WO2017140173A1 - Additif utilisé pour un polymère, sa composition d'additif et sa composition polymère - Google Patents

Additif utilisé pour un polymère, sa composition d'additif et sa composition polymère Download PDF

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WO2017140173A1
WO2017140173A1 PCT/CN2016/111239 CN2016111239W WO2017140173A1 WO 2017140173 A1 WO2017140173 A1 WO 2017140173A1 CN 2016111239 W CN2016111239 W CN 2016111239W WO 2017140173 A1 WO2017140173 A1 WO 2017140173A1
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additive
polymer
tert
butyl
ppm
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黄秀茹
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黄秀茹
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    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • 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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/50—Phosphorus bound to carbon only
    • 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
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • 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
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K2003/026—Phosphorus
    • 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 A for a polymer, an additive composition composed thereof, a polymer composition and use thereof as a light stabilizer.
  • Existing benzotriazole compounds are widely used in the field of polymer additives, and can be used in light stabilizers, etc., which are known to be synthesized by different methods, mainly from azobenzene compounds as raw materials, according to different reduction processes. Perform cyclization.
  • the existing reduction methods include: hydrazine hydrate reduction method, zinc powder reduction method, sulfide reduction method, and the like.
  • the benzotriazole-based light stabilizer is prepared by one-step method using hydrazine hydrate as a reducing agent.
  • the reported patents include US4001266, DE2454889, FR2292708, etc.
  • the other method is hydrazine hydrate-zinc powder method, which is based on azobenzene compounds.
  • the benzotriazole compound is used as an additive in a polymer, and is usually used for a light stabilizer or the like, but the adverse effect thereof is to cause a certain decrease in chemical resistance of the polymer, and the inventors have been greatly researched. It has been found that when a specific content of silicon-containing and phosphorus-containing substances is added to a benzotriazole compound, the corresponding chemical resistance of the polymer can be significantly improved.
  • R1, R2 are the same or different and are represented by H, C1-C6 alkyl or C6-C18 aryl;
  • R3 is H or halogen; wherein, based on the total weight of the additive A, the weight of the silicon element is 5 ppm to 900 ppm, It is preferably 20 ppm to 400 ppm, more preferably 30 ppm to 200 ppm, and the phosphorus element has a weight content of 1 ppm to 980 ppm, preferably 10 ppm to 400 ppm, more preferably 25 ppm to 200 ppm, based on the total weight of the additive A. .
  • the silicon element is derived from a silicon-containing substance
  • the silicon-containing substance is selected from the group consisting of sodium silicate, sodium metasilicate, monocalcium silicate, dicalcium silicate, calcium magnesium silicate, calcium metasilicate mineral, bentonite
  • the silicon material may also be selected from the group consisting of silicone resins, alkoxysilanes, and polysiloxanes.
  • the silicon-containing substance may be one or a combination of the above.
  • the monocalcium silicate, dicalcium silicate, calcium magnesium silicate, sodium silicate, sodium metasilicate are all products currently on the market, and calcium metasilicate minerals (wollastonite) are a natural product.
  • the non-metallic minerals have a chemical formula of CaSiO 3 , usually a needle-like, fibrous aggregate, and the color is white.
  • the calcium metasilicate mineral used in the present invention is, for example, Lishu County Shuofeng Powder Material Factory, Beijing Hengye COSCO Calcium metasilicate mineral produced by Chemical Co., Ltd.
  • the bentonite is a non-metallic mineral with montmorillonite as a main mineral component, and the montmorillonite structure is a 2:1 type crystal structure composed of two silicon oxide tetrahedrons sandwiched by an aluminum octahedron, which is used in the present invention.
  • Bentonite can be various types of bentonite, such as Shandong Xianquan bentonite plant, and sodium bentonite produced by Xinyang Jiaxin bentonite plant.
  • the silicone resin can be any of various types of resin copolymers described in detail in U.S. Patent No. 5,695,551 (December 9, 1999). However, most of the preferred applications herein are those resin copolymers as described below:
  • a siloxane of a resin copolymer prepared by a method comprising the steps of: (i) forming a silanol comprising a resin copolymer siloxane having R" 3 SiO 1/2 units and SiO 4/2 units; Wherein b and c are a positive integer and an acidic homogenous mixture of an organohydrogenpolysiloxane of an exemplary R" b H c SiO (4-bc)/2 and an organic solvent of less than 4, preferably 1.9 to 2.1, and (ii) The mixture is heated to remove substantially all of the organic solvent.
  • R" can be an alkyl group of 1 to 6 carbon atoms; an aryl group such as a phenyl group, a tolyl group and a xylyl group; an alkenyl group such as a vinyl group and an allyl group; or a trifluoropropyl group.
  • R" can also be an aralkyl group. a group such as ⁇ phenyl propyl; or an alicyclic group such as a cyclopentyl group, a cyclohexyl group and a cyclohexenyl group;
  • R" is directly as defined above. This resin contains 2.5% by weight of silicon-bonded OH groups. This resin may also contain R" 2 SiO 2/2 units and R"SiO 3/2 units.
  • a silicone resin which is particularly preferably suitable for use herein and which represents such a resin copolymer consists essentially of (CH 3 ) 3 SiO 1/2 units and SiO 2 units in a molar ratio close to 0.75:1 and contains 2.4-2.9.
  • the silicone resin can be a phenyl silsesquioxane resin, or a mixture of phenyl silsesquioxanes.
  • a phenyl silsesquioxane resin is an organopolysiloxane having at least one simple (C 6 H 5 SiO 3/2 ) siloxy unit, which is Containing (R 3 SiO 1/2 ), (R 2 SiO 2/2 ) or (SiO 4/2 ) siloxy units independently selected from the group wherein R can be any monovalent organic group (also referred to herein as It is a polymer of a siloxy unit of M, D, T, or Q unit).
  • siloxy units can be combined in various ways to form a cyclic, linear or branched structure.
  • the chemical and physical properties of such resulting polymer structures can vary.
  • organopolysiloxanes can be volatile or low viscosity fluids, high viscosity fluids/gums, elastomers or rubbers, and resins, depending on the choice of each siloxy unit in the organopolysiloxane.
  • the silsesquioxane is typically characterized as having at least one or several (RSiO 3/2 ) or T siloxy units.
  • such an organopolysiloxane suitable for use in the present disclosure may have (R 3 SiO 1/2 ), (R 2 SiO 2/2 ), (RSiO 3/2 ) or (SiO 4/2 ). Any combination of siloxy units, provided that it has at least one siloxy unit of the formula (C 6 H 5 SiO 3/2 ) wherein C 6 H 5 represents a phenyl group.
  • the phenyl silsesquioxane resin may have an average formula comprising at least 40 mol% of a simple formula (R' 2 SiO 2 having a monovalent hydrocarbon group in which x and y have a value of 0.05 to 0.95 and R' is 1 to 8 carbon atoms. /2 ) a siloxy unit of x (C 6 H 5 SiO 3/2 ) y .
  • x and y represent the molar fraction of R' 2 SiO 2/2 and C 6 H 5 SiO 3/2 siloxy units present in the phenyl silsesquioxane resin relative to each other (ie, D and T phenylsiloxy units).
  • the molar fraction of the R' 2 SiO 2/2 and C 6 H 5 SiO 3/2 siloxy units can each independently be from 0.05 to 0.95.
  • the R' 2 SiO 2/2 and C 6 H 5 SiO 3/2 siloxy units present must be combined to account for at least all of the siloxy units present in the phenyl silsesquioxane resin. 40 mol%, alternatively 80 mol%, or alternatively 95 mol%.
  • R' can be a linear or branched alkyl group such as ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl. Typically, R' is a methyl group.
  • the molecular weight of the phenyl silsesquioxane resin is not critical, but typically the number average molecular weight (as measured according to ASTM D5296-05 and calculated as polystyrene molecular weight equivalent) is between 500 and 10,000, or alternatively 500 to 2,000 g. /mol range.
  • the viscosity of the phenyl silsesquioxane at 25 ° C is not critical, but the typical viscosity should be less than 100 mPa.s (cP), alternatively in the range of 10 mPa.s (cP) - 50 mPa.s (cP) .
  • phenyl silsesquioxane resins suitable as disclosed herein include the following representative non-limiting examples: DOW CORNIN 3037 intermediate and DOW CORNING 3074 (Dow Corning Corp., Midland, MI).
  • the alkoxysilane can constitute a single alkoxysilane or can be a mixture of alkoxysilanes.
  • the alkoxysilane may have the formula R 8 a Si(OR 9 ) (4-3) .
  • R 8 represents an alkyl group having 1 to 30 carbon atoms, preferably 1 to 12 carbon atoms, an aryl group such as a phenyl group, or a halogenated alkyl group such as a chloropropyl group and a trifluoropropyl group.
  • the value of a is 1 or 2.
  • R 9 represents an alkyl group having 1 to 6 carbon atoms.
  • R 8 is n-octyl and R 9 is methyl or ethyl.
  • the alkoxysilane compound (B) is an alkyltrialkoxysilane having 1 to 12 carbon atoms in the alkyl chain and 1 to 6 carbon atoms in the alkoxy chain.
  • Some suitable alkoxysilanes are methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, ethyltributoxysilane, propyltrimethoxy Silane, propyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, butyltriethoxysilane, hexyltrimethoxysilane, n-octyltriethoxysilane , iso-octyltriethoxysilane, n-octyltrimethoxysilane, iso-octyltrimethoxysilane,
  • alkoxysilanes are commercially available from Dow Corning Corporation, Midland, Mich., and are described, for example, in U.S. Patent No. 5,300,327 (April 5, 1994), U.S. Patent No. 5,695,551 (December 9, 1997) And U.S. Patent No. 5,919,296 (JuI.6, July 6, 1999). Such alkoxysilanes are capable of partial hydrolysis and thus contain siloxane and/or silanol groups.
  • the polysiloxane is preferably a polydialkylsiloxane having the following general formula:
  • R 9 is as defined above and z represents the degree of polymerization and is greater than 1.
  • R 3 is H in the case of a hydroxyl terminated polymer or Si(CH 3 ) 3 .
  • the polydialkylsiloxane is a hydroxy or trimethylsilyl terminated polydimethylsiloxane having a degree of polymerization greater than 1, alternatively from 1 to 500, alternatively 5 -200, or alternatively 10-100.
  • the polysiloxane compound is a diorganosiloxane having from 1 to 12 carbon atoms per organic group.
  • the phosphorus element is derived from a phosphorus-containing substance, and the phosphorus-containing substance may be one or a combination of the following.
  • phosphorus-containing material refers to or includes elemental phosphorus as well as organic and inorganic phosphorus compounds and/or phosphorus-containing compounds and hydrolysates or salts thereof.
  • Elemental phosphorus is involved in four allotrope variants, white phosphorus, red phosphorus, black phosphorus and purple phosphorus. Depending on these basic types, different crystal structures are formed, which also brings about differences in physical properties and reactivity. Red phosphorus is preferably used in this patent.
  • Suitable inorganic phosphorus compounds advantageously include (poly)phosphates, such as unconcentrated salts of phosphorous acid or concentrated salts of phosphoric acid, such as ammonium phosphate and ammonium polyphosphate.
  • the organophosphorus compound (I) (II) of the formula (I) or (II) used in the present invention may be selected from an organophosphorus compound such as a monomeric organophosphorus compound, or a polymer organophosphorus compound, an inorganic phosphorus compound. And wherein R 1 , R 2 and R 3 independently of each other represent an organic or inorganic group known to the skilled person from the prior art.
  • the substituents or groups R are independent of one another and may be the same or different, or not at all.
  • the groups R may preferably be represented independently of each other: -H, substituted or unsubstituted C 1 -C 15 -alkyl, C 1 -C 15 -alkenyl, C 3 -C 8 -cycloalkyl, C 6 - C 18 -aryl, C 7 -C 30 -alkylaryl, C 1 -C 8 -alkoxy or C 1 -C 8 -alkylthio, or -OH or -SH and its alkali metal salt, alkaline earth metal Salt, ammonium salt.
  • alkyl moiety of the optional substituent R of the phosphorus compound of formula (I) represents a saturated and unsaturated aliphatic compound which may be unbranched or branched, with unsaturated groups being preferred.
  • the substituent R preferably includes a short-chain alkyl group having not more than 6, more preferably not more than 4 or 3, more preferably not more than 2 carbon atoms, or a phenyl group as an aryl group. Particularly useful phosphorus compounds are preferably as unsubstituted as possible.
  • Examples of those phosphorus compounds of the formula (I) or (II) are organophosphorus compounds and salts thereof, such as organic phosphorus compounds of monomers, including phosphate compounds, phosphoric acid amide ester compounds and phosphazene compounds, organic compounds of phosphorous acid. , such as phosphorous Acid esters, compounds of hypophosphorous acid, phosphines and phosphine oxides such as triphenylphosphine, triphenylphosphine oxide and toluene phosphine oxide.
  • R1 and R2 are different, R1 is H, R2 is a methyl group, and R3 is H, and the expression is:
  • 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:
  • R1 and R2 are the same, which is a tert-amyl group, and R3 is H, and the expression is:
  • R1 and R2 are different, R1 is 1,1 dimethylphenyl, R2 is 1,1,3,3-tetramethylbutyl, and R3 is H, expressed as:
  • R1 and R2 are different, R1 is H, R2 is a tert-octyl group, and R3 is H, and the expression is:
  • the invention also provides the use of an additive A for a polymer as a light stabilizer.
  • the invention also provides an additive composition comprising:
  • the above additive A, and at least one other additive B wherein the total weight content of the additive A is from 50 to 99.9%, preferably from 70 to 95% by weight based on the total weight of the additive composition, and the at least one other additive B is from 0.1 to 50 by weight. %; preferably 5 to 30%.
  • the other additive B is one or more of the following:
  • Antioxidants including the following types:
  • 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,
  • O-, N- and S-benzyl compounds for example 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, 4-hydroxy-3,5-di Octadecylmethylbenzyl mercaptoacetate, tridecyl 4-hydroxy-3,5-di-tert-butylbenzyl decylacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl Amine, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl) Sulfide, isooctyl 3,5-di-tert-butyl-4-hydroxybenzyl mercaptoacetate.
  • 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-hydroxy- 2,6-Dimethylbenzyl)isocyanurate, 2,4,6--
  • 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 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.
  • 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, Single with or without other ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid
  • Alkyl esters such as nickel salts of methyl or ethyl esters, nickel complexes of ketone oximes such as 2-hydroxy-4-methylphenylundecyl oxime, 1-phenyl-4-lauroyl-5-hydroxyl
  • a nickel complex of pyrazole with or without other ligands 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
  • 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
  • Oxalamides such as 4,4'-dioctyloxyoxalylamine, 2,2'-diethoxyoxalylaniline, 2,2'-dioctyloxy-5,5'-di-uncle Butyl oxanilide, 2,2'-bis(dodecyloxy)-5,5'-di-tert-butyloxalylanilide, 2-ethoxy-2'-ethyloxalylanilide , N,N'-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2'-ethyloxalylaniline and its 2-ethoxy- a mixture of 2'-ethyl-5,4'-di-tert-butyl oxalic acid anilide, a mixture of o- and p-methoxy disubstituted oxalanilide, and o- and p-ethoxy di
  • 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, tris(nonylphenyl) phosphite, phosphorous acid tris Lauryl ester, tris(octadecyl)phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite Ester, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl- 4-methylphenyl) pentaerythr
  • 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 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).
  • 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).
  • 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.
  • the present invention also provides a polymer composition
  • a polymer composition comprising the additive A for a polymer, or an additive composition of the composition of the additive A and the additive B, wherein the additive A or the additive composition consisting of the additive A and the additive B
  • the polymer composition has a weight content of 0.1 to 10%, the polymer has a weight content of 30 to 99.9%, and the filler has a weight content of 0 to 60%.
  • thermosetting and thermoplastic polymers 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 a polymer of an olefin, such as a polymer of cyclopentene or norbornene, Polyethylene (optional cross-linking), such as high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultra high molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE).
  • 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 chlorine a copolymer of ethylene, an epichlorohydrin homopolymer and a copolymer, especially a polymer of a halogen-containing vinyl compound, such as polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride; Copolymers such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.
  • halogen-containing polymers such as polychloroprene, chlorinated rubber, chlorinated or brominated copolymers of isobutylene isoprene (halogenated rubber), chlorinated or chloros
  • 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, propylene glycol oxalate, polybutylene oxalate, hexamethylene oxalate, polysebacic acid
  • Ethylene glycol esters polypropylene glycol phthalate, polybutylene phthalate and polylactic acid (PLA) and corresponding polyesters modified with polycarbonate or MBS.
  • 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, said other Monomer such as hydroxycarboxylic acid Such as glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid, 5-hydroxyvaleric acid, 6-hydroxycaproic acid and cyclic forms thereof;
  • lactic acid or "lactide” includes L-lactic acid, D-lactic acid, mixtures thereof and dimers, namely L-lactide, D-lactide, meso-lactide and any mixtures thereof.
  • 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. 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 the polymer additive A of the present invention and/or the polymer additive composition of the present invention with a polymer pellet and a filler in a mixer, and They are homogenized in the polymer melt in an extruder apparatus at relatively high temperatures, and the homogenized polymer extrudate is then withdrawn, cooled, and pelletized.
  • the extruder unit is selected from a single screw extruder or a twin screw extruder.
  • the preferred processing temperature is 170 to 200 ° C for polystyrene, 200 to 300 ° C for polypropylene, 250 to 290 ° C for polyethylene terephthalate (PET), and polybutylene terephthalate.
  • the alcohol ester (PBT) is 230 to 270 ° C, 260 to 290 ° C for polyamide-6 (PA6), 260 to 290 ° C for polyamide 66 (PA66), and 280 to 320 ° C for polycarbonate.
  • the compounding device which can be used in the present invention is a single screw extruder or a twin screw extruder, and the effective screw length for the present invention is 20 to 40 D in the case of a single screw extruder; effective in the present invention The screw length is 8 to 48 D in the case of a twin screw extruder.
  • a compound having the following chemical formula was prepared in a similar manner to that of Example 2, and the starting material was 2-nitro-4-chloro-2-hydroxy-3,5-di-tert-butylazobenzene.
  • the compounds prepared in Examples 1-5 were respectively compounded with sodium silicate, silicone resin, alkoxysilane, and the weight of the product of Example 1-5 in the polymer additive A was adjusted to obtain a polymer having a specific silicon content.
  • Additive C The specific compounding method is as follows: firstly, the compound prepared in Examples 1-5 and the silicide-containing material are compounded according to the ratio of Table 1 to a mother sample having a higher silicon content, and the weight content of the silicon element is measured, and then according to the final As a result, the content of the silicon element required was calculated to calculate the weight of the product of Examples 1-5 to be added for the second time, and finally the polymer additive C was obtained, and then the weight of the silicon element was measured again. content.
  • a polymer additive D containing a phosphorus element was obtained in the same manner. According to the content ratio of the silicon element and the phosphorus element which are finally required, the polymer additive C and the polymer additive D in a corresponding ratio are weighed to obtain a polymer additive A.
  • the weight content of the silicon element and the phosphorus element is determined by the following method: accurately weighing the polymer additive A 2g in an analytical balance, pouring it into a 100 ml digestion bottle, and then adding 97% concentrated sulfuric acid 5 ml at a preset temperature of 300 °C iron plate heating equipment for 10 minutes, then add 68% of nitric acid 5ml, and then keep heating for 20 minutes, the particles are completely decomposed, cooled to room temperature, added to 20ml of hydrogen peroxide and acid to pH value of 7, after use The liquid was diluted with ionized water, and the liquid was introduced into an ICP detector through a sample introduction tube to measure the concentrations of silicon and phosphorus.
  • Alkoxysilane Dow Corning OFS-6070
  • Red phosphorus analytical pure, Jining Baichuan Chemical Co., Ltd.
  • Triphenylphosphine Shanghai Changgen Chemical Technology Co., Ltd.
  • 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.
  • Comparative example 4 Comparative example 5 Comparative example 6 Comparative Example 1 product 0.1 Comparative Example 2 product 0.3 Comparative product 3 1 Polypropylene 69.9 99 Polystyrene 99.7 Antioxidant talcum powder glass fiber 30 Chemical resistance (%) 40 37 41
  • the chemical resistance test is carried out according to the following criteria:
  • a film having a thickness of 200 ⁇ m was prepared by hot pressing at a temperature higher than the melting point of the polymer by about 20 ° C, and a test piece was obtained by punching using a JIS No. 3 dumbbell method.
  • the test piece was immersed in methanol at 23 ° C for 7 days, and then in accordance with JIS K7113 The method was tested for tensile strength.
  • the tensile strength retention ratio (%) was calculated in comparison with the tensile strength value before immersion in methanol.

Abstract

L'invention concerne un additif (A) utilisé pour un polymère, comprenant le composé tel que représenté par la formule (I), R1 et R2 étant identiques ou différents, et étant représentés par H, un alkyle en C1-C8, ou un aryle en C6-C18 ; R3 étant H ou un halogène ; ledit additif (A) comprenant également un élément silicium et un élément phosphore ; lorsqu'il est ajouté à un polymère, ledit additif (A) utilisé pour un polymère améliore très nettement la résistance chimique de la composition polymère.
PCT/CN2016/111239 2016-02-17 2016-12-21 Additif utilisé pour un polymère, sa composition d'additif et sa composition polymère WO2017140173A1 (fr)

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