CN105694098B

CN105694098B - A kind of additive for polymer

Info

Publication number: CN105694098B
Application number: CN201610132999.4A
Authority: CN
Inventors: 不公告发明人
Original assignee: RIANLON Corp
Current assignee: Rianlon Corporation
Priority date: 2016-03-09
Filing date: 2016-03-09
Publication date: 2017-09-15
Anticipated expiration: 2036-03-09
Also published as: WO2017152684A1; CN105694098A

Abstract

The invention discloses it is a kind of as shown in formula I for additive A of polymer and preparation method thereof, and the polymer composition being made from it,

Description

A kind of additive for polymer

Technical field

The present invention relates to a kind of additive, and in particular to a kind of for additive of thermoplastic polymer and preparation method thereof And the polymer composition being made from it.

Background technology

Thermoplastic polymer is widely used in the fields such as household electrical appliances, packaging, automobile, traffic and finishing, under some use conditions Need good surface slipperiness energy.But plastics are low due to case hardness, or because the reasons such as auxiliary agent migration cause surface Coefficient of friction increases, if be not modified, it is impossible to meet surface slipperiness can use standard require, then many first skills Art improves the surface slipperiness energy of plastics by number of ways, and publication number CN1236375A patent is by improving polypropylene material Crystallinity improve surface slipperiness energy；Publication No. CN1294614A patent improves resin by adding graft copolymer Surface slipperiness energy.These technologies solve the defect of polymer surfaces sliding capability difference to a certain extent, but are both needed to New auxiliary agent is added, the decline of other performance can be caused.

Four (the β-(3,5- di-t-butyl -4- hydroxy benzenes as described in above formula Base) propanoyloxymethyl) methane is a kind of important commercial additive for thermoplastic polymer.For example, it protects organic Material, especially thermoplastic polymer with resist heat, oxidation and/or photochemical degraded.In general, by 2,6- di-tert-butyls Phenol and methyl acrylate first carry out addition reaction, generate β-(3,5- di-tert-butyl-hydroxy phenyl) methyl propionate, then again with Pentaerythrite carries out ester exchange reaction and is made.(β-(3,5- di-tert-butyl-hydroxy phenyls) propionyl oxygen four made from common process Ylmethyl) methane can not be improved the surface slipperiness of thermoplastic polymer, or even reduction to a certain degree can be caused.Mirror In such a contradiction, effort of the those skilled in the art for improving surface slipperiness energy is continuing always.

The content of the invention

The present inventor is had surprisingly found that by many experiments, as four (β-(3,5- di-tert-butyl-hydroxy phenyl) propionyl oxygen Ylmethyl) methane as additive be used for polymer in when, pass through adjust four (β-(3,5- di-tert-butyl-hydroxy phenyl) third Pivaloyloxymethyl) methane synthesis technique so as to obtaining a kind of four (β-(3,5- of particular range angle of repose (also referred to as angle of repose) Di-tert-butyl-hydroxy phenyl) propanoyloxymethyl) methane compounds, add it in polymer, to polymer skid The raising of energy has obvious effect.Study carefully its principle, it may be possible to because particular range angle of repose four (β-(3,5- di-t-butyls- 4- hydroxy phenyls) propanoyloxymethyl) methane compounds are added in thermoplastic polymer, change some thermoplastic polymers Crystallinity, so as to improve the cohesive force of polymer so that polymer shows good sliding capability.

The present invention is achieved by the following technical solutions：

A kind of additive A for polymer, as the structural formula as shown in formula I compound group into：

Formula I, its chemical name can be：Four (β-(3,5- di-t-butyls- 4- hydroxy phenyls) propanoyloxymethyl) methane, the angle of repose of the additive A is 38 ° -48 °, preferably 40 ° -45 °.It is described quiet Angle till, refers to that unrestricted and under helping, the oblique of the cone that is formed on horizontal plane is fallen on by high point naturally for particle The angle that face is constituted with cone baseplane, also referred to as angle of repose, are tested according to GB 11986-89.

The additive A has an at least 55J/g fusion enthalpy, preferably the fusion enthalpy with 60-80J/g, more preferably has 70-75J/g fusion enthalpy, wherein the fusion enthalpy is determined according to ISO11357-1/2, and wherein differential scanning calorimetry (DSC) carried out with the rate of heat addition of 20K/ minutes.

The heap density of the additive A is 0.30g/cm³~0.60g/cm³, preferably 0.40g/cm³~0.50g/cm³。

To obtain the additive A of particular range angle of repose of the present invention, preparation technology of the invention is different from common process.

Conventional produces four (β-(3,5- di-tert-butyl-hydroxy phenyls) by initiation material of 2,6 di t butyl phenol Propanoyloxymethyl) process route of methane has one-step method, two step method, and domestic enterprise is mainly based on two step method.

So-called two step method is exactly:2,6 di t butyl phenol and methyl acrylate are subjected to contraposition addition in the basic conditions Reaction, generates intermediate product 3,5- di-t-butyl -4- hydroxy phenylpropionic acid methyl esters, 3,5- di-t-butyl -4- hydroxy phenylpropionic acid methyl esters Carry out ester exchange reaction under conditions of tin-containing catalyst with pentaerythrite again after crystallization and purification, generate four (β-(3,5- bis- Tert-butyl-hydroxy phenyl) propanoyloxymethyl) methane crude product, obtain final products after crude product is refined.It is this to pass through 3, The technique for carrying out ester exchange reaction after the purification of 5- di-t-butyl -4- hydroxy phenylpropionic acids methyl esters with pentaerythrite again, referred to as two step method Technique.

The preparation technology that the present invention is used is by improving 3,5- di-t-butyls -4- hydroxy phenylpropionic acids methyl esters and pentaerythrite Reaction and prepare the ester exchange method of four (β-(3,5- di-tert-butyl-hydroxy phenyl) propanoyloxymethyl) methane, that is, change Enter the second step process of two step method, and the first step process can be reacted using common process.Wherein this patent is improved Preparation technology is carried out in the presence of the ester exchange catalyst conjugate being made up of aluminium hydroxide and sodium iso-octoate, and wherein this is anti- Should be by being carried out with the next stage:Wherein only have the first stage that aluminium hydroxide catalyst is present in reactant mixture, then work as After reaction 5-12 hours, sodium iso-octoate catalyst is added in reactant mixture and starts second stage.

The present invention also provides a kind of compositions of additives, is different from additive A comprising described additive A and at least one Other additive Bs；The compositions of additives preferably comprises the additive A and 0.1 to 50% weight of 50 to 99.9% weight At least one other additive Bs different from additive A.

Other additive Bs are the one or more of following material：

1. antioxidant, including following species：

1.1 alkylation monophenols, such as 2,6- di-tert-butyl-4-methy phenols, 2- tert-butyl groups -4,6- xylenol, 2, 6- di-t-butyl -4- ethyl -phenols, 2,6- di-t-butyl -4- normal-butyls phenol, 2,6- di-t-butyl -4- isobutyl groups phenol, 2, 6- bicyclopentyl -4- methylphenols, 2- (Alpha-Methyl cyclohexyl) -4,6- xylenols, 2,6- bis- (octadecyl) -4- methyl Phenol, 2,4,6- thricyclohexyl phenol, 2,6- di-t-butyl -4- methoxymetllyl-phenols, side chain are linear or branched nonyl Phenol such as 2,6- dinonyl -4- methylphenols, 2,4- dimethyl -6- (1'- methylundecane -1'- bases) phenol, 2,4- diformazans Base -6- (1'- methyl heptadecane -1'- bases) phenol, 2,4- dimethyl -6- (1'- methyltridec -1'- bases) phenol and its mixing Thing.

1.2 Alkyithiomethylphenols, the pungent butylthiomethyl -6- tert-butyl phenols of such as 2,4- bis-, the pungent butylthiomethyls of 2,4- bis- - Pungent butylthiomethyl -6- the ethyl -phenols of 6- methylphenols, 2,4- bis-, 2,6- bis- (dodecylthio) methyl -4- nonyl phenols.

1.3 hydroquinones and alkvlated hydroquinones, such as 2,6- di-t-butyl -4- metoxyphenols, 2,5- di-t-butyl hydrogen Quinone, 2,5 di tert amlyl hydroquinone, 2,6- diphenyl -4- octade-cyloxyphenols, 2,6- di-tert-butyl hydroquinones, the tertiary fourths of 2,5- bis- Base -4-HA, 3,5- di-t-butyls -4-HA, stearic acid 3,5- di-t-butyl -4- hydroxylphenyl esters, oneself two Sour double (3,5- di-tert-butyl-hydroxy phenyls) esters.

1.4 tocopherols, such as alpha-tocopherol, betatocopherol, Gamma-Tocopherol, Delta-Tocopherol and its mixture (vitamin E)。

1.5 Hydroxylated thiodiphenyl ethers, such as 2,2'- thiobis (6- tert-butyl-4-methyl-Phenols), 2,2'- thiobis (4- octyl phenols), 4,4'- thiobis (the 6- tert-butyl group -3- methylphenols), 4,4'- thiobis (the 6- tert-butyl group -2- methylbenzenes Phenol), 4,4'- thiobis (3,6- di-sec-amyls phenol), double (2,6- dimethyl -4- hydroxy phenyls) disulfides of 4,4'-.

1.6 alkylidene bisphenols, such as 2,2'- di-2-ethylhexylphosphine oxides (6- tert-butyl-4-methyl-Phenols), 2,2'- di-2-ethylhexylphosphine oxides (6- The tert-butyl group -4- ethyl -phenols), 2,2' methylene bis [4- methyl -6- (Alpha-Methyl cyclohexyl) phenol], 2,2' methylene bis (4- methyl -6- cyclohexylphenols), 2,2' methylene bis (6- nonyl -4- methylphenols), the 2,2' methylene bis (uncles of 4,6- bis- Butylphenol), 2,2'- ethylenebis (4,6- DI-tert-butylphenol compounds), 2,2'- ethylenebis (the 6- tert-butyl group -4- isobutyl-benzenes Phenol), 2,2' methylene bis [6- (α-methylbenzyl) -4- nonyl phenols], 2,2' methylene bis [6- (bis (alpha, alpha-dimethylbenzyl) base) - 4- nonyl phenols], 4,4' methylene bis (2,6 di t butyl phenol), 4,4' methylene bis (the 6- tert-butyl group -2- methylphenols), Double (5- tertiary butyl-4-hydroxy -2- aminomethyl phenyls) butane of 1,1-, double (the 3- tert-butyl group -5- methyl -2- the hydroxybenzyls) -4- of 2,6- Double (5- tertiary butyl-4-hydroxy -2- the first of methylphenol, 1,1,3- tri- (5- tertiary butyl-4-hydroxy -2- aminomethyl phenyls) butane, 1,1- Base phenyl) it is -3- dodecyl sulfydryls butane, ethylene glycol double [double (the 3'- tert-butyl group -4'- hydroxy phenyls) butyrates of 3,3-], double (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) bicyclopentadiene, it is double [2- (the 3'- tert-butyl group -2'- hydroxyl -5'- methyl-benzyls) - The 6- tert-butyl group -4- aminomethyl phenyls] terephthalate, double (3,5- dimethyl -2S- hydroxy phenyls) butane of 1,1-, 2,2S- are double Double (5- tertiary butyl-4-hydroxy -2- the aminomethyl phenyls) -4- dodecyls of (3,5- di-tert-butyl-hydroxy phenyls) propane, 2,2- Sulfydryl butane, 1,1,5,5- tetra- (5- tertiary butyl-4-hydroxy -2- aminomethyl phenyls) pentane.

1.7O-, N- and S- benzyl compounds, such as 3,5,3', 5'- tetra-tert -4,4'- dihydroxy dibenzyl ether, 4- Hydroxyl -3,5- dimethyl benzyl TGAs stearyl, 4- hydroxyl -3,5- di-t-butyl Benzylmercapto acetic acid tridecyls Ester, three (3,5- di-tert-butyl-4-hydroxyl benzyls) amine, double (the 4- tert-butyl group -3- hydroxyl -2,6- dimethyl benzyls) two are thio to benzene Dicarboxylic acid esters, double (3,5- di-tert-butyl-4-hydroxyl benzyls) sulfide, 3,5- di-tert-butyl-4-hydroxyl benzyl TGAs are different Octyl group ester.

1.8 Aromatic hydroxybenzyl compounds, such as 1,3,5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyl) -2,4,6- tri- Methylbenzene, 1,4- double (3,5- di-tert-butyl-4-hydroxyl benzyls) -2,3,5,6- durols, (the tertiary fourths of 3,5- bis- of 2,4,6- tri- Base -4- hydroxybenzyls) phenol.

Double (the octylmercapto) -6- (3,5- di-t-butyl -4- hydroxy benzenes amido) -1,3 of 1.9 triaizine compounds, such as 2,4-, 5- triazines, 2- octylmercaptos -4,6- double (3,5- di-t-butyl -4- hydroxy benzenes amido) -1,3,5- triazines, 2- octylmercapto -4, 6- double (3,5- di-t-butyl -4- hydroxyphenoxies) -1,3,5- triazines, (3,5- di-t-butyl -4- hydroxy benzenes oxygen of 2,4,6- tri- Base) -1,2,3- triazines, 1,3,5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyls) isocyanuric acid ester, 1,3,5- tri- (the 4- tert-butyl groups - 3- hydroxyl -2,6- dimethyl benzyls) isocyanuric acid ester, 2,4,6- tri- (3,5- di-tert-butyl-hydroxy phenyls ethyl) -1,3,5- Triazine, 1,3,5- tri- (3,5- di-tert-butyl-hydroxy phenyls propiono)-hexahydro -1,3,5- the triazines, (3,5- bis- of 1,3,5- tri- Cyclohexyl -4- hydroxybenzyls) isocyanuric acid ester.

1.10 benzylphosphonic acid esters, such as 2,5- di-tert-butyl-4-hydroxyl benzyls dimethyl phosphonate, 3,5- di-t-butyls -4- Benzylphosphonic acid diethylester, 3,5- di-tert-butyl-4-hydroxyl benzyls phosphonic acids two (octadecyl) ester, 5- tertiary butyl-4-hydroxies- 3- methylbenzylphosphonic acids two (octadecyl) ester, the calcium salt of the mono ethyl ester of 3,5- di-tert-butyl-4-hydroxyl benzyl phosphonic acids.

1.11 Acylamino phenol classes, such as 4- hydroxylauranilides, 4- hydroxystearanilides, N- (3,5- bis- Tert-butyl-hydroxy phenyl) carbamic acid octyl ester.

1.12 β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid and following monohydric alcohol or the ester of polyalcohol：For example with first Alcohol, ethanol, n-octyl alcohol, isooctanol, octadecanol, 1,6-HD, 1,9- nonanediols, ethylene glycol, 1,2- propane diols, new penta 2 Alcohol, thiodiglycol, diethylene glycol (DEG), triethylene glycol, pentaerythrite, three (ethoxy) isocyanuric acid esters, N, double (ethoxy) oxalyl of N'- Amine, 3- thiaundecanols, 3- thiapentadecanols, trimethyl hexylene glycol, trimethylolpropane, 4- hydroxymethyl -1- phosphas - The ester of 2,6,7- trioxa-l-phosphabicyclos [2.2.2] octane.

1.13 β-(5- tertiary butyl-4-hydroxy -3- aminomethyl phenyls) propionic acid and following monohydric alcohol or the ester of polyalcohol：For example with Methanol, ethanol, n-octyl alcohol, isooctanol, octadecanol, 1,6-HD, 1,9- nonanediols, ethylene glycol, 1,2- propane diols, new penta Glycol, thiodiglycol, diethylene glycol (DEG), triethylene glycol, pentaerythrite, three (ethoxy) isocyanuric acid esters, N, double (ethoxy) oxalyl of N'- Amine, 3- thiaundecanols, 3- thiapentadecanols, trimethyl hexylene glycol, trimethylolpropane, 4- hydroxymethyl -1- phosphas - Double [2- { 3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) the propionyl oxygen of 2,6,7- trioxa-l-phosphabicyclos [2.2.2] octane, 3,9- Base } -1,1- dimethyl ethyls] -2,4,8,10- four oxaspiro [5.5] undecanoic ester.

1.14 β-(3,5- dicyclohexyl -4- hydroxy phenyls) propionic acid and following monohydric alcohol or the ester of polyalcohol：For example with first Alcohol, ethanol, octanol, octadecanol, 1,6-HD, 1,9- nonanediols, ethylene glycol, 1,2- propane diols, neopentyl glycol, sulphur two are sweet Alcohol, diethylene glycol (DEG), triethylene glycol, pentaerythrite, three (ethoxy) isocyanuric acid esters, N, N'- double (ethoxy) oxamides, 3- thias ten One alkanol, 3- thiapentadecanols, trimethyl hexylene glycol, trimethylolpropane, the oxygen of 4- hydroxymethyl -1- phosphas -2,6,7- three The ester of miscellaneous bicyclic [2.2.2] octane.

1.15 3,5- di-tert-butyl-hydroxy phenyls acetic acid and following monohydric alcohol or the ester of polyalcohol：For example with methanol, Ethanol, octanol, octadecanol, 1,6-HD, 1,9- nonanediols, ethylene glycol, 1,2- propane diols, neopentyl glycol, thiodiglycol, Diethylene glycol (DEG), triethylene glycol, pentaerythrite, three (ethoxy) isocyanuric acid esters, N, N'- double (ethoxy) oxamides, 3- thias 11 Alkanol, 3- thiapentadecanols, trimethyl hexylene glycol, trimethylolpropane, 4- hydroxymethyl -1- phospha -2,6,7- trioxas The ester of bicyclic [2.2.2] octane.

The acid amides of 1.16 β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid, such as N, double (3, the 5- di-t-butyl -4- of N'- Hydroxyphenylpro-pionyl) hexamethylene diamine, N, double (the 3,5- di-tert-butyl-hydroxy phenyls propiono) trimethylenes two of N'- Amine, N, N'- double (3,5- di-tert-butyl-hydroxy phenyls propiono) hydrazine, N, the double [2- (3- [3,5- di-t-butyl -4- hydroxyls of N'- Phenyl] propionyloxy) ethyl] oxamides.

2. ultra-violet absorber

2.1 2- hydroxy benzophenone ketones, such as 4- hydroxyls, 4- methoxyl groups, 4- octyloxies, 4- decyloxies, 4- dodecane oxygen Base, 4- benzyloxies, 4,2', 4'- trihydroxies and 2'- hydroxyl -4,4'- dimethoxy derivatives.

2.2 substitutions and the ester of unsubstituting phenenyl formic acid, such as salicylic acid 4- tert-butyl groups phenyl ester, phenyl salicylate, bigcatkin willow are misery Base phenyl ester, DBR, double (4- tert-butyl benzoyls) resorcinols, benzoyl resorcinol, the tertiary fourths of 3,5- bis- Base -4-HBA 2,4- 6- di-tert-butyl phenyl esters, 3,5- di-tert-butyl-4-hydroxybenzoic acids cetyl ester, the uncles of 3,5- bis- Butyl -4-HBA stearyl, 3,5- di-tert-butyl-4-hydroxybenzoic acid 2- methyl -4,6- 6- di-tert-butyl phenyl esters.

2.3 esters of acrylic acids, such as alpha-cyano-β, β-diphenyl-ethyl acrylate, alpha-cyano-β, β-diphenylacrylate Different monooctyl ester, α-carbomethoxy-cinnamic acid methyl esters, alpha-cyano-Beta-methyl methyl p-methoxy cinnamate, α) cyano-beta-methyl is to methoxy Base butyl cinnamate, α-carbomethoxy methyl p-methoxy cinnamate, N- (beta-carbomethoxy-3-beta-cyano vinyl)-2- methyl dihydros Indoles, four (alpha-cyano-β, β-diphenyl) acrylic acid neopentyl esters.

2.4 nickel compounds, the nickel complex of such as 2,2'- thiobis [4- (1,1,3,3- tetramethyl butyl) phenol], example Such as 1:1 or 1:2 complexs, it is with or without other parts such as n-butylamine, triethanolamine or N- cyclohexyldis, two Butyl aminodithioformic acid nickel, the nickel salt of the monoalkyl ester such as methyl esters or ethyl ester of 4- hydroxyl -3,5- di-t-butyl benzylphosphonic acids, The nickel complex of ketoxime such as 2- hydroxy-4-methyls phenyl-undecane base ketoxime, 1- phenyl -4- lauroyl -5- hydroxypyrazoles Nickel complex, it is with or without other parts.

2.5 bulky amines, such as double (1- hendecane epoxides -2,2,6,6- tetramethyl -4- piperidyls) carbonic esters, it is double (2,2, 6,6- tetramethyl -4- piperidyls) sebacate, double (2,2,6,6- tetramethyl -4- piperidyls) succinates, it is double (1,2,2,6, 6- pentamethyl -4- piperidyls) sebacate, double (1- octyloxy -2,2,6,6- tetramethyl -4- piperidyls) sebacates, it is double (1, 2,2,6,6- pentamethyl -4- piperidyls) normal-butyl -3,5- di-tert-butyl-4-hydroxyl benzyls malonate, 1- (2- ethoxys) - Double (the 2,2,6,6- tetramethyl -4- piperidyls) six of condensation product, the N of 2,2,6,6- tetramethyl -4- hydroxy piperidines and butanedioic acid, N'- Linear or ring-shaped condensate, the three (2,2,6,6- tetra- of methylene diamine and the chloro- 1,3,5- triazines of 4- t-octyl amino -2,6- two Methyl -4- piperidyls) nitrilotriacetate, four (2,2,6,6- tetramethyl -4- piperidyls) -1,2,3,4- ethylene-dimalonic acids Ester, 1,1'- (1,2- ethylidene)-bis- (3,3,5,5- tetramethyls piperazinones), 4- benzoyl -2,2,6,6- tetramethyl piperidines, 4- tristearin epoxide -2,2,6,6- tetramethyl piperidines, double (1,2,2,6,6- pentamethvls base) -2- normal-butyls -2- (2- hydroxyls - 3,5- di-t-butyls benzyl) malonate, 3- n-octyls -7,7,9,9- tetramethyl -1,3,8- thriazaspiros [4.5] decyl- 2,4- Diketone, double (1- octyloxy -2,2,6,6- tetramethyl-piperidyls) sebacates, double (1- octyloxy -2,2,6,6- tetramethyl piperidines Base) succinate, N, N'- is double-(2,2,6,6- tetramethyl -4- piperidyls) hexamethylene diamine and 4- morpholinyls -2,6- two it is chloro- The chloro- 4,6- of linear or ring-shaped condensate, 2- double (4- n-butylamino -2,2,6,6- tetramethyl-piperidyls) of 1,3,5- triazines - Double (3- amino propyl aminos) ethane of 1,3,5- triazines and 1,2- the chloro- 4,6- bis- of condensation product, 2- (4- n-butylamino -1,2, 2,6,6- pentamethvls base) condensation product of double (3- amino propyl aminos) ethane of -1,3,5- triazines and 1,2-, 8- acetyl group - 3- dodecyls -7,7,9,9- tetramethyl -1,3,8- thriazaspiros [4.5] decane -2,4- diketone, 3- dodecyls -1- (2,2, 6,6- tetramethyl -4- piperidyls) pyrrolidine-2,5-dione, 3- dodecyls -1- (1,2,2,6,6- pentamethyl -4- piperidyls) Mixture, the N of the stearic epoxide -2,2,6,6- tetramethyl piperidines of pyrrolidine-2,5-dione, 4- hexadecane epoxides-and 4-, N'- are double (2,2,6,6- tetramethyl -4- piperidyls) hexamethylene diamine and the condensation of the chloro- 1,3,5- triazines of 4- Cyclohexylaminos -2,6- two Double (3- amino propyl aminos) ethane of thing, 1,2- and the chloro- 1,3,5- triazines of 2,4,6- tri- and 4- butylaminos -2,2,6,6- four The condensation product (CAS registration numbers [136504-96-6]) of methyl piperidine；1,6- hexamethylene diamines and the chloro- 1,3,5- triazines of 2,4,6- tri- with And the condensation product (CAS registration numbers [192268-64-7]) of N, N- dibutyl amine and 4- butylamino -2,2,6,6- tetramethyl piperidines； N- (2,2,6,6- tetramethyl -4- piperidyls) dodecyl succinimide, N- (1,2,2,6,6- pentamethyl -4- piperidyls) Dodecyl succinimide, 2- undecyl -7,7,9,9- tetramethyl -1- oxa- -3,8- diaza -4- oxos spiral shell [4, 5] decane, 7,7,9,9- tetramethyl -2- ring undecyl -1- oxa-s -3,8- diazas -4- oxos spiral shell [4,5] decane and table chlorine Double (1,2,2,6,6- pentamethyl -4- piperidyls Epoxide carbonyl) -2- (4- methoxyphenyls) ethene of the reaction product of alcohol, 1,1-, Double (2,2,6,6- tetramethyl -4- piperidyls) hexamethylene diamines of N, N'- double formoxyl-N, N'-, 4- methoxymethylenes the third two Diester, the poly- [methyl-propyl -3- epoxides -4- (2,2,6,6- tetramethyls -4- of acid and 1,2,2,6,6- pentamethyl -4- hydroxy piperidines Piperidyl)] siloxanes, maleic anhydride-alpha olefin copolymer and 2,2,6,6- tetramethyl -4- amino piperidines or 1,2,2,6,6- five Double [N- (1- cyclohexyloxy -2,2,6,6- tetramethyl piperidine -4- the bases)-N- fourths of the reaction product of methyl -4- amino piperidines, 2,4- Base amino] -6- (2- ethoxys) amino -1,3,5- triazines, 1- (2- hydroxy-2-methyls propoxyl group) -4- stearyls epoxide -2, 2,6,6- tetramethyl piperidines, 5- (2- ethyl hexyls acyl group) epoxide methyl -3,3,5- trimethyl -2- morpholones, Sanduvor (Clariant；CAS registration numbers [106917-31-1]), 5- (2- ethyl hexyls acyl group) epoxide methyl -3,3,5- trimethyls -2- Double [(1- cyclohexyloxy -2,2,6,6- piperidin-4-yls) butylamino] the chloro- s- triazines of -6- of quinoline ketone, 2,4- and double (the 3- ammonia of N, N'- Base propyl group) ethylenediamine) reaction product, (N- cyclohexyl-N- (the 2,2,6,6- tetramethyl piperazine -3- ketone -4- bases) ammonia of 1,3,5- tri- Base)-s- triazines, 1,3,5- tri- (N- cyclohexyl-N- (1,2,2,6,6- pentamethyl piperazine -3- ketone -4- bases) amino)-s- triazines.

2.6 oxamides, the octyloxy oxanilides of such as 4,4'- bis-, 2,2'- diethoxies oxanilide, 2,2'- bis- Octyloxy -5,5'- di-t-butyls oxanilide, 2,2'- bis- (dodecyloxy) -5,5'- di-t-butyls oxanilide, 2- Ethyoxyl -2'- ethyl oxanilides, N, double (3- dimethylaminopropyls) oxamides of N'-, the 2- ethyoxyl -5- tert-butyl groups - 2'- ethyl oxanilides and its mixture with 2- ethyoxyl -2'- ethyl -5,4'- di-t-butyl oxanilides, it is o- and The mixture and o- and p- ethyoxyl two of the p- substitution of methoxyl group two oxanilide replace the mixture of oxanilide.

2.7 2- (2- hydroxy phenyls) -1,3,5-triazines class, such as 2,4,6- tri- (2- hydroxyl -4- octyloxyphenyls) -1, 3,5- triazines, 2- (2- hydroxyl -4- octyloxyphenyls) -4,6- double (2,4- 3,5-dimethylphenyls) -1,3,5- triazines, 2- (2,4- bis- Hydroxy phenyl) double (2,4- the 3,5-dimethylphenyls) -1,3,5- triazines of -4,6-, double (2- hydroxyl -4- the propoxyphenyls) -6- of 2,4- (2, 4- 3,5-dimethylphenyls) -1,3,5- triazines, double (4- the aminomethyl phenyls) -1,3,5- three of 2- (2- hydroxyl -4- octyloxyphenyls) -4,6- Piperazine, 2- (2- hydroxyl -4- dodecyloxies phenyl) -4,6- double (2,4- 3,5-dimethylphenyls) -1,3,5- triazines, 2- (2- hydroxyls -4- Tridecane epoxide phenyl) -4,6- double (2,4- 3,5-dimethylphenyls) -1,3,5- triazines, 2- [2- hydroxyls -4- (2- hydroxyl -3- fourth oxygen Base propoxyl group) phenyl] -4,6- double (2,4- dimethyl) -1,3,5- triazines, 2- [2- hydroxyls -4- (2- hydroxyl -3- the third oxygen of octyloxy Base) phenyl] -4,6- double (2,4- dimethyl) -1,3,5- triazines, 2- [4- (dodecyloxies/tridecane epoxide -2- the third oxygen of hydroxyl Base) -2- hydroxy phenyls] -4,6- double (2,4- 3,5-dimethylphenyls) -1,3,5- triazines, 2- [2- hydroxyls -4- (2- hydroxyls -3- 12 Alkoxypropan epoxide) phenyl] double (2,4- the 3,5-dimethylphenyls) -1,3,5- triazines of -4,6-, 2- (2- hydroxyl -4- hexyloxies) phenyl - 4,6- diphenyl -1,3,5- triazines, 2- (2- hydroxyl -4- methoxyphenyls) -4,6- diphenyl -1,3,5- triazines, 2,4,6- tri- [2- hydroxyls -4- (3- butoxy -2- hydroxy propyloxy groups) phenyl] -1,3,5- triazines, 2- (2- hydroxy phenyls) -4- (4- methoxyl groups Phenyl) -6- phenyl -1,3,5- triazines, 2- { 2- hydroxyls -4- [3- (2- ethylhexyl -1- epoxides) -2- hydroxy propyloxy groups] benzene Base } -4,6- couples of (2,4- 3,5-dimethylphenyls) -1,3,5- triazines, double (4- [2- ethyl hexyl oxies] -2- the hydroxy phenyls) -6- of 2,4- (4- methoxyphenyls) -1,3,5- triazines.

3. metal deactivator, such as N, N'- bis, N- salicylide-N'- salicylyl hydrazines, N, the double (bigcatkin willows of N'- Acyl) hydrazine, N, N'- double (3,5- di-tert-butyl-hydroxy phenyls propionyl) hydrazine, 3- salicyloyl amino -1,2,4- triazoles, double (benzal Base) two hydrazine of oxalyl, oxanilide, m-p-hthaloyl dihydrazide, decanedioyl double phenyl hydrazine, N, N'- diacetyl adipyl dihydrazide, N, The double hydrazines of (salicyloyl) oxalyl two of N'-, N, double (salicyloyl) the thio hydrazines of propionyl two of N'-.

4. phosphite ester and phosphinate, such as triphenyl phosphite, phosphorous acid diphenyl alkyl ester, phenyl two Arrcostab, phosphorous acid three (nonyl phenyl) ester, trilauryl, phosphorous acid three (octadecyl) ester, distearyl season It is penta tetrol diphosphites, phosphorous acid three (2,4- di-tert-butyl-phenyls) ester, diiso decyl pentaerythritol diphosphites, double It is (2,4- di-tert-butyl-phenyls) pentaerythritol diphosphites, double (2,4- dicumylphenyls) pentaerythritol diphosphites, double It is (2,6- di-t-butyl -4- aminomethyl phenyls) pentaerythritol diphosphites, two isodecyl epoxide pentaerythritol diphosphites, double (2,4- di-t-butyl -6- aminomethyl phenyls) pentaerythritol diphosphites, double (2,4,6- tri- (tert-butyl-phenyl) pentaerythrites two Phosphite ester, three stearyl D-sorbite triphosphite esters, the phosphonous acid four (2,4- di-tert-butyl-phenyls) of 4,4'- biphenylenes two The different ring of octyloxy -2,4,8,10- tetra-terts -12H- dibenzo [d, g] -1,3,2- dioxaphosphepins eight of ester, 6-, phosphorous acid are double (2,4- di-t-butyl -6- aminomethyl phenyls) methyl esters, phosphorous acid double (2,4- di-t-butyl -6- aminomethyl phenyls) ethyl ester, 6- fluoro- 2,4, 8,10- tetra-tert -12- the methyldiphenyls simultaneously ring of [d, g] -1,3,2- dioxaphosphepins eight, 2,2', 2 "-nitrilo- [triethyl group three (3,3', 5,5'- tetra-tert -1,1'- biphenyl -2,2'- diyls) phosphite ester], (3,3', 5,5'- tetra-tert -1,1'- join Benzene -2,2'- diyls) phosphorous acid 2- ethylhexyls, 5- butyl -5- ethyls -2- (2,4,6- tri-butyl-phenoxies) -1,3,2- two Oxa- phospha cyclopropane.

5. azanol, such as N, N- dibenzyl hydroxylamines, N, N- diethyl hydroxylamines, N, N- Ndioctylhydroxylamines, N, N- dilauryls Azanol, N, N- bis- (myristyl) azanol, N, N- bis- (cetyl) azanol, N, N- bis- (octadecyl) azanol, N- hexadecanes Base-N- octadecyl hydroxylamines, N- heptadecyl-N- octadecyl hydroxylamines, the N derived from hydrogenated tallow amine, N- dialkyl group Azanol.

6. nitrone, such as N- benzyl-alpha-phenyinitrones, N- ethyl-α-methylnitrones, N- octyl alpha-heptylnitrones, the N- months Gui Ji-α-undecyinitrone, N- myristyls-α-tridecyinitrone, N- cetyls-α-pentadecylnitrone, N- ten Eight alkyl-α-heptadecyl-nitrone, N- hexadecyl-al-phas nitrone, N- octadecyls-α-pentadecylnitrone, N- Heptadecyl-α-heptadecyl-nitrone, N- octadecyls-α-cetyl nitrone, derived from N, N- dialkylhydroxyamines (are derived from Hydrogenated tallow amine) nitrone.

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

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

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

10. Basic co-stabilisers, such as melamine, polyvinylpyrrolidone, dicyandiamide, cyanuric acid alkatriene propyl diester, Urea derivative, hydrazine derivate, amine, polyamide, polyurethane, the alkali metal salt and alkali salt of higher fatty acids, such as it is stearic Sour calcium, zinc stearate, behenic acid magnesium, magnesium stearate, sodium ricinate and potassium palmitate, pyrocatechuic acid antimony or pyrocatechuic acid zinc.

11. nucleator, such as inorganic substances such as talcum, metal oxides such as titanium dioxide or magnesia, preferably alkaline earth are golden Phosphate, carbonate or the sulfate of category；Organic compound such as single-or polycarboxylic acids and its salt, such as 4- p t butylbenzoic acids, oneself Diacid, diphenyl acetic acid, sodium succinate or sodium benzoate；Polymerizable compound such as ionic copolymer (ionomer).Especially preferably 1,3:2,4- double (3', 4'- dimethyl benzylidene) D-sorbite, 1,3:(to the methyldibenzylidene) D-sorbites of 2,4- bis- and 1, 3:2,4- bis- (benzal) D-sorbite.

12. other additives, such as plasticizer, lubricant, emulsifying agent, pigment, rheologic additive, catalyst, flowing are adjusted Save agent, fluorescent whitening agent, fire retardant, antistatic additive and foaming agent.

It is preferred that additive B be：

1) other antioxidants beyond the present invention.

2) processing additives it is for example anti-skidding/anti-caking additive, plasticizer, fluorescent whitening agent, antistatic additive and foaming agent.

3) UV absorbers.

The present invention also provides a kind of polymer composition, includes the polymer that weight content is 30-99.9%, weight content The additive A for polymer prepared for 0-60% filler, weight content for the 0.1-10% present invention.

The present invention also provides a kind of polymer composition, includes the polymer that weight content is 30-99.9%, weight content For 0-60% filler, weight content is 0.1-10% compositions of additives.

The polymer that the present invention can be used is thermosetting and thermoplastic polymer, one kind in following material or one More than kind：

1. the polymer of monoolefine and alkadienes, such as polypropylene, polyisobutene, polybutene, poly- 4- methylpentenes, poly- second The polymerization of the polymer of alkenyl hexamethylene, polyisoprene or polybutadiene and cycloolefin, such as cyclopentene or ENB Thing, such as polyethylene (optionally crosslinkable), high density polyethylene (HDPE) (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) (LDPE), LLDPE (LLDPE).

2. the mixture of the mixture of the polymer referred in 1, such as polypropylene and polyisobutene, polypropylene and poly- second The mixture (such as PP/HDPE, PP/LDPE) of alkene and the mixture (such as LDPE/HDPE) of different type polyethylene.

3. the copolymer between monoolefine and alkadienes or with other vinyl monomers, such as ethylene/propylene copolymer Thing, LLDPE (LLDPE) and its mixture, propylene/but-1-ene copolymerization with low density polyethylene (LDPE) (LDPE) Thing, propylene/isobutylene copolymers, ethene/but-1-ene copolymer, ethylene/hexene copolymer, ethene/methylpentene copolymer, Ethene/heptene copolymer, ethylene/octene, ethylene/vinyl butylcyclohexane copolymer, ethene/cyclic olefine copolymer (example Such as ethene/ENB, such as COC), ethene/1- olefin copolymers (wherein 1- alkene original position is produced)；Propylene/butadiene is common Polymers, isobutene/isoprene copolymer, ethylene/vinyl cyclohexene copolymer, ethylene/alkyl acrylate copolymer, second Alkene/methacrylate copolymer, ethylene/vinyl acetate or ethylene/acrylic acid copolymer and its salt are (from poly- Thing) and ethene and propylene and the terpolymer of diene (such as hexadiene, bicyclopentadiene or ethylidene norbornene)； Mixture between these copolymers and with it is above-mentioned 1) in the mixture of polymer that refers to, such as polypropylene/second Alkene-propylene copolymer, LDPE/ vinyl-vinyl acetate copolymers (EVA), LDPE/ ethylene-acrylic acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA and its mixture with other polymers (such as polyamide).

4. hydrocarbon resin (such as C5-C9), including its hydrogenation modification product (such as tackifier) and polyalkylene and starch Mixture.

1-4 homopolymer and copolymer can have any stereochemical structure, including a rule, isotactic, half isotactic or random；Wherein It is preferred that atactic polymer.Also stereoblock polymer is included.

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

6. the aromatic homopolymers and copolymer of derived from ethylene base aromatic monomer, the monomer include styrene, Alpha-Methyl All isomers of styrene, vinyltoluene, particularly to vinyltoluene, all isomers, the propyl group of ethyl styrene Styrene, vinyl biphenyl, vinyl naphthalene and vinyl anthracene and its mixture.Homopolymer and copolymer can have any three-dimensional knot Structure, including a rule, isotactic, half isotactic or random；Wherein preferred atactic polymer.Also stereoblock polymer is included.

6a. includes above-mentioned vi-ny l aromatic monomers and the copolymer selected from following comonomers：Ethene, propylene, diene, Nitrile, acid, maleic acid anhydride, maleimide, vinyl acetate and vinyl chloride or acrylic and its mixture, example Such as phenylethylene/butadiene, styrene/acrylonitrile, styrene/ethylene (copolymer), styrene/methacrylic acid Arrcostab, benzene Ethene/butadiene/alkyl acrylate, phenylethylene/butadiene/alkyl methacrylate, phenylethylene/maleic anhydride, benzene second Alkene/acrylonitrile/methyl acrylate；Styrol copolymer and other polymers (such as polyacrylate, diene polymer or second Alkene/propylene/diene terpolymer) high-impact mixture；And the block copolymer of styrene such as phenylethylene/butadiene/ Styrene, styrene/isoprene/styrene, styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/benzene second Alkene.

6b. hydrogenating aromatic polymers as derived from the polymer hydrogenation referred in above-mentioned 6, especially including by random polyphenyl Poly- cyclohexyl. vinyl (PCHE), commonly referred to as polyvinyl eyclohexane (PVCH) made from ethylene hydrogenation.

6c. hydrogenating aromatic polymers as derived from the polymer hydrogenation referred in above-mentioned 6a.

7. the graft copolymer of vi-ny l aromatic monomers (such as styrene or α-methylstyrene), such as styrene-grafted Polybutadiene, styrene-grafted Polybutadiene-styrene or polybutadiene-acrylonitrile copolymer；Styrene and acrylonitrile (or Methacrylonitrile) grafting polybutadiene；The polybutadiene of styrene, acrylonitrile and methyl methacrylate-grafted；Styrene The polybutadiene being grafted with maleic anhydride；Styrene, acrylonitrile and maleic anhydride or the polybutadiene of maleimide grafting；Benzene Ethene and the polybutadiene of maleimide grafting；It is poly- that styrene and alkyl acrylate or alkyl methacrylate are grafted Butadiene；The ethylene/propylene/diene terpolymers of styrene and acrylonitrile grafting；Poly- the third of styrene and acrylonitrile grafting Olefin(e) acid Arrcostab or polyalkyl methacrylate；The acrylate/butadiene copolymers of styrene and acrylonitrile grafting and its With 6) in listed copolymer mixture, such as referred to as mixture of the copolymer of ABS, MBS, ASA or AES polymer.

8. halogen-containing polymer, such as polychlorobutadiene, chlorinated rubber, the chlorination of isobutylene-isoprene or bromination Copolymer (halogen butyl rubber), chlorination or chlorosulfonated polyethylene, the copolymer of ethene and ethlyene dichloride, epichlorohydrin homopolymers and copolymerization Thing, it is the polymer of especially halogen-containing vinyl compound, such as polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, poly- inclined Difluoroethylene；And its copolymer such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate Ester copolymer.

9. the polymer of derived from alpha, beta-unsaturated acid and its derivative, such as polyacrylate and polymethylacrylic acid Ester；Polymethyl methacrylate, polyacrylamide and polyacrylonitrile, it carries out impact modification with butyl acrylate.

10. the copolymer between the monomer mentioned in 9 or the copolymer with other unsaturated monomers, such as third Alkene nitrile/butadiene copolymer, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or propylene Nitrile/vinyl halide copolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymer.

11. the polymer derived from unsaturated alcohol and amine or its acyl derivative or acetal, such as polyvinyl alcohol, poly- acetic acid Vinyl acetate, polyvinyl stearate, polyvinyl benzoate, poly vinyl acetate, polyvinyl butyral resin, poly- O-phthalic Sour allyl ester or polyallyl melamine；And its copolymer with the alkene mentioned in above-mentioned 1.

12. the homopolymer and copolymer of cyclic ethers, such as PAG, polyethylene glycol oxide, PPOX or its with The copolymer of diglycidyl ether.

13. polyacetals such as polyformaldehyde and contain ethylene oxide as polyformaldehyde comonomer；Use thermoplastic poly ammonia The polyacetals that ester, acrylate or MBS are modified.

14. polyphenylene oxide and polyphenylene sulfide and polyphenylene oxide and styrene polymer or the mixture of polyamide.

15. polyurethane, its one side is derived from hydroxy-end capped polyethers, polyester or polybutadiene, on the other hand it is derived from Aliphatic series or aromatic polyisocyanate and its precursor.

16. polyamide and copolyamide, it is derived from diamines and dicarboxylic acids and/or derived from amino carboxylic acid or corresponding interior acyl Amine, such as polyamide 4, polyamide 6, polyamide 6/6,6/10,6/9,6/12,4/6,12/12, polyamide 11, polyamide 12, by The aromatic polyamides that m-xylene diamine and adipic acid are obtained；It is sub- by six under presence or absence of the elastomer as modifying agent The polyamide that methanediamine is prepared with M-phthalic acid and/or terephthalic acid (TPA), such as poly- 2,4,4- tri-methyl hexamethylene pair Benzenedicarboxamide or poly- metaphenylene isophtalamide；And above-mentioned polyamide and polyolefin, olefin copolymer, ionomer or The block copolymer of chemical bonding or the elastomer of grafting；Or and polyethers, such as with polyethylene glycol, polypropylene glycol or poly- four methylene The block copolymer of base glycol；And the polyamide or copolyamide being modified with EPDM or ABS；And be condensed in process Polyamide (RIM polyamide systems).

17. polyester, it is derived from dicarboxylic acids and glycol and/or derived from hydroxycarboxylic acid or corresponding lactone or lactide, example Such as polyethylene terephthalate, polybutylene terephthalate (PBT), poly- 1,4- hydroxymethyl-cyclohexanes terephthalic acid (TPA) Ester, poly- alkylene naphthalate and poly- hydroxybenzoate and the copolyether ester derived from hydroxyl terminated polyether；And use The polyester that makrolon or MBS are modified.Copolyesters may include, such as (but not limited to)：Polybutylene succinate/terephthaldehyde Sour butanediol ester, poly adipate succinic acid ester/mutual-phenenyl two acid bromide two alcohol ester, polyadipate tetramethylene ester/terephthalic acid (TPA) Tetramethylene ester, polybutylene succinate/tetramethylene adipate, polybutylene succinate/carbonic ester, poly- 3- hydroxyls Butyrate/3- Hydroxyoctanoic acids ester copolymer, poly- 3-hydroxybutyrate ester/3- hydroxycaproic esters/3- hydroxydecanoic acid ester ternary polymerizations Thing.In addition, aliphatic polyester may include, such as (but not limited to)：Poly- (hydroxy alkane acid ester) class, in particular poly- propiolactone, poly- fourth Lactone, poly- pivalolactone, poly- valerolactone and polycaprolactone, polydiethylene glycol succinate, poly- amber acid propylene glycol ester, poly- butanedioic acid Butanediol ester, poly- butanedioic acid hexa-methylene ester, polyethylene glycol adipate, polypropylene glycol adipate, polybutyleneadipate Ester, polyadipate hexa-methylene ester, poly- oxalic acid glycol ester, poly- oxalic acid propylene glycol ester, poly- oxalic acid butanediol ester, poly- oxalic acid six are sub- Methyl ester, polyethylene glycol sebacate, poly- decanedioic acid propylene glycol ester, polydiethylene glycol sebacate and PLA (PLA) and use The corresponding polyester that makrolon or MBS are modified.Term " PLA (PLA) " represent be preferably PLLA homopolymer and Its any blend or alloy with other polymers；The copolymer of lactic acid or lactide and other monomers, the other monomers For example hydroxycarboxylic acid for example glycolic, 3-hydroxybutyrate, 4 hydroxybutyric acid, 4- hydroxypentanoic acids, 5- hydroxypentanoic acids, 6 hydroxycaproic acid and Its annular form；Term " lactic acid " or " lactide " include Pfansteihl, D-ALPHA-Hydroxypropionic acid, its mixture and dimer, i.e. L- lactides, D- lactides, Study of Meso-Lactide and its any mixture.

18. makrolon and polyestercarbonate.

19. polyketone.

20. polysulfones, polyether sulfone and polyether-ketone.

21. cross-linked polymer, its one side is derived from aldehyde, on the other hand derived from phenols, ureas and melamine class, example Such as phenol/formaldehyde resins, urea/formaldehyde resin and melamine/formaldehyde resin.

22. dryness and Non-dry alkyd resin.

23. unsaturated polyester resin, it derives self-saturation and unsaturated dicarboxylic and polyalcohol and is used as crosslinking agent The copolyesters of vinyl compound, and its low combustible halogen modified product.

24. cross-linking acrylic resin, its acrylate derived from substitution, such as acrylic acid epoxy ester, amino first Acid esters acrylate or polyester acrylate.

25. handed over melmac, urea resin, isocyanates, isocyanuric acid ester, polyisocyanates or epoxy resin Alkyd resin, polyester resin and the acrylate of connection.

26. cross-linked epoxy resin, it is derived from aliphatic, alicyclic, heterocyclic or aromatic glycidyl compounds, for example The product of bisphenol-A and the diglycidyl ether of Bisphenol F, it uses conventional hardeners such as acid anhydrides under presence or absence of accelerator Or amine crosslinking.

27. the blend (blend polymer) of above-mentioned polymer, 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/ heat Plasticity PUR, PC/ thermoplasticity 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 synthesis organic material, it is pure monomer compound or the mixture of these compounds, such as mineral Oil, animal and plant fat, oil and wax or based on synthetic ester (such as phthalic acid ester, adipate ester, phosphate or inclined benzene Three acid esters) oil, fat and wax and synthetic ester and mineral oil any weight ratio mixture, typically as spinning The water-based emulsion of those and these materials of composition.

It is preferred that organic material be：

1) olefinic monomer such as ethene and propylene and higher level 1- alkene such as 1- butylene, 1- amylenes, 1- hexenes or 1- octenes Homopolymer and copolymer.It is preferred that polyethylene LDPE and LLDPE, HDPE and polypropylene.

2) olefinic monomer and diolefinic monomer such as the homopolymer of butadiene, isoprene and cycloolefin such as ENB and it is total to Polymers.

3) one or more 1- alkene and/or alkadienes with carbon monoxide and/or with other vinyl monomers, including but not It is limited to the copolymer of vinyl acetate, vinyl ketone, styrene, maleic anhydride and vinyl chloride.

4) polyvinyl alcohol.

5) other thermoplastics such as polystyrene, SAN, acrylonitrile-butadiene-styrene (ABS) is common It is polymers, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyvinyl alcohol butyraldehyde, ethylene-vinyl alcohol copolymer, poly- to benzene Naphthalate (PET), polybutylene terephthalate (PBT) (PBT), liquid crystal polyester (LCP), polyacetals (such as POM), Polyamide (PA), makrolon, polyurethane and polyphenylene sulfide (PPS)；The polymer of two or more these resins formation is total to Mixed thing or polymer alloy；And by adding filler such as glass fibre, carbon fiber, partial carbonization fiber, cellulose fiber peacekeeping glass Glass pearl, fire retardant, foaming agent, antimicrobial, crosslinking agent, vistanex fine powder, polyolefin-wax, ethylene bisamides wax, The compound that metallic soap etc. is obtained to these resins alone or in combination.On the other hand, the example of thermosetting resin may include thermosetting Property resin such as epoxy resin, melamine resin and unsaturated polyester resin；And by mix filler for example glass fibre, carbon fiber, The compound that partial carbonization fiber, cellulose fiber peacekeeping bead, fire retardant etc. are obtained to these resins alone or in combination.

Other preferred polymer are：The biodegradable polymers in natural or synthetic source, including but not limited to poly- amber Amber acid glycol ester, polybutylene succinate, polybutylene succinate/tetramethylene adipate, poly- butanedioic acid butanediol Ester/carbonic acid butanediol ester, polybutylene succinate/mutual-phenenyl two acid bromide two alcohol ester, polycaprolactone, poly- (hydroxyl alkane acid Ester), poly- 3-hydroxybutyrate ester, PLA, polyesteramide or these materials and natural or modified starch, polysaccharide, lignin, wood powder, The blend of cellulose or chitin.

The polymer is preferably the natural or synthetic polymer of thermoplasticity, especially one kind in above-mentioned group.It is preferred that Polyolefin homopolymer or copolymer, starch conversion polyolefin or starch-based polymer composite, particularly preferred polyethylene, poly- third Alkene, polyethylene and ethylene copolymers or polypropylene copolymer.

The filler includes：Such as calcium carbonate, silica, glass fibre, glass envelope, talcum, kaolin, mica, sulphur Sour barium, metal oxide and hydroxide, carbon black, graphite, wood powder, the powder of other natural products, synthetic fibers, as filler Stearate such as calcium stearate or zinc stearate.

The polymer molding compositions of the present invention are applied to production fiber, coating, film or moulded work.

The present invention also provides a kind of method for preparing polymer composition, including by the present invention for polymer The compositions of additives of additive A and/or the present invention are mixed with polymeric aggregate and dispensable filler in mixer, and They are homogenized in polymer melt in extruder device at relatively high temperature, and is subsequently indexed out the homogenized polymerization Thing extrudate, cooling, pelletizing.Extruder device is selected from single screw extrusion machine, or double screw extruder.It is preferred that processing temperature pair It is 170 to 200 DEG C in polystyrene, is 200 to 300 DEG C for polypropylene, is for polyethylene terephthalate (PET) 250 to 290 DEG C, be 230 to 270 DEG C for polybutylene terephthalate (PBT) (PBT), for polyamide -6 (PA6) be 260 to 290 DEG C, be 260 to 290 DEG C for polyamide -66 (PA66), and is 280 to 320 DEG C for makrolon.Available for the present invention Compounding combination unit be single screw extrusion machine, or double screw extruder, effective spiro rod length for the present invention is in single screw rod It is 20 to 4OD in the case of extruder；Effective spiro rod length in the present invention is 8 to 48D in the case of double screw extruder.

Embodiment

The present invention is further illustrated below by embodiment, following examples are the present invention preferably embodiment party Formula, but embodiments of the present invention are not limited by following embodiments.

Embodiment 1：

By 3,5- di-t-butyl -4- hydroxy phenylpropionic acids methyl esters (416g, it is excessive 15%), pentaerythrite (42g) and hydroxide Aluminium (0.73g) is fed in 10OOml four-neck flask, and the flask equipped has agitator, thermometer, pump intake and installation Still head on to condenser, the condenser is connected on the liquid-liquid exchanger equipped with water and hexamethylene again.Pump is used for hexamethylene It is recycled back to the speed of about 0.4 gram of hexamethylene/gram 3,5- di-t-butyl -4- hydroxy phenylpropionic acids methyl esters/hour from exchanger instead Answer in device, so that hexamethylene+by-product carbinol is continuously distilled (the latter is extracted into water by exchanger).Will reaction Material is heated to 175 DEG C, distills hexamethylene and methanol.Two batches sodium iso-octoate (0.32g) catalyst adds behind 5 hours and 12 hours Enter.

Purification step is diluted using hexamethylene, washing, and separate aqueous layer is dried, and is crystallized in hexamethylene, is prepared four (β-(3,5- di-tert-butyl-hydroxy phenyl) propanoyloxymethyl) methane, as shown in formula I, the angle of repose for measuring product is 40 °, fusion enthalpy is 69J/g.

Embodiment 2：

Embodiment 1 is repeated, excessive 3,5- di-t-butyl -4- hydroxy phenylpropionic acids methyl esters (390g, excess except reducing 8%) a collection of sodium iso-octoate (0.64g) is added, and only after 5h.The angle of repose for measuring product is 45 °, and fusion enthalpy is 70J/g。

Embodiment 3：

Embodiment 1 is repeated, excessive 3,5- di-t-butyl -4- hydroxy phenylpropionic acids methyl esters (390g, excess except reducing 8%) a collection of sodium iso-octoate (0.64g) is added, and only after 12h.The angle of repose for measuring product is 43 °, and fusion enthalpy is 75J/g。

Comparative example 1：

Selection Dibutyltin oxide is catalyst, by catalyst and reaction raw materials 3,5- di-t-butyl -4- hydroxy phenylpropionic acids Methyl esters and pentaerythrite are added in reactor, wherein 3,5- di-t-butyl -4- hydroxy phenylpropionic acids methyl esters 380g, pentaerythrite 42g, Both mol ratios are about 4.2, and catalyst amount is 0.3g, and regulation reactor pressure is 650Pa, are reacted at 175 DEG C after 7h It is warming up to 200 DEG C to continue to react 1h, is cooled to 145 DEG C, carries out the neutralization reaction of half an hour.Obtained product selection methanol is knot Brilliant solvent, crystallisation by cooling suction filtration is that can obtain target product, and the angle of repose for measuring product is 52 °, and fusion enthalpy is 92J/g.

Comparative example 2：

Reaction raw materials 3 are put into reactor, 5- di-t-butyl -4- hydroxy phenylpropionic acids methyl esters 410g, pentaerythrite 44g have Machine tin catalyst 2g, magnesium silicate 1.6g, give kettle inflated with nitrogen, after 0.5 hour, heating, after material fine melt, open stirring, control 160 DEG C -180 DEG C of reaction temperature, nitrogen flow rate is kept in course of reaction, and generation methanol is taken out of, into condenser, condensed back Receive, after reaction 10 hours, stop reaction.Obtained product selection methanol is recrystallisation solvent, and crystallisation by cooling suction filtration is that can obtain Target product, the angle of repose for measuring product is 53 °, and fusion enthalpy is 99J/g.

Embodiment 4-8, comparative example 3-5

By the product obtained by embodiment 1-3, comparative example 1-2 in the product component weight content percentage as described in Tables 1 and 2 Weigh.

Polypropylene：Basel, EP548R

Polystyrene：Yangtze BASF, 158K

UV absorbers：Qingdao Hua En Chemical Co., Ltd.s, UV327

Glass fibre：PPG, Chop Vantage 3540

Talcum powder：Luzenac R7

When polymer is selected from polypropylene, it is about 1000rpm's that above-mentioned polypropylene and other each components are first put into rotating speed Dry-mixing 1 minute in super mixer, if any talcum powder, then adds talcum powder and remixes 3 minutes.The raw material of mixing is put Through melting extrusion in double screw extruder, granulate, its process conditions is：One 200 DEG C of area, two 210 DEG C of areas, three 220 DEG C of areas, four 215 DEG C of area；Double screw extruder draw ratio is 35, and screw speed is 450 revs/min, and the residence time is 1 minute, and pressure is 10Mpa。

When polymer is selected from polystyrene, above-mentioned polypropylene and other each components are first put into rotating speed about 1000rpm Super mixer in dry-mixing 3 minutes, the raw material of mixing is placed in double screw extruder through melting extrusion, granulation, its work Skill condition is：Each zone temperature of barrel is maintained at 200 DEG C, and double screw extruder draw ratio is 35, and screw speed is 450 revs/min Clock；Residence time is 1 minute, and pressure is 10Mpa.

Table 1 (percent by weight)

Table 2 (percent by weight)

Sliding capability

The resin combination obtained in embodiment prepares long 10 centimetres, wide 4 centimetres, thick 1 millimeter injection-molded item (examination Bar), and it is stood 48 hours hereafter at 23 DEG C in over dry air, having that the S45C steel for carrying 500 grammes per square metre things is made The metal needle of 3 mm dia cones is placed on length in the strip and mobile 5 centimetres.The depth surface roughness of the ditch of gained Instrument is determined.Groove is more shallow, and sliding capability is better." good " refers to that gash depth is less than 10 microns, " medium " expression at least 10 Micron and less than 20 microns, " poor " refers at least 20 microns.

Claims

1. a kind of additive A for polymer, by structural formula shown in formula I compound group into：

Characterized in that, the angle of repose of the additive A is 40 ° -45 °, the angle of repose is tested according to GB11986-89.

2. a kind of additive A for polymer as claimed in claim 1, it is characterised in that additive A has at least 55J/ G fusion enthalpy, wherein the fusion enthalpy is determined according to ISO11357-1/2, and wherein differential scanning calorimetry (DSC) with The rate of heat addition of 20K/ minutes is carried out.

3. a kind of additive A for polymer as claimed in claim 1, it is characterised in that additive A has 60-80J/g Fusion enthalpy, wherein the fusion enthalpy is determined according to ISO11357-1/2, and wherein differential scanning calorimetry (DSC) is with 20K/ The rate of heat addition of minute is carried out.

4. a kind of additive A for polymer as claimed in claim 1, it is characterised in that additive A has 70-75J/g Fusion enthalpy, wherein the fusion enthalpy is determined according to ISO11357-1/2, and wherein differential scanning calorimetry (DSC) is with 20K/ The rate of heat addition of minute is carried out.

5. a kind of additive A for polymer as claimed in claim 1, it is characterised in that the heap density of additive A is 0.30g/cm³~0.60g/cm³。

6. a kind of additive A for polymer as claimed in claim 1, it is characterised in that the heap density of additive A is 0.40g/cm³~0.50g/cm³。

7. a kind of compositions of additives, it is characterised in that include a kind of adding for polymer as claimed in claim 1 or 2 Plus agent A and at least one other additive Bs different from additive A.

8. compositions of additives as claimed in claim 7, it is characterised in that include the additive A of 50 to 99.9% weight, and At least one other additive Bs different from additive A of 0.1 to 50% weight.

9. a kind of compositions of additives, it is characterised in that include a kind of additive as claimed in claim 3 for polymer A and at least one other additive Bs different from additive A.

10. compositions of additives as claimed in claim 9, it is characterised in that include the additive A of 50-99.9% weight, and At least one other additive Bs different from additive A of 0.1 to 50% weight.

11. a kind of compositions of additives, it is characterised in that include a kind of addition as claimed in claim 4 for polymer Agent A and at least one other additive Bs different from additive A.

12. compositions of additives as claimed in claim 11, it is characterised in that include the additive A of 50-99.9% weight, With at least one other additive Bs different from additive A of 0.1 to 50% weight.

13. a kind of compositions of additives, it is characterised in that include a kind of addition as claimed in claim 6 for polymer Agent A and at least one other additive Bs different from additive A.

14. compositions of additives as claimed in claim 13, it is characterised in that include the additive A of 50-99.9% weight, With at least one other additive Bs different from additive A of 0.1 to 50% weight.

15. a kind of polymer composition, it is characterised in that be used for the additive of polymer comprising as claimed in claim 1 or 2 A。

16. a kind of polymer composition, it is characterised in that be used for the additive A of polymer comprising as claimed in claim 3.

17. a kind of polymer composition, it is characterised in that be used for the additive A of polymer comprising as claimed in claim 4.

18. a kind of polymer composition, it is characterised in that be used for the additive A of polymer comprising as claimed in claim 6.

19. polymer composition as claimed in claim 15, it is characterised in that comprising weight content be 30-99.9% Polymer, weight content be 0-60% filler, weight content be 0.1-10% additive A.

20. a kind of polymer composition as required by claim 15, it is characterised in that the polymer is polypropylene, gathered One or more compositions in ethene, ABS, polystyrene, polyamide, polyvinyl chloride, polyester, polyformaldehyde.