WO2017140168A1 - Additif pour polymère, procédé de fabrication correspondant et composition polymère comportant l'additif - Google Patents

Additif pour polymère, procédé de fabrication correspondant et composition polymère comportant l'additif Download PDF

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WO2017140168A1
WO2017140168A1 PCT/CN2016/111233 CN2016111233W WO2017140168A1 WO 2017140168 A1 WO2017140168 A1 WO 2017140168A1 CN 2016111233 W CN2016111233 W CN 2016111233W WO 2017140168 A1 WO2017140168 A1 WO 2017140168A1
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tert
butyl
polymer
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黄秀茹
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    • 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
    • C08L23/04—Homopolymers or copolymers of ethene
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    • 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
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
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    • C08K2003/026—Phosphorus
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    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
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    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/324—Alkali metal phosphate

Definitions

  • the present invention relates to an additive, and more particularly to an additive for a thermoplastic polymer, a process for the preparation thereof, and a polymer composition composed of the same.
  • Tetrakis( ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propanoyloxymethyl)methane as described above is an important commercial additive for thermoplastic polymers. For example, it protects organic materials, especially thermoplastic polymers, from degradation by heat, oxidation and/or actinic. Generally, the addition reaction of 2,6-di-tert-butylphenol and methyl acrylate is carried out to form methyl ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and then It is obtained by transesterification with pentaerythritol.
  • the tetrakis( ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propanoyloxymethyl)methane described in the above formula is used as an additive for polypropylene, polystyrene, polyethylene, polyamide Among polymers such as ABS, resins are excellent in chemical properties, physical properties, and molding processability, and are inexpensive, and are used in a wide range of applications including food containers and pharmaceutical containers.
  • the resin is organic when it is used to hold organic liquids such as fuels, edible oils, and cosmetics. The liquid is easily permeable from the container prepared from the resin, which seriously affects normal use.
  • the present inventors have discovered through a great deal of research that when a specific content is added to the tetrakis ( ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propanoyloxymethyl)methane described in the above formula.
  • the organic barrier property of the corresponding polymer container can be significantly improved.
  • the addition of trace amounts of phosphorus-containing materials and titanium-containing materials can significantly improve the organic barrier properties of polymer articles.
  • the invention is achieved by the following technical solutions:
  • Formula X which may have the chemical name: tetrakis( ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propanoyloxymethyl)methane.
  • the total weight content of the phosphorus element and the titanium element is from 10 ppm to 525 ppm, more preferably from 22 ppm to 308 ppm, based on the total weight of the additive A.
  • the phosphorus element content is greater than the titanium element content.
  • 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 the like, wherein R1, R2 and R3 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 C1-C15-alkyl, C1-C15-alkenyl, C3-C8-cycloalkyl, C6-C18-aryl, C7- C30-alkylaryl, C1-C8-alkoxy or C1-C8-alkylthio, or -OH or -SH and its alkali metal salts, alkaline earth metal salts, ammonium salts.
  • 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.
  • the titanium element is derived from a titanium-containing substance, and the titanium-containing substance may be one or a combination of the following.
  • titanium-containing substance is not particularly limited as long as it contains a titanium element, but is preferably a powder of titanium dioxide. Titanium dioxide can be amorphous or crystalline. Examples of the crystal form of titanium dioxide include an anatase type, a rutile type, and a brookite type. More preferably, it is anatase or rutile type titanium dioxide.
  • titanium-containing substance other titanium-containing compounds or monomers may also be used.
  • the compound include a titanium salt, a titanium alkoxide, titanium hydroxide, titanium nitride, and titanium sulfide.
  • titanium salt examples include titanium trichloride, titanium tetrachloride, titanium sulfide, and titanium sulfate.
  • titanium alkoxide examples include titanium ethoxide, titanium methoxide, titanium t-butoxide, titanium isobutoxide, titanium n-propoxide, titanium tetraisopropoxide, and a chelate thereof.
  • the particle diameter of the titanium dioxide is preferably in a range of 0.1 to 20 ⁇ m, and more preferably in a range of 0.1 to 10 ⁇ m, in which the particle diameter (D50) corresponding to a volume-based cumulative percentage of 50% is measured by a laser diffraction method, and further, It is preferably in the range of 0.1 to 1 ⁇ m. Further, the particle diameter (D90) of the titanium oxide obtained by the laser diffraction method and corresponding to a volume-based cumulative percentage of 90% is preferably 0.1 to 20 ⁇ m, more preferably 0.1 to 10 ⁇ m, still more preferably 0.2 to 1.5 ⁇ m.
  • the invention also provides an additive composition comprising a compound of the formula:
  • At least one other additive B different from the compound of formula X wherein the total weight content of phosphorus element and titanium element is from 10 ppm to 525 ppm, more preferably from 22 ppm to 308 ppm, based on the total weight of the additive composition; based on the additive composition
  • the total weight preferably comprises from 50 to 99.9% by weight of a compound of formula X, and from 0.1 to 50% by weight of at least one other additive B different from the compound of formula X, wherein the additive composition is based on
  • the total weight of the phosphorus and titanium elements is from 10 ppm to 525 ppm, more preferably from 22 ppm to 308 ppm.
  • the other additive B is one or more of the following:
  • Antioxidants including the following types:
  • alkylated monophenols such as 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethyl Phenolic, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-( ⁇ -methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2 , 6-di-tert-butyl-4-methoxymethylphenol, a linear or branched nonylphenol such as 2,6-dimercapto-4-methylphenol, 2,4-dimethyl -6-(1'-methylundecane-1'-yl)phenol, 2,4-di
  • alkylthiomethylphenol such as 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctyl Thiomethyl-6-ethylphenol, 2,6-di(dodecylthio)methyl-4-nonylphenol.
  • hydroquinones and alkylated hydroquinones such as 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2 ,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4 -hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.
  • 2,6-di-tert-butyl-4-methoxyphenol 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2 ,6-dip
  • Tocopherols such as alpha-tocopherol, beta-tocopherol, gamma-tocopherol, delta-tocopherol and mixtures thereof (vitamin E).
  • hydroxylated thiodiphenyl ether such as 2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'-thiobis(4-octylphenol), 4, 4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-2-methylphenol), 4,4'-thiobis (3,6-di-sec-amylphenol), 4,4'-bis(2,6-dimethyl-4-hydroxyphenyl)disulfide.
  • 2,2'-thiobis(6-tert-butyl-4-methylphenol 2,2'-thiobis(4-octylphenol), 4, 4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-2-methylphenol), 4,4'-thiobis (3,6-di-sec-amylphenol), 4,4'-bis(2,6-di
  • 1.6 alkylene bisphenols such as 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'-methylenebis(6-tert-butyl-4-ethyl Phenol), 2,2'-methylenebis[4-methyl-6-( ⁇ -methylcyclohexyl)phenol], 2,2'-methylenebis(4-methyl-6-ring Hexylphenol), 2,2'-methylenebis(6-fluorenyl-4-methylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2 '-Ethylene bis(4,6-di-tert-butylphenol), 2,2'-ethylenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylene Bis[6-( ⁇ -methylbenzyl)-4-nonylphenol], 2,2'-methylenebis[6-( ⁇ , ⁇ -dimethylbenzyl)-4-nonylphenol] , 4,
  • N- and S-benzyl compounds for example 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, 4-hydroxyl -3,5-dimethylbenzyl mercaptoacetic acid octadecyl ester, 4-hydroxy-3,5-di-tert-butylbenzyl mercaptoacetic acid tridecyl ester, 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) Alkyl-4-hydroxybenzyl) sulfide, 3,5-di-tert-butyl-4-hydroxybenzyl mercaptoacetic acid isooctyl ester.
  • Aromatic hydroxybenzyl compound for example 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,4-double ( 3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl Phenyl).
  • Triazine compounds such as 2,4-bis(octylfluorenyl)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylfluorenyl -4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octyldecyl-4,6-bis (3,5-di-tert Butyl-4-hydroxyphenoxy)-1,3,5-triazine, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3 Triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxyl -2,6-dimethylbenzyl)isocyanurate, 2,4,
  • benzylphosphonate such as dimethyl 2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 3, Bis(octadecyl) 5-di-tert-butyl-4-hydroxybenzylphosphonate, di(octadecyl) 5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, Calcium salt of monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.
  • Amidophenols for example 4-hydroxylauranilide, 4-hydroxystearylanilide, octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.
  • An ester of 1.12 ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with a monohydric or polyhydric alcohol for example with methanol, ethanol, n-octanol, isooctanol, stearyl alcohol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiglycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyl) Isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecyl alcohol, 3-thiapentadecanol, trimethylhexanediol, trishydroxyl
  • an ester of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with a monohydric or polyhydric alcohol for example with methanol, ethanol, octanol, stearyl alcohol, 1,6-hexanediol, 1, 9-decanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiglycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N, N'-bis(hydroxyethyl)oxamide, 3-thiaundecyl alcohol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1 An ester of p-hetero-2,6,7-trioxabicyclo[2.2.2]octane.
  • An amide of 1.16 ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propanoic acid such as N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropanoyl)hexa Methylenediamine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamine, N,N'-bis(3,5-di-tert-butyl) 4-Hydroxyphenylpropionyl)ruthenium, N,N'-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propanoyloxy)ethyl]oxamide .
  • 2-hydroxybenzophenones such as 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives.
  • esters of substituted and unsubstituted benzoic acids such as 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis(4-tert-butyl) Benzoyl) resorcinol, benzoylresorcinol, 2,5-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, 3,5-di-tert-butyl Cetyl 4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2,5-di-tert-butyl-4-hydroxybenzoic acid 2-methyl Base-4,6-di-tert-butylphenyl ester.
  • acrylates such as ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate, ⁇ -cyano- ⁇ , ⁇ -diphenyl isooctyl acrylate, ⁇ -methyl cinnamate methyl ester, ⁇ - cyano- ⁇ -methyl-p-methoxycinnamate methyl ester, ⁇ -cyano- ⁇ -methyl-p-methoxycinnamate butyl ester, ⁇ -methyl ester-p-methoxycinnamate methyl ester, N - ( ⁇ -carbomethoxy- ⁇ -cyanovinyl)-2-methylindoline, tetrakis( ⁇ -cyano- ⁇ , ⁇ -diphenyl) neopentyl acrylate.
  • Nickel compounds such as nickel complexes of 2,2'-thiobis[4-(1,1,3,3-tetramethylbutyl)phenol, such as 1:1 or 1:2 complexes, 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)-2,2,6, a condensate of 6-tetramethyl-4-hydroxypiperidine with succinic acid, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenedi
  • oxalic acid amides such as 4,4'-dioctyloxyoxalylamine, 2,2'-diethoxyoxalylaniline, 2,2'-dioctyloxy-5,5'-di-uncle Butyl oxanilide, 2,2'-bis(dodecyloxy)-5,5'-di-tert-butyloxalylanilide, 2-ethoxy-2'-ethyloxalylanilide , N,N'-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2'-ethyloxalylaniline and its 2-ethoxy- a mixture of 2'-ethyl-5,4'-di-tert-butyl oxalic acid anilide, a mixture of o- and p-methoxy disubstituted oxalanilide, and o- and
  • Metal deactivators such as N,N'-diphenyl oxamide, N-salicylaldehyde-N'-salicyloyl hydrazide, N,N'-bis(salicyl) hydrazine, N,N'-double (3,5-di-tert-butyl-4-hydroxyphenylpropionyl)indole, 3-salicylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxalyl Aniline, isophthalic dioxime, sebacyl bisphenyl hydrazine, N, N'-diacetyladipate dihydrazide, N, N'-bis(salicyl) oxalyl dihydrazide, N, N '-Bis(salicyloyl)thiopropionyl dioxime.
  • Phosphites and phosphonites such as triphenyl phosphite, diphenylalkyl phosphite, phenyl dialkyl phosphite, 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 invention also provides a polymer composition
  • a polymer composition comprising a polymer in an amount of from 30 to 99.9% by weight, a filler in an amount of from 0 to 60% by weight, and a polymer content of from 0.1 to 10% by weight of the invention.
  • Additive A is a polymer composition comprising a polymer in an amount of from 30 to 99.9% by weight, a filler in an amount of from 0 to 60% by weight, and a polymer content of from 0.1 to 10% by weight of the invention.
  • the present invention also provides a polymer composition
  • a polymer composition comprising a polymer in an amount of from 30 to 99.9% by weight, a filler in an amount of from 0 to 60% by weight, and an additive composition in an amount of from 0.1 to 10% by weight.
  • 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 Polymer 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 ester, polypropylene phthalate, polybutylene adipate and polylactic acid (PLA) and corresponding modification with polycarbonate or MBS Polyester.
  • PPA polylactic acid
  • polylactic acid means a homopolymer preferably of poly-L-lactide and any blend or alloy thereof with other polymers; a copolymer of lactic acid or lactide with other monomers, Other monomers such as hydroxycarboxylic acids such as glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid, 5-hydroxyvaleric acid, 6-hydroxycaproic acid and cyclic forms thereof; the term "lactic acid "Or Lactide” includes L-lactic acid, D-lactic acid, mixtures thereof and dimers, ie, L-lactide, D-lactide, meso-lactide, and any mixture thereof.
  • Crosslinked polymers which are derived from aldehydes on the one hand and phenols, ureas and melamines on the other hand, such as phenol/formaldehyde resins, urea/formaldehyde resins and melamine/formaldehyde resins.
  • An unsaturated polyester resin derived from a copolyester of a saturated and unsaturated dicarboxylic acid and a polyol and a vinyl compound as a crosslinking agent, and a halogen-containing modified product thereof having low flammability.
  • a crosslinkable acrylic resin derived from a substituted acrylate such as an epoxy acrylate, urethane acrylate or polyester acrylate.
  • a promoter is crosslinked using a conventional hardener such as an acid anhydride or an amine.
  • Blends (polymer blends) of the above polymers such as PP/EPDM, polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC /ASA, PC/PBT, PVC/CPE, PVC/Acrylate, POM/Thermoplastic PUR, PC/Thermoplastic PUR, POM/Acrylate, POM/MBS, PPO/HIPS, PPO/PA66 and Copolymer, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.
  • Natural and synthetic organic materials which are pure monomeric compounds or mixtures of these compounds, such as mineral oils, animal and vegetable fats, oils and waxes, or based on synthetic esters (eg phthalates, adipic acid) Oils, fats and waxes of esters, phosphates or trimellitates, and mixtures of synthetic esters and mineral oils in any weight ratio, typically those used as spinning compositions, and aqueous emulsions of these materials.
  • Preferred organic materials are:
  • olefin monomers such as ethylene and propylene and higher 1-olefins such as 1-butene, 1-pentene, 1-hexene or 1-octene. 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 comprising the additive A of the present invention and/or the additive composition of the present invention, together with polymer pellets and optional fillers.
  • 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 mixing device is a single screw extruder or a twin screw extruder, and the effective screw length used in the present invention is 20 to 40 D in the case of a single screw extruder; the effective screw length in the present invention is in a twin screw extrusion In the case of the exit, it is 8 to 48D.
  • the dibutyltin oxide is selected as a catalyst, and the catalyst and the reaction raw material methyl 3,5-di-tert-butyl-4-hydroxyphenylpropionate (commercially available) and pentaerythritol (commercially available) are added to the reaction vessel, wherein 3, 5 - 380 g of di-tert-butyl-4-hydroxyphenylpropionate and 42 g of pentaerythritol, the molar ratio of the two is about 4.2, the amount of the catalyst is 0.3 g, the pressure of the reaction vessel is adjusted to 650 Pa, and the temperature is raised after the reaction at 175 ° C for 7 hours.
  • the reaction was continued at 200 ° C for 1 h, and the temperature was lowered to 145 ° C for a half hour neutralization reaction.
  • the obtained product is selected from methanol as a crystallization solvent, and the target product is obtained by cooling and crystallization filtration.
  • the compound prepared in Example 1 was separately compounded with a phosphorus-containing substance, and the polymer additive C having a specific phosphorus element content was obtained by adjusting the weight of the product of Example 1 in the polymer additive A.
  • the specific compounding method is as follows: firstly, the compound prepared in Example 1 and the phosphorus-containing substance are compounded into a mother sample having a higher phosphorus element content, and the weight content of the phosphorus element is measured, and then the phosphorus content required according to the final result is determined. Calculate the second amount. Further, a polymer additive D containing a titanium element was obtained in the same manner. According to the content ratio of the phosphorus element and the titanium 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.
  • Red phosphorus analytical pure, Jining Baichuan Chemical Co., Ltd.
  • Triphenylphosphine Shanghai Changgen Chemical Technology Co., Ltd.
  • Nano titanium dioxide T104943, Shanghai Aladdin Biochemical Technology Co., Ltd.
  • Tetrabutyl titanate Shanghai Aladdin Biochemical Technology Co., Ltd.
  • the phosphorus element in Examples 2 and 5 is derived from: red phosphorus
  • the phosphorus element in Examples 3 and 6 is derived from: potassium dihydrogen phosphate
  • the phosphorus elements in Examples 4, 7, and 8 are derived from: triphenylphosphine
  • the titanium elements in Examples 2 and 5 are derived from: nano titanium dioxide
  • the titanium element in Examples 3 and 6 is derived from: tetrabutyl titanate
  • the titanium elements in Examples 4, 7, and 8 are derived from: titanium dichloride
  • Example 2 The compounds prepared in Example 1 were compounded according to the above methods, and the specific contents are shown in Table 2:
  • the phosphorus element in Comparative Example 1 comes from: red phosphorus
  • the phosphorus element in Comparative Example 2 is derived from: potassium dihydrogen phosphate
  • the phosphorus element in Comparative Example 3 is derived from: triphenylphosphine
  • the titanium element in Comparative Example 1 is derived from: nano titanium dioxide
  • the titanium element in Comparative Example 2 is derived from: tetrabutyl titanate
  • the titanium element in Comparative Example 3 is derived from: dichlorotitanium dichloride
  • Polyethylene FB2230, Borealis
  • Fiberglass PPG, Chop Vantage 3540
  • the polyethylene 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 2 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 40, the screw speed is 450 rpm, the residence time is 1 minute, and the pressure is 10 MPa.
  • the above polyamide and other components are first dry mixed in a high-speed mixer rotating at about 1000 rpm for 3 minutes, and the mixed raw materials are placed in a twin-screw extruder and melt-extruded.
  • the process conditions are: the temperature of each section of the barrel is maintained at 280 ° C, the twin-screw extruder has a length to diameter ratio of 40, 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 0.3 Comparative Example 2 product 0.1 Comparative product 3 0.5 Polyethylene 79.7 69.1 Polyamide 99.9 Ultraviolet light absorber 0.4 talcum powder 20 glass fiber 30 Organic barrier properties (mg/day) 49.3 62.4 78.3
  • a tube having an outer diameter of 10 mm, a wall thickness of 2 mm, and a length of 100 mm was prepared, one end of which was sealed, and the inside was filled with ethanol and toluene according to 60/
  • the obtained organic liquid was mixed at a volume ratio of 40, and the other end was also sealed, and the overall weight was measured. Then, the tube was placed in an oven at 60 ° C for 50 days, and the change in weight was measured to evaluate the barrier property of the organic substance.

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Abstract

L'invention concerne un additif A pour un polymère tel qu'illustré en formule X, comprenant un composé de formule (X). L'additif A comprend aussi un élément phosphore et un élément titane ; lorsqu'il est ajouté à un polymère, l'additif A lui confère des propriétés de barrière organique significativement meilleures.
PCT/CN2016/111233 2016-02-17 2016-12-21 Additif pour polymère, procédé de fabrication correspondant et composition polymère comportant l'additif Ceased WO2017140168A1 (fr)

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