• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention relates to synergistic formulations of certain phenolic antioxidants for use in thermoplastic polymers, in particular polyolefin conduits and other thermoplastic molding materials in prolonged contact with water. The formulations of the present invention exhibit better resistance to oxidative degradation when measured against oxidation induction time (OIT), color, and other technically important parameters as known in the art.
    公开号:KR20020091098A
    申请号:KR1020027011022
    申请日:2001-02-21
    公开日:2002-12-05
    发明作者:코흐하랄드；리치트블라우알렉산더；초흐마티아스；크뢴케크리스토프
    申请人:클라리언트 파이넌스 (비브이아이)리미티드；
    IPC主号:
    专利说明:

    Synergistic Blend of Phenolic Antioxidants {SYNERGISTIC COMBINATIONS OF PHENOLIC ANTIOXIDANTS}
    [2] The service life of partially crosslinked polyolefin conduits and other thermoplastics, especially those with long-term contact with water, such as geotextiles, water pipes, heat pipes, etc., can be determined by the mechanical properties, density, molar mass and mass distribution of the polymer. It is affected by a number of variables. Depending on the end use and the local conditions (temperature, stress and environmental influences) during the period of use, its lifespan should be guaranteed for several decades. In recent years, the expected life expectancy is more than 50 years. For water applications, certain requirements that can be achieved by adding appropriate stabilizers and maintaining stabilizer conditions must be met. The effect of adding such stabilizers and maintaining stabilization conditions can be measured under accelerated test conditions at elevated temperatures as they are stored in hot water. As an important technical criterion, use oxidation induction time (OIT) and mechanical stability. To evaluate the stable state of the polyolefin conduit or other polyolefin-based molding material. Although the problem has often been discussed that extrapolated values of OIT-data often result in too good results compared to conventional oven aging test results, the OIT-test is still well known and technically important. It is used as. Effects in the polymer matrix, such as changes in crystallinity, free volume, morphology, diffusion kinetics coefficients and reaction kinetics coefficients, change the degradation mechanism. Nevertheless, in particular polyethylene (PE) -MD-sectors and PE-HD-sectors require an OIT-limit of at least 30 minutes at 210 ° C. Another technical criterion that must be met as a specific technical requirement is the color determined by the yellowness (YI).
    [3] Additional technical criteria for determining the quality of the resin used to contact water are the amount of stabilizer remaining after storage in hot water (95 ° C), which is part of the standard test program used by relevant resin producers and manufacturers of end products. to be.
    [4] The problems are described in the following publications:
    [5] 1) Higuchi, Y., Nishimura, H., Tamamura, H., and Harada Tea of Osaka Gas Co., Ltd., Japan. Harada, T., Proc. Int. Gas Res. Conf ., 3 , 67-75, 1998; And
    [6] 2) Schmutz, Th., Kramer, E., Zweifel, H of Ciba Specialty Chemicals, Inc., Basel, Switzerland .) And Dorner, G., Advanced extraction resistant long-term thermal stabilizers for polyolefin pipes, J. Elastomers Plast ., 30 (1), 55-67, 1998.
    [7] One of the critical criteria for preventing rapid oxidative degradation of polyolefin conduits or other shaped articles based on thermoplastic polymers is the use of long-lived stabilizers. The effect depends on the compatibility, solubility, flowability and movement of the additives in the conduit resin.
    [8] Phenol-based antioxidants have been used with phosphites or phosphonites and sometimes with alpha-tocopherols to stabilize polyethylene-based thermoplastic polymers (WO-A-97 / 49758). Information on stabilizing polyolefins with phenolic antioxidants is also described in R. Gachter, H. Muller, Handbook "Plastic Additives" ("Kunststoffadditive"), 3. German Edition, Carl Hanser Publishers, Munich, Vienna, p68, 1990.
    [9] Stabilizer systems used in polymer matrices for long-term contact with extractable media have a particular technical need to be improved to maintain the long-term stability of the system (for problems related to stability against migration, hydrolysis).
    [1] The present invention relates to synergistic formulations of phenolic antioxidants for use in polyolefin conduits and other thermoplastic molding materials, especially conduits and molding materials in contact with water.
    [10] It has now been found that certain combinations of phenolic antioxidants provide a synergistic effect with respect to long term thermal stabilization of thermoplastic products, in particular polyolefin products, to be used under extractive conditions of water before and after storage in hot water. The stabilizer formulations of the present invention are surprisingly shown to be superior to the stabilizers of the prior art in terms of resistance to oxidative degradation, color and other variables.
    [11] The object of the present invention,
    [12] (a) bis- [3,3-bis- (4'-hydroxy-3'-tert-butylphenyl) butanoic acid] -glycol ester (I),
    [13] 4,4 ', 4 "-[(2,4,6-trimethyl-1,3,5-benzenetriyl) tris (methylene)]-tris [2,6-bis (1,1-dimethylethyl) phenol ] (II),
    [14] 1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,3,5-tris [[4- (1,1-dimethylethyl) -3-hydroxy- 2,6-dimethylphenyl] methyl] (III),
    [15] Phenol, 4,4 ', 4 "-(1-methyl-1-propaneyl-3-ylidene) tris [2- (1,1-dimethylethyl) -5-methyl (IV),
    [16] Phenol, 2,6-bis [[3- (1,1-dimethylethyl) -2-hydroxy-5-methylphenyl] octahydro-4,7-methano-1H-indenyl] -4-methyl (V ), And
    [17] Benzenepropanoic acid, 3- (1,1-dimethylethyl) -4-hydroxy-5-methyl-, 2,4,8,10-tetraoxaspiro [5.5] undecane-3,9-diyl-bis ( At least one phenolic antioxidant selected from the group consisting of 2,2-dimethyl-2,1-ethanediyl) ester (VI); And
    [18] (b) tetrakisethylene (3,5-di-tert-butyl-4-hydroxyphenyl) -hydrocinnamate (VII), and
    [19] One or more phenolic antioxidants selected from the group consisting of octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate (VIII)
    [20] To provide a stabilizer composition for use in thermoplastic polymers, in particular polyolefins, in a weight ratio of component (a) to component (b) of 1:10 to 10: 1, preferably from 1: 2 to 2: 1. will be.
    [21] Compounds (I) to (VIII) are each commercially available products having the chemical structure of Formulas I to VIII:
    [22]
    [23]
    [24]
    [25]
    [26]
    [27]
    [28]
    [29]
    [30] In particular, stabilizer compositions are preferred wherein component (a) is a compound of formula (I), (II) or (III) or mixtures thereof. Particular preference is given to compounds of the formula (I).
    [31] Another phenolic antioxidant suitable for component (a) is:
    [32] 1,4-bis (3,5-di-tert-butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene;
    [33] 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) phenol;
    [34] 2,4-bisoctylmercapto-6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine;
    [35] 2-octylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine;
    [36] 2-octylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,3,5-triazine;
    [37] 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,2,3-triazine;
    [38] 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate;
    [39] 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate;
    [40] 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenylethyl) -1,3,5-triazine;
    [41] 1,3,5-tris (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexahydro-1,3,5-triazine; or
    [42] 1,3,5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.
    [43] In particular for long-term use of polyethylene-HD and polyethylene-MD products that have been in contact with water before, during and after storage in water, all phenolic antioxidants are 0.001 to 2.000 weight based on the weight of the thermoplastic polymer to be stabilized. %, Preferably at a concentration of 0.020 to 0.200% by weight.
    [44] Thus, another object of the present invention is to stabilize the stabilizer composition from 0.001 to 2.000% by weight, preferably from 0.020 to based on the weight of the polymer, in order to stabilize thermoplastic polymers, in particular polyolefins, which are in prolonged contact with an extractable medium such as water. It is to provide a method of using at a concentration of 0.20% by weight.
    [45] It is a further object of the present invention to incorporate 0.001 to 2.000% by weight, preferably 0.020 to 0.20% by weight of said stabilizer composition in thermoplastic polymers, in particular polyolefins, which are in prolonged contact with an extractable medium such as water. It is to provide a method for stabilizing the polymer.
    [46] Suitable thermoplastic polymers to be stabilized according to the invention are, for example, the polymers disclosed in 1-30 below:
    [47] 1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, and polymers of cycloolefins For example cyclopentene or norbornene; Also polyethylene (which may be optionally crosslinked) such as high density polyethylene (HDPE), high density and high molar mass polyethylene (HDPE-HMW), high density and ultra high molar mass polyethylene (HDPE-UHMW), medium density polyethylene ( HMDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), branched low density polyethylene (BLDPE).
    [48] The polyolefins, ie the polymers of the monoolefins exemplified in the paragraphs above, in particular polyethylene and polypropylene, can be produced by various preparation methods, in particular by the following methods (a) or (b):
    [49] a) free radical polymerization method (typically under high pressure and elevated temperature); or
    [50] b) A catalytic polymerization process using a catalyst which normally contains one or more metals of Groups 4b, 5b, 6b or 8 of the Periodic Table of the Elements.
    [51] These metals typically have one or more ligands such as oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and / or aryls, which may be π- or σ-coordinated. These metal complexes may be in free form or immobilized on a substrate, such as activated magnesium chloride, titanium (III) chloride, alumina or silicon oxide. These catalysts may be soluble or insoluble in the polymerization medium. Such catalysts are active in the polymerization process by themselves or by other activators, for example metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, wherein the metal is an element of the Periodic Table 1a, It is an element of group 2a and / or group 3a). The activator can be modified, for example, with further ester, ether, amine or silyl ether groups. These catalyst systems are typically Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalyst ( SSC).
    [52] 2. Mixtures of the polymers disclosed in No. 1, for example, mixtures of polypropylene and polyisobutylene, mixtures of polyethylene and polyisobutylene, mixtures of polypropylene and polyethylene (eg PP / HDPE / LDPE) And mixtures of different types of polyethylenes with one another (eg, LDPE / HDPE).
    [53] 3. Copolymers of monoolefins and diolefins with one another or copolymers thereof with other vinyl monomers, for example ethylene-propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene- But-1-ene copolymer, propylene-isobutylene copolymer, ethylene-but-1-ene copolymer, ethylene-hexene copolymer, ethylene-methylpentene copolymer, ethylene-heptene copolymer, ethylene-octene copolymer , Propylene-butadiene copolymer, isobutylene-isoprene copolymer, ethylene-alkyl acrylate copolymer, ethylene-alkyl methacrylate copolymer, ethylene-vinyl acetate copolymer and copolymer of these and carbon monoxide or ethylene-acrylic acid air Copolymers and their salts (ionomers), and ethylene and propylene and dienes such as hexadiene, dicyclopentadiene or ethylidene-no Terpolymer of norbornene; And mixtures of the copolymers with each other and mixtures of the copolymers with the polymers disclosed in No. 1, for example polypropylene-ethylene-propylene copolymers, LDPE-ethylene-vinyl acetate copolymers, LDPE-ethylene-acrylic acid air Copolymers, LLDPE-ethylene-vinyl acetate copolymers, LLDPE-ethylene-acrylic acid copolymers and alternating or random polyalkylene-carbon monoxide copolymers, and mixtures thereof with other polymers such as polyamides .
    [54] 4. Hydrocarbon resins (eg C 5 -C 9 ), for example hydrogenation modifiers thereof (eg tackifier resins) and mixtures of polyalkylenes and starches.
    [55] 5. Polystyrene, poly (p-methylstyrene), poly (α-methylstyrene).
    [56] 6. Copolymers of styrene or α-methylstyrene with diene or acrylic acid derivatives, for example styrene-butadiene, styrene-acrylonitrile, styrene-alkyl methacrylate, styrene-butadiene-alkyl acrylate, styrene-butadiene-alkyl Methacrylate, styrene-maleic anhydride, styrene-acrylonitrile-methacrylate; Mixtures of high impact strength styrene copolymers with other polymers such as polyacrylates, diene polymers or ethylene-propylene-diene terpolymers; And block copolymers of styrene, for example styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene / butylene-styrene or styrene-ethylene / propylene-styrene.
    [57] 7. Graft copolymers of styrene or α-methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymer, styrene on polybutadiene and acrylonitrile (or methacrylonitrile) Nitrile); Styrene, acrylonitrile and methyl methacrylate on polybutadiene; Styrene and maleic anhydride on polybutadiene; Styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; Styrene and maleimide on polybutadiene; Styrene and alkyl acrylates or alkyl methacrylates on polybutadiene; Styrene and acrylonitrile on ethylene-propylene-diene terpolymers; Styrene and acrylonitrile on polyalkyl acrylate or polyalkyl methacrylate; Styrene and acrylonitrile on acrylate-butadiene copolymers; Mixtures of these with the copolymers disclosed in No. 6, for example copolymer mixtures known as ABS, MBS, ASA or AES polymers.
    [58] 8. Halogen-containing polymers such as polychloroprene, rubber rubber, isobutylene-isoprene chlorinated and brominated copolymers (halobutyl rubber), chlorinated or sulfochloride polyethylene, copolymers of ethylene and ethylene chloride, epichlorohigh Broughtin homopolymers and copolymers, especially copolymers of halogen-containing vinyl compounds, such as polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride; And copolymers thereof such as vinyl chloride-vinylidene chloride, vinyl chloride-vinyl acetate or vinylidene chloride-vinyl acetate.
    [59] 9. Polymethyl methacrylates impact-modified with polymers derived from α, β-unsaturated acids and derivatives thereof such as polyacrylates and polymethacrylates, polyacrylonitrile, polyacrylamides and butyl acrylates .
    [60] 10. Copolymers of monomers disclosed in No. 9 or copolymers of these with other unsaturated monomers, for example acrylonitrile-butadiene copolymers, acrylonitrile-alkyl acrylate copolymers, acrylonitrile- Alkoxyalkyl acrylate copolymers, acrylonitrile-vinyl halide copolymers or acrylonitrile-alkyl methacrylate-butadiene terpolymers.
    [61] 11. Polymers derived from unsaturated alcohols, unsaturated amines or acyl derivatives or acetals thereof such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, Polyallyl phthalate or polyallyl melamine; And copolymers of these with olefins as described above.
    [62] 12. Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, polyethylene oxides, polypropylene oxides or copolymers thereof with bisglycidyl ethers.
    [63] 13. polyacetals such as polyoxymethylene containing polyoxymethylene and comonomers (eg ethylene oxide); And polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
    [64] 14. Polyphenylene oxides and polyphenylene sulfides, and mixtures thereof with styrene polymers or polyamides.
    [65] 15. Polyurethanes derived from hydroxyl-terminated polyethers, polyesters and polybutadienes and on the other hand polyurethanes derived from aliphatic or aromatic polyisocyanates, and precursors thereof.
    [66] 16. Polyamides and copolyamides derived from diamines and dicarboxylic acids, and / or polyamides and copolyamides derived from aminocarboxylic acids or the corresponding lactams, for example polyamides 4, 6, 6/6, 6 / 10, 6/9, 6/12, 4/6, 12/12, 11 and 12; aromatic polyamides starting from m-xylene, diamine and adipic acid; Polyamides prepared from hexamethylenediamine and isophthalic acid and / or terephthalic acid, with or without an elastomer as modifier, for example poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthal amides; Block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; Or block copolymers of the aforementioned polyamides with polyethers such as polyethylene glycol, polypropylene glycol or polytetramethylene glycol; In addition, polyamides or copolyamides modified with EPDM or ABS, and polyamides condensed during processing (RIM polyamide systems).
    [67] 17. Polyureas, polyimides, polyamide-imides, polyester amides, polyhydantoin and polybenzimidazoles.
    [68] 18. Polyesters derived from dicarboxylic acids and dialcohols, and / or polyesters derived from hydroxycarboxylic acids or the corresponding lactones, for example polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylol Block polyether esters derived from cyclohexaneterephthalate, polyhydroxybenzoate, and hydroxyl-terminated polyethers; Also polyesters modified with polycarbonate or MBS.
    [69] 19. Polycarbonates and polyester carbonates.
    [70] 20. Polysulfones, polyether sulfones and polyether ketones.
    [71] 21. Crosslinked polymers derived from aldehydes and crosslinked polymers derived from phenol, urea or melamine on the other hand, for example phenol / formaldehyde resins, urea / formaldehyde resins and melamine / formaldehyde resins.
    [72] 22. Anhydrous alkyd resins and hydrous alkyd resins.
    [73] 23. Unsaturated polyester resins derived from copolyesters of polyhydric alcohols and vinyl compounds as saturated and unsaturated dicarboxylic acids with crosslinkers, and halogen-containing low-flammable modifiers thereof.
    [74] 24. Crosslinkable acrylic resins derived from substituted acrylates such as epoxy acrylates, urethane acrylates or polyester acrylates.
    [75] 25. Alkyd resins, polyester resins and acrylic resins crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins.
    [76] 26. Conventional curing agents (eg, anhydrides or amines) derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds such as bisphenol A diglycidyl ether or bisphenol F diglycidyl ether Epoxy resins crosslinked, for example, with or without accelerators.
    [77] 27. Natural polymers such as cellulose, natural rubber, gelatin, derivatives thereof chemically modified in a polymer-homogenized manner such as cellulose acetate, cellulose propionate and cellulose butyrate, or cellulose ethers (eg , Methyl cellulose), and rosin and derivatives.
    [78] 28. Mixtures of the foregoing polymers (polyblends), for example 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 PUR, POM / acrylate, POM / MBS, PPO / MBS, PPO / HIPS, PPO / PA 6.6 and copolymers, PA / HDPE, PA / PP, PA / PPO, PBT / ABS or PBT / PET / PC.
    [79] 29. Natural and synthetic organic components constituting the pure monomeric compounds or mixtures thereof, such as mineral oil, animal or vegetable fats, oils and waxes, or synthetic esters (eg phthalates, adipates, phosphates or trimellitates) Oils, waxes and fats based on C), and also blends of any desired weight ratios of mineral oil and synthetic esters, as used, for example, as a spin finish, and aqueous emulsions thereof.
    [80] 30. Aqueous emulsions of natural or synthetic rubber, such as latex of natural rubber latex or carboxylated styrene-butadiene copolymers.
    [81] The stabilizer composition of the invention or the thermoplastic polymer to be stabilized may also optionally contain further additives such as antioxidants, light stabilizers, metal deactivators, antistatic agents, flame retardants, lubricants, nucleators, acid scavengers (basic basics). Purifiers), pigments and fillers. Examples of suitable additives that may additionally be used in the formulations include the following compounds:
    [82] 1. Antioxidant
    [83] 1.1 alkylated monophenols such as 2,6-di-tert-butyl-4-methylphenol, 2-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol , 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, linear or branched-branched nonylphenol, for example 2,6-dinonyl-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 and Mixtures thereof.
    [84] 1.2 alkylthiomethylphenols, for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6 Ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol.
    [85] 1.3 hydroquinones and alkylated hydroquinones such as 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert Amylhydroquinone, 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, bis (3,5-di-tert-butyl- 4-hydroxyphenyl) adipate.
    [86] 1.4 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-tert-amylphenol), 4,4'-bis (2,6-dimethyl-4-hydroxyphenyl) disulfide.
    [87] 1.5 alkylidenebisphenols, for example 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'-methylene Bis (6-nonyl-4-methylphenol), 2,2'-methylenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (4,6-di-tertiary -Butylphenol), 2,2'-ethylidenebis (6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis [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-dodecylmer Tobutane, bis (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-tertiary -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, ethylene glycol bis [3,3-bis (3'-tert-butyl-4'-hydroxyphenyl) butyrate].
    [88] 1.6 O-, N- and S-benzyl compounds such as 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl 4-hydroxy Hydroxy-3,5-dimethylbenzylmercaptoacetate, 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-hydroxybenzylmercapto Acetate, tridecyl 4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate.
    [89] 1.7 hydroxybenzylated malonates, for example dioctadecyl 2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, dioctadecyl 2- (3-3 Tert-butyl-4-hydroxy-5-methylbenzyl) -malonate, dododecyl mercaptoethyl-2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, Di- [4- (1,1,3,3-tetramethylbutyl) phenyl] 2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate.
    [90] 1.8 benzylphosphonates, for example dimethyl 2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphate Fonates, dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl 5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, and Ca salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.
    [91] 1.9 acylaminophenols such as 4-hydroxyuramide, 4-hydroxysteaanylide, octyl N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate.
    [92] 1.10 β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid and monohydric or polyhydric alcohols such as methanol, ethanol, n-octanol, isooctanol, 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) oxalamide, 3-thiaoundaneol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-force Ester of pa-2,6,7-trioxabicyclo [2.2.2] octane.
    [93] 1.11 β- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid and monohydric or polyhydric alcohols such as methanol, ethanol, n-octanol, isooctanol, octadecanol, 1, 6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) iso Cyanurate, N, N'-bis (hydroxyethyl) oxalamide, 3-thiaoundaneol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha Esters of -2,6,7-trioxabicyclo [2.2.2] octane.
    [94] 1.12 β- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid and monohydric or polyhydric alcohols such as methanol, ethanol, n-octanol, isooctanol, octadecanol, 1,6- Hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanu Latex, N, N'-bis (hydroxyethyl) oxalamide, 3-thiaoundaneol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2 Ester of 6,7-trioxabicyclo [2.2.2] octane.
    [95] 1.13 3,5-di-tert-butyl-4-hydroxyphenylacetic acid and monohydric or polyhydric alcohols such as methanol, ethanol, n-octanol, isooctanol, octadecanol, 1,6-hexane Diol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate , N, N'-bis (hydroxyethyl) oxalamide, 3-thiaoundaneol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2, Ester of 6,7-trioxabicyclo [2.2.2] octane.
    [96] 1.14 3,3-bis (3'-tert-butyl-4'-hydroxyphenyl) butyric acid with monohydric or polyhydric alcohols such as methanol, ethanol, n-octanol, isooctanol, octadecanol, 1 , 6-hexanediol, 1,9-nonanediol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanu Late, N, N'-bis- (hydroxyethyl) oxalamide, 3-thiaoundaneol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha- Esters of 2,6,7-trioxabicyclo [2.2.2] octane.
    [97] 1.15 Amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, for example N, N'-bis (3,5-di-tert-butyl-4-hydroxy Oxyphenylpropionyl) hexamethylenediamine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylenediamine, N, N'-bis (3,5- Di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine.
    [98] 1.16 Tocopherols such as α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof (vitamin E).
    [99] 1.17 Ascorbic acid (vitamin C).
    [100] 1.18 amine antioxidants such as N, N'-diisopropyl-p-phenylenediamine, N, N'-di-tert-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'-di (naphthyl-2-)-p -Phenylenediamine, 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- (toluenesulfonamido) diphenylamine, N, N'-dimethyl-N, N'-di-tert-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N- (4 -Tert-octylphenyl) -1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, for example p, p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, di (4-methoxyphenyl) amine, 2 , 6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N, N, N ', N'-tetra Methyl-4,4'-diaminodiphenylmethane, 1,2-di-[(2-methylphenyl) amino] ethane, 1,2-di- (phenylamino) propane, (o-tolyl) biguanide, di -[4- (1 ', 3'-dimethylbutyl) phenyl] amine, tert-octylated N-phenyl-1-naphthylamine, monoalkylated and dialkylated tert-butyl tert-octyldiphenylamine , Mixtures of monoalkylated and dialkylated nonyldiphenylamines, mixtures of monoalkylated and dialkylated dodecyldiphenylamines, mixtures of monoalkylated and dialkylated isopropyl / isohexyl-diphenylamines, monoalkylated and dialkylated 3 Mixture of tert-butyldiphenylamine, 2,3-dihydro-3,3-dimethyl-4H-1,4- Benzothiazine, phenothiazine, mixture of monoalkylated and dialkylated tert-butyl / 3 tert-octyl-phenothiazine, mixture of monoalkylated and dialkylated tert-octylphenothiazine, N-allylphenothiazine , N, N, N ', N'-tetraphenyl-1,4-diaminobut-2-ene, N, N-bis (2,2,6,6-tetramethylpiperidin-4-yl) Hexamethylenediamine, bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6 , 6-tetramethylpiperidin-4-ol.
    [101] 2. UV absorbers and light stabilizers
    [102] 2.1 2- (2'-hydroxyphenyl) benzotriazoles, for example 2- (2'-hydroxy-5'-methylphenyl) -benzotriazole, 2- (3 ', 5'-di-tertiary -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-chlorobenzotriazole, 2- (3'-tert-butyl-5'-tert-butyl-2'-hydride Hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) 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-chlorobenzotriazole, 2- (3'-tert-butyl- 5 '-[2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy -5 '-(2-methoxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbo Nylethyl) 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 A mixture of -5'-methylphenyl) benzotriazole and 2- (3'-tert-butyl-2'-hydroxy-5 '-(2-isooctyloxycarbonylethyl) phenyl) benzotriazole; 2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-ylphenol]; 2- [3'-tert-butyl-5 '-(2 -Methoxycarbonylethyl) -2'-hydroxyphenyl] bene Triazole and a transesterification reaction product of polyethylene glycol 300; [R-CH 2 CH 2 -COO (CH 2) 3] 2 ( wherein, R represents 3'-tert-butyl-4'-hydroxy-5'- 2H-benzotriazol-2-ylphenyl).
    [103] 2.2 2-hydroxybenzophenones such as 4-hydroxy derivatives, 4-methoxy derivatives, 4-octyloxy derivatives, 4-decyloxy derivatives, 4-dodecyloxy derivatives, 4-benzyloxy derivatives, 4,2 ', 4'-trihydroxy derivatives and 2'-hydroxy-4,4'-dimethoxy derivatives.
    [104] 2.3 Substituted or unsubstituted esters of benzoic acid, for example 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylesorcinol, bis (4-tert) -Butyl benzoyl) resorcinol, benzoyl isorcinol, 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, 2-methyl-4,6-di-tert-butylphenyl 3 , 5-di-tert-butyl-4-hydroxybenzoate.
    [105] 2.4 acrylates 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 and N- (β Carbomethoxy-β-cyanovinyl) -2-methylindolin.
    [106] 2.5 nickel compounds such as 2,2'-thio-bis [4- (1,1, with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexyl diethanolamine 3,3-tetramethylbutyl) phenol] (eg 1: 1 or 1: 2 complex); Nickel dibutyldithiocarbamate; Nickel salts of monoalkyl esters such as methyl or ethyl esters; Nickel salt of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid; Nickel complex or 1-phenyl-4-lauroyl-5-hydroxypyrazole of ketoxime (eg, 2-hydroxy-4-methylphenyl undecyl ketoxime), with or without additional ligands Nickel complexes.
    [107] 2.6 hindered amines such as bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (2,2,6,6-tetramethylpiperidine-4- I) glutarate, bis (2,2,6,6-tetramethylpiperidin-4-yl) succinate, bis (1,2,2,6,6-pentamethylpiperidin-4-yl ) Sebacate, bis (1,2,2,6,6-pentamethylpiperidin-4-yl) glutarate, 2,2,6,6-tetramethylpiperidyl behenate, 1,2, 2,6,6-pentamethylpiperidyl behenate, condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine with succinic acid, N, N'-bis Condensation product of-(2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine with 4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine , Tris (2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3, 4-butanetetraoate, 1,1 '-(1,2-ethanediyl) -bis (3,3,5,5-tetramethylpipera Non-), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2, 2,6,6-tetramethylpiperidine, 4-stearyloxy-1,2,2,6,6-pentamethylpiperidine, 4-stearoyloxy-1,2,2,6,6 Pentamethylpiperidine, bis (1,2,2,6,6-pentamethylpiperidyl) 2-n-butyl-2- (2-hydroxy-3,5-di-tert-butylbenzyl ) Malonate, bis (1,2,2,6,6-pentamethylpiperidyl) 2-n-butyl-2- (4-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, Condensation product of 6-tetramethyl-4-piperidyl) hexamethylenediamine with 4-morpholino-2,6-dichloro-1,3,5-triazine, N, N'-bis (2,2, 6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4- Condensation product of cyclohexylamino-2,6-dichloro-1,3,5-triazine, 2-chloro-4,6-di- (4-n-butylamino-2,2,6,6-tetramethyl Condensation product of piperidyl) -1,3,5-triazine with 1,2-bis (3-aminopropylamino) ethane, 2-chloro-4,6-di- (4-methoxypropylamino-2 Condensation product of 2,6,6-tetramethylpiperidyl) -1,3,5-triazine with 1,2-bis (3-aminopropylamino) ethane, 2-chloro-4,6-di- Condensation product of (4-methoxypropylamino-1,2,2,6,6-pentamethylpiperidyl) -1,3,5-triazine with 1,2-bis- (3-aminopropylamino) ethane , 2-chloro-4,6-di- (4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl) -1,3,5-triazine and 1,2-bis- Condensation product of (3-aminopropylamino) ethane, 2-chloro-4,6-di- (4-n-butylamino-2,2,6,6-tetramethylpiperidyl) -1,3,5 Triazines and mono- or polyfunctional amines in which one to all active hydrogen atoms on the amine are replaced, eg Reaction products of ethylenediamine, diethylenetriamine, triethylenetetraamine, hexamethylenediamine, 1,2-bis (3-aminopropylamino) ethane, 2-chloro-4,6-di- (4-n- Mono- or polyfunctional amines in which butylamino-1,2,2,6,6-pentamethylpiperidyl) -1,3,5-triazine and one to all active hydrogen atoms on the amine are replaced, e.g. Reaction products of ethylenediamine, diethylenetriamine, triethylenetetraamine, hexamethylenediamine, 1,2-bis (3-aminopropylamino) ethane, 2-chloro-4,6-di- (4-n- Butylamino-2,2,6,6-tetramethylpiperidyl) -1,3,5-triazine and 4-tert-octylamino-2,6-dichloro-1,3,5-s-tria Gin and monofunctional or polyfunctional amines substituted with one to all active hydrogen atoms on the amine, for example ethylenediamine, diethylenetriamine, triethylenetetraamine, hexamethylenediamine, 1,2-bis (3-amino Profile Reaction product of mino) ethane, 2-chloro-4,6-di- (4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl) -1,3,5-triazine And 4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine and mono- or polyfunctional amines in which one to all active hydrogen atoms on the amine are replaced, for example ethylenediamine , Reaction product of diethylenetriamine, triethylenetetraamine, hexamethylenediamine, 1,2-bis (3-aminopropylamino) ethane, 2-chloro-4,6-di- (4-n-butylamino- 2,2,6,6-tetramethylpiperidyl) -1,3,5-triazine and 4- (4-n-butylamino-2,2,6,6-tetramethylpiperidyl) -2 Mono- or polyfunctional amines substituted with 6-dichloro-1,3,5-s-triazine and from 1 to all active hydrogen atoms on the amines, for example ethylenediamine, diethylenetriamine, triethylenetetraamine , Hexamethylenediamine, reaction product of 1,2-bis (3-aminopropylamino) ethane, 2-chloro -4,6-di- (4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl) -1,3,5-triazine and 4- (4-n-butylamino -2,2,6,6-tetramethylpiperidyl) -2,6-dichloro-1,3,5-s-triazine and mono- or polyfunctional with one to all active hydrogen atoms replaced on the amine Amines such as ethylenediamine, diethylenetriamine, triethylenetetraamine, hexamethylenediamine, reaction products of 1,2-bis (3-aminopropylamino) ethane, 1,2-bis (3-aminopropylamino ) Condensation products of ethane and 2,4,6-trichloro-1,3,5-triazine, and also 4-butylamino-2,2,6,6-tetramethylpiperidine, N- (2, 2,6,6-tetramethyl-4-piperidyl) -n-dodecylsuccinimide, N- (1,2,2,6,6-pentamethyl-4-piperidyl) -n-dode Silsuccinimide, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, oligomerization 2,2 , 4,4-tetramethyl-20- (oxyranylmethyl) -7-oxa-3,20-diaza-dis Fatigue [5.1.11.2] Henoic Acid-21-one, oligomerized 1,2,2,4,4-pentamethyl-20- (oxyranylmethyl) -7-oxa-3,20-diaza-disspiro [5.1.11.2] Henicoic Acid-21-one, oligomerized 1-acetyl-2,2,4,4-tetramethyl-20- (oxyranylmethyl) -7-oxa-3,20-diaza-dis Fatigue [5.1.11.2] Henoic Acid-21-one, 3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidyl) pyrrolidine-2,5-dione, 3 -Dodecyl-1- (1,2,2,6,6-pentamethyl-4-piperidyl) pyrrolidine-2,5-dione, 2,2,4,4-tetramethyl-7-oxa -3,20-diaza-disspiro [5.1.11.2] henicoic acid-21-one, 2,2,4,4-tetramethyl-7-oxa-21-oxo-3,20-diaza- Disspiro [5.1.11.2] henenoic acid-3-propanoic acid dodecyl ester, 2,2,4,4-tetramethyl-7-oxa-21-oxo-3,20-diaza-disspiro [5.1. 11.2] Henoic acid-3-propanoic acid tetradecyl ester, 2,2,3,4,4-pentamethyl-7-oxa-3,20-diaza-disspiro [5.1.11.2] henic acid-21 -One, 2,2,3,4,4-pentamethyl-7-oxa-21-oxo-3,20-diaza- Spiro [5.1.11.2] henenoic acid-3-propanoic acid dodecyl ester, 2,2,3,4,4-pentamethyl-7-oxa-21-oxo-3,20-diaza-disspiro [5.1 .11.2] Henicoic acid-3-propanoic acid tetradecyl ester, 3-acetyl-2,2,4,4-tetramethyl-7-oxa-3,20-diaza-disspiro [5.1.11.2] henico Acid-21-one, 3-acetyl-2,2,4,4-tetramethyl-7-oxa-21-oxo-3,20-diaza-disspiro [5.1.11.2] henenoic acid-3-propane Acid dodecyl ester, 3-acetyl-2,2,4,4-tetramethyl-7-oxa-21-oxo-3,20-diaza-disspiro [5.1.11.2] henenoic acid-3-propanoic acid Tetradecyl ester, 1,1 ', 3,3', 5,5'-hexahydro-2,2 ', 4,4', 6,6'-hexaaza-2,2 ', 6,6'- Bismethano-7,8-dioxo-4,4'-bis (1,2,2,6,6-pentamethyl-4-piperidyl) biphenyl, poly-N, N'-bis- ( 2,2,6,6-tetramethyl-4-piperidyl) -1,8-diazaylene, 2,2,6,6-tetramethyl-4-allyloxypiperidine and polymethylhydridosiloxane Adduct of (molar mass of 4000 or less), 1, Adduct of 2,2,6,6-pentamethyl-4-allyloxypiperidine and polymethylhydridosiloxane (molar mass of 4000 or less), N, N'-diformyl-N, N'-bis (2,2,6,6-tetramethyl-4-piperidinyl) -hexamethylenediamine, N, N'-diformyl-N, N'-bis (1,2,2,6,6-penta Methyl-4-piperidinyl) -hexamethylenediamine, 5,11-bis (2,2,6,6-tetramethyl-4-piperidinyl) -3,5,7,9,11,13-hexa tetra-aza-bicyclo [7.4.0.0 2,7 .1 3,13] tetradecane -8,14- dione, 5,11- bis (1,2,2,6,6-pentamethyl-4-piperidinyl ) -3,5,7,9,11,13- hexamethylene tetra-aza-bicyclo [7.4.0.0 2,7 .1 3,13] tetradecane -8,14- dione, [(4-methoxyphenyl) methylene ] Propanediic acid bis (2,2,6,6-tetramethyl-4-piperidinyl) ester, [(4-methoxyphenyl) methylene] propanediic acid bis (1,2,2,6,6-pentamethyl -4-piperidinyl) ester, 2,4,6-tris (N-cyclohexyl-N- [2- (3,3,4,5,5-pentamethylpiperazinone-1-yl) ethyl] Amino) -1,3,5-triazine, 4-amino-2,2,6,6-te Methyl styrene and maleic anhydride and styrene copolymers reacted with lamethylpiperidine and octadecylamine, 4-amino-1,2,2,6,6-pentamethylpiperidine and octadecylamine copolymer of -methylstyrene and maleic anhydride with styrene, having 2,2 '-[(2,2,6,6-tetramethyl-4-piperidinyl) imino] bis [ethanol] as a diol component Polycarbonate, polycarbonate containing 2,2 '-[(1,2,2,6,6-pentamethyl-4-piperidinyl) imino] bis [ethanol] as a diol component, 4-amino-2 Copolymer of maleic anhydride reacted with 2,6,6-tetramethylpiperidine and α-olefin up to C 30 , 1-acetyl-4-amino-2,2,6,6-tetramethylpiperi Copolymer of maleic anhydride and C 30 or less α-olefin reacted with dean, maleic anhydride and C 30 or less α reacted with 4-amino-1,2,2,6,6-pentamethylpiperidine Copolymers of -olefins, and also free NH groups on piperidine N-alkyl-oxy derivatives and N-aryl-oxy derivatives of the compounds having, in particular α-methylbenzyloxy and C 1 to C 18 alkyloxy.
    [108] 2.7 oxalamides such as 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyanilide, 2,2'-dioctyloxy-5,5'-di-tertiary- Butyloxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butyloxanilide, 2-ethoxy-2'-ethyloxanilide, N, N'-bis ( 3-dimethylaminopropyl) oxalamide, 2-ethoxy-5-tert-butyl-2'-ethyloxanide and 2-ethoxy-2'-ethyl-5,4'-di-tertiary -A mixture of butyloxanilides, a mixture of o-methoxy-disubstituted oxanilides and p-methoxy-disubstituted oxanilides, and o-ethoxy-disubstituted oxanilides and p-ethoxy-disubstituted Mixture of oxanilides.
    [109] 2.8 2- (2-hydroxyphenyl) -1,3,5-triazines, for example 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-tri Azine, 2- (2-hydroxy-4-octyloxyphenyl) -4 ', 6-bis (2', 4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-di Hydroxyphenyl) -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-tri Azine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxy Phenyl) -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- (2-hydroxy-4-tridecyl Cyphenyl) -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-dodecyl Oxypropoxy) 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-methoxy Phenyl) -6-phenyl-1,3,5-triazine.
    [110] 3. Metal deactivators such as N, N'-diphenyloxalamide, N-salicyl-N'-salicyloylhydrazine, 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 dihydra Zides, oxanilides, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N, N'-diacetyladifoyl dihydrazide, N, N'-bis (salicyloyl) oxalyl di Hydrazide, N, N'-bis (salicyloyl) thiopropionyl dihydrazide.
    [111] 4. phosphites and phosphonites such as triphenyl phosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, Distearyl pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) penta Erythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bisisodecyloxy pentaerythritol diphosphite, bis (2,4-di-tert- Butyl-6-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di -Tert-butylphenyl) 4,4'-biphenylenediphosphonite, 6-isooctyloxy-2,4,8,10-te La-tert-butyl-12H-dibenzo [d, g] -1,3,2-dioxaphosphosine, 6-fluoro-2,4,8,10-tet-tert-butyl-12- Methyl-dibenzo [d, g] -1,3,2-dioxaphosphosine, bis (2,4, -di-tert-butyl-6-methylphenyl) methylphosphite, bis (2,4-di Tert-butyl-6-methylphenyl) ethyl phosphite, tris (2-tert-butyl-4-thio (2'-methyl-4'-hydroxy-5'-tert-butyl) phenyl-5- Methyl) phenyl phosphite, 2,2 ', 2 "-nitrilo [triethyl tris (3,3', 5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2 ' -Diyl) phosphite], bis [2-methyl-4,6-bis (1,1-dimethylethyl) phenol] phosphate ethyl ester.
    [112] 5. Hydrosylamines such as N, N-dibenzylhydroxylamine, N, N-diethylhydroxylamine, N, N-dioctylhydroxylamine, N, N-dilaurylhydroxylamine, N , N-ditetedecylhydroxylamine, N, N-dihexadecylhydroxylamine, N, N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl- N-octadecylhydroxylamine, N, N-dialkylhydroxylamine prepared from hydrogenated tallow fatty amine.
    [113] 6. 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 nitrile, N-hexadecyl alpha-pentadecyl nitrile, N-octadecyl alpha-heptadecyl nitron, N-hexadecyl alpha-heptadecyl nitron, N-octadecyl alpha-pentadidecyl nitron , Nitron derived from N, N-dialkylhydroxylamine prepared from N-heptadecyl alpha-heptadecyl nitron, N-octadecyl alpha-hexadecyl nitron, hydrogenated tallow fatty amine.
    [114] 7. Zeolites and hydrotalcites, for example DHT 4A®.
    [115] This type of hydrotalcite can be described as a compound of Formula (IX):
    [116] [(M 2+ ) 1-x (M 3+ ) x (OH) 2 (A n- ) x / n yH 2 O]
    [117] Where
    [118] (M 2+ ) is Mg, Ca, Sr, Ba, Zn, Pb, Sn or Ni;
    [119] (M 3+ ) is Al, B or Bi;
    [120] A n is an anion of valence n;
    [121] n is an integer from 1 to 4;
    [122] A is OH -, Cl -, Br - , I -, ClO 4 -, CH 3 COO -, C 6 H 5 COO -, CO 3 2-, SO 4 2-, (OOC-COO) 2-, (CHOHCOO ) 2 2-, (CHOH) 4 CH 2 OHCOO -, C 2 H 4 (COO) 2 2-, (CH 2 COO) 2 2-, CH 3 CHOHCOO -, SiO 3 2-, SiO 4 4-, Fe (CN) 6 3- , Fe (CN) 6 4- , BO 3 3- , PO 3 3- or HPO 4 2- ;
    [123] x is a number from 0 to 0.5;
    [124] y is a number from 0 to 2.
    [125] Wherein (M 2+ ) is (Ca 2+ ), (Mg 2+ ), or a mixture of (Mg 2+ ) and (Zn 2+ ), and (A n- ) is CO 3 2- , BO 3 3 Or hydrotalcite, wherein PO 3 3 − , x is a number from 0 to 0.5, and y is a number from 0 to 2. It is also possible to use hydrotalcites, which may be described as compounds of formula X:
    [126] [(M 2+ ) x (Al 3+ ) 2 (OH) 2x + 6nz (A n- ) 2 yH 2 O]
    [127] Where
    [128] (M 2+ ) is Mg 2+ or Zn 2+ , more preferably Mg 2+ ;
    [129] (A n-) is an anion, in particular CO 3 2-, (OOC-COO ) 2-, OH - , and anions selected from the group consisting of 2-, and S, where n is the valence of the anion;
    [130] y is an integer, more preferably 0 to 5, in particular 0.5 to 5;
    [131] x and y are integers and z should be less than 2 when x is preferably 2-6.
    [132] Particular preference is given to hydrotalcites of the formulas XI to XVII:
    [133] Al 2 O 3 x 6MgO x CO 2 x 12H 2 O
    [134] Mg 4.5 Al 2 (OH) 13 x CO 3 x 3.5H 2 O
    [135] 4 MgO x Al 2 O 3 x CO 2 x 9H 2 O
    [136] 4 MgO x Al 2 O 3 x CO 2 x 6H 2 O
    [137] ZnO x 3 MgO x Al 2 O 3 x CO 2 x 8-9H 2 O
    [138] ZnO x 3 MgO x Al 2 O 3 x CO 2 x 5-6H 2 O
    [139] Mg 4.5 Al 2 (OH) 13 x CO 3
    [140] Hydrotalcite is preferably applied to the polymer at a concentration of 0.01 to 5% by weight, in particular 0.2 to 3% by weight, based on the weight of the total polymer blend.
    [141] 8. Thiosynergists such as dilauryl thiodipropionate and distearyl thiodipropionate.
    [142] 9. Peroxide scavengers, for example esters of β-thiodipropionic acid (eg lauryl ester, stearyl ester, myristyl ester or tridecyl ester), mercaptobenzimidazole, 2-mercaptobenzimimi Zinc salt of dozol, zinc alkyldithiocarbamate, zinc dibutyldithiocarbamate, dioctadecyl monosulfide, dioctadecyl disulfide, pentaerythritol tetrakis (β-dodecylmercapto) propionate.
    [143] 10. Polyamide stabilizers such as copper salts in combination with iodide and / or phosphorus compounds, and divalent manganese salts.
    [144] 11. Basic coarse stabilizers such as melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamines, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids For example, calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate, potassium palmitate, antimony or tin pyrocatecholate, alkali metal salts and alkaline earth metal salts of lactic acid, and Also zinc salts or aluminum salts.
    [145] 12. Nucleating agents, for example inorganic components such as talc, metal oxides (eg titanium oxide or magnesium oxide), preferably phosphates, carbonates or sulfates of alkaline earth metals; Organic compounds such as monocarboxylic acids or polycarboxylic acids and salts thereof such as 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate, aromatic aldehydes and polyfunctional alcohols (eg Acetals of sorbitol), for example 1,3-2,4-di (benzylidene) -D-sorbitol, 1,3-2,4-di (4-tollylidene) -D-sorbitol, 1 , 3-2,4-di (4-ethylbenzylidene) -D-sorbitol; Polymeric compounds such as ionic copolymers (ionomers).
    [146] 13. Fillers and reinforcing agents such as calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, metal oxides, metal hydroxides, carbon black, graphite, wood flour, and other natural products Powder or fiber, synthetic fiber.
    [147] 14. Other additives such as plasticizers, lubricants, emulsifiers, pigments, rheological additives, catalysts, leveling aids, fluorescent brighteners, flame retardants, antistatic agents, blowing agents.
    [148] 15. Benzofuranone and indolins, for example US Pat. No. 4,325,863, US Pat. No. 4,338,244, US Pat. No. 5,175,312, US Pat. No. 5,216,052, US Pat. No. 5,252,643, German Patent Application DE-A- 4316611, German Patent Application DE-A-4316622, German Patent Application DE-A-4316876, European Patent Application EP-A-0589839 or European Patent Application EP-A-0591102 Benzofuranone and indolin, or 3- [4- (2-acetoxyethoxy) phenyl] -5,7-di-tert-butylbenzofuran-2-one, 5,7-di-tert- Butyl-3- [4- (2-stearoyloxyethoxy) phenyl] benzofuranone-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-butylbenzofuran-2-one, 3- (3,5-diethyl-4-pivaloyloxyphenyl) -5,7 Di-tert-butylbenzofuran-2-one.
    [149] When using the stabilizer compositions of the invention in products made of thermoplastic polymers, in particular polyolefins, which are used under water-extracting conditions before, during or after storage in water, these products are subject to oxidation induction time (OIT). Excellent performance for a long time when measured by a standard test method such as. The polyolefin resin herein can be composed of thick sections or thin layers, and thus also can be applied as a coating or lamination onto metal products such as steel-conduits or subsea-cables.
    [150] The stabilizer system of the present invention, used to stabilize all kinds of products made from thermoplastic polymers exposed to water-extracting conditions before, during and after heat treatment, prevents the initial wear out by the migration of the polymer resin. can do. This behavior clearly improves the long term stability of the products.
    [151] Oxidation induction time (OIT), a technically important parameter used to predict the service life of plastic materials, was measured in polyolefin products stabilized with a binary mixture of hindered phenols. OIT-values measured before and after storage in water markedly exceeded those measured in samples containing only one hindered phenol. These results indicate an improvement over the prior art.
    [152] The present application is described in detail with reference to the following examples.
    [153] Example 1
    [154] Preparation and Testing of Blue Colored PE-HD-Conduit Specimens
    [155] Preparation of Powdered Mixture of Polyethylene-HD and Stabilizer
    [156] In a flask, 100 parts by weight of polyethylene-HD (PE-HD CRP 100 type, uncolored, type 2 molecular weight distribution, produced by Elenac GmbH, Frankfurt, Germany), 0.1 part by weight of calcium stearate, 0.1 Basic stabilizer consisting of parts by weight of tris (2,4-di-tert-butylphenyl) phosphite and 0.1 parts by weight of phenolic components (compound (I) or compound (VII), or a 1: 1 mixture of these phenols) Mixed with the composition.
    [157] Using a blue-colored test specimen, a masterbatch called Remafin-Blue 154 (registered trademark) containing 4.1 wt% blue pigment and 2.8 wt% TiO 2 (magenta type) masterbatch) 2 parts by weight were further added.
    [158] After the additives were dissolved in acetone in the presence of the polymer, the solvent was evaporated in vacuo.
    [159] A single screw extruder (Brabender type, shaft diameter 16 mm, L / D = 20) was homogenized using 125 rpm at 210 to 240 ° C. By adding the pigment-masterbatches, another three times extrusion process was carried out under the same conditions.
    [160] The test sample was pressurized plaque (300 × 300 mm, thickness 1 mm) prepared under a contact pressure of 30 bar for 5 minutes and a final pressure of 200 bar for 3 minutes using a steam-heated / water-cooled hydraulic pressure at a temperature of 185 ° C. Perforation).
    [161] Test procedure
    [162] Samples were stored in hot water at 90 ° C. for 2 months.
    [163] Oxidation induction time (OIT) was measured at 200 ° C. using a heating rate of 20 K / min and an oxygen-flow rate of 60 ml / min.
    [164] 0.1 parts by weight of tris (2,4-di-tert-butylphenyl) phosphite as a basic additive + 0.1 parts by weight of calcium stearate + 2.0 parts by weight of Refamin-Blau CEL® 154 Added.
    [165] OIT-results of blue colored water pipes are shown in Table 1 below:
    [166] Phenolic Concentration / CompositionOIT / min Before water treatmentAfter water treatment 0.1% by weight of compound VII (comparative)32.14.8 0.1% by weight of compound (I) (for comparison)33.815.0 0.05% by weight of compound (I) and 0.05% by weight of compound (VII)47.918.0
    [167] Example 2
    [168] Colors of talc-reinforced polypropylene after being stored in hot water and processed at high temperatures
    [169] Test polypropylene-plaques were prepared by injection molding 1 mm thick plaques on a Toshiba IS100EN at a size of 60 × 60 mm at 210-240 ° C.
    [170] Preparation of Powdered Mixture of Polypropylene and Stabilizer
    [171] In a flask, 100 parts by weight of polypropylene (PP homopolymer type, injection molding grade), 0.1 part by weight of calcium stearate, 0.1 part by weight of tris (2,4-di-tert-butylphenyl) phosphite, 0.2 part by weight of amide 35 parts by weight of Talc Prever M 30, 3 parts by weight of titanium dioxide (Kronos 2220® type), 0.2 weight, coated with wax (Licowax C® type) It was mixed with a basic stabilizer composition consisting of a negative sulfur component (β, β'-thio-di (propionic acid-stearylester)) and 0.1 parts by weight of a phenolic component (components as described in Table 2 below).
    [172] To test color stability, individual test specimens were stored for 21 days in hot water (T = 95 ° C.). Thereafter, the color (YI: yellowness) was measured. The data is shown in Table 2 below:
    [173] Phenolic Concentration / CompositionYI before hot water storageYI after hot water storage 0.1% by weight of compound (I) (for comparison)6.58.3 0.1% by weight of compound VII (comparative)5.116.8 0.1 wt% Compound (I) / (VII) (0.05 wt%: 0.05 wt%)5.310.6 Theoretical YI Value for 0.1 wt% Compound (I) / (VII)5.812.55
    [174] The YI measured in the mixture was better than the calculated theoretical values, and therefore it can be clearly seen that the combination of the present invention has a synergistic effect compared to a single compound as known in the prior art.
    [175] To simulate the harsh conditions in the hot slide system, the individual stabilized polypropylene melts were left for 10 minutes at a temperature of 240 to 280 ° C. in the hot zone of the injection molding machine.
    [176] Injection molded plaques (thickness 1 mm) were prepared using the thermally pretreated material as described above to measure the yellowness as described in Example 2. Collected data is shown in Table 3 below. There was a difference between the yellowness of plaques prepared under standard process conditions and the yellowness of plaques prepared under harsh process conditions.
    [177] Phenolic Concentration / CompositionΔYI between YI under standard conditions and YI after heat treatment (280 ° C) for 10 minutes in an injection molding apparatus. 0.1% by weight of compound (I) (for comparison)1.25 0.1% by weight of compound VII (comparative)0.34 0.1 wt% Compound (I) / (VII) (0.05 wt%: 0.05 wt%)0.79 Theoretical YI Value for 0.1 (%) of Compound (I) / (VII)0.80
    [178] From the above experimental data it is surprisingly found that the compositions of the present invention have better stabilizing properties than the stabilizers of the prior art.
    权利要求:
    Claims (9)
    [1" claim-type="Currently amended] (a) bis- [3,3-bis- (4'-hydroxy-3'-tert-butylphenyl) butanoic acid] -glycol ester of formula (I)
    4,4 ', 4 "-[(2,4,6-trimethyl-1,3,5-benzenetriyl) tris (methylene)]-tris [2,6-bis (1,1-) Dimethylethyl) phenol],
    1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,3,5-tris [[4- (1,1-dimethylethyl) -3, -Hydroxy-2,6-dimethylphenyl] methyl],
    Phenol of formula IV, 4,4 ', 4 "-(1-methyl-1-propaneyl-3-ylidene) tris [2- (1,1-dimethylethyl) -5-methyl,
    Phenol 2,6-bis [[3- (1,1-dimethylethyl) -2-hydroxy-5-methylphenyl] octahydro-4,7-methano-1H-indenyl] -4 Methyl, and
    Benzenepropanoic acid of formula VI, 3- (1,1-dimethylethyl) -4-hydroxy-5-methyl-, 2,4,8,10-tetraoxaspiro [5.5] undecane-3,9- At least one phenolic antioxidant selected from the group consisting of diyl-bis (2,2-dimethyl-2,1-ethanediyl) ester; And
    (b) tetrakisethylene (3,5-di-tert-butyl-4-hydroxyphenyl) -hydrocinnamate of formula (VII), and
    At least one phenolic antioxidant selected from the group consisting of octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate of formula (VIII)
    A stabilizer composition for use in a thermoplastic polymer, comprising a by weight ratio of component (a) to component (b) of 1:10 to 10: 1:
    Formula I

    Formula II

    Formula III

    Formula IV

    Formula V

    Formula VI

    Formula VII

    Formula VIII

    [2" claim-type="Currently amended] The method of claim 1,
    A stabilizer composition comprising (a) a compound of formula (I), a compound of formula (II), a compound of formula (III), or a mixture thereof.
    [3" claim-type="Currently amended] The method of claim 1,
    Stabilizer composition comprising a compound of formula (I) as component (a).
    [4" claim-type="Currently amended] The method according to any one of claims 1 to 3,
    Stabilizer composition wherein the weight ratio of component (a) to component (b) is from 1: 2 to 2: 1.
    [5" claim-type="Currently amended] A method of using the stabilizer composition according to claim 1, wherein the stabilizer composition according to claim 1 is incorporated into the polymer in an amount of 0.001 to 2.000% by weight, based on the weight of the thermoplastic polymer.
    [6" claim-type="Currently amended] A method of using the stabilizer composition according to claim 1, wherein the stabilizer composition according to claim 1 is incorporated into the polymer in an amount of 0.020 to 0.20% by weight, based on the weight of the thermoplastic polymer.
    [7" claim-type="Currently amended] The method according to claim 5 or 6,
    The method of use wherein the thermoplastic polymer is polyolefin.
    [8" claim-type="Currently amended] A method of stabilizing thermoplastic polymers in prolonged contact with water, comprising incorporating a stabilizing amount of the stabilizer composition according to any one of claims 1 to 4 before or during processing.
    [9" claim-type="Currently amended] The method of claim 8,
    The stabilizer composition is added in an amount of 0.020 to 0.20% by weight based on the weight of the thermoplastic polymer.
    类似技术:
    公开号 | 公开日 | 专利标题
    KR101472608B1|2014-12-16|Dopo flame retardant compositions
    EP3149059B1|2018-09-12|Use ofcopolymers or polymers containing oxo imide moieties as flame retardants, stabilisers, rheology modifiers for resins, initiators for polymerisation and grafting, cross-linking agents or couplers as well as moulding matters containing such |polymers
    JP5554666B2|2014-07-23|Stabilizer combination for rotational molding
    KR100449430B1|2004-11-26|Block oligomers containing 2,2,6,6-tetramethyl-4-piperidyl groups as stabilizers for organic materials
    ES2267869T3|2007-03-16|Polypropylene resin compositions.
    DE602004003500T2|2007-10-04|Flame-resistant polymic acid
    US5922794A|1999-07-13|Compositions stabilized with tertiary amine oxides
    EP1190622B1|2006-06-07|Mixtures of phenolic and inorganic materials with antimicrobial activity
    CA2355824C|2008-12-23|Synthetic polymers comprising additive blends with enhanced effect
    ES2256724T5|2009-11-27|Waterproof dispersions for antioxidants.
    ES2246008T3|2006-02-01|Stabilization of synthetic polymers.
    JP4352235B2|2009-10-28|Flame retardant composition
    AU780925B2|2005-04-28|Synergistic mixtures of UV-absorbers in polyolefins
    JP3062977B2|2000-07-12|Bisbenzofuran-2-one
    RU2230758C2|2004-06-20|Stabilized polymer composition, stabilizer contained therein, and a method for preparation thereof
    US7132467B2|2006-11-07|Stabilization of polyolefins in permanent contact with chlorinated water
    EP2450401B1|2013-04-17|Flame-resistant compound containing a phosphoric acid derivative
    US7820744B2|2010-10-26|Stabilizer mixtures
    US5969015A|1999-10-19|Monomeric and oligomeric bisphosphites as stabilisers for polyvinyl chloride
    KR100949751B1|2010-03-25|Agricultural articles and method for controlling the weathering resistance and the degradation of agricultural articles
    EP1401832B1|2005-02-16|High molecular weight hydroxyphenylbenzotriazole uv-absorbers for thin film applications
    EP1454948B1|2008-10-22|Flameproof agent-stabiliser-combination for thermoplastic polymers
    EP1892261B1|2010-08-18|Utilisation of polymer powder containing UV absorber for stabilising polymers against the effects of UV rays
    EP0728806B2|2003-05-14|Synergistic stabiliser mixture
    EP1461384B1|2009-08-12|Novel flame retarding compounds
    同族专利:
    公开号 | 公开日
    CA2399131A1|2001-08-30|
    JP2003524049A|2003-08-12|
    DE60103141D1|2004-06-09|
    AT266058T|2004-05-15|
    AU3217301A|2001-09-03|
    DE60103141T2|2004-10-21|
    US20030045616A1|2003-03-06|
    CA2399131C|2009-10-27|
    GB0004437D0|2000-04-12|
    HU0303581A2|2004-03-01|
    EP1268642A1|2003-01-02|
    WO2001062839A1|2001-08-30|
    EP1268642B1|2004-05-06|
    US6646035B2|2003-11-11|
    ES2219502T3|2004-12-01|
    MXPA02008013A|2003-01-28|
    KR100712787B1|2007-05-02|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2000-02-25|Priority to GB0004437.0
    2000-02-25|Priority to GBGB0004437.0A
    2001-02-21|Application filed by 클라리언트 파이넌스 (비브이아이)리미티드
    2002-12-05|Publication of KR20020091098A
    2007-05-02|Application granted
    2007-05-02|Publication of KR100712787B1
    优先权:
    申请号 | 申请日 | 专利标题
    GB0004437.0|2000-02-25|
    GBGB0004437.0A|GB0004437D0|2000-02-25|2000-02-25|Synergistic combinations of phenolic antioxidants|
    [返回顶部]