WO2017140173A1 - Additive used for polymer, and additive composition thereof and polymer composition thereof - Google Patents

Abstract

Provided is an additive A used for a polymer, comprising the compound as represented by formula I, wherein R₁ and R₂ are the same or different, and are represented by H, a C1-C8 alkyl, or a C6-C18 aryl; R₃ being H or a halogen; said additive A also comprising a silicon element and a phosphorus element; when added to a polymer, said additive A used for a polymer very clearly improves the chemical resistance of the polymer composition.

Description

Additive for polymer and additive composition thereof, polymer composition Technical field

The present invention relates to an additive A for a polymer, an additive composition composed thereof, a polymer composition and use thereof as a light stabilizer.

Background technique

Existing benzotriazole compounds are widely used in the field of polymer additives, and can be used in light stabilizers, etc., which are known to be synthesized by different methods, mainly from azobenzene compounds as raw materials, according to different reduction processes. Perform cyclization. The existing reduction methods include: hydrazine hydrate reduction method, zinc powder reduction method, sulfide reduction method, and the like.

The benzotriazole-based light stabilizer is prepared by one-step method using hydrazine hydrate as a reducing agent. The reported patents include US4001266, DE2454889, FR2292708, etc. The other method is hydrazine hydrate-zinc powder method, which is based on azobenzene compounds. The use of hydrazine hydrate as a reducing agent to reduce an azobenzene compound to an intermediate benzotriazole oxynitride, and then using zinc powder as a reducing agent to reduce the intermediate benzotriazole oxynitride to a benzotriazole light stable Agent, the reported patents are JP53063379, patent CN1455773A, etc.; another method is hydrazine hydrate-safety powder method, which uses azobenzene compound as raw material to reduce azobenzene compound to intermediate by using hydrazine hydrate as reducing agent. The benzotriazole oxynitride is then reduced to a benzotriazole light stabilizer using a safe powder as a reducing agent. The reported patent is CN101029032A.

The benzotriazole compound is used as an additive in a polymer, and is usually used for a light stabilizer or the like, but the adverse effect thereof is to cause a certain decrease in chemical resistance of the polymer, and the inventors have been greatly researched. It has been found that when a specific content of silicon-containing and phosphorus-containing substances is added to a benzotriazole compound, the corresponding chemical resistance of the polymer can be significantly improved.

Summary of the invention

It is an object of the present invention to provide an additive A for a polymer which can significantly improve the chemical resistance of a polymer article by adding a trace amount of a silicon-containing substance and a phosphorus-containing substance to the benzotriazole compound.

The invention is achieved by the following technical solutions:

An additive A for a polymer comprising a compound as shown in formula I,

Wherein R1, R2 are the same or different and are represented by H, C1-C6 alkyl or C6-C18 aryl; R3 is H or halogen; wherein, based on the total weight of the additive A, the weight of the silicon element is 5 ppm to 900 ppm, It is preferably 20 ppm to 400 ppm, more preferably 30 ppm to 200 ppm, and the phosphorus element has a weight content of 1 ppm to 980 ppm, preferably 10 ppm to 400 ppm, more preferably 25 ppm to 200 ppm, based on the total weight of the additive A. .

Wherein the silicon element is derived from a silicon-containing substance, and the silicon-containing substance is selected from the group consisting of sodium silicate, sodium metasilicate, monocalcium silicate, dicalcium silicate, calcium magnesium silicate, calcium metasilicate mineral, bentonite, The silicon material may also be selected from the group consisting of silicone resins, alkoxysilanes, and polysiloxanes. The silicon-containing substance may be one or a combination of the above.

The monocalcium silicate, dicalcium silicate, calcium magnesium silicate, sodium silicate, sodium metasilicate are all products currently on the market, and calcium metasilicate minerals (wollastonite) are a natural product. The non-metallic minerals have a chemical formula of CaSiO ₃ , usually a needle-like, fibrous aggregate, and the color is white. The calcium metasilicate mineral used in the present invention is, for example, Lishu County Shuofeng Powder Material Factory, Beijing Hengye COSCO Calcium metasilicate mineral produced by Chemical Co., Ltd. The bentonite is a non-metallic mineral with montmorillonite as a main mineral component, and the montmorillonite structure is a 2:1 type crystal structure composed of two silicon oxide tetrahedrons sandwiched by an aluminum octahedron, which is used in the present invention. Bentonite can be various types of bentonite, such as Shandong Xianquan bentonite plant, and sodium bentonite produced by Xinyang Jiaxin bentonite plant.

The silicone resin can be any of various types of resin copolymers described in detail in U.S. Patent No. 5,695,551 (December 9, 1999). However, most of the preferred applications herein are those resin copolymers as described below:

1. A siloxane of a resin copolymer prepared by a method comprising the steps of: (i) forming a silanol comprising a resin copolymer siloxane having R" ₃ SiO _1/2 units and SiO _4/2 units; Wherein b and c are a positive integer and an acidic homogenous mixture of an organohydrogenpolysiloxane of an exemplary R" _b H _c SiO _(4-bc)/2 and an organic solvent of less than 4, preferably 1.9 to 2.1, and (ii) The mixture is heated to remove substantially all of the organic solvent. R" can be an alkyl group of 1 to 6 carbon atoms; an aryl group such as a phenyl group, a tolyl group and a xylyl group; an alkenyl group such as a vinyl group and an allyl group; or a trifluoropropyl group. R" can also be an aralkyl group. a group such as β phenyl propyl; or an alicyclic group such as a cyclopentyl group, a cyclohexyl group and a cyclohexenyl group;

2. A siloxane resin copolymer containing R" ₃ SiO _1/2 units and SiO _4/2 units in a molar ratio of a number average molecular weight of 1,200 to 10,000 g/mol. Preferably, the molar ratio is 0.7:1.0. The number average molecular weight is 5,000 g/mol. R" is directly as defined above. This resin contains 2.5% by weight of silicon-bonded OH groups. This resin may also contain R" ₂ SiO _2/2 units and R"SiO _3/2 units.

A silicone resin which is particularly preferably suitable for use herein and which represents such a resin copolymer consists essentially of (CH ₃ ) ₃ SiO _1/2 units and SiO ₂ units in a molar ratio close to 0.75:1 and contains 2.4-2.9. A wt% hydroxy siloxane resin copolymer, which is based on immobilization as determined by FTIR according to American Society for Testing and Materials (ASTM) Test Method E-168.

The silicone resin can be a phenyl silsesquioxane resin, or a mixture of phenyl silsesquioxanes. As used herein, a phenyl silsesquioxane resin is an organopolysiloxane having at least one simple (C ₆ H ₅ SiO _3/2 ) siloxy unit, which is Containing (R ₃ SiO _1/2 ), (R ₂ SiO _2/2 ) or (SiO _4/2 ) siloxy units independently selected from the group wherein R can be any monovalent organic group (also referred to herein as It is a polymer of a siloxy unit of M, D, T, or Q unit). These siloxy units can be combined in various ways to form a cyclic, linear or branched structure. The chemical and physical properties of such resulting polymer structures can vary. For example, organopolysiloxanes can be volatile or low viscosity fluids, high viscosity fluids/gums, elastomers or rubbers, and resins, depending on the choice of each siloxy unit in the organopolysiloxane. And dosage. The silsesquioxane is typically characterized as having at least one or several (RSiO _3/2 ) or T siloxy units. Therefore, such an organopolysiloxane suitable for use in the present disclosure may have (R ₃ SiO _1/2 ), (R ₂ SiO _2/2 ), (RSiO _3/2 ) or (SiO _4/2 ). Any combination of siloxy units, provided that it has at least one siloxy unit of the formula (C ₆ H ₅ SiO _3/2 ) wherein C ₆ H ₅ represents a phenyl group.

The phenyl silsesquioxane resin may have an average formula comprising at least 40 mol% of a simple formula (R' ₂ SiO _{2 having} a monovalent hydrocarbon group in which x and y have a value of 0.05 to 0.95 and R' is 1 to 8 carbon atoms. _/2 ) a siloxy unit of _x (C ₆ H ₅ SiO _3/2 ) _y . As used herein, x and y represent the molar fraction of R' ₂ SiO _2/2 and C ₆ H ₅ SiO _3/2 siloxy units present in the phenyl silsesquioxane resin relative to each other (ie, D and T phenylsiloxy units).

Therefore, the molar fraction of the R' ₂ SiO _2/2 and C ₆ H ₅ SiO _3/2 siloxy units can each independently be from 0.05 to 0.95. However, the R' ₂ SiO _2/2 and C ₆ H ₅ SiO _3/2 siloxy units present must be combined to account for at least all of the siloxy units present in the phenyl silsesquioxane resin. 40 mol%, alternatively 80 mol%, or alternatively 95 mol%. R' can be a linear or branched alkyl group such as ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl. Typically, R' is a methyl group.

The molecular weight of the phenyl silsesquioxane resin is not critical, but typically the number average molecular weight (as measured according to ASTM D5296-05 and calculated as polystyrene molecular weight equivalent) is between 500 and 10,000, or alternatively 500 to 2,000 g. /mol range.

The viscosity of the phenyl silsesquioxane at 25 ° C is not critical, but the typical viscosity should be less than 100 mPa.s (cP), alternatively in the range of 10 mPa.s (cP) - 50 mPa.s (cP) .

Commercially available phenyl silsesquioxane resins suitable as disclosed herein include the following representative non-limiting examples: DOW CORNIN 3037 intermediate and DOW CORNING 3074 (Dow Corning Corp., Midland, MI).

The alkoxysilane can constitute a single alkoxysilane or can be a mixture of alkoxysilanes. The alkoxysilane may have the formula R ⁸ _a Si(OR ⁹ ) _(4-3) . In the formula, R ⁸ represents an alkyl group having 1 to 30 carbon atoms, preferably 1 to 12 carbon atoms, an aryl group such as a phenyl group, or a halogenated alkyl group such as a chloropropyl group and a trifluoropropyl group. The value of a is 1 or 2. And R ⁹ represents an alkyl group having 1 to 6 carbon atoms. Typically, R ⁸ is n-octyl and R ⁹ is methyl or ethyl.

Preferably, the alkoxysilane compound (B) is an alkyltrialkoxysilane having 1 to 12 carbon atoms in the alkyl chain and 1 to 6 carbon atoms in the alkoxy chain. Some suitable alkoxysilanes are methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, ethyltributoxysilane, propyltrimethoxy Silane, propyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, butyltriethoxysilane, hexyltrimethoxysilane, n-octyltriethoxysilane , iso-octyltriethoxysilane, n-octyltrimethoxysilane, iso-octyltrimethoxysilane dimethyldimethoxysilane, dimethyldiethoxysilane, diethyl dimethyl Oxysilane, diisobutyldimethoxysilane, phenyltrimethoxysilane, dibutyldiethoxysilane and dihexyldimethoxysilane.

Such alkoxysilanes are commercially available from Dow Corning Corporation, Midland, Mich., and are described, for example, in U.S. Patent No. 5,300,327 (April 5, 1994), U.S. Patent No. 5,695,551 (December 9, 1997) And U.S. Patent No. 5,919,296 (JuI.6, July 6, 1999). Such alkoxysilanes are capable of partial hydrolysis and thus contain siloxane and/or silanol groups.

The polysiloxane is preferably a polydialkylsiloxane having the following general formula:

[R ⁹ ₂ Si(OR ³ )O _1/2 ][R ⁹ ₂ SiO _2/2 ]z[SiR ⁹ ₂ (OR ³ )O _1/2 ]

Wherein R ^{9 is} as defined above and z represents the degree of polymerization and is greater than 1. R ³ is H in the case of a hydroxyl terminated polymer or Si(CH ₃ ) ₃ .

Typically, the polydialkylsiloxane is a hydroxy or trimethylsilyl terminated polydimethylsiloxane having a degree of polymerization greater than 1, alternatively from 1 to 500, alternatively 5 -200, or alternatively 10-100.

More preferably, the polysiloxane compound is a diorganosiloxane having from 1 to 12 carbon atoms per organic group.

The phosphorus element is derived from a phosphorus-containing substance, and the phosphorus-containing substance may be one or a combination of the following.

The term "phosphorus-containing material" as used herein refers to or includes elemental phosphorus as well as organic and inorganic phosphorus compounds and/or phosphorus-containing compounds and hydrolysates or salts thereof.

Elemental phosphorus is involved in four allotrope variants, white phosphorus, red phosphorus, black phosphorus and purple phosphorus. Depending on these basic types, different crystal structures are formed, which also brings about differences in physical properties and reactivity. Red phosphorus is preferably used in this patent.

Suitable inorganic phosphorus compounds advantageously include (poly)phosphates, such as unconcentrated salts of phosphorous acid or concentrated salts of phosphoric acid, such as ammonium phosphate and ammonium polyphosphate.

The organophosphorus compound (I) (II) of the formula (I) or (II) used in the present invention may be selected from an organophosphorus compound such as a monomeric organophosphorus compound, or a polymer organophosphorus compound, an inorganic phosphorus compound. And wherein R ₁ , R ₂ and R ₃ independently of each other represent an organic or inorganic group known to the skilled person from the prior art.

The substituents or groups R are independent of one another and may be the same or different, or not at all. The groups R may preferably be represented independently of each other: -H, substituted or unsubstituted C ₁ -C ₁₅ -alkyl, C ₁ -C ₁₅ -alkenyl, C ₃ -C ₈ -cycloalkyl, C ₆ - C ₁₈ -aryl, C ₇ -C ₃₀ -alkylaryl, C ₁ -C ₈ -alkoxy or C ₁ -C ₈ -alkylthio, or -OH or -SH and its alkali metal salt, alkaline earth metal Salt, ammonium salt.

The "alkyl" moiety of the optional substituent R of the phosphorus compound of formula (I) represents a saturated and unsaturated aliphatic compound which may be unbranched or branched, with unsaturated groups being preferred. The substituent R preferably includes a short-chain alkyl group having not more than 6, more preferably not more than 4 or 3, more preferably not more than 2 carbon atoms, or a phenyl group as an aryl group. Particularly useful phosphorus compounds are preferably as unsubstituted as possible.

Examples of those phosphorus compounds of the formula (I) or (II) are organophosphorus compounds and salts thereof, such as organic phosphorus compounds of monomers, including phosphate compounds, phosphoric acid amide ester compounds and phosphazene compounds, organic compounds of phosphorous acid. , such as phosphorous Acid esters, compounds of hypophosphorous acid, phosphines and phosphine oxides such as triphenylphosphine, triphenylphosphine oxide and toluene phosphine oxide.

In the formula I, it is preferred that R1 and R2 are different, R1 is H, R2 is a methyl group, and R3 is H, and the expression is:

Preferably, R1 and R2 are the same, and are 1,1-dimethylphenyl, and R3 is H, and the expression is:

Preferably, R1 and R2 are different, R1 is a tert-butyl group, R2 is a methyl group, and R3 is Cl, and the expression is:

Preferably, R1 and R2 are the same, which is a tert-butyl group, and R3 is Cl, and the expression is:

Preferably, R1 and R2 are the same, which is a tert-amyl group, and R3 is H, and the expression is:

Preferably, R1 and R2 are different, R1 is 1,1 dimethylphenyl, R2 is 1,1,3,3-tetramethylbutyl, and R3 is H, expressed as:

Preferably, R1 and R2 are different, R1 is H, R2 is a tert-octyl group, and R3 is H, and the expression is:

The invention also provides the use of an additive A for a polymer as a light stabilizer.

The invention also provides an additive composition comprising:

The above additive A, and at least one other additive B; wherein the total weight content of the additive A is from 50 to 99.9%, preferably from 70 to 95% by weight based on the total weight of the additive composition, and the at least one other additive B is from 0.1 to 50 by weight. %; preferably 5 to 30%.

The other additive B is one or more of the following:

1. Antioxidants, including the following types:

1.1 Alkylation of monophenols, such as 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethyl Phenolic, 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, a linear or branched nonylphenol such as 2,6-dimercapto-4- Methylphenol, 2,4-dimethyl-6-(1'-methylundecane-1'-yl)phenol, 2,4-dimethyl-6-(1'-methylheptadecane -1 '-yl)phenol, 2,4-dimethyl-6-(1'-methyltridecane-1'-yl)phenol, and mixtures thereof.

1.2 alkylthiomethylphenol, such as 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctyl Thiomethyl-6-ethylphenol, 2,6-di(dodecylthio)methyl-4-nonylphenol.

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.

1.4 Tocopherols such as alpha-tocopherol, beta-tocopherol, gamma-tocopherol, delta-tocopherol and mixtures thereof (vitamin E).

1.5 Hydroxylated thiodiphenyl ether, 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.

1.6 alkylene bisphenols, such as 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'-methylenebis(6-tert-butyl-4-ethyl Phenol), 2,2'-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol], 2,2'-methylenebis(4-methyl-6-ring Hexylphenol), 2,2'-methylenebis(6-fluorenyl-4-methylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2 '-Ethylene bis(4,6-di-tert-butylphenol), 2,2'-ethylenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylene Bis[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-double (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-methylbenzene 3-n-dodecyldecylbutane, 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-dual ( 3,5-di-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecyldecyl butyl Alkane, 1,1,5,5-tetrakis(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.

1.7 O-, N- and S-benzyl compounds, for example 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, 4-hydroxy-3,5-di Octadecylmethylbenzyl mercaptoacetate, tridecyl 4-hydroxy-3,5-di-tert-butylbenzyl decylacetate, 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-hydroxybenzyl mercaptoacetate.

1.8 Aromatic hydroxybenzyl compound, for example 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,4-double ( 3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl Phenyl).

1.9 Triazine compounds, such as 2,4-bis(octylfluorenyl)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylfluorenyl -4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octyldecyl-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) 1,2,3- 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.

1.10 benzylphosphonate, such as dimethyl 2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 3, Bis(octadecyl) 5-di-tert-butyl-4-hydroxybenzylphosphonate, di(octadecyl) 5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, Calcium salt of monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

1.11 Amidophenols, for example 4-hydroxylauranilide, 4-hydroxystearylanilide, octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

1.12 Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with the following monohydric or polyhydric alcohols: for example with methanol, ethanol, n-octanol, isooctanol, stearyl alcohol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiglycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyl) Isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecyl alcohol, 3-thiapentadecanol, trimethylhexanediol, trishydroxyl An ester of propane, 4-hydroxymethyl-1-phosphono-2,6,7-trioxabicyclo[2.2.2]octane.

1.13 Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propanoic acid with the following monohydric or polyhydric alcohols: for example with methanol, ethanol, n-octanol, isooctanol, octadecane Alcohol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiglycol, diethylene glycol, triethylene glycol, pentaerythritol, three ( Hydroxyethyl)isocyanurate, N,N'-double (hydroxyl) Glycine, 3-thiaundecyl alcohol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phosphonium-2,6 ,7-trioxabicyclo[2.2.2]octane, 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy}- Esters of 1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane.

1.14 An ester of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with a monohydric or polyhydric alcohol: for example with methanol, ethanol, octanol, stearyl alcohol, 1,6-hexane Alcohol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiglycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanuric acid Ester, N, N'-bis(hydroxyethyl)oxamide, 3-thiaundecyl alcohol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxyl Esters of methyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.15 an ester of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with a monohydric or polyhydric alcohol: for example with methanol, ethanol, octanol, stearyl alcohol, 1,6-hexanediol, 1, 9-decanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiglycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N, N'-bis(hydroxyethyl)oxamide, 3-thiaundecyl alcohol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1 An ester of p-hetero-2,6,7-trioxabicyclo[2.2.2]octane.

1.16 Amide of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoic acid, for example, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl) Methylenediamine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamine, N,N'-bis(3,5-di-tert-butyl) 4-Hydroxyphenylpropionyl)ruthenium, N,N'-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propanoyloxy)ethyl]oxamide .

2. Other UV absorbers other than the additive A of the present invention

2.1 2-hydroxybenzophenones such as 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives.

2.2 Esters of substituted and unsubstituted benzoic acids, such as 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis(4-tert-butyl) Benzoyl) resorcinol, benzoylresorcinol, 2,5-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, 3,5-di-tert-butyl Cetyl 4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2,5-di-tert-butyl-4-hydroxybenzoic acid 2-methyl Base-4,6-di-tert-butylphenyl ester.

2.3 Acrylates, such as α-cyano-β, β-diphenylacrylate, α-cyano-β, β-diphenyl isooctyl acrylate, α-methyl cinnamate methyl ester, α - cyano-β-methyl-p-methoxycinnamate methyl ester, α-cyano-β-methyl-p-methoxycinnamate butyl ester, α-methyl ester-p-methoxycinnamate methyl ester, N - (β-carbomethoxy-β-cyanovinyl)-2-methylindoline, tetrakis(α-cyano-β,β-diphenyl) neopentyl acrylate.

2.4 Nickel compounds, such as nickel complexes of 2,2'-thiobis[4-(1,1,3,3-tetramethylbutyl)phenol, such as 1:1 or 1:2 complexes, Single with or without other ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid Alkyl esters such as nickel salts of methyl or ethyl esters, nickel complexes of ketone oximes such as 2-hydroxy-4-methylphenylundecyl oxime, 1-phenyl-4-lauroyl-5-hydroxyl A nickel complex of pyrazole with or without other ligands.

a hindered amine such as bis(1-undecyloxy-2,2,6,6-tetramethyl-4-piperidinyl) carbonate, bis(2,2,6,6-tetramethyl) 4-piperidinyl) sebacate, bis(2,2,6,6-tetramethyl-4-piperidinyl) succinate, bis(1,2,2,6,6-penta 4-piperidinyl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2, 2,6,6-pentamethyl-4-piperidinyl)n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, 1-(2-hydroxyethyl)-2 a condensate of 2,6,6-tetramethyl-4-hydroxypiperidine with succinic acid, N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)hexa Linear or cyclic condensate of methyl diamine with 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, tris(2,2,6,6-tetramethyl-4 -piperidinyl)nitrilotriacetate, tetrakis(2,2,6,6-tetramethyl-4-piperidinyl)-1,2,3,4-butane tetracarboxylate, 1 ,1'-(1,2-ethylidene)-bis(3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylper Pyridine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis(1,2,2,6,6-pentamethylpiperidinyl )-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]indole-2,4-dione, bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate, double (1-octyloxy-2,2,6,6-tetramethylpiperidinyl) succinate, N,N'-bis-(2,2,6,6-tetramethyl-4-piperidine a linear or cyclic condensate of hexamethylenediamine with 4-morpholinyl-2,6-dichloro-1,3,5-triazine, 2-chloro-4,6-bis(4- Condensate of n-butylamino-2,2,6,6-tetramethylpiperidinyl-1,3,5-triazine with 1,2-bis(3-aminopropylamino)ethane, 2 -Chloro-4,6-bis(4-n-butylamino-1,2,2,6,6-pentamethylpiperidinyl)-1,3,5-triazine and 1,2-double (3 -Aminopropylamino)ethane condensate, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]癸Alkane-2,4-dione, 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione, 3-ten Dialkyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, 4-hexadecyloxy- and 4-stearyl Oxy-2 a mixture of 2,6,6-tetramethylpiperidine, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-cyclohexyl a condensate of amino-2,6-dichloro-1,3,5-triazine, 1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3, a condensate of 5-triazine and 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Registry Number [136504-96-6]); 1,6-hexanediamine and 2, Condensate of 4,6-trichloro-1,3,5-triazine and N,N-dibutylamine with 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Registry Number) [192268-64-7]); N-(2,2,6,6-tetramethyl-4-piperidinyl)-n-dodecylsuccinimide, N-(1,2,2,6 ,6-pentamethyl-4-piperidinyl)n-dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8 -diaza-4-oxospiro[4,5]nonane, 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza Reaction product of 4-oxospiro[4,5]nonane with epichlorohydrin, 1,1-bis(1,2,2,6,6-pentamethyl-4-piperidinyloxycarbonyl) -2-(4-methoxyphenyl)ethene, N,N'-bisformyl-N,N'-bis(2,2,6, 6-four Di-4-methylpiperidinyl hexamethylenediamine, 4-methoxymethylenemalonic acid and diester of 1,2,2,6,6-pentamethyl-4-hydroxypiperidine, Poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidinyl)]siloxane, maleic anhydride-α-olefin copolymer and 2, Reaction product of 2,6,6-tetramethyl-4-aminopiperidine or 1,2,2,6,6-pentamethyl-4-aminopiperidine, 2,4-bis[N-(1- Cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-N-butylamino]-6-(2-hydroxyethyl)amino-1,3,5-triazine , 1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine, 5-(2-ethylhexanoyl) Oxymethyl-3-,3,5-trimethyl-2-morpholinone, Sanduvor (Clariant; CAS Registry Number [106917-31-1]), 5-(2-ethylhexanoyl)oxymethyl 3-,3,5-trimethyl-2-morpholinone, 2,4-bis[(1-cyclohexyloxy-2,2,6,6-piperidin-4-yl)butylamino a reaction product of -6-chloro-s-triazine with N,N'-bis(3-aminopropyl)ethylenediamine, 1,3,5-tris(N-cyclohexyl-N-(2, 2,6,6-tetramethylpiperazin-3-one-4-yl)amino)-s-triazine, 1,3,5-tris(N-cyclohexyl-N-(1,2,2, 6 -Pentamethyl-piperazin-3-yl) amino) -s- triazine.

2.6 Oxalamides such as 4,4'-dioctyloxyoxalylamine, 2,2'-diethoxyoxalylaniline, 2,2'-dioctyloxy-5,5'-di-uncle Butyl oxanilide, 2,2'-bis(dodecyloxy)-5,5'-di-tert-butyloxalylanilide, 2-ethoxy-2'-ethyloxalylanilide , N,N'-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2'-ethyloxalylaniline and its 2-ethoxy- a mixture of 2'-ethyl-5,4'-di-tert-butyl oxalic acid anilide, a mixture of o- and p-methoxy disubstituted oxalanilide, and o- and p-ethoxy disubstituted grasses A mixture of anilides.

2.7 2-(2-Hydroxyphenyl)-1,3,5-triazines, for example 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-three Oxazine, 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-propoxyphenyl) )-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis (4-methyl) Phenyl)-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-three Oxazine, 2-[2-hydroxy-4-(2-hydroxy-3-butoxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5- Triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5 -Triazine, 2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethyl Phenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6- (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-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropoxy]phenyl}- 4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(4-[2-ethylhexyloxy]-2-hydroxyphenyl) -6-(4-Methoxyphenyl)-1,3,5-triazine.

3. Metal deactivators, such as N,N'-diphenyl oxamide, N-salicylaldehyde-N'-salicyloyl hydrazide, N,N'-bis(salicyl) hydrazine, N,N'-double (3,5-di-tert-butyl-4-hydroxyphenylpropionyl)indole, 3-salicylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxalyl Aniline, isophthalic dioxime, sebacyl bisphenyl hydrazine, N, N'-diacetyladipate dihydrazide, N, N'-bis(salicyl) oxalyl dihydrazide, N, N '-Bis(salicyloyl)thiopropionyl dioxime.

4. Phosphites and phosphonites such as triphenyl phosphite, diphenylalkyl phosphite, phenyl dialkyl phosphite, tris(nonylphenyl) phosphite, phosphorous acid tris Lauryl ester, tris(octadecyl)phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite Ester, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl- 4-methylphenyl) pentaerythritol diphosphite, diisodecyloxy pentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite, double ( 2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearyl sorbitol triphosphite, 4,4'-biphenylene diphosphinic acid tetrakis (2,4- Di-tert-butylphenyl)ester, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo[d,g]-1,3,2-dioxaphosphorus Heterocyclic, bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite, bis(2,4-di-tert-butyl-6-methyl phosphite Phenyl)ethyl ester, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyldibenzo[d,g]-1,3,2-dioxaphosphorane, 2,2',2"-indolyl[triethyltris(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl)phosphoric acid Ester], (3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) 2-ethylhexyl phosphite, 5-butyl-5 -ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxaphospholene.

5. Hydroxylamines such as N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-di(tetradecane) Hydroxyamine, N,N-di(hexadecyl)hydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecane Base-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived from hydrogenated tallow fatty amine.

6. A nitrone, such as N-benzyl-α-phenyl nitrone, N-ethyl-α-methyl nitrone, N-octyl-α-heptyl nitrone, N-lauryl-α-ten Monoalkyl nitrone, N-tetradecyl-α-tridecyl nitrone, N-hexadecyl-α-pentadecyl nitrone, N-octadecyl-α-heptadecane Nitrosone, N-hexadecyl-α-heptadecyl nitrone, N-octadecyl-α-pentadecyl nitrone, N-heptadecyl-α-heptadecyl nitrate Ketone, N-octadecyl-α-hexadecyl nitrone, nitrone derived from N,N-dialkylhydroxylamine (derived from hydrogenated tallow fatty amine).

7. A thio-association agent such as dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate or distearyl disulfide.

8. Peroxide scavengers, for example esters of beta-thiodipropionic acid, such as lauryl ester, stearyl ester, myristyl or tridecyl ester, mercaptobenzimidazole or 2-mercaptobenzoene A zinc salt of imidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis(β-dodecylmercapto)propionate.

9. Polyamide stabilizers, for example copper salts and divalent manganese salts in combination with iodine and/or phosphorus compounds.

10. Alkaline co-stabilizers such as melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, anthraquinone derivatives, amines, polyamides, polyurethanes, alkali metal salts of higher fatty acids and Alkaline earth metal salts such as calcium stearate, zinc stearate, magnesium sulphate, magnesium stearate, sodium ricinolate and potassium palmitate, bismuth catechin or zinc pyrocate.

11. Nucleating agents, for example inorganic substances such as talc, metal oxides such as titanium dioxide or magnesium oxide, preferably phosphates, carbonates or sulfates of alkaline earth metals; organic compounds such as mono- or polycarboxylic acids and salts thereof, for example 4 -tert-Butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds such as ionic copolymers (ionomers). Particularly preferred is 1,3:2,4-bis(3',4'-dimethylbenzylidene) sorbitol, 1,3:2,4-di(p-methyldibenzylidene) sorbose Alcohol and 1,3:2,4-di(benzylidene)sorbitol.

12. Other additives such as plasticizers, lubricants, emulsifiers, pigments, rheological additives, catalysts, flow regulators, fluorescent whitening agents, flame retardants, antistatic agents and blowing agents.

Preferred additive B is:

1) Other UV absorbers other than the present invention.

2) Processing additives such as anti-skid/anti-caking additives, plasticizers, fluorescent whitening agents, antistatic agents and foaming agents.

3) Antioxidants.

The present invention also provides a polymer composition comprising the additive A for a polymer, or an additive composition of the composition of the additive A and the additive B, wherein the additive A or the additive composition consisting of the additive A and the additive B The polymer composition has a weight content of 0.1 to 10%, the polymer has a weight content of 30 to 99.9%, and the filler has a weight content of 0 to 60%.

The polymers which can be used in the present invention are thermosetting and thermoplastic polymers selected from one or more of the following:

1. Polymers of monoolefins and diolefins, such as polypropylene, polyisobutylene, polybutene, poly-4-methylpentene, polyvinylcyclohexane, polyisoprene or polybutadiene, and rings a polymer of an olefin, such as a polymer of cyclopentene or norbornene, Polyethylene (optional cross-linking), 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).

2. A mixture of polymers mentioned in 1, for example a mixture of polypropylene and polyisobutylene, a mixture of polypropylene and polyethylene (for example PP/HDPE, PP/LDPE) and a mixture of different types of polyethylene (for example LDPE/ HDPE).

3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, such as 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/xin Ene copolymer, ethylene/vinylcyclohexane copolymer, ethylene/cycloolefin copolymer (such as ethylene/norbornene, such as COC), ethylene/1-olefin copolymer (where 1-olefin is produced in situ); propylene /butadiene copolymer, isobutylene/isoprene copolymer, ethylene/vinylcyclohexene copolymer, ethylene/alkyl acrylate copolymer, ethylene/alkyl methacrylate copolymer, ethylene/vinyl acetate Ester copolymer or ethylene/acrylic acid copolymer and its salt (ionomer), and a terpolymer of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene norbornene; And a mixture of these copolymers with each other and with the polymer mentioned in 1) above For example, polypropylene/ethylene-propylene copolymer, LDPE/ethylene-vinyl acetate copolymer (EVA), LDPE/ethylene-acrylic acid copolymer (EAA), LLDPE/EVA, LLDPE/EAA and other polymers (such as poly a mixture of amides.

4. Hydrocarbon resins (e.g., C5-C9), including hydrogenated modified products thereof (e.g., tackifiers) and mixtures of polyalkylenes and starches.

The homopolymers and copolymers of 1-4 may have any stereostructure, including syndiotactic, isotactic, semi-isotactic or random; among them, a random polymer is preferred. Also included are stereoblock polymers.

5. Polystyrene, poly-p-methyl styrene, poly-α-methyl styrene.

6. Aromatic homopolymers and copolymers derived from vinyl aromatic monomers, including all isomers of styrene, alpha-methylstyrene, vinyltoluene, especially p-vinyltoluene , all isomers of ethyl styrene, propyl styrene, vinyl biphenyl, vinyl naphthalene and vinyl anthracene and mixtures thereof. The homopolymers and copolymers can have any stereostructure, including syndiotactic, isotactic, semi-isotactic or random; among them, random polymers are preferred. Also included are stereoblock polymers.

6a. comprising the above vinyl aromatic monomer and a copolymer selected from the group consisting of ethylene, propylene, diene, nitrile, acid, maleic anhydride, maleimide, vinyl acetate and chlorine Ethylene or acrylic derivatives and mixtures thereof, such as styrene/butadiene, styrene/acrylonitrile, styrene/ethylene (copolymer), styrene/alkyl methacrylate, styrene/butadiene/ Alkyl acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride, styrene/ Acrylonitrile/methyl acrylate; a high impact mixture of a styrene copolymer with other polymers such as polyacrylates, diene polymers or ethylene/propylene/diene terpolymers; and block copolymerization of styrene Such as styrene / butadiene / styrene, styrene / isoprene / styrene, styrene / ethylene / butene / styrene or styrene / ethylene / propylene / styrene.

6b. Hydrogenated aromatic polymers derived from the hydrogenation of the polymers mentioned in the above 6, especially comprising polycyclohexylethylene (PCHE) obtained by hydrogenation of atactic polystyrene, commonly referred to as polyvinylcyclohexane (PVCH).

6c. A hydrogenated aromatic polymer derived from the hydrogenation of the polymer mentioned in 6a above.

7. A graft copolymer of a vinyl aromatic monomer such as styrene or alpha-methylstyrene, such as styrene grafted polybutadiene, styrene grafted polybutadiene-styrene or Polybutadiene-acrylonitrile copolymer; styrene and acrylonitrile (or methacrylonitrile) grafted polybutadiene; styrene, acrylonitrile and methyl methacrylate grafted polybutadiene; benzene Ethylene and maleic anhydride grafted polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide grafted polybutadiene; styrene and maleimide grafted polybutadiene Alkene; polybutadiene grafted with styrene and alkyl acrylate or alkyl methacrylate; ethylene/propylene/diene terpolymer grafted with styrene and acrylonitrile; grafted with styrene and acrylonitrile Polyalkyl acrylate or polyalkyl methacrylate; styrene and acrylonitrile grafted acrylate/butadiene copolymer, and mixtures thereof with the copolymers listed in 6), for example, referred to as ABS, A mixture of copolymers of MBS, ASA or AES polymers.

8. Halogen-containing polymers such as polychloroprene, chlorinated rubber, chlorinated or brominated copolymers of isobutylene isoprene (halogenated rubber), chlorinated or chlorosulfonated polyethylene, ethylene and chlorine a copolymer of ethylene, an epichlorohydrin homopolymer and a copolymer, especially a polymer of a halogen-containing vinyl compound, such as polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride; Copolymers such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.

9. Polymers derived from α,β-unsaturated acids and derivatives thereof, such as polyacrylates and polymethacrylates; polymethyl methacrylate, polyacrylamide and polyacrylonitrile, using butyl acrylate Perform impact modification.

10. Copolymers of monomers referred to in 9 or copolymers with other unsaturated monomers, such as acrylonitrile/butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile / Alkoxyalkyl acrylate or acrylonitrile / vinyl halide copolymer or acrylonitrile / alkyl methacrylate / butadiene terpolymer.

11. Polymers derived from unsaturated alcohols and amines or their acyl derivatives or acetals, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl polystearate, poly(vinyl benzoate), vinyl polymaleate , polyvinyl butyral, polyallyl phthalate or polyallyl melamine; and copolymers thereof with the olefins mentioned in the above 1.

12. Homopolymers and copolymers of cyclic ethers, such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with diglycidyl ether.

13. Polyacetals such as polyoxymethylene and those polyoxymethylenes containing ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.

14. Polyphenylene ether and polyphenylene sulfide, and mixtures of polyphenylene ether with styrene polymers or polyamides.

15. Polyurethanes which are derived on the one hand from hydroxyl terminated polyethers, polyesters or polybutadienes and on the other hand from aliphatic or aromatic polyisocyanates and their precursors.

16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or derived from aminocarboxylic acids or corresponding lactams, for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6 /9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aramid obtained from meta-xylene diamine and adipic acid; elasticity in the presence or absence of modifier a polyamide prepared from hexamethylenediamine and isophthalic acid and/or terephthalic acid, such as poly-2,4,4-trimethylhexamethylene terephthalamide or poly a phenylene isophthalamide; and a block copolymer of the above polyamide with a polyolefin, an olefin copolymer, an ionomer or a chemically bonded or grafted elastomer; or with a polyether, for example, with a polyethylene glycol a block copolymer of polypropylene glycol or polytetramethylene glycol; and a polyamide or copolyamide modified with EPDM or ABS; and a polyamide (RIM polyamide system) condensed during processing.

17. A polyester derived from a dicarboxylic acid and a diol and/or derived from a hydroxycarboxylic acid or a corresponding lactone or lactide, such as polyethylene terephthalate, polybutylene terephthalate , poly-1,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate and polyhydroxybenzoate, and copolyetherester derived from a hydroxyl terminated polyether; Polyester modified with polycarbonate or MBS. Copolyesters may include, for example, but are not limited to, polybutylene succinate/butylene terephthalate, polybutylene adipate/butylene terephthalate, polyhexyl Tetramethylene dimethane / tetramethylene terephthalate, butylene glycol polysuccinate / butylene glycol adipate, butylene glycol polyacrylate / carbonate, poly-3-hydroxyl Butyrate/3-hydroxyoctanoate copolymer, poly-3-hydroxybutyrate/3-hydroxyhexanoate/3-hydroxydecanoate terpolymer. In addition, aliphatic polyesters may include, for example, but are not limited to, poly(hydroxyalkanoates), especially polypropiolactone, polybutyrolactone, polypivalolactone, polyvalerolactone, and polyhexanolate. Lactone, polyethylene succinate, propylene glycol polysuccinate, polybutylene succinate, hexamethylene polysuccinate, polyethylene adipate, propylene glycol adipate, Polybutylene adipate, polyhexamethylene adipate, polyethylene oxalate, propylene glycol oxalate, polybutylene oxalate, hexamethylene oxalate, polysebacic acid Ethylene glycol esters, polypropylene glycol phthalate, polybutylene phthalate and polylactic acid (PLA) and corresponding polyesters modified with polycarbonate or MBS. The term "polylactic acid (PLA)" means a homopolymer preferably of poly L lactide and any blend or alloy thereof with other polymers; a copolymer of lactic acid or lactide with other monomers, said other Monomer such as hydroxycarboxylic acid Such as glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid, 5-hydroxyvaleric acid, 6-hydroxycaproic acid and cyclic forms thereof; the term "lactic acid" or "lactide" includes L-lactic acid, D-lactic acid, mixtures thereof and dimers, namely L-lactide, D-lactide, meso-lactide and any mixtures thereof.

18. Polycarbonates and polyester carbonates.

19. Polyketone.

20. Polysulfone, polyethersulfone and polyetherketone.

21. Crosslinked polymers which are derived from aldehydes on the one hand and phenols, ureas and melamines on the other hand, such as phenol/formaldehyde resins, urea/formaldehyde resins and melamine/formaldehyde resins.

22. Dry and non-dry alkyd resins.

23. An unsaturated polyester resin derived from a copolyester of a saturated and unsaturated dicarboxylic acid and a polyol and a vinyl compound as a crosslinking agent, and a halogen-containing modified product thereof having low flammability.

24. A crosslinkable acrylic resin derived from a substituted acrylate such as an epoxy acrylate, urethane acrylate or polyester acrylate.

25. Alkyd resins, polyester resins and acrylate resins crosslinked with melamine resin, urea resin, isocyanate, isocyanurate, polyisocyanate or epoxy resin.

26. A crosslinked epoxy resin derived from an aliphatic, alicyclic, heterocyclic or aromatic glycidyl compound, such as the product of bisphenol A and diglycidyl ether of bisphenol F, in the presence or absence The presence of a promoter is crosslinked using a conventional hardener such as an acid anhydride or an amine.

27. Blends (polymer blends) of the above polymers, 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 PUR, POM/Acrylate, POM/MBS, PPO/HIPS, PPO/PA66 and Copolymer, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.

28. Natural and synthetic organic materials which are pure monomeric compounds or mixtures of these compounds, such as mineral oils, animal and vegetable fats, oils and waxes, or based on synthetic esters (eg phthalates, adipic acid) Oils, fats and waxes of esters, phosphates or trimellitates, and mixtures of synthetic esters and mineral oils in any weight ratio, typically those used as spinning compositions, and aqueous emulsions of these materials.

Preferred organic materials are:

1) Homopolymers and copolymers of olefin monomers such as ethylene and propylene and higher 1-olefins such as 1-butene, 1-pentene, 1-hexene or 1-octene. Preference is given to polyethylene LDPE and LLDPE, HDPE and polypropylene.

2) Homopolymers and copolymers of olefin monomers with diolefin monomers such as butadiene, isoprene and cyclic olefins such as norbornene.

3) copolymerization of one or more 1-olefins and/or diolefins with carbon monoxide and/or with other vinyl monomers including, but not limited to, vinyl acetate, vinyl ketone, styrene, maleic anhydride and vinyl chloride Things.

4) Polyvinyl alcohol.

5) Other thermoplastics such as polystyrene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyvinyl butyral , ethylene-vinyl alcohol copolymer, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), liquid crystal polyester (LCP), polyacetal (such as POM), poly Amide (PA), polycarbonate, polyurethane, and polyphenylene sulfide (PPS); polymer blends or polymer alloys formed from two or more of these resins; and by adding fillers such as glass fibers, carbon fibers, and half Carbonized fiber, cellulose fiber and glass beads, flame retardant, foaming agent, antimicrobial agent, crosslinking agent, polyolefin resin fine powder, polyolefin wax, ethylene bisamide wax, metal soap, etc., alone or in combination Compounds obtained from these resins. On the other hand, examples of the thermosetting resin may include thermosetting resins such as epoxy resins, melamine resins, and unsaturated polyester resins; and by incorporating fillers such as glass fibers, carbon fibers, semi-carbonized fibers, cellulose fibers, and glass beads, A compound obtained by emulsifier or the like, alone or in combination with these resins.

Other preferred polymers are: biodegradable polymers of natural or synthetic origin including, but not limited to, polyethylene succinate, polybutylene succinate, butylene polysuccinate/butyl adipate Glycol ester, polybutylene succinate/butylene carbonate, polybutylene succinate/butylene terephthalate, polycaprolactone, poly(hydroxyalkanoate), poly -3-hydroxybutyrate, polylactic acid, polyester amide or a blend of these materials with natural or modified starch, polysaccharide, lignin, wood flour, cellulose or chitin.

The polymer is preferably a thermoplastic natural or synthetic polymer, especially one selected from the group consisting of the above. Preference is given to polyolefin homopolymers or copolymers, starch-modified polyolefins or starch-based polymer composites, particular preference being given to polyethylene, polypropylene, polyethylene copolymers or polypropylene copolymers.

The filler includes, for example, calcium carbonate, silica, glass fiber, glass bubbles, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood powder, powder of other natural products, Synthetic fiber, stearate used as a filler such as calcium stearate or zinc stearate.

The polymer molding compositions of the present invention are suitable for use in the production of fibers, coatings, films or moldings.

The present invention also provides a process for preparing a polymer composition comprising mixing the polymer additive A of the present invention and/or the polymer additive composition of the present invention with a polymer pellet and a filler in a mixer, and They are homogenized in the polymer melt in an extruder apparatus at relatively high temperatures, and the homogenized polymer extrudate is then withdrawn, cooled, and pelletized. The extruder unit is selected from a single screw extruder or a twin screw extruder. The preferred processing temperature is 170 to 200 ° C for polystyrene, 200 to 300 ° C for polypropylene, 250 to 290 ° C for polyethylene terephthalate (PET), and polybutylene terephthalate. The alcohol ester (PBT) is 230 to 270 ° C, 260 to 290 ° C for polyamide-6 (PA6), 260 to 290 ° C for polyamide 66 (PA66), and 280 to 320 ° C for polycarbonate. The compounding device which can be used in the present invention is a single screw extruder or a twin screw extruder, and the effective screw length for the present invention is 20 to 40 D in the case of a single screw extruder; effective in the present invention The screw length is 8 to 48 D in the case of a twin screw extruder.

detailed description

The invention is further illustrated by the following detailed description of the preferred embodiments of the invention, but the embodiments of the invention are not limited by the following examples.

Example 1:

288 g of 2-nitro-2-hydroxy-5-methylazobenzene, 160 g of 50% by mass sodium hydroxide, 380 g of o-xylene and water were added to a 1000 ml reactor at a controlled temperature of 75 ° C. 37.6 g of hydrazine hydrate was slowly added dropwise as a reducing agent, and the addition was continued for 40 minutes. After stirring for 2 hours, the reaction was completed and then analyzed by high performance liquid chromatography (HPLC). The completion of the reduction reaction in the first step can be carried out by the disappearance of 2-nitro-2-hydroxy-5-methylazobenzene as a starting material and 2-(2-hydroxy-5-benzyl)-2 hydrogen. The formation of benzotriazole oxynitride was confirmed. After neutralizing the above reaction product with sulfuric acid, the lower portion of the aqueous layer was removed by separation, and the remaining portion was washed with water.

Subsequently, 380 g of water and 85 g of zinc powder were added to the product solution, and then 154 g of sulfuric acid (95%) was added dropwise at a controlled temperature of 75 ° C, and the addition was continued for 40 minutes to carry out a second reduction reaction. After the reaction was stirred for 2 hours, the reaction was completed, unreacted zinc powder was removed by filtration, and the lower half of the aqueous layer was separated. The dyed material in the organic layer of the product was removed by extraction with sulfuric acid, and after the solution was decolorized with a decolorizing agent, 600 g of methanol was added to crystallize the product.

The obtained solid matter was washed and dried to obtain 198.1 g of a high purity compound having the following chemical formula:

Example 2:

346 g of 2-nitro-4-chloro-2-hydroxy-3-tert-butyl-5-methylazobenzene, 100 g of 50% by mass sodium hydroxide, 420 g of o-xylene as solvent and 200 g of water were added In a 2000 ml reactor, the temperature was controlled at 85 ° C, and 31 g of hydrazine hydrate as a reducing agent was slowly added dropwise for 50 minutes. After stirring for 4 hours, the reaction was completed and then analyzed by HPLC. The completion of the first reduction reaction can be eliminated from 2-nitro-4-chloro-2-hydroxy-3-tert-butyl-5-methylazobenzene used as a starting material, and 2-(2-hydroxyl) is produced. 3-tert-Butyl-5-methylphenyl)-5-chloro-2 hydrogen-benzotriazole-N-oxide was confirmed. After neutralizing the reaction product with sulfuric acid, the lower portion of the aqueous layer was removed by separation, and the remaining portion was washed with water.

Subsequently, 400 g of water and 68 g of zinc powder were added to the product solution, and then the temperature was controlled to 75 ° C, and 130 g of sulfuric acid (95%) was added dropwise for 50 minutes to carry out the second reduction reaction. After the reaction was stirred for 1 hour, the reaction was completed, unreacted zinc powder was removed by filtration, and the lower half of the aqueous layer was removed by separation. The dyed material in the organic layer of the product was removed by extraction with sulfuric acid, and after the solution was decolorized with a decolorizing agent, 800 g of methanol was added to crystallize the product.

The obtained solid matter was washed and dried to obtain 174.1 g of a highly pure compound having the following chemical formula:

Example 3:

A compound having the following chemical formula was prepared in a similar manner to that of Example 2, and the starting material was 2-nitro-4-chloro-2-hydroxy-3,5-di-tert-butylazobenzene.

Example 4:

The following compound was prepared in a similar manner to that of Example 2, and the starting material was 2-nitro-2-hydroxy-3,5-di-t-pentylazobenzene.

Example 5:

The following compound was prepared in a similar manner to that of Example 2, and the starting material was 2-nitro-2-hydroxy-5-tert-octylazobenzene.

Example 6-12

The compounds prepared in Examples 1-5 were respectively compounded with sodium silicate, silicone resin, alkoxysilane, and the weight of the product of Example 1-5 in the polymer additive A was adjusted to obtain a polymer having a specific silicon content. Additive C. The specific compounding method is as follows: firstly, the compound prepared in Examples 1-5 and the silicide-containing material are compounded according to the ratio of Table 1 to a mother sample having a higher silicon content, and the weight content of the silicon element is measured, and then according to the final As a result, the content of the silicon element required was calculated to calculate the weight of the product of Examples 1-5 to be added for the second time, and finally the polymer additive C was obtained, and then the weight of the silicon element was measured again. content. Further, a polymer additive D containing a phosphorus element was obtained in the same manner. According to the content ratio of the silicon element and the phosphorus element which are finally required, the polymer additive C and the polymer additive D in a corresponding ratio are weighed to obtain a polymer additive A.

The weight content of the silicon element and the phosphorus element is determined by the following method: accurately weighing the polymer additive A 2g in an analytical balance, pouring it into a 100 ml digestion bottle, and then adding 97% concentrated sulfuric acid 5 ml at a preset temperature of 300 °C iron plate heating equipment for 10 minutes, then add 68% of nitric acid 5ml, and then keep heating for 20 minutes, the particles are completely decomposed, cooled to room temperature, added to 20ml of hydrogen peroxide and acid to pH value of 7, after use The liquid was diluted with ionized water, and the liquid was introduced into an ICP detector through a sample introduction tube to measure the concentrations of silicon and phosphorus.

Sodium silicate: Shandong Haihua Co., Ltd.

Silicone Resin: Dow Corning RSN-0805

Alkoxysilane: Dow Corning OFS-6070

Red phosphorus: analytical pure, Jining Baichuan Chemical Co., Ltd.

Potassium dihydrogen phosphate: Changzhou Chuan Phosphorus Chemical Co., Ltd.

Triphenylphosphine: Shanghai Changgen Chemical Technology Co., Ltd.

Table 1

Comparative example 1-3

The compounds prepared in Examples 1-3 were separately compounded with sodium silicate, silicone resin and alkoxysilane according to the above method, and the specific contents are shown in Table 2:

Table 2

Examples 13-19, Comparative Examples 4-6

The polymer additives obtained in Examples 6-12 and Comparative Examples 1-3 were weighed in the percentage by weight of the product components described in Tables 3 and 4.

Polypropylene: Basel, EP548R

Polystyrene: Yangtze BASF, 158K

Antioxidant: BASF, Irganox 1010

Fiberglass: PPG, Chop Vantage 3540

Talc powder: Luzenac R7

When the polymer is selected from polypropylene, the above polypropylene and other components are first dry mixed in a high speed mixer at a speed of about 1000 rpm for 1 minute. If talc is added, the talc filler is added and mixed for another 3 minutes. The mixed raw materials are placed in a twin-screw extruder and melt-extruded and granulated. The process conditions are: one zone 200 ° C, two zones 210 ° C, three zones 220 ° C, four zones 215 ° C; twin-screw extruder The aspect ratio is 35, the screw speed is 450 rpm, the residence time is 1 minute, and the pressure is 10 MPa.

When the polymer is selected from polystyrene, the above polypropylene and other components are first dry mixed in a high speed mixer at a speed of about 1000 rpm for 3 minutes, and the mixed raw materials are placed in a twin screw extruder to be melted. Extrusion, granulation, the process conditions are: the temperature of each section of the barrel is maintained at 200 ° C, the twin-screw extruder has a length to diameter ratio of 35, the screw speed is 450 rpm, the residence time is 1 minute, and the pressure is 10 MPa.

Table 3 (percent weight)

Table 4 (percent weight)

	Comparative example 4	Comparative example 5	Comparative example 6
Comparative Example 1 product	0.1
Comparative Example 2 product		0.3
Comparative product 3			1
Polypropylene	69.9		99
Polystyrene		99.7
Antioxidant
talcum powder
glass fiber	30
Chemical resistance (%)	40	37	41

It can be seen from the test results of Tables 3 and 4 above that the polymer material prepared by using the additive A prepared by the invention can significantly improve the chemical resistance of the polymer.

The chemical resistance test is carried out according to the following criteria:

A film having a thickness of 200 μm was prepared by hot pressing at a temperature higher than the melting point of the polymer by about 20 ° C, and a test piece was obtained by punching using a JIS No. 3 dumbbell method. The test piece was immersed in methanol at 23 ° C for 7 days, and then in accordance with JIS K7113 The method was tested for tensile strength. The tensile strength retention ratio (%) was calculated in comparison with the tensile strength value before immersion in methanol.

Claims (8)

1. An additive A for a polymer comprising a compound as shown in formula I,

   

   In the formula I, R1, R2 are the same or different and are represented by H, C1-C8 alkyl or C6-C18 aryl; R3 is H or halogen; wherein, based on the total weight of the additive A, the weight of the silicon element is 5 ppm- 900 ppm, preferably 20 ppm to 400 ppm, more preferably 30 ppm to 200 ppm, based on the total weight of the additive A, the phosphorus element is contained in an amount of from 1 ppm to 980 ppm, preferably from 10 ppm to 400 ppm, more preferably from 25 ppm to 200 ppm.
2. An additive A for a polymer according to claim 1, wherein in the formula I:

   Preferably, R1 and R2 are different, R1 is H, R2 is methyl, and R3 is H, expressed as:

   

   Preferably, R1 and R2 are the same, and are 1,1-dimethylphenyl, and R3 is H, and the expression is:

   

   Preferably, R1 and R2 are different, R1 is a tert-butyl group, R2 is a methyl group, and R3 is Cl, and the expression is:

   

   Preferably, R1 and R2 are the same, which is a tert-butyl group, and R3 is Cl, and the expression is:

   

   Preferably, R1 and R2 are the same, which is a tert-amyl group, and R3 is H, and the expression is:

   

   Preferably, R1 and R2 are different, R1 is 1,1 dimethylphenyl, R2 is 1,1,3,3-tetramethylbutyl, and R3 is H, expressed as:

   

   Preferably, R1 and R2 are different, R1 is H, R2 is a tert-octyl group, and R3 is H, and the expression is:

   
3. An additive composition comprising the additive A according to any one of claims 1 to 2 and other additives B; preferably comprising from 50 to 99.9% by weight of any one of claims 1 to 2 Additive A, and 0.1 to 50% by weight of at least one other additive B; preferably comprising 70 to 95% by weight of the additive A of the polymer according to any one of claims 1 to 2, and 5 to 30 % by weight of at least one other additive B.
4. The additive composition according to claim 3, wherein said other additive B is an antioxidant, a plasticizer, an optical brightener, an antistatic agent, a foaming agent, and claims 1-2 One or more of other UV absorbers than others.
5. A polymer composition comprising the additive A for a polymer according to any one of claims 1 to 2, or the method according to any one of claims 3 to 4 Additive composition.
6. A polymer composition as claimed in claim 5, characterized in that it comprises a polymer in an amount of from 30 to 99.9% by weight, a filler in an amount of from 0 to 60% by weight, and a weight content of from 0.1 to 10%. The additive A for a polymer according to any one of 2, or the additive composition according to any one of claims 3 to 4, in an amount of 0.1 to 10% by weight.
7. The polymer composition according to any one of claims 5 to 6, wherein the polymer is polypropylene, polyethylene, ABS, polystyrene, polyamide, polyvinyl chloride, polyester, poly One or more compositions of formaldehyde, preferably one or more of polypropylene, polystyrene, ABS.
8. Use of an additive A for a polymer as a light stabilizer according to any one of claims 1 to 2.