WO2017140170A1 - Additif contenant du phosphore pour polymère - Google Patents

Additif contenant du phosphore pour polymère Download PDF

Info

Publication number
WO2017140170A1
WO2017140170A1 PCT/CN2016/111235 CN2016111235W WO2017140170A1 WO 2017140170 A1 WO2017140170 A1 WO 2017140170A1 CN 2016111235 W CN2016111235 W CN 2016111235W WO 2017140170 A1 WO2017140170 A1 WO 2017140170A1
Authority
WO
WIPO (PCT)
Prior art keywords
tert
additive
polymer
butyl
bis
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2016/111235
Other languages
English (en)
Chinese (zh)
Inventor
黄秀茹
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Publication of WO2017140170A1 publication Critical patent/WO2017140170A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • 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
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
    • 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
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • 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
    • 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
    • C08K2003/321—Phosphates
    • C08K2003/324—Alkali metal phosphate
    • 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.
  • a benzotriazole compound When a benzotriazole compound is used as an additive in a polymer, it is usually used as a light stabilizer or the like.
  • heat treatment such as melt molding is performed, physical properties such as intrinsic viscosity change before and after the treatment, and the above physical properties are observed.
  • the change causes a change in the mechanical properties of the obtained molded product or a variation in quality. Therefore, it has been strongly desired to obtain a polymer which can maintain the stability at the time of the above heat treatment, that is, the retention stability is maintained at a high level.
  • the present inventors have discovered by a great deal of research that when a specific content of a phosphorus-containing substance is added to a benzotriazole compound, the corresponding polymer retention stability can be significantly improved.
  • An additive A for polymers comprising:
  • 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 phosphorus element has a weight content of 5 ppm to 980 ppm, It is preferably from 20 ppm to 500 ppm, more preferably from 30 ppm to 200 ppm.
  • 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.
  • 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.
  • esters of phosphorous acid, 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 an additive composition comprising:
  • 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 weight content of the at least one other additive B is from 0.1 to 50%; preferably 5 Up to 30%.
  • 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,
  • 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-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(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thia eleven Alkanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane.
  • 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, 3,5-di-tert-butyl 2,4-di-tert-butylphenyl-4-hydroxybenzoate, cetyl 3,5-di-tert-butyl-4-hydroxybenzoate, 3,5-di-tert-butyl-4-hydroxybenzene Octadecyl formate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
  • 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
  • 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 dioxime, oxalyl anilide , isophthaloyl dihydrazide, sebacic acid bisphenyl hydrazine, N, N'-diacetyl adipyl 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 nitrate Ketone, N-octadecyl- ⁇ -heptadecyl nitrone, N-hexadecyl- ⁇ -heptadecyl nitrone, N-octadecyl- ⁇ -pentadecyl nitrone, N-heptadecyl- ⁇ -heptadecyl nitrone, N-octadecyl- ⁇ -hexadecyl nitrone, derived from N,N-dial
  • 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
  • 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 polyester May include, for example but not limited to: poly(hydroxyalkanoates), especially polypropiolactone, polybutyrolactone, polypivalolactone, polyvalerolactone and polycaprolactone, polysuccinic acid Ethylene glycol ester, polybutyl succinate, polybutylene succinate, hexamethylene polysuccinate, polyethylene adipate, propylene glycol adipate, polybutyl adipate Alcohol ester, polyhexamethylene adipate, polyethylene oxalate, propylene glycol oxalate, polybutylene oxalate, hexamethylene oxalate, polyethylene sebacate, poly Propylene glycol sebacate, polybutylene phthalate and polylactic acid (PLA) and corresponding polyesters modified with polycarbonate or MBS.
  • poly(hydroxyalkanoates) especially polypropiolactone, polybutyrolactone, polypivalolactone, poly
  • 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/PP0, 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 polymer composition comprising the polymer additive of the present invention and/or the polymer additive composition of the present invention in combination with polymer pellets and optional fillers in a mixer Mixing, and homogenizing them in the polymer melt in an extruder apparatus at relatively high temperatures, and then withdrawing the homogenized polymer extrudate, cooling, pelletizing.
  • 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 red phosphorus, potassium dihydrogen phosphate, and triphenylphosphine, and the weight of the product of Example 1-5 in the polymer additive A was adjusted to obtain a polymer having a specific phosphorus content.
  • Additive A the specific content is shown in Table 1.
  • the specific compounding method is as follows: firstly, the compound prepared in Examples 1-5 is compounded with the phosphorus-containing substance according to the ratio of Table 1. As a mother sample having a higher phosphorus element content, the weight content of the phosphorus element is measured, and then the weight of the product of the second addition of Examples 1-5 is calculated according to the content of the phosphorus element required for the final result, and finally the polymer additive is obtained.
  • the weight content of the phosphorus element is determined by the following method: accurately weigh the polymer additive A 2g in the analytical balance, pour it into a 100 ml digestion bottle, and then add 97% concentrated sulfuric acid 5 ml, at a preset temperature of 300 ° C iron plate Heating in a heating apparatus for 10 minutes, then adding 6 ml of 68% nitric acid, and then heating for 20 minutes, completely disintegrating the particles, cooling to room temperature, adding 20 ml of hydrogen peroxide and acidifying to pH 7, and diluting with deionized water. For the above liquid, the liquid is introduced into the ICP detector through a sample introduction tube to measure the concentration of the phosphorus element.
  • 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
  • the retention stability test is performed as follows:
  • the polymer composition of the above examples was injected using an 80-ton injection molding machine manufactured by Nissei Resin Co., Ltd. at a cylinder temperature of 330 ° C for 5 minutes, and the intrinsic viscosity before and after the injection was measured to evaluate the stability of the intrinsic viscosity. .
  • G good
  • M medium
  • the absolute value of the difference was 0.10 dl/g or more, the evaluation was "poor”.
  • the intrinsic viscosity test is carried out as follows:
  • the inherent viscosity ⁇ inh of the sample at 30 ° C, 0.05 g / dl, 0.1 g / dl, 0.2 g / dl, 0.4 g / dl concentration was determined by the following formula, The concentration was extended to 0, and the obtained value was taken as the intrinsic viscosity ⁇ .
  • t 0 represents the solvent dripping time (seconds)
  • t 1 represents the dropping time (seconds) of the sample solution
  • C represents the concentration (g/dl) of the sample in the solution.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne un additif (A) pour un polymère, comprenant un composé tel que représenté en formule (I). R1 et R2, étant soit identiques, soit différents, représentent H, alkyle en C1-C8 ou aryle en C6-C18; R3 est H ou halogène; l'additif (A) comprend également un élément phosphore; un ajout de l'additif (A) pour polymère dans un polymère peut améliorer significativement la stabilité de rétention dudit polymère.
PCT/CN2016/111235 2016-02-17 2016-12-21 Additif contenant du phosphore pour polymère Ceased WO2017140170A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201610089401.8 2016-02-17
CN201610089401.8A CN105542314A (zh) 2016-02-17 2016-02-17 一种用于聚合物的含磷添加剂

Publications (1)

Publication Number Publication Date
WO2017140170A1 true WO2017140170A1 (fr) 2017-08-24

Family

ID=55821896

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2016/111235 Ceased WO2017140170A1 (fr) 2016-02-17 2016-12-21 Additif contenant du phosphore pour polymère

Country Status (2)

Country Link
CN (1) CN105542314A (fr)
WO (1) WO2017140170A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2026027355A1 (fr) 2024-07-29 2026-02-05 Basf Se Procédé de décoloration de photostabilisants

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105542314A (zh) * 2016-02-17 2016-05-04 黄秀茹 一种用于聚合物的含磷添加剂
CN105694099B (zh) * 2016-03-09 2017-03-15 天津利安隆新材料股份有限公司 一种用于聚合物的添加剂

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1681886A (zh) * 2002-09-30 2005-10-12 三菱工程塑料株式会社 使用精整模的挤出成形用聚碳酸酯系树脂组合物和成形体
CN101139459A (zh) * 2007-08-30 2008-03-12 上海金发科技发展有限公司 一种无卤阻燃耐热聚碳酸脂和丙烯腈-丁二烯-苯乙烯接枝共聚物合金树脂及其制备方法
CN101163746A (zh) * 2005-04-13 2008-04-16 旭化成化学株式会社 聚酰胺-聚苯醚树脂组合物
CN102432937A (zh) * 2011-08-18 2012-05-02 长园集团股份有限公司 一种核电站用1e级k1类无卤阻燃热缩管及其制备方法
CN105542314A (zh) * 2016-02-17 2016-05-04 黄秀茹 一种用于聚合物的含磷添加剂

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100383919B1 (ko) * 2001-01-15 2003-05-14 주식회사 엘지화학 2-(2-히드록시페닐)-2ｈ-벤조트리아졸의 제조방법
CN105348562A (zh) * 2014-09-25 2016-02-24 黄秀茹 一种用于聚合物的添加剂

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1681886A (zh) * 2002-09-30 2005-10-12 三菱工程塑料株式会社 使用精整模的挤出成形用聚碳酸酯系树脂组合物和成形体
CN101163746A (zh) * 2005-04-13 2008-04-16 旭化成化学株式会社 聚酰胺-聚苯醚树脂组合物
CN101139459A (zh) * 2007-08-30 2008-03-12 上海金发科技发展有限公司 一种无卤阻燃耐热聚碳酸脂和丙烯腈-丁二烯-苯乙烯接枝共聚物合金树脂及其制备方法
CN102432937A (zh) * 2011-08-18 2012-05-02 长园集团股份有限公司 一种核电站用1e级k1类无卤阻燃热缩管及其制备方法
CN105542314A (zh) * 2016-02-17 2016-05-04 黄秀茹 一种用于聚合物的含磷添加剂

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2026027355A1 (fr) 2024-07-29 2026-02-05 Basf Se Procédé de décoloration de photostabilisants

Also Published As

Publication number Publication date
CN105542314A (zh) 2016-05-04

Similar Documents

Publication Publication Date Title
DE3727977C2 (de) 1,2,2,6,6-Pentamethyl-4-piperidylaminotriazin- Derivate und stabilisierte Zusammensetzungen
JP5980365B2 (ja) 立体障害アミン安定剤
CN104262678B (zh) 一种用于聚合物的添加剂
JP4787160B2 (ja) 難燃性組成物
RU2593997C2 (ru) Стабилизация органического материала соединениями манниха на основе аминотриазина
WO2017140173A1 (fr) Additif utilisé pour un polymère, sa composition d'additif et sa composition polymère
JPH03204872A (ja) ３―フェニルベンゾフラン―２―オン類
DE69611535T2 (de) Antioxidantien mit phenol- und aromatischen amingruppen
WO2017140169A1 (fr) Additif pour polymère
WO2017140168A1 (fr) Additif pour polymère, procédé de fabrication correspondant et composition polymère comportant l'additif
DE3877508T2 (de) Aliphatische ester 1,3,2-oxazaphospholidinen.
WO2017140123A1 (fr) Additif pour polymère, procédé de préparation correspondant et composition polymère comprenant l'additif
WO2017140171A1 (fr) Additif pour polymère, procédé de préparation correspondant et composition polymère comprenant l'additif
EP0255478A1 (fr) Tris(hydroxyphényl substitué thio) trithio-orho-esters
WO2017161934A1 (fr) Additif
WO2017152685A1 (fr) Additif pour polymère
WO2017140172A1 (fr) Additif destiné à être utilisé dans un polymère, composition d'additif et composition polymère de l'additif et utilisations correspondantes en tant que photostabilisant
CN105542314A (zh) 一种用于聚合物的含磷添加剂
WO2017152684A1 (fr) Additif pour polymère
WO2017140167A1 (fr) Additif pour polymère, préparation de celui-ci et composition polymère comprenant l'additif
JPS635058A (ja) アミノオキシスクシネ−ト、及び該化合物で安定化された有機物質
WO2017140174A1 (fr) Additif pour polymère, procédé de préparation correspondant et composition polymère comprenant l'additif
EP0274351B1 (fr) Stabilisants à structure 1,3,4-oxathiazol-2-one substituée

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16890394

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC

122 Ep: pct application non-entry in european phase

Ref document number: 16890394

Country of ref document: EP

Kind code of ref document: A1