CN105542314A

CN105542314A - Phosphorus-containing additive for polymer

Info

Publication number: CN105542314A
Application number: CN201610089401.8A
Authority: CN
Inventors: 不公告发明人
Original assignee: Huang Xiuru
Current assignee: Rianlon Corporation
Priority date: 2016-02-17
Filing date: 2016-02-17
Publication date: 2016-05-04
Also published as: WO2017140170A1

Abstract

The invention discloses an additive A for a polymer. The additive A comprises a compound shown in the formula I (please see the specification), wherein R1 and R2 are same or different and represent H and C1-C8 alkyl or C6-C18 aryl; R3 is H or halogen. The additive A further comprises phosphorus elements. When the additive A for the polymer is added into the polymer, the retention stability performance of the polymer can be obviously improved.

Description

A kind of phosphor-included additive for polymkeric substance

Technical field

The present invention relates to a kind of additive A for polymkeric substance, and consisting of compositions of additives, polymer composition and the purposes as photostabilizer thereof.

Background technology

Existing benzotriazole compound is widely used in polymeric additive field, can be used for photostabilizer etc., and known its synthesizes by diverse ways, is mainly raw material from azobenzene compound, carries out cyclisation according to different reducing process.Its existing method of reducing has: hydrazine hydrate reduction method, zinc powder reduction method, sulfide reduction method etc.

Be that reductive agent single stage method obtains benzotriazole light stabilizer with hydrazine hydrate, the patent of report has US4001266, DE2454889, FR2292708 etc.; Another kind method is hydrazine hydrate-zinc powder method, take azobenzene compound as raw material, use hydrazine hydrate is reductive agent, azobenzene compound is reduced to intermediate benzotriazole oxynitride, then be reductive agent with zinc powder be benzotriazole light stabilizer by intermediate benzotriazole reduction of nitrogen oxide, the patent of report has JP53063379, patent CN1455773A etc.; Another kind method is hydrazine hydrate-vat powder method, the method is take azobenzene compound as raw material take hydrazine hydrate as reductive agent, azobenzene compound is reduced to intermediate benzotriazole oxynitride, then use vat powder for reductive agent be benzotriazole light stabilizer by intermediate benzotriazole reduction of nitrogen oxide.The patent of report has CN101029032A.

Benzotriazole compound is used in polymkeric substance as additive, be generally used for photostabilizer etc., when implementing the heat treated such as melt molding, before treatment with process after have the physical property such as limiting viscosity to change problem, the change of above-mentioned physical property causes the mechanics physical property change of gained forming composition or the inequality of quality.Therefore, people wish to obtain stability when can make above-mentioned heat treated strongly, are namely detained stability and keep high-caliber polymkeric substance.And the present inventor is through the surprised discovery of large quantity research, when adding certain content phosphorus containg substances in benzotriazole compound, can make it corresponding polymer retention stability has and very significantly improves.

Summary of the invention

The object of the present invention is to provide a kind of additive A for polymkeric substance, this additive A, by adding micro-phosphorus containg substances in benzotriazole compound, obviously can improve the delay stability of polymer product.

The present invention is achieved by the following technical solutions:

For an additive A for polymkeric substance, comprising:

There is the compound of following structural formula,

Wherein, R1, R2 are identical or different, are expressed as H, C1-C6 alkyl or C6-C18 aryl; R3 is H or halogen; Wherein, based on the gross weight of additive A, the weight content of phosphoric is 5ppm-980ppm, preferred 20ppm-500ppm, more preferably 30ppm-200ppm.

Wherein phosphoric derives from phosphorus containg substances, and phosphorus containg substances can be one or more following combination.

Term " phosphorus containg substances " in this article refers to or comprises element phosphor and organic and inorganic phosphorous compound and/or P contained compound and hydrolyzate thereof or salt.

Element phosphor relates to four kinds of allotropic substance variants, is white phosphorus, red phosphorus, black phosphorus and violet phosphorus.According to the difference of these base types, form different crystalline structure, thus also bring the difference in physicals and reactivity.Preferably red phosphorus is used in this patent.

Suitable inorganic phosphorous compound advantageously comprises (many) phosphoric acid salt, as the not concentrated salt of phosphorous acid or the concentrated salt of phosphoric acid, as ammonium phosphate and ammonium polyphosphate.

Organo phosphorous compounds (I) (II) of the general formula (I) that the present invention uses or (II) can be selected from organo phosphorous compounds, as the organo phosphorous compounds of monomer, or the organo phosphorous compounds of polymkeric substance, inorganic phosphorus compound etc., wherein, R ₁, R ₂and R ₃the organic or inorganic group known from prior art of presentation technology personnel independently of one another.

Substituting group or radicals R are independent of each other, and can be identical or different, do not have even completely.Radicals R preferably can distinguish expression independently of one another :-H, substituted or unsubstituted C ₁-C ₁₅-alkyl, C ₁-C ₁₅-thiazolinyl, C ₃-C ₈-cycloalkyl, C ₆-C ₁₈-aryl, C ₇-C ₃₀-alkaryl, C ₁-C ₈-alkoxyl group or C ₁-C ₈-alkylthio, or-OH or-SH and an alkali metal salt thereof, alkaline earth salt, ammonium salt.

" alkyl " part expression of the optional substituent R of formula (I) phosphorus compound can be the saturated and unsaturated lipid compounds of group of non-branching or branching, wherein preferred unsaturated group.Substituent R preferably includes to have and is no more than 6, and more preferably no more than 4 or 3, more preferably no more than the short-chain alkyl of 2 carbon atoms, or phenyl is as aryl.Useful especially phosphorus compound is preferably unsubstituted as far as possible.

The example of those phosphorus compounds of general formula (I) or (II) is organo phosphorous compounds and salt thereof, as the organo phosphorous compounds of monomer, comprise phosphate compound, phosphoamide ester cpds and phosphazene compound, the organic compound of phosphorous acid, the ester of such as phosphorous acid, the compound of Hypophosporous Acid, 50, phosphine and phosphine oxide, such as triphenylphosphine, triphenylphosphine oxide and trimethylbenzene phosphine oxide etc.

In formula I, preferred R1, R2 are different, and R1 is H, R2 is methyl, and R3 is H, is expressed as:

Preferred R1, R2 are identical, and be 1,1-3,5-dimethylphenyl, R3 is H, is expressed as:

Preferred R1, R2 are different, and R1 is the tertiary butyl, and R2 is methyl, and R3 is Cl, is expressed as:

Preferred R1, R2 are identical, and be the tertiary butyl, R3 is Cl, is expressed as:

Preferred R1, R2 are identical, and be tert-pentyl, R3 is H, is expressed as:

Preferred R1, R2 are different, and R1 is 1,1 3,5-dimethylphenyl, and R2 is 1,1,3,3-tetramethyl butyl, and R3 is H, is expressed as:

Preferred R1, R2 are different, and R1 is H, R2 is tertiary octyl group, and R3 is H, is expressed as:

The present invention also provides a kind of compositions of additives, comprises:

Above-mentioned additive A,

With other additive B of at least one; Wherein the gross weight content of additive A accounts for 50 to 99.9% of compositions of additives gross weight, and preferably 70 to 95%, the weight content of other additive B of at least one is 0.1 to 50%; Preferably 5 to 30%.

Other additive B described is one or more of following material:

1. oxidation inhibitor, comprises following kind:

1.1 alkylation list phenol, such as 2, 6-di-tert-butyl-4-methy phenol, the 2-tertiary butyl-4, 6-xylenol, 2, 6-di-t-butyl-4-ethylphenol, 2, 6-di-t-butyl-4-normal-butyl phenol, 2, 6-di-t-butyl-4-isobutyl-phenol, 2, 6-bicyclopentyl-4-methylphenol, 2-(Alpha-Methyl cyclohexyl)-4, 6-xylenol, 2, 6-bis-(octadecyl)-4-methylphenol, 2, 4, 6-thricyclohexyl phenol, 2, 6-di-t-butyl-4-methoxymetllyl-phenol, side chain is linear or the nonyl phenol of branching such as 2, 6-dinonyl-4-methylphenol, 2, 4-dimethyl-6-(1'-methylundecane-1'-base) phenol, 2, 4-dimethyl-6-(1'-methyl heptadecane-1'-base) phenol, 2, 4-dimethyl-6-(1'-methyltridec-1'-base) phenol and composition thereof.

1.2 Alkyithiomethylphenols, such as 2,4-bis-pungent butylthiomethyl-6-tert.-butyl phenols, 2,4-bis-pungent butylthiomethyl-6-methylphenols, 2,4-bis-pungent butylthiomethyl-6-ethylphenols, 2,6-bis-(dodecylthio) methyl-4-nonylphenol.

1.3 hydroquinones and alkvlated hydroquinones, such as 2,6-di-t-butyl-4-methoxyphenol, 2,5 di tert butylhydroquinone, 2,5 di tert amlyl hydroquinone, 2,6-phenylbenzene-4-octade-cyloxyphenol, 2,6-di-tert-butyl hydroquinone, 2,5-di-t-butyls-4-HA, 3,5-di-t-butyls-4-HA, stearic acid 3, two (3, the 5-di-tert-butyl-hydroxy phenyl) ester of 5-di-t-butyl-4-hydroxylphenyl ester, hexanodioic acid.

1.4 tocopherols, such as alpha-tocopherol, 5,8-dimethyl tocol, Gamma-Tocopherol, Delta-Tocopherol and composition thereof (vitamin-E).

1.5 Hydroxylated thiodiphenyl ethers, such as 2,2'-thiobis (6-tert-butyl-4-methyl-Phenol), 2,2'-thiobis (4-octyl phenol), 4,4'-thiobiss (the 6-tertiary butyl-3-methylphenol), 4,4'-thiobiss (the 6-tertiary butyl-2-methylphenol), 4,4'-thiobis (3,6-di-sec-amyl phenol), 4,4'-two (2,6-dimethyl-4-hydroxy phenyl) disulfides.

1.6 alkylidene bisphenols, such as 2,2'-methylene-biss (6-tert-butyl-4-methyl-Phenol), 2,2'-methylene-bis (the 6-tertiary butyl-4-ethylphenol), 2,2'-methylene-bis [4-methyl-6-(Alpha-Methyl cyclohexyl) phenol], 2,2'-methylene-bis(4-methyl-6-cyclohexyl phenol), 2,2'-methylene-bis (6-nonyl-4-methylphenol), 2,2'-methylene-bis (4,6-DI-tert-butylphenol compounds), 2,2'-ethylenebis (4,6-DI-tert-butylphenol compounds), 2,2'-ethylenebis (the 6-tertiary butyl-4-isobutyl-phenol), 2,2'-methylene-bis [6-(α-methylbenzyl)-4-nonyl phenol], 2,2'-methylene-bis [6-(alpha, alpha-dimethylbenzyl)-4-nonyl phenol], 4,4'-methylene-bis (2,6 di t butyl phenol), 4,4'-methylene-bis (the 6-tertiary butyl-2-methylphenol), two (5-tertiary butyl-4-hydroxy-2-aminomethyl phenyl) butane of 1,1-, two (the 3-tertiary butyl-5-methyl-2-the hydroxybenzyl)-4-methylphenol of 2,6-, 1,1,3-tri-(5-tertiary butyl-4-hydroxy-2-aminomethyl phenyl) butane, two (5-tertiary butyl-4-hydroxy-2-the aminomethyl phenyl)-3-dodecyl sulfydryl butane of 1,1-, ethylene glycol bis [two (the 3'-tertiary butyl-4'-hydroxy phenyl) butyric ester of 3,3-], two (3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) Dicyclopentadiene (DCPD), two [2-(the 3'-tertiary butyl-2'-hydroxyl-5'-the methyl-benzyl)-6-tertiary butyl-4-aminomethyl phenyl] terephthalate, two (3, the 5-dimethyl-2-hydroxy phenyl) butane of 1,1-, two (3, the 5-di-tert-butyl-hydroxy phenyl) propane of 2,2-, two (5-tertiary butyl-4-hydroxy-2-the aminomethyl phenyl)-4-dodecyl sulfydryl butane of 2,2-, 1,1,5,5-tetra-(5-tertiary butyl-4-hydroxy-2-aminomethyl phenyl) pentane.

1.7O-, N-and S-benzyl compounds, such as 3,5,3', 5'-tetra-tert-4,4'-dihydroxyl dibenzyl ether, 4-hydroxyl-3,5-dimethyl benzyl Thiovanic acid stearyl, 4-hydroxyl-3,5-di-t-butyl Benzylmercapto acetic acid tridecyl ester, three (3,5-di-tert-butyl-4-hydroxyl benzyl) amine, two (the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl) dithioterephthalate, two (3,5-di-tert-butyl-4-hydroxyl benzyl) sulfide, 3,5-di-tert-butyl-4-hydroxyl benzyl Thiovanic acid isooctyl acrylate.

1.8 Aromatic hydroxybenzyl compounds, such as 1,3,5-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl)-2,4,6-Three methyl Benzene, Isosorbide-5-Nitrae-bis-(3,5-di-tert-butyl-4-hydroxyl benzyl)-2,3,5,6-tetramethyl-benzene, 2,4,6-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) phenol.

1.9 triaizine compounds, such as 2, two (the octylmercapto)-6-(3 of 4-, 5-di-t-butyl-4-hydroxybenzene amido)-1, 3, 5-triazine, 2-octylmercapto-4, 6-two (3, 5-di-t-butyl-4-hydroxybenzene amido)-1, 3, 5-triazine, 2-octylmercapto-4, 6-two (3, 5-di-t-butyl-4-hydroxyphenoxy)-1, 3, 5-triazine, 2, 4, 6-tri-(3, 5-di-t-butyl-4-hydroxyphenoxy)-1, 2, 3-triazine, 1, 3, 5-tri-(3, 5-di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid ester, 1, 3, 5-tri-(the 4-tertiary butyl-3-hydroxyl-2, 6-dimethyl benzyl) isocyanuric acid ester, 2, 4, 6-tri-(3, 5-di-tert-butyl-hydroxy phenyl ethyl)-1, 3, 5-triazine, 1, 3, 5-tri-(3, 5-di-tert-butyl-hydroxy phenyl propionyl)-six hydrogen-1, 3, 5-triazine, 1, 3, 5-tri-(3, 5-dicyclohexyl-4-hydroxybenzyl) isocyanuric acid ester.

1.10 benzylphosphonic acid ester, such as 2,5-di-tert-butyl-4-hydroxyl benzyl dimethyl phosphonate, 3,5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphonate, 3, the calcium salt of the mono ethyl ester of 5-di-tert-butyl-4-hydroxyl benzyl phosphonic acids two (octadecyl) ester, 5-tertiary butyl-4-hydroxy-3-methylbenzylphosphonic acid two (octadecyl) ester, 3,5-di-tert-butyl-4-hydroxyl benzyl phosphonic acids.

1.11 Acylamino phenol classes, such as 4-hydroxylauranilide, 4-hydroxystearanilide, N-(3,5-di-tert-butyl-hydroxy phenyl) carbamic acid octyl ester.

1.12 β-(3,5-di-tert-butyl-hydroxy phenyl) ester of propionic acid and following monohydroxy-alcohol or polyvalent alcohol: such as with methyl alcohol, ethanol, n-Octanol, isooctyl alcohol, Stearyl alcohol, 1,6-hexylene glycol, 1,9-nonanediol, ethylene glycol, 1,2-propylene glycol, neopentyl glycol, thiodiglycol, glycol ether, triglycol, tetramethylolmethane, three (hydroxyethyl) isocyanuric acid ester, N, N'-two (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylammonium hexylene glycol, TriMethylolPropane(TMP).

The ester of 1.13 β-(5-tertiary butyl-4-hydroxy-3-aminomethyl phenyl) propionic acid and following monohydroxy-alcohol or polyvalent alcohol: such as with methyl alcohol, ethanol, n-Octanol, isooctyl alcohol, Stearyl alcohol, 1, 6-hexylene glycol, 1, 9-nonanediol, ethylene glycol, 1, 2-propylene glycol, neopentyl glycol, thiodiglycol, glycol ether, triglycol, tetramethylolmethane, three (hydroxyethyl) isocyanuric acid ester, N, two (hydroxyethyl) oxamide of N'-, 3-thiaundecanol, 3-thiapentadecanol, trimethylammonium hexylene glycol, TriMethylolPropane(TMP), 4-hydroxymethyl-1-phospha-2, 6, 7-trioxa-l-phosphabicyclo [2.2.2] octane, 3, 9-pair [2-{3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy }-1, 1-dimethyl ethyl]-2, 4, 8, 10-tetra-oxaspiro [5.5] undecanoic ester.

1.14 β-(3, 5-dicyclohexyl-4-hydroxy phenyl) ester of propionic acid and following monohydroxy-alcohol or polyvalent alcohol: such as with methyl alcohol, ethanol, octanol, Stearyl alcohol, 1, 6-hexylene glycol, 1, 9-nonanediol, ethylene glycol, 1, 2-propylene glycol, neopentyl glycol, thiodiglycol, glycol ether, triglycol, tetramethylolmethane, three (hydroxyethyl) isocyanuric acid ester, N, two (hydroxyethyl) oxamide of N'-, 3-thiaundecanol, 3-thiapentadecanol, trimethylammonium hexylene glycol, TriMethylolPropane(TMP), 4-hydroxymethyl-1-phospha-2, 6, the ester of 7-trioxa-l-phosphabicyclo [2.2.2] octane.

1.153, the ester of 5-di-tert-butyl-hydroxy phenyl acetic acid and following monohydroxy-alcohol or polyvalent alcohol: such as with methyl alcohol, ethanol, octanol, Stearyl alcohol, 1,6-hexylene glycol, 1,9-nonanediol, ethylene glycol, 1,2-propylene glycol, neopentyl glycol, thiodiglycol, glycol ether, triglycol, tetramethylolmethane, three (hydroxyethyl) isocyanuric acid ester, N, N'-two (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylammonium hexylene glycol, TriMethylolPropane(TMP), 4-hydroxymethyl-1-phospha-2, the ester of 6,7-trioxa-l-phosphabicyclo [2.2.2] octane.

1.16 β-(3; 5-di-tert-butyl-hydroxy phenyl) acid amides of propionic acid; such as N; N'-two (3; 5-di-tert-butyl-hydroxy phenyl propionyl) hexamethylene-diamine, N; N'-two (3; 5-di-tert-butyl-hydroxy phenyl propionyl) trimethylene diamine, N; N'-two (3; 5-di-tert-butyl-hydroxy phenyl propionyl) hydrazine, N; two [2-(3-[3, the 5-di-tert-butyl-hydroxy phenyl] propionyloxy) ethyl] oxamide of N'-.

2. other UV absorption agent outside instant component I

2.12-hydroxy benzophenone ketone, such as 4-hydroxyl, 4-methoxyl group, 4-octyloxy, 4-oxygen in last of the ten Heavenly stems base, 4-dodecyloxy, 4-benzyloxy, 4,2', 4'-trihydroxyies and 2'-hydroxyl-4,4'-dimethoxy derivatives.

The ester of 2.2 replacements and unsubstituting phenenyl formic acid, such as Whitfield's ointment 4-tertiary butyl phenyl ester, salol, Whitfield's ointment octyl octylphenyl, dibenzoyl resorcinol, two (4-tert-butyl benzoyl) Resorcinol, benzoyl Resorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid 2,4-6-di-tert-butyl phenyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid cetyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid stearyl, 3,5-di-tert-butyl-4-hydroxybenzoic acid 2-methyl-4,6-6-di-tert-butyl phenyl ester.

2.3 esters of acrylic acid, such as alpha-cyano-β, β-diphenyl-ethyl acrylate, alpha-cyano-β, β-diphenyl 2-Propenoic acid-2-ethylhexyl ester, α-carbomethoxy-cinnamic acid methyl esters, alpha-cyano-Beta-methyl methyl p-methoxy cinnamate, alpha-cyano-Beta-methyl p-methoxycinnamic acid butyl ester, α-methoxycarbonyl methyl p-methoxy cinnamate, N-(beta-carbomethoxy-3-beta-cyano vinyl)-2-methyl indoline, four (alpha-cyano-β, β-phenylbenzene) vinylformic acid neo-pentyl ester.

2.4 nickel compound; such as 2; 2'-thiobis [4-(1; 1; 3; 3-tetramethyl butyl) phenol] nickel complex; such as 1:1 or 1:2 title complex; it has or does not have other parts as n-Butyl Amine 99, trolamine or N-cyclohexyldi, nickel dibutyl dithiocarbamate, 4-hydroxyl-3; the mono alkyl ester of 5-di-t-butyl benzylphosphonic acid is as the nickel salt of methyl esters or ethyl ester; ketoxime is as the nickel complex of 2-hydroxy-4-methyl phenyl-undecane base ketoxime, and the nickel complex of 1-phenyl-4-lauroyl-5-hydroxypyrazoles, it has or does not have other parts.

2.5 bulky amine, such as two (1-undecane oxygen base-2, 2, 6, 6-tetramethyl--4-piperidyl) carbonic ether, two (2, 2, 6, 6-tetramethyl--4-piperidyl) sebate, two (2, 2, 6, 6-tetramethyl--4-piperidyl) succinate, two (1, 2, 2, 6, 6-pentamethyl--4-piperidyl) sebate, two (1-octyloxy-2, 2, 6, 6-tetramethyl--4-piperidyl) sebate, two (1, 2, 2, 6, 6-pentamethyl--4-piperidyl) normal-butyl-3, 5-di-tert-butyl-4-hydroxyl benzyl malonic ester, 1-(2-hydroxyethyl)-2, 2, 6, the condenses of 6-tetramethyl--4-hydroxy piperidine and succsinic acid, N, N'-two (2, 2, 6, 6-tetramethyl--4-piperidyl) hexamethylene-diamine and the tertiary octyl amino-2 of 4-, 6-bis-chloro-1, 3, linear or the ring-shaped condensate of 5-triazine, three (2, 2, 6, 6-tetramethyl--4-piperidyl) nitrilotriacetate, four (2, 2, 6, 6-tetramethyl--4-piperidyl)-1, 2, 3, 4-ethylene-dimalonic acid ester, 1, 1'-(1, 2-ethylidene)-bis-(3, 3, 5, 5-tetramethyl-piperazinones), 4-benzoyl-2, 2, 6, 6-tetramethyl piperidine, the stearic oxygen base-2 of 4-, 2, 6, 6-tetramethyl piperidine, two (1, 2, 2, 6, 6-pentamethvl base)-2-normal-butyl-2-(2-hydroxyl-3, 5-di-t-butyl benzyl) malonic ester, 3-n-octyl-7, 7, 9, 9-tetramethyl--1, 3, 8-thriazaspiro [4.5] last of the ten Heavenly stems-2, 4-diketone, two (1-octyloxy-2, 2, 6, 6-tetramethyl-piperidyl) sebate, two (1-octyloxy-2, 2, 6, 6-tetramethyl-piperidyl) succinate, N, N'-two-(2, 2, 6, 6-tetramethyl--4-piperidyl) hexamethylene-diamine and 4-morpholinyl-2, 6-bis-chloro-1, 3, linear or the ring-shaped condensate of 5-triazine, 2-chloro-4, two (the 4-n-butylamino-2 of 6-, 2, 6, 6-tetramethyl-piperidyl)-1, 3, 5-triazine and 1, the condenses of two (3-amino propyl amino) ethane of 2-, 2-chloro-4, 6-bis-(4-n-butylamino-1, 2, 2, 6, 6-pentamethvl base)-1, 3, 5-triazine and 1, the condenses of two (3-amino propyl amino) ethane of 2-, 8-ethanoyl-3-dodecyl-7, 7, 9, 9-tetramethyl--1, 3, 8-thriazaspiro [4.5] decane-2, 4-diketone, 3-dodecyl-1-(2, 2, 6, 6-tetramethyl--4-piperidyl) tetramethyleneimine-2, 5-diketone, 3-dodecyl-1-(1, 2, 2, 6, 6-pentamethyl--4-piperidyl) tetramethyleneimine-2, 5-diketone, 4-n-Hexadecane oxygen base-and the stearic oxygen base-2 of 4-, 2, 6, the mixture of 6-tetramethyl piperidine, N, N'-two (2, 2, 6, 6-tetramethyl--4-piperidyl) hexamethylene-diamine and 4-Cyclohexylamino-2, 6-bis-chloro-1, 3, the condenses of 5-triazine, 1, two (3-amino propyl amino) ethane and 2 of 2-, 4, 6-tri-chloro-1, 3, 5-triazine and 4-butyl amino-2, 2, 6, the condenses (CAS registration number [136504-96-6]) of 6-tetramethyl piperidine, the condenses (CAS registration number [192268-64-7]) of 1,6-hexanediamine and 2,4,6-tri-chloro-1,3,5-triazines and N, N-dibutylamine and 4-butyl amino-2,2,6,6-tetramethylpiperidine, N-(2, 2, 6, 6-tetramethyl--4-piperidyl) dodecyl succinimide, N-(1, 2, 2, 6, 6-pentamethyl--4-piperidyl) dodecyl succinimide, 2-undecyl-7, 7, 9, 9-tetramethyl--1-oxa--3, 8-diaza-4-oxo spiral shell [4, 5] decane, 7, 7, 9, 9-tetramethyl--2-ring undecyl-1-oxa--3, 8-diaza-4-oxo spiral shell [4, 5] reaction product of decane and Epicholorohydrin, 1, 1-two (1, 2, 2, 6, 6-pentamethyl--4-piperidyl oxygen base carbonyl)-2-(4-p-methoxy-phenyl) ethene, N, two formyl radical-the N of N'-, N'-two (2, 2, 6, 6-tetramethyl--4-piperidyl) hexamethylene-diamine, 4-methoxymethylene propanedioic acid and 1, 2, 2, 6, the diester of 6-pentamethyl--4-hydroxy piperidine, poly-[methyl-propyl-3-oxygen base-4-(2, 2, 6, 6-tetramethyl--4-piperidyl)] siloxanes, maleic anhydride-alpha-olefin copolymer and 2, 2, 6, 6-tetramethyl--4-amino piperidine or 1, 2, 2, 6, the reaction product of 6-pentamethyl--4-amino piperidine, 2, two [N-(the 1-cyclohexyloxy-2 of 4-, 2, 6, 6-tetramethyl piperidine-4-base)-N-butyl amino]-6-(2-hydroxyethyl) amino-1, 3, 5-triazine, 1-(2-hydroxy-2-methyl propoxy-)-4-octadecane acyloxy-2, 2, 6, 6-tetramethyl piperidine, 5-(2-ethyl hexyl acyl group) oxygen ylmethyl-3, 3, 5-trimethylammonium-2-morpholone mai, Sanduvor (Clariant, CAS registration number [106917-31-1]), 5-(2-ethyl hexyl acyl group) oxygen ylmethyl-3, 3, 5-trimethylammonium-2-morpholone mai, 2,4-two [(1-cyclohexyloxies-2,2, 6, 6-piperidin-4-yl) butyl is amino] the chloro-s-triazine of-6-and two (3-aminopropyl) quadrol of N, N'-) and reaction product, 1,3, 5-tri-(N-cyclohexyl-N-(2, 2,6,6-tetramethyl-piperazine-3-ketone-4-base) amino)-s-triazine, 1, 3, 5-tri-(N-cyclohexyl-N-(1,2,2, 6,6-pentamethyl-piperazine-3-ketone-4-base) amino)-s-triazine.

2.6 oxamide, such as 4, 4'-bis-octyloxy oxanilide, 2, 2'-diethoxy oxanilide, 2, 2'-bis-octyloxy-5, 5'-di-t-butyl oxanilide, 2, 2'-bis-(dodecyloxy)-5, 5'-di-t-butyl oxanilide, 2-oxyethyl group-2'-ethyl oxanilide, N, two (3-dimethylaminopropyl) oxamide of N'-, 2-oxyethyl group-5-the tertiary butyl-2'-ethyl oxanilide and with 2-oxyethyl group-2'-ethyl-5, the mixture of 4'-di-t-butyl oxanilide, o-and p-methoxyl group two replaces the mixture that the mixture of oxanilide and o-and p-oxyethyl group two replace oxanilide.

2.72-(2-hydroxy phenyl)-1, 3, 5-triazines, such as 2, 4, 6-tri-(2-hydroxyl-4-octyloxyphenyl)-1, 3, 5-triazine, 2-(2-hydroxyl-4-octyloxyphenyl)-4, 6-two (2, 4-3,5-dimethylphenyl)-1, 3, 5-triazine, 2-(2, 4-dihydroxy phenyl)-4, 6-two (2, 4-3,5-dimethylphenyl)-1, 3, 5-triazine, 2, two (2-hydroxyl-4-the propoxyphenyl)-6-(2 of 4-, 4-3,5-dimethylphenyl)-1, 3, 5-triazine, 2-(2-hydroxyl-4-octyloxyphenyl)-4, two (the 4-aminomethyl phenyl)-1 of 6-, 3, 5-triazine, 2-(2-hydroxyl-4-dodecyloxy phenyl)-4, 6-two (2, 4-3,5-dimethylphenyl)-1, 3, 5-triazine, 2-(2-hydroxyl-4-tridecane oxygen base phenyl)-4, 6-two (2, 4-3,5-dimethylphenyl)-1, 3, 5-triazine, 2-[2-hydroxyl-4-(2-hydroxyl-3-butoxy propoxy) phenyl]-4, 6-two (2, 4-dimethyl)-1, 3, 5-triazine, 2-[2-hydroxyl-4-(2-hydroxyl-3-octyloxy propoxy-) phenyl]-4, 6-two (2, 4-dimethyl)-1, 3, 5-triazine, 2-[4-(dodecyloxy/tridecane oxygen base-2-hydroxy propyloxy group)-2-hydroxy phenyl]-4, 6-two (2, 4-3,5-dimethylphenyl)-1, 3, 5-triazine, 2-[2-hydroxyl-4-(2-hydroxyl-3-dodecyloxy propoxy-) phenyl]-4, 6-two (2, 4-3,5-dimethylphenyl)-1, 3, 5-triazine, 2-(2-hydroxyl-4-hexyloxy) phenyl-4, 6-phenylbenzene-1, 3, 5-triazine, 2-(2-hydroxyl-4-p-methoxy-phenyl)-4, 6-phenylbenzene-1, 3, 5-triazine, 2, 4, 6-tri-[2-hydroxyl-4-(3-butoxy-2-hydroxy propyloxy group) phenyl]-1, 3, 5-triazine, 2-(2-hydroxy phenyl)-4-(4-p-methoxy-phenyl)-6-phenyl-1, 3, 5-triazine, 2-{2-hydroxyl-4-[3-(2-ethylhexyl-1-oxygen base)-2-hydroxy propyloxy group] phenyl }-4, 6-two (2, 4-3,5-dimethylphenyl)-1, 3, 5-triazine, 2, two (4-[2-ethyl hexyl oxy]-2-the hydroxy phenyl)-6-(4-p-methoxy-phenyl)-1 of 4-, 3, 5-triazine.

3. metal passivator, such as N, N'-bis, N-salicylic aldehyde-N'-salicylyl hydrazine, N, N'-two (salicylyl) hydrazine, N, N'-two (3,5-di-tert-butyl-hydroxy phenyl propionyl) hydrazine, 3-salicylyl amino-1,2,4-triazole, two (benzylidene) oxalyl two hydrazine, oxanilide, m-p-hthaloyl dihydrazide, sebacoyl two phenyl hydrazine, N, N'-diacetyl adipyl dihydrazide, N, two (salicylyl) oxalyl two hydrazine of N'-, two (salicylyl) sulfo-propionyl two hydrazine of N, N'-.

4. phosphorous acid ester and phosphinate, such as triphenyl phosphite, phosphorous acid diphenyl alkyl ester, phenyl dialkyl, tricresyl phosphite (nonyl phenyl) ester, trilauryl, tricresyl phosphite (octadecyl) ester, distearyl pentaerythrityl diphosphite, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester, diiso decyl pentaerythritol diphosphites, two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites, two (2,4-dicumylphenyl) pentaerythritol diphosphites, two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites, two isodecyl oxygen base pentaerythritol diphosphites, two (2,4-di-t-butyl-6-aminomethyl phenyl) pentaerythritol diphosphites, two (2,4,6-tri-(tert-butyl-phenyl) pentaerythritol diphosphites, three stearyl Sorbitol Powder GW-540s, 4,4'-biphenylene two phosphonous acid four (2,4-di-tert-butyl-phenyl) ester, 6-different octyloxy-2,4,8,10-tetra-tert-12H-dibenzo [d, g]-1,3,2-dioxaphosphepin eight ring, two (2, the 4-di-t-butyl-6-aminomethyl phenyl) methyl esters of phosphorous acid, two (2, the 4-di-t-butyl-6-aminomethyl phenyl) ethyl ester of phosphorous acid, fluoro-2,4,8, the 10-tetra-tert-12-methyldiphenyls of 6-are [d, g]-1,3,2-dioxaphosphepin eight ring also, 2,2', 2 "-nitrilo [triethyl three (3,3', 5,5'-tetra-tert-1,1'-biphenyl-2,2'-bis-base) phosphorous acid ester], (3,3', 5,5'-tetra-tert-1,1'-biphenyl-2,2'-bis-base) phosphorous acid 2-ethylhexyl, 5-butyl-5-ethyl-2-(2,4,6-tri-butyl-phenoxy)-1,3,2-dioxaphosphepin cyclopropane.

5. azanol, such as N, N-dibenzyl hydroxylamine, N, N-diethyl hydroxylamine, N, N-Ndioctylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-bis-(tetradecyl) azanol, N, N-bis-(hexadecyl) azanol, N, N-bis-(octadecyl) azanol, N-hexadecyl-N-octadecyl base azanol, N-heptadecyl-N-octadecyl hydroxylamine, N derived from hydrogenated tallow amine, N-dialkylhydroxyamines.

6. nitrone, such as N-benzyl-alpha-phenyinitrone, N-ethyl-α-methylnitrone, N-octyl alpha-heptylnitrone, N-lauryl-α-undecyinitrone, N-tetradecyl-α-tridecyinitrone, N-hexadecyl-α-pentadecylnitrone, N-octadecyl-α-heptadecyl-nitrone, N-hexadecyl-al-pha nitrone, N-octadecyl-α-pentadecylnitrone, N-heptadecyl-α-heptadecyl-nitrone, N-octadecyl-α-hexadecyl nitrone, nitrone derived from N, N-dialkylhydroxyamines (derived from hydrogenated tallow amine).

7. Thiosvnergists, such as thiodipropionate dilauryl, thio-2 acid myristyl ester, thio-2 acid distearyl ester or distearyl disulfide.

8. peroxide scavenger, the such as ester of β-thio-2 acid, such as zinc salt, zinc dibutyl dithiocarbamate, two (octadecyl) disulfide, tetramethylolmethane four (β-dodecy) propionic ester of Lauryl Ester, stearyl, myristyl ester or tridecyl ester, mercaptobenzimidazole or 2-mercaptobenzimidazole.

9. Polvamide stabilisers, the mantoquita such as combined with iodine and/or phosphorus compound and manganous salt.

10. Basic co-stabilisers, the an alkali metal salt of such as trimeric cyanamide, polyvinylpyrrolidone, Dyhard RU 100, cyanuric acid alkatriene propyl diester, urea derivatives, hydrazine derivative, amine, polymeric amide, urethane, higher fatty acid and alkaline earth salt, such as calcium stearate, Zinic stearas, mountain acid magnesium, Magnesium Stearate, sodium ricinate and potassium palmitate, pyrocatechuic acid antimony or pyrocatechuic acid zinc.

11. nucleators, such as inorganic substance are as talcum, metal oxides such as titanium dioxide or magnesium oxide, the phosphoric acid salt of preferred bases earth metals, carbonate or vitriol; Organic compound such as, as single-or poly carboxylic acid and salt, 4-p t butylbenzoic acid, hexanodioic acid, diphenyl acetic acid, sodium succinate or Sodium Benzoate; Polymerizable compound is as ionic copolymer (ionomer).Especially 1,3:2,4-two (3', 4'-dimethyl benzylidene) Sorbitol Powder, 1,3:2,4-bis-(to methyldibenzylidene) Sorbitol Powder and 1,3:2,4-bis-(benzylidene) Sorbitol Powder is preferably.

12. other additives, such as softening agent, lubricant, emulsifying agent, pigment, rheologic additive, catalyzer, flowing regulator, white dyes, fire retardant, static inhibitor and whipping agent.

Preferred additive B is:

1) other UV absorption agent beyond the present invention.

2) processing additives is as anti-skidding/anti-caking additive, softening agent, white dyes, static inhibitor and whipping agent.

3) antioxidant.

The present invention also provides a kind of polymer composition, comprise the described additive A for polymkeric substance, or the compositions of additives of the composition of additive A and additive B, wherein additive A or the compositions of additives that is made up of additive A and additive B account for the weight content 0.1-10% of polymer composition, the weight content of polymkeric substance is 30-99.9%, and the weight content of filler is 0-60%.

The operable polymkeric substance of the present invention is thermoset and thermoplastic polymer, is selected from one or more in following material:

1. the polymkeric substance of monoolefine and diolefine, such as polypropylene, polyisobutene, polybutene, poly-4-methylpentene, polyvinyl eyclohexane, polyisoprene or polyhutadiene, and the polymkeric substance of cycloolefin, the polymkeric substance of such as cyclopentenes or norbornylene, polyethylene (optionally crosslinkable), such as high density polyethylene(HDPE) (HDPE), high-density and High molecular weight polyethylene (HDPE-HMW), high-density and ultrahigh molecular weight polyethylene(UHMWPE) (HDPE-UHMW), medium-density polyethylene (MDPE), Low Density Polyethylene (LDPE), linear low density polyethylene (LLDPE).

2. the mixture of the polymkeric substance mentioned in 1, the mixture of such as polypropylene and polyisobutene, polypropylene and poly mixture (such as PP/HDPE, PP/LDPE) and dissimilar poly mixture (such as LDPE/HDPE).

3. monoolefine and diolefine each other or with the multipolymer of other vinyl monomers, such as ethylene/propene copolymer, linear low density polyethylene (LLDPE) and the mixture with Low Density Polyethylene (LDPE) thereof, propylene/but-1-ene multipolymer, propylene/isobutylene copolymers, ethene/but-1-ene multipolymer, ethylene/hexene multipolymer, ethene/methylpentene copolymer, ethene/heptene copolymer, ethylene/octene, ethylene/vinyl butylcyclohexane multipolymer, ethene/cyclic olefine copolymer (such as ethene/norbornylene, such as COC), ethene/1-olefin copolymer (wherein 1-alkene original position produces), the terpolymer of propylene/butadienecopolymer, iso-butylene/isoprene copolymer, ethylene/vinyl cyclohexene copolymer, ethylene/alkyl acrylate copolymer, ethylene/methacrylic acid alkyl ester copolymer, ethylene/vinyl acetate or ethylene/acrylic acid copolymer and salt (ionomer) and ethene and propylene and diene (such as hexadiene, Dicyclopentadiene (DCPD) or ethylidene norbornene), with these multipolymers mixture each other and with above-mentioned 1) in the mixture of polymkeric substance mentioned, such as polypropylene/ethylene-propylene copolymer, LDPE/ vinyl-vinyl acetate copolymer (EVA), LDPE/ ethylene-acrylic acid copolymer (EAA), LLDPE/EVA, LLDPE/EAA and the mixture with other polymkeric substance (as polymeric amide) thereof.

4. hydrocarbon resin (such as C5-C9), comprises the mixture of its hydrogenation modification product (such as tackifier) and polyalkylene and starch.

The homopolymer of 1-4 and multipolymer can have any three-dimensional arrangement, rule, isotactic, half isotactic or random between comprising; Wherein preferred unregulated polymer.Also stereoblock polymer is comprised.

5. polystyrene, poly-p-methylstyrene, poly alpha methylstyrene.

6. the aromatic homopolymers of derived from ethylene base aromatic monomer and multipolymer, described monomer comprises all isomer of vinylbenzene, alpha-methyl styrene, Vinyl toluene, particularly to Vinyl toluene, all isomer of ethyl styrene, propylstyrene, vinyl biphenyl, vinyl naphthalene and vinyl anthracene and composition thereof.Homopolymer and multipolymer can have any three-dimensional arrangement, rule, isotactic, half isotactic or random between comprising; Wherein preferred unregulated polymer.Also stereoblock polymer is comprised.

6a. comprises above-mentioned vi-ny l aromatic monomers and is selected from the multipolymer of following comonomer: ethene, propylene, diene, nitrile, acid, maleic anhydride class, maleimide, vinyl-acetic ester and vinylchlorid or acrylic and composition thereof, such as phenylethylene/butadiene, styrene/acrylonitrile, styrene/ethylene (multipolymer), styrene/methacrylic acid alkyl ester, phenylethylene/butadiene/alkyl acrylate, phenylethylene/butadiene/alkyl methacrylate, phenylethylene/maleic anhydride, vinylbenzene/

Acrylonitrile/methyl acrylate; The high-impact mixture of styrol copolymer and other polymkeric substance (such as polyacrylic ester, diene polymer or ethylene/propylene/diene terpolymers); And cinnamic segmented copolymer is as styrene/butadiene/styrene, styrene/isoprene/styrene, styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/styrene.

6b., by the derivative hydrogenating aromatic polymers of the polymer hydrogenation mentioned in above-mentioned 6, especially comprises the poly-cyclohexyl. vinyl (PCHE) obtained by random polystyrene hydrogenation, is commonly referred to polyvinyl eyclohexane (PVCH).

The hydrogenating aromatic polymers that 6c. is derived by the polymer hydrogenation mentioned in above-mentioned 6a.

7. the graft copolymer of vi-ny l aromatic monomers (as vinylbenzene or alpha-methyl styrene), such as styrene-grafted poly-fourth two

Alkene, styrene-grafted Polybutadiene-styrene or polybutadiene-acrylonitrile copolymer; The polyhutadiene of vinylbenzene and vinyl cyanide (or methacrylonitrile) grafting; The polyhutadiene of vinylbenzene, vinyl cyanide and methyl methacrylate-grafted; The polyhutadiene of vinylbenzene and maleic anhydride graft; The polyhutadiene of vinylbenzene, vinyl cyanide and maleic anhydride or maleimide grafting; The polyhutadiene of vinylbenzene and maleimide grafting; The polyhutadiene of vinylbenzene and alkyl acrylate or alkyl methacrylate grafting; The ethylene/propylene/diene terpolymers of vinylbenzene and acrylonitrile grafting; The polyalkyl acrylate of vinylbenzene and acrylonitrile grafting or polyalkyl methacrylate; The acrylate/butadiene copolymers of vinylbenzene and acrylonitrile grafting and with 6) in the mixture of listed multipolymer, be such as called the mixture of the multipolymer of ABS, MBS, ASA or AES polymkeric substance.

8. halogen-containing polymkeric substance, the multipolymer of the chlorination of such as sovprene, chlorinated rubber, isobutylene-isoprene or brominated copolymer (halogen butyl rubber), chlorination or chlorosulfonated polyethylene, ethene and ethylene chloride, epichlorohydrin homopolymers and multipolymer, the polymkeric substance of especially halogen-containing vinyl compound, such as polyvinyl chloride, polyvinylidene dichloride, fluorinated ethylene propylene, poly(vinylidene fluoride); And multipolymer is as vinylchlorid/vinylidene chloride, vinylchlorid/vinyl-acetic ester or vinylidene chloride/vinyl acetate copolymer.

9. derived from alpha, the polymkeric substance of beta-unsaturated acid and derivative thereof, such as polyacrylic ester and polymethacrylate; Polymethylmethacrylate, polyacrylamide and polyacrylonitrile, it carries out impact modification with butyl acrylate.

10. monomer multipolymer each other mentioned in 9 or the multipolymer with other unsaturated monomers, such as acrylonitrile/butadiene multipolymer, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or vinyl cyanide/vinyl halide copolymers or vinyl cyanide/alkyl methacrylate/butadiene terpolymer.

11. derived from the polymkeric substance of unsaturated alcohol and amine or its acyl derivative or acetal, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polymaleic acid vinyl acetate, polyvinyl butyral acetal, poly-allyl phthalate or polyallyl melamine; And with above-mentioned 1 in the multipolymer of mentioned alkene.

The homopolymer of 12. cyclic ethers and multipolymer, the such as multipolymer of polyalkylene glycol, polyoxyethylene, polyoxytrimethylene or itself and diglycidyl ether.

13. polyacetal are as polyoxymethylene with containing ethylene oxide those polyoxymethylene as comonomer; With the polyacetal of thermoplastic polyurethane, acrylate or MBS modification.

The mixture of 14. polyphenylene oxide and polyphenylene sulfide and polyphenylene oxide and styrene polymer or polymeric amide.

15. urethane, it is on the one hand derived from hydroxy-end capped polyethers, polyester or polyhutadiene, on the other hand derived from aliphatic series or aromatic polyisocyanate and precursor thereof.

16. polymeric amide and copolyamide, it is derived from diamines and dicarboxylic acid and/or derived from aminocarboxylic acid or corresponding lactan, such as polymeric amide 4, polyamide 6, polyamide 6/6,6/10,6/9,6/12,4/6,12/12, polymeric amide 11, polymeric amide 12, the aromatic poly amide that obtained by m-xylene diamine and hexanodioic acid; The polymeric amide prepared with m-phthalic acid and/or terephthalic acid by hexamethylene-diamine under the elastomerics of presence or absence as properties-correcting agent, such as poly-2,4,4-tri-methyl hexamethylene terephthalamides or poly-metaphenylene isophtalamide; And the elastomeric segmented copolymer of above-mentioned polymeric amide and polyolefine, olefin copolymer, ionomer or chemical bonding or grafting; Or and polyethers, such as, with the segmented copolymer of polyoxyethylene glycol, polypropylene glycol or polytetramethylene glycol; And with the polymeric amide of EPDM or ABS modification or copolyamide; And the polymeric amide of condensation in the course of processing (RIM polyamide system).

17. polyester, it is derived from dicarboxylic acid and glycol and/or derived from hydroxycarboxylic acid or corresponding lactone or lactide, such as polyethylene terephthalate, polybutylene terephthalate, poly-Isosorbide-5-Nitrae-hydroxymethyl-cyclohexane terephthalate, poly-alkylene naphthalate and poly-hydroxybenzoate and the copolyether ester derived from hydroxyl terminated polyether; And with the polyester of polycarbonate or MBS modification.Copolyesters can comprise, such as (but being not limited to): polybutylene succinate/mutual-phenenyl two acid bromide two alcohol ester, poly adipate succinic acid ester/mutual-phenenyl two acid bromide two alcohol ester, poly-tetramethylene adipate/terephthalic acid tetramethylene ester, polybutylene succinate/tetramethylene adipate, polybutylene succinate/carbonic ether, poly-3-hydroxybutyrate ester/3-Hydroxyoctanoic acid ester copolymer, poly-3-hydroxybutyrate ester/3-hydroxycaproic ester/3-hydroxydecanoic acid ester terpolymer.In addition, aliphatic polyester can comprise, such as (but being not limited to): poly-(hydroxy alkane acid ester) class, especially be poly-propiolactone, poly-butyrolactone, poly-pivalolactone, poly-valerolactone and polycaprolactone, polydiethylene glycol succinate, poly-succsinic acid propylene glycol ester, polybutylene succinate, poly-succsinic acid hexa-methylene ester, polyethylene glycol adipate, polypropylene adipate (PPA), poly adipate succinic acid ester, poly-hexanodioic acid hexa-methylene ester, poly-oxalic acid glycol ester, poly-oxalic acid propylene glycol ester, poly-oxalic acid butanediol ester, poly-oxalic acid hexa-methylene ester, polyethylene glycol sebacate, poly-sebacic acid propylene glycol ester, polydiethylene glycol sebacate and poly(lactic acid) (PLA) and the corresponding polyester with polycarbonate or MBS modification.Term " poly(lactic acid) (PLA) " represent the homopolymer that is preferably PLLA and with any blend of other polymkeric substance or alloy; The multipolymer of lactic acid or rac-Lactide and other monomers, other monomers described such as hydroxycarboxylic acid is as oxyacetic acid, 3-hydroxybutyrate, 4 hydroxybutyric acid, 4-hydroxypentanoic acid, 5-hydroxypentanoic acid, 6 hydroxycaproic acid and annular form thereof; Term " lactic acid " or " rac-Lactide " comprise Pfansteihl, D-ALPHA-Hydroxypropionic acid, its mixture and dipolymer, i.e. L-rac-Lactide, D-rac-Lactide, Study of Meso-Lactide and any mixture thereof.

18. polycarbonate and polyestercarbonate.

19. polyketone.

20. polysulfones, polyethersulfone and polyetherketone.

21. cross-linked polymers, it is on the one hand derived from aldehyde, on the other hand derived from phenols, ureas and melamine class, such as phenol/formaldehyde resins, urea/formaldehyde resin and melamine/formaldehyde resin.

22. dryness and non-dry alkyd resin.

23. unsaturated polyester resins, it is derived from saturated and unsaturated dicarboxylic acid and polyvalent alcohol and the vinyl compound as linking agent copolyesters, and the Halogen modified product of low combustible.

24. crosslinkable acrylic resins, it is derived from the acrylate replaced, such as acrylic acid epoxy ester, urethane acrylate or polyester acrylate.

25. with the Synolac of melamine resin, urea resin, isocyanic ester, isocyanuric acid ester, polyisocyanates or cross linking of epoxy resin, vibrin and acrylate resin.

26. cross-linked epoxy resins, it is derived from aliphatic, alicyclic, heterocycle race or aromatic glycidyl compounds, the product of the diglycidylether of such as dihydroxyphenyl propane and Bisphenol F, and it uses conventional hardeners such as acid anhydrides or amine to be cross-linked under presence or absence promotor.

The blend (blend polymer) of 27. above-mentioned polymkeric substance, such as PP/EPDM, polymeric amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/ acrylate, POM/ thermoplasticity PUR, PC/ thermoplasticity PUR, POM/ acrylate, POM/MBS, PPO/HIPS, PPO/PA66 and multipolymer, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.

The 28. natural organic materialss with synthesizing, it is the mixture of pure monomer compound or these compounds, such as mineral oil, animal and plant fat, oil and wax or the mixture based on oil, fat and the wax of synthetic ester (such as phthalic ester, adipic acid ester, phosphoric acid ester or trimellitate) and any weight ratio of synthetic ester and mineral oil, typically be the water-based emulsion of those and these material as spinning component.

Preferred organic materials is:

1) olefinic monomer is if ethene and propylene and more senior 1-alkene are as the homopolymer of 1-butylene, 1-amylene, 1-hexene or 1-octene and multipolymer.Preferably polyethylene LDPE and LLDPE, HDPE and polypropylene.

2) olefinic monomer and diolefinic monomer are if divinyl, isoprene and cycloolefin are as the homopolymer of norbornylene and multipolymer.

3) one or more 1-alkene and/or diolefine and carbon monoxide and/or with other vinyl monomers, include but not limited to the multipolymer of vinyl-acetic ester, vinyl ketone, vinylbenzene, maleic anhydride and vinylchlorid.

4) polyvinyl alcohol.

5) other thermoplasticss are as polystyrene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, polyvinyl chloride, polyvinylidene dichloride, polyvinyl acetate, polyvinyl alcohol butyraldehyde, ethylene-vinyl alcohol copolymer, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), liquid crystal polyester (LCP), polyacetal (such as POM), polymeric amide (PA), polycarbonate, urethane and polyphenylene sulfide (PPS), the blend polymer of two or more these resin formation or polymer alloy, and by adding filler if glass fibre, carbon fiber, partial carbonization fiber, cellulose fiber peacekeeping granulated glass sphere, fire retardant, whipping agent, biocide, linking agent, polyolefin resin fine powder, polyolefin-wax, ethylene bisamides wax, metallic soap etc. are alone or in combination to the compound that these resins obtain.On the other hand, the example of thermosetting resin can comprise thermosetting resin as epoxy resin, melamine resin and unsaturated polyester resin; And by mixing filler if glass fibre, carbon fiber, partial carbonization fiber, cellulose fiber peacekeeping granulated glass sphere, fire retardant etc. are alone or in combination to the compound that these resins obtain.

Other preferred polymkeric substance are: the biodegradable polymers that natural or synthesis is originated, include but not limited to polydiethylene glycol succinate, polybutylene succinate, polybutylene succinate/tetramethylene adipate, polybutylene succinate/carbonic acid butanediol ester, polybutylene succinate/mutual-phenenyl two acid bromide two alcohol ester, polycaprolactone, poly-(hydroxy alkane acid ester), poly-3-hydroxybutyrate ester, poly(lactic acid), polyesteramide or these materials and natural or treated starch, polysaccharide, lignin, wood powder, Mierocrystalline cellulose or chitinous blend.

Described polymkeric substance is preferably the natural or synthetic polymer of thermoplasticity, is especially selected from the one in above-mentioned group.Preferred polyolefm homopolymer or multipolymer, starch conversion polyolefine or starch-based polymer matrix material, particularly preferably polyethylene, polypropylene, polyethylene and ethylene copolymers or polypropylene copolymer.

Described filler comprises: the powder of such as calcium carbonate, silicon-dioxide, glass fibre, glass envelope, talcum, kaolin, mica, barium sulfate, metal oxide and oxyhydroxide, carbon black, graphite, wood powder, other natural products, synthon, as the stearate of filler as calcium stearate or Zinic stearas.

Polymer molding compositions of the present invention is applicable to producd fibers, coating, film or moulded work.

The present invention also provides a kind of method for the preparation of polymer composition, comprise and polymeric additive of the present invention and/or Inventive polymers compositions of additives are mixed with polymeric aggregate and dispensable filler in mixing machine, at relatively high temperature in forcing machine device by they homogenizes in polymer melt, and draw the polymer extrudate of this homogenize subsequently, cooling, pelletizing.Forcing machine device is selected from single screw extrusion machine, or twin screw extruder.Preferred processing temperature is 170 to 200 DEG C for polystyrene, it is 200 to 300 DEG C for polypropylene, it is 250 to 290 DEG C for polyethylene terephthalate (PET), it is 230 to 270 DEG C for polybutylene terephthalate (PBT), it is 260 to 290 DEG C for polymeric amide-6 (PA6), be 260 to 290 DEG C for polymeric amide-66 (PA66), and be 280 to 320 DEG C for polycarbonate.Compounding combination unit used in the present invention is single screw extrusion machine, or twin screw extruder, is 20 to 4OD on the case of a single screw extruder for effective spiro rod length of the present invention; Effective spiro rod length in the present invention is 8 to 48D when twin screw extruder.

Embodiment

Further illustrate the present invention below by embodiment, following examples are the present invention's preferably embodiment, but embodiments of the present invention are not by the restriction of following embodiment.

Embodiment 1:

By 288g2-nitro-2-hydroxy-5-methyl base nitrogen benzide, the sodium hydroxide of 160g50% mass concentration, 380g o-Xylol and water join in the reactor of a 1000ml, and control temperature is at 75 DEG C, dropwise add the hydrazine hydrate of 37.6g slowly as reductive agent, drip and continue 40 minutes.Stir after 2 hours, reaction completes, and then uses high performance liquid chromatography (HPLC) to analyze.Completing of the first step reduction reaction can be confirmed by the disappearance of 2-nitro-2-hydroxy-5-methyl base nitrogen benzide and the generation of 2-(2-hydroxyl-5-phenmethyl)-2 hydrogen-benzotriazole oxynitride being used as starting raw material.Use in sulfuric acid and after above-mentioned reaction product, the water layer of lower part is removed through being separated, more remaining part is washed with water.

Subsequently, join in reaction mixture by 380g water and 85g zinc powder, then control temperature is 75 DEG C and dropwise adds 154g sulfuric acid (95%), drips and continues 40 minutes, carry out second step reduction reaction.Stirring reaction reacted after 2 hours, filtering unreacted zinc powder, being separated the water layer of removing lower part by crossing.By using the coloring matter in sulfuric acid extraction removing product organic layer, after solution bleaching agent bleaching, adding 600g methyl alcohol and crystallization is carried out to product.

The solid matter that washing obtains also is dried and is obtained the highly purified compound with following chemical formula of 198.1g:

Embodiment 2:

By the 346g2-nitro-4-chlorine-2-hydroxyl-3-tertiary butyl-5-methyl-benzene, the sodium hydroxide of 100g50% mass concentration, 420g joins in the reactor of a 2000ml as the o-Xylol of solvent and 200g water, control temperature is at 85 DEG C, dropwise add the hydrazine hydrate of 31g as reductive agent slowly, continue 50 minutes.Stir after 4 hours, reaction completes, and then analyzes with HPLC.Completing of the first step reduction reaction can disappear from being used as the raw-material 2-nitro-4-chlorine-2-hydroxyl-3-tertiary butyl-5-methyl-benzene, and generation 2-(the 2-hydroxyl-3-tertiary butyl-5-aminomethyl phenyl) chloro-2 hydrogen of-5--benzotriazole-N-oxide compound is confirmed.After using sulfuric acid neutralization reaction product, the water layer of lower part is removed through being separated, more remaining part is washed with water.

Subsequently, join in reaction mixture by 400g water and 68g zinc powder, then control temperature is 75 DEG C, dropwise adds 130g sulfuric acid (95%) and continues 50 minutes, carry out second step reduction reaction.Stirring reaction reacted after 1 hour, crossed and filtered unreacted zinc powder, by being separated the water layer of removing lower part.By using the coloring matter in sulfuric acid extraction removing product organic layer, after solution bleaching agent bleaching, adding 800g methyl alcohol and crystallization treatment is carried out to product.

Wash the solid matter obtained, the obtained highly purified compound with following chemical formula of 174.1g after drying:

Embodiment 3:

Have the compound of following chemical formula with the method preparation of similar embodiment 2, initial action material is 2-nitro-4-chlorine-2-hydroxyl-3,5-di-t-butyl nitrogen benzide.

Embodiment 4:

Be prepared as follows compound by the method for similar embodiment 2, initial action material is 2-nitro-2-hydroxyl-3,5-bis-t-amylazo benzene.

Embodiment 5:

Be prepared as follows compound by the method for similar embodiment 2, initial action material is the tertiary octyl group nitrogen benzide of 2-nitro-2-hydroxyl-5-.

Embodiment 6-12

The compound prepared by embodiment 1-5 is composite with red phosphorus, potassium primary phosphate, triphenylphosphine respectively, and by the weight of embodiment 1-5 product in adjustment polymeric additive A, obtain the polymeric additive A of specific phosphorus element content, concrete content is as shown in table 1.Concrete preparation method is, first the compound prepared by embodiment 1-5 and phosphorus containg substances are re-dubbed female sample with higher phosphorous constituent content according to the proportioning of table 1, record the weight content of phosphoric, the products weight of embodiment 1-5 that the cubage second time of the phosphoric then required for net result adds, finally obtain polymeric additive A, again record the weight content of phosphoric afterwards.The weight content of described phosphoric adopts to measure with the following method: accurate weighing polymeric additive A2g in analytical balance, pouring 100ml into clears up in bottle, then the vitriol oil 5ml of 97% is added, heat 10 minutes in preset temp 300 DEG C of iron plate heating instruments, and then add the nitric acid 5ml of 68%, keep heating again 20 minutes, room temperature is cooled to after particulate matter is decomposed completely, to add in the hydrogen peroxide of 20ml and acid to pH value be after 7, dilute aforesaid liquid with deionized water, liquid is imported the concentration measuring phosphoric in ICP detecting instrument by sample feeding pipe.

Red phosphorus: analytical pure, Jining Bai Chuan Chemical Co., Ltd.

Potassium primary phosphate: Changzhou river phosphorous chemical industry company limited

Triphenylphosphine: Shanghai long root chemistry Science and Technology Ltd.

Table 1

Comparative example 1-3

The compound prepared by embodiment 1-3 is composite according to the method described above with red phosphorus, potassium primary phosphate, triphenylphosphine respectively, and concrete content is as shown in table 2:

Table 2

Embodiment 13-19, comparative example 4-6

The polymeric additive of embodiment 6-12 and comparative example 1-3 gained is being taken by product component weight content per-cent described in table 3 and table 4.

Polypropylene: Basel, EP548R

Polystyrene: raise sub-BASF, 158K

Oxidation inhibitor: BASF, Irganox1010

Glass fibre: PPG, ChopVantage3540

Talcum powder: LuzenacR7

When polymkeric substance is selected from polypropylene, above-mentioned polypropylene and other each component is first put into the super mixer dry blending 1 minute that rotating speed is about 1000rpm, if any talcum powder, then add talcum powder remix 3 minutes.The raw material of mixing is placed in twin screw extruder through melt extruding, granulation, its processing condition are: 200 DEG C, a district, two 210 DEG C, districts, three 220 DEG C, districts, four 215 DEG C, districts; Twin screw extruder length-to-diameter ratio is 35, and screw speed is 450 revs/min, and the residence time is 1 minute, and pressure is 10Mpa.

When polymkeric substance is selected from polystyrene, above-mentioned polypropylene and other each component are first put into the super mixer dry blending 3 minutes that rotating speed is about 1000rpm, the raw material of mixing is placed in twin screw extruder through melt extruding, granulation, its processing condition are: each zone temperature of barrel remains on 200 DEG C, twin screw extruder length-to-diameter ratio is 35, and screw speed is 450 revs/min; The residence time is 1 minute, and pressure is 10Mpa.

Table 3 (percent by weight)

Table 4 (percent by weight)

As can be seen from the test result of upper table 3, table 4, the polymer materials that the additive adopting the present invention to prepare is obtained, can make polymer retention stability have clear improvement.

Be detained stability test to be undertaken by following standard:

Use 80 tons of injection moulding machines that Nissei Plastic Industrial Co., Ltd manufactures, be detained 5 minutes at barrel temperature 330 DEG C, then inject the polymer composition in above-described embodiment, measure the limiting viscosity before and after injection, evaluate the stability of limiting viscosity.The absolute value of the difference of " limiting viscosity after injection " and " limiting viscosity before injection " is more little more preferred.Here, when the absolute value of difference is lower than 0.03dl/g, be evaluated as " good (G) ", difference absolute value be more than 0.03dl/g, lower than 0.10dl/g time, be evaluated as " medium (M) ", when the absolute value of difference is more than 0.10dl/g, be evaluated as " bad ".

Limiting viscosity test is undertaken by following standard:

In concentrated sulfuric acid, obtain at 30 DEG C by following formula, the logarithmic viscosity number η of the sample of 0.05g/dl, 0.1g/dl, 0.2g/dl, 0.4g/dl concentration _inh, be extended down to concentration 0, using income value as limiting viscosity { η } by outside it.In formula, t ₀represent solvent Drain time (second), t ₁represent the Drain time (second) of sample solution, C represents the concentration (g/dl) of sample in solution.When sample solution contains solid matter, by the frit in 0.5 μm, described solid matter aperture, gained filtrate is used for measure.

Formula is: η inh=[ln (t ₁/ t ₀)]/C.

Claims

1., for an additive A for polymkeric substance, it comprises such as formula the compound shown in I,

In formula I, R1, R2 are identical or different, are expressed as H, C1-C8 alkyl or C6-C18 aryl; R3 is H or halogen; Wherein, based on the gross weight of additive A, the weight content of phosphoric is 5ppm-980ppm, preferred 20ppm-500ppm, more preferably 30ppm-200ppm.

2. a kind of additive A for polymkeric substance as claimed in claim 1, is characterized in that, in described formula I:

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

Preferred R1, R2 are identical, and be tert-pentyl, R3 is H, is expressed as:

3. a compositions of additives, is characterized in that, comprises the additive A according to any one of claim 1 to 2 and other additive B; Preferably comprise the additive A according to any one of claim 1 to 2 of 50 to 99.9% weight, and other additive B of at least one of 0.1 to 50% weight; Preferably comprise the additive A of the polymkeric substance according to any one of claim 1 to 2 of 70 to 95% weight, and other additive B of at least one of 5 to 30% weight.

4. compositions of additives as described in claim 3, it is characterized in that, other wherein said additive B is one or more in other UV absorption agent beyond oxidation inhibitor, softening agent, white dyes, static inhibitor, whipping agent, claim 1-2.

5. a polymer composition, is characterized in that, comprises as the additive A for polymkeric substance in claim 1 to 2 as described in arbitrary, or comprises as the compositions of additives in claim 3 to 4 as described in arbitrary.

6. polymer composition as claimed in claim 5, it is characterized in that, comprise the polymkeric substance that weight content is 30-99.9%, weight content is the filler of 0-60%, and weight content is that the additive A for polymkeric substance in the claim 1 to 2 of 0.1-10% described in arbitrary one or weight content are for 0.1-10% is as the compositions of additives in claim 3 to 4 as described in arbitrary.

7. the polymer composition according to any one of claim 5 to 6, it is characterized in that, described polymkeric substance is one or more compositions in polypropylene, polyethylene, ABS, polystyrene, polymeric amide, polyvinyl chloride, polyester, polyoxymethylene, one or more in optimization polypropylene, polystyrene, ABS.

8. if a kind of additive A for polymkeric substance in claim 1 to 2 as described in arbitrary is as the purposes of photostabilizer.