WO2017140167A1

WO2017140167A1 - Additive for polymer, preparation thereof, and polymer composition comprising the same

Info

Publication number: WO2017140167A1
Application number: PCT/CN2016/111232
Authority: WO
Inventors: 黄秀茹
Original assignee: 黄秀茹
Priority date: 2016-02-17
Filing date: 2016-12-21
Publication date: 2017-08-24
Also published as: CN105504349A

Abstract

An additive A for a polymer as shown in formula X comprises a compound as shown in formula X. The additive A further comprises titanium. The polymer added with the additive A for the polymer can have a sufficiently reduced production of the particles of the polymer.

Description

Additive for polymer and preparation method thereof, and polymer composition composed thereof

Technical field

The present invention relates to an additive, and more particularly to an additive for a thermoplastic polymer, a process for the preparation thereof, and a polymer composition composed of the same.

Background technique

Tetrakis(β-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoyloxymethyl)methane as described above is an important commercial additive for thermoplastic polymers. For example, it protects organic materials, especially thermoplastic polymers, from degradation by heat, oxidation and/or actinic. Generally, the addition reaction of 2,6-di-tert-butylphenol and methyl acrylate is carried out to form methyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and then It is obtained by transesterification with pentaerythritol.

The tetrakis(β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxymethyl)methane described in the above formula is used as an additive in polymers such as polypropylene and polystyrene, usually These resin molded articles generally require the addition of a reinforcing filler to improve mechanical strength, but there is a problem in that when electrical and electronic parts and optical parts are manufactured from a resin molded article containing such a reinforcing filler added thereto, Foreign particulate matter (particles) may be formed on the surface of the part. The generation of such particles can result in a decrease in the yield of parts in the assembly step and a failure in the use of the product.

The present inventors have discovered through a great deal of research that when a specific content is added to the tetrakis (β-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoyloxymethyl)methane described in the above formula. When the titanium-containing substance is used, the amount of particles generated by the corresponding polymer can be sufficiently lowered.

Summary of the invention

It is an object of the present invention to provide an additive A for a polymer which is passed in tetrakis(β-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoyloxymethyl)methane. The addition of a trace amount of titanium-containing material can significantly reduce the amount of particles produced by the polymer. The invention is achieved by the following technical solutions:

An additive A for a polymer consisting of a compound of the formula:

Formula X, which may have the chemical name: tetrakis(β-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoyloxymethyl)methane. Among them, the titanium element has a weight content of from 2 ppm to 455 ppm, preferably from 11 ppm to 202 ppm, more preferably from 11 ppm to 76 ppm, based on the total weight of the additive A.

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

The term "titanium-containing substance" is not particularly limited as long as it contains a titanium element, but is preferably a powder of titanium dioxide. Titanium dioxide can be amorphous or crystalline. Examples of the crystal form of titanium dioxide include an anatase type, a rutile type, and a brookite type. More preferably, it is anatase or rutile type titanium dioxide.

As the titanium-containing substance, other titanium-containing compounds or monomers may also be used. Examples of the compound include a titanium salt, a titanium alkoxide, titanium hydroxide, titanium nitride, and titanium sulfide.

Specific examples of the titanium salt include titanium trichloride, titanium tetrachloride, titanium sulfide, and titanium sulfate. Specific examples of the titanium alkoxide include titanium ethoxide, titanium methoxide, titanium t-butoxide, titanium isobutoxide, titanium n-propoxide, titanium tetraisopropoxide, and a chelate thereof.

The particle diameter of the titanium dioxide is preferably in a range of 0.1 to 20 μm, and more preferably in a range of 0.1 to 10 μm, in which the particle diameter (D50) corresponding to a volume-based cumulative percentage of 50% is measured by a laser diffraction method, and further, It is preferably in the range of 0.1 to 1 μm. Further, the particle diameter (D90) of the titanium oxide obtained by the laser diffraction method and corresponding to a volume-based cumulative percentage of 90% is preferably 0.1 to 20 μm, more preferably 0.1 to 10 μm, still more preferably 0.2 to 1.5 μm.

The invention also provides an additive composition comprising a compound of the formula:

And at least one other additive B different from the compound of formula X, wherein the titanium element has a weight content of from 2 ppm to 455 ppm, preferably from 11 ppm to 202 ppm, more preferably from 11 ppm to 76 ppm, based on the total weight of the additive composition; The total weight of the substance preferably comprises from 50 to 99.9% by weight of a compound of formula X, and from 0.1 to 50% by weight The amount of at least one other additive B different from the compound of the formula X, wherein the titanium element has a weight content of from 2 ppm to 455 ppm, preferably from 11 ppm to 202 ppm, more preferably from 11 ppm to 76 ppm, based on the total weight of the additive composition.

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

1. Antioxidants, including the following types:

1.1 alkylated monophenols, such as 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethyl Phenolic, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(α-methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2 , 6-di-tert-butyl-4-methoxymethylphenol, a linear or branched nonylphenol such as 2,6-dimercapto-4-methylphenol, 2,4-dimethyl -6-(1'-methylundecane-1'-yl)phenol, 2,4-dimethyl-6-(1'-methylheptadecan-1'-yl)phenol, 2,4 -Dimethyl-6-(1'-methyltridecane-1'-yl)phenol and mixtures thereof.

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

1.3 hydroquinones and alkylated hydroquinones, such as 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2 ,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4 -hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

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

1.5 hydroxylated thiodiphenyl ether, such as 2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'-thiobis(4-octylphenol), 4, 4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-2-methylphenol), 4,4'-thiobis (3,6-di-sec-amylphenol), 4,4'-bis(2,6-dimethyl-4-hydroxyphenyl)disulfide.

1.6 alkylene bisphenols, such as 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'-methylenebis(6-tert-butyl-4-ethyl Phenol), 2,2'-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol], 2,2'-methylenebis(4-methyl-6-ring Hexylphenol), 2,2'-methylenebis(6-fluorenyl-4-methylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2 '-Ethylene bis(4,6-di-tert-butylphenol), 2,2'-ethylenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylene Bis[6-(α-methylbenzyl)-4-nonylphenol], 2,2'-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol] , 4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'-methylenebis(6-tert-butyl-2-methylphenol), 1,1-double (5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol 1,1,3-Tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methylbenzene 3-n-dodecyldecylbutane, ethylene glycol bis[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)butyrate], Bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene, bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl) -6-tert-butyl-4-methylphenyl]p-benzene Dicarboxylate, 1,1-bis(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane , 2,2-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecyldecylbutane, 1,1,5,5-tetrakis (5-tert-butyl) 4--4-hydroxy-2-methylphenyl)pentane.

1.7O-, N- and S-benzyl compounds, for example 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, 4-hydroxy-3,5-di Octadecylmethylbenzyl mercaptoacetate, tridecyl 4-hydroxy-3,5-di-tert-butylbenzyl decylacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl Amine, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl) Sulfide, isooctyl 3,5-di-tert-butyl-4-hydroxybenzyl mercaptoacetate.

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

1.9 Triazine compounds, such as 2,4-bis(octylfluorenyl)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylfluorenyl -4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octyldecyl-4,6-bis (3,5-di-tert Butyl-4-hydroxyphenoxy)-1,3,5-triazine, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3 Triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxyl -2,6-dimethylbenzyl)isocyanurate, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-three Pyrazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine, 1,3,5-tris (3, 5-Dicyclohexyl-4-hydroxybenzyl)isocyanurate.

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

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

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

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

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

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

An amide of 1.16β-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoic acid, such as N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropanoyl)hexa Methylenediamine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamine, N,N'-bis(3,5-di-tert-butyl) 4-Hydroxyphenylpropionyl)ruthenium, N,N'-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propanoyloxy)ethyl]oxamide .

2. UV absorber

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

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

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

2.4 Nickel compounds, such as nickel complexes of 2,2'-thiobis[4-(1,1,3,3-tetramethylbutyl)phenol, such as 1:1 or 1:2 complexes, Single with or without other ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid Alkyl esters such as nickel salts of methyl or ethyl esters, nickel complexes of ketone oximes such as 2-hydroxy-4-methylphenylundecyl oxime, 1-phenyl-4-lauroyl-5-hydroxyl a nickel complex of pyrazole, It has or does not have other ligands.

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

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

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

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

4. Phosphites and phosphonites such as triphenyl phosphite, diphenylalkyl phosphite, phenyl dialkyl phosphite, tris(nonylphenyl) phosphite, phosphorous acid tris Lauryl ester, tris(octadecyl)phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite Ester, double (2,4- Di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol Diphosphite, diisodecyloxypentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tri ( Tert-butylphenyl)pentaerythritol diphosphite, tristearyl sorbitol triphosphite, 4,4'-biphenylene diphosphinate tetrakis(2,4-di-tert-butylphenyl) ester , 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo[d,g]-1,3,2-dioxaphosphorane, bisphosphite 2,4-di-tert-butyl-6-methylphenyl)methyl ester, bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite, 6-fluoro-2,4, 8,10-Tetra-tert-butyl-12-methyldibenzo[d,g]-1,3,2-dioxaphosphorane, 2,2',2"-nitrilo[三乙Tris(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite], (3,3',5,5'- Tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl)phosphoric acid 2-ethylhexyl, 5-butyl-5-ethyl-2-(2 4,6-tri-t-butylphenoxy) 1,3,2-phospholene oxide.

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

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

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

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

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

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

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

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

Preferred additive B is:

1) Other antioxidants other than the present invention.

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

3) Ultraviolet light absorber.

The invention also provides a polymer composition comprising a polymer in an amount of from 30 to 99.9% by weight, a filler in an amount of from 0 to 60% by weight, and a polymer content of from 0.1 to 10% by weight of the invention. Additive A.

The present invention also provides a polymer composition comprising a polymer in an amount of from 30 to 99.9% by weight, a filler in an amount of from 0 to 60% by weight, and an additive composition in an amount of from 0.1 to 10% by weight.

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

1. Polymers of monoolefins and diolefins, such as polypropylene, polyisobutylene, polybutene, poly-4-methylpentene, polyvinylcyclohexane, polyisoprene or polybutadiene, and rings Polymers of olefins, such as polymers of cyclopentene or norbornene, polyethylene (optionally crosslinked), such as high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high Density and ultra high molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE).

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

18. Polycarbonates and polyester carbonates.

19. Polyketone.

20. Polysulfone, polyethersulfone and polyetherketone.

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

22. Dry and non-dry alkyd resins.

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

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

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

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

27. Blends (polymer blends) of the above polymers, such as PP/EPDM, polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC /ASA, PC/PBT, PVC/CPE, PVC/Acrylate, POM/Thermoplastic PUR, PC/Thermoplastic PUR, POM/Acrylate, POM/MBS, PPO/HIPS, PPO/PA66 and Copolymer, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.

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

Preferred organic materials are:

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

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

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

4) Polyvinyl alcohol.

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

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

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

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

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

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

detailed description

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

Example 1:

The dibutyltin oxide is selected as a catalyst, and the catalyst and the reaction raw material methyl 3,5-di-tert-butyl-4-hydroxyphenylpropionate (commercially available) and pentaerythritol (commercially available) are added to the reaction vessel, wherein 3, 5 - 380 g of di-tert-butyl-4-hydroxyphenylpropionate and 42 g of pentaerythritol, the molar ratio of the two is about 4.2, the amount of the catalyst is 0.3 g, the pressure of the reaction vessel is adjusted to 650 Pa, and the temperature is raised after the reaction at 175 ° C for 7 hours. The reaction was continued at 200 ° C for 1 h, and the temperature was lowered to 145 ° C for a half hour neutralization reaction. The obtained product is selected from methanol as a crystallization solvent, and the target product is obtained by cooling and crystallization filtration.

Example 2-7, Comparative Example 1-2

The compound prepared in Example 1 was separately compounded with titanium dioxide, tetrabutyl titanate, and titanium dichlorotitanate. By adjusting the weight of the product of Example 1 in the polymer additive A, a polymer additive A having a specific titanium element content was obtained. The specific content is shown in Table 1. The specific compounding method is as follows: firstly, the compound prepared in Example 1 and the titanium-containing substance are compounded into a mother sample having a higher titanium element content according to the ratio of Table 1, and the weight content of the titanium element is measured, and then according to the final result. The content of the desired titanium element was calculated by weighting the product of the second addition of Example 1, and finally the polymer additive A was obtained, and then the weight content of the titanium element was measured again. The weight content of the titanium element is determined by the following method: accurately weighing the polymer additive A 2g in an analytical balance, pouring into a 100 ml digestion bottle, and then adding 97% concentrated sulfuric acid 5 ml, at a preset temperature of 300 ° C iron plate Heating in a heating apparatus for 10 minutes, then adding 68% nitric acid 5m1, and then heating for 20 minutes, the particles are completely decomposed, cooled to room temperature, added to 20ml of hydrogen peroxide and acidified to pH 7, and diluted with deionized water. For the above liquid, the liquid is introduced into the ICP detector through a sample introduction tube to measure the concentration of the titanium element.

Nano titanium dioxide: T104943, Shanghai Aladdin Biochemical Technology Co., Ltd.

Tetrabutyl titanate: Shanghai Aladdin Biochemical Technology Co., Ltd.

Dichlorotitanium dichloride: Shanghai Aladdin Biochemical Technology Co., Ltd.

Table 1

The compound prepared in Example 1 was separately compounded with titanium dioxide, tetrabutyl titanate and titanium dichlorotitanate according to the above method, and the specific content is shown in Table 2:

Table 2

Examples 8-13, Comparative Examples 3-4

The polymer additives obtained in Examples 2-7 and Comparative Examples 1-2 were weighed in the percentage by weight of the product components described in Tables 3 and 4.

Polypropylene: Basel, EP548R

Polystyrene: Yangtze BASF, 158K

Ultraviolet light absorber: Shandong Qingdao Huaen Chemical Co., Ltd., UV327

Fiberglass: PPG, Chop Vantage 3540

Talc powder: Luzenac R7

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

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

Table 3 (percent weight)

Table 4 (percent weight)

Method for particle number measurement:

The amount of particles is represented by the number of particles (count) corresponding to the diameter (μm) of each particle.

Using the polymer compositions obtained in Examples 8-13 and Comparative Examples 3-4, a flat test piece of 64 mm (length) × 64 mm (width) × 1 mm (thickness) was prepared by injection molding, and the test piece was suspended in inclusion. 500 mL of ultrapure water in a 500 mL beaker (so that the gate portion of the test piece is not in contact with ultrapure water); the test piece suspended in the beaker was cleaned by ultrasonic (36 Hz) irradiation for 60 seconds, and a beaker was used. Aqueous solution in water as test water; 1iquid-borne particle counting system manufactured by RION Co., Ltd. (including syringe sampler KZ-30W1 (for collecting particle dispersion), particle sensor KS-65 and control KL-11A)), the number of particles having a size of 2 μm to 100 μm dispersed in 10 mL of the wash solution was measured. The particle measurement process was further carried out by taking four washes to obtain a total of five data on the number of particles, and the arithmetic mean of the five data was used as the number of particles.

Claims

An additive A for a polymer comprising a compound of the formula:

Among them, the titanium element has a weight content of from 2 ppm to 455 ppm, preferably from 11 ppm to 202 ppm, more preferably from 11 ppm to 76 ppm, based on the total weight of the additive A.
An additive composition comprising a compound of the formula:

And at least one other additive B different from the compound of formula X, wherein the titanium element has a weight content of from 2 ppm to 455 ppm, preferably from 11 ppm to 202 ppm, more preferably from 11 ppm to 76 ppm, based on the total weight of the additive composition; The total weight of the substance preferably comprises from 50 to 99.9% by weight of a compound of the formula X, and from 0.1 to 50% by weight of at least one other additive B different from the compound of the formula X, wherein the additive combination The total weight of the material, the weight content of the titanium element is from 2 ppm to 455 ppm, preferably from 11 ppm to 202 ppm, more preferably from 11 ppm to 76 ppm.
A polymer composition comprising the additive A for a polymer as claimed in claim 1 or the additive composition as claimed in claim 2.
A polymer composition as claimed in claim 3, characterized in that it comprises a polymer in an amount of from 30 to 99.9% by weight, a filler in an amount of from 0 to 60% by weight, and a weight content of from 0.1 to 10%, as claimed in the claims The additive A or polymer content for the polymer described in 1 is from 0.1 to 10% by weight of the additive composition as claimed in claim 2.
A polymer composition as claimed in any one of claims 3 to 4, wherein the polymer is polypropylene, polyethylene, ABS, polystyrene, polyamide, polyvinyl chloride, polyester One or more compositions of polyoxymethylene, preferably one or more of polypropylene, polystyrene, ABS.