to C ₆ alkenyl, C ₁ to C ₁₈ alkynyl group, one, two or three C ₁ a C ₇ to C ₉ to C ₄ substituted or unsubstituted phenyl-alkyl phenylalkyl, or Aliphatic C ₁ to C ₈ acyl; R ² is hydrogen, C ₁ to C ₈ alkyl or benzyl; R ³ , R ⁴ , R ⁵ and R ⁶ are each hydrogen, C ₁ to C ₈ alkyl, benzyl or phenethyl, or two in situ R additions together with the carbon to which they are attached form C ₅ to C ₁₀ cycloalkyl To do it;
Formula II

[Wherein i, j, k and l are integers from about 0 to 300, the sum of i, j, k and l is greater than 2 and E-F is as follows;

E-F 'is as follows;

E'-F is as follows;

E'-F 'is as follows;

S is a hydrogen or piperidine-4-ol or 4-aminopiperidine floating unit having the structure

T is a unit derived from hydrogen or a multifunctional carbonyl compound having the structure

In which D is a hydrocarbyl group, n is an integer from 1 to 15, m is 0 or 1, and s is 0 or an integer from 1 to 10; R ^a , R ^b , R ^c and R ^d are each hydrogen or hydrocarbyl group; Y is CO-C (R ^e R ^f ) _p (where R ^e and R ^f are each hydrogen or hydrocarbyl groups and p is an integer from 0 to 20) or CO-C ₆ H _4- (where phenyl The substitution pattern on the ethylene group is an ortho, meta or para substitution pattern and one or more hydrogens of the phenylene group may be substituted with a hydrocarbyl group or a functional group); R ² is hydrogen, C ₁ to C ₈ alkyl or benzyl; R ³ , R ⁴ , R ⁵ and R ⁶ are each hydrogen, C ₁ to C ₈ alkyl, benzyl or phenethyl, or two in situ R moieties together with the carbon to which they are attached form C ₅ to C ₁₀ cycloalkyl and; Z is -O- or NG, wherein G is H, C ₁ to C ₁₂ alkyl; when s is greater than 0, P is NH or O; when s is 0, P is O or OLO, where L is hydrocarbylene;
Formula III

[Wherein i and j are integers from about 0 to 300 and the sum of i and j is greater than 2;
M-F is as follows;

M-F 'is as follows;

T is a unit derived from hydrogen or a multifunctional carbonyl compound having the structure:

In which D is a hydrocarbyl group, n is an integer from about 1 to 15, m is 0 or 1, and R ^a , R ^b , R ^c and R ^d are each hydrogen or hydrocarbyl group; Y is CO-C (R ^e R ^f ) _p (where R ^e and R ^f are each hydrogen or hydrocarbyl groups and p is an integer from about 0 to 20) or CO-C ₆ H ₄ − (where The substitution pattern on the phenylene group is an ortho, meta or para substitution pattern and one or more hydrogens of the phenylene group may be substituted with a hydrocarbyl group or a functional group); M is one or more diamino or dihydroxy groups comprising a 4-aminopiperidine radical represented by the formula: which is bound to the multifunctional carbonyl compound by a hydroxy or amino group of M:

Wherein R ¹ is hydrogen, C ₁ to C ₁₈ alkyl, O, OH, C ₁ to C ₁₈ alkoxy, C ₁ to C ₁₈ hydroxyalkoxy, C ₅ to C ₁₂ cycloalkoxy, C ₅ to C ₁₂ hydroxy C ₇ to C ₉ which is phenyl unsubstituted or substituted with cycloalkoxy, CH ₂ CN, C ₃ to C ₆ alkenyl, C ₁ to C ₁₈ alkynyl, 1, 2 or 3 C ₁ to C ₄ alkyl Phenylalkyl, or aliphatic C ₁ to C ₈ acyl; R ² is hydrogen, C ₁ to C ₈ alkyl or benzyl; R ³ , R ⁴ , R ⁵ and R ⁶ are each hydrogen, C ₁ to C ₈ alkyl, benzyl or phenethyl, or two in situ R moieties together with the carbon to which they are attached form C ₅ to C ₁₀ cycloalkyl do].
[2" claim-type="Currently amended] The polymeric article of claim 1, wherein the content of at least one compound is between about 0.01 to 10 weight percent of the polymeric article.
[3" claim-type="Currently amended] The method of claim 1, wherein the polymeric material is selected from the group consisting of polyolefins; Polyester; Polyethers; Polyketones; Polyamides; Natural and synthetic rubbers; Polyurethane; polystyrene; High impact polystyrene; Polyacrylates; Polymethacrylates; Polyacetals; Polyacrylonitrile; Polybutadiene; polystyrene; ABS; SAN (styrene acrylonitrile); ASA (acrylate styrene acrylonitrile); Cellulose acetate butyrate; Cellulose polymers; Polyimide; Polyamideimide; Polyetherimide; Polyphenylsulfide; PPO; Polysulfones; Polyethersulfones; Polyvinyl chloride; Polycarbonate; Polyketones; Aliphatic polyketones; Thermoplastic TPO; Amino resin crosslinked polyacrylates and polyesters; Polyisocyanate crosslinked polyesters and polyacrylates; Phenol / formaldehyde, urea / formaldehyde and melamine / formaldehyde resins; Dry and undrying alkyd resins; Alkyd resins; Polyester resins; Acrylate resins crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, carbamates and epoxy resins; Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic and aromatic glycidyl compounds crosslinked with anhydrides or amines; Polysiloxanes; Activated unsaturation of amines or blocked amines and Michael addition polymers with methylene compounds, ketimines with activated unsaturated and michael addition polymers with methylene compounds, polyketimines and unsaturated acrylic resins in combination with unsaturated acrylic polyacetoacetate resins Combined polyketamine; Radiation curable compositions; Epoxy melamine resins; Organic dyes; Beauty products; Cellulosic paper compositions; Photographic film paper; ink; And polymeric articles thereof.
[4" claim-type="Currently amended] The polymeric article of claim 3, wherein the polymeric material comprises a polyamide or a homopolymer or copolymer of polyolefin.
[5" claim-type="Currently amended] The method according to claim 1, wherein the antioxidant, UV absorber and light stabilizer, metal deactivator, phosphite and phosphonite, hydroxylamine, nitron, thiosynergist, peroxide impurity remover, polyamide stabilizer, basic safety Purifiers, nucleating agents, fillers and reinforcing agents, benzofuranone, indolinone, acid impurity removers, antistatic agents, blowing agents, catalysts, purifiers, emulsifiers, fillers, refractory materials, fluorescent bleaches, infrared absorbers, leveling aids, lubricants, metal deactivators, A polymeric article characterized by further comprising one or more additives selected from the group consisting of mold release agents, nucleating agents, optical brighteners, pigments, plasticizers, flow additives, and mixtures thereof.
[6" claim-type="Currently amended] The polymeric article of claim 5, wherein one or more additives are provided in an amount of up to about 10% by weight of the polymeric article.
[7" claim-type="Currently amended] (a) at least one compound of formula (I), (II) or (III)
(b) a composition comprising at least one other additive selected from the group consisting of UV absorbers, light stabilizers and antioxidants:
Formula I
RZ-CO-CR ^a R ^b -(-CR ^c R ^d- ) _n -NH- (Y) _m -CO-A
[Wherein n is an integer from 1 to 15 and m is 0 or 1; R ^a , R ^b , R ^c and R ^d are each hydrogen or hydrocarbyl group; Y is CO-C (R ^e R ^f ) _p (where R ^e and R ^f are each hydrogen or hydrocarbyl groups and p is 0 or an integer from 1 to 20) or CO-C ₆ H ₄ − (where , The substitution pattern on the phenylene group is an ortho, meta or para substitution pattern and one or more hydrogens of the phenylene group may be substituted with a hydrocarbyl group or a functional group); Z is -O- or -NG-, wherein G is H, C ₁ to C ₁₂ alkyl or radical R; R is represented by the following formula; A is a ZR or hydrocarbyl group.

In this expression,
R ¹ is hydrogen, C ₁ to C ₁₈ alkyl, O, OH, CH ₂ CN, C ₁ to C ₁₈ alkoxy, C ₁ to C ₁₈ hydroxyalkoxy, C ₅ to C ₁₂ cycloalkoxy, C ₅ to C ₁₂ hydro cycloalkoxy, C ₃ to C ₆ alkenyl, C ₁ to C ₁₈ alkynyl group, one, two or three C ₁ a C ₇ to C ₉ to C ₄ substituted or unsubstituted phenyl-alkyl phenylalkyl, or Aliphatic C ₁ to C ₈ acyl; R ² is hydrogen, C ₁ to C ₈ alkyl or benzyl; R ³ , R ⁴ , R ⁵ and R ⁶ are each hydrogen, C ₁ to C ₈ alkyl, benzyl or phenethyl, or two in situ R additions together with the carbon to which they are attached form C ₅ to C ₁₀ cycloalkyl To do it;
Formula II

[Wherein i, j, k and l are integers from about 0 to 300, the sum of i, j, k and l is greater than 2 and E-F is as follows;

E-F 'is as follows;

E'-F is as follows;

E'-F 'is as follows;

S is a unit derived from hydrogen or a piperidin-4-ol or 4-aminopiperidine moiety having the structure

T is a unit derived from hydrogen or a multifunctional carbonyl compound having the structure

In which D is a hydrocarbyl group, n is an integer from 1 to 15, m is 0 or 1, and s is 0 or an integer from 1 to 10; R ^a , R ^b , R ^c and R ^d are each hydrogen or hydrocarbyl group; Y is CO-C (R ^e R ^f ) _p (where R ^e and R ^f are each hydrogen or hydrocarbyl groups and p is an integer from 0 to 20) or CO-C ₆ H _4- (where phenyl The substitution pattern on the ethylene group is an ortho, meta or para substitution pattern and one or more hydrogens of the phenylene group may be substituted with a hydrocarbyl group or a functional group); R ² is hydrogen, C ₁ to C ₈ alkyl or benzyl; R ³ , R ⁴ , R ⁵ and R ⁶ are each hydrogen, C ₁ to C ₈ alkyl, benzyl or phenethyl, or two in situ R moieties together with the carbon to which they are attached form C ₅ to C ₁₀ cycloalkyl and; Z is -O- or NG, wherein G is H, C ₁ to C ₁₂ alkyl; when s is greater than 0, P is NH or O; when s is 0, P is O or OLO, where L is hydrocarbylene;
Formula III

[Wherein i and j are integers from about 0 to 300 and the sum of i and j is greater than 2;
M-F is as follows;

M-F 'is as follows;

T is a unit derived from hydrogen or a multifunctional carbonyl compound having the structure:

Wherein D is a hydrocarbyl group, n is an integer from about 1 to 15, m is 0 or 1, and R ^a , R ^b , R ^c and R ^d are each hydrogen or hydrocarbyl group; Y is CO-C (R ^e R ^f ) _p (where R ^e and R ^f are each hydrogen or hydrocarbyl groups and p is an integer from about 0 to 20) or CO-C ₆ H ₄ − (where The substitution pattern on the phenylene group is an ortho, meta or para substitution pattern and one or more hydrogens of the phenylene group may be substituted with a hydrocarbyl group or a functional group); M is one or more diamino or dihydroxy groups comprising a 4-aminopiperidine radical represented by the formula: which is bound to the multifunctional carbonyl compound by a hydroxy or amino group of M:

Wherein R ¹ is hydrogen, C ₁ to C ₁₈ alkyl, O, OH, C ₁ to C ₁₈ alkoxy, C ₁ to C ₁₈ hydroxyalkoxy, C ₅ to C ₁₂ cycloalkoxy, C ₅ to C ₁₂ hydroxy C ₇ to C ₉ which is phenyl unsubstituted or substituted with cycloalkoxy, CH ₂ CN, C ₃ to C ₆ alkenyl, C ₁ to C ₁₈ alkynyl, 1, 2 or 3 C ₁ to C ₄ alkyl Phenylalkyl, or aliphatic C ₁ to C ₈ acyl; R ² is hydrogen, C ₁ to C ₈ alkyl or benzyl; R ³ , R ⁴ , R ⁵ and R ⁶ are each hydrogen, C ₁ to C ₈ alkyl, benzyl or phenethyl, or two in situ R moieties together with the carbon to which they are attached form C ₅ to C ₁₀ cycloalkyl do].
[8" claim-type="Currently amended] The method of claim 7, wherein the one or more other additives are 2- (2′-hydroxyphenyl) benzotriazole, oxamide, 2- (2-hydroxyphenyl) -1,3,5-triazine, 2- A composition characterized in that it is selected from the group consisting of hydroxybenzophenone, steric hindered amine and hindered phenol antioxidant.
[9" claim-type="Currently amended] The method of claim 7, wherein the one or more additives
2- (2'-hydroxy-5'-methylphenyl) benzotriazole;
2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) benzotriazole;
2- (5'-tert-butyl-2'-hydroxyphenyl) benzotriazole;
2- (2'-hydroxy-5 '-(1,1,3,3-tetramethylbutyl) phenyl) benzotriazole;
2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) -5-chlorobenzotriazole;
2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) -5-chloro-benzotriazole;
2- (3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl) -benzotriazole;
2- (2'-hydroxy-4'-octoxyphenyl) benzotriazole;
2- (3 ', 5'-di-tert-amyl-2'-hydroxyphenyl) benzotriazole;
2- (3 ', 5'-bis (α, α-dimethylbenzyl) -2'-hydroxyphenyl) -benzotriazole;
2- (3'-tert-butyl-2'-hydroxy-5 '-(2-octyloxycarbonylethyl) phenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-5 '-[2- (2-ethylhexyloxy) -carbonylethyl] -2'-hydroxyphenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy -5 '-(2-methoxycarbonylethyl) phenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonyl Ethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '-(2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert- Butyl-5 '-[2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'- A mixture of methylphenyl) benzotriazole and 2- (3'-tert-butyl-2'-hydroxy-5 '-(2-isooctyloxycarbonylethyl) phenylbenzotriazole;
2- [3'-tert-butyl-5 '-(2-methoxycarbonylethyl) -2'-hydroxyphenyl] benzotriazole and polyethylene glycol 300 [R-CH ₂ CH-COO (CH ₂ ) ₃ ] 2,2-methylenebis, a transesterification product of ₂ B, wherein R is 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl 4- (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-ylphenol];
Bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate;
Bis (2,2,6,6-tetramethylpiperidin-4-yl) succinate;
Bis (1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate;
Bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate;
Bis (1,2,2,6,6-pentamethylpiperidin-4-yl) -n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate;
Condensates of 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine with succinic acid;
N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine Condensates of;
Tris (2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate;
Tetrakis (2,2,6,6-tetramethylpiperidin-4-yl) -1,2,3,4-butanetetracarboxylate;
1,1 '-(1,2-ethanediyl) bis (3,3,5,5-tetramethylpiperazinone);
4-benzoyl-2,2,6,6-tetramethylpiperidine;
4-stearyloxy-2,2,6,6-tetramethylpiperidine;
Bis (1,2,2,6,6-pentamethylpiperidyl) -2-n-butyl-2- (2-hydroxy-3,5-di-tert-butylbenzyl) malonate;
3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione;
Bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate;
Bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate;
N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) hexamethylenediamine with 4-morpholino-2,6-dichloro-1,3,5-triazine Condensates;
2-chloro-4,6-bis (4-n-butylamino-2,2,6,6-tetramethylpiperidyl) -1,3,5-triazine and 1,2-bis (3-aminopropyl Condensates of amino) ethanes;
2-chloro-4,6-bis (4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl) -1,3,5-triazine and 1,2-bis- (3 Condensates of -aminopropylamino) ethane;
8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione;
3-dodecyl-1- (2,2,6,6-tetramethylpiperidin-4-yl) pyrrolidine-2,5-dione;
3-dodecyl-1- (1-ethanoyl-2,2,6,6-tetramethylpiperidin-4-yl) pyrrolidine-2,5-dione;
3-dodecyl-1- (1,2,2,6,6-pentamethylpiperidin-4-yl) pyrrolidine-2,5-dione;
Mixtures of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine;
Of N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine Condensates;
1,2-bis (3-aminopropylamino) ethane, 2,4,6-trichloro-1,3,5-triazine and 4-butylamino-2,2,6,6-tetramethylpiperidine Condensates of;
2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospyro [4.5] decane;
Oxo-piperazinyl-triazine and 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospyro [4.5] decane and epichlorohydrin Reaction product;
2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine;
2- (2-hydroxy-4-n-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine;
2- (2-hydroxy-4- (mixed isooctyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine;
2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine;
2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine;
2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine;
2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine;
2- (2-hydroxy-4-tridecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine;
2- [2-hydroxy-4- (2-hydroxy-3-butyloxypropyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine;
2- [2-hydroxy-4- (2-hydroxy-3-octyloxypropyloxy) -phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine;
2- [4-dodecyloxy / tridecyloxy-2-hydroxypropoxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-tri Azine;
2- [2-hydroxy-4- (2-hydroxy-3-dodecyloxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine;
2- (2-hydroxy-4-hexyloxy) phenyl-4,6-diphenyl-1,3,5-triazine;
2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine;
2,4,6-tris [2-hydroxy-4- (3-butoxy-2-hydroxypropoxy) phenyl] -1,3,5-triazine;
2- (2-hydroxyphenyl) -4- (4-methoxyphenyl) -6-phenyl-1,3,5-triazine;
2,4-dihydroxybenzophenone; 2-hydroxy-4-methoxybenzophenone;
2-hydroxy-4-octyloxybenzophenone; 2-hydroxy-4-decyloxybenzophenone;
2-hydroxy-4-dodecyloxybenzophenone; 2-hydroxy-4-benzyloxybenzophenone;
4,2 ', 4-trishydroxybenzophenone; 2'-hydroxy-4,4'-dimethoxybenzophenone;
1,3,5-tris (2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl) isocyanurate;
1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate;
1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene;
2,6-di-tert-butyl-4-methylphenol; 2,2'-ethylidene-bis (4,6-di-tert-butylphenol);
1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane;
Esters of mono- or polyhydric alcohols with b- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid;
Esters of monohydric or polyhydric alcohols with b- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid;
Dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate;
Diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate;
Dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate;
Dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate; And
Calcium salt of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester;
Amides of b- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, for example N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl Hexamethylenediamine;
N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylenediamine; And
N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine
Composition characterized in that it is selected from the group consisting of.
[10" claim-type="Currently amended] A composition according to claim 9, wherein at least one compound is a compound represented by formula (I).
[11" claim-type="Currently amended] 10. The composition of claim 9, wherein at least one compound is a compound represented by formula (II).
[12" claim-type="Currently amended] 10. A composition according to claim 9, wherein at least one compound is a compound represented by formula III.
[13" claim-type="Currently amended] 8. The method of claim 7, further comprising a material to be stabilized, wherein the material is
Polyolefins; Polyester; Polyethers; Polyketones; Polyamides; Natural and synthetic rubbers; Polyurethane; polystyrene; High impact polystyrene; Polyacrylates; Polymethacrylates; Polyacetals; Polyacrylonitrile; Polybutadiene; polystyrene; ABS; Styrene acrylonitrile; Acrylate styrene acrylonitrile; Cellulose acetate butyrate; Cellulose polymers; Polyimide; Polyamideimide; Polyetherimide; Polyphenylsulfide; Polyphenylene oxides; Polysulfones; Polyethersulfones; Polyvinyl chloride; Polycarbonate; Polyketones; Aliphatic polyketones; Thermoplastic TPO; Amino resin crosslinked polyacrylates and polyesters; Polyisocyanate crosslinked polyesters and polyacrylates; Phenol / formaldehyde, urea / formaldehyde and melamine / formaldehyde resins; Dry and undrying alkyd resins; Alkyd resins; Polyester resins; Acrylate resins crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, carbamates and epoxy resins; Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic and aromatic glycidyl compounds crosslinked with anhydrides or amines; Polysiloxanes; Michael addition polymers of amines or blocked amines with activated unsaturated and methylene compounds, Michael addition polymers of ketimines with activated unsaturated and methylene compounds, polyketimines and unsaturated acrylic resins in combination with unsaturated acrylic polyacetoacetate resins; Combined polyketamine; Radiation curable compositions; Epoxy melamine resins; Organic dyes; Beauty products; Cellulosic paper compositions; Photographic film paper; ink; And a mixture thereof.

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同族专利:

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公开号 | 公开日

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US6727300B2|2004-04-27|

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CA2427838A1|2002-08-15|

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IL155555D0|2003-11-23|

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BR0115098A|2003-12-30|

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US20020161075A1|2002-10-31|

引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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法律状态:
1999-09-09|Priority to US????

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2000-11-03|Priority to US70484000A

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2000-11-03|Priority to US09/704,840

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2001-10-25|Priority to US10/087,266

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2001-10-26|Application filed by 사이텍 테크놀러지 코포레이션

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2001-10-26|Priority to PCT/US2001/049872

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2003-06-25|Publication of KR20030051771A

优先权:

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申请号 | 申请日 | 专利标题

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US????|1999-09-09|

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US70484000A| true| 2000-11-03|2000-11-03|

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US09/704,840|2000-11-03|

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US10/087,266|US6727300B2|2000-11-03|2001-10-25|Polymeric articles containing hindered amine light stabilizers based on multi-functional carbonyl compounds|

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PCT/US2001/049872|WO2002062885A2|2000-11-03|2001-10-26|Polymeric articles containing hindered amine light stabilizers based on multi-functional carbonyl compounds|