WO2004031282A1 - Combinaisons synergiques d'antioxydants phenoliques - Google Patents

Combinaisons synergiques d'antioxydants phenoliques Download PDF

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Publication number
WO2004031282A1
WO2004031282A1 PCT/IB2003/004359 IB0304359W WO2004031282A1 WO 2004031282 A1 WO2004031282 A1 WO 2004031282A1 IB 0304359 W IB0304359 W IB 0304359W WO 2004031282 A1 WO2004031282 A1 WO 2004031282A1
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WIPO (PCT)
Prior art keywords
tert
bis
butyl
hydroxy
methyl
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PCT/IB2003/004359
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English (en)
Inventor
Ernesto Dongiovanni
Christoph Kroehnke
Tania Weyland
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Clariant International Ltd
Clariant Finance (Bvi) Limited
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Priority to AU2003265080A priority Critical patent/AU2003265080A1/en
Publication of WO2004031282A1 publication Critical patent/WO2004031282A1/fr

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    • 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
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • 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
    • 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
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl 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
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K

Definitions

  • the invention relates to synergistic combinations of phenolic antioxidants in engineering plastics and other thermoplastic molding materials especially polyamides.
  • the invention also relates to combinations of such synergistic mixtures with organo- phosph(on)ites.
  • the usability and lifetime of plastic articles is influenced by numerous parameters such as mechanical properties, density, molar mass and mass distribution of the polymer.
  • mechanical properties such as mechanical properties, density, molar mass and mass distribution of the polymer.
  • a lifetime of up to several decades must be guaranteed which can only be reached with the appropriate stabilizers and stabilizer combinations. Their contribution can be determined under accelerated test conditions at elevated temperatures.
  • the color measured as yellowness index is used to assess the stabilization of polymer articles like those made out of polyamide. Effects in the polymer matrix e.g. change in cristallinity, free volume, morphology, and co- efficient of diffusion and reaction kinetics cause changes in the degradation mechanism.
  • phenolic antioxidants inhibits early autoxidation especially during thermal treatment and therefore enables excellent retention of physical properties.
  • phenolic antioxidants improve the initial color after polyconden- sation and processing. Those stabilizers can be added already during the polyconden- sation prior to the termination of the reaction (3).
  • This invention relates primarily to the synergistic behavior and advantageous use of synergistic combinations of hydrolytically stable with hydrolytically less stable phenolic antioxidants for long-term thermal stabilization.
  • the claimed combinations of those sterically hindered phenols surprisingly offer the possibility to outperform the state of the art in terms of technical key parameters.
  • a second aspect of the invention are formulations consisting of the mentioned phenol-combinations and sterically hindered phosph(on)ites which give rise to a further improved color during long term use at elevated temperatures.
  • Phenolic antioxidants have been used in combination with organo-phosphites or organo-phosphonites and sometimes with other stabilizers like alpha-tocopherol for the stabilization of polyolefin-based thermoplastic polymers (WO-A-97/49758). Stabilization of polyolefins with phenolic antioxidants has also been described in R. Gachter, H.M ⁇ ller; Handbook “Plastic Additives”("Kunststoffadditive”), 3. German Edition, Carl Hanser Publishers, Kunststoff, Vienna 1990; pp 68.
  • Object of the instant invention are stabilizer compositions for thermoplastic polymers, especially for polyamides, comprising
  • weight ratio of component a) to component b) is from 1:10 to 10:1 , preferably from 1 :2 to 2:1.
  • component a) is compound (I), (II) or (III) or any mixture thereof. Especially preferred is compound (I).
  • phenolic antioxidants of group a) are:
  • All phenolic components are used in a range between 0.001 and 2.000% weight- percent, preferentially in concentrations between 0.020 and 0.200 weight-percent, related to the thermoplastic polymer to be stabilized, for the long term use especially in polyamide articles.
  • a further object of the instant invention therefore is a method of use of said stabilizer compositions for the stabilization of thermoplastic polymers, especially polyamides, in concentrations of 0.001 % to 2.000 %, preferably 0.020 % to 0.20 % by weight, based on the polymer.
  • Another object of the instant invention is a process of stabilizing thermoplastic polymers, especially polyamides, by incorporating 0.001 % to 2.000 %, preferably 0.020 % to 0.20 % of said stabilizer compositions by weight, based on the polymer, of said stabilizer compositions.
  • a further aspect of the invention are stabilizer compositions for thermoplastic polymers, especially for polyamides, comprising the abovementioned compositions of phenolic antioxidants in combination with sterically hindered phosph(on)ites of the general formulae
  • Phosphonites P-(OAr) 3 .
  • Ar and Ar have the meaning of an aromatic rest which is preferably sub- stituted by branched alkyl rests.
  • Compound (X) is an example for the class of phosphonites.
  • All sterically hindered phosph(on)ites are used in a range between 0.001 and 2.000% weight-percent, preferably in concentrations between 0.020 and 0.200 weight-percent, related to the thermoplastic polymer to be stabilized, for the long term use especially in polyamide articles.
  • the ratio between the phenolic components and the sterically hindered phosph(on)ites to be used is between 10:1 and 1:10, preferentially between 4:1 and 1:4.
  • the mixtures according to the invention also outperform single tailor-made sterically hindered phenolic antioxidants such as Irganox ® 1098 (Irganox is a Trademark of Ciba Specialities).
  • thermoplastic polymers to be stabilized according to the instant invention are the following ones:
  • Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams such as polyamide 4, polyamide 6, polyamide 6/6, polyamide 6/10, polyamide 6/9, polyamide 6/12, polyamide 4/6, polyamide 12/12, polyamide 11 and polyamide 12, aromatic polyamides starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and iso-phthalic and/or terephthalic acid and with or without an elastomer as modifier, for example poly-2,4,4-trimethylhexa-methylene terephthalamide or poly-m-phenylene isophthalamide.
  • Blends of polyamides with all kinds of other polymers including polyolefins e.g. Nylex ® based on Multibase ® alloying technology.
  • Other commercially important blends are those of polyamides and polyesters, often compatibilized by addition of ionomers, but also wool-polyamide blends.
  • blends of polyamides with viscose, polyurethanes (Spandex) and cotton are also described in the following list of polymers which generally can be stabilized by compositions according to the invention.
  • Polymers of monoolefins and diolefins for example polypropylene, polyiso- butylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for example of cyclopentene or norbomene; furthermore polyethylene (which optionally can be crosslinked); for example, high density polyethylene (HDPE), polyethylene of high density and high molar mass (HDPE-HMW), polyethylene of high density and ultrahigh molar mass (HDPE- UHMW), medium density polyethylene (HMDPE), low density polyethylene
  • HDPE high density polyethylene
  • HDPE-HMW polyethylene of high density and high molar mass
  • HDPE- UHMW polyethylene of high density and ultrahigh molar mass
  • HMDPE medium density polyethylene
  • LDPE linear low density polyethylene
  • LLDPE linear low density polyethylene
  • BLDPE branched low density polyethylene
  • Polyolefins i.e. polymers of monoolefins exemplified in the preceding paragraph, in particular polyethylene and polypropylene, can be prepared by various, and especially by the following, methods:
  • a catalyst that normally contains one or more metals of group IVb, Vb, Vlb or VIII of the Periodic Table.
  • These metals usually have one or more ligands, such as oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either ⁇ - or ⁇ -coordinated.
  • ligands such as oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either ⁇ - or ⁇ -coordinated.
  • These metal complexes may be in the free form or fixed on substrates, for example on activated magnesium chloride, titanium(lll) chloride, alumina or silicon oxide.
  • These catalysts may be soluble or insoluble in the polymerization medium.
  • the catalysts can be active as such in the polymerization or further activators may be used, for example metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, the metals being elements of groups la, I la and/or Ilia of the Periodic Table.
  • the activators may be modified, for example, with further ester, ether, amine or silyl ether groups.
  • These catalyst systems are usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC). 2.
  • Mixtures of the polymers mentioned under 1 for example mixtures of polypropylene with polyisobutylene, polyethylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE/LDPE) and mixtures of different types of polyethylene (for example LDPE/HDPE) with one another.
  • Copolymers of monoolefins and diolefins with each other or with other vinyl monomers for example ethylene-propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene-but-1-ene copolymers, propylene-isobutylene copolymers, ethylene- but-1-ene copolymers, ethylene-hexene copolymers, ethylene-methylpentene copolymers, ethylene-heptene copolymers, ethylene-octene copolymers, propylene-butadiene copolymers, isobutylene-isoprene copolymers, ethylene- alkyl acrylate copolymers, ethylene-alkyl methacrylate copolymers, ethylene-vinyl acetate copolymers and their copolymers with carbon monoxide or ethylene- acrylic acid copolymers and their salts (ionomers,
  • Hydrocarbon resins for example C 5 -C 9
  • hydrogenated modifications thereof e.g. tackifier resins
  • mixtures of polyalkylenes and starch
  • Polystyrene poly(p-methylstyrene), poly( ⁇ -methylstyrene).
  • Copolymers of styrene or ⁇ -methylstyrene with dienes or acrylic derivatives for example styrene-butadiene, styrene-acrylonitrile, styrene-alkyl methacrylate, styrene-butadiene-alkyl acrylate, styrene-butadiene-alkyl methacrylate, styrene- maleic anhydride, styrene-acrylonitrile-methacrylate; mixtures of high impact strength of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene-propylene-diene terpolymer; and block copoly- mers of styrene, such as styrene-butadiene-styrene, styrene-isoprene-styrene, styrene
  • Graft copolymers of styrene or ⁇ -methylstyrene for example styrene on poly- butadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers, styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl acrylates or alkyl methacrylates on polybutadiene, styrene and acrylonitrile on ethylene-propylene-diene terpolymers, styrene
  • Halogen-containing polymers such as polychloroprene, chlorinated rubber, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl ruuber), chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinyl- idene chloride, polyvinyl fluoride, polyvinylidene fluoride; as well as copolymers thereof such as vinyl chloride-vinylidene chloride, vinyl chloride-vinyl acetate or vinylidene chloride-vinyl acetate.
  • Copolymers of the monomers mentioned under 9) with each other or with other unsaturated monomers for example acrylonitrile-butadiene copolymers, acrylo- nitrile-alkyl acrylate copolymers, acrylonitrile-alkoxyalkyl acrylate copolymers, acrylonitrile-vinyl halide copolymers or acrylonitrile-alkyl methacrylate-butadiene terpolymers.
  • acrylonitrile-butadiene copolymers for example acrylonitrile-butadiene copolymers, acrylo- nitrile-alkyl acrylate copolymers, acrylonitrile-alkoxyalkyl acrylate copolymers, acrylonitrile-vinyl halide copolymers or acrylonitrile-alkyl methacrylate-butadiene terpolymers.
  • cyclic ethers such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.
  • Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain comonomers, for example ethylene oxide; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
  • Polyureas Polyimides, polyamide-imides, polyether imides, polyester amides, polyhydantoins and polybenzimidazoles.
  • Polyesters derived from dicarboxylic acids and dialcohols and/or from hydroxy- carboxylic acids or the corresponding lactones such as polyethylene tere- phthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane tere- phthalate, polyhydroxybenzoates, as well as block polyether esters derived from hydroxyl-terminated polyethers; and also polyesters modified with polycarbonates or MBS.
  • Polysulfones, polyether sulfones and polyether ketones 19.
  • 20. Crosslinked polymers derived from aldehydes on the one hand and phenols, urea or melamine on the other hand, such as phenol/formaldehyde resins, urea/- formaldehyde resins and melamine/formaldehyde resins.
  • Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, and also halogen-containing modifications thereof of low flammability.
  • Crosslinkable acrylic resins derived from substituted acrylates for example from epoxy acrylates, urethane acrylates or polyester acrylates.
  • Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, examples being products of bisphenol A diglycidyl ethers, bisphenol F diglycidyl ethers, which are crosslinked by means of customary hardeners, such as anhydrides or amines, for example, with or without accelerators.
  • Natural polymers such as cellulose, natural rubber, gelatin and derivatives there- of which have been chemically modified in a polymer-homologous manner, for example cellulose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers such as methyl cellulose; as well as rosins and derivatives.
  • Natural and synthetic organic substances which constitute pure monomeric compounds or mixtures thereof, examples being mineral oils, animal or vegetable fats, oils and waxes, or oils, waxes and fats based on synthetic esters (e.g. phthalates, adipates, phosphates or trimellitates), and also blends of synthetic esters with mineral oils in any desired proportion by weight, as are employed, for example, as spin finishes, and aqueous emulsions thereof.
  • synthetic esters e.g. phthalates, adipates, phosphates or trimellitates
  • synthetic esters e.g. phthalates, adipates, phosphates or trimellitates
  • synthetic esters e.g. phthalates, adipates, phosphates or trimellitates
  • synthetic esters e.g. phthalates, adipates, phosphates or trimellitates
  • synthetic esters e.g. phthalates, adipates, phosphates or trimellitates
  • the stabilizer compositions of the instant invention or the thermoplastic polymers to be stabilized may, if desired, also comprise further additives, examples being antioxidants, light stabilizers, metal deactivators, antistatic agents, flame retardants, lubricants, nucleating agents, acid scavengers (basic costabilizers), pigments and fillers.
  • suitable additives which can additionally be employed in combination are compounds as set out below:
  • Alkylated monophenols for example 2,6-di-tert-butyl-4-methylphenol, 2-butyl-4,6- dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-( ⁇ -methyl- cyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclo- hexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, linear or sidechain- branched nonylphenols, such as 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1- methylundec-1 '-yl)-phenol, 2,4-d-d
  • Alkylthiomethylphenols for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4- dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di- dodecylthiomethyl-4-nonylphenol .
  • Hydroquinones and alkylated hydroquinones for example 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-hydroxy- phenyl 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- dipheny
  • Hydroxylated thiodiphenyl ethers for example 2,2'-thiobis(6-tert-butyl-4-methyl- phenol), 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-methyl- phenol 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'-
  • Alkylidenebisphenols for example 2,2'-methylenebis(6-tert-butyl-4-methyl- phenol), 2,2'-methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4- methyl-6-( ⁇ -methylcyclohexyl)phenol], 2,2'-methylenebis(4-methyl-6-cyclohexyl- phenol), 2,2'-methylenebis(6-nonyl-4-methylphenol), 2,2'-methylenebis(4,6-di- tert-butylphenol), 2,2'-ethylidenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(6- tert-butyl-4-isobutylphenol), 2,2'-methylenebis[6-( ⁇ -methylbenzyl)-4-nonylphenol], 2,2'-methylenebis[6-( ⁇ , ⁇ -dimethylbenzyl)
  • O-, N- and S-benzyl compounds for example 3,5,3',5'-tetra-tert-butyl-4,4'-di- hydroxydibenzyl ether, octadecyl 4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4-tert-butyl-3-hydroxy-2,6-di- methylbenzyl) dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate, tridecyl 4-hydroxy-3,5- di-tert-butylbenzylmercaptoacetate.
  • Hydroxybenzylated malonates for example dioctadecyl 2,2-bis(3,5-di-tert-butyl-2- hydroxybenzyl)malonate, dioctadecyl 2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)- malonate, didodecyl mercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)- malonate, di-[4-(1 ,1 ,3,3-tetramethylbutyl)phenyl] 2,2-bis(3,5-di-tert-butyl-4- hydroxybenzyl)malonate.
  • Benzylphosphonates for example dimethyl 2,5-di-tert-butyl-4-hydroxybenzyl- phosphonate, diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl 5-tert-butyl-4-hydroxy- 3-methylbenzylphosphonate, the Ca salt of the monoethyl ester of 3,5-di-tert- butyl-4-hydroxybenzylphosphonic acid .
  • Acylaminophenols for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.
  • esters of ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or poly- hydric alcohols e.g. with methanol, ethanol, n-octanol, isooctanol, octadecanol, 1 ,6-hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxalamide, 3-thiaun- decanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxy- methyl-1-phospha-2,
  • esters of ⁇ -(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, n-octanol, isooctanol, octa- decanol, 1 ,6-hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N.N'-bisfhydroxyethy oxalamide, 3- thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4- hydroxymethyl-1-phospha-2,6,7-trimeth
  • esters of ⁇ -(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, n-octanol, isooctanol, octadecanol, 1 ,6-hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxalamide, 3-thiaun- decanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxy- methyl-1 -phospha-2,6,7-
  • esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, n-octanol, isooctanol, octadecanol, 1 ,6- hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris- (hydroxyethyl) isocyanurate, N,N'-bis-(hydroxyethyl)oxalamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1- phospha-2,6,7-trioxabicyclo
  • esters of 3,3-bis(3'tert-butyl-4'-hydroxyphenyl)butyric acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, n-octanol, isooctanol, octadecanol, 1 ,6-hexanediol, 1 ,9-nonanediol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) iso- cyanurate, N,N'-bis-(hydroxyethyl)oxalamide, 3-thia-undecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha- 2,6,7-trioxabicyclo[
  • Tocopherol such as ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol and mixtures thereof (vitamin E).
  • Amine antioxidants for example N,N'-diisopropyl-p-phenylenediamine, N.N'di- sec-butyl-p-phenylenediamine, N,N'-bis(1 ,4-dimethylpentyl)-p-phenylenediamine,
  • 2-Hydroxybenzophenones for example the 4-hydroxy, 4-methoxy, 4-octoxy, 4- decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 , ,4'-trihydroxy and 2'-hydroxy-4,4'-di- methoxy derivative.
  • Esters of substituted or unsubstituted benzoic acids for example 4-tert-butyl- phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl 3,5- di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
  • Nickel compounds for example nickel complexes of 2,2'-thio-bis-[4-(1 , 1 ,3,3- tetramethylbutyl)phenol], such as the 1 :1 or 1 :2 complex, with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldi- ethanolamine, nickel dibutyldithiocarbamate, nickel salts of monoalkyl esters, such as of the methyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzyl- phosphonic acid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methyl- phenyl undecyl ketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxy- pyrazole, with or without additional ligands.
  • additional ligands such as n-butylamine, triethanolamine or N-cyclohexyld
  • Sterically hindered amines for example bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis(2,2,6,6-tetramethylpiperidin-4-yl) glutarate, bis(2,2,6,6-tetramethyl- piperidin-4-yl) succinate, bis(1 ,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, bis- (1 ,2,2,6,6-pentamethylpiperidin-4-yl) glutarate, 2,2,6,6-tetramethylpiperidyl behenate, 1 ,2,2,6,6-pentamethylpiperidyl behenate, the condensate of 1- hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, the condensate of N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)hexamethylendiamine and 4-tert-octylamin
  • Oxalamides for example 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyanilide, 2,2'-di- octyloxy-5,5'-di-tert-butyloxanilide, 2,2'-didodecyloxy-5,5 , -di-tert-butyloxanilide, 2- ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)-oxalamide, 2-ethoxy-5- tert-butyl-2'-ethyloxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyl- oxanilide and mixtures of o- and p-methoxy-disubstituted and of o- and p-ethoxy- disubstituted oxanilides.
  • Metal deactivators for example, N.N'-diphenyloxalamide, N-salicylal-N'-salicyloyl- hydrazine, N,N'-bis(salicyloyl)hydrazine, N,N'-bis(3,5-di-tert-butyl-4-hydroxy- phenylpropionyl)hydrazine, 3-salicyloylamino-1 ,2,4-triazole, bis(benzylidene)- oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenyl- hydrazide, N,N'-diacetyladipoyl dihydrazide, N,N'-bis(salicyloyl)oxalyl di- hydrazide, N,N , -bis(salicyloyl)thiopropionyl dihydrazi
  • Phosphites and phosphonites for example triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di- tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert- butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bisisodecyloxy pentaerythritol diphosphite, bisis
  • Hydroxylamines examples being N,N-dibenzylhydroxylamine, N,N-diethyl- hydroxylamine, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-di- tetradecylhydroxylamine, N,N-dihexadecylhydroxylamine, N,N-dioctadecyl- hydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octa- decylhydroxylamine, N,N-dialkylhydroxylamines prepared from hydrogenated tallow fatty amine.
  • Nitrones examples being N-benzyl alpha-phenyl nitrone, N-ethyl alpha-methyl nitrone, N-octyl alpha-heptyl nitrone, N-lauryl alpha-undecyl nitrone, N-tetradecyl alpha-tridecyl nitrone, N-hexadecyl alpha-pentadecyl nitrone, N-octadecyl alpha- heptadecyl nitrone, N-hexadecyl alpha-heptadecyl nitrone, N-octadecyl alpha- pentadecyl nitrone, N-heptadecyl alpha-heptadecyl nitrone, N-octadecyl alpha- hexadecyl nitrone, nitrones derived from N,N-dial
  • (M 2+ ) is Mg, Ca, Sr, Ba, Zn, Pb, Sn, Ni (M 3+ ) is Al, B, Bi
  • A" is an anion of valence n n is an integer from 1 - 4 x is a value between 0 and 0.5 y is a value between 0 and 2 A is OH " , Cr, Br “ , I “ , CIO 4 -, CH 3 COO-, C 6 H 5 COO-, CO 3 2' , SO 4 2" , (OOC-COO) 2” , (CHOHCOO) 2 2 -, (CHOH) 4 CH 2 OHCOO-, C 2 H 4 (COO) 2 2 -, (CH 2 COO) 2 2" , CH 3 CHOHCOO-, SiO 3 2 -, Si ⁇ Fe(CN) 6 3' , Fe(CN) 6 4 ⁇ BO 3 3” , PO 3 3” , HPO 4 2 ⁇
  • hydrotalcites in which (M 2+ ) is (Ca 2+ ), (Mg 2+ ) or a mixture of (Mg 2+ ) and (Zn 2+ ); (A n" ) is CO 3 2" , BO 3 3' , PO 3 3" ; x has a value from 0 to 0.5 and y has a value from 0 to 2. It is also possible to employ hydrotalcites that can be described with the formula
  • (M 2+ ) is Mg 2+ , Zn 2+ , but more preferably Mg 2+ .
  • (A n" ) is an anion, in particular from the group consisting of CO 3 2" , (OOC-COO) 2' , OH " and S 2" , where n describes the valency of the ion.
  • y is a positive number, more preferably between 0 and 5, especially between 0.5 and 5.
  • x and z have positive values, which in the case of x are preferably between 2 and 6 and in the case of z should be less than 2.
  • the hydrotalcites of the following formulae are to be regarded with particular preference:
  • Hydrotalcites are employed in the polymer preferably in a concentration of from 0.01 to 5 % by weight, in particular from 0.2 to 3 % by weight, based on the overall polymer formulation.
  • Peroxide scavengers examples being esters of ⁇ -thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl ester, mecaptobenzimidazole, the zinc salt of 2-mercaptobenzimidazole, zinc alkyldithiocarbamates, zinc dibutyldi- thiocarbamate, dioctadecyl monosulfide, dioctadecyl disulfide, pentaerythritol tetrakis( ⁇ -dodecylmercapto)propionate.
  • esters of ⁇ -thiodipropionic acid for example the lauryl, stearyl, myristyl or tridecyl ester, mecaptobenzimidazole, the zinc salt of 2-mercaptobenzimidazole, zinc alkyldithiocarbamates, zinc dibutyldi- thiocarbamate
  • Polyamide stabilizers examples being copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.
  • Basic costabilizers examples being melamin, polyvinylpyrrolidone, dicyandi- amide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, poly- amines, polyurethanes, alkali metal and alkaline earth metal salts of higher fatty acids, for example Ca stearate, Zn stearate, Mg behenate, Mg stearate, Na ricinoleate, K palmitate, antimony pyrocatecholate or tin pyrocatecholate, alkali metal and alkaline earth metal salts and also the zinc salt, the calcium salt or the aluminum salt of lactic acid.
  • Nucleating agents such as inorganic substances, examples being talc, metal oxides, such as titanium oxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals, organic compounds, such as mono- or polycarboxylic acids and also their salts, examples being 4-tert-butylbenzoic acid, adipic acid; diphenylacetic acid; sodium succinate or sodium benzoate; acetals of aromatic aldehydes and polyfunctional alcohols such as sorbitol, for example, such as 1,3-2,4-di(benzylidene)-D-sorbitol, 1,3-2,4-di(4-tolylidene)-D- sorbitol, 1 ,3-2,4-di(4-ethylbenzylidene)-D-sorbitol, polymeric compounds, such as ionic copolymers (ionomers), for example.
  • metal oxides such as titanium oxide or magnesium oxide
  • Fillers and reinforcing agents examples being calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and metal hydroxides, carbon black, graphite, wood flour and other flours or fibers of other natural products, synthetic fibers.
  • additives examples being plasticizers, lubricants, emulsifiers, pigments, rheological additives, catalysts, leveling assistants, optical brighteners, flame- proofing agents, antistatics, blowing agents.
  • the instant stabilizer compositions are employed in articles made of thermoplastic polymers, especially of polyamides, those articles show superior long term performance as measured by standard test methods such as yellowness index (YI).
  • YI yellowness index
  • the polyamide resin can consist of thick sections or thin layers and therefore can be applied also as coated or laminated layer on metal articles such as steel-pipes or sea-cables.
  • the instant stabilizer systems used to stabilize all kinds of articles prepared from thermoplastic polymers are able to resist to an early consumption by migration out of the polymer resin. This behavior improves clearly the long term stability of the referred articles.
  • Composition A is a mixture of 1 part Compound I and 1 part of Compound VII.
  • the pure polymer shows a pronounced yellowing already after 20 hours exposure measured by the parameter b*.
  • formulations based on phenolic antioxidants alone (Hostanox ® O 3, O 10 and Irganox ® 1098) all show a significant yellowing (b*>2) already after 50 hours.
  • Hostanox ® O 310 outperforms the above mentioned single sterically hindered phenols. Furthermore all formulations based on combinations of the phosphite-based processing stabilizer / phenolic antioxidant show much better color retention (lower b * ). Particularly the combinations Hostanox ® O3/Hostanox ® PAR 24 (1/1) and Hostanox ® O310 / Hostanox ® PAR 24 (1/1) show surprisingly better performance as compared to the established combination Irganox ® 1098 / Hostanox ® PAR24 (1/1) which reflects the state of the art.

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

Abstract

L'invention concerne des combinaisons synergiques de certains antioxydants phénoliques dans des polymères thermoplastiques, et notamment dans des polyamides et d'autres matières de moulage thermoplastiques. Les présentes combinaisons permettent d'obtenir une meilleure résistance contre la décomposition par oxydation, caractéristique mesurée en fonction de l'indice de jaunissement (YI), de la couleur et d'autres paramètres techniquement importants connus dans la technique.
PCT/IB2003/004359 2002-10-01 2003-09-30 Combinaisons synergiques d'antioxydants phenoliques WO2004031282A1 (fr)

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GB0222670.2 2002-10-01

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Cited By (3)

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Publication number Priority date Publication date Assignee Title
WO2007059109A2 (fr) * 2005-11-14 2007-05-24 Invista Technologies S.A R.L. Elasthanne a blancheur renforcee, et tissus et vetements le comprenant
WO2007136565A1 (fr) * 2006-05-17 2007-11-29 Cytec Technology Corp. Formules stabilisantes
US10273348B2 (en) * 2015-08-24 2019-04-30 Dtr Co., Ltd. Glass fiber-reinforced polyamide 66 resin composition with high tensile strength and method of manufacturing the same

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EP0238140A2 (fr) * 1986-03-19 1987-09-23 Akzo N.V. Composition de polyester à résistance à la chaleur excellente
WO1997049758A1 (fr) * 1996-06-27 1997-12-31 Clariant International Limited Compositions stabilisatrices
WO2001062839A1 (fr) * 2000-02-25 2001-08-30 Clariant Finance (Bvi) Limited Combinaisons synergiques d'antioxydants phenoliques
EP1334994A1 (fr) * 2002-02-08 2003-08-13 SOLVAY POLYOLEFINS EUROPE - BELGIUM (Société Anonyme) Composition à base de polyéthylène

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
EP0238140A2 (fr) * 1986-03-19 1987-09-23 Akzo N.V. Composition de polyester à résistance à la chaleur excellente
WO1997049758A1 (fr) * 1996-06-27 1997-12-31 Clariant International Limited Compositions stabilisatrices
WO2001062839A1 (fr) * 2000-02-25 2001-08-30 Clariant Finance (Bvi) Limited Combinaisons synergiques d'antioxydants phenoliques
EP1334994A1 (fr) * 2002-02-08 2003-08-13 SOLVAY POLYOLEFINS EUROPE - BELGIUM (Société Anonyme) Composition à base de polyéthylène

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007059109A2 (fr) * 2005-11-14 2007-05-24 Invista Technologies S.A R.L. Elasthanne a blancheur renforcee, et tissus et vetements le comprenant
WO2007059109A3 (fr) * 2005-11-14 2007-07-26 Invista Tech Sarl Elasthanne a blancheur renforcee, et tissus et vetements le comprenant
EP2050844A1 (fr) * 2005-11-14 2009-04-22 Invista Technologies S.a.r.l. Élasthanne disposant d'une blancheur améliorée et tissus et vêtements le comportant
KR101367082B1 (ko) 2005-11-14 2014-02-24 인비스타 테크놀러지스 에스.에이.알.엘. 백색도가 증가된 스판덱스, 및 이를 포함하는 직물 및 의류
WO2007136565A1 (fr) * 2006-05-17 2007-11-29 Cytec Technology Corp. Formules stabilisantes
US7759417B2 (en) 2006-05-17 2010-07-20 Cytec Technology Corp. Stabilizer compositions
CN101448888B (zh) * 2006-05-17 2011-10-05 氰特技术公司 稳定剂组合物
CN102417611A (zh) * 2006-05-17 2012-04-18 氰特技术公司 稳定剂组合物
US8501846B2 (en) 2006-05-17 2013-08-06 Cytec Technology Corp. Stabilizer compositions
CN102417611B (zh) * 2006-05-17 2014-07-02 氰特技术公司 稳定剂组合物
US10273348B2 (en) * 2015-08-24 2019-04-30 Dtr Co., Ltd. Glass fiber-reinforced polyamide 66 resin composition with high tensile strength and method of manufacturing the same

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