CA2143168A1 - Stabiliser mixtures - Google Patents
Stabiliser mixturesInfo
- Publication number
- CA2143168A1 CA2143168A1 CA 2143168 CA2143168A CA2143168A1 CA 2143168 A1 CA2143168 A1 CA 2143168A1 CA 2143168 CA2143168 CA 2143168 CA 2143168 A CA2143168 A CA 2143168A CA 2143168 A1 CA2143168 A1 CA 2143168A1
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- Prior art keywords
- tert
- butyl
- styrene
- bis
- formula
- Prior art date
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
- C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
- C09K15/06—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing oxygen
- C09K15/08—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing oxygen containing a phenol or quinone moiety
-
- 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
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A composition comprising a) a polystyrene, a substituted polystyrene, a copolymer or terpolymer of styrene or substituted styrene, a polycarbonate, a polyester carbonate, a polyurethane, a polyamide, a copolyamide, a polyacetal or a polyphenylene oxide,b) at least one compound of formula I
(I), wherein R1 is methyl or ethyl, R2 is C2-C30 alkyl and R3 is C1-C4 alkyl; and c) at least one compound of formula II
(I), wherein R1 is methyl or ethyl, R2 is C2-C30 alkyl and R3 is C1-C4 alkyl; and c) at least one compound of formula II
Description
A-19X67/A 21~3168 Stabiliser mixtures The present invention relates to compositions comprising selected organic polymers, for example an acry1onitri1-o,/but~lien~ ylclle terpolymer, to n~ wes of 6-substituted 2,4-dialkylphenols and to organic material stabilised therewith against thermal, oxidative and actinic degradation.
A number of trialkylphenols, for example 2,4-dimethyl-6-(l-methylpentadecyl)phenol, and their use for stabilising organic m~ten~1 are known (US 5,098,945). US 3,535,249 discloses the stabilisation of polymers with alkyl-substituted bisphenols or low-molecular alkyl-substituted polyphenols.
However, the he~clofole known phenolic stahi1i~çrs cannot fully meet the requirements made of them. Accordingly, the ~ w~ of two phenolic stabilisers, described in detail hereinafter, is proposed, in particular for the enh~ncement of thermal stability.
The present invention relates to compositions comp i~ing a) a poly~yl-,ne, a sub~lilu~d polys~y~ e, a copolymer or terpolymer of styrene or subslilul~,d styrene, a polycdll,onate, a polyester carbonate, a polyurethane, a polyamide, a copolyamide, a polyacetal or a polyphenylene oxide, b) at least one compound of formula I
OH ~Rl H3C~3,,CH~R2 (I), wherein Rl is methyl or ethyl, R2 is C2-C30alkyl and R3 iS Cl-C4alkyl; and c) at least one compound of formula II
- 2143~68 OH OH
R4 ~ ~R4 R3 _ 3 n wherein R3 iS Cl-C4allcyl, R4 iS tert-butyl or cyclohexyl, L -CH2- or tricyclo[5.2.1.02 63decane-3,8-ylene, and n > 1.
R2 is typically ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pel~t~decyl, heY~-lecyl, octadecyl, non~(lecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pçnt~cosyl, helr~rQsyl, heptacosyl, octacosyl, nonacosyl or triacontyl.
A p,efell~,d meaning of R2 is C8-C30aLkyl, typically C8-Cl8aLI~yl or C10-C30aLkyl. A
particularly ~l~,rell~,d meaning of R2 is Cl2-Cl8aL~Yl-R3 iS methyl, ethyl, propyl, iso-propyl, n-butyl, sec-butyl or tert-butyl. R3 iS most preferably methyl.
n is preferably 1 or 1-5.
Intert;sLing colllposiLions are those whel~in the compound of formula I is OH ~ CH3 OH ~ CH3 H3C ~3~' C14H29 ~l$cH~cl6H33 .
Also of interest are compositions comprising instead of a single compound of formula (I) a mixture of the compounds 21~316~
OH ,CH3 OH ~C2HS
H3C ~ CH~ R2' H3C ~ CH~ R2"
(Ia) and ~ (Ib), wherein R2' is -CmH2m+l and R2" is -Cm lH2m l, and m is an integer from 2-30 and is identical in the radicals R2' and R2".
The weight ratio of the compounds (Ia)/(Ib) is ~ypically from 1/99 to 99/1, preferably from 99/1 to 70/30 and, most preferably, from 95/5 to 80/20.
Further interesting coml)o~iLions are those wherein the compound of formula II is OH -- OH --(H3C)3C ~ ~C(CH3)3 CH3 _ CH3-- n (average molecular weight: 600-700) or OH OH
(H3C)3C ~ CH2~C(CH3)3 The compounds of formula (II) can also be a mixture of single compounds.
Also preferred are compositions wherein component a) is a polystyrene, a substituted polystyrene, a copolymer or terpolymer of poly~Lyrelle or a substituted polystyrene.
Illustrative examples are:
1) Polystyrene, poly(p-methylstyrene), poly(a-methylstyrene).
2) Copolymers of styrene or a-methylstyrene with dienes or acrylic derivatives, for example styrene/butadiene, styrene/acrylonitrile, styrene/alkyl methacrylate, styrene/buta-diene/alkyl acrylate, styrene/maleic anhydride, styrene/acrylonitrile/methyl acrylate;
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 copolymers of styrene such as styrene/but~lien~/styrene, styrene/isoprene/styrene, styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/ styrene.
A number of trialkylphenols, for example 2,4-dimethyl-6-(l-methylpentadecyl)phenol, and their use for stabilising organic m~ten~1 are known (US 5,098,945). US 3,535,249 discloses the stabilisation of polymers with alkyl-substituted bisphenols or low-molecular alkyl-substituted polyphenols.
However, the he~clofole known phenolic stahi1i~çrs cannot fully meet the requirements made of them. Accordingly, the ~ w~ of two phenolic stabilisers, described in detail hereinafter, is proposed, in particular for the enh~ncement of thermal stability.
The present invention relates to compositions comp i~ing a) a poly~yl-,ne, a sub~lilu~d polys~y~ e, a copolymer or terpolymer of styrene or subslilul~,d styrene, a polycdll,onate, a polyester carbonate, a polyurethane, a polyamide, a copolyamide, a polyacetal or a polyphenylene oxide, b) at least one compound of formula I
OH ~Rl H3C~3,,CH~R2 (I), wherein Rl is methyl or ethyl, R2 is C2-C30alkyl and R3 iS Cl-C4alkyl; and c) at least one compound of formula II
- 2143~68 OH OH
R4 ~ ~R4 R3 _ 3 n wherein R3 iS Cl-C4allcyl, R4 iS tert-butyl or cyclohexyl, L -CH2- or tricyclo[5.2.1.02 63decane-3,8-ylene, and n > 1.
R2 is typically ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pel~t~decyl, heY~-lecyl, octadecyl, non~(lecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pçnt~cosyl, helr~rQsyl, heptacosyl, octacosyl, nonacosyl or triacontyl.
A p,efell~,d meaning of R2 is C8-C30aLkyl, typically C8-Cl8aLI~yl or C10-C30aLkyl. A
particularly ~l~,rell~,d meaning of R2 is Cl2-Cl8aL~Yl-R3 iS methyl, ethyl, propyl, iso-propyl, n-butyl, sec-butyl or tert-butyl. R3 iS most preferably methyl.
n is preferably 1 or 1-5.
Intert;sLing colllposiLions are those whel~in the compound of formula I is OH ~ CH3 OH ~ CH3 H3C ~3~' C14H29 ~l$cH~cl6H33 .
Also of interest are compositions comprising instead of a single compound of formula (I) a mixture of the compounds 21~316~
OH ,CH3 OH ~C2HS
H3C ~ CH~ R2' H3C ~ CH~ R2"
(Ia) and ~ (Ib), wherein R2' is -CmH2m+l and R2" is -Cm lH2m l, and m is an integer from 2-30 and is identical in the radicals R2' and R2".
The weight ratio of the compounds (Ia)/(Ib) is ~ypically from 1/99 to 99/1, preferably from 99/1 to 70/30 and, most preferably, from 95/5 to 80/20.
Further interesting coml)o~iLions are those wherein the compound of formula II is OH -- OH --(H3C)3C ~ ~C(CH3)3 CH3 _ CH3-- n (average molecular weight: 600-700) or OH OH
(H3C)3C ~ CH2~C(CH3)3 The compounds of formula (II) can also be a mixture of single compounds.
Also preferred are compositions wherein component a) is a polystyrene, a substituted polystyrene, a copolymer or terpolymer of poly~Lyrelle or a substituted polystyrene.
Illustrative examples are:
1) Polystyrene, poly(p-methylstyrene), poly(a-methylstyrene).
2) Copolymers of styrene or a-methylstyrene with dienes or acrylic derivatives, for example styrene/butadiene, styrene/acrylonitrile, styrene/alkyl methacrylate, styrene/buta-diene/alkyl acrylate, styrene/maleic anhydride, styrene/acrylonitrile/methyl acrylate;
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 copolymers of styrene such as styrene/but~lien~/styrene, styrene/isoprene/styrene, styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/ styrene.
3) Graft copolymers of styrene or a-methylstyrene, for example styrene on polybut~lieT-e, styrene on polybutadiene-styrene or polybut~ ne-acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polyb~ lit nç; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or m~l~.imitlç on polybut~ .ne; styrene and maleimide on polybut~(1iene; styrene and alkyl acrylates or m-o.th~crylates on polybnt~rlien~ styrene and acrylonitrile on ethylene/propylene/diene terpolymers; styrene and acrylonitrile on polyalkyl acrylates or polyaLl~yl methacrylates, styrene and acrylonitrile on acrylate/buta-diene copolymers, as well as mixtures thereof with the copolymers listed under 2), for example the copolymer mixtures known as ABS, MBS, ASA or AES polymers.
Component a) is preferably impact-resistant poly~lyl~,ne (IPS), styrene-acrylonitrile copolymers (SAN) and acrylonitril~./bl~t~liPn-o,/styrene terpolymers (ABS), in particular acrylonitrile/butadiene/~yl~l,c terpolyrners (ABS) and methylmethacrylate/but~diene/-styrene graft copolymers (MBS).
Component a) may also be selected form the group consisting of polycarbonate, polyester carbonate, polyurethane, polyamide, copolyamide, polyacetal and polyphenylene oxide.
Illustrative examples are:
I) Polyurethanes derived from hydroxyl-termin~tecl polyethers, polyesters or polybuta-dienes on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as precursors thereof.
II) Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or - 214316~
from aminocarboxylic acids or the corresponding lactams, for example polyamide 4, poly-amide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, polyamide 11, polyamide 12, aromatic poly-amides starting from m-xylene diamine and adipic acid; polyamides prepared from hexa-methylenediamine and isophthalic or/and terephthalic acid and with or without anelastomer as modifier, for example poly-2,4,4,-trimethylhe~methylene terephth~l~mi-le or poly-m-phenylene isophth~l~mide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or graf-ted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol; as well as polyamides or copolyamides modified with EPDM
or ABS; and polyamides condensed during processing (RIM polyamide systems).
III) Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer, polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
The pl~al~tion of the compounds of formulae I and II is carried out by known methods as described, inter alia, in "Die Stabilisierung der Klln~t~toffe gegen Licht and Warme" by J. Voigt, Springer Verlag Berlin-~eidelberg-New York, 1966.
The novel composition conveniently comprise from 0.01 to 10 %, preferably from 0.05 to 5 % and, most preferably, from 0.1 to 2 %, based on the total weight of the organic m~teri~l to be stabilised, of a ~ ule of at least one colll~und of formula (I) and at least one compound of formula (II).
With the novel compositions it is possible to achieve an enhancement of the thermal stability of the organic material. Furthermore, a llPi,5Lul~ of components b) and c) constitutes an emulsion which is easy to handle, whereas so far component c) on its own has proved difficult to emulsify.
.
Besides compounds of formulae (I) and (II), the novel compositions can ~ddition~lly contain customary additives such as:
1. Antioxidants 1.1. Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, - ~143168 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(a-methylcyclo-hexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6-(l'-methylundec-l'-yl)phenol, 2,4-dimethyl-6-(1'-methylheptadec-1'-yl)phenol, 2,4-di-methyl-6-(1'-methyltridec- l'-yl)phenol and mixtures thereof.
1.2. ALkylthiomethylphenols, for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-dido-decylthiomethyl-4-nonylphenol.
1.3. Hydroquinones and aL~ylated hydro luinol~s, for example 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydro~luinolle, 2,5-di-tert-amylhydroquinone, 2,6-di-phenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxy-anisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis(3,5-di-tert-butyl-4-hyd,~yl,he.lyl) ~ rate 1.4. ~ydl~xylated thiodiphenyl ethers, for eY~mple 2,2'-thiobis(6-tert-butyl-4-methyl-phenol), 2,2'-thiobis(4-oclyll)hellol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thio-bis(6-tert-butyl-2-methylphenol), 4,4'-thiobis(3,6-di-sec-amylphenol), 4,4'-bis(2,6-dim-ethyl-4-hydlu~yphenyl) disulfide.
1.5. AL~lidenebisphenols, for eY~mple 2,2'-methylenebis(6-tert-butyl-4-melhylphellol), 2,2'-methylenebis(6-tert-butyl-4-elhylphellol), 2,2'-methylenebis[4-methyl-6-(a-methyl-cyclohexyl)phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylene-bis(6-nonyl4-melllylphellol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-ethylidene-bis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methy-lenebis[6-(a-methylbenzyl)-4-nonylphenol], 2,2'-methylenebis[6-(a,a-dimethylbenzyl)-4-nonylphenol], 4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'-methylenebis(6-tert-butyl-2-methylphenol), 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-tris(5-tert-butyl~-hydroxy-2-methylphenyl)butane, 1,1-bis(5-tert-butyl4-hydroxy-2-methyl-phenyl)-3-n-dodecylmer-captobutane, ethylene glycol bis[3,3-bis(3'-tert-butyl4'-hyd~ yphenyl)bulyl~le], bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopent~i~nP, bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl4-methylphenyl]terephth~l~te, 1,1-bis(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis(3,5-di-tert-butyl-4-hyd~o~y~henyl)propane, 2,2-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane, 1,1,5,5-tetra(5-tert-butyl-21~3168 4-hydroxy-2-methylphenyl)pentane.
1.6. O-, N- and S-benzyl compounds, for example 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxy-dibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmt;l.;aptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithio-terephthalate, bis(3,5-di-tert-butyl-4-hydlv,~yl,ellzyl)sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmelcal~toacet~te 1.7. Hydroxybenzylated malonates, for example dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)m~lon~tç, dioctadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malo-nate, didodecylme.~;aptoetllyl-2,2-bis(3,5-di-tert-butyl-4-llydl~ylJellzyl)malonate, bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydlo,~yben~rl)m~lon~te.
1.8. Aromatic hydr~ybenzyl co~ )oullds, for example 1,3,5-tris(3,5-di-tert-butyl-4-hy-droxybenzyl)-2,4,6-trimethylhen7~nP., 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hy(Lo,~yl,cll,yl)phenol.
1.9. Triazine compounds, for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-tri~7in~., 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxy-anilino)-1,3,5-tri~7ine, 2-oclyLK~ ;a~o-4,6-bis(3,5-di-tert-butyl-4-hydl~."yl,henoxy)-1,3,5-triazine, 2,4,6-tris(3,5-di-tert-butyl-4-hydL~ y~helloxy)-1,2,3-tn~7ine, 1,3,5-tris-(3,5-di-tert-butyl4-hydroxybenzyl)iso~;~allul~e, 1,3,5-tris(4-tert-butyl-3-hy(Lo~y-2,6-di-methylbenzyl)isocyanurate, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-tri-azine, 1,3,5-tris(3,5-di-tert-butyl-4-hyd.~y~henylpropionyl)hexahydro-1,3,5-triazine, 1,3,5-tris(3,5-dicyclohexyl-4-hy(Lw~ybellzyl)isocyanurate.
1.10. Benzylphosphonates, for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphos-phonate, diethyl-3,5-di-tert-butyl-4-hy~yl,enzylphosphonate, dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydlo,~y-3-methylbenzyl-phosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzyl-phosphonic acid.
1.11. Acylaminophenols, for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.
1.12. Esters of ~-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or poly-- 21~3168 hydric alcohols, e.g. with methanol, ethanol, octadecanol, 1,6-hexanediol, l,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hy~u~yel}lyl) isocyanurate, N,N'-bis(hy-droxyethyl)oxamide, 3-thi~nndec~nol, 3-thiapent~-lec~nol, trimethylhexanediol, trimethyl-olpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.13. Esters of ,B-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonane-diol, ethylene glycol, 1,2-yrvy~ ol~ neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, ~e~ yllllilul, tris(hy~llù~yell,yl) isocy~lur~le, N,N'-bis-(hyd uAyethyl)~Y~mi~e~ 3-thi~nn-lec~nr1 3-thi~pent~dçc~nol~ trimethylheY~n~liol, tri-methylolpropane, 4-hydlvAy~ Lyl-l-phospha-2,6,7-trioxabicyclot2.2.2]octane.
1.14. Esters of l~-(3.5-dicYclohexYl-4-hydluAy~,hellyl)propionic acid with mono- or poly-hydric alcohols, e.g. with meth~nol, ethanol, oct~e~nQl, 1,6-hçlr~nediol, l,9-non~ne~liol, ethylene glycol, 1,2-prop~n~liol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pe~ ol, tris(hydlv~e~lyl) isocy~lul~e, N,N'-bis(hy-dlv~yt;~lyl)ox~mi-le, 3-th~ n~lec~nol~ 3-thi~Ilent~ec~nol~ trimethylh~Y~ne(liol, trimethyl-olyrvpalle, 4-hydlv~ylllethyl-1-phosph~-2,6,7-trioxabicyclo[2.2.2]octane.
1.15. Esters of 3.5-di-tert-butyl-4-hydlv~y~Jhenyl acetic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, oct~dec~nol, 1,6-he~r~n~liol, 1,9-nonanediol, ethy-lene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxy-ethyl)oxamide, 3-thi~lndec~nol 3-thiapent~iec~nol~ trimethylh~Y~n~ liol, trimethylolpro-pane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.yoctane.
1.16. Amides of l~-(3.5-di-tert-butYl-4-l,ydl~v~Y~hellyl)prvpionic acid e.g. N,N'-bis(3,5-di-tert-butyl-4-hydrvxyphenylpropionyl)hexamethylene~ mine, N,N'-bis(3,5-di-tert-butyl-4-hydlvxyyhellylylvpionyl)trimethylenedi~mine, N,N'-bis(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl)hydrazine .
2. UV absorbers and li~ht stabilisers 2.1. 2-(2'-Hydroxyphenyl)benzotriazoles, for example 2-(2'-hy~v~y-5'-methylphenyl)-benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-(1,1,3,3-tetrarnethylbutyl)phenyl)benzo-triazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-S-chloro-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl)-S-chloro-benzotriazole, 2-(3'-sec-butyl-S'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-4'-octyloxyphenyl)benzoLIiazole, 2-(3',5'-di-tert-amyl-2'-hydr~xy~henyl)benzotn~70le, 2-(3',5'-bis-(a,a-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole, mixture of 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycar-bonylethyl)phenyl)-5-chloro-benzot~riazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)-car-bonylethyl]-2'-hydroxyphenyl)-S-chloro-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-S-chloro-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)bel~o~ 7~le, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyl-oxycarbonylethyl)phenyl)bc~ 7~ ,, 2-(3~-tert-butyl-5~-[2-(2-ethylhexyloxy)call~ol~yl-ethyl]-2'-hydlu~yphenyl)bel~zolliazole, 2-(3'-dodecyl-2'-hy~lluAy-5'-mclllylphellyl)benzo-triazole, and 2-(3'-tert-butyl-2'-l.y~llu,~y-5'-(2-isooctylo~ycall,ollylethyl)phenylbenzoL,i-azole, 2,2'-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzol,iazole-2-ylphenol]; the tr~n~esterifis~tion product of 2-[3'-tert-butyl-5'-(2-metho~ycall,ollylethyl)-2'-hydlo~y-phenyl]-2H-benzotriazole with polyethylene glycol 300; [R-CH2CH2-COO(CH2)3~, where R = 3'-tert-butyl-4'-hy~lu~y-5'-2H-benzotriazol-2-ylphenyl.
2.2. 2-Hydroxybenzophenones, for example the 4-hydlu~y, 4-methoxy, 4-octyloxy, 4-de-cyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-t~ihydluAy and 2'-llydluAy-4,4'-dimethoxy derivatives.
2.3. Esters of substituted and unsubstituted benzoic acids, as for example 4-tertbutyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl) resorcinol, benzoyl resorcinol, 2,4-di-tertbutylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hex~decyl 3,5-di-tert-butyl-4-hy~llu~ybe~-70~te, octadecyl 3,5-di-tert-butyl-4-hyd~uxybellzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-lly(llu~y-benzoate.
2.4. Acrylates, for example ethyl a-cyano-,B"B-diphenylacrylate, isooctyl a-cyano-,B,~-di-phenylacrylate, methyl a-carbomethoxycinn~m~te, methyl a-cyano-,B-methyl-p-methoxy-cinnamate, butyl a-cyano-~-methyl-p-methoxy-cinn~m~te, methyl a-carbomethoxy-p-methoxycinnamate and N-(~B-carbomethoxy-,~-cyanovinyl)-2-methylindoline.
2.5. Nickel compounds, for example nickel complexes of 2,2'-thio-bis[4-(1, 1 ,3,3-tetra-methylbutyl)phenol], such as the 1:1 or 1:2 complex, with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldi-thiocarbamate, nickel salts of the monoaL~cyl esters, e.g. the methyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, nickel complexes of ketoxhnes, e.g. of 2-hydroxy-4-methylphenyl undecylk~toxi.~e, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional lig~n~ls.
2.6. Sterically hindered ~mines, for example bis(2,2,6,6-tetramethyl-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-piperidyl)succinate, bis(1,2,2,6,6-pentamelhylpipelidyl)sebacate, bis(1,2,2,6,6-pentamethylpiperidyl) n-butyl-3,5-di-tert-butyl-4-hydloxyl~ellzylm~lon~te, the conrle.n~t~. of 1-(2-hydl~ yelllyl)-2,2,6,6-tetramethyl-4-hydroxy~il)e.idine and succi-nic acid, the conden~tP of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)h~ methylenedi-amine and 4-tert-octylamino-2,6-dichloro-1,3,5-tri~7ine, tris(2,2,6,6-tetrarnethyl-4-piperi-dyl) nitrilotriacetate, tetrakis(2,2,6,6-tetramethyl-4- piperidyl)-1,2,3,4-butane-tetracar-boxylate, 1,1'-(1,2-ethanediyl)bis(3,3,5,5-tetramethylpil)Gl~zinone), 4-benzoyl-2,2,6,6-tetrame~hylpipe. ;dine, 4-stearyloxy-2,2,6,6-tetrame~lylpi~ ;(line, bis(l,2,2,6,6-penta-melllylpi~lidyl)-2-n-butyl-2-(2-llyd~ y-3,5-di-tert-butylbenzyl)m~lon~te, 3-n-octyl-7,7,9,9-le~ ethyl-1,3,8-triazasprio[4.5]decane-2,4-dione, bis(1-octyloxy-2,2,6,6-tetra-methylpiperidyl)seb~r~to" bis(l-octyloxy-2,2,6,6-tetramelllylpipc~idyl)sucrin~te, the condensate of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)helr~methylen~i~mine and 4-mor-pholino-2,6-dichloro-1,3,5-triazine, the con~en~te of 2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramelhyli)i~lidyl )-1,3,5-triazine and 1,2-bis(3-amin~l~ylamino)ethane, the condensate of 2-chloro-4,6-di(4-n-butylamino-1,2,2,6,6-pentamelllyl~ ,lidyl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)eth~ne, 8-acetyl-3-dodecyl-7,7,9,9-tetra-methyl- 1 ,3,8-triazaspiro[4.5]decane-2,4-dione, 3-dodecyl- 1-(2,2,6,6-~~ lyl~piperi-dyl)pyrrolidine-2,5-dione, 3-dodecyl-1-(1,2,2,6,6-pentamethyl~piperidyl)pyrrolidine-2,5-dione.
2.7. Ox~mides, for example 4,4'-dioctyloxyox~nilide, 2,2'-dioctyloxy-5,5'-di-tert-butox-anilide, 2,2'--lidodecyloxy-5,5'-di-tert-buto~nili~e, 2-ethoxy-2'-ethylox~nili-le, N,N'-bis(3-dimethylaminopropyl)ox~mide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mix-ture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide and mixtures of ortho- and para-methoxy-disubstituted ox~nili-les and Illi~lulGs of o- and p-ethoxy-disubstituted oxani-lides.
2.8. 2-(2-Hydroxyphenyl)-1,3,5-triazines, for example 2,4,6-tris(2-hydroxy-4-octyloxy-phenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-`- 2143168 1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hy-droxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyl-oxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-butyloxy-propoxy)phenyl]-4,6-bis(2,4~imethyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxy-propyloxy)phenyl]-4,6-bis(2,4-dimethyl)- 1 ,3,5-triazine.
3. Metal deactivators, for example N,N'-diphenylox~mide, N-salicylal-N'-salicyloyl hydrazine, N,N'-bis(salicyloyl) hy~me, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenyl-propionyl) hydrazine, 3-salicyloylamino-1,2,4-tri~701.o., bis(benzylidene)oxalyl di-hydrazide, o~nili~le, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,N'-di-acetyladipoyl dihydrazide, N,N'-bis(salicyloyl)oxalyl dihydrazide, N,N'-bis(salicyloyl)-thiopropionyl dihy-lra7i~1~
4. Phosphites and phosphonites, for example ~ )hel~yl phosphite, diphenyl alkyl phos-phites, phenyl diaL~yl phosphites, tris(no,lyllJhe.lyl) phosphite, trilauryl phosphite, triocta-decyl phosphite, distearyl pentat;,yllnilol ~1irhosphite~ tris(2,4-di-tert-butylphenyl) phos-phite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-~methylphenyl)pent~e~yll.lilol diphosphite, bis(isode-cyloxy)penta~ly~ ol diphosphite, bis(2,4-di-tert-butyl-6-mclllyll~henyl)pell~.yllllitol diphosphite, bis(2,4,6-tris(tert-butylphenyl)~n~lylluitol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-bulylphenyl) 4,4'-bil)henylene diphosphonite, 6-isooctyl-oxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin, bis(2,4-di-tert-butyl-6-methylphenyl)methylphosphite, bis(2,4-di-tert-butyl-6-methyl~hcnyl)ethylphosphite.
5. Peroxide scavengers, for example esters of ,B-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters""~ ;~be~-7.i.~-id~71~le or the zinc salt of 2-mercaptoben7imi(1~701e, zinc dibutyldithiocarb~m~te, dioctadecyl ~ llfi~le~ penta-erythritol tetrakis(,B-dodecylmercapto)propionate.
Component a) is preferably impact-resistant poly~lyl~,ne (IPS), styrene-acrylonitrile copolymers (SAN) and acrylonitril~./bl~t~liPn-o,/styrene terpolymers (ABS), in particular acrylonitrile/butadiene/~yl~l,c terpolyrners (ABS) and methylmethacrylate/but~diene/-styrene graft copolymers (MBS).
Component a) may also be selected form the group consisting of polycarbonate, polyester carbonate, polyurethane, polyamide, copolyamide, polyacetal and polyphenylene oxide.
Illustrative examples are:
I) Polyurethanes derived from hydroxyl-termin~tecl polyethers, polyesters or polybuta-dienes on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as precursors thereof.
II) Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or - 214316~
from aminocarboxylic acids or the corresponding lactams, for example polyamide 4, poly-amide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, polyamide 11, polyamide 12, aromatic poly-amides starting from m-xylene diamine and adipic acid; polyamides prepared from hexa-methylenediamine and isophthalic or/and terephthalic acid and with or without anelastomer as modifier, for example poly-2,4,4,-trimethylhe~methylene terephth~l~mi-le or poly-m-phenylene isophth~l~mide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or graf-ted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol; as well as polyamides or copolyamides modified with EPDM
or ABS; and polyamides condensed during processing (RIM polyamide systems).
III) Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer, polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
The pl~al~tion of the compounds of formulae I and II is carried out by known methods as described, inter alia, in "Die Stabilisierung der Klln~t~toffe gegen Licht and Warme" by J. Voigt, Springer Verlag Berlin-~eidelberg-New York, 1966.
The novel composition conveniently comprise from 0.01 to 10 %, preferably from 0.05 to 5 % and, most preferably, from 0.1 to 2 %, based on the total weight of the organic m~teri~l to be stabilised, of a ~ ule of at least one colll~und of formula (I) and at least one compound of formula (II).
With the novel compositions it is possible to achieve an enhancement of the thermal stability of the organic material. Furthermore, a llPi,5Lul~ of components b) and c) constitutes an emulsion which is easy to handle, whereas so far component c) on its own has proved difficult to emulsify.
.
Besides compounds of formulae (I) and (II), the novel compositions can ~ddition~lly contain customary additives such as:
1. Antioxidants 1.1. Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, - ~143168 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(a-methylcyclo-hexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6-(l'-methylundec-l'-yl)phenol, 2,4-dimethyl-6-(1'-methylheptadec-1'-yl)phenol, 2,4-di-methyl-6-(1'-methyltridec- l'-yl)phenol and mixtures thereof.
1.2. ALkylthiomethylphenols, for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-dido-decylthiomethyl-4-nonylphenol.
1.3. Hydroquinones and aL~ylated hydro luinol~s, for example 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydro~luinolle, 2,5-di-tert-amylhydroquinone, 2,6-di-phenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxy-anisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis(3,5-di-tert-butyl-4-hyd,~yl,he.lyl) ~ rate 1.4. ~ydl~xylated thiodiphenyl ethers, for eY~mple 2,2'-thiobis(6-tert-butyl-4-methyl-phenol), 2,2'-thiobis(4-oclyll)hellol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thio-bis(6-tert-butyl-2-methylphenol), 4,4'-thiobis(3,6-di-sec-amylphenol), 4,4'-bis(2,6-dim-ethyl-4-hydlu~yphenyl) disulfide.
1.5. AL~lidenebisphenols, for eY~mple 2,2'-methylenebis(6-tert-butyl-4-melhylphellol), 2,2'-methylenebis(6-tert-butyl-4-elhylphellol), 2,2'-methylenebis[4-methyl-6-(a-methyl-cyclohexyl)phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylene-bis(6-nonyl4-melllylphellol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-ethylidene-bis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methy-lenebis[6-(a-methylbenzyl)-4-nonylphenol], 2,2'-methylenebis[6-(a,a-dimethylbenzyl)-4-nonylphenol], 4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'-methylenebis(6-tert-butyl-2-methylphenol), 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-tris(5-tert-butyl~-hydroxy-2-methylphenyl)butane, 1,1-bis(5-tert-butyl4-hydroxy-2-methyl-phenyl)-3-n-dodecylmer-captobutane, ethylene glycol bis[3,3-bis(3'-tert-butyl4'-hyd~ yphenyl)bulyl~le], bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopent~i~nP, bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl4-methylphenyl]terephth~l~te, 1,1-bis(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis(3,5-di-tert-butyl-4-hyd~o~y~henyl)propane, 2,2-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane, 1,1,5,5-tetra(5-tert-butyl-21~3168 4-hydroxy-2-methylphenyl)pentane.
1.6. O-, N- and S-benzyl compounds, for example 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxy-dibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmt;l.;aptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithio-terephthalate, bis(3,5-di-tert-butyl-4-hydlv,~yl,ellzyl)sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmelcal~toacet~te 1.7. Hydroxybenzylated malonates, for example dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)m~lon~tç, dioctadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malo-nate, didodecylme.~;aptoetllyl-2,2-bis(3,5-di-tert-butyl-4-llydl~ylJellzyl)malonate, bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydlo,~yben~rl)m~lon~te.
1.8. Aromatic hydr~ybenzyl co~ )oullds, for example 1,3,5-tris(3,5-di-tert-butyl-4-hy-droxybenzyl)-2,4,6-trimethylhen7~nP., 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hy(Lo,~yl,cll,yl)phenol.
1.9. Triazine compounds, for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-tri~7in~., 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxy-anilino)-1,3,5-tri~7ine, 2-oclyLK~ ;a~o-4,6-bis(3,5-di-tert-butyl-4-hydl~."yl,henoxy)-1,3,5-triazine, 2,4,6-tris(3,5-di-tert-butyl-4-hydL~ y~helloxy)-1,2,3-tn~7ine, 1,3,5-tris-(3,5-di-tert-butyl4-hydroxybenzyl)iso~;~allul~e, 1,3,5-tris(4-tert-butyl-3-hy(Lo~y-2,6-di-methylbenzyl)isocyanurate, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-tri-azine, 1,3,5-tris(3,5-di-tert-butyl-4-hyd.~y~henylpropionyl)hexahydro-1,3,5-triazine, 1,3,5-tris(3,5-dicyclohexyl-4-hy(Lw~ybellzyl)isocyanurate.
1.10. Benzylphosphonates, for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphos-phonate, diethyl-3,5-di-tert-butyl-4-hy~yl,enzylphosphonate, dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydlo,~y-3-methylbenzyl-phosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzyl-phosphonic acid.
1.11. Acylaminophenols, for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.
1.12. Esters of ~-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or poly-- 21~3168 hydric alcohols, e.g. with methanol, ethanol, octadecanol, 1,6-hexanediol, l,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hy~u~yel}lyl) isocyanurate, N,N'-bis(hy-droxyethyl)oxamide, 3-thi~nndec~nol, 3-thiapent~-lec~nol, trimethylhexanediol, trimethyl-olpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.13. Esters of ,B-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonane-diol, ethylene glycol, 1,2-yrvy~ ol~ neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, ~e~ yllllilul, tris(hy~llù~yell,yl) isocy~lur~le, N,N'-bis-(hyd uAyethyl)~Y~mi~e~ 3-thi~nn-lec~nr1 3-thi~pent~dçc~nol~ trimethylheY~n~liol, tri-methylolpropane, 4-hydlvAy~ Lyl-l-phospha-2,6,7-trioxabicyclot2.2.2]octane.
1.14. Esters of l~-(3.5-dicYclohexYl-4-hydluAy~,hellyl)propionic acid with mono- or poly-hydric alcohols, e.g. with meth~nol, ethanol, oct~e~nQl, 1,6-hçlr~nediol, l,9-non~ne~liol, ethylene glycol, 1,2-prop~n~liol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pe~ ol, tris(hydlv~e~lyl) isocy~lul~e, N,N'-bis(hy-dlv~yt;~lyl)ox~mi-le, 3-th~ n~lec~nol~ 3-thi~Ilent~ec~nol~ trimethylh~Y~ne(liol, trimethyl-olyrvpalle, 4-hydlv~ylllethyl-1-phosph~-2,6,7-trioxabicyclo[2.2.2]octane.
1.15. Esters of 3.5-di-tert-butyl-4-hydlv~y~Jhenyl acetic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, oct~dec~nol, 1,6-he~r~n~liol, 1,9-nonanediol, ethy-lene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxy-ethyl)oxamide, 3-thi~lndec~nol 3-thiapent~iec~nol~ trimethylh~Y~n~ liol, trimethylolpro-pane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.yoctane.
1.16. Amides of l~-(3.5-di-tert-butYl-4-l,ydl~v~Y~hellyl)prvpionic acid e.g. N,N'-bis(3,5-di-tert-butyl-4-hydrvxyphenylpropionyl)hexamethylene~ mine, N,N'-bis(3,5-di-tert-butyl-4-hydlvxyyhellylylvpionyl)trimethylenedi~mine, N,N'-bis(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl)hydrazine .
2. UV absorbers and li~ht stabilisers 2.1. 2-(2'-Hydroxyphenyl)benzotriazoles, for example 2-(2'-hy~v~y-5'-methylphenyl)-benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-(1,1,3,3-tetrarnethylbutyl)phenyl)benzo-triazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-S-chloro-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl)-S-chloro-benzotriazole, 2-(3'-sec-butyl-S'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-4'-octyloxyphenyl)benzoLIiazole, 2-(3',5'-di-tert-amyl-2'-hydr~xy~henyl)benzotn~70le, 2-(3',5'-bis-(a,a-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole, mixture of 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycar-bonylethyl)phenyl)-5-chloro-benzot~riazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)-car-bonylethyl]-2'-hydroxyphenyl)-S-chloro-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-S-chloro-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)bel~o~ 7~le, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyl-oxycarbonylethyl)phenyl)bc~ 7~ ,, 2-(3~-tert-butyl-5~-[2-(2-ethylhexyloxy)call~ol~yl-ethyl]-2'-hydlu~yphenyl)bel~zolliazole, 2-(3'-dodecyl-2'-hy~lluAy-5'-mclllylphellyl)benzo-triazole, and 2-(3'-tert-butyl-2'-l.y~llu,~y-5'-(2-isooctylo~ycall,ollylethyl)phenylbenzoL,i-azole, 2,2'-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzol,iazole-2-ylphenol]; the tr~n~esterifis~tion product of 2-[3'-tert-butyl-5'-(2-metho~ycall,ollylethyl)-2'-hydlo~y-phenyl]-2H-benzotriazole with polyethylene glycol 300; [R-CH2CH2-COO(CH2)3~, where R = 3'-tert-butyl-4'-hy~lu~y-5'-2H-benzotriazol-2-ylphenyl.
2.2. 2-Hydroxybenzophenones, for example the 4-hydlu~y, 4-methoxy, 4-octyloxy, 4-de-cyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-t~ihydluAy and 2'-llydluAy-4,4'-dimethoxy derivatives.
2.3. Esters of substituted and unsubstituted benzoic acids, as for example 4-tertbutyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl) resorcinol, benzoyl resorcinol, 2,4-di-tertbutylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hex~decyl 3,5-di-tert-butyl-4-hy~llu~ybe~-70~te, octadecyl 3,5-di-tert-butyl-4-hyd~uxybellzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-lly(llu~y-benzoate.
2.4. Acrylates, for example ethyl a-cyano-,B"B-diphenylacrylate, isooctyl a-cyano-,B,~-di-phenylacrylate, methyl a-carbomethoxycinn~m~te, methyl a-cyano-,B-methyl-p-methoxy-cinnamate, butyl a-cyano-~-methyl-p-methoxy-cinn~m~te, methyl a-carbomethoxy-p-methoxycinnamate and N-(~B-carbomethoxy-,~-cyanovinyl)-2-methylindoline.
2.5. Nickel compounds, for example nickel complexes of 2,2'-thio-bis[4-(1, 1 ,3,3-tetra-methylbutyl)phenol], such as the 1:1 or 1:2 complex, with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldi-thiocarbamate, nickel salts of the monoaL~cyl esters, e.g. the methyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, nickel complexes of ketoxhnes, e.g. of 2-hydroxy-4-methylphenyl undecylk~toxi.~e, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional lig~n~ls.
2.6. Sterically hindered ~mines, for example bis(2,2,6,6-tetramethyl-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-piperidyl)succinate, bis(1,2,2,6,6-pentamelhylpipelidyl)sebacate, bis(1,2,2,6,6-pentamethylpiperidyl) n-butyl-3,5-di-tert-butyl-4-hydloxyl~ellzylm~lon~te, the conrle.n~t~. of 1-(2-hydl~ yelllyl)-2,2,6,6-tetramethyl-4-hydroxy~il)e.idine and succi-nic acid, the conden~tP of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)h~ methylenedi-amine and 4-tert-octylamino-2,6-dichloro-1,3,5-tri~7ine, tris(2,2,6,6-tetrarnethyl-4-piperi-dyl) nitrilotriacetate, tetrakis(2,2,6,6-tetramethyl-4- piperidyl)-1,2,3,4-butane-tetracar-boxylate, 1,1'-(1,2-ethanediyl)bis(3,3,5,5-tetramethylpil)Gl~zinone), 4-benzoyl-2,2,6,6-tetrame~hylpipe. ;dine, 4-stearyloxy-2,2,6,6-tetrame~lylpi~ ;(line, bis(l,2,2,6,6-penta-melllylpi~lidyl)-2-n-butyl-2-(2-llyd~ y-3,5-di-tert-butylbenzyl)m~lon~te, 3-n-octyl-7,7,9,9-le~ ethyl-1,3,8-triazasprio[4.5]decane-2,4-dione, bis(1-octyloxy-2,2,6,6-tetra-methylpiperidyl)seb~r~to" bis(l-octyloxy-2,2,6,6-tetramelllylpipc~idyl)sucrin~te, the condensate of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)helr~methylen~i~mine and 4-mor-pholino-2,6-dichloro-1,3,5-triazine, the con~en~te of 2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramelhyli)i~lidyl )-1,3,5-triazine and 1,2-bis(3-amin~l~ylamino)ethane, the condensate of 2-chloro-4,6-di(4-n-butylamino-1,2,2,6,6-pentamelllyl~ ,lidyl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)eth~ne, 8-acetyl-3-dodecyl-7,7,9,9-tetra-methyl- 1 ,3,8-triazaspiro[4.5]decane-2,4-dione, 3-dodecyl- 1-(2,2,6,6-~~ lyl~piperi-dyl)pyrrolidine-2,5-dione, 3-dodecyl-1-(1,2,2,6,6-pentamethyl~piperidyl)pyrrolidine-2,5-dione.
2.7. Ox~mides, for example 4,4'-dioctyloxyox~nilide, 2,2'-dioctyloxy-5,5'-di-tert-butox-anilide, 2,2'--lidodecyloxy-5,5'-di-tert-buto~nili~e, 2-ethoxy-2'-ethylox~nili-le, N,N'-bis(3-dimethylaminopropyl)ox~mide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mix-ture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide and mixtures of ortho- and para-methoxy-disubstituted ox~nili-les and Illi~lulGs of o- and p-ethoxy-disubstituted oxani-lides.
2.8. 2-(2-Hydroxyphenyl)-1,3,5-triazines, for example 2,4,6-tris(2-hydroxy-4-octyloxy-phenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-`- 2143168 1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hy-droxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyl-oxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-butyloxy-propoxy)phenyl]-4,6-bis(2,4~imethyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxy-propyloxy)phenyl]-4,6-bis(2,4-dimethyl)- 1 ,3,5-triazine.
3. Metal deactivators, for example N,N'-diphenylox~mide, N-salicylal-N'-salicyloyl hydrazine, N,N'-bis(salicyloyl) hy~me, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenyl-propionyl) hydrazine, 3-salicyloylamino-1,2,4-tri~701.o., bis(benzylidene)oxalyl di-hydrazide, o~nili~le, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,N'-di-acetyladipoyl dihydrazide, N,N'-bis(salicyloyl)oxalyl dihydrazide, N,N'-bis(salicyloyl)-thiopropionyl dihy-lra7i~1~
4. Phosphites and phosphonites, for example ~ )hel~yl phosphite, diphenyl alkyl phos-phites, phenyl diaL~yl phosphites, tris(no,lyllJhe.lyl) phosphite, trilauryl phosphite, triocta-decyl phosphite, distearyl pentat;,yllnilol ~1irhosphite~ tris(2,4-di-tert-butylphenyl) phos-phite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-~methylphenyl)pent~e~yll.lilol diphosphite, bis(isode-cyloxy)penta~ly~ ol diphosphite, bis(2,4-di-tert-butyl-6-mclllyll~henyl)pell~.yllllitol diphosphite, bis(2,4,6-tris(tert-butylphenyl)~n~lylluitol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-bulylphenyl) 4,4'-bil)henylene diphosphonite, 6-isooctyl-oxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin, bis(2,4-di-tert-butyl-6-methylphenyl)methylphosphite, bis(2,4-di-tert-butyl-6-methyl~hcnyl)ethylphosphite.
5. Peroxide scavengers, for example esters of ,B-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters""~ ;~be~-7.i.~-id~71~le or the zinc salt of 2-mercaptoben7imi(1~701e, zinc dibutyldithiocarb~m~te, dioctadecyl ~ llfi~le~ penta-erythritol tetrakis(,B-dodecylmercapto)propionate.
6. Polyamide stabilisers, for example, copper salts in combination with iodides and/or phosphorus compounds and salts of divalent m~ng~nese.
7. Basic co-stabilisers, for example, mel~minP" polyvinylpyrrnlidone, dicy~n~ mi(lP, tri-allyl cyanurate, urea derivatives, hydrazine derivatives, ~mines~ polyamides, polyure-thanes, alkali metal salts and ~Ik~line earth metal salts of higher fatty acids for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium rici-noleate and potassium palmitate, antimony pyroc~techolate or tin pyrocatecholate.
8. Nucleatin~ agents, for example, 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid.
9. Fillers and reinforcin~ agents, for example, c~lcil]m carbonate, ~ ptes, glass fibres, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite.
10. Other additives, for example, plasticisers, l~lbric~nts~ çm~ ifi~rs, ri m~nt~, optical bri~llte.le~ s, fl~lle~uorlng agents, al,~tic agents and blowing agents.
11. Bell~orul~lones and in(lolinon~s for example those disclosed in US-A-4 325 863, US-A-4 338 244 or US-A-5 175 312, or 3-[4-(2-ace~o~yellloxy)phenyl]-5,7-di-tert-butyl-benzofuran-2-one, 5,7-di-tert-butyl-3-[4-(2-~alo~loxyethoxy)phenyl]benzoru~l-2-one, 3,3'-bis[5,7-di-tert-butyl-3-(~[2-hy~ ycll~oxy]phenyl)~n~rul~l-2-one], 5,7-di-tert-bu-tyl-3-(4-ethoxyphenyl)benzoruldll-2-one, 3-(4-acetoxy-3S-dimell.ylphellyl)-5,7-di-tert-butyl-benzofulall-2-one, 3-(3,5-dimethyl-4-pivaloyl~yphenyl)-5,7-di-tert-butyl-benzofu-ran-2-one.
Further ylcrcll~,d additives are those of group 5.
The incoll,ol~ion of the colll~ullds of fnrmlllae (I) and (II) and further optional additives into the organic m~teri~l is car ied out by known methods, typically before or during shaping or also by applying the dissolved or dispel~Gd compounds to the organic m~t~.ri~l, if necessary with subsequent e~a~ola~ion of the solvent. The compounds of fi)rmulaP (I) and (II) can also be added to the m~t~n~l~ to be stabilised in form of a master-batch comprising them in a con~entration of 2.5 to 25% by weight.
The compounds of formulae (I) and (II) can also be added before or during polymerisation or before crosslinkin~
The compounds of formulae (I) and (II) can be incorporated into the m~teri~l to be stabilised in pure form or enc~ps~ tYl in waxes, oils or polymers.
The materials stabilised in this manner can be used in any form of presentation, e.g. as ~llms, fibres, ribbons, mo~ ling~, profiles or as binders for paint ~y~e-lls, adhesives or putties.
The invention is further illustrated by the following Example. Parts and percentages are by weight, unless otherwise stated.
Example 1: Stabili~tion of acryll nitril~ /bllt~ n~ yr~l~ terpolymer (ABS).
0.1 g of B-l, 0.2 g of C-l and 0.6 g of dilaurylthiodipropionate are dissolved in 40 ml of a solvent Illi~Ult; of hexanefisopr~allol. With efficient stirrin~, the sol~ltion is added to a dispersion of 100 g of ABS in 600 g of water, wh~lGu~on the solution is completely absorbed by the ABS in a short time (c. 1 minute). The ABS powder is collected by suction filtration and dried for 40 hours under vacuum at 40C.
To determine the thermal stability, samples of 10 mg each of ABS powder are put into a thermodirrerelltial analyser (Mettler TA 2000) and the time it takes to reach the maximum of the exothermic reaction at 170C is det~rmin~l. The time until the maximum is reached is 345 min.
The following compounds are used:
OH ~ CH3 H3C ~ C14H29 B-l:
OH -- OH --C 1: (H3C)3C ~ ~,C(CH3)3 CH3 _ CH3-- n (average molecular weight: 600-700)
Further ylcrcll~,d additives are those of group 5.
The incoll,ol~ion of the colll~ullds of fnrmlllae (I) and (II) and further optional additives into the organic m~teri~l is car ied out by known methods, typically before or during shaping or also by applying the dissolved or dispel~Gd compounds to the organic m~t~.ri~l, if necessary with subsequent e~a~ola~ion of the solvent. The compounds of fi)rmulaP (I) and (II) can also be added to the m~t~n~l~ to be stabilised in form of a master-batch comprising them in a con~entration of 2.5 to 25% by weight.
The compounds of formulae (I) and (II) can also be added before or during polymerisation or before crosslinkin~
The compounds of formulae (I) and (II) can be incorporated into the m~teri~l to be stabilised in pure form or enc~ps~ tYl in waxes, oils or polymers.
The materials stabilised in this manner can be used in any form of presentation, e.g. as ~llms, fibres, ribbons, mo~ ling~, profiles or as binders for paint ~y~e-lls, adhesives or putties.
The invention is further illustrated by the following Example. Parts and percentages are by weight, unless otherwise stated.
Example 1: Stabili~tion of acryll nitril~ /bllt~ n~ yr~l~ terpolymer (ABS).
0.1 g of B-l, 0.2 g of C-l and 0.6 g of dilaurylthiodipropionate are dissolved in 40 ml of a solvent Illi~Ult; of hexanefisopr~allol. With efficient stirrin~, the sol~ltion is added to a dispersion of 100 g of ABS in 600 g of water, wh~lGu~on the solution is completely absorbed by the ABS in a short time (c. 1 minute). The ABS powder is collected by suction filtration and dried for 40 hours under vacuum at 40C.
To determine the thermal stability, samples of 10 mg each of ABS powder are put into a thermodirrerelltial analyser (Mettler TA 2000) and the time it takes to reach the maximum of the exothermic reaction at 170C is det~rmin~l. The time until the maximum is reached is 345 min.
The following compounds are used:
OH ~ CH3 H3C ~ C14H29 B-l:
OH -- OH --C 1: (H3C)3C ~ ~,C(CH3)3 CH3 _ CH3-- n (average molecular weight: 600-700)
Claims (11)
1. A composition comprising a) a polystyrene, a substituted polystyrene, a copolymer or terpolymer of styrene or substituted styrene, a polycarbonate, a polyester carbonate, a polyurethane, a polyamide, a copolyamide, a polyacetal or a polyphenylene oxide,b) at least one compound of formula I
(I) wherein R1 is methyl or ethyl, R2 is C2-C30 alkyl and R3 is C1-C4 alkyl; and c) at least one compound of formula II
(II), wherein R3 is C1-C4 alkyl, R4 is tert-butyl or cyclohexyl, L-CH2-or tricyclo[5.2.1.02.6]decane-3,8-ylene, and n ? 1.
(I) wherein R1 is methyl or ethyl, R2 is C2-C30 alkyl and R3 is C1-C4 alkyl; and c) at least one compound of formula II
(II), wherein R3 is C1-C4 alkyl, R4 is tert-butyl or cyclohexyl, L-CH2-or tricyclo[5.2.1.02.6]decane-3,8-ylene, and n ? 1.
2. A compound according to claim 1, wherein R2 in compounds of formula (I) is C8-C30 alkyl.
3. A composition according to claim 1, wherein R3 in compounds of formulae (I) and (II) is methyl.
4. A composition according to claim 1, wherein component b) is a compound of formula or
5. A composition according to claim 1, wherein component a) is a polystyrene, a substi-tuted polystyrene or a copolymer or terpolymer of styrene or substituted styrene.
6. A composition according to claim 1, wherein component a) is impact-resistant poly-styrene (IPS), a styrene/acrylonitrile copolymer (SAN) or an acrylonitrile/butadiene/styrene terpolymer (ABS).
7. A composition according to claim 1, wherein component a) is an acrylonitrile/buta-diene/styrene terpolymer (ABS).
8. Use of at least one compound of formula I
(I), wherein R1 is methyl or ethyl, R2 is C2-C30 alkyl and R3 is C1-C4 alkyl;
and at least one compound of formula II
(II), wherein R3 is C1-C4alkyl, R4 is tert-butyl or cyclohexyl, L-CH2-or tricyclo[5.2.1.02.6]decane-3,8-ylene, and n ? 1;
for stabilising polystyrene, substituted polystyrene, copolymers or terpolymers of styrene or substituted styrene, polycarbonate, polyester carbonate, polyurethane, polyamide, copolyamide, polyacetal or polyphenylene oxide against thermal, oxidative and actinic degradation.
(I), wherein R1 is methyl or ethyl, R2 is C2-C30 alkyl and R3 is C1-C4 alkyl;
and at least one compound of formula II
(II), wherein R3 is C1-C4alkyl, R4 is tert-butyl or cyclohexyl, L-CH2-or tricyclo[5.2.1.02.6]decane-3,8-ylene, and n ? 1;
for stabilising polystyrene, substituted polystyrene, copolymers or terpolymers of styrene or substituted styrene, polycarbonate, polyester carbonate, polyurethane, polyamide, copolyamide, polyacetal or polyphenylene oxide against thermal, oxidative and actinic degradation.
9. Use according to claim 8, wherein the compound of formula I is or
10. A method of stabilising polystyrene, substituted polystyrene, copolymers or terpolymers of styrene or substituted styrene, polycarbonate, polyester carbonate, polyurethane, polyamide, copolyamide, polyacetal or polyphenylene oxide against thermal, oxidative and actinic degradation, which comprises the use of at least one compound of formula I
(I), wherein R1 is methyl or ethyl, R2 is C2-C30alkyl and R3 is C1-C4alkyl;
and at least one compound of formula II
(II), wherein R3 is C1-C4 alkyl, R4 is tert-butyl or cyclohexyl, L-CH2-or tricyclo[5.2.1.02.6]decane-3,8-ylene, and n ? 1.
(I), wherein R1 is methyl or ethyl, R2 is C2-C30alkyl and R3 is C1-C4alkyl;
and at least one compound of formula II
(II), wherein R3 is C1-C4 alkyl, R4 is tert-butyl or cyclohexyl, L-CH2-or tricyclo[5.2.1.02.6]decane-3,8-ylene, and n ? 1.
11. A method according to claim 10, which comprises the use of a compound of formula or
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
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| CH541/94-3 | 1994-02-24 | ||
| CH54194 | 1994-02-24 |
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| CA2143168A1 true CA2143168A1 (en) | 1995-08-25 |
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ID=4189382
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| CA 2143168 Abandoned CA2143168A1 (en) | 1994-02-24 | 1995-02-22 | Stabiliser mixtures |
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| EP (1) | EP0669367A1 (en) |
| JP (1) | JPH07258463A (en) |
| CA (1) | CA2143168A1 (en) |
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Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4761247A (en) * | 1987-03-06 | 1988-08-02 | Morton Thiokol, Inc. | Phenol-stabilized microbiocidal compositions |
| DE59010722D1 (en) * | 1989-06-30 | 1997-07-10 | Ciba Geigy Ag | 2,4-dimethyl-6-s-alkylphenols |
| TW276260B (en) * | 1992-07-15 | 1996-05-21 | Ciba Geigy Ag |
-
1995
- 1995-02-15 EP EP95810098A patent/EP0669367A1/en not_active Withdrawn
- 1995-02-22 CA CA 2143168 patent/CA2143168A1/en not_active Abandoned
- 1995-02-23 JP JP5978495A patent/JPH07258463A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6835776B2 (en) | 2000-05-31 | 2004-12-28 | Basf Aktiengesellschaft | Stabilized thermoplastic molding materials |
| US9644090B2 (en) | 2012-08-08 | 2017-05-09 | Ineos Styrolution Europe Gmbh | Polymer mixtures with optimized toughness/stiffness ratio and optical properties |
| US10072145B2 (en) | 2013-11-26 | 2018-09-11 | Ineos Styrolution Group Gmbh | Thermoplastic moulding compositions with appropriately designed graft shell |
| US9982123B2 (en) | 2014-04-02 | 2018-05-29 | Ineos Styrolution Group Gmbh | Process for producing thermoplastic moulding compositions with improved mechanical properties |
| US10654249B2 (en) | 2014-05-19 | 2020-05-19 | Ineos Styrolution Group Gmbh | Styrene copolymer composite film |
| US10815342B2 (en) | 2016-06-06 | 2020-10-27 | Ineos Styrolution Group Gmbh | Process for producing a stabilizer dispersion and process for producing a thermoplastic composition stabilized with the stabilizer dispersion |
| US10975240B2 (en) | 2016-11-15 | 2021-04-13 | Sanko Co., Ltd. | Method for producing antioxidant and method for producing elastic polyurethane fiber |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0669367A1 (en) | 1995-08-30 |
| JPH07258463A (en) | 1995-10-09 |
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