WO2000008096A1 - Stabilizing mixture having a melting point lower than that of the highest melting component - Google Patents

Stabilizing mixture having a melting point lower than that of the highest melting component Download PDF

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Publication number
WO2000008096A1
WO2000008096A1 PCT/EP1999/005468 EP9905468W WO0008096A1 WO 2000008096 A1 WO2000008096 A1 WO 2000008096A1 EP 9905468 W EP9905468 W EP 9905468W WO 0008096 A1 WO0008096 A1 WO 0008096A1
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Prior art keywords
butyl
bis
hydroxy
hydroxyphenyl
copolymers
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PCT/EP1999/005468
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French (fr)
Inventor
Luciano Pallini
Silvestro Costanzi
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Great Lakes Chemical (Europe) Gmbh
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Publication of WO2000008096A1 publication Critical patent/WO2000008096A1/en

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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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids

Definitions

  • the present invention relates to a stabilizing mixture having a melting point lower than that of tne highest melting component .
  • the present invention relates to a stabilizing mixture having a melting point lower than that of the highest melting component comprising octadecyl-3- (3 ' , 5 ' -d ⁇ -t-butyl-4 ' -hydroxyphenyl) propionate and tetra is [3- (3, 5-d ⁇ -t-butyl-4-hydroxyphenyl) propionyloxymethyl] ethane and its use as stabilizer for the oxidative degradation of organic polymers caused by light and/or heat.
  • the present invention also relates to the polymeric compositions stabilized with the above stabilizing mixture and to the end-articles obtained from these compositions.
  • tetrakis [3- (3, 5-di-t-butyl-4- hydroxyphenyl) propionyloxymethyl] methane can only partially melt creating problems of distribution heterogeneity, with the consequent formation of fragility zones in the end- article obtained as a result of the presence of segregate crystals.
  • the present invention therefore relates to a stabilizing mixture comprising: (a) tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionyl- oxymethyl] methane having formula [ I ]
  • Component (a) having formula (I) and component (b) having formula (II) are used in a ratio ranging from 9:1 to 1:9, preferably from 3:1 to 1:3.
  • Component (a) having formula (I) is known under the following trade-names: Anox 20 of Great Lakes, Irganox 1010 of Ciba.
  • Component (b) having formula (II) is known under the following trade-names: Anox PP18 of Great Lakes, Irganox 1076 of Ciba.
  • the stabilizing mixture of the present invention can be obtained by means of various processes.
  • a first process consists m taking the fine powders of the two components (a) and (b) and mixing them thoroughly under grinding.
  • a second process consists in dispersing the high melting component (a) in the low melting molten compound (b) and leaving the mixture of the two components, optionally under stirring, at a temperature ranging from 50°C to 60°C, until a homogeneous dispersion is obtained.
  • This dispersion is subsequently left to cool to room temperature, until a solid is obtained which is then ground or flaked.
  • a third process consists m melting both components (a) and (b) and leaving the mixture of the two components, optionally under stirring, at a temperature ranging from 120 °C to 130°C, until a homogeneous solution is obtained.
  • This solution is subsequently left to cool to room temperature, until a solid is obtained which is then ground or flaked.
  • a fourth process consists in the co- crystallization of the two components (a) and (b) , in the desired ratios, from an organic solvent m which these components are both soluble under heat and insoluble at cold such as, for example, methanol, a mixture of methanol/water, a mixture of acetone/water, etc.
  • the above stabilizing mixtures can be used as stabilizers for the oxidative degradation of organic polymers caused by light and/or heat.
  • organic polymers which can be stabilized are:
  • Polymers of mono-olefins and diolefins such as, for example, polypropylene, polyisobutylene, polybut-1-ene, poly-4- methylpent-1-ene, polyisoprene or polybutadiene; as well as polymers of cyclo-olefins such as, for example, cyclopentene or norbornene; polyethylene (which can be optionally cross- linked) such as, for example, high density polyethylene (HDPE) , high density and high molecular weight polyethylene (HDPE-HMW) , high density and ultrahigh molecular weight poly ⁇ ethylene (HDPE-UHMW) , medium density polyethylene (MDPE) , low density polyethylene (LDPE) , linear low density polyethylene (LLDPE) , branched low density polyethylene (BLDPE) .
  • HDPE high density polyethylene
  • HDPE-HMW high density and high molecular weight polyethylene
  • HDPE-UHMW high density and ultrahigh
  • Polyolefins such as, for example the monolefins men ⁇ tioned in the above paragraph, preferably polyethylene and polypropylene, can be prepared with various methods known in literature, preferably using the following methods:
  • radicalic polymerization (generally carried out at a high pressure and high temperature) ;
  • a catalyst which normally contains one or more metals of groups IVb, Vb, VIb or VIII of the Periodic Table.
  • metals generally have one or more iigands such as, for example, oxides, hal- ides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls which can be ⁇ - or ⁇ -coordinated.
  • iigands such as, for example, oxides, hal- ides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls which can be ⁇ - or ⁇ -coordinated.
  • These metal complexes can be in free form or supported on substrates such as, for example activated magnesium chloride, titanium (III) chloride, alumina or silicon oxide.
  • These catalysts can be soluble or insoluble in the reaction medium.
  • the catalysts can be used alone or in the presence of other activators such as, for example, metal alkyls, metal hydrides, halides of metal alkyls, oxides of metal alkyls or metal alkyloxanes, these metals being elements belonging to groups la, Ila and/or Ilia of the Periodic Table.
  • the activators can be conveniently modified with other ester, ether, amine or si- lyl-ether groups. These catalytic systems are usually called Phillips, Standard Oil Indiana, Ziegler (-Natta) , TNZ (Du-Pont), metallocene or "single site catalyst” (SSC) .
  • Copolymers of mono-olefins and diolefins with each other or with other vinyl monomers such as, for example, ethylene- propylene copolymers, linear low density polyethylene (LLDPE) and its mixtures with low density polyethylene (LDPE) , pro- pylene/but-1-ene copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copoly- mers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/alkyl ac- rylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers and their copolymers with carbon monoxide or ethylene/
  • Hydrocarbon resins for example, C 5 -C 9
  • hydrogenated modifications for example, adhesive agents
  • Copolymers of styrene or ⁇ -methylstyrene with dienes or acrylic derivatives such as, for example, styrene/butadiene, styrene/acrylonitrile, styrene/alkyl methacrylate, styrene/ butadiene/alkyl acrylate, styrene/butadiene/alkyl methacryla- te, styrene/maleic anhydride, styrene/acrylonitrile/methyl acrylate; mixtures, having a high impact strength, between copolymers of styrene and another polymer such as, for example, a polyacrylate, a polymer of a diene or an ethy- lene/propylene/diene terpolymer, block
  • Grafted copolymers of styrene or of ⁇ -methylstyrene such as, for example, styrene on polybutadiene, styrene on polybu- tadiene or polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methylmethacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkylacrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene/propylene/diene ter- polymers, styrene and acryl
  • halobutyl rubber chlorinated or chlorosulfonated polyethylene, ethylene and chlorinated ethylene copolymers, homopolymers and copolymers of epichlorohydrin, in particular polymers of vinyl compounds containing halogens such as, for example, polyvinyl chloride, polyvinylidenechloride, polyvinyl fluoride or polyvinylidene- fluoride; and also their copolymers such as, for example, vinyl chloride/vinyiidenechloride, vinyl chloride/vinyl acetate or vinylidenechloride vinyl acetate.
  • halobutyl rubber chlorinated or chlorosulfonated polyethylene
  • ethylene and chlorinated ethylene copolymers homopolymers and copolymers of epichlorohydrin
  • vinyl compounds containing halogens such as, for example, polyvinyl chloride, polyvinylidenechloride, polyvinyl fluoride or polyvinylidene- fluor
  • Polymers deriving from ⁇ , ⁇ -unsaturated acids and their derivatives such as, for example, polyacrylates and poly- methacrylates, polymethyl methacrylates, polyacrylamides and polyacryionitriles, modified with butyl acrylate. 10.
  • Copolymers of monomers according to point (9) with each other or with other unsaturated monomers such as, for exam ⁇ ple, acrylonitrile/butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate co ⁇ polymers or acrylonitrile/vinyl halide copolymers or acrylo ⁇ nitrile/alkyl met acrylate/butadiene terpolymers.
  • Homopolymers and copolymers of open-chain ethers or cyclic ethers such as, for example, polyalkylene glycols, polyethylene oxide, polypropylene oxide, or copolymers of the compounds described above with bis-glycidyl ethers.
  • Polyacetais such as, for example, polyoxymethylene and those polyoxymethylenes containing ethylene oxide as comono- mer; polyacetais modified with thermoplastic poiyurethanes, acrylates or MBS.
  • Polyamides and copolyamides deriving from diamines and dicarboxylic acids and/or aminocarboxylic acids or from the corresponding lactams such as, for example, polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides obtained starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic and/or terephthalic acid and with or without an elastomer as modifier, for example, poly-2, 4, 4-trimethylhexamethylene tereph- thalamide or poly-m-phenylene isophthalamide; and also block copolymers of the above polyamides with polyolefins, olefinic copolymers, ionomers or elastomers chemically bound or grafted; or with polyethers such as, for example, polyethylene glycol, polypropylene glycol or polyte
  • Polyesters deriving from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or from the corresponding lactones such as, for example, polyethylene terephthalate, polybutylene terephthalate, poly-1, 4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates, as well as block co- polyether esters deriving from polyethers with ydroxyl- terminated groups; and also polyesters modified with polycarbonates or MBS.
  • Alkyd resins resins based on polyesters or acrylated resins cross-linked with melamine resins, resins based on urea, resins based on isocyanates, resins based on iso- cyanurates, resins based on polyisocyanates or epoxy resins.
  • Cross-linked epoxy resins deriving from aliphatic, cy- cloaliphatic, heterocyclic or aromatic glycidyl compounds such as, for example, products of diglycidyl ethers of bisphenol A and bisphenol F, which are cross-linked with the usual hardening agents such as, for example, anhydrides or amines, in the presence of or without accelerating agents.
  • Natural polymers such as, for example, cellulose, rubber, gelatine, and their derivatives chemically modified to give homologous polymers such as, for example, cellulose ace- tates, propionates and butyrates, or cellulose ethers such as, for example, methyl-cellulose; as well as hydrocarbon resins ("rosins”) and their derivatives.
  • polybiends such as, for example, PP/EPDM, polyamides/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylates, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS, PBT/PET/PC. 29.
  • polybiends such as, for example, PP/EPDM, polyamides/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acryl
  • Natural or synthetic organic materials which are pure monomeric compounds or mixtures of said compounds, such as, for example, mineral oils, animal or vegetable oils, fats or waxes, oils, fats or waxes based on synthetic esters (for example, phthalates, adipates, phosphates, trimellitates) , as well as mixtures of synthetic esters with mineral oils in any weight ratio, in particular those used in spinning compositions, as well as aqueous emulsions of said organic materials.
  • synthetic esters for example, phthalates, adipates, phosphates, trimellitates
  • synthetic esters for example, phthalates, adipates, phosphates, trimellitates
  • mixtures of synthetic esters with mineral oils in any weight ratio in particular those used in spinning compositions
  • aqueous emulsions of said organic materials such as, for example, natural latex or latexes based on carboxy- lated styrene-butadiene copolymers.
  • the present invention also relates to polymeric compositions containing an organic polymer and an effective quantity of the above stabilizing mixture.
  • the stabilizing mixture of the present invention is particularly useful in the stabilization of syntnetic organic polymers selected from those listed above. It is preferably used m the stabilization of organic polymers which are subjected to processing at relatively low temperatures such as, for example, m the peptization of natural rubber which is carried out at 90°C.
  • a further object of the present invention relates to the end-articles obtained from the processing of the above polymeric compositions.
  • the stabilizing mixture of the present invention is added to the organic polymers to be stabilized m a quantity ranging from 0.01% to 5% with respect to the total weight of the polymer to be stabilized, preferably from 0.05% to 3%, even more preferably from 0.1% to 1%.
  • the staoilizmg mixture of the present invention can be incorporated into the organic polymer to be stabilized using the known techniques .
  • the stabilizing mixture of the present invention can be combined with other conventional additives or their mixtures. These additives are added m a quantity ranging from about 0.1% to about 5% by weight with respect to the weight of the polymeric compositions to be stabilized, preferably from about 0.5% to about 3% by weight. Some of the additives used are listed below as an example. 1.
  • Antioxidants 1.1 Alkylated monophenols such as, for example: 2,6-di-t- butyl-4-methylphenol; 2-t-butyI-4, 6-d ⁇ methylphenol; 2, 6-di-t- butyi-4-ethylphenol; 2, 6-d ⁇ -t-butyl-4-n-butylphenol; 2,6-di- t-butyl-4-isobutylphenol; 2, 6-di-cyclopentyl-4-methylphenol; 2- ( ⁇ -methylcyclohexyl) -4, 6-dimethylphenol; 2, 6-dioctadecyl-4- methylphenol; 2 , 4 , 6-tr ⁇ cyclohexylphenol; 2, 6-di-t-butyl-4- methoxymethylphenol; nonylphenols with a linear or branched alkyl chain such as, for example, 2, 6-d ⁇ -nonyl-4-me- thylphenol; 2 , 4-d ⁇ methyl-6- (1 ' -methylund
  • Alkylthiomethylphenols such as, for example: 2,4-d ⁇ oc- tylthiomethyl-6-t-butylphenol; 2, 4-d ⁇ octylthiomethyl-6-me- thylphenol; 2, 4-d ⁇ octylth ⁇ omethyl- ⁇ -ethylphenol; 2,6-d ⁇ do- decylth ⁇ omethyl-4-nonylphenol .
  • Hydroquinones and alkylated hydroqumones such as, for example: 2, 6-di-t-butyl-4-methoxyphenol; 2, 5- ⁇ -t-butylhydro- quinone; 2, 5-di-t-amylhydroqu ⁇ none; 2, 6-di-phenyl-4-octade- cyloxyphenol; 2, 6-di-t-butylhydroquinone; 2, 5-d ⁇ -t-butyl-4- hydroxyanisole; 3, 5-d ⁇ -t-butyl-4-hydroxyanisole; 3,5-d ⁇ -t-bu- tyl-4-hydroxyphenyl stearate; bis (3, 5-di-t-butyl-4-hydro- xyphenyl) adipate .
  • Tocopherols such as, for example: ⁇ -tocopherol, ⁇ - tocopherol, ⁇ -tocopherol, ⁇ -tocopherol and their mixtures (Vi- tamin E) .
  • Hydroxylated thiodiphenyl ethers such as, for example 2,2' -thiobis- ( 6-t-butyl-4-methylphenol ) ; 2,2' -thiobis- ( 4- octylphenol ) ; 4,4' -thiobis- ( 6-t-butyl-3-methylphenol ) ; 4 , 4 ' - thiobis- ( 6-t-butyl-2-methylphenol ) ; 4, 4 ' -thiobis- (3, 6-di-s- amylphenol) ;4, 4 '-bis- (2, 6-dimethyl-4 ⁇ hydroxyphenyl) isulfide.
  • Alkylidene-bisphenols such as, for example: 2, 2 '-met yl- enebis- ( 6-t-butyl-4-methylphenol ) ; 2,2' -methylenebis- ( 6-t-bu- tyl-4-ethylphenol) ; 2,2 '-methylenebis [4-methyl-6- ( ⁇ -methylcyclohexyl) phenol] ; 2,2' -methylenebis (4-methyl-6-cyclo-hexyl- phenol); 2, 2 ' -methylenebis (6-nonyl-4-methyl-phenol) ; 2, 2' -methylenebis (4, 6-di-t-butylphenol) ; 2, 2 '-ethylidene-bis (4, 6-di- t-butylphenol ) ; 2,2' -ethylidenebis ( 6-t-butyl-4-isobutyl-phen- ol) ; 2,2' -methylenebis [6- ( ⁇ -met
  • Benzyl compounds containing 0, N or S such as, for example: 3, 5, 3 ' , 5 ' -tetra-t-butyl-4, 4 ' -dihydroxydibenzyl ether; octadecyl-4-hydroxy-3, 5-d ⁇ methylbenzylmercaptoacetate; tride- cyl-4-hydroxy-3, 5-d ⁇ -t-butyl-benzylmercaptoacetate; tris (3, 5- d ⁇ -t-butyl-4-hydroxybenzyl) amine; bis (4-t-butyl-3-hydroxy- 2, 6-d ⁇ methylbenzyl) dithioterephthalate; bis (3, 5-d ⁇ -t-butyl-4- hydroxybenzyl) sulfide; ⁇ so-octyl-3, 5-d ⁇ -t-butyl-4-hydroxyben- zylmercaptoacetate .
  • Hydroxybenzylated malonates such as, for example: d ⁇ octadecyl-2, 2-bis (3, 5-d ⁇ -t-butyl-2-hydroxybenzyl) malonate; d ⁇ octadecyl-2- ( 3-t-butyl-4-hydroxy-5-methylbenzyl) malonate; d ⁇ dodecylmercaptoethyl-2, 2-b ⁇ s (3, 5-d ⁇ -t-butyl-4-hydroxyben- zyl) malonate; bis [4- ( 1, 1, 3, 3-tetramethylbutyl) phenyl] -2, 2- bis (3, 5-d ⁇ -t-butyl-4-hydroxybenzyl) alonate .
  • Aromatic hydroxyoenzyl compounds such as, for example: 1, 3, 5-tr ⁇ s (3, 5-d ⁇ -t-butyl-4-hydroxybenzyl) -2,4, 6-t ⁇ methyl- benzene; 1, 4-b ⁇ s- (3, 5-d ⁇ -t-butylhydroxybenzyl) -2, 3, 5, 6-te- tramethylbenzene; 2,4, 6-tr ⁇ s (3, 5-d ⁇ -t-butyl-4-hydroxybenzyl) phenol .
  • Triazine compounds such as, for example: 2 , 4-b ⁇ s (octyl- mercapto) -6- (3, 5-d ⁇ -t-butyl-4-hydroxyan ⁇ lme) -1,3, 5-tnaz ⁇ ne; 2-octylmercapto-4, 6-b ⁇ s (3, 5-d ⁇ -t-butyl-4-hydroxyan ⁇ lme) -1, - 3, 5-tr ⁇ azme; 2-octylmercapto-4 , 6-DIS (3, 5-d ⁇ -t-butyl-4-hy- droxyphenoxy) -1,3, 5-triazine; 2,4, 6-tris- (3, 5-di-t-butyl-4- hydroxyphenoxy) -1, 2, 3-triazine; 1, 3, 5-tris (3, 5-di-t-butyl-4- hydroxybenzyl) isocyanurate; 1, 3, 5-tris (4-t-butyl-3-hydroxy- 2, 6-dimethylbenzyl) isocyanurate
  • Benzylphosphonates such as, for example: dimethyl-2, 5- di-t-butyl-4-hydroxybenzylphosphonate; diethyl-3, 5-di-t-butyl -4-hydroxybenzylphosphonate; dioctadecyl-3, 5-di-t-butyl-4-hy- droxybenzylphosphonate; dioctadecyl-5-t-butyl-4-hydroxy-3-me- thylbenzylphosphonate; calcium salts of monoethyl ester of 3, 5-di-t-butyl-4-hydroxybenzylphosphonic acid.
  • Acylaminophenois such as, for example: 4-hydroxylaura- nilide; 4-hydroxystearanilide; octyl-N- (3, 5-di-t-butyl-4- hydroxyphenyl) carbamate .
  • esters of ⁇ - (3, 5-di-t-butyl-4-hydroxyphenyl) propionic acid with monohydric or polyhydric alcohols such as, for example: methanol, ethanol, n-octanol, i-octanol, octadecanol, 1, 6-hexandiol, 1, 9-nonandiol, ethylene glycol, 1,2-propa- nediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxye- thyl) isocyanurate, N, N ' -bis (hydroxyethyl) oxamide, 3-thio- undecanol, 3-thiopentadecanol, trimethylhexandiol, trimethyl- olpropane, 4-hydroxymethyl-l-phospho-2 , 6, 7-trioxabicyclo [2.
  • esters of ⁇ - (5-t-butyl-4-hydroxy-3-methylphenyl) propionic acid with monohydric or polyhydric alcohols such as, for example: methanol, ethanol, n-octanol, i-octanol, octade- canol, 1, 6-hexandiol, 1, -nonandiol, ethylene glycol, 1,2- propanediol, neopentyl glycol, thiodiethylene glycol, dieth- ylene glycol, triethylene glycol, pentaerythritol, tris (hy- droxyethyl) isocyanurate, N, N ' -bis (hydroxyethyl) oxamide, 3- thioundecanol, 3-thiopentadecanol, trimethylhexandiol, tri- methylolpropane, 4-hydroxymethyl-l-phospho-2, 6, 7-trioxabicycl
  • esters of ⁇ - (3, 5-dicyclohexyl-4-hydroxyphenyl) propionic acid with monohydric or polyhydric alcohols such as, for example: methanol, ethanol, n-octanol, i-octanol, octadecanol, 1, 6-hexandiol, 1, 9-nonandiol, ethylene glycol, 1,2-propane- diol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxy ⁇ ethyl) isocyanurate, N,N ' -bis (hydroxyethyl) oxamide, 3-thioun- decanol, 3-thiopentadecanol, trimethylhexandiol, trimethylol- propane, 4-hydroxymethyl-l-phospho-2, 6, 7-trioxabicyclo [2.2.2] octan
  • esters of (3, 5-di-t-butyl-4-hydroxyphenyI) acetic acid with monohydric or polyhydric alcohols such as, for example: methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6- hexandiol, 1, 9-nonandiol, ethylene glycol, 1, 2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N,N' -bis (hydroxyethyl) oxamide, 3-thioundecanol, 3- thiopentadecanol, trimethylhexandiol, trimethylolpropane, 4- hydroxymethyl-l-phospho-2, 6, 7-trioxabicyclo [2.2.2] octane
  • vitamin C Ascorbic acid
  • Amine Antioxidants such as, for example, N,N'-di- isopropyl-p-phenylenediamine; N, N' -di-s-butyl-p-phenylene- diamine; N, N' -bis (1, 4-dimethylpentyl) -p-phenylenediamine; N, N ' -bis (l-ethyl-3-methylpentyl) -p-phenylenediamine; N,N'- bis ( 1-methylheptyl) -p-phenylenediamine; N, N' -dicyclohexyl- p-phenylenediamine; N, N' -diphenyl-p-phenylenediamine; N,N'- bis (2-naphthyl) -p-phenylenediamine; N-isopropyl-N' -phenyl-p- phenylene-diamine; N- (1, 3-dimethylbutan
  • 2-hydroxybenzophenones such as, for example: 4-hydroxy-; 4-methoxy-; 4-octyloxy-; 4-decyloxy-; 4- dodecyloxy-; 4-benzyloxy-; 4, 2 ' , 4 ' -trihydroxy-; 2 ' -hydroxy- 4, 4 ' -dimethoxy .
  • Esters of benzoic acids optionally substituted, such as, for example: phenyl salicylate, 4-t-butylphenyl salicy- late, octylphenyl salicylate, benzoyl resorcinol, bis(4-t- butylbenzoyl) resorcinol, dibenzoyl resorcinol, 2,4-di-t- butylphenyl-3, 5-di-t-butyl-4-hydroxybenzoate, hexadecyl-3, 5- di-t-butyi-4-hydroxybenzoate, octadecyl-3, 5-di-t-butyl-4- hydroxybenzoate, 2-methyi-4, 6-di-t-butylphenyl-3, 5-di-t-but- yl-4-hydroxybenzoate.
  • benzoyl resorcinol bis(4-t- butylbenzoyl) resorcinol,
  • Acrylates such as, for example, ethyl or isoctyl ⁇ - cyano- ⁇ , ⁇ -diphenylacry!ate; methyl ⁇ -carbomethoxycinnamate, methyl or butyl ⁇ -cyano- ⁇ -methyl-p-methoxycinnamate, methyl ⁇ -carbomethoxy-p-methoxycinnamate, N- ( ⁇ -carbomethoxy- ⁇ -cyano- vinyl ) -2-methylindoline .
  • Nickel compounds such as, for example, complexes of 2,2'-thio-bis-[4- ( 1, 1, 3, 3-tetramethylbutyl) phenol] , for example 1:1 or 1:2 complexes, with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldi- ethanolamine, nickel dibutyldithiocarbamate, nickel salts of monoalkyl esters of 4-hydroxy-3, 5-di-t-butyl-benzyl- phosphonic acid, such as methyl or ethyl esters, nickel com- plexes with ketoximes such as 2-hydroxy-4-methylphenyl unde- cyl ketoxime, nickel complexes of l-phenyl-4-lauroyl-5- hydroxypyrazol with or without additional ligands.
  • additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldi- ethanolamine, nickel dibuty
  • Sterically hindered amines such as, for example: poly- methylpropyl-3-oxy- [4-2, 2, 6, 6-tetramethyl) -piperidmyl] silox- ane, polymethylpropyl-3-oxy- [4- (1, 2, 2, 6, 6-pentamethyl) -piperidmyl] siloxane, bis (2, 2 , ⁇ , 6-tetramethyl-4-p ⁇ pe ⁇ dyl) sebacate; bis (2, 2, 6, 6-tetramethyl-4-p ⁇ per ⁇ dyl) succmate; bis (1,2,2,6, 6-pentamethyl-4-piperidyl) sebacate; bis (1-octyloxy- 2,2,6, 6-tetramethyl-4-p ⁇ pe ⁇ dyl) sebacate; bis (1, 2, 2, 6, 6-pen- tamethyl-4-p ⁇ pe ⁇ dyl) n-butyl-3, 5-d ⁇ -t-butyl-4-hydroxyben- zylmalonate; condensation product between l-(2-
  • Oxamides such as, for example: 4, 4 ' -dioctyloxyox- anilide; 2, 2 ' -diethoxyoxanilide; 2, 2 ' -dioctyloxy-5, 5' -di- t-butoxanilide; 2,2' -didodecyloxy-5, 5 ' -di-t-butoxanilide; 2-ethoxy-2 ' -ethyloxanilide; N, ' -bis ( 3-dimethylaminopro- pyl) oxamide; 2-ethoxy-5-t-butyl-2 ' -ethoxanilide and its mixtures with 2-ethoxy-2 '-ethyl-5, 4 '-di-t-butoxanilide; and mixtures of disubstituted ortho- and para-methoxy anilides and mixtures of disubstituted ortho and para-ethoxy anilides and mixture
  • Metal-deactivators such as, for example: N,N-d ⁇ - phenyloxamide, N-salicylal-N ' -salicyloyl-hydrazme, N,N'- bis (salicyloyl) hydrazme, N,N' -bis (3, 5-d ⁇ -t-butyl-4-hydroxy- phenylpropionyl) hy ⁇ raz ne, 3-sal ⁇ cyloyIammo-l, 2, 4-tr ⁇ azole, bis (benzylidene) oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N, N ' -diacetyladi- poyl dihydrazide, N, N ' -bis (salicyloyl) oxallyl dihydrazide, N,N ' -bis (s
  • Phosphites and phosphonites such as, for example: t ⁇ - phenyl phosphite, diphenyl alkyl phosphites, pnenyl dialkyl phosphites, tris (nonylphenyl) phosphite, trilauryl phosphite, t ⁇ octadecyl phosphite, distearyl pentaerythritol diphos- phite, tris (2, 4-d ⁇ -t-butylphenyl) phosphite, dnsodecyl pentaerythritol diphosphite, bis (2, 4-d ⁇ -t-butylphenyl) pentae- ryth ⁇ tol diphosphite, bis (2, 6-d ⁇ -t-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyloxypentaeryth
  • Hydroxylammes such as, for example: N,N-d ⁇ ben- zylhydroxylamme; N, N-diethylhydroxylamme; N,N-d ⁇ octyl- hydroxylamme; N, N-dilaurylhydroxylamme; N,N-d ⁇ tetradecyl- hydroxylamme; N, N-dihexadecylhydroxylamme; N,N-d ⁇ octa- decylhydroxylamme; N-hexadecyl-N-octadecylhydroxylamme; N- heptadecyl-N-octadecylhydroxylamme; N, N-hydroxylamme deriving from hydrogenated tallow amine.
  • Nitrones such as, for example: N-benzyl- -phenyl- nitrone; N-ethyl- ⁇ -phenyl-nitrone; N-octyl- ⁇ -heptyl-mtrone; N-lauryl- ⁇ -undecyl -nit rone; N-tetradecyl- ⁇ -tridecyl-nitrone; N-hexadecyl- ⁇ -pentadecyl-nitrone; N-octaoecyl- ⁇ -heptadecyl- nitrone; N-hexadecyl- ⁇ -heptadecyl-mtrone; N-octadecyl- ⁇ - pentadecyl-nitrone; N-heptadecyl- -heptadecyl-mtrone; N- octadeyl- ⁇ -hexadecyl-nitrone; nitro
  • Thiosynergizmg agents such as, for example: dilauryl thiodipropionate; distearyl thiodipropionate .
  • Agents which are capable of destroying peroxides such as, for example, esters of ⁇ -thiodipropionic acid such as lauryl, stearyl, myristyl or t ⁇ decyl esters, mercaptobenz- lmidazole or zinc salt of 2-mercaptobenz ⁇ m ⁇ dazole, z nc di- butylditmocarbamate, dioctadecyldisulfide, pentaerythritol tetrakis ( ⁇ -dodecylmercapto) propionate .
  • esters of ⁇ -thiodipropionic acid such as lauryl, stearyl, myristyl or t ⁇ decyl esters
  • mercaptobenz- lmidazole or zinc salt of 2-mercaptobenz ⁇ m ⁇ dazole z nc di- butylditmocarbamate, dioctadecyldisulfide
  • Stabilizers of polyamide such as, for example, copper salts combined with compounds of iodine and/or phosphorous, divalent manganese salts.
  • Basic co-stabilizers such as, for example: melamine, polyv ylpyrrolidone, dicyanodiamide, triallyl cyanurate, derivatives of urea, derivatives of hydrazme, amines, poly- amides, poiyurethanes, salts of alkaline metals and salts of earth-alkaline metals of fatty acids with a high molecular weight such as, for example, Ca-stearate, Zn-stearate, Mg- stearate, Mg-behenate, Na-ricmoleate, K-palmitate, antimo- nium-pyrocatecholate, tm-pyrocatecholate . 11.
  • Basic co-stabilizers such as, for example: melamine, polyv ylpyrrolidone, dicyanodiamide, triallyl cyanurate, derivatives of urea, derivatives of hydrazme, amines, poly- amides, poiyurethane
  • Nucleating agents such as, for example: inorganic substances sucn as talc, metal oxides (for example, titanium dioxide or magnesium oxide), phosphates, carbonates or sul- fates (preferably of earth-alkaline metals); organic compounds such as mono- or polycarboxylic acids and their salts (for example, 4-t-butylbenzo ⁇ c acid, adipic acid, diphen- ylacetic acid, sodium succmate, sodium benzoate) ; polymeric compounds such as ionic copolymers ("lonomers" ) . 12.
  • Fillers and reinforcing agents such as, for example: calcium carbonate, silicates, glass fibres, asbestos, talc, kaolm, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flours or fibres of other natural products, synthetic fibres.
  • additives such as, for example: plasticizers, lubricants, emulsifying agents, pigments, rheological addi- tives, catalysts, slip agents, optical brighteners, flame- retardants (for example bromurates, chlorurates, phosphorates and phosphorous/halogen mixtures), antistatic agents, blowing agents.
  • Benzofuranones and indolinones such as, for example: 3- [4- (2-acetoxyethoxy) phenyl] -5, 7-di-t-butylbenzofuran-2- one; 5, 7-di-t-butyl-3- [4- (2-stearoyloxyethoxy) phenyl] benzo- furan-2-one; 3,3' -bis [5, 7-di-t-butyl-3- [4- (2-hydroxyethoxy) phenyl] benzofuran-2-one] ; 5, 7-di-t-butyl-3- (4-ethoxyphenyl) - benzofuran-2-one; 3- (4-acetoxy-3, 5-dimethyl-phenyl) -5, 7-di- t-butyl-benzofuran-2-one; 3- (3, 5-di-methyl-4-pivaloyloxy- phenyl) -5, 7-di-t-butyl-benz
  • EXAMPLE 1 60 g of octadecyl-3- (3 ', 5 ' -di-t-butyl-4 ' -hydroxy- phenyl )propionate (Anox PP18 of Great Lakes) are melted at a temperature ranging from 50°C to 60°C. 40 g of tetrakis [3- (3, 5-di-t-butyl-4-hydroxy-phenyl) propionyloxymethyl]methane (Anox 20 of Great Lakes) are subsequently added: the whole mixture is maintained at a temperature ranging from 50°C to 60°C until complete homogenization.
  • the homogeneous dispersion obtained is left to cool to room temperature obtaining a solid which is subsequently ground.
  • a powder is obtained which is subjected to DSC (Differential Scanning Calorimetry) analysis and the result obtained is indicated in Figure 1.
  • the powder obtained is also subjected to X-Ray analysis and the spectrum from powders obtained is indicated in Figure 2.
  • Figure 1 clearly shows that the mixture obtained has a melting peak at about 50°C, close to the melting point of octadecyl-3- ( 3 ' , 5 ' -di-t-butyl-4 ' -hydroxyphenyl ) propionate .
  • the melting point of tetrakis [3-(3,5-di- t-butyl-4-hydroxyphenyl) propionyloxymethyl] methane is not indicated: in fact, Figure 1 does not show any endothermic melting peak at about 110°C-125°C typical of tetrakis [3-
  • the above mixture is cooled to 0°C obtaining a precipitate which, after filtration and drying, is analyzed.
  • the quantitative analysis indicates a content of Anox PP18 of 52.6% and a content of Anox 20 of 47.4% and the DSC (Differential Scanning Calorimetry) analysis shows an analogous result to that indicated in Figure 1.

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Abstract

Stabilizing mixture comprising: (a) tetrakis [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxymethyl]methane; (b) octadecyl-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate; characterized in that it has a melting point ranging from 50 °C to 60 °C. The above mixture can be used as stabilizer for the oxidative degradation of organic polymers caused by light and/or heat.

Description

STABILIZING MIXTURE HAVING A MELTING POINT LOWER THAN THAT OF THE HIGHEST MELTING COMPONENT.
The present invention relates to a stabilizing mixture having a melting point lower than that of tne highest melting component .
More specifically, the present invention relates to a stabilizing mixture having a melting point lower than that of the highest melting component comprising octadecyl-3- (3 ' , 5 ' -dι-t-butyl-4 ' -hydroxyphenyl) propionate and tetra is [3- (3, 5-dι-t-butyl-4-hydroxyphenyl) propionyloxymethyl] ethane and its use as stabilizer for the oxidative degradation of organic polymers caused by light and/or heat.
The present invention also relates to the polymeric compositions stabilized with the above stabilizing mixture and to the end-articles obtained from these compositions.
It is known in the art that the relatively high melting point, 110°C-125°C, of tetrakis [3- (3, 5-dι-t-butyl-4-hydro- xyphenyl) propionyloxymethyl] methane is a problem in the sta- bilization of organic polymers in those fields of applica- tion in which the polymer is processed at relatively low temperatures as, for example, in the case of blow-moulding of low or high density polyethylene, in the processing of natural rubber, or in hot-melts. In the above cases, tetrakis [3- (3, 5-di-t-butyl-4- hydroxyphenyl) propionyloxymethyl] methane can only partially melt creating problems of distribution heterogeneity, with the consequent formation of fragility zones in the end- article obtained as a result of the presence of segregate crystals.
The Applicant has now found that it is possible to lower the melting point of tetrakis [3- (3, 5-di-t-butyl-4- hydroxyphenyl) propionyloxymethyl] methane by mixing it with octadecyl-3- ( 3 ' , 5 ' -di-t-butyl-4 ' -hydroxyphenyl ) propionate . In this way a mixture of the two stabilizers is obtained characterized in that it has a melting range from 50°C to 60°C: this melting range is consequently close to the melting point of octadecyl-3- (3 ', 5 ' -di-t-butyl-4 ' -hydroxyphenyl) proprionate which, as is known, is 49°C-53DC. The above mixture can be used at low temperatures allowing a better homogenization inside the polymer to be stabilized thus overcoming the disadvantages of the known art.
The present invention therefore relates to a stabilizing mixture comprising: (a) tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionyl- oxymethyl] methane having formula [ I ]
Figure imgf000005_0001
/ /
HO ' > CH CH C00CH — C ( I )
Figure imgf000005_0002
(b) octadecyl-3- (3 ' , 5 ' -di-t-butyl-4 ' -hydroxyphenyl) propion- ate having formula (II) :
Figure imgf000005_0003
characterized in that it has a melting point ranging from 50°C to 60°C.
Component (a) having formula (I) and component (b) having formula (II) are used in a ratio ranging from 9:1 to 1:9, preferably from 3:1 to 1:3. Component (a) having formula (I) is known under the following trade-names: Anox 20 of Great Lakes, Irganox 1010 of Ciba.
Component (b) having formula (II) is known under the following trade-names: Anox PP18 of Great Lakes, Irganox 1076 of Ciba. The stabilizing mixture of the present invention can be obtained by means of various processes.
A first process consists m taking the fine powders of the two components (a) and (b) and mixing them thoroughly under grinding.
A second process consists in dispersing the high melting component (a) in the low melting molten compound (b) and leaving the mixture of the two components, optionally under stirring, at a temperature ranging from 50°C to 60°C, until a homogeneous dispersion is obtained.
This dispersion is subsequently left to cool to room temperature, until a solid is obtained which is then ground or flaked.
A third process consists m melting both components (a) and (b) and leaving the mixture of the two components, optionally under stirring, at a temperature ranging from 120 °C to 130°C, until a homogeneous solution is obtained.
This solution is subsequently left to cool to room temperature, until a solid is obtained which is then ground or flaked.
Finally, a fourth process consists in the co- crystallization of the two components (a) and (b) , in the desired ratios, from an organic solvent m which these components are both soluble under heat and insoluble at cold such as, for example, methanol, a mixture of methanol/water, a mixture of acetone/water, etc.
The above stabilizing mixtures can be used as stabilizers for the oxidative degradation of organic polymers caused by light and/or heat. Examples of organic polymers which can be stabilized are:
1. Polymers of mono-olefins and diolefins such as, for example, polypropylene, polyisobutylene, polybut-1-ene, poly-4- methylpent-1-ene, polyisoprene or polybutadiene; as well as polymers of cyclo-olefins such as, for example, cyclopentene or norbornene; polyethylene (which can be optionally cross- linked) such as, for example, high density polyethylene (HDPE) , high density and high molecular weight polyethylene (HDPE-HMW) , high density and ultrahigh molecular weight poly¬ ethylene (HDPE-UHMW) , medium density polyethylene (MDPE) , low density polyethylene (LDPE) , linear low density polyethylene (LLDPE) , branched low density polyethylene (BLDPE) .
Polyolefins such as, for example the monolefins men¬ tioned in the above paragraph, preferably polyethylene and polypropylene, can be prepared with various methods known in literature, preferably using the following methods:
(a) radicalic polymerization (generally carried out at a high pressure and high temperature) ;
(b) catalytic polymerization using a catalyst which normally contains one or more metals of groups IVb, Vb, VIb or VIII of the Periodic Table. These metals generally have one or more iigands such as, for example, oxides, hal- ides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls which can be π- or σ-coordinated. These metal complexes can be in free form or supported on substrates such as, for example activated magnesium chloride, titanium (III) chloride, alumina or silicon oxide. These catalysts can be soluble or insoluble in the reaction medium. The catalysts can be used alone or in the presence of other activators such as, for example, metal alkyls, metal hydrides, halides of metal alkyls, oxides of metal alkyls or metal alkyloxanes, these metals being elements belonging to groups la, Ila and/or Ilia of the Periodic Table. The activators can be conveniently modified with other ester, ether, amine or si- lyl-ether groups. These catalytic systems are usually called Phillips, Standard Oil Indiana, Ziegler (-Natta) , TNZ (Du-Pont), metallocene or "single site catalyst" (SSC) .
2. Mixtures of the polymers described under point (1) such as, for example, mixtures of polypropylene with polyisobutyl- ene; mixtures of polypropylene with polyethylene (for example, PP/HDPE, PP/LDPE); mixtures of different types of poly¬ ethylene (for example, LDPE/HDPE) .
3. Copolymers of mono-olefins and diolefins with each other or with other vinyl monomers such as, for example, ethylene- propylene copolymers, linear low density polyethylene (LLDPE) and its mixtures with low density polyethylene (LDPE) , pro- pylene/but-1-ene copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copoly- mers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/alkyl ac- rylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers and their copolymers with carbon monoxide or ethylene/acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with polypropylene and a diene such as, for example, hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of these copolymers with each other or with the polymers cited in paragraph (1) such as, for example, polypropyl- ene/ethylene/propylene copolymers, LDPE/ethylene/vinylacetate (EVA) copolymers, LDPE/ethylene/acrylic acid (EAA) copolymers, LLDPE/EVA, LLDPE/EAA, and alternating or random polyal- kylene/carbon monoxide copolymers and their mixtures with other polymers such as, for example, polyamides.
4. Hydrocarbon resins (for example, C5-C9) comprising their hydrogenated modifications (for example, adhesive agents) and mixtures with polyalkylene and starch.
5. Polystyrene, poly (p-methylstyrene) , poly (α-methylstyre- ne) . 6. Copolymers of styrene or α-methylstyrene with dienes or acrylic derivatives such as, for example, styrene/butadiene, styrene/acrylonitrile, styrene/alkyl methacrylate, styrene/ butadiene/alkyl acrylate, styrene/butadiene/alkyl methacryla- te, styrene/maleic anhydride, styrene/acrylonitrile/methyl acrylate; mixtures, having a high impact strength, between copolymers of styrene and another polymer such as, for example, a polyacrylate, a polymer of a diene or an ethy- lene/propylene/diene terpolymer, block copolymers of styrene such as, for example, styrene/butadiene/styrene, styrene/iso- prene/styrene, styrene/ethylene/butylene/styrene or styrene/ ethylene/propylene/styrene .
7. Grafted copolymers of styrene or of α-methylstyrene such as, for example, styrene on polybutadiene, styrene on polybu- tadiene or polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methylmethacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkylacrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene/propylene/diene ter- polymers, styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on ac- rylate/butadiene copolymers, as well as mixtures of the co- polymers listed above with the copolymers cited under point (6) such as, for example, mixtures of known copolymers such as ABS, MBS, ASA or AES .
8. Polymers containing halogens such as, for example, poly- chloroprene, chlorinated rubbers, chlorinated or brominated isobutylene-isoprene copolymers ("halobutyl rubber"), chlorinated or chlorosulfonated polyethylene, ethylene and chlorinated ethylene copolymers, homopolymers and copolymers of epichlorohydrin, in particular polymers of vinyl compounds containing halogens such as, for example, polyvinyl chloride, polyvinylidenechloride, polyvinyl fluoride or polyvinylidene- fluoride; and also their copolymers such as, for example, vinyl chloride/vinyiidenechloride, vinyl chloride/vinyl acetate or vinylidenechloride vinyl acetate. 9. Polymers deriving from α, β-unsaturated acids and their derivatives such as, for example, polyacrylates and poly- methacrylates, polymethyl methacrylates, polyacrylamides and polyacryionitriles, modified with butyl acrylate. 10. Copolymers of monomers according to point (9) with each other or with other unsaturated monomers such as, for exam¬ ple, acrylonitrile/butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate co¬ polymers or acrylonitrile/vinyl halide copolymers or acrylo¬ nitrile/alkyl met acrylate/butadiene terpolymers. 11. Polymers deriving from unsaturated alcohols and amines, or their acyl or acetal derivatives such as, for example, polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyrral, polyallyl phthalate or poiyallyl melamine; and also their co- polymers with the olefins listed under point (1).
12. Homopolymers and copolymers of open-chain ethers or cyclic ethers such as, for example, polyalkylene glycols, polyethylene oxide, polypropylene oxide, or copolymers of the compounds described above with bis-glycidyl ethers. 13. Polyacetais such as, for example, polyoxymethylene and those polyoxymethylenes containing ethylene oxide as comono- mer; polyacetais modified with thermoplastic poiyurethanes, acrylates or MBS.
14. Polyphenylene oxides and sulfides and mixtures of poly- phenylene oxides with styrene or polyamide polymers.
15. Poiyurethanes deriving from hydroxyl-terminated poly- ethers, polyesters or polybutadienes on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as the precursors of the above compounds . 16. Polyamides and copolyamides deriving from diamines and dicarboxylic acids and/or aminocarboxylic acids or from the corresponding lactams such as, for example, polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides obtained starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic and/or terephthalic acid and with or without an elastomer as modifier, for example, poly-2, 4, 4-trimethylhexamethylene tereph- thalamide or poly-m-phenylene isophthalamide; and also block copolymers of the above polyamides with polyolefins, olefinic copolymers, ionomers or elastomers chemically bound or grafted; or with polyethers such as, for example, polyethylene glycol, polypropylene glycol or polytetramethylene gly- col; as well as polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing ("RIM polyamide system") .
17. Polyureas, polyimides, polyamide-i ides, polyetheri- mides, polyesterimides, polyhydantoins, and polybenzoimid- azoles . 18. Polyesters deriving from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or from the corresponding lactones such as, for example, polyethylene terephthalate, polybutylene terephthalate, poly-1, 4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates, as well as block co- polyether esters deriving from polyethers with ydroxyl- terminated groups; and also polyesters modified with polycarbonates or MBS.
19. Polycarbonates and polyester carbonates.
20. Polysulfones, polyethersulfones and polyetherketones . 21. Cross-linked polymers deriving from aldehydes on the one hand and from phenols, urea and melamines on the other, such as, for example, phenol/formaldehyde resins, urea/formaldehyde resins and melamine/formaldehyde resins. 22. Drying or non-drying alkyd resins. 23. Resins based on unsaturated polyesters deriving from co- polyesters of dicarboxyl acids saturated and unsaturated with polyhydric alcohols and vinyl compounds as cross-linking agents, and also the above resins containing halogens and having a good flame-resistance. 24. Cross-linkable acrylic resins deriving from substituted acrylates such as, for example, epoxy acrylates, urethane ac- rylates or polyester acrylates.
25. Alkyd resins, resins based on polyesters or acrylated resins cross-linked with melamine resins, resins based on urea, resins based on isocyanates, resins based on iso- cyanurates, resins based on polyisocyanates or epoxy resins.
26. Cross-linked epoxy resins deriving from aliphatic, cy- cloaliphatic, heterocyclic or aromatic glycidyl compounds such as, for example, products of diglycidyl ethers of bisphenol A and bisphenol F, which are cross-linked with the usual hardening agents such as, for example, anhydrides or amines, in the presence of or without accelerating agents.
27. Natural polymers such as, for example, cellulose, rubber, gelatine, and their derivatives chemically modified to give homologous polymers such as, for example, cellulose ace- tates, propionates and butyrates, or cellulose ethers such as, for example, methyl-cellulose; as well as hydrocarbon resins ("rosins") and their derivatives.
28. Mixtures of the above polymers ( "polybiends" ) such as, for example, PP/EPDM, polyamides/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylates, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS, PBT/PET/PC. 29. Natural or synthetic organic materials which are pure monomeric compounds or mixtures of said compounds, such as, for example, mineral oils, animal or vegetable oils, fats or waxes, oils, fats or waxes based on synthetic esters (for example, phthalates, adipates, phosphates, trimellitates) , as well as mixtures of synthetic esters with mineral oils in any weight ratio, in particular those used in spinning compositions, as well as aqueous emulsions of said organic materials. 30. Aqueous emulsions of natural or synthetic rubbers such as, for example, natural latex or latexes based on carboxy- lated styrene-butadiene copolymers.
The present invention also relates to polymeric compositions containing an organic polymer and an effective quantity of the above stabilizing mixture. The stabilizing mixture of the present invention is particularly useful in the stabilization of syntnetic organic polymers selected from those listed above. It is preferably used m the stabilization of organic polymers which are subjected to processing at relatively low temperatures such as, for example, m the peptization of natural rubber which is carried out at 90°C.
A further object of the present invention relates to the end-articles obtained from the processing of the above polymeric compositions. The stabilizing mixture of the present invention is added to the organic polymers to be stabilized m a quantity ranging from 0.01% to 5% with respect to the total weight of the polymer to be stabilized, preferably from 0.05% to 3%, even more preferably from 0.1% to 1%. The staoilizmg mixture of the present invention can be incorporated into the organic polymer to be stabilized using the known techniques .
The stabilizing mixture of the present invention can be combined with other conventional additives or their mixtures. These additives are added m a quantity ranging from about 0.1% to about 5% by weight with respect to the weight of the polymeric compositions to be stabilized, preferably from about 0.5% to about 3% by weight. Some of the additives used are listed below as an example. 1. Antioxidants 1.1 Alkylated monophenols such as, for example: 2,6-di-t- butyl-4-methylphenol; 2-t-butyI-4, 6-dιmethylphenol; 2, 6-di-t- butyi-4-ethylphenol; 2, 6-dι-t-butyl-4-n-butylphenol; 2,6-di- t-butyl-4-isobutylphenol; 2, 6-di-cyclopentyl-4-methylphenol; 2- (α-methylcyclohexyl) -4, 6-dimethylphenol; 2, 6-dioctadecyl-4- methylphenol; 2 , 4 , 6-trιcyclohexylphenol; 2, 6-di-t-butyl-4- methoxymethylphenol; nonylphenols with a linear or branched alkyl chain such as, for example, 2, 6-dι-nonyl-4-me- thylphenol; 2 , 4-dιmethyl-6- (1 ' -methylundec-1 ' -yl) phenol; 2,4 -dimethyl-6- ( 1 ' -methylheptadec-1 ' -yl) phenol; 2, 4-dimethyl-6- (1 ' -methyltridec-1 ' -yl) phenol; and their mixtures.
1.2 Alkylthiomethylphenols such as, for example: 2,4-dιoc- tylthiomethyl-6-t-butylphenol; 2, 4-dιoctylthiomethyl-6-me- thylphenol; 2, 4-dιoctylthιomethyl-β-ethylphenol; 2,6-dιdo- decylthιomethyl-4-nonylphenol .
1.3 Hydroquinones and alkylated hydroqumones such as, for example: 2, 6-di-t-butyl-4-methoxyphenol; 2, 5-αι-t-butylhydro- quinone; 2, 5-di-t-amylhydroquιnone; 2, 6-di-phenyl-4-octade- cyloxyphenol; 2, 6-di-t-butylhydroquinone; 2, 5-dι-t-butyl-4- hydroxyanisole; 3, 5-dι-t-butyl-4-hydroxyanisole; 3,5-dι-t-bu- tyl-4-hydroxyphenyl stearate; bis (3, 5-di-t-butyl-4-hydro- xyphenyl) adipate .
1.4 Tocopherols such as, for example: α-tocopherol, β- tocopherol, γ-tocopherol, δ-tocopherol and their mixtures (Vi- tamin E) . 1.5 Hydroxylated thiodiphenyl ethers such as, for example 2,2' -thiobis- ( 6-t-butyl-4-methylphenol ) ; 2,2' -thiobis- ( 4- octylphenol ) ; 4,4' -thiobis- ( 6-t-butyl-3-methylphenol ) ; 4 , 4 ' - thiobis- ( 6-t-butyl-2-methylphenol ) ; 4, 4 ' -thiobis- (3, 6-di-s- amylphenol) ;4, 4 '-bis- (2, 6-dimethyl-4~hydroxyphenyl) isulfide.
1.6 Alkylidene-bisphenols such as, for example: 2, 2 '-met yl- enebis- ( 6-t-butyl-4-methylphenol ) ; 2,2' -methylenebis- ( 6-t-bu- tyl-4-ethylphenol) ; 2,2 '-methylenebis [4-methyl-6- (α-methylcyclohexyl) phenol] ; 2,2' -methylenebis (4-methyl-6-cyclo-hexyl- phenol); 2, 2 ' -methylenebis (6-nonyl-4-methyl-phenol) ; 2, 2' -methylenebis (4, 6-di-t-butylphenol) ; 2, 2 '-ethylidene-bis (4, 6-di- t-butylphenol ) ; 2,2' -ethylidenebis ( 6-t-butyl-4-isobutyl-phen- ol) ; 2,2' -methylenebis [6- (α-methylbenzyl) -4-nonylphenol] ; 2, 2 '-methylenebis [6- (α,α-dimethylbenzyl) -4-nonylphenol] ; 4,4' -methylenebis (2, 6-di-t-butylphenol) ; 4,4' -methylenebis (6- t-butyl-2-methylphenol) ; 1, 1-bis (5-t-butyl-4-hydroxy-2-me- thylphenyl) butane; 2, 6-bis (3-t-butyl-5-methyl-2-hydroxyben- zyl) -4-methylphenol; 1, 1, 3-tris- (5-t-butyl-4-hydroxy-2-me- thylphenyl) butane; 1, 1-bis (5-t-butyl-4-hydroxy-2-methylphe- nyl) -3-n-dodecylmercaptobutane; ethyleneglycol bis[3,3-bis- (3'-t-butyl-4 ' -hydroxyphenyl )butyrate] ; bis (3-t-butyl-4-hy- droxy-5-methylphenyI) dicyclopentadiene; bis [2- ( 3 ' -t-butyl-2 ' - hydroxy-5 '-methylbenzyl) -6-t-butyl-4-methylphenyl] terephthalate; 1, 1-bis (3, 5-dimethyl-2-hydroxyphenyl) butane; 2,2-bis- (3, 5-di-t-butyl-4-hydroxyphenyl) propane; 2, 2-bis (5-t-butyl-4- hydroxy-2-methylphenyl) -4-n-dodecylmercaptobutane; 1,1,5, 5-tetra (5-t-dutyl-4-hydroxy-2-methylphenyl) pentane.
1.7 Benzyl compounds containing 0, N or S such as, for example: 3, 5, 3 ' , 5 ' -tetra-t-butyl-4, 4 ' -dihydroxydibenzyl ether; octadecyl-4-hydroxy-3, 5-dιmethylbenzylmercaptoacetate; tride- cyl-4-hydroxy-3, 5-dι-t-butyl-benzylmercaptoacetate; tris (3, 5- dι-t-butyl-4-hydroxybenzyl) amine; bis (4-t-butyl-3-hydroxy- 2, 6-dιmethylbenzyl) dithioterephthalate; bis (3, 5-dι-t-butyl-4- hydroxybenzyl) sulfide; ιso-octyl-3, 5-dι-t-butyl-4-hydroxyben- zylmercaptoacetate .
1.8 Hydroxybenzylated malonates such as, for example: dιoctadecyl-2, 2-bis (3, 5-dι-t-butyl-2-hydroxybenzyl) malonate; dιoctadecyl-2- ( 3-t-butyl-4-hydroxy-5-methylbenzyl) malonate; dιdodecylmercaptoethyl-2, 2-bιs (3, 5-dι-t-butyl-4-hydroxyben- zyl) malonate; bis [4- ( 1, 1, 3, 3-tetramethylbutyl) phenyl] -2, 2- bis (3, 5-dι-t-butyl-4-hydroxybenzyl) alonate .
1.9 Aromatic hydroxyoenzyl compounds such as, for example: 1, 3, 5-trιs (3, 5-dι-t-butyl-4-hydroxybenzyl) -2,4, 6-tπmethyl- benzene; 1, 4-bιs- (3, 5-dι-t-butylhydroxybenzyl) -2, 3, 5, 6-te- tramethylbenzene; 2,4, 6-trιs (3, 5-dι-t-butyl-4-hydroxybenzyl) phenol .
1.10 Triazine compounds such as, for example: 2 , 4-bιs (octyl- mercapto) -6- (3, 5-dι-t-butyl-4-hydroxyanιlme) -1,3, 5-tnazιne; 2-octylmercapto-4, 6-bιs (3, 5-dι-t-butyl-4-hydroxyanιlme) -1, - 3, 5-trιazme; 2-octylmercapto-4 , 6-DIS (3, 5-dι-t-butyl-4-hy- droxyphenoxy) -1,3, 5-triazine; 2,4, 6-tris- (3, 5-di-t-butyl-4- hydroxyphenoxy) -1, 2, 3-triazine; 1, 3, 5-tris (3, 5-di-t-butyl-4- hydroxybenzyl) isocyanurate; 1, 3, 5-tris (4-t-butyl-3-hydroxy- 2, 6-dimethylbenzyl) isocyanurate; 2,4, 6-tris- (3, 5-di-t-butyl -4-hydroxyphenylethyl) -1, 3, 5-triazine; 1, 3, 5-tris (3, 5-di-t- butyl-4-hydroxyphenylpropionyl) hexahydro-1, 3, 5-triazine; 1, 3, 5-tris (3, 5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.
1.11 Benzylphosphonates such as, for example: dimethyl-2, 5- di-t-butyl-4-hydroxybenzylphosphonate; diethyl-3, 5-di-t-butyl -4-hydroxybenzylphosphonate; dioctadecyl-3, 5-di-t-butyl-4-hy- droxybenzylphosphonate; dioctadecyl-5-t-butyl-4-hydroxy-3-me- thylbenzylphosphonate; calcium salts of monoethyl ester of 3, 5-di-t-butyl-4-hydroxybenzylphosphonic acid.
1.12 Acylaminophenois such as, for example: 4-hydroxylaura- nilide; 4-hydroxystearanilide; octyl-N- (3, 5-di-t-butyl-4- hydroxyphenyl) carbamate .
1.13 Esters of β- (3, 5-di-t-butyl-4-hydroxyphenyl) propionic acid with monohydric or polyhydric alcohols such as, for example: methanol, ethanol, n-octanol, i-octanol, octadecanol, 1, 6-hexandiol, 1, 9-nonandiol, ethylene glycol, 1,2-propa- nediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxye- thyl) isocyanurate, N, N ' -bis (hydroxyethyl) oxamide, 3-thio- undecanol, 3-thiopentadecanol, trimethylhexandiol, trimethyl- olpropane, 4-hydroxymethyl-l-phospho-2 , 6, 7-trioxabicyclo [2. - 2 . 2 ] octane .
1.14 Esters of β- (5-t-butyl-4-hydroxy-3-methylphenyl) propionic acid with monohydric or polyhydric alcohols such as, for example: methanol, ethanol, n-octanol, i-octanol, octade- canol, 1, 6-hexandiol, 1, -nonandiol, ethylene glycol, 1,2- propanediol, neopentyl glycol, thiodiethylene glycol, dieth- ylene glycol, triethylene glycol, pentaerythritol, tris (hy- droxyethyl) isocyanurate, N, N ' -bis (hydroxyethyl) oxamide, 3- thioundecanol, 3-thiopentadecanol, trimethylhexandiol, tri- methylolpropane, 4-hydroxymethyl-l-phospho-2, 6, 7-trioxabicyclo [2.2.2] octane .
1.15 Esters of β- (3, 5-dicyclohexyl-4-hydroxyphenyl) propionic acid with monohydric or polyhydric alcohols such as, for example: methanol, ethanol, n-octanol, i-octanol, octadecanol, 1, 6-hexandiol, 1, 9-nonandiol, ethylene glycol, 1,2-propane- diol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxy¬ ethyl) isocyanurate, N,N ' -bis (hydroxyethyl) oxamide, 3-thioun- decanol, 3-thiopentadecanol, trimethylhexandiol, trimethylol- propane, 4-hydroxymethyl-l-phospho-2, 6, 7-trioxabicyclo [2.2.2] octane .
1.16 Esters of (3, 5-di-t-butyl-4-hydroxyphenyI) acetic acid with monohydric or polyhydric alcohols such as, for example: methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6- hexandiol, 1, 9-nonandiol, ethylene glycol, 1, 2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N,N' -bis (hydroxyethyl) oxamide, 3-thioundecanol, 3- thiopentadecanol, trimethylhexandiol, trimethylolpropane, 4- hydroxymethyl-l-phospho-2, 6, 7-trioxabicyclo [2.2.2] octane.
1.17 Amides of β- (3, 5-di-t-butyl-4-hydroxyphenyl) propionic acid such as, for example: N,N' -bis (3, 5-di-t-butyl-4-hydro- xyphenylpropionyl) hexamethylenediamine; N,N ' -bis (3, 5-di-t-bu- tyl-4-hydroxyphenylpropionyl) trimethylenediamine; N,N ' -bis (3, 5-di-t-butyl-4-hydroxyphenylpropionyl) hydrazine .
1.18 Ascorbic acid (vitamin C) .
1.19 Amine Antioxidants such as, for example, N,N'-di- isopropyl-p-phenylenediamine; N, N' -di-s-butyl-p-phenylene- diamine; N, N' -bis (1, 4-dimethylpentyl) -p-phenylenediamine; N, N ' -bis (l-ethyl-3-methylpentyl) -p-phenylenediamine; N,N'- bis ( 1-methylheptyl) -p-phenylenediamine; N, N' -dicyclohexyl- p-phenylenediamine; N, N' -diphenyl-p-phenylenediamine; N,N'- bis (2-naphthyl) -p-phenylenediamine; N-isopropyl-N' -phenyl-p- phenylene-diamine; N- (1, 3-dimethylbutyl) -N' -phenyl-p-pheny- lenediamine; N- ( 1-methylheptyl) -N' -phenyl-p-phenylenediami- ne; N-cyclohexyl-N' -phenyl-p-phenylenediamine; 4-(p- toluenesulfamoyl) diphenyleneamine; N,N' -dimethyl-N, N' -di-s- butyl-p-phenylenediamine; diphenylamine; N-allyl-diphenyl- amine; 4-isopropoxydiphenylamine; N-phenyl-1-naphthylamine ; N- (4-t-octylphenyl) 1-naphthylamine; N-phenyl-2-naphthyl- amine; diphenylamine octylate such as, for example, p,p'- di-t-octyldiphenylamine; 4-n-butylaminophenol; 4-butiryiami- nophenol; 4-nonanoyiaminophenol; 4-dodecanoylaminophenol; 4- octadecanoylaminophenol; bis (4-methoxy-phenyl) amine; 2,6- di-t-butyl-4-dimethylaminomethylphenol; 2, 4' -di-aminodi- phenylmethane; 4 , 4' -diamino-diphenylmethane; N,N,N' ,N' -te- tramethyl-4, 4' -diamino-diphenylmethane; 1, 2-bis [ (2-methyl- phenyl) amino] ethane; 1, 2-bis (phenylamino) propane; (o-to- lyDbiguanide; bis [4- ( 1' , 3' -dimethylbutyl) phenyl] amine; N- phenyi-1-naphthylamine t-octylate; mixture of mono- and dialkylated t-butyl/t-octyldiphenylamines; mixture of ono- and dialkylated nonyldiphenylamines; mixture of mono- and dialkylated dodecyldiphenylamines; mixture of mono- and dialkylated isopropyl/isohexyldiphenylamines; mixture of mo- no- and dialkylated t-butyldiphenylamines; 2, 3-dihydro-3, 3- dimethyl-4H-l, 4-benzothiazine; phenothiazine; mixture of mono- and dialkylated t-butyl/t-octylphenothiazines; mixture of mono- and dialkylated t-octylphenothiazines; N-allyl- phenothiazine; N,N,N' ,N' -tetraphenyl-1, 4-diaminobut-2-ene; N,N-bis (2,2,6, 6-tetramethyl-piperid-4-yl ) hexamethylene- diamine; bis (2, 2, 6, 6-tetramethylpiperid-4-yl) sebacate; 2,2,
6, 6-tetramethyl-piperidin-4-one; 2,2,6, 6-tetramethylρiperi- din-4-ol.
2. UV ray and light stabilizers. 2.1 Derivatives of 2- (2 ' -hydroxyphenyl) benzotriazoles such as, for example: 2- (2 ' -hydroxy-5 'methylphenyl) benzotriazole; 2- (3 ' , 5 ' -di-t-butyl-2 ' -hydroxyphenyl) benzotriazole; 2- (5 ' - t-butyl-2 ' -hydroxyphenyl) benzotriazole; 2- [2 ' -hydroxy- 5 ' - (1, 1, 3, 3-tetramethylbutyl) phenyl] benzotriazole; 2- (3 ' , 5 ' - di-t-butyl-2 ' -hydroxyphenyl) -5-chlorobenzotriazole; 2-(3'-t- butyl-2 ' -hydroxy-5 ' -methylphenyl) -5-chlorobenzotriazole; 2- (3 ' -sec-butyl-5 ' -t-butyl-2 ' -hydroxyphenyl) benzotriazole; 2- (2 ' -hydroxy-4 ' -octyloxyphenyl) benzotriazole; 2- (3 ' , 5 ' -di-t- amyl-2 ' -hydroxyphenyl) benzotriazole; 2- [3 ' , 5 ' -bis (α,α-di- methylbenzyl) -2 ' -hydroxyphenyl] benzotriazole; mixtures of 2- [3 ' -t-butyl-2 ' -hydroxy-5 ' - (2-octyloxycarbonylethyl) phenyl] -5- chlorobenzotriazole, 2- [3 ' -t-butyl-5 ' - (2- (2-ethylhexyloxy) carbonylethyl) -2 ' -hydroxyphenyl] -5-chlorobenzotriazole, 2- [3 ' -t-butyl-2 ' -hydroxy-5 ' - (2-methoxycarbonylethyl) phenyl] -5- chlorobenzotriazole, 2- [3 ' -t-butyl-2 ' -hydroxy-5 '- (2-methoxycarbonylethyl) phenyl] benzotriazole, 2- [3 ' -t-butyl-2 ' -hydroxy- 5 ' - (2-octyloxycarbonylethyl) phenyl] benzotriazole, 2- [3 ' -t-bu¬ tyl-5 ' - (2- (2-ethylhexyloxy) carbonylethyl) -2 ' -hydroxyphenyl] benzotriazole, 2- (3 ' -dodecyl-2 ' -hydroxy-5 ' -methylphenyl) ben- zotriazole and 2- [3 ' -t-butyl-2 ' -hydroxy-5 '- (2-iso-octyloxy- carbonylethyl) phenyl] benzotriazole, 2,2' --methylene--bis [4- (1,1,3, 3-tetramethylbutyl) -6-benzotriazol-2-yl-phenol] ; transesterification product of 2- [3 ' -t-butyl-5 '- (2-methoxycarbonylethyl) -2 ' -hydroxyphenyl] -2H-benzotriazole with po- lyethylene glycol 300; [R-CH2CH2-C00 (CH2) 3 -] 2- wherein R = 3 ' -t-butyl-4-hydroxy-5 ' -2H-benzotriazol-2-yl-phenyl .
2.2 Derivatives of 2-hydroxybenzophenones such as, for example: 4-hydroxy-; 4-methoxy-; 4-octyloxy-; 4-decyloxy-; 4- dodecyloxy-; 4-benzyloxy-; 4, 2 ' , 4 ' -trihydroxy-; 2 ' -hydroxy- 4, 4 ' -dimethoxy .
2.3 Esters of benzoic acids, optionally substituted, such as, for example: phenyl salicylate, 4-t-butylphenyl salicy- late, octylphenyl salicylate, benzoyl resorcinol, bis(4-t- butylbenzoyl) resorcinol, dibenzoyl resorcinol, 2,4-di-t- butylphenyl-3, 5-di-t-butyl-4-hydroxybenzoate, hexadecyl-3, 5- di-t-butyi-4-hydroxybenzoate, octadecyl-3, 5-di-t-butyl-4- hydroxybenzoate, 2-methyi-4, 6-di-t-butylphenyl-3, 5-di-t-but- yl-4-hydroxybenzoate.
2.4 Acrylates such as, for example, ethyl or isoctyl α- cyano-β,β-diphenylacry!ate; methyl α-carbomethoxycinnamate, methyl or butyl α-cyano-β-methyl-p-methoxycinnamate, methyl α-carbomethoxy-p-methoxycinnamate, N- (β-carbomethoxy-β-cyano- vinyl ) -2-methylindoline .
2.5 Nickel compounds such as, for example, complexes of 2,2'-thio-bis-[4- ( 1, 1, 3, 3-tetramethylbutyl) phenol] , for example 1:1 or 1:2 complexes, with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldi- ethanolamine, nickel dibutyldithiocarbamate, nickel salts of monoalkyl esters of 4-hydroxy-3, 5-di-t-butyl-benzyl- phosphonic acid, such as methyl or ethyl esters, nickel com- plexes with ketoximes such as 2-hydroxy-4-methylphenyl unde- cyl ketoxime, nickel complexes of l-phenyl-4-lauroyl-5- hydroxypyrazol with or without additional ligands. 2.6 Sterically hindered amines such as, for example: poly- methylpropyl-3-oxy- [4-2, 2, 6, 6-tetramethyl) -piperidmyl] silox- ane, polymethylpropyl-3-oxy- [4- (1, 2, 2, 6, 6-pentamethyl) -piperidmyl] siloxane, bis (2, 2 , β, 6-tetramethyl-4-pιpeπdyl) sebacate; bis (2, 2, 6, 6-tetramethyl-4-pιperιdyl) succmate; bis (1,2,2,6, 6-pentamethyl-4-piperidyl) sebacate; bis (1-octyloxy- 2,2,6, 6-tetramethyl-4-pιpeπdyl) sebacate; bis (1, 2, 2, 6, 6-pen- tamethyl-4-pιpeπdyl) n-butyl-3, 5-dι-t-butyl-4-hydroxyben- zylmalonate; condensation product between l-(2- hydroxyethyl) -2, 2, 6, 6-tetra-4-hydroxypιpeπdme and succinic acid; condensation product between N,N ' -bis (2, 2, 6, 6- tetramethyl-4-pιperιdyl) hexamethylenediamme and 4-t- octylammo-2, 6-dιchloro-l, 3, -5-trιazme; tris (2,2,6,6- tetramethyl-4-pιperιdyl) -mtrilotriacetate; tetrakis
(2,2,6, 6-tetramethyl-4-pιperιdyl) -1,2,3, 4-butanetetra- carboxylate; 1, 1 ' - (1, 2-ethanodιyl) bis (3,3,5,5-te- tramethylpiperazmone; 4-benzoyl-2, 2, 6, 6- tetramethylpiperid e; 4-stearyloxy-2, 2, 6, 6-tetra- methylpipeπdme ; bis (1,2,2, 6 , 6-pentamethylpιperιdyl ) -2-n- butyl-2- (2-hydroxy-3, 5-dι-t-butylbenzyl) malonate; 3-n-octyl- 7,7,9, 9-tetramethyl-i, 3, 8-trιazaspιro [4.5] decan-2, 4-dιone; bis (l-octyloxy-2 ,2,6, 6-tetramethylpιpeπdyl) sebacate; bis (l-octyloxy-2, 2,6, 6-tetramethylpιperιdyl) succmate; condensation product between N, N ' -bis (2, 2, 6, 6-tetramethyl-4- pipeπdyl) hexamethylenediamme and 4-morpholme-2, 6- dιchloro-1, 3, 5-tπazme; condensation product between 2- chloro-4, 6-dι- (4-n-butylammo-2, 2, 6, 6-tetramethyl piperi- dyl) -1, 3, 5-trιazme and 1, 2-bis (3-ammopropylammo) ethane; condensation product between 2-chloro-4 , 6-dι- (4-n-butyl- ammo-1, 2,2,6, 6-pentamethylpιperιdyl) -1,3, 5-tπazme and
1, 2-bis ( 3-ammopropylammo) ethane; 8-acetyl-3-dodecyl-7 , 7 , - 9, 9-tetramethyl-l, 3, 8-trιazaspιro [4.5] decano-2, 4-dιone; 3- dodecyl-1- (2,2,6, 6-tetramethyl-4-pιpeπdyl) pyrrolιdm-2, 5- dione; 3-dodecyl-l- (1,2,2,6, 6-pentamethyl-4-pιpeπdyl) - pyrrolιdm-2, 5-dιone; mixture of hexadecyloxy- and 4- stearyloxy-2, 2, 6, 6-tetramethylpιpeπdme; condensation prod- uct between N-N ' -bis (2, 2, 6, 6-tetramethyl-4-pιpeπdyl) hexamethylenediamme and 4-cyclohexylammo-2, 6-dιchloro-l, 3, 5- triazme; condensation product between l,2-bιs(3- am opropylammo) ethane and 2, 4, 6-trιchloro-l, 3, 5-tπazme, as well as 4-butylammo-2, 2, 6, 6-tetramethylpιperidine (CAS Reg. Nr. [136504-96-6]; N- (2, 2, 6, 6-tetramethyl-4-pιpendyl) - n-dodecylsuccmimide; N- (1, 2, 2, 6, 6-pentamethyl-4-pιpeπdyl) - n-dodecylsuccinimide ; 2-undecyl-7 ,7,9, 9-tetramethyl-l-oxa- 3, 8-dιaza-4-oxospιro [4, 5] decane; reaction product between 7,7,9, 9-tetramethyl-2-cycloundecyl-l-oxa-3, 8-dιaza-4-oxospι- ro [4 , 5] decane and epichlorohydrm. 2.7 Oxamides such as, for example: 4, 4 ' -dioctyloxyox- anilide; 2, 2 ' -diethoxyoxanilide; 2, 2 ' -dioctyloxy-5, 5' -di- t-butoxanilide; 2,2' -didodecyloxy-5, 5 ' -di-t-butoxanilide; 2-ethoxy-2 ' -ethyloxanilide; N, ' -bis ( 3-dimethylaminopro- pyl) oxamide; 2-ethoxy-5-t-butyl-2 ' -ethoxanilide and its mixtures with 2-ethoxy-2 '-ethyl-5, 4 '-di-t-butoxanilide; and mixtures of disubstituted ortho- and para-methoxy anilides and mixtures of disubstituted ortho and para-ethoxy anilides . 2.8 2- (2-hydroxyphenyl) -1,3, 5-triazines such as, for example : 2,4, 6-tris (2-hydroxy-4-octyloxyphenyl ) -1 , 3, 5-triazine; 2- (2-hydroxy-4-octyloxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) - 1, 3, 5-triazine; 2- (2, 4-di-hydroxyphenyl) -4, 6-bis- (2, 4-di¬ methylphenyl) -1, 3, 5-triazine; 2, 4-bis- (2-hydroxy-4-propyl- oxyphenyl) -6- (2, 4-dimethylphenyl) -1, 3, 5-triazine; 2- (2- hydroxy-4-octyloxyphenyl) -4, 6-bis (4-methylphenyl) -1,3, 5- triazine; (2-hydroxy-4-dodecyloxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1, 3, 5-triazine; 2- [2-hydroxy-4- (2-hydroxy-3- butyloxypropoxy) phenyl] -4, 6-bis (2, 4-dimethyl) -1,3, 5-triazi- ne; 2- [2-hydroxy-4- (2-hydroxy-3-octyloxypropyloxy) phenyl] - 4, 6-bis (2, 4-dimethyl) -1, 3, 5-triazine; 2- (2-hydroxy-4-tride- cyloxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1, 3, 5-triazine; 2- [4- (dodecyloxy/tridecyloxy-2-hydroxypropoxy) -2-hydroxyphenyl] -4, 6-bis (2, 4-dimethylphenyl) -1, 3, 5-triazine; 2- [2-hydro- xy-4- (2-hydroxy-3-dodecyloxy-propoxy) phenyl] -4, 6-bis (2,4- dimethylphenyl) -1, 3, 5-trιazme; 2- (2-hydroxy-4-hexyloxyphe- nyl) -4, 6-dιphenyl-l, 3, 5-tπazme; 2- (2-hydroxy-4-methoxy- phenyl) -4, 6-dιphenyl-l, 3, 5-tπazme; 2,4, 6-tris [2-hydroxy-4- (3-butoxy-2-hydroxypropoxy) phenyl] -1,3, 5-trιazme; 2- (2- hydroxyphenyl) -4- (4-methoxyphenyl) -6-phenyl-l, 3, 5-trιazme .
3. "Metal-deactivators" such as, for example: N,N-dι- phenyloxamide, N-salicylal-N ' -salicyloyl-hydrazme, N,N'- bis (salicyloyl) hydrazme, N,N' -bis (3, 5-dι-t-butyl-4-hydroxy- phenylpropionyl) hyαraz ne, 3-salιcyloyIammo-l, 2, 4-trιazole, bis (benzylidene) oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N, N ' -diacetyladi- poyl dihydrazide, N, N ' -bis (salicyloyl) oxallyl dihydrazide, N,N ' -bis (salicyloyl) thiopropionyl dihydrazide .
4. Phosphites and phosphonites such as, for example: tπ- phenyl phosphite, diphenyl alkyl phosphites, pnenyl dialkyl phosphites, tris (nonylphenyl) phosphite, trilauryl phosphite, tπoctadecyl phosphite, distearyl pentaerythritol diphos- phite, tris (2, 4-dι-t-butylphenyl) phosphite, dnsodecyl pentaerythritol diphosphite, bis (2, 4-dι-t-butylphenyl) pentae- rythπtol diphosphite, bis (2, 6-dι-t-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis (2, 4-dι-t-butyl-6-methylphenyl) pentaerythritol diphosphite, bis [2, 4 , 6-tris (t-butylphenyl) ] pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis- (2 , 4-dι-t-butylphenyl) -4,4' -diphenylenediphospho- mte, 6-ιso-octyloxy-2, 4,8, 10-tetra-t-butyl-12H-dιbenzo-
[d, g] -1, 3, 2-dιoxaphosphocme, 6-fluoro-2, 4,8, 10-tetra-t-bu- tyl-12-methyl-dιbenzo [d, g] -1, 3, 2-dιoxaphosphocme, bis- (2,4- di-t-butyl-6-methylphenyl)methylphospmte, bis (2, 4-dι-t-bu- tyl-6-methylphenyl) ethylphosphite .
5. Hydroxylammes such as, for example: N,N-dιben- zylhydroxylamme; N, N-diethylhydroxylamme; N,N-dιoctyl- hydroxylamme; N, N-dilaurylhydroxylamme; N,N-dιtetradecyl- hydroxylamme; N, N-dihexadecylhydroxylamme; N,N-dιocta- decylhydroxylamme; N-hexadecyl-N-octadecylhydroxylamme; N- heptadecyl-N-octadecylhydroxylamme; N, N-hydroxylamme deriving from hydrogenated tallow amine.
6. Nitrones such as, for example: N-benzyl- -phenyl- nitrone; N-ethyl-α-phenyl-nitrone; N-octyl-α-heptyl-mtrone; N-lauryl-α-undecyl -nit rone; N-tetradecyl-α-tridecyl-nitrone; N-hexadecyl-α-pentadecyl-nitrone; N-octaoecyl-α-heptadecyl- nitrone; N-hexadecyl-α-heptadecyl-mtrone; N-octadecyl-α- pentadecyl-nitrone; N-heptadecyl- -heptadecyl-mtrone; N- octadeyl-α-hexadecyl-nitrone; nitrone deriving from hydro- genated tallow amine.
7. Thiosynergizmg agents such as, for example: dilauryl thiodipropionate; distearyl thiodipropionate .
8. Agents which are capable of destroying peroxides such as, for example, esters of β-thiodipropionic acid such as lauryl, stearyl, myristyl or tπdecyl esters, mercaptobenz- lmidazole or zinc salt of 2-mercaptobenzιmιdazole, z nc di- butylditmocarbamate, dioctadecyldisulfide, pentaerythritol tetrakis (β-dodecylmercapto) propionate .
9. Stabilizers of polyamide such as, for example, copper salts combined with compounds of iodine and/or phosphorous, divalent manganese salts.
10. Basic co-stabilizers such as, for example: melamine, polyv ylpyrrolidone, dicyanodiamide, triallyl cyanurate, derivatives of urea, derivatives of hydrazme, amines, poly- amides, poiyurethanes, salts of alkaline metals and salts of earth-alkaline metals of fatty acids with a high molecular weight such as, for example, Ca-stearate, Zn-stearate, Mg- stearate, Mg-behenate, Na-ricmoleate, K-palmitate, antimo- nium-pyrocatecholate, tm-pyrocatecholate . 11. Nucleating agents such as, for example: inorganic substances sucn as talc, metal oxides (for example, titanium dioxide or magnesium oxide), phosphates, carbonates or sul- fates (preferably of earth-alkaline metals); organic compounds such as mono- or polycarboxylic acids and their salts (for example, 4-t-butylbenzoιc acid, adipic acid, diphen- ylacetic acid, sodium succmate, sodium benzoate) ; polymeric compounds such as ionic copolymers ("lonomers" ) . 12. Fillers and reinforcing agents such as, for example: calcium carbonate, silicates, glass fibres, asbestos, talc, kaolm, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flours or fibres of other natural products, synthetic fibres.
13. Other additives such as, for example: plasticizers, lubricants, emulsifying agents, pigments, rheological addi- tives, catalysts, slip agents, optical brighteners, flame- retardants (for example bromurates, chlorurates, phosphorates and phosphorous/halogen mixtures), antistatic agents, blowing agents.
14. Benzofuranones and indolinones such as, for example: 3- [4- (2-acetoxyethoxy) phenyl] -5, 7-di-t-butylbenzofuran-2- one; 5, 7-di-t-butyl-3- [4- (2-stearoyloxyethoxy) phenyl] benzo- furan-2-one; 3,3' -bis [5, 7-di-t-butyl-3- [4- (2-hydroxyethoxy) phenyl] benzofuran-2-one] ; 5, 7-di-t-butyl-3- (4-ethoxyphenyl) - benzofuran-2-one; 3- (4-acetoxy-3, 5-dimethyl-phenyl) -5, 7-di- t-butyl-benzofuran-2-one; 3- (3, 5-di-methyl-4-pivaloyloxy- phenyl) -5, 7-di-t-butyl-benzofuran-2-one; or those described in U.S. patents 4,325,863, 4,338,244, 5,175,312, 5,216,052, 5,252,643; in German patents DE 4,316,611, 4,316,622 and 4,316,876; or in European patent applications 589,839 and 591,102.
Some illustrative but non-limiting examples are provided hereunder for a better understanding of the present invention and for its embodiment. EXAMPLE 1 60 g of octadecyl-3- (3 ', 5 ' -di-t-butyl-4 ' -hydroxy- phenyl )propionate (Anox PP18 of Great Lakes) are melted at a temperature ranging from 50°C to 60°C. 40 g of tetrakis [3- (3, 5-di-t-butyl-4-hydroxy-phenyl) propionyloxymethyl]methane (Anox 20 of Great Lakes) are subsequently added: the whole mixture is maintained at a temperature ranging from 50°C to 60°C until complete homogenization.
The homogeneous dispersion obtained is left to cool to room temperature obtaining a solid which is subsequently ground. A powder is obtained which is subjected to DSC (Differential Scanning Calorimetry) analysis and the result obtained is indicated in Figure 1.
The powder obtained is also subjected to X-Ray analysis and the spectrum from powders obtained is indicated in Figure 2. The X-ray diffraction spectrum from powders is effected using Cu-Kα radiation (λ = 1.54178).
Figure 1 clearly shows that the mixture obtained has a melting peak at about 50°C, close to the melting point of octadecyl-3- ( 3 ' , 5 ' -di-t-butyl-4 ' -hydroxyphenyl ) propionate . On the contrary, the melting point of tetrakis [3-(3,5-di- t-butyl-4-hydroxyphenyl) propionyloxymethyl] methane is not indicated: in fact, Figure 1 does not show any endothermic melting peak at about 110°C-125°C typical of tetrakis [3-
(3, 5-di-t-butyl-4-hydroxyphenyl) propionyloxymethyl]methane . Figure 2 shows that tetrakis [3- (3, 5-di-t-butyl-4- hydroxyphenyl) propionyloxymethyl] methane is present in crystalline form (as is also octadecyl-3- (3 ', 5 ' -di-t-butyl-4 ' - hydroxyphenyl) propionate) and in particular, in this case, it is present in its β form. EXAMPLE 2
7.5 g of octadecyl-3- (3 ', 5 ' -di-t-butyl-4 ' -hydroxy-phenyl) propionate (Anox PP18 of Great Lakes) , in the form of a fine powder having dimensions of < 50 μm, and 2.5 g of tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionyloxyme- thyl] methane (Anox 20 of Great Lakes) , in the form of a fine powder having dimensions of < 50 μm, are homogenized in a laboratory grinder.
The mixture thus obtained is subjected to DSC (Differential Scanning Calorimetry) analysis and the result ob- tained is analogous to that indicated in Figure 1. EXAMPLE 3
10 g of a mixture 1/1 by weight of octadecyl-3- ( 3 ', 5 ' -di-t- butyl-4 ' -hydroxyphenyl) propionate (Anox PP18 of Great Lakes) and tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) pro- pionyloxymethyl] methane (Anox 20 of Great Lakes), are dissolved in 25 ml of acetone containing 20% of water.
The above mixture is cooled to 0°C obtaining a precipitate which, after filtration and drying, is analyzed.
The quantitative analysis indicates a content of Anox PP18 of 52.6% and a content of Anox 20 of 47.4% and the DSC (Differential Scanning Calorimetry) analysis shows an analogous result to that indicated in Figure 1.

Claims

1. A stabilizing mixture comprising:
(a) tetrakis [3- (3, 5-di-t-butyl-4-hydroxy-phenyl) propionyloxymethyl] methane having formula (I):
CH2 COOCH2 ( I )
Figure imgf000036_0001
Figure imgf000036_0002
;b) octadecyl-3- (3 '-5 '-di-t-butyl-4 '-hydroxy-phenyi; propionate having formula (II):
Figure imgf000036_0003
characterized in that it has a melting point ranging from 50┬░C to 60┬░C.
2. The stabilizing mixture according to claim 1, wherein component (a) having formula (I) and component (b) having formula (II) are used in a ratio ranging from 9:1 to 1:9.
3. The stabilizing mixture according to claim 2, wherein component (a) having formula (I) and component (b) hav- ing formula (II) are used in a ratio ranging from 3:1 to 1:3.
4. Polymeric compositions containing an organic polymer and an effective quantity of the stabilizing mixture accord- ing to any of the previous claims.
5. The polymeric compositions according to claim 4, wherein the stabilizing mixture is combined with other stabilizers or their mixtures.
6. Use of the stabilizing mixture according to any of the claims from 1 to 3, as a stabilizer for the oxidative degradation of organic polymers caused by light and/or heat .
7. End-articles obtained from the processing of the polymeric compositions according to claim 4 or 5.
PCT/EP1999/005468 1998-08-05 1999-07-30 Stabilizing mixture having a melting point lower than that of the highest melting component WO2000008096A1 (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0411628A2 (en) * 1989-08-02 1991-02-06 Montell North America Inc. Process for the stabilization of polyolefin and products obtained thereby
EP0730001A1 (en) * 1995-02-22 1996-09-04 F. Hoffmann-La Roche Ag Stabilizers for plastic materials

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0411628A2 (en) * 1989-08-02 1991-02-06 Montell North America Inc. Process for the stabilization of polyolefin and products obtained thereby
EP0730001A1 (en) * 1995-02-22 1996-09-04 F. Hoffmann-La Roche Ag Stabilizers for plastic materials

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