WO2017152685A1 - 一种用于聚合物的添加剂 - Google Patents

一种用于聚合物的添加剂 Download PDF

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WO2017152685A1
WO2017152685A1 PCT/CN2016/111244 CN2016111244W WO2017152685A1 WO 2017152685 A1 WO2017152685 A1 WO 2017152685A1 CN 2016111244 W CN2016111244 W CN 2016111244W WO 2017152685 A1 WO2017152685 A1 WO 2017152685A1
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tert
additive
polymer
butyl
formula
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PCT/CN2016/111244
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French (fr)
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黄秀茹
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黄秀茹
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
    • C07D249/18—Benzotriazoles
    • C07D249/20—Benzotriazoles with aryl radicals directly attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3472—Five-membered rings
    • C08K5/3475—Five-membered rings condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Definitions

  • the present invention relates to an additive for a polymer, and more particularly to an ultraviolet absorber containing a benzotriazole compound.
  • Existing benzotriazole compounds are widely used in the field of polymer additives, and can be used for ultraviolet absorbers, etc., which are known to be synthesized by different methods, mainly from azobenzene compounds as raw materials, according to different reduction processes. Perform cyclization.
  • the existing reduction methods include: hydrazine hydrate reduction method, zinc powder reduction method, sulfide reduction method, and the like.
  • the benzotriazole-based light stabilizer is prepared by one-step method using hydrazine hydrate as a reducing agent.
  • the reported patents include US4001266, DE2454889, FR2292708, etc.
  • the other method is hydrazine hydrate-zinc powder method, which is based on azobenzene compounds.
  • the burrs are generated during the processing of plastics, mostly in the parting surface of the mold, the inserting surface of the insert or the ejector and the insert core.
  • the burrs are largely due to poor precision of the mold manufacturing, deformation of the parts or Insufficient clamping force of the injection molding machine, mainly due to the reasons of the injection molding machine, the reason of the plastic raw materials, the reason of the mold and the molding process, etc., to solve this problem, such as Friedrich Johannaber, Walter Michaeli, Handbuch Spritzgiessen As described in "Handbook of Injection Molding" (Second Edition, Hanser garbuchverlag 2004, ISBN 9783446229662), the degree of burr formation can be minimized by the precision of the mold and the optimization of the processing parameters.
  • it is often necessary to remove the burrs in a time-consuming manual manner since the wear of the sidebands leads to edges with unclean colors as well as by plastic during use. Functional interference caused by particles.
  • the present inventors have surprisingly found that when a benzotriazole compound is used as an additive in a polymer, a benzotriazole compound having a specific range of stability angle is obtained by adjusting a synthesis process of a benzotriazole compound. Adding it to the polymer has a significant inhibitory effect on the formation of polymer burrs.
  • R1, R2 are the same or different and are represented by H, C1-C8 alkyl or C6-C18 aryl or aralkyl; R3 is H or halogen;
  • R1 and R2 are different, R1 is H, R2 is methyl, and R3 is H, expressed as:
  • R1 and R2 are the same, and are 1,1-dimethylphenyl, and R3 is H, and the expression is:
  • R1 and R2 are different, R1 is a tert-butyl group, R2 is a methyl group, and R3 is Cl, and the expression is:
  • R1 and R2 are the same, which is a tert-butyl group, and R3 is Cl, and the expression is:
  • the stability angle of the compound of the formula of formula I is from 50° to 56°, preferably from 52° to 54°.
  • the stability The angle refers to the angle formed by the inclined surface of the cone formed by the particle naturally falling from the high point to the horizontal surface without any restriction and help, and is also called the angle of repose, according to GB 11986-89. test.
  • the compound of the formula of the formula I has a bulk bulk density of from 0.60 g/cm 3 to 0.75 g/cm 3 , preferably from 0.65 g/cm 3 to 0.70 g/cm 3 .
  • a method of preparing the above additive A for a polymer comprising the steps of:
  • step (b) adding water and hydroiodic acid to the compound of formula III obtained by the step (a) with or without a phase inversion catalyst, and performing a second reduction reaction,
  • R 1 and R 2 are the same or different and are represented by H, C1-C8 alkyl, C6-C18 aryl or aralkyl; and R 3 is H or halogen.
  • the non-polar solvent used in step (a) is at least one selected from the group consisting of o-xylene, m-xylene, p-xylene and mixtures thereof, ethylbenzene, toluene and benzene.
  • the phase inversion catalyst used in the step (a) and the step (b) is at least one selected from the group consisting of tetraethylbenzylamine chloride, tetrabutylammonium chloride, tetrabutylammonium bromide. , hydroquinone and catechol.
  • the preparation method according to the present invention wherein the intermediate product having the formula III is prepared by adding red phosphorus as a reducing agent to an o-nitrophenyl hydroxyphenyl azo compound having the formula II.
  • a solvent composed of a low-priced water and a non-polar solvent is used as a reaction solvent.
  • the second reduction reaction can then be carried out by adding water and the hydrioic acid used as a reducing agent to the intermediate product obtained in the above step without the product separation or the additional purification step.
  • the reaction process is simplified, and the possibility of product loss due to solvent replacement can be avoided, thereby providing a cost-effective reaction process.
  • the additive A for a polymer is used as a UV absorber.
  • the invention also provides a polymer composition comprising 30-99.9 parts by weight of a polymer, 0-60 parts by weight of a filler, and 0.1-10 parts by weight of the preparation prepared by the invention.
  • the additive A of the polymer may also optionally comprise from 0 to 5 parts by weight of other additives B for the polymer different from the additive A prepared according to the invention.
  • the other additive B is one or more of the following:
  • Antioxidants including the following types:
  • 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-( ⁇ -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-di
  • 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.
  • 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.
  • 2,6-di-tert-butyl-4-methoxyphenol 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2 ,6-dip
  • Tocopherols such as alpha-tocopherol, beta-tocopherol, gamma-tocopherol, delta-tocopherol and mixtures thereof (vitamin E).
  • 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.
  • 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-di
  • 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-( ⁇ -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-( ⁇ -methylbenzyl)-4-nonylphenol], 2,2'-methylenebis[6-( ⁇ , ⁇ -dimethylbenzyl)-4-nonylphenol] , 4,
  • 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.
  • 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).
  • 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,
  • 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.
  • Amidophenols for example 4-hydroxylauranilide, 4-hydroxystearylanilide, octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.
  • An ester of 1.12 ⁇ -(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 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 1.16 ⁇ -(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-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.
  • 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.
  • acrylates such as ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate, ⁇ -cyano- ⁇ , ⁇ -diphenyl isooctyl acrylate, ⁇ -methyl cinnamate methyl ester, ⁇ - cyano- ⁇ -methyl-p-methoxycinnamate methyl ester, ⁇ -cyano- ⁇ -methyl-p-methoxycinnamate butyl ester, ⁇ -methyl ester-p-methoxycinnamate methyl ester, N - ( ⁇ -carbomethoxy- ⁇ -cyanovinyl)-2-methylindoline, tetrakis( ⁇ -cyano- ⁇ , ⁇ -diphenyl) neopentyl acrylate.
  • 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, With or without other ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, dibutyl Nickel dithiocarbamate, a monoalkyl ester of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid such as a nickel salt of a methyl or ethyl ester, a ketone oxime such as 2-hydroxy-4-methylbenzene A nickel complex of an undecylketone oxime, a nickel complex of 1-phenyl-4-lauroyl-5-hydroxypyrazole with or without other ligands.
  • ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, dibutyl Nickel dithiocarbamate, a monoalky
  • 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
  • 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
  • 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.
  • Phosphites and phosphonites such as triphenyl phosphite, diphenylalkyl phosphite, phenyl dialkyl phosphite Ester, tris(nonylphenyl) phosphite, trilauryl phosphite, tris(octadecyl)phosphite, distearyl pentaerythritol diphosphite, tris (2,4-di) Tert-butylphenyl) ester, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol Diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol dip
  • 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.
  • a nitrone such as N-benzyl- ⁇ -phenyl nitrone, N-ethyl- ⁇ -methyl nitrone, N-octyl- ⁇ -heptyl nitrone, N-lauryl- ⁇ -ten Monoalkyl nitrone, N-tetradecyl- ⁇ -tridecyl nitrone, N-hexadecyl- ⁇ -pentadecyl nitrone, N-octadecyl- ⁇ -heptadecane Nitrosone, N-hexadecyl- ⁇ -heptadecyl nitrone, N-octadecyl- ⁇ -pentadecyl nitrone, N-heptadecyl- ⁇ -heptadecyl nitrate Ketone, N-octadecyl- ⁇ -hexadecyl nitrone, nitrone derived from N,N
  • a thio-association agent such as dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate or distearyl disulfide.
  • Peroxide scavengers for example esters of beta-thiodipropionic acid, such as lauryl ester, stearyl ester, myristyl or tridecyl ester, mercaptobenzimidazole or 2-mercaptobenzoene
  • 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( ⁇ -dodecylmercapto)propionate.
  • Polyamide stabilizers for example copper salts and divalent manganese salts in combination with iodine and/or phosphorus compounds.
  • 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.
  • 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
  • Nucleating agents such as inorganic materials such as talc, metal oxides such as titanium dioxide or magnesium oxide, preferably alkaline earth metals Phosphate, carbonate or sulfate; organic compounds such as mono- or polycarboxylic acids and salts thereof, such as 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds Such as ionic copolymers (ionomers).
  • inorganic materials such as talc, metal oxides such as titanium dioxide or magnesium oxide, preferably alkaline earth metals Phosphate, carbonate or sulfate
  • organic compounds such as mono- or polycarboxylic acids and salts thereof, such as 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate
  • polymeric compounds Such as ionic copolymers (ionomers).
  • 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:
  • Processing additives such as anti-skid/anti-caking additives, plasticizers, fluorescent whitening agents, antistatic agents and foaming agents.
  • thermosetting and/or thermoplastic polymer selected from one or more of the following:
  • 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).
  • HDPE high density polyethylene
  • HDPE-HMW high density and high molecular weight polyethylene
  • HDPE-UHMW high Density and ultra high molecular weight polyethylene
  • MDPE medium density polyethylene
  • LDPE low density polyethylene
  • LLDPE linear low density polyethylene
  • 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,
  • 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.
  • Polystyrene poly-p-methyl styrene, poly- ⁇ -methyl styrene.
  • 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.
  • PCHE polycyclohexylethylene
  • PVCH polyvinylcyclohexane
  • 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
  • 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.
  • halogen-containing polymers such as polychloroprene, chlorinated rubber, chlorinated or brominated copolymers of isobutylene-isoprene (halogenated rubber), chlorinated or
  • 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.
  • 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.
  • cyclic ethers such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with diglycidyl ether.
  • Polyacetals such as polyoxymethylene and those polyoxymethylenes containing ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
  • 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.
  • 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 glyco
  • 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.
  • aliphatic polyesters may include, for example, but are not limited to, poly(hydroxyalkanoates), especially polypropiolactone, polybutyrolactone, polypivalolactone, polyvalerolactone, and polyhexanolate.
  • Lactone polyethylene succinate, propylene glycol polysuccinate, polybutylene succinate, hexamethylene polysuccinate, polyethylene adipate, propylene glycol adipate, Polybutylene adipate, polyhexamethylene adipate, Polyethylene oxalate, polyglycolic acid propylene glycol ester, polybutylene oxalate, polyhexamethylene oxalate, polyethylene sebacate, polypropylene phthalate, polybutylene phthalate Ester and polylactic acid (PLA) and corresponding polyesters modified with polycarbonate or MBS.
  • PPA polylactic acid
  • polylactic acid 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.
  • 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.
  • 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.
  • a crosslinkable acrylic resin derived from a substituted acrylate such as an epoxy acrylate, urethane acrylate or polyester acrylate.
  • a promoter is crosslinked using a conventional hardener such as an acid anhydride or an amine.
  • 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.
  • 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:
  • olefin monomers such as ethylene and propylene and higher 1-olefins such as 1-butene, 1-pentene, 1-hexene or 1-octene And copolymers. Preference is given to polyethylene LDPE and LLDPE, HDPE and polypropylene.
  • 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
  • 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.
  • thermosetting resins such as epoxy resins, melamine resins, and unsaturated polyester resins
  • 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.
  • 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
  • a process for preparing a polymer composition comprising mixing a polymer additive of the present invention and/or a polymer additive composition of the present invention with a polymer pellet and/or a filler in a mixer, and They are homogenized in the polymer melt in a extruder apparatus at relatively high temperatures, and the homogenized polymer extrudate is then withdrawn, cooled, and pelletized.
  • the extruder unit is selected from a single screw extruder or a twin screw extruder.
  • the preferred processing temperature is 170 to 200 ° C for polystyrene, 200 to 300 ° C for polypropylene, and 250 to 290 ° C for polyethylene terephthalate (PET).
  • Polybutylene terephthalate is 230 to 270 ° C, 260 to 290 ° C for polyamide-6 (PA6), 260 to 290 ° C for polyamide 66 (PA66), and for polycarbonate
  • the ester is 280 to 320 °C.
  • 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.
  • Example 2 The same procedure as in Example 2 was carried out except that 183 g of 2-nitro-4-chloro-2-hydroxy-3,5-di-tert-butylazobenzene was used as the initial starting material, and as a result, 90.6 g of high purity was obtained. -(2-Hydroxy-3,5-di-tert-butylphenyl)-5-chloro-benzotriazole. The stability angle of the product was determined to be 52°.
  • Example 3 The same procedure as in Example 3 was carried out except that 183 g of 2-nitro-4-chloro-2-hydroxy-3,5-di-tert-butylazobenzene was used as the initial starting material, and as a result, 91.2 g of high purity was obtained. -(2-Hydroxy-3,5-di-tert-butylphenyl)-5-chloro-benzotriazole. The stability angle of the product was measured to be 56°.
  • Polystyrene Yangtze BASF, 158K
  • Antioxidant BASF, Irganox 1010
  • Fiberglass PPG, Chop Vantage 3540
  • the above polypropylene and other components are first dry mixed in a high speed mixer at a speed of about 1000 rpm for 1 minute. If talc is added, the talc filler is added and mixed for another 3 minutes.
  • the mixed raw materials are placed in a twin-screw extruder and melt-extruded and granulated.
  • the process conditions are: one zone 200 ° C, two zones 210 ° C, three zones 220 ° C, four zones 215 ° C; twin-screw extruder
  • the aspect ratio is 35, the screw speed is 450 rpm, the residence time is 1 minute, and the pressure is 10 MPa.
  • 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.
  • 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.
  • the above polyamide and other components are first dry mixed in a high-speed mixer rotating at about 1000 rpm for 3 minutes, and the mixed raw materials are placed in a twin-screw extruder and melt-extruded.
  • the process conditions are: one zone temperature 230 ° C, two zone temperature 250 ° C, three zone temperature 250 ° C, four zone temperature 250 ° C, five zone temperature 240 ° C, six zone temperature 240 ° C, seven zone temperature 240 °C, the temperature in the eight zone is 230 °C, the temperature in the nine zone is 230 °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.
  • the tool used to determine the formation of the burrs was a two-plate mold having a six-arm type test body with a center sprue.
  • the length, width and thickness of the arms are 90 x 10 x 1.5 mm.
  • Vents are located at the front and end of each arm.
  • the vents at the end of the flow path have different gap sizes. As shown in Fig. 1, the gap sizes of the respective vents are 0, 4, 8, 12, 20 and 30 ⁇ m.
  • the width of the vent is 2.95mm (see Figure 2).
  • the burr length G of the test body (see Figure 3) is ventilated with a size of 30 ⁇ m The flow path end of the arm of the gap is evaluated.
  • Figures 2 and 3 show the ends of the arms of the test body having a venting gap size of 30 ⁇ m, which components are not shown to scale but are schematically shown in order to be able to see the principle of operation.
  • the burr of the material protrudes beyond the end of the arm of the test body, which penetrates into the venting gap at the flow path end.
  • Fig. 3 is exaggeratedly enlarged, and the burr length G is indicated.
  • test bodies were manufactured by an injection molding machine of the type Krauss Maffei 100-380CX. These parts are removed manually, otherwise the burrs will be damaged.
  • the injection speed was 100 mm/s
  • the screw speed was 50 RPM
  • the dynamic pressure was 100 bar
  • the holding pressure was 400 bar. 250 ° C was chosen as the melting temperature and 90 ° C was used as the mold temperature.
  • the burr length G was determined from the image, and the image was recorded at a magnification of 40-50 times using a microscope of the Leica/Wild M420 optical microscope, and the burr was recorded over the entire width by using a 2.0 ⁇ focusing lens.
  • the burr length G is generated from the distance between the baseline (the end of the test body) and the measurement line.
  • the measurement line is intended such that the depressed and raised regions are mutually compensated (see Figure 3).
  • the final measured burr length G is the arithmetic mean of the measurements from 5 different test bodies.

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Abstract

提供了一种如式I所示的用于聚合物的添加剂及其制备方法，以及由其组成的聚合物组合物，其中，R1、R2相同或不同，表示为H、C1-C8烷基或C6-C18芳基或芳烷基；R3为H或卤素。该添加剂可应用于热塑性聚合物中，使用了该添加剂的热塑性聚合物模塑材料的特征在于：在90℃的模具温度下，以及在100巴的动态压力和400巴的保持压力下进行的注塑成型毛边形成测试中，在具有30μm的通风间隙尺寸的模制臂的流径端产生了长度G至多为24μm的毛边。

Description

一种用于聚合物的添加剂 技术领域
本发明涉及一种用于聚合物的添加剂，具体涉及一种含有苯并三唑类化合物的紫外线吸收剂。
背景技术
现有苯并三唑类化合物被广泛应用于聚合物添加剂领域，可用于紫外线吸收剂等，已知其可通过不同的方法进行合成，主要是从偶氮苯化合物为原料，按照不同的还原工艺进行环化。其现有还原方法有：水合肼还原法、锌粉还原法、硫化物还原法等。
以水合肼为还原剂一步法制得苯并三唑类光稳定剂，报道的专利有US4001266、DE2454889、FR2292708等；另一种方法是水合肼-锌粉法，是以偶氮苯化合物为原料，使用水合肼为还原剂，将偶氮苯化合物还原为中间体苯并三唑氮氧化物，然后用锌粉为还原剂将中间体苯并三唑氮氧化物还原为苯并三唑类光稳定剂，报道的专利有JP53063379、专利CN1455773A等；另一种方法是水合肼-保险粉法，该方法是以偶氮苯化合物为原料以水合肼为还原剂，将偶氮苯化合物还原为中间体苯并三唑氮氧化物，然后使用保险粉为还原剂将中间体苯并三唑氮氧化物还原为苯并三唑类光稳定剂，报道的专利有CN101029032A。
塑料加工过程中会产生毛边，大多发生在模具的分型面、镶件结合面或顶出件和镶件型芯配合面上，毛边在很大程度上是由于模具制造精度差、零件变形或注塑机锁模力不足造成，原因主要有注塑机的原因、塑料原料的原因、模具的原因以及成型工艺等方面的原因，为解决这一问题，如Friedrich Johannaber，Walter Michaeli，Handbuch Spritzgiessen所著的《Handbook of Injection Molding》(第二版，Hanser Fachbuchverlag2004，ISBN9783446229662)中所叙述，能够通过模具的精确度和加工参数的优化来使毛边形成的程度最小化。然而，尤其是该些在随后着色的注塑模制部件常常必须要先以耗时的手动方式来去除毛边，因为在使用过程中，边带的磨损会导致带有不洁净颜色的边缘以及由塑料颗粒带来的功能性干扰。
发明内容
本发明人惊奇的发现，当苯并三唑类化合物作为添加剂用于聚合物中时，通过调整苯并三唑类化合物的合成工艺从而得到一种特定范围安定角的苯并三唑类化合物，将其加入到聚合物中，对聚合物毛边的形成具有明显的抑制作用。
本发明是通过以下技术方案实现的：
一种用于聚合物的添加剂A，具有如式I所示结构式的化合物：
Figure PCTCN2016111244-appb-000001
其中，R1，R2相同或不同，表示为H、C1-C8烷基或C6-C18芳基或芳烷基；R3为H或卤素；
优选R1、R2不同，R1为H，R2为甲基，R3为H，表达为：
Figure PCTCN2016111244-appb-000002
优选R1、R2相同，为1，1-二甲基苯基，R3为H，表达为：
Figure PCTCN2016111244-appb-000003
优选R1、R2不同，R1为叔丁基，R2为甲基，R3为Cl，表达为：
Figure PCTCN2016111244-appb-000004
优选R1、R2相同，为叔丁基，R3为Cl，表达为：
Figure PCTCN2016111244-appb-000005
其中，所述式I所示结构式的化合物的安定角是50°-56°，优选52°-54°。所述安定 角，是指颗粒在不受任何限制和帮助下，由高点自然落到水平面上所形成的圆锥体的斜面与锥底平面构成的夹角，也称为休止角，按照GB 11986-89进行测试。
所述式I所示结构式的化合物的松散堆积密度为0.60g/cm3～0.75g/cm3，优选0.65g/cm3～0.70g/cm3。
制备上述用于聚合物的添加剂A的方法，包括如下步骤：
(a)使用或不使用相转化催化剂，在由非极性溶剂、水和一种碱性化合物组成的溶剂的存在下，向分子式为式II的化合物中加入红磷，进行第一步还原反应制得分子式为式III的化合物；和
(b)使用或不使用相转化催化剂，向由步骤(a)制得的分子式为式III的化合物中加入水和氢碘酸，进行第二步还原反应，
Figure PCTCN2016111244-appb-000006
式II和式III中，R1，R2相同或不同，表示为H、C1-C8烷基、C6-C18芳基或芳烷基；R3为H或卤素。
步骤(a)所使用的非极性溶剂至少是选自下面所列溶剂中的一种：邻二甲苯，间二甲苯，对二甲苯以及他们的混合物，乙苯，甲苯和苯。
步骤(a)和步骤(b)中使用的相转化催化剂至少是选自下面所列物质中的一种：四乙基苄基氯化胺，四丁基氯化胺，四丁基溴化铵，对苯二酚和邻苯二酚。
本发明涉及的制备方法，其中具有分子式为式III的中间产物的制备是通过向具有分子式为式II的邻-硝基苯基羟苯基偶氮化合物中加入作为还原剂的红磷，利用由低价格的水和非极性溶剂组成的溶剂作为反应溶剂。然后可以不经产物分离或额外的提纯步骤，只需向上述步骤所制得的中间产物中加入水以及用作还原剂的氢碘酸进行第二步还原反应。根据本发明，在第一步还原反应中，只需将非极性溶剂与水混合作为反应溶剂，在第二步还原反应中，只需加入水，无需再加入任何有机溶剂。因此，反应过程被简化，也可以避免由于更换溶剂而产生产物流失的可能性，从而提供了一个经济高效的反应过程。
所述用于聚合物的添加剂A用作紫外线吸收剂的用途。
本发明还提供一种聚合物组合物，包含重量份数为30-99.9份的聚合物，重量份数为0-60份的填料，重量份数为0.1-10份的本发明制备的用于聚合物的添加剂A，还可以选择性的包含重量份为0-5份的不同于本发明制备的添加剂A的其它用于聚合物的添加剂B。
所述其它添加剂B为以下物质的一种或一种以上：
1.抗氧剂，包括如下种类：
1.1烷基化单酚，例如2，6-二叔丁基-4-甲基苯酚、2-叔丁基-4，6-二甲基苯酚、2，6-二叔丁基-4-乙基苯酚、2，6-二叔丁基-4-正丁基苯酚、2，6-二叔丁基-4-异丁基苯酚、2，6-二环戊基-4-甲基苯酚、2-(α-甲基环己基)-4，6-二甲基苯酚、2，6-二(十八烷基)-4-甲基苯酚、2，4，6-三环己基苯酚、2，6-二叔丁基-4-甲氧基甲基苯酚，侧链为线性或支化的壬基酚例如2，6-二壬基-4-甲基苯酚、2，4-二甲基-6-(1’-甲基十一烷-1’-基)苯酚、2，4-二甲基-6-(1’-甲基十七烷-1’-基)苯酚、2，4-二甲基-6-(1’-甲基十三烷-1’-基)苯酚及其混合物。
1.2烷硫基甲基苯酚，例如2，4-二辛硫基甲基-6-叔丁基苯酚、2，4-二辛硫基甲基-6-甲基苯酚、2，4-二辛硫基甲基-6-乙基苯酚、2，6-二(十二烷硫基)甲基-4-壬基苯酚。
1.3氢醌类和烷基化氢醌类，例如2，6-二叔丁基-4-甲氧基苯酚、2，5-二叔丁基氢醌、2，5-二叔戊基氢醌、2，6-二苯基-4-十八烷氧基苯酚、2，6-二叔丁基氢醌、2，5-二叔丁基-4-羟基茴香醚、3，5-二叔丁基-4-羟基茴香醚、硬脂酸3，5-二叔丁基-4-羟基苯酯、己二酸双(3，5-二叔丁基-4-羟基苯基)酯。
1.4生育酚类，例如α-生育酚、β-生育酚、γ-生育酚、δ-生育酚及其混合物(维生素E)。
1.5羟基化硫代二苯醚，例如2，2’-硫代双(6-叔丁基-4-甲基苯酚)、2，2’-硫代双(4-辛基苯酚)、4，4’-硫代双(6-叔丁基-3-甲基苯酚)、4，4’-硫代双(6-叔丁基-2-甲基苯酚)、4，4’-硫代双(3，6-二仲戊基苯酚)、4，4’-双(2，6-二甲基-4-羟基苯基)二硫醚。
1.6亚烷基双酚，例如2，2’-亚甲基双(6-叔丁基-4-甲基苯酚)、2，2’-亚甲基双(6-叔丁基-4-乙基苯酚)、2，2’-亚甲基双[4-甲基-6-(α-甲基环己基)苯酚]、2，2’-亚甲基双(4-甲基-6-环己基苯酚)、2，2’-亚甲基双(6-壬基-4-甲基苯酚)、2，2’-亚甲基双(4，6-二叔丁基苯酚)、2，2’-亚乙基双(4，6-二叔丁基苯酚)、2，2’-亚乙基双(6-叔丁基-4-异丁基苯酚)、2，2’-亚甲基双[6-(α-甲基苄基)-4-壬基酚]、2，2’-亚甲基双[6-(α，α-二甲基苄基)-4-壬基酚]、4，4’-亚甲基双(2，6-二叔丁基苯酚)、4，4’-亚甲基双(6-叔丁基-2-甲基苯酚)、1，1-双(5-叔丁基-4-羟基-2-甲基苯基)丁烷、2，6-双(3-叔丁基-5-甲基-2-羟基苄基)-4-甲基苯酚、1，1，3-三(5-叔丁基-4-羟基-2-甲基苯基)丁烷、1，1-双(5-叔丁基-4-羟基-2-甲基苯基)-3-正十二烷基 巯基丁烷、乙二醇双[3，3-双(3’-叔丁基-4’-羟基苯基)丁酸酯]、双(3-叔丁基-4-羟基-5-甲基苯基)二环戊二烯、双[2-(3’-叔丁基-2’-羟基-5’-甲基苄基)-6-叔丁基-4-甲基苯基]对苯二甲酸酯、1，1-双(3，5-二甲基-2-羟基苯基)丁烷、2，2-双(3，5-二叔丁基-4-羟基苯基)丙烷、2，2-双(5-叔丁基-4-羟基-2-甲基苯基)-4-正十二烷基巯基丁烷、1，1，5，5-四(5-叔丁基-4-羟基-2-甲基苯基)戊烷。
1.7O-、N-和S-苄基化合物，例如3，5，3’，5’-四叔丁基-4，4’-二羟基二苄基醚、4-羟基-3，5-二甲基苄基巯基乙酸十八烷基酯、4-羟基-3，5-二叔丁基苄基巯基乙酸十三烷基酯、三(3，5-二叔丁基-4-羟基苄基)胺、双(4-叔丁基-3-羟基-2，6-二甲基苄基)二硫代对苯二甲酸酯、双(3，5-二叔丁基-4-羟基苄基)硫化物、3，5-二叔丁基-4-羟基苄基巯基乙酸异辛基酯。
1.8芳族羟基苄基化合物，例如1，3，5-三(3，5-二叔丁基-4-羟基苄基)-2，4，6-三甲基苯、1，4-双(3，5-二叔丁基-4-羟基苄基)-2，3，5，6-四甲基苯、2，4，6-三(3，5-二叔丁基-4-羟基苄基)苯酚。
1.9三嗪化合物，例如2，4-双(辛基巯基)-6-(3，5-二叔丁基-4-羟基苯胺基)-1，3，5-三嗪、2-辛基巯基-4，6-双(3，5-二叔丁基-4-羟基苯胺基)-1，3，5-三嗪、2-辛基巯基-4，6-双(3，5-二叔丁基-4-羟基苯氧基)-1，3，5-三嗪、2，4，6-三(3，5-二叔丁基-4-羟基苯氧基)-1，2，3-三嗪、1，3，5-三(3，5-二叔丁基-4-羟基苄基)异氰脲酸酯、1，3，5-三(4-叔丁基-3-羟基-2，6-二甲基苄基)异氰脲酸酯、2，4，6-三(3，5-二叔丁基-4-羟基苯基乙基)-1，3，5-三嗪、1，3，5-三(3，5-二叔丁基-4-羟基苯基丙酰基)-六氢-1，3，5-三嗪、1，3，5-三(3，5-二环己基-4-羟基苄基)异氰脲酸酯。
1.10苄基膦酸酯，例如2，5-二叔丁基-4-羟基苄基膦酸二甲酯、3，5-二叔丁基-4-羟基苄基膦酸二乙酯、3，5-二叔丁基-4-羟基苄基膦酸二(十八烷基)酯、5-叔丁基-4-羟基-3-甲基苄基膦酸二(十八烷基)酯、3，5-二叔丁基-4-羟基苄基膦酸的单乙酯的钙盐。
1.11酰氨基苯酚类，例如4-羟基月桂酰替苯胺、4-羟基硬脂酰替苯胺、N-(3，5-二叔丁基-4-羟基苯基)氨基甲酸辛酯。
1.12β-(3，5-二叔丁基-4-羟基苯基)丙酸与如下一元醇或多元醇的酯：例如与甲醇、乙醇、正辛醇、异辛醇、十八烷醇、1，6-己二醇、1，9-壬二醇、乙二醇、1，2-丙二醇、新戊二醇、硫二甘醇、二甘醇、三甘醇、季戊四醇、三(羟乙基)异氰脲酸酯、N，N’-双(羟乙基)草酰胺、3-硫杂十一烷醇、3-硫杂十五烷醇、三甲基己二醇、三羟甲基丙烷、4-羟基甲基-1-磷杂-2，6，7-三氧杂双环[2.2.2]辛烷的酯。
1.13β-(5-叔丁基-4-羟基-3-甲基苯基)丙酸与如下一元醇或多元醇的酯：例如与甲醇、乙醇、正辛醇、异辛醇、十八烷醇、1，6-己二醇、1，9-壬二醇、乙二醇、1，2-丙二醇、新戊 二醇、硫二甘醇、二甘醇、三甘醇、季戊四醇、三(羟乙基)异氰脲酸酯、N，N’-双(羟乙基)草酰胺、3-硫杂十一烷醇、3-硫杂十五烷醇、三甲基己二醇、三羟甲基丙烷、4-羟基甲基-1-磷杂-2，6，7-三氧杂双环[2.2.2]辛烷、3，9-双[2-{3-(3-叔丁基-4-羟基-5-甲基苯基)丙酰氧基}-1，1-二甲基乙基]-2，4，8，10-四氧杂螺[5.5]十一烷的酯。
1.14β-(3，5-二环己基-4-羟基苯基)丙酸与如下一元醇或多元醇的酯：例如与甲醇、乙醇、辛醇、十八烷醇、1，6-己二醇、1，9-壬二醇、乙二醇、1，2-丙二醇、新戊二醇、硫二甘醇、二甘醇、三甘醇、季戊四醇、三(羟乙基)异氰脲酸酯、N，N’-双(羟乙基)草酰胺、3-硫杂十一烷醇、3-硫杂十五烷醇、三甲基己二醇、三羟甲基丙烷、4-羟基甲基-1-磷杂-2，6，7-三氧杂双环[2.2.2]辛烷的酯。
1.15 3，5-二叔丁基-4-羟基苯基乙酸与如下一元醇或多元醇的酯：例如与甲醇、乙醇、辛醇、十八烷醇、1，6-己二醇、1，9-壬二醇、乙二醇、1，2-丙二醇、新戊二醇、硫二甘醇、二甘醇、三甘醇、季戊四醇、三(羟乙基)异氰脲酸酯、N，N’-双(羟乙基)草酰胺、3-硫杂十一烷醇、3-硫杂十五烷醇、三甲基己二醇、三羟甲基丙烷、4-羟基甲基-1-磷杂-2，6，7-三氧杂双环[2.2.2]辛烷的酯。
1.16β-(3，5-二叔丁基-4-羟基苯基)丙酸的酰胺，例如N，N’-双(3，5-二叔丁基-4-羟基苯基丙酰基)六亚甲基二胺、N，N’-双(3，5-二叔丁基-4-羟基苯基丙酰基)三亚甲基二胺、N，N’-双(3，5-二叔丁基-4-羟基苯基丙酰基)肼、N，N’-双[2-(3-[3，5-二叔丁基-4-羟基苯基]丙酰氧基)乙基]草酰胺。
2.本发明制备的添加剂A之外的其它紫外线吸收剂
2.1 2-羟基二苯甲酮类，例如4-羟基、4-甲氧基、4-辛氧基、4-癸氧基、4-十二烷氧基、4-苄氧基、4，2’，4’-三羟基和2’-羟基-4，4’-二甲氧基衍生物。
2.2取代和未取代苯甲酸的酯，例如水杨酸4-叔丁基苯酯、水杨酸苯酯、水杨酸辛基苯酯、二苯甲酰间苯二酚、双(4-叔丁基苯甲酰)间苯二酚、苯甲酰间苯二酚、3，5-二叔丁基-4-羟基苯甲酸2，4-二叔丁基苯酯、3，5-二叔丁基-4-羟基苯甲酸十六烷基酯、3，5-二叔丁基-4-羟基苯甲酸十八烷基酯、3，5-二叔丁基-4-羟基苯甲酸2-甲基-4，6-二叔丁基苯酯。
2.3丙烯酸酯类，例如α-氰基-β，β-二苯基丙烯酸乙酯、α-氰基-β，β-二苯基丙烯酸异辛酯、α-甲酯基肉桂酸甲酯、α-氰基-β-甲基对甲氧基肉桂酸甲酯、α-氰基-β-甲基对甲氧基肉桂酸丁酯、α-甲酯基对甲氧基肉桂酸甲酯、N-(β-甲酯基-β-氰基乙烯基)-2-甲基二氢吲哚、四(α-氰基-β，β-二苯基)丙烯酸新戊基酯。
2.4镍化合物，例如2，2’-硫代双[4-(1，1，3，3-四甲基丁基)苯酚]的镍配合物，例如1∶1或1∶2配合物，其具有或不具有其他配体如正丁胺、三乙醇胺或N-环己基二乙醇胺，二丁基 二硫代氨基甲酸镍，4-羟基-3，5-二叔丁基苄基膦酸的单烷基酯如甲酯或乙酯的镍盐，酮肟如2-羟基-4-甲基苯基十一烷基酮肟的镍配合物，1-苯基-4-月桂酰基-5-羟基吡唑的镍配合物，其具有或不具有其他配体。
2.5位阻胺，例如双(1-十一烷氧基-2，2，6，6-四甲基-4-哌啶基)碳酸酯、双(2，2，6，6-四甲基-4-哌啶基)癸二酸酯、双(2，2，6，6-四甲基-4-哌啶基)琥珀酸酯、双(1，2，2，6，6-五甲基-4-哌啶基)癸二酸酯、双(1-辛氧基-2，2，6，6-四甲基-4-哌啶基)癸二酸酯、双(1，2，2，6，6-五甲基-4-哌啶基)正丁基-3，5-二叔丁基-4-羟基苄基丙二酸酯、1-(2-羟乙基)-2，2，6，6-四甲基-4-羟基哌啶与琥珀酸的缩合物、N，N’-双(2，2，6，6-四甲基-4-哌啶基)六亚甲基二胺与4-叔辛基氨基-2，6-二氯-1，3，5-三嗪的线性或环状缩合物、三(2，2，6，6-四甲基-4-哌啶基)次氮基三乙酸酯、四(2，2，6，6-四甲基-4-哌啶基)-1，2，3，4-丁烷四甲酸酯、1，1’-(1，2-亚乙基)-双(3，3，5，5-四甲基哌嗪酮)、4-苯甲酰基-2，2，6，6-四甲基哌啶、4-硬脂氧基-2，2，6，6-四甲基哌啶、双(1，2，2，6，6-五甲基哌啶基)-2-正丁基-2-(2-羟基-3，5-二叔丁基苄基)丙二酸酯、3-正辛基-7，7，9，9-四甲基-1，3，8-三氮杂螺[4.5]癸-2，4-二酮、双(1-辛氧基-2，2，6，6-四甲基哌啶基)癸二酸酯、双(1-辛氧基-2，2，6，6-四甲基哌啶基)琥珀酸酯、N，N’-双-(2，2，6，6-四甲基-4-哌啶基)六亚甲基二胺与4-吗啉基-2，6-二氯-1，3，5-三嗪的线性或环状缩合物、2-氯-4，6-双(4-正丁基氨基-2，2，6，6-四甲基哌啶基)-1，3，5-三嗪与1，2-双(3-氨基丙基氨基)乙烷的缩合物、2-氯-4，6-二(4-正丁基氨基-1，2，2，6，6-五甲基哌啶基)-1，3，5-三嗪与1，2-双(3-氨基丙基氨基)乙烷的缩合物、8-乙酰基-3-十二烷基-7，7，9，9-四甲基-1，3，8-三氮杂螺[4.5]癸烷-2，4-二酮、3-十二烷基-1-(2，2，6，6-四甲基-4-哌啶基)吡咯烷-2，5-二酮、3-十二烷基-1-(1，2，2，6，6-五甲基-4-哌啶基)吡咯烷-2，5-二酮、4-十六烷氧基-和4-硬脂氧基-2，2，6，6-四甲基哌啶的混合物、N，N’-双(2，2，6，6-四甲基-4-哌啶基)六亚甲基二胺与4-环己基氨基-2，6-二氯-1，3，5-三嗪的缩合物、1，2-双(3-氨基丙基氨基)乙烷与2，4，6-三氯-1，3，5-三嗪以及4-丁基氨基-2，2，6，6-四甲基哌啶的缩合物(CAS登记号[136504-96-6])；1，6-己二胺与2，4，6-三氯-1，3，5-三嗪以及N，N-二丁胺与4-丁基氨基-2，2，6，6-四甲基哌啶的缩合物(CAS登记号[192268-64-7])；N-(2，2，6，6-四甲基-4-哌啶基)正十二烷基琥珀酰亚胺、N-(1，2，2，6，6-五甲基-4-哌啶基)正十二烷基琥珀酰亚胺、2-十一烷基-7，7，9，9-四甲基-1-氧杂-3，8-二氮杂-4-氧代螺[4，5]癸烷、7，7，9，9-四甲基-2-环十一烷基-1-氧杂-3，8-二氮杂-4-氧代螺[4，5]癸烷与表氯醇的反应产物、1，1-双(1，2，2，6，6-五甲基-4-哌啶基氧基羰基)-2-(4-甲氧基苯基)乙烯、N，N’-双甲酰基-N，N’-双(2，2，6，6-四甲基-4-哌啶基)六亚甲基二胺、4-甲氧基亚甲基丙二酸与1，2，2，6，6-五甲基-4-羟基哌啶的二酯、聚[甲基丙基-3-氧基-4-(2，2，6，6-四甲基-4-哌啶基)]硅氧烷、马来酸酐-α-烯烃共聚物与2，2，6，6-四甲基-4-氨基 哌啶或1，2，2，6，6-五甲基-4-氨基哌啶的反应产物、2，4-双[N-(1-环己氧基-2，2，6，6-四甲基哌啶-4-基)-N-丁基氨基]-6-(2-羟乙基)氨基-1，3，5-三嗪、1-(2-羟基-2-甲基丙氧基)-4-十八烷酰氧基-2，2，6，6-四甲基哌啶、5-(2-乙基己酰基)氧基甲基-3，3，5-三甲基-2-吗啉酮、Sanduvor(Clariant；CAS登记号[106917-31-1])、5-(2-乙基己酰基)氧基甲基-3，3，5-三甲基-2-吗啉酮、2，4-双[(1-环己氧基-2，2，6，6-哌啶-4-基)丁基氨基]-6-氯-s-三嗪与N，N’-双(3-氨基丙基)乙二胺)的反应产物、1，3，5-三(N-环己基-N-(2，2，6，6-四甲基哌嗪-3-酮-4-基)氨基)-s-三嗪、1，3，5-三(N-环己基-N-(1，2，2，6，6-五甲基哌嗪-3-酮-4-基)氨基)-s-三嗪。
2.6草酰胺，例如4，4’-二辛氧基草酰替苯胺、2，2’-二乙氧基草酰替苯胺、2，2’-二辛氧基-5，5’-二叔丁基草酰替苯胺、2，2’-二(十二烷氧基)-5，5’-二叔丁基草酰替苯胺、2-乙氧基-2’-乙基草酰替苯胺、N，N’-双(3-二甲基氨基丙基)草酰胺、2-乙氧基-5-叔丁基-2’-乙基草酰替苯胺及其与2-乙氧基-2’-乙基-5，4’-二叔丁基草酰替苯胺的混合物、邻-和对-甲氧基二取代草酰替苯胺的混合物以及邻-和对-乙氧基二取代草酰替苯胺的混合物。
2.7 2-(2-羟基苯基)-1，3，5-三嗪类，例如2，4，6-三(2-羟基-4-辛氧基苯基)-1，3，5-三嗪、2-(2-羟基-4-辛氧基苯基)-4，6-双(2，4-二甲基苯基)-1，3，5-三嗪、2-(2，4-二羟基苯基)-4，6-双(2，4-二甲基苯基)-1，3，5-三嗪、2，4-双(2-羟基-4-丙氧基苯基)-6-(2，4-二甲基苯基)-1，3，5-三嗪、2-(2-羟基-4-辛氧基苯基)-4，6-双(4-甲基苯基)-1，3，5-三嗪、2-(2-羟基-4-十二烷氧基苯基)-4，6-双(2，4-二甲基苯基)-1，3，5-三嗪、2-(2-羟基-4-十三烷氧基苯基)-4，6-双(2，4-二甲基苯基)-1，3，5-三嗪、2-[2-羟基-4-(2-羟基-3-丁氧基丙氧基)苯基]-4，6-双(2，4-二甲基)-1，3，5-三嗪、2-[2-羟基-4-(2-羟基-3-辛氧基丙氧基)苯基]-4，6-双(2，4-二甲基)-1，3，5-三嗪、2-[4-(十二烷氧基/十三烷氧基-2-羟基丙氧基)-2-羟基苯基]-4，6-双(2，4-二甲基苯基)-1，3，5-三嗪、2-[2-羟基-4-(2-羟基-3-十二烷氧基丙氧基)苯基]-4，6-双(2，4-二甲基苯基)-1，3，5-三嗪、2-(2-羟基-4-己氧基)苯基-4，6-二苯基-1，3，5-三嗪、2-(2-羟基-4-甲氧基苯基)-4，6-二苯基-1，3，5-三嗪、2，4，6-三[2-羟基-4-(3-丁氧基-2-羟基丙氧基)苯基]-1，3，5-三嗪、2-(2-羟基苯基)-4-(4-甲氧基苯基)-6-苯基-1，3，5-三嗪、2-{2-羟基-4-[3-(2-乙基己基-1-氧基)-2-羟基丙氧基]苯基}-4，6-双(2，4-二甲基苯基)-1，3，5-三嗪、2，4-双(4-[2-乙基己氧基]-2-羟基苯基)-6-(4-甲氧基苯基)-1，3，5-三嗪。
3.金属减活剂，例如N，N’-二苯基草酰胺、N-水杨醛-N’-水杨酰肼、N，N’-双(水杨酰)肼、N，N’-双(3，5-二叔丁基-4-羟基苯基丙酰)肼、3-水杨酰氨基-1，2，4-三唑、双(亚苄基)草酰二肼、草酰替苯胺、间苯二甲酰二肼、癸二酰双苯基肼、N，N’-二乙酰己二酰二肼、N，N’-双(水杨酰)草酰二肼、N，N’-双(水杨酰)硫代丙酰二肼。
4.亚磷酸酯和亚膦酸酯，例如亚磷酸三苯酯、亚磷酸二苯基烷基酯、亚磷酸苯基二烷基 酯、亚磷酸三(壬基苯基)酯、亚磷酸三月桂基酯、亚磷酸三(十八烷基)酯、二硬脂基季戊四醇二亚磷酸酯、亚磷酸三(2，4-二叔丁基苯基)酯、二异癸基季戊四醇二亚磷酸酯、双(2，4-二叔丁基苯基)季戊四醇二亚磷酸酯、双(2，4-二枯基苯基)季戊四醇二亚磷酸酯、双(2，6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯、二异癸氧基季戊四醇二亚磷酸酯、双(2，4-二叔丁基-6-甲基苯基)季戊四醇二亚磷酸酯、双(2，4，6-三(叔丁基苯基)季戊四醇二亚磷酸酯、三硬脂基山梨糖醇三亚磷酸酯、4，4’-亚联苯基二亚膦酸四(2，4-二叔丁基苯基)酯、6-异辛氧基-2，4，8，10-四叔丁基-12H-二苯并[d，g]-1，3，2-二氧杂磷杂八环、亚磷酸双(2，4-二叔丁基-6-甲基苯基)甲酯、亚磷酸双(2，4-二叔丁基-6-甲基苯基)乙酯、6-氟-2，4，8，10-四叔丁基-12-甲基二苯并[d，g]-1，3，2-二氧杂磷杂八环、2，2’，2”-次氮基[三乙基三(3，3’，5，5’-四叔丁基-1，1’-联苯-2，2’-二基)亚磷酸酯]、(3，3’，5，5’-四叔丁基-1，1’-联苯-2，2’-二基)亚磷酸2-乙基己酯、5-丁基-5-乙基-2-(2，4，6-三叔丁基苯氧基)-1，3，2-二氧杂磷杂环丙烷。
5.羟胺，例如N，N-二苄基羟胺、N，N-二乙基羟胺、N，N-二辛基羟胺、N，N-二月桂基羟胺、N，N-二(十四烷基)羟胺、N，N-二(十六烷基)羟胺、N，N-二(十八烷基)羟胺、N-十六烷基-N-十八烷基羟胺、N-十七烷基-N-十八烷基羟胺、衍生自氢化牛油脂肪胺的N，N-二烷基羟胺。
6.硝酮，例如N-苄基-α-苯基硝酮、N-乙基-α-甲基硝酮、N-辛基-α-庚基硝酮、N-月桂基-α-十一烷基硝酮、N-十四烷基-α-十三烷基硝酮、N-十六烷基-α-十五烷基硝酮、N-十八烷基-α-十七烷基硝酮、N-十六烷基-α-十七烷基硝酮、N-十八烷基-α-十五烷基硝酮、N-十七烷基-α-十七烷基硝酮、N-十八烷基-α-十六烷基硝酮、衍生自N，N-二烷基羟胺(衍生自氢化牛油脂肪胺)的硝酮。
7.硫代协合剂，例如硫代二丙酸二月桂基酯、硫代二丙酸二肉豆蔻基酯、硫代二丙酸二硬脂基酯或二硬脂基二硫醚。
8.过氧化物清除剂，例如β-硫代二丙酸的酯，例如月桂基酯、硬脂基酯、肉豆蔻基酯或十三烷基酯、巯基苯并咪唑或2-巯基苯并咪唑的锌盐、二丁基二硫代氨基甲酸锌、二(十八烷基)二硫醚、季戊四醇四(β-十二烷基巯基)丙酸酯。
9.聚酰胺稳定剂，例如与碘和/或磷化合物组合的铜盐和二价锰盐。
10.碱性共稳定剂，例如三聚氰胺、聚乙烯吡咯烷酮、双氰胺、氰脲酸三烯丙基酯、脲衍生物、肼衍生物、胺、聚酰胺、聚氨酯、高级脂肪酸的碱金属盐和碱土金属盐，例如硬脂酸钙、硬脂酸锌、山酸镁、硬脂酸镁、蓖麻醇酸钠和棕榈酸钾、焦儿茶酸锑或焦儿茶酸锌。
11.成核剂，例如无机物质如滑石，金属氧化物如二氧化钛或氧化镁，优选碱土金属的 磷酸盐、碳酸盐或硫酸盐；有机化合物如单-或聚羧酸及其盐，例如4-叔丁基苯甲酸、己二酸、二苯基乙酸、琥珀酸钠或苯甲酸钠；聚合化合物如离子共聚物(离聚物)。尤其优选为1，3：2，4-双(3’，4’-二甲基亚苄基)山梨糖醇、1，3：2，4-二(对甲基二亚苄基)山梨糖醇和1，3：2，4-二(亚苄基)山梨糖醇。
12.其他添加剂，例如增塑剂、润滑剂、乳化剂、颜料、流变添加剂、催化剂、流动调节剂、荧光增白剂、阻燃剂、抗静电剂和发泡剂。
优选的添加剂B为：
1)本发明以外的其它紫外线吸收剂。
2)加工添加剂如防滑/防结块添加剂、增塑剂、荧光增白剂、抗静电剂和发泡剂。
3)抗氧化剂。
本发明可以使用的聚合物是热固性和/或热塑性聚合物，选自以下物质中的一种或一种以上：
1.单烯烃和二烯烃的聚合物，例如聚丙烯、聚异丁烯、聚丁烯、聚4-甲基戊烯、聚乙烯基环己烷、聚异戊二烯或聚丁二烯、以及环烯烃的聚合物，例如环戊烯或降冰片烯的聚合物，聚乙烯(可任选交联)，例如高密度聚乙烯(HDPE)、高密度和高分子量聚乙烯(HDPE-HMW)、高密度和超高分子量聚乙烯(HDPE-UHMW)、中密度聚乙烯(MDPE)、低密度聚乙烯(LDPE)、线性低密度聚乙烯(LLDPE)。
2.在1中提及的聚合物的混合物，例如聚丙烯与聚异丁烯的混合物、聚丙烯与聚乙烯的混合物(例如PP/HDPE、PP/LDPE)以及不同类型聚乙烯的混合物(例如LDPE/HDPE)。
3.单烯烃和二烯烃彼此之间或与其他乙烯基单体的共聚物，例如乙烯/丙烯共聚物、线性低密度聚乙烯(LLDPE)及其与低密度聚乙烯(LDPE)的混合物、丙烯/丁-1-烯共聚物、丙烯/异丁烯共聚物、乙烯/丁-1-烯共聚物、乙烯/己烯共聚物、乙烯/甲基戊烯共聚物、乙烯/庚烯共聚物、乙烯/辛烯共聚物、乙烯/乙烯基环己烷共聚物、乙烯/环烯烃共聚物(例如乙烯/降冰片烯，例如COC)、乙烯/1-烯烃共聚物(其中1-烯烃原位产生)；丙烯/丁二烯共聚物、异丁烯/异戊二烯共聚物、乙烯/乙烯基环己烯共聚物、乙烯/丙烯酸烷基酯共聚物、乙烯/甲基丙烯酸烷基酯共聚物、乙烯/乙酸乙烯酯共聚物或乙烯/丙烯酸共聚物及其盐(离聚物)、以及乙烯与丙烯及二烯(例如己二烯、二环戊二烯或亚乙基降冰片烯)的三元共聚物；和这些共聚物彼此之间的混合物以及与上述1)中提及的聚合物的混合物，例如聚丙烯/乙烯-丙烯共聚物、LDPE/乙烯-乙酸乙烯酯共聚物(EVA)、LDPE/乙烯-丙烯酸共聚物(EAA)、LLDPE/EVA、LLDPE/EAA及其与其他聚合物(如聚酰胺)的混合物。
4.烃树脂(例如C5-C9)，包括其氢化改性产物(例如增粘剂)及聚亚烷基和淀粉的混合物。 1-4的均聚物及共聚物可具有任何立体结构，包括间规、等规、半等规或无规；其中优选无规聚合物。也包括立体嵌段聚合物。
5.聚苯乙烯、聚对甲基苯乙烯、聚α-甲基苯乙烯。
6.衍生自乙烯基芳族单体的芳族均聚物和共聚物，所述单体包括苯乙烯、α-甲基苯乙烯、乙烯基甲苯的所有异构体，特别是对乙烯基甲苯、乙基苯乙烯的所有异构体、丙基苯乙烯、乙烯基联苯、乙烯基萘和乙烯基蒽及其混合物。均聚物和共聚物可具有任何立体结构，包括间规、等规、半等规或无规；其中优选无规聚合物。也包括立体嵌段聚合物。
6a.包括上述乙烯基芳族单体及选自下述共聚单体的共聚物：乙烯、丙烯、二烯、腈、酸、马来酸酐类、马来酰亚胺类、乙酸乙烯酯和氯乙烯或丙烯酸系衍生物及其混合物，例如苯乙烯/丁二烯、苯乙烯/丙烯腈、苯乙烯/乙烯(共聚物)、苯乙烯/甲基丙烯酸烷基酯、苯乙烯/丁二烯/丙烯酸烷基酯、苯乙烯/丁二烯/甲基丙烯酸烷基酯、苯乙烯/马来酸酐、苯乙烯/丙烯腈/丙烯酸甲酯；苯乙烯共聚物与其他聚合物(例如聚丙烯酸酯、二烯聚合物或乙烯/丙烯/二烯三元共聚物)的高抗冲混合物；以及苯乙烯的嵌段共聚物如苯乙烯/丁二烯/苯乙烯、苯乙烯/异戊二烯/苯乙烯、苯乙烯/乙烯/丁烯/苯乙烯或苯乙烯/乙烯/丙烯/苯乙烯。
6b.由上述6中提及的聚合物氢化衍生的氢化芳族聚合物，尤其是包括由无规聚苯乙烯氢化制得的聚环己基乙烯(PCHE)，通常称为聚乙烯基环己烷(PVCH)。
6c.由上述6a中提及的聚合物氢化衍生的氢化芳族聚合物。
7.乙烯基芳族单体(如苯乙烯或α-甲基苯乙烯)的接枝共聚物，例如苯乙烯接枝的聚丁二烯、苯乙烯接枝的聚丁二烯-苯乙烯或聚丁二烯-丙烯腈共聚物；苯乙烯和丙烯腈(或甲基丙烯腈)接枝的聚丁二烯；苯乙烯、丙烯腈和甲基丙烯酸甲酯接枝的聚丁二烯；苯乙烯和马来酸酐接枝的聚丁二烯；苯乙烯、丙烯腈和马来酸酐或马来酰亚胺接枝的聚丁二烯；苯乙烯和马来酰亚胺接枝的聚丁二烯；苯乙烯和丙烯酸烷基酯或甲基丙烯酸烷基酯接枝的聚丁二烯；苯乙烯和丙烯腈接枝的乙烯/丙烯/二烯三元共聚物；苯乙烯和丙烯腈接枝的聚丙烯酸烷基酯或聚甲基丙烯酸烷基酯；苯乙烯和丙烯腈接枝的丙烯酸酯/丁二烯共聚物、及其与6)中所列共聚物的混合物，例如称为ABS、MBS、ASA或AES聚合物的共聚物的混合物。
8.含卤素的聚合物，例如聚氯丁二烯、氯化橡胶、异丁烯-异戊二烯的氯化或溴化共聚物(卤丁橡胶)、氯化或氯磺化聚乙烯、乙烯和氯化乙烯的共聚物、表氯醇均聚物及共聚物，尤其是含卤素的乙烯基化合物的聚合物，例如聚氯乙烯、聚偏二氯乙烯、聚氟乙烯、聚偏二氟乙烯；及其共聚物如氯乙烯/偏二氯乙烯、氯乙烯/乙酸乙烯酯或偏二氯乙烯/乙酸乙烯酯共聚物。
9.衍生自α，β-不饱和酸及其衍生物的聚合物，例如聚丙烯酸酯和聚甲基丙烯酸酯；聚甲基丙烯酸甲酯、聚丙烯酰胺和聚丙烯腈，其用丙烯酸丁酯进行抗冲击改性。
10.在9中所提及的单体彼此之间的共聚物或与其他不饱和单体的共聚物，例如丙烯腈/丁二烯共聚物、丙烯腈/丙烯酸烷基酯共聚物、丙烯腈/丙烯酸烷氧基烷基酯或丙烯腈/乙烯基卤共聚物或丙烯腈/甲基丙烯酸烷基酯/丁二烯三元共聚物。
11.衍生自不饱和醇及胺或其酰基衍生物或缩醛的聚合物，例如聚乙烯醇、聚乙酸乙烯酯、聚硬脂酸乙烯酯、聚苯甲酸乙烯酯、聚马来酸乙烯酯、聚乙烯醇缩丁醛、聚邻苯二甲酸烯丙基酯或聚烯丙基三聚氰胺；及其与上述1中所提及的烯烃的共聚物。
12.环醚的均聚物和共聚物，例如聚亚烷基二醇、聚氧化乙烯、聚氧化丙烯或其与二缩水甘油基醚的共聚物。
13.聚缩醛如聚甲醛和含有氧化乙烯作为共聚单体的那些聚甲醛；用热塑性聚氨酯、丙烯酸酯或MBS改性的聚缩醛。
14.聚苯醚和聚苯硫醚、以及聚苯醚与苯乙烯聚合物或聚酰胺的混合物。
15.聚氨酯，其一方面衍生自羟基封端的聚醚、聚酯或聚丁二烯，另一方面衍生自脂族或芳族多异氰酸酯及其前体。
16.聚酰胺和共聚酰胺，其衍生自二胺和二羧酸和/或衍生自氨基羧酸或相应内酰胺，例如聚酰胺4、聚酰胺6、聚酰胺6/6、6/10、6/9、6/12、4/6、12/12、聚酰胺11、聚酰胺12、由间二甲苯二胺和己二酸获得的芳族聚酰胺；在存在或不存在作为改性剂的弹性体下由六亚甲基二胺与间苯二甲酸和/或对苯二甲酸制备的聚酰胺，例如聚-2，4，4-三甲基六亚甲基对苯二甲酰胺或聚间亚苯基间苯二甲酰胺；以及上述聚酰胺与聚烯烃、烯烃共聚物、离聚物或化学键合或接枝的弹性体的嵌段共聚物；或与聚醚，例如与聚乙二醇、聚丙二醇或聚四亚甲基二醇的嵌段共聚物；以及用EPDM或ABS改性的聚酰胺或共聚酰胺；以及在加工过程中缩合的聚酰胺(RIM聚酰胺体系)。
17.聚酯，其衍生自二羧酸和二醇和/或衍生自羟基羧酸或相应的内酯或交酯，例如聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚-1，4-二羟甲基环己烷对苯二甲酸酯、聚萘二甲酸亚烷基酯和聚羟基苯甲酸酯以及衍生自羟基封端聚醚的共聚醚酯；以及用聚碳酸酯或MBS改性的聚酯。共聚酯可包括，例如(但不限于)：聚琥珀酸丁二醇酯/对苯二甲酸丁二醇酯、聚己二酸丁二醇酯/对苯二甲酸丁二醇酯、聚己二酸四亚甲基酯/对苯二甲酸四亚甲基酯、聚琥珀酸丁二醇酯/己二酸丁二醇酯、聚琥珀酸丁二醇酯/碳酸酯、聚-3-羟基丁酸酯/3-羟基辛酸酯共聚物、聚-3-羟基丁酸酯/3-羟基己酸酯/3-羟基癸酸酯三元共聚物。此外，脂族聚酯可包括，例如(但不限于)：聚(羟基链烷酸酯)类，尤其为聚丙内酯、聚丁内酯、聚新戊内酯、聚戊内酯和聚己内酯、聚琥珀酸乙二醇酯、聚琥珀酸丙二醇酯、聚琥珀酸丁二醇酯、聚琥珀酸六亚甲基酯、聚己二酸乙二醇酯、聚己二酸丙二醇酯、聚己二酸丁二醇酯、聚己二酸六亚甲基酯、 聚草酸乙二醇酯、聚草酸丙二醇酯、聚草酸丁二醇酯、聚草酸六亚甲基酯、聚癸二酸乙二醇酯、聚癸二酸丙二醇酯、聚癸二酸丁二醇酯及聚乳酸(PLA)以及用聚碳酸酯或MBS改性的相应聚酯。术语“聚乳酸(PLA)”表示优选为聚-L-丙交酯的均聚物及其与其他聚合物的任何共混物或合金；乳酸或丙交酯与其他单体的共聚物，所述其他单体例如羟基羧酸如乙醇酸、3-羟基丁酸、4-羟基丁酸、4-羟基戊酸、5-羟基戊酸、6-羟基己酸及其环状形式；术语“乳酸”或“丙交酯”包括L-乳酸、D-乳酸、其混合物及二聚物，即L-丙交酯、D-丙交酯、内消旋丙交酯及其任何混合物。
18.聚碳酸酯和聚酯碳酸酯。
19.聚酮。
20.聚砜、聚醚砜和聚醚酮。
21.交联聚合物，其一方面衍生自醛，另一方面衍生自酚类、脲类和三聚氰胺类，例如苯酚/甲醛树脂、尿素/甲醛树脂及三聚氰胺/甲醛树脂。
22.干性和非干性醇酸树脂。
23.不饱和聚酯树脂，其衍生自饱和和不饱和二羧酸与多元醇以及作为交联剂的乙烯基化合物的共聚酯，及其低可燃性的含卤改性产物。
24.可交联丙烯酸系树脂，其衍生自取代的丙烯酸酯，例如丙烯酸环氧酯、氨基甲酸酯丙烯酸酯或聚酯丙烯酸酯。
25.用三聚氰胺树脂、尿素树脂、异氰酸酯、异氰脲酸酯、多异氰酸酯或环氧树脂交联的醇酸树脂、聚酯树脂和丙烯酸酯树脂。
26.交联环氧树脂，其衍生自脂族、脂环族、杂环族或芳族缩水甘油基化合物，例如双酚A及双酚F的二缩水甘油醚的产物，其在存在或不存在促进剂下使用常规硬化剂如酸酐或胺交联。
27.上述聚合物的共混物(聚合物共混物)，例如PP/EPDM、聚酰胺/EPDM或ABS、PVC/EVA、PVC/ABS、PVC/MBS、PC/ABS、PBTP/ABS、PC/ASA、PC/PBT、PVC/CPE、PVC/丙烯酸酯、POM/热塑性PUR、PC/热塑性PUR、POM/丙烯酸酯、POM/MBS、PPO/HIPS、PPO/PA66及共聚物、PA/HDPE、PA/PP、PA/PPO、PBT/PC/ABS或PBT/PET/PC。
28.天然和合成的有机材料，其为纯单体化合物或这些化合物的混合物，例如矿物油、动物和植物脂肪、油和蜡、或基于合成酯(例如邻苯二甲酸酯、己二酸酯、磷酸酯或偏苯三酸酯)的油、脂肪和蜡、以及合成酯与矿物油的任意重量比的混合物，典型地为用作纺丝组合物的那些、以及这些材料的水性乳液。
优选的有机材料为：
1)烯烃单体如乙烯和丙烯以及更高级1-烯烃如1-丁烯、1-戊烯、1-己烯或1-辛烯的均聚物 和共聚物。优选聚乙烯LDPE和LLDPE、HDPE和聚丙烯。
2)烯烃单体与二烯烃单体如丁二烯、异戊二烯和环烯烃如降冰片烯的均聚物和共聚物。
3)一种或多种1-烯烃和/或二烯烃与一氧化碳和/或与其他乙烯基单体，包括但不限于乙酸乙烯酯、乙烯基酮、苯乙烯、马来酸酐和氯乙烯的共聚物。
4)聚乙烯醇。
5)其他热塑性塑料如聚苯乙烯、苯乙烯-丙烯腈共聚物、丙烯腈-丁二烯-苯乙烯共聚物、聚氯乙烯、聚偏二氯乙烯、聚乙酸乙烯酯、聚乙烯醇丁醛、乙烯-乙烯醇共聚物、聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、液晶聚酯(LCP)、聚缩醛(例如POM)、聚酰胺(PA)、聚碳酸酯、聚氨酯和聚苯硫醚(PPS)；两种或更多种这些树脂形成的聚合物共混物或聚合物合金；以及通过添加填料如玻璃纤维、碳纤维、半碳化纤维、纤维素纤维和玻璃珠、阻燃剂、发泡剂、抗微生物剂、交联剂、聚烯烃树脂细粉、聚烯烃蜡、亚乙基双酰胺蜡、金属皂等单独或组合至这些树脂获得的化合物。另一方面，热固性树脂的实例可包括热固性树脂如环氧树脂、蜜胺树脂和不饱和聚酯树脂；以及通过掺入填料如玻璃纤维、碳纤维、半碳化纤维、纤维素纤维和玻璃珠、阻燃剂等单独或组合至这些树脂获得的化合物。
其他优选的聚合物为：天然或合成来源的可生物降解聚合物，包括但不限于聚琥珀酸乙二醇酯，聚琥珀酸丁二醇酯，聚琥珀酸丁二醇酯/己二酸丁二醇酯，聚琥珀酸丁二醇酯/碳酸丁二醇酯，聚琥珀酸丁二醇酯/对苯二甲酸丁二醇酯，聚己内酯，聚(羟基链烷酸酯)，聚-3-羟基丁酸酯，聚乳酸，聚酯酰胺或这些材料与天然或改性淀粉、多糖、木素、木粉、纤维素或几丁质的共混物。
所述聚合物优选为热塑性天然或合成聚合物，尤其是选自上述组中的一种。优选聚烯烃均聚物或共聚物，淀粉改性聚烯烃或淀粉基聚合物复合材料，特别优选聚乙烯、聚丙烯、聚乙烯共聚物或聚丙烯共聚物。
所述填料包括：例如碳酸钙、二氧化硅、玻璃纤维、玻璃泡、滑石、高岭土、云母、硫酸钡、金属氧化物和氢氧化物、炭黑、石墨、木粉、其他天然产物的粉、合成纤维、用作填料的硬脂酸盐如硬脂酸钙或硬脂酸锌。
本发明的聚合物模塑组合物适用于生产纤维、涂料、膜或模塑品。
本发明还提供一种用于制备聚合物组合物的方法，包括将本发明的聚合物添加剂和/或本发明聚合物添加剂组合物与聚合物粒料和/或填料在混合机中混合，和在相对高的温度下在挤出机装置中将它们在聚合物熔体中匀化，并随后引出该匀化的聚合物挤出物，冷却，切粒。挤出机装置选自单螺杆挤出机，或双螺杆挤出机。优选的加工温度对于聚苯乙烯是170至200℃，对于聚丙烯是200至300℃，对于聚对苯二甲酸乙二醇酯(PET)是250至290℃，对于 聚对苯二甲酸丁二醇酯(PBT)是230至270℃，对于聚酰胺-6(PA6)是260至290℃，对于聚酰胺-66(PA66)是260至290℃，和对于聚碳酸酯是280至320℃。可用于本发明的配混组合装置是单螺杆挤出机，或双螺杆挤出机，用于本发明的有效螺杆长度在单螺杆挤出机的情况下是20至40D；本发明中的有效螺杆长度在双螺杆挤出机的情况下是8至48D。
具体实施方式
下面通过具体实施方式来进一步说明本发明，以下实施例为本发明较佳的实施方式，但本发明的实施方式并不受下述实施例的限制。
实施例1：制备
Figure PCTCN2016111244-appb-000007
将288g 2-硝基-2-羟基-5-甲基偶氮苯，160g氢氧化钠(质量浓度50％)，380g邻二甲苯和水加入到一个1000ml的反应器中，控制温度在60-80℃，缓慢的加入45g的红磷作为还原剂。搅拌3小时后，反应完成，然后用高效液相色谱(HPLC)进行分析。第一步还原的完成可以通过用作起始原料的2-硝基-2-羟基-5-甲基偶氮苯的消失以及2-(2-羟基-5-苯甲基)-苯并三唑氮氧化物的生成得以证实。使用硫酸中和上述反应产物后，下部分的水层经分离被除去，再将剩下的部分用水洗涤。
随后，将380g水和50g氢碘酸(质量浓度56％)加入到产物溶液中，然后控制温度为60-80℃进行第二步还原反应。搅拌反应2.5小时后反应完成，通过过滤、分离除去下半部分的水层，再加入600g甲醇对产物进行结晶。洗涤得到的固体物质并烘干得到194.2g高纯度的2-(2-羟基-5-苯甲基)-苯并三唑，测得产物的安定角为50°。
实施例2：制备
Figure PCTCN2016111244-appb-000008
将173g 2-硝基-4-氯-2-羟基-3-叔丁基-5-甲基偶氮苯，46g氢氧化钠(质量浓度50％)，对苯二酚，207g作为溶剂的邻二甲苯和104g水加入到一个1000ml的反应器中，控制温度在70-96℃，缓慢的加入42.1g作为还原剂的红磷。搅拌5小时后，反应完成，然后用HPLC进行分析。第一步还原反应的完成可以从用作原材料的2-硝基-4-氯-2-羟基-3-叔丁基-5-甲基偶氮苯已经消失，以及产生2-(2-羟基-3-叔丁基-5-甲基苯基)-5-氯-苯并三唑-氮氧化物得到证实。使用硫酸中和反应产物后，下部分的水层经分离被移去，再将剩下部分用水洗涤。
随后，将200g水和39.6g氢碘酸(质量浓度56％)一次性加入到产物溶液中，然后控制温度为70-80℃，进行第二步还原反应。搅拌反应1.5小时后反应完成，通过过滤、分离除去下半部分的水层，加入400g甲醇对产物进行结晶处理。洗涤得到的固体物质，烘干后制得84.1g高纯度的2-(2-羟基-3-叔丁基-5-甲基苯基)-5-氯-苯并三唑。测得产物的安定角为52°。
实施例3：制备
Figure PCTCN2016111244-appb-000009
将173g 2-硝基-4-氯-2-羟基-3-叔丁基-5-甲基偶氮苯，46g氢氧化钠(质量浓度50％)，对苯二酚，207g作为溶剂的邻二甲苯和104g水加入到一个1000ml的反应器中，控制温度在70-96℃，缓慢的加入42.1g作为还原剂的红磷。搅拌5小时后，反应完成，然后用HPLC进行分析。第一步还原反应的完成可以从用作原材料的2-硝基-4-氯-2-羟基-3-叔丁基-5-甲基偶氮苯已经消失，以及产生2-(2-羟基-3-叔丁基-5-甲基苯基)-5-氯-苯并三唑-氮氧化物得到证实。使用硫酸中和反应产物后，下部分的水层经分离被移去，再将剩下部分用水洗涤。
随后，将200g水加入到产物溶液中，然后控制温度为70-80℃，逐滴加入39.6g氢碘酸(质量浓度56％)持续30分钟以上，进行第二步还原反应。搅拌反应1.5小时后反应完成，通过过滤、分离除去下半部分的水层，加入400g甲醇对产物进行结晶处理。洗涤得到的固体物质，烘干后制得85.2g高纯度的2-(2-羟基-3-叔丁基-5-甲基苯基)-5-氯-苯并三唑。测得产物的安定角为53°。
实施例4：制备
Figure PCTCN2016111244-appb-000010
采用与实施例2相同的方法，只是使用183g 2-硝基-4-氯-2-羟基-3，5-二叔丁基偶氮苯为最初始的原料，结果得到90.6g高纯度的2-(2-羟基-3，5-二叔丁基苯基)-5-氯-苯并三唑。测得产物的安定角为52°。
实施例5：制备
Figure PCTCN2016111244-appb-000011
采用与实施例3相同的方法，只是使用183g 2-硝基-4-氯-2-羟基-3，5-二叔丁基偶氮苯为最初始的原料，结果得到91.2g高纯度的2-(2-羟基-3，5-二叔丁基苯基)-5-氯-苯并三唑。测得产物的安定角为56°。
实施例6：制备
Figure PCTCN2016111244-appb-000012
采用与实施例3相同的方法，只是使用362g 2-硝基-2-羟基-3，5-二-α，α-二甲基苄基偶氮苯为最初始的原料，结果得到178.2g高纯度2-(2-羟基-3，5-二-α，α-二甲基苄基苯基)-2-氢-苯并三唑。测得产物的安定角为54°。
对比例1：制备
Figure PCTCN2016111244-appb-000013
将288g 2-硝基-2-羟基-5-甲基偶氮苯，160g氢氧化钠(质量浓度50％)，380g邻二甲苯和水加入到一个1000ml的反应器中，控制温度在60-80℃，缓慢的加入45g的水合肼(质量浓度为80％)作为还原剂。搅拌2.5小时后，反应完成，然后用高效液相色谱(HPLC)进行分析。第一步还原的完成可以通过用作起始原料的2-硝基-2-羟基-5-甲基偶氮苯的消失以及2-(2-羟基-5-苯甲基)-苯并三唑氮氧化物的生成得以证实。使用硫酸中和上述反应产物后，下部分的水层经分离被除去，再将剩下的部分用水洗涤。
随后，将380g水和85.2g锌粉加入到产物溶液中，然后控制温度为60-80℃逐滴加入150g硫酸(质量浓度为95％)，滴加持续30分钟以上，进行第二步还原反应。搅拌反应2小时后反应完成，通过过滤除去未反应的锌粉，分离除去下半部分的水层，再加入600g甲醇对产物进行结晶。洗涤得到的固体物质并烘干得到195.8g高纯度的2-(2-羟基-5-苯甲基)-苯并三唑，测得产物的安定角为44°。
对比例2：制备
Figure PCTCN2016111244-appb-000014
将173g 2-硝基-4-氯-2-羟基-3-叔丁基-5-甲基偶氮苯，46g氢氧化钠(质量浓度50％)，对苯二酚，207g作为溶剂的邻二甲苯和104g水加入到一个1000ml的反应器中，控制温度在70-96℃，缓慢的逐滴加入15.5g作为还原剂的水合肼(质量浓度为80％)，持续40分钟以上。搅拌4小时后，反应完成，然后用HPLC进行分析。第一步还原反应的完成可以从用作原材料的2-硝基-4-氯-2-羟基-3-叔丁基-5-甲基偶氮苯已经消失，以及产生2-(2-羟基-3-叔丁基-5-甲基苯基)-5-氯-苯并三唑-氮氧化物得到证实。使用硫酸中和反应产物后，下部分的水层经分离被移去，再将剩下部分用水洗涤。
随后，将207g水和34g锌粉加入到产物溶液中，然后控制温度为60-80℃，逐滴加入63g硫酸(质量浓度为95％)持续40分钟以上，进行第二步还原反应。搅拌反应1小时后反应完成，过滤除去未反应的锌粉，通过分离除去下半部分的水层，加入400g甲醇对产物进行结晶处理。
洗涤得到的固体物质，烘干后制得86.5g高纯度的2-(2-羟基-3-叔丁基-5-甲基苯基)-5-氯-苯并三唑。测得产物的安定角为43°。
对比例3：制备
Figure PCTCN2016111244-appb-000015
采用与对比例2相同的方法，只是使用183g 2-硝基-4-氯-2-羟基-3，5-二叔丁基偶氮苯为最初始的原料，结果得到90.6g高纯度的2-(2-羟基-3，5-二叔丁基苯基)-5-氯-苯并三唑。测得产物的安定角为45°。
对比例4：制备
Figure PCTCN2016111244-appb-000016
采用与对比例2相同的方法，只是使用362g 2-硝基-2-羟基-3，5-二-α，α-二甲基苄基偶氮苯为最初始的原料，结果得到179.6g高纯度2-(2-羟基-3，5-二-α，α-二甲基苄基苯 基)-2-氢-苯并三唑。测得产物的安定角为43°。
实施例7-12，对比例5-8
将实施例1-6、对比例1-4所得的产物在按表1和表2所述产品组分重量份数称取。
聚丙烯：巴塞尔，EP548R
聚苯乙烯：扬子巴斯夫，158K
抗氧剂：巴斯夫，Irganox 1010
玻璃纤维：PPG，Chop Vantage 3540
滑石粉：Luzenac R7
当聚合物选自聚丙烯时，将上述聚丙烯和其它各组分先放入转速约为1000rpm的高速混合器中干混合1分钟，如有滑石粉，则加入滑石粉填料再混合3分钟。将混合的原料置于双螺杆挤出机中经熔融挤出，造粒，其工艺条件为：一区200℃，二区210℃，三区220℃，四区215℃；双螺杆挤出机长径比为35，螺杆转速为450转/分钟，停留时间为1分钟，压力为10Mpa。
当聚合物选自聚苯乙烯时，将上述聚丙烯和其它各组分先放入转速约为1000rpm的高速混合器中干混合3分钟，将混合的原料置于双螺杆挤出机中经熔融挤出，造粒，其工艺条件为：螺筒各分区温度保持在200℃，双螺杆挤出机长径比为35，螺杆转速为450转/分钟；停留时间为1分钟，压力为10Mpa。
当聚合物选自聚酰胺时，将上述聚酰胺和其它各组分先放入转速约为1000rpm的高速混合器中干混合3分钟，将混合的原料置于双螺杆挤出机中经熔融挤出，造粒，其工艺条件为：一区温度230℃，二区温度250℃，三区温度250℃，四区温度250℃，五区温度240℃，六区温度240℃，七区温度240℃，八区温度230℃，九区温度230℃；；双螺杆挤出机长径比为35，螺杆转速为450转/分钟，停留时间为1分钟，压力为10Mpa。
表1(重量份数)
Figure PCTCN2016111244-appb-000017
Figure PCTCN2016111244-appb-000018
表2(重量份数)
Figure PCTCN2016111244-appb-000019
毛边形成测试：
用于测定毛边形成的工具是双板模具，其具有带有中心浇注口的六臂型测试体。所述臂的长度、宽度和厚度为90×10×1.5mm。通风口位于每一臂的前端和末端。位于流径端的通风口具有不同的间隙尺寸。如图1所示，各个通风口的间隙尺寸是0、4、8、12、20和30μm。通风口的宽度是2.95mm(见图2)。测试体的毛边长度G(见图3)在具有30μm尺寸的通风 间隙的所述臂的流径端被评估。图2和3示出测试体的具有30μm通风间隙尺寸的臂的端部，该部件不是按比例而是示意性地示出，以便能够从中看出操作原理。在图3中，材料的毛边凸出并超出测试体的臂的末端，它在流径端透入通风间隙内，为了说明起见图3是夸张地放大，且毛边长度G被标明。
这些测试体由型号为Krauss Maffei100-380CX的注塑成型机制造。这些部件是手动移除，否则的话会对毛边产生损坏。注塑速度是100mm/s，螺杆转速为50RPM，动态压力是100巴，且保持压力为400巴。选用250℃作为熔化温度，而用90℃作为模具温度。
毛边长度G根据图像来确定，采用型号为Leica/Wild M420光学显微镜的显微镜在40-50倍的放大倍率来记录图像，通过采用2.0×的聚焦透镜，毛边在整个宽度上都被记录。毛边长度G从基线(测试体端部)和测量线之间的距离产生。该测量线是拟定的，使得凹陷和凸起的区域可相互补偿(参见图3)。最终测得的毛边长度G是来自5个不同的测试体的测量值的算术平均值。
Figure PCTCN2016111244-appb-000020

Claims (10)

  1. 一种用于聚合物的添加剂A，具有如式I所示结构式的化合物：
    Figure PCTCN2016111244-appb-100001
    其中，R1，R2相同或不同，表示为H、C1-C8烷基或C6-C18芳基或芳烷基；R3为H或卤素。
  2. 如权利要求1所述的一种用于聚合物的添加剂A，其特征在于，所述式I所示结构式的化合物中：
    优选R1、R2不同，R1为H，R2为甲基，R3为H，表达为：
    Figure PCTCN2016111244-appb-100002
    优选R1、R2相同，为1，1-二甲基苯基，R3为H，表达为：
    Figure PCTCN2016111244-appb-100003
    优选R1、R2不同，R1为叔丁基，R2为甲基，R3为Cl，表达为：
    Figure PCTCN2016111244-appb-100004
    优选R1、R2相同，为叔丁基，R3为Cl，表达为：
    Figure PCTCN2016111244-appb-100005
  3. 如权利要求1至2任一项所述的一种用于聚合物的添加剂A，其特征在于，所述式I所示结构式的化合物的安定角是50°-56°，优选52°-54°。
  4. 如权利要求1至2任一项所述的一种用于聚合物的添加剂A，其特征在于，所述式I所示结构式的化合物的松散堆积密度为0.60g/cm3～0.75g/cm3，优选0.65g/cm3～0.70g/cm3。
  5. 根据权利要求1-4任一项所述的用于聚合物的添加剂A的制备方法，包括如下步骤：
    (a)使用或不使用相转化催化剂，在由非极性溶剂、水和一种碱性化合物组成的溶剂的存在下，向分子式为式II的化合物中加入红磷，进行第一步还原反应制得分子式为式III的化合物；和
    (b)使用或不使用相转化催化剂，向由步骤(a)制得的分子式为式III的化合物中加入水和氢碘酸，进行第二步还原反应，
    Figure PCTCN2016111244-appb-100006
    式II和式III中，R1，R2相同或不同，表示为H、C1-C8烷基、C6-C18芳基或芳烷基；R3为H或卤素。
  6. 根据权利要求5所述的用于聚合物的添加剂A制备方法，其特征在于步骤(a)所使用的非极性溶剂至少是选自下面所列溶剂中的一种：邻二甲苯，间二甲苯，对二甲苯以及他们的混合物，乙苯，甲苯和苯。
  7. 根据权利要求5所述的用于聚合物的添加剂A制备方法，其特征在于步骤(a)和步骤(b)中使用的相转化催化剂至少是选自下面所列物质中的一种：四乙基苄基氯化胺，四丁基氯化胺，四丁基溴化铵，对苯二酚和邻苯二酚。
  8. 根据权利要求1～4任一项所述用于聚合物的添加剂A用作紫外线吸收剂的用途。
  9. 一种包含权利要求1～4任一项所述用于聚合物的添加剂A的热塑性和/或热固性聚合物组合物。
  10. 根据权利要求9中所述的聚合物组合物，包含重量份数为30-99.9份的聚合物，重量份数为0-60份的填料，重量份数为0.1-10份的权利要求1～4中至少一项所要求的用于聚合物的添加剂A，重量份数为0-5份的用于聚合物的添加剂B，所述聚合物为聚丙烯、聚乙烯、ABS、聚苯乙烯、聚酰胺、聚氯乙烯、聚酯、聚甲醛中的一种或多种组合物，优选聚丙烯、聚苯乙烯、聚酰胺、聚酯中的一种或多种。
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