CA2000891A1 - Polymeric substrates stabilized with n-substituted hindered amines - Google Patents
Polymeric substrates stabilized with n-substituted hindered aminesInfo
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- CA2000891A1 CA2000891A1 CA 2000891 CA2000891A CA2000891A1 CA 2000891 A1 CA2000891 A1 CA 2000891A1 CA 2000891 CA2000891 CA 2000891 CA 2000891 A CA2000891 A CA 2000891A CA 2000891 A1 CA2000891 A1 CA 2000891A1
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- tert
- tetramethylpiperidine
- butyl
- hydroxy
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3435—Piperidines
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
POLYMERIC SUBSTRATES STABILIZED WITH N-SUBSTITUTED HINDERED
AMINES
Abstract of the Disclosure Hindered amines based on various 2,2,6,6-tetralkylated nitrogen-containing heterocyclic moieties wherein the hindered nitrogen atom on the ring is substituted with OR1 substituents and the 4-position of the ring is substituted with OR2 substituents are effective in protecting a variety of polymeric substrates against the adverse effects of light, heat and oxygen.
AMINES
Abstract of the Disclosure Hindered amines based on various 2,2,6,6-tetralkylated nitrogen-containing heterocyclic moieties wherein the hindered nitrogen atom on the ring is substituted with OR1 substituents and the 4-position of the ring is substituted with OR2 substituents are effective in protecting a variety of polymeric substrates against the adverse effects of light, heat and oxygen.
Description
9:1L
POLYMERIC SUBSTRATES STABILIZED WITH N-SUBSTITUTED HINDERED
~MINES
It is well known that polymeric substrates undergo progressive changes in their physical properties, including color changes, embrittlement and loss of mechanical properties, when exposed to processing conditions or to sunlight or other sources of ultraviolet radiation.
Retardation of these deleterious effects has been achieved utilizing a broad range of additives, including those exhibiting light-stabilizing properties, such additives including benzophenones, benzotriazoles, substituted benzoic acid ester, nickel complexes, aromatic oxamides and sterically hindered amines~
The latter group of chemicals and their stabilizing activity in a wide variety of substrates are likewise well known and have been described in a broad range of patents and technical literature. In view of the extensive nature of such art, reference is made to U.S. 4,426,471, U.S. 4,426,472, U.S.
4,344,876, U.S. 4,590,231 and U.S. 4,691,015 for a summary of representative hindered amine light stabilizers.
It has now been surprisingly determined that the polymeric substrates recited herein can be effectively stabilized by the incorporation therein of the indicated N-OR1 substituted hindered amines. Thus, these compounds serve to protect the polymeric materials against the adverse effects of actinic, oxidative and thermal degradation. In particular, they serve to reduc.e color formation resulting from processingcon-ditions and are especially effective in stabilizingorganic 2~0~89~
materials against the degradative effects of actinicstimuli.
Since these stabilizers are considerably less basicthan conventional hindered amines, they also have little orno determinal effect on the thermal stability of thepolymer during processing at elevated temperatures. They alsoprotect the polymers against tlle gas fading that may beexperienced upon exposure to the combustion products ofnatural gas.
Certain effects are specifically to be noted in polyvinyl chloride formulations wherein conventional hindered amines adversely impact on thermal stability during processing.
Thus, these PVC formulations contain various organotin and/or mixed metal heat stabilizers for the specific purpose of providing thermal stability during processing and subsequent use. The conventional hindered amines added to provide light stability negate at least a portion of the thermal stability thereby resulting in discolored and/or degraded products. In contrast, the substitution pattern of the instant compounds, particularly the -NOAlkyl compounds, provides the desired long term light stability without a substantial concomitant negation of thermal stability. Improvements are also to be seen in weatherability during outdoor exposure. In addition, the instant compounds significantly reduce the pigment interactions such as color drift and flocculation encountered ~ith the conventional hindered amines when present in pi~mented substrates.
The substituted hindered amine compounds applicable for use in this invention contain a group of the formula (A) RCH2~R
Rlo - N ~ oR2 (A) 2~ 39~l.
wherein R is hydrogen or methyl, Rl iS Cl-C8alkYll C2-Clgalkenyl~ C2-Clgalkynyl, C5-Cl2cy alkyl, C6-C1obicycloalkyl, C5-C8cycloalkenyl, C6-C1oaryl, C7-Cgaralkyl, C7-Cgaralkyl substi~uted byC1-C4alkyl or o C6-C1oaryl, or R1 is -C-D wherein D isC1-C18alkyl, C1-C1g-alkoxy, phenyl, phenyl substituted byhydroxy, C1-C4alkyl or C1-C4alkoxy, or amino or amino mono-ordisubstituted by C1-C12alkyl or phenyl and R2 is hydrogen, C1-C1galkyl optionally interrupted by one or more oxygen atoms, C2-C12alkenyl, C6-ClOarYl~ C7-C18aralkY
glycidyl, a monovalent acyl radical of an aliphatic, cyclo-aliphatic, araliphatic or aromatic carboxylic acid, orof a carbamic acid, preferably an acyl radical of analiphatic carboxylic acid having 2-18 C atoms, of acycloaliphatic carboxylic acid having 5-12 C atoms or of an aromaticcarbox-ylic acid have 7-15 C atoms.
If in formula (A) R1 or R2 are C1-C1galkyl, they are for example methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl. Typical cycloalkyl groups include cyclopentyl and cyclohexyl; typical cycloalkenyl groups includecyclo-hexenyl; while typical aralkyl groups include benzyl, alpha-methyl-benzyl, alpha,alpha-dimethylbenzyl orphenethyl.
C1-Cl2alkyl and cyclohexyl are preferred.
If R2 is a monovalent acyl radical of a carboxylic acid, it is for example an acyl radical of acetic acid, propionic acid, butyric acid, valeric acid, capronic acid, stearic acid, salicylic acid, benzoic acid, hexahydrobenzoic acid or ~-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid~
If R2 is a monovalent acyl radical of a carbamic acid it is , .
2~0891 preferably a radical of an aliphatic C2-C13carbamic acid or ofphenyl carbamic acid. Examples for aliphatic carbamicacids are methyl, butyl, octyl, dodecyl, dimethyl, diethyl or dibutyl carbamic acid.
Preferably R1 is C1-C18alkyl, C2-C1galkenyl, C5-C12cyclo-alkyl, C7-Cgaralkyl or C7-C9aralkyl substituted by alkyl or aryl.
The following compounds are examples of compounds of for-mula (A):
1. 1,4-dimethoxy-2,2,6,6-tetramethylpiperidine 2. 4-benzyloxy-1-ethoxy-2,2,6,6-tetramethylpiperidine 3. l,4-dibenzyloxy-2,2,6,6-te-tramethylpiperidine 4.1-cyclohexyloxy-4-glycidyloxy-2,2,6,6-tetrametyhl-piperidine 5. 1-cyclohexyloxy-4-octadecanoyloxy-2,2,6,6-tetramethyl-piperidine 6. 4-benzoyloxy-1-methoxy-2,2,6,6-tetramethylpiperidine 7. 4-benzoyloxy-1-cyclohexyloxy-2,2,6,6-tetramethyl-piperidine 8. 4-benzoyloxy-1-(a-methylbenzyloxy)-2,2,6,6-tetramethyl-piperidine 9. 4-benzoyloxy-1-benzyloxy-2,2,6,6-tetramethylpiperidine 10. (1-cyclohexyLoxy-2,2,6,6-tetramethylpiperidin-4-yl)-3,5-di-tert.butyl-4-hydroxybenzoate 11. 1,4-diacetoxy-2,2,6,6-tetramethylpiperidine 12. 1-acetoxy-4-hydroxy-2,2,6,6-tetramethylpiperidine 13. 1-propionoxy-4-stearoyloxy-2,2,6,6-tetramethylpiperidine 14. 1-acetoxy-4-benzyloxy-2,2,6,6-tetramethylpiperidine 15. (1-acetoxy-2,2,6,6-tetramethylpiperidin-4-yl)-4-hydroxy-3,5-di-tert.butylbenzoate 16. 1,4-di(-4-hydroxy-3,5-di-tert.butylbenzoyloxy)-2,2,6,6-tetramethylpiperidine - : :
2(~ 891~
POLYMERIC SUBSTRATES STABILIZED WITH N-SUBSTITUTED HINDERED
~MINES
It is well known that polymeric substrates undergo progressive changes in their physical properties, including color changes, embrittlement and loss of mechanical properties, when exposed to processing conditions or to sunlight or other sources of ultraviolet radiation.
Retardation of these deleterious effects has been achieved utilizing a broad range of additives, including those exhibiting light-stabilizing properties, such additives including benzophenones, benzotriazoles, substituted benzoic acid ester, nickel complexes, aromatic oxamides and sterically hindered amines~
The latter group of chemicals and their stabilizing activity in a wide variety of substrates are likewise well known and have been described in a broad range of patents and technical literature. In view of the extensive nature of such art, reference is made to U.S. 4,426,471, U.S. 4,426,472, U.S.
4,344,876, U.S. 4,590,231 and U.S. 4,691,015 for a summary of representative hindered amine light stabilizers.
It has now been surprisingly determined that the polymeric substrates recited herein can be effectively stabilized by the incorporation therein of the indicated N-OR1 substituted hindered amines. Thus, these compounds serve to protect the polymeric materials against the adverse effects of actinic, oxidative and thermal degradation. In particular, they serve to reduc.e color formation resulting from processingcon-ditions and are especially effective in stabilizingorganic 2~0~89~
materials against the degradative effects of actinicstimuli.
Since these stabilizers are considerably less basicthan conventional hindered amines, they also have little orno determinal effect on the thermal stability of thepolymer during processing at elevated temperatures. They alsoprotect the polymers against tlle gas fading that may beexperienced upon exposure to the combustion products ofnatural gas.
Certain effects are specifically to be noted in polyvinyl chloride formulations wherein conventional hindered amines adversely impact on thermal stability during processing.
Thus, these PVC formulations contain various organotin and/or mixed metal heat stabilizers for the specific purpose of providing thermal stability during processing and subsequent use. The conventional hindered amines added to provide light stability negate at least a portion of the thermal stability thereby resulting in discolored and/or degraded products. In contrast, the substitution pattern of the instant compounds, particularly the -NOAlkyl compounds, provides the desired long term light stability without a substantial concomitant negation of thermal stability. Improvements are also to be seen in weatherability during outdoor exposure. In addition, the instant compounds significantly reduce the pigment interactions such as color drift and flocculation encountered ~ith the conventional hindered amines when present in pi~mented substrates.
The substituted hindered amine compounds applicable for use in this invention contain a group of the formula (A) RCH2~R
Rlo - N ~ oR2 (A) 2~ 39~l.
wherein R is hydrogen or methyl, Rl iS Cl-C8alkYll C2-Clgalkenyl~ C2-Clgalkynyl, C5-Cl2cy alkyl, C6-C1obicycloalkyl, C5-C8cycloalkenyl, C6-C1oaryl, C7-Cgaralkyl, C7-Cgaralkyl substi~uted byC1-C4alkyl or o C6-C1oaryl, or R1 is -C-D wherein D isC1-C18alkyl, C1-C1g-alkoxy, phenyl, phenyl substituted byhydroxy, C1-C4alkyl or C1-C4alkoxy, or amino or amino mono-ordisubstituted by C1-C12alkyl or phenyl and R2 is hydrogen, C1-C1galkyl optionally interrupted by one or more oxygen atoms, C2-C12alkenyl, C6-ClOarYl~ C7-C18aralkY
glycidyl, a monovalent acyl radical of an aliphatic, cyclo-aliphatic, araliphatic or aromatic carboxylic acid, orof a carbamic acid, preferably an acyl radical of analiphatic carboxylic acid having 2-18 C atoms, of acycloaliphatic carboxylic acid having 5-12 C atoms or of an aromaticcarbox-ylic acid have 7-15 C atoms.
If in formula (A) R1 or R2 are C1-C1galkyl, they are for example methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl. Typical cycloalkyl groups include cyclopentyl and cyclohexyl; typical cycloalkenyl groups includecyclo-hexenyl; while typical aralkyl groups include benzyl, alpha-methyl-benzyl, alpha,alpha-dimethylbenzyl orphenethyl.
C1-Cl2alkyl and cyclohexyl are preferred.
If R2 is a monovalent acyl radical of a carboxylic acid, it is for example an acyl radical of acetic acid, propionic acid, butyric acid, valeric acid, capronic acid, stearic acid, salicylic acid, benzoic acid, hexahydrobenzoic acid or ~-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid~
If R2 is a monovalent acyl radical of a carbamic acid it is , .
2~0891 preferably a radical of an aliphatic C2-C13carbamic acid or ofphenyl carbamic acid. Examples for aliphatic carbamicacids are methyl, butyl, octyl, dodecyl, dimethyl, diethyl or dibutyl carbamic acid.
Preferably R1 is C1-C18alkyl, C2-C1galkenyl, C5-C12cyclo-alkyl, C7-Cgaralkyl or C7-C9aralkyl substituted by alkyl or aryl.
The following compounds are examples of compounds of for-mula (A):
1. 1,4-dimethoxy-2,2,6,6-tetramethylpiperidine 2. 4-benzyloxy-1-ethoxy-2,2,6,6-tetramethylpiperidine 3. l,4-dibenzyloxy-2,2,6,6-te-tramethylpiperidine 4.1-cyclohexyloxy-4-glycidyloxy-2,2,6,6-tetrametyhl-piperidine 5. 1-cyclohexyloxy-4-octadecanoyloxy-2,2,6,6-tetramethyl-piperidine 6. 4-benzoyloxy-1-methoxy-2,2,6,6-tetramethylpiperidine 7. 4-benzoyloxy-1-cyclohexyloxy-2,2,6,6-tetramethyl-piperidine 8. 4-benzoyloxy-1-(a-methylbenzyloxy)-2,2,6,6-tetramethyl-piperidine 9. 4-benzoyloxy-1-benzyloxy-2,2,6,6-tetramethylpiperidine 10. (1-cyclohexyLoxy-2,2,6,6-tetramethylpiperidin-4-yl)-3,5-di-tert.butyl-4-hydroxybenzoate 11. 1,4-diacetoxy-2,2,6,6-tetramethylpiperidine 12. 1-acetoxy-4-hydroxy-2,2,6,6-tetramethylpiperidine 13. 1-propionoxy-4-stearoyloxy-2,2,6,6-tetramethylpiperidine 14. 1-acetoxy-4-benzyloxy-2,2,6,6-tetramethylpiperidine 15. (1-acetoxy-2,2,6,6-tetramethylpiperidin-4-yl)-4-hydroxy-3,5-di-tert.butylbenzoate 16. 1,4-di(-4-hydroxy-3,5-di-tert.butylbenzoyloxy)-2,2,6,6-tetramethylpiperidine - : :
2(~ 891~
17. n-butyl-(4-benzoyloxy-2,2,6,6-tetramethylpiperidin-~-yl)-carbonate 18. 1,4-di-(2-ethylhexanoyloxy)-2,2,6,6-tetramethylpiperidine 19. 1-carbamoyloxy-4-benzoyloxy-2,2,6,6-tetramethylpiperidine 20. 1-dimethylcarbamoyloxy-4-benzoyl-2,2,6,6-tetramethyl-piperidine 21. 4-benzoyloxy-1-heptyloxy-2,2,6,6-tetramethylpiperidine The compounds of formula (A) are generally prepared by oxidizing the corresponding NH derivatives with an appro-priate peroxy compound such as hydrogen peroxide ortert-butyl hydroperoxide in the presence of a metal carbonyl or metal oxide catalyst followed by reduction of the oxyl intermediate formed to the desired N-hydroxy derivative, preferably by catalytic hydrogenation. Thereafter, the N-acyloxy derivatives are prepared by reacting the N-hydroxy hindered amine with the appropriate acid chloride, anhydride, isocyanate or substituted chloroformate. The catalytic hydrogenation can also be conducted in acetic anhydride to prepare the N-acetoxy derivative.
O-alkyl substituted N-hydroxy derivatives can be synthesized by several routes. The N-hydroxy derivative can be alkylated with sodium hydride and halogenated hydrocarbons such as benzyl bromide and ethyl iodide. N-methoxy variants can be prepared by thermolysis of a chlorobenzene solution of nitroxyl radical and di-tert-butyl peroxide. The product is formed by a coupling reaction between the nitroxyl radical and methyl radical generated from ~-scission of a t-butoxy radical. Other N-alkoxy variants are synthesized by coupling nitroxyl radicals with hydrocarbon radicals generated from thermal decomposition of di-tert-bu~yl peroxide in the presence of hydrocarbon solvents such as cylcohexane, toluene, and ethylbenzene.
A preferred approach is the preparation of N-alkoxy hindered . ~.
.-:
2~ 891 amines directly from the NH derivatives. For example, a mixture of 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, aqueous t-butyl hydroperoxide, molybdenum oxide, andethyl-benzene gives a 90 ~ yield of the N-alpha-methylbenyloxy piperidine.
The NH derivative precursors are largely commercially available or can be prepared by known methods.
The use of the compounds of formula (A) as stabilizers for ambient curable or acid catalized thermosetting coatings is subject of two prior patent applications now published as European Application EP-A-309 400 and 309 402.
According to the instant invention these compounds are also suitable for stabilizing polyolefins or those organic polymers which contain hetero atoms, double bonds or aromatic rings.
The polyolefins may be homopolymers or copolymers of an alpha olefin.
The polyolefins useful in the instant compositions are the polymers derived from monoolefins, such as polyethylene, which can be crosslinked, polypropylene, polyisobutylene, polybutene-1, poly-3-methylbutene-1 andpoly-4-methyl-pentene-1. Polyethylene may be for example medium density, high density or linear low density polyethylene.
Mixtures of the homopolymers cited above, for example mixtures of polypropylene and polyethylene, polypropylene and polybutene-1-, or polypropylene and polyisobutylene and the like, may also be used.
Copolymers of monolefins may also be used in the instant compositions, for example ethylene/propylene copolymers, Z~891 propylene-butene-1 copolymers, propylene/octene-1 copolymers, ethylene/butene-1 copolymers, ethylene/octene-1 copolymers as well as ethylene/vinyl acetate copolymers.
~specially preferred polyolefin substrates are polypropylene, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, poly(butene-1), ethylene/vinyl acetate copolymer, ethylene/-propylene copolymer and copolymers of ethylene or of propylene with higher alpha olefins.
The most preferred polyolefin substrate polypropylene, high density polyethylene, ethylene/propylene copolymer or a copolymer of ethylene or of propylene with another alpha olefin.
Examples of organic polymers whch contain hetero atoms, double bonds or aromatic rings are the following:
1. polymers derived from doubly unsaturated hydrocarbons, e.g. polyisoprene or polybutadiene;
2. polystyrene;
3. copolymers of styrene or alpha-methyl styrene with dienes or acryl derivatives, such as styrene-butadiene, styrene-acrylonitrile, styrene-acrylonitrile-methacrylate, mixturesof high impact strength from styrene-copolymersandanother polymer, such as polyacrylate, a diene-polymer or anethylene propylene-diene terpolymer, as well as block copolymers of styrene such as styrene-butadiene-styrene, styrene-isoprene-styrene orstyrene-ethylene/butylene-styrene;
4. graft polymers of styrene, such as styrene orpoly-butadiene, styrene and acrylonitrile on polybutadiene, as well as mixtures with the copolymers mentioned under (3), , :
- :: -2~ 089~
such as those known as ABS polymers~
5. halogen-containing vinyl polymers, such as polyvinyl chloride, polyvinylidene chloride, polyvinylfluoride, polychloroprene, chlorinated rubber, vinyl chloride/-vinylidene chloride.copolymers, vinyl chloride/vinyl acetate copolymers or vinylidene chloride/vinyl acetate copolymers;
6. polymers derived from alpha-beta-unsaturated acids and derivatives thereof, polyacrylates and polymethacrylates, polyacrylic amides and polyacrylonitrile;
7. polymers derived from unsaturated alcohols or their acyl derivatives or acetals, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl butyral, polyallyl phthalate, polyallyl melamine and copolymers thereof with other vinyl compounds, such as ethylene/vinyl acetate copolymers;
8. polyacetals such as polyoxymethylene, and also those polyoxymethylenes containing as comonomers, e.g. ethylene oxide;
9. polyurethanes;
10. polycarbonates;
ll. aliphatic and aromatic polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, such as polyamide 6, polyamide 6/6, polyamide 6/10, polyamide 11 and polyamide 12;
12. polyesters derived from dicarboxylic acids and dialcohols and/or from hydroxycarboxylic acids or corresponding lactones, such as polyethylene glycol terephthalate and .
, 2C~89~.
g poly-1,4-dimethylol-cyclohexaneterephthalate.
Substrates of particular interest are polyvinyl chloride, particularly pigmented rigid polyvinyl chloride, polyurethanes and styrenic polymers such as ABS polymers.
In general, the compounds of formula (A) are employed ln from about 0.01 to about 5 %by weight of the stabilized com-position, although this will vary with the particular substrate and application. An advantageous range is from about 0.05 to about 2 %, andespecially 0.1 to about 1 %.
The stabilizers of the instant invention may readily be incorporated into the indicated polymeric substrates by conventional techniques, at any convenient state prior to the manufacture of shaped articles therefrom. For example, the stabilizer may be mixed with the polymer in dry powder form, or a suspension or emulsion of the stabilizer may be mixed with a solution, suspension, or emulsion of the polymer. The resulting stabilized polymer composition of the invention may optionally also contain various conventional additives, such as the following.
1. Antioxidants 1.1. Alkylated monophenols, forexample2,6-di-tert-butyl-4-methyl-phenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-iso-butylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-~-methylcyclohexyl~-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexyl-phenol, 2,6-di-tert-butyl-4-methoxymethylphenol, 2,6-di-nonyl-4-methyl-phenol.
1.2. Alkylated hydroquinones,for example2,6-di-tert-butyl-4-methoxy- phenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-.... : .
Z~ 39~
amylhydroquinone, 2, 6-diphenyl-4-octadecyloxyphenol.
1.3. Hydroxylated thiodiphenyl ethers, for example 2,2'-thio-bis(6-tert-butyl-4-methylphenol), 2,2'-thiobis(4-octyl-phenol), 4,4'-thiobis (6-tert-butyl-3-methylphenol), 4,4'-thio-bis(6-tert-butyl-2-methylphenol).
1.4. Alkylidenebisphenols, for example2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'-methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6- (o~-methylcyclo-hexyl)phenol], 2,2'-methylenebis(4-methyl-6-cyclohexyl-phenol), 2,2'-methylenebis (6-nonyl-4-methylphenol), 2,2'-methylenebis(4, 6-di-tert-butylphenol), 2,2'-ethyl-idenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis[6- (c~-methyl-benzyl)-4-nonylphenol], 2,2'-methylenebis[6- (c~ -dimethyl-benzyl)-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-methyl-phenol, 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis[3,3-bis-(3'-tert-butyl-4'-hydroxyphenyl)butyrate], bis~3-tert-butyl-4-hydroxy-S-methyl-phenyl) dicyclopentadiene, bis[2- (3'-tert-butyl-2'-hydroxy-5'-methyl- benzyl)-6-tert-butyl-4-methylphenyl]terephthalate.
1.5. Benzyl compounds, for examplel,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4, 6-trimethylbenzene, bis(3,5-di-tert-butyl-4-hydroxy-benzyl) sulfide, isooctyl 3,5-di-tert-butyl-4-hydroxybenzylmercapto-acetate, bis(4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) dithiolterephthalate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate~
1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, dioctadecyl 3,5-di-tert-butyl-4-hydroxy-: ' . ~ .
2~ 391 benzylphosphonate, calcium salt ofmonoethyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 1,3,5-tris-(3,5-dicyclo-hexyl-4-hydroxybenzyl)isocyanurate.
1.6. Acylaminophenols, for example lauric acid4-hydroxy-anilide, stearic acid 4-hydroxyanilide, 2,4-bis(octyl-mercapto)-6-(3,5-di-tert-butyl-9-hydroxyanilino)-s-trlazine, octylN-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate.
1.7. Esters of~-(3,5-di-tert-butYl-4-hvdroxyphenvl)propionic acid withmono- or polyhydric alcohols, e.g. withmethanol, diethylene glycol, octadecanol, triethylene glycol, 1,6-hexanediol, pentaerythritol, neopentyl glycol, tris-(hydroxyethyl) isocyanurate, thiodiethylene glycol, N,N'-bis(hydroxyethyl)oxalic acid diamide.
1.8. Esters of~-(5-tert-butYl-4-hYdroxY-3-methYlphenyl)-propionic acidwith mono- or polyhydric alcohols, e.g. with methanol, diethylene glycol, octadecanol, triethylene glycol 1,6-hexanediol, pentaerythritol, neopentyl glycol, tris-(hydroxyethyl) isocyanurate, thiodiethylene glycol, N,N'-bis(hydroxyethyl)oxalic acid diamide.
1.9. Esters of~-(3,5-dicYclohexyl-4-hYdroxyphenYl)Propionic acid withmono- or polyhydric alcohols, e.g. with methanol, diethyleneglycol, octadecanol, triethylene glycol, 1,6-hexanediol, pentaerythritol, neopentyl glycol, tris-(hydroxyethyl) isocyanurate, thiodiethylene glycol, N,N'-bis(hydroxyethyl)oxalic acid diamide.
1.10. Amides ofb-(3,5-di-tert-butyl-4-hydroxyphenYl~-ProPionic acid e.g.N,N'-bis(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl)hexamethylene-diamine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)tri-methylene-diamine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine.
2Q~ 8~L
2. UV absorbers and liqht stabilisers 2.1. 2-(2'-Hydroxyphenyl)benzotriazoles, for example the 5'-methyl, 3',5'-di-tert-butyl, 5'-tert-butyl, 5'-(1,1,3,3-tetramethylbutyl), 5-chloro-3',5'-di-tert-butyl, 5-chloro-3'-tert-butyl-5'-methyl, 3'-sec-butyl-5'-tert-butyl, 4'-octoxy, 3',5'-di-tert-amyl and3',5'-bis (a, a- dimethyl-benzyl) derivatives.
.
2.2. 2-Hydroxybenzophenones, for example the4-hydroxy, 4-methoxy, 4-octoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives.
2.3. Esters of substituted and unsubstituted benzoicacids, for example, 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)-resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate and hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate.
2.4. Acrylates, for example ethyl a-cyano-~,~-diphenyl-acrylate, isooctyla-cyano-~ diphenylacrylate, methyl a-carbomethoxycinnamate, methyla-cyano-~-methyl-p-methoxy-cinnamate, butyla-cyano-~-methyl-p-methoxy-cinnamate, methyl a-carbomethoxy-p-methoxycinnamate and N-(~-carbo-methoxy-~-cyanovinyl)-2-methylindoline.
2.5. Nickel comPounds, for example nickel complexesof 2,2'-thio-bis-[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or 1:2 complex, with or without additional ligands such as n-butylamine, triethanolamine orN-cyclohexyldi-ethanolamine, nickel dibutyldithiocarbamate, nickel saltsof 4-hydroxy-3,5-di-tert-butylbenzyl-phosphonicacidmonoalkyl esters, e.g. of the methyl or ethyl ester, nickelcomplexes OI
ketoximes, e.g. of2-hydroxy-4-methyl-phenylundecylketoxime, Z~ 89~
nickel complexesofl-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.
2.6. Sterically hindered amines, for examplebist2,2,6,6-tetramethyl-piperidyl) sebacate, bis(1,2,2,6,6-penta-methylpiperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-piperidyl) n-bu-tyl-3,5-di-tert-butyl-4-hydroxy-benzyl-malonate, the condensation product ofl-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidineand succinic acid, the condensation product ofN,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-tert-octylamino-2,6-dichloro-1,3,5-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane-tetracarboxylate, 1,1'-(1,2-ethane-diyl)bis-(3,3,5,5-tetramethylpiperazinone).
2.7. Oxalic acid diamides, for example4,4'-dioctyloxy-oxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butyloxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butyloxanilide, 2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylamino-propyl)oxalamide, 2-ethoxy-5-tert-butyi-2'-ethyloxanilide anditsmixturewith 2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide and mixtures of ortho- and para-methoxy-disubstitutedoxanilides and mixtures of o- and p-ethoxy-disubsti-tutedoxanilides.
2.8. 2-(2-HydroxY~henYl)-1,3,5-triazines, for example 2,4,6-tris(2- hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxy-phenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxy-phenyl)-9,6-bis(2,4-dimethylphenyl)-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-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.
3. Metal deactivators, for exampleN,N'-diphenyloxalic acid ,~
- .
.
9~
diamide, N-salicylal-N'-salicyloylhydrazine, N,N'-bis(salicyl-oyl)hydrazine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenyl-propionyl)hydrazine, 3-salicyl-oylamino-1,2,4-triazole, bis(benzylidene~oxalodihydrazide.
4. Phosphites and phosphoni~es, for example triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl) phosphite, trilaurylphosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diiso-decyl pentaerythritol diphosphite, bis(2,4-di-tertbutyl-phenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl) 4,4'-bi-phenylene diphosphonite, 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane.
S. Peroxide scavenqers, for example esters of~-thiodi-propionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritoltetrakis(~-dodecyl-mercapto)propionate.
6. PolYamide stabilisers, for example, copper salts in combination with iodides and/orphosphorus compounds andsalts of divalent manganese.
7. Basic co-stabilisers, for example, melamine, polyvinyl-pyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids for example Ca stearate, Zn stearate, Mg stearate, Na ricinoleate and K palmitate, antimony pyrocatecholate or zinc pyrocatecholate.
8. Nucleatinq aqents, for example, 4-tert.butyl-benzoic acid, 26~ 39~.
adipic acid, diphenylacetic acid.
9. Fillers and reinforcinq aqents, for example, calcium carbonate, silicates, glass fibres, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxydes, carbon black, graphite.
10. Other additives, for example, plasticisers, lubricants, emulsifiers, pigments, optical brighteners, flameproofing agents, antistatic agents and blowing agents.
Of particular value in the instant compositions are the benzotriazoles of high molecular weight and low volatility such as2-[2-hydroxy-3,5-di(alpha,alpha-dimethylbenzyl)-phenyl]-2H-benzotriazole, 2-(2-hydroxy-3,5-di-tert-octyl-phenyl)-2H-benzotriazole, 2-(2-hydroxy-3-alpha-alpha-dimethylbenzyl-5-tert-octyl-phenyl)-2H-benzotriazole, 2-(2-hydroxy-3-tert-octyl-5-alpha,alpha-dimethylbenzyl-phenyl)-2H-benzotriazole, 2-(2-hydroxy-3,5-di-tert-amyl-phenyl)-2H-benzotriazole, 2-[2-hydroxy-3-tert-butyl-5-(2-(omega-hydroxy-octa-(ethyleneoxy)carbonyl)-ethyl-phenyl]-2H-benzotriazole and the 5-chloro compoundscorre-sponding toeach of the above namedbenzotriazoles.
Most preferably the benzotriazoles ùseful in the instant compositions are 2-[2-hydroxy-3,5-di(alpha,alpha-dimethyl-benzyl)phenyl]-2H-benzotriazole and2-[2-hydroxy-3-tert-butyl-5-(2-(omega-hydroxy-octa-(ethyleneoxy)-carbonyl)-ethylphenyl]-2H-benzotriazole.
Of particular interest in connection with the stabilization of polyvinyl halides are formulations containing (1) a polyvinyl halide, (2) a thermal stabilizer and (3) an NOR1 hindered amine derivative of the instant invention, prefer-ably a NOR1 derivative wherein R1 is not an acyl group.
Thermal stabilizers are generally known. Includedamong such : ' ~: '~ .' -:: ' : :
..
z~
derivatives are organotin carboxylate compounds characterized by having an oxygen atom bonded directly to thetin atom.Such compounds may be identified as carboxylates oralcoholates containing Sn-ORad, Sn-OOCRad, RadCOO-Sn-O-Sn-OOCRad or Sn-OOCCH=CHCOORad groups wherein "Rad" defines a series of alkyl, cycloalkyl, aryl or aralkylsubstituents. Other organotins include organotin mercaptoestes and organotin mercaptides, the formercontaining groups of Sn-[S(CH2)u-COORad] while the lattercorrespond to thegeneral formula (RadS)-Sn-Rad.
Other categories of thermal stabilizers are barium/cadmium, barium/zinc, calcium/zinc, atimony and lead compounds, including salts of fatty acids.
These formulations can contain optional ingredients such as titanium dioxide, other pigments, fillers, plasticizers, and the like, as well as the UV absorbers and antioxidants noted hereinabove.
The following examples further illustrate the embodiments of the instant invention. All parts given are by weight unless otherwise noted.
Example 1: Liqht Stabilization of Polypropylene Polypropylene powder (Hercules Profax 6501) stabili~ed with 0.2 % octadecyl 3,5-di-tert.butyl-4-hydroxy hydrocinnamate antioxidant is thoroughly blended with 0.1 % of the stabilizer indicated in the table. The blended materials are then milled on a two-roll mill at 182C for 5 minutes, after which time the stabilized polypropylene is sheeted from the mill and allowed to cool. The milled polypropylene is then cut into pieces and compression molded on a hydraulic press at 250C and 175 psi tl.2 x 106 Pa) into 5 mil (0.127 mm) films. The sample is exposed in a fluorescent sunlight/black light chamber until failure. Failure is taken as the hours -891.
required to reach 0.5 carbonyl absorbance by infrared spectroscopy on the exposed films.
Table 1 Stabilizer Hours to Failure none 340 Example 2: This example ill~strates the performance of the instant compounds in polyvinyl chloride formulations. In particular, it illustrates the manner in which the instant compounds minimize the detrimental effect on thermal stability during processing of such formulations, which detrimental effect is encountered with conventional hindered amine light stabilizers.
The following rigid polyvinyl chloride formulations are prepared.
, - .
,.: , ~ , ~, 91.
Parts A B
polyvinyl chloride resin1 100.0 100.0 tin mercaptide2 1.5 tin carboxylate3 - 2.5 methacrylic acid/ester 1.5 1.5 processing aid4 acrylic impact modifier56.0 6.0 paraffin wax 1.0 Q.3 polyethylene wax 0.1 0.1 calcium stearate 1.0 brown pigment6 0.9 0.9 pigment7 0.1 0.1 1 - GEON 103EP-76 from B.F. Goodrich Co.
2 - THERMOLITE T-137 from M&T Chemicals 3 - IRGASTAB T-634 from CIBA-GEIGY Corp.
4 - ACRYLOID K120N from Rohm and Haas 5 - ACRYLOID K323B from Rohm and Haas 6 - CROMOPHTAL BROWN from CIBA-GEIGY Corp.
7 - MONARCH X-3228 from CIBA-GEIGY Corp.
The ingredients are blended together with one part per hundred of the indicated stabilizer Thereafter, 60 gram samples are tested in a Brabender Plasti-Corder at 190C.
Changes in torque are measured over time. Longer times to degradation are indicative of reduced detrimental effects of the light stabilizer on the thermal stability of the PVC
during processing.
:
:
Z~1~()89~.
~ 19 -Table 2 Stabilizer Degradation Time ~min) PVC-A PVC-B
none 24.0 20.0 A 14.5 1~.0 6 23.0 24.5 26.0 23.5 14 25.0 23.5 A = bis(2,2,6,6-tetramethylpiperidin-4-yl)-sebacate Exam~le 3: The polyvinyl chloride formulation B of example 2 is belnded with one part per 100 parts of PVC of the stabi-lizers indicated in ~able 3. The samples are milled on atwo roll mill ~front roll 171C - back roll 165C) for aperiodof three minutes after band formation. The resultingmaterialis then compression molded (temperature 182C, 2 minutes contrapressure, 1 minute pumping pressure, 2 minutes full pressure, cool to 38C) and cut into test plaques (5.1 cm x 5.1 cm). The plaques are exposed in a Xenon ArcWeatherometer at black panel temperature of 60-66C and relative humidityof 25-35 %. Samples are withdrawn at periodic intervals and~
values measured according to ASTMD-1925-63T utilizing an Applied Color System Spectro-SensorII Colorimeter. Higher values are indicative of less stability.
Table 3 Stabilizer none 6.7 6 2.8 7 5.0 21 9.7 , . . . ~:
- : ~ ,:.: ~ ; ., 2~0891.
Example 4: This example illustrates the stabilization performance of the instant compounds in acrylonitrile/-butadiene/styrene polymer.
The ABS polymer (DOW 342EZ) is blended with 4 %, by weight, TiO2-containing pigment and with the indicated amounts of stabilizer, compounded on a two roll mill at 150C/163~C for five minutes and compression molded at 218C to form 5 cm x 5 cm x 0.2 cm test plaques. The plaques are then exposed in the Interior Automative Xenon Arc Weatherometer at 89~C and 100 % relative humidity in the dark cycle. Yellowness Index values and ~E values are determined originally and after 400hoursexposure.
Conc. YI (~E) after hours Stabilizer (% by wt.)0 400 - - 14 43 (15.1) 1 l.0 14 28 (7.3) B/1 0.5/0.5 14 27 (6.4) 9 l.0 14 30 (8.5) B/9 0.5/0.5 14 29 (8.0) Stabilizer B =2-[3,5-di(l,1-dimethylpropyl)-2-hydroxy-phenyl]-benzotri~zole .
- :
O-alkyl substituted N-hydroxy derivatives can be synthesized by several routes. The N-hydroxy derivative can be alkylated with sodium hydride and halogenated hydrocarbons such as benzyl bromide and ethyl iodide. N-methoxy variants can be prepared by thermolysis of a chlorobenzene solution of nitroxyl radical and di-tert-butyl peroxide. The product is formed by a coupling reaction between the nitroxyl radical and methyl radical generated from ~-scission of a t-butoxy radical. Other N-alkoxy variants are synthesized by coupling nitroxyl radicals with hydrocarbon radicals generated from thermal decomposition of di-tert-bu~yl peroxide in the presence of hydrocarbon solvents such as cylcohexane, toluene, and ethylbenzene.
A preferred approach is the preparation of N-alkoxy hindered . ~.
.-:
2~ 891 amines directly from the NH derivatives. For example, a mixture of 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, aqueous t-butyl hydroperoxide, molybdenum oxide, andethyl-benzene gives a 90 ~ yield of the N-alpha-methylbenyloxy piperidine.
The NH derivative precursors are largely commercially available or can be prepared by known methods.
The use of the compounds of formula (A) as stabilizers for ambient curable or acid catalized thermosetting coatings is subject of two prior patent applications now published as European Application EP-A-309 400 and 309 402.
According to the instant invention these compounds are also suitable for stabilizing polyolefins or those organic polymers which contain hetero atoms, double bonds or aromatic rings.
The polyolefins may be homopolymers or copolymers of an alpha olefin.
The polyolefins useful in the instant compositions are the polymers derived from monoolefins, such as polyethylene, which can be crosslinked, polypropylene, polyisobutylene, polybutene-1, poly-3-methylbutene-1 andpoly-4-methyl-pentene-1. Polyethylene may be for example medium density, high density or linear low density polyethylene.
Mixtures of the homopolymers cited above, for example mixtures of polypropylene and polyethylene, polypropylene and polybutene-1-, or polypropylene and polyisobutylene and the like, may also be used.
Copolymers of monolefins may also be used in the instant compositions, for example ethylene/propylene copolymers, Z~891 propylene-butene-1 copolymers, propylene/octene-1 copolymers, ethylene/butene-1 copolymers, ethylene/octene-1 copolymers as well as ethylene/vinyl acetate copolymers.
~specially preferred polyolefin substrates are polypropylene, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, poly(butene-1), ethylene/vinyl acetate copolymer, ethylene/-propylene copolymer and copolymers of ethylene or of propylene with higher alpha olefins.
The most preferred polyolefin substrate polypropylene, high density polyethylene, ethylene/propylene copolymer or a copolymer of ethylene or of propylene with another alpha olefin.
Examples of organic polymers whch contain hetero atoms, double bonds or aromatic rings are the following:
1. polymers derived from doubly unsaturated hydrocarbons, e.g. polyisoprene or polybutadiene;
2. polystyrene;
3. copolymers of styrene or alpha-methyl styrene with dienes or acryl derivatives, such as styrene-butadiene, styrene-acrylonitrile, styrene-acrylonitrile-methacrylate, mixturesof high impact strength from styrene-copolymersandanother polymer, such as polyacrylate, a diene-polymer or anethylene propylene-diene terpolymer, as well as block copolymers of styrene such as styrene-butadiene-styrene, styrene-isoprene-styrene orstyrene-ethylene/butylene-styrene;
4. graft polymers of styrene, such as styrene orpoly-butadiene, styrene and acrylonitrile on polybutadiene, as well as mixtures with the copolymers mentioned under (3), , :
- :: -2~ 089~
such as those known as ABS polymers~
5. halogen-containing vinyl polymers, such as polyvinyl chloride, polyvinylidene chloride, polyvinylfluoride, polychloroprene, chlorinated rubber, vinyl chloride/-vinylidene chloride.copolymers, vinyl chloride/vinyl acetate copolymers or vinylidene chloride/vinyl acetate copolymers;
6. polymers derived from alpha-beta-unsaturated acids and derivatives thereof, polyacrylates and polymethacrylates, polyacrylic amides and polyacrylonitrile;
7. polymers derived from unsaturated alcohols or their acyl derivatives or acetals, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl butyral, polyallyl phthalate, polyallyl melamine and copolymers thereof with other vinyl compounds, such as ethylene/vinyl acetate copolymers;
8. polyacetals such as polyoxymethylene, and also those polyoxymethylenes containing as comonomers, e.g. ethylene oxide;
9. polyurethanes;
10. polycarbonates;
ll. aliphatic and aromatic polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, such as polyamide 6, polyamide 6/6, polyamide 6/10, polyamide 11 and polyamide 12;
12. polyesters derived from dicarboxylic acids and dialcohols and/or from hydroxycarboxylic acids or corresponding lactones, such as polyethylene glycol terephthalate and .
, 2C~89~.
g poly-1,4-dimethylol-cyclohexaneterephthalate.
Substrates of particular interest are polyvinyl chloride, particularly pigmented rigid polyvinyl chloride, polyurethanes and styrenic polymers such as ABS polymers.
In general, the compounds of formula (A) are employed ln from about 0.01 to about 5 %by weight of the stabilized com-position, although this will vary with the particular substrate and application. An advantageous range is from about 0.05 to about 2 %, andespecially 0.1 to about 1 %.
The stabilizers of the instant invention may readily be incorporated into the indicated polymeric substrates by conventional techniques, at any convenient state prior to the manufacture of shaped articles therefrom. For example, the stabilizer may be mixed with the polymer in dry powder form, or a suspension or emulsion of the stabilizer may be mixed with a solution, suspension, or emulsion of the polymer. The resulting stabilized polymer composition of the invention may optionally also contain various conventional additives, such as the following.
1. Antioxidants 1.1. Alkylated monophenols, forexample2,6-di-tert-butyl-4-methyl-phenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-iso-butylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-~-methylcyclohexyl~-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexyl-phenol, 2,6-di-tert-butyl-4-methoxymethylphenol, 2,6-di-nonyl-4-methyl-phenol.
1.2. Alkylated hydroquinones,for example2,6-di-tert-butyl-4-methoxy- phenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-.... : .
Z~ 39~
amylhydroquinone, 2, 6-diphenyl-4-octadecyloxyphenol.
1.3. Hydroxylated thiodiphenyl ethers, for example 2,2'-thio-bis(6-tert-butyl-4-methylphenol), 2,2'-thiobis(4-octyl-phenol), 4,4'-thiobis (6-tert-butyl-3-methylphenol), 4,4'-thio-bis(6-tert-butyl-2-methylphenol).
1.4. Alkylidenebisphenols, for example2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'-methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6- (o~-methylcyclo-hexyl)phenol], 2,2'-methylenebis(4-methyl-6-cyclohexyl-phenol), 2,2'-methylenebis (6-nonyl-4-methylphenol), 2,2'-methylenebis(4, 6-di-tert-butylphenol), 2,2'-ethyl-idenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis[6- (c~-methyl-benzyl)-4-nonylphenol], 2,2'-methylenebis[6- (c~ -dimethyl-benzyl)-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-methyl-phenol, 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis[3,3-bis-(3'-tert-butyl-4'-hydroxyphenyl)butyrate], bis~3-tert-butyl-4-hydroxy-S-methyl-phenyl) dicyclopentadiene, bis[2- (3'-tert-butyl-2'-hydroxy-5'-methyl- benzyl)-6-tert-butyl-4-methylphenyl]terephthalate.
1.5. Benzyl compounds, for examplel,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4, 6-trimethylbenzene, bis(3,5-di-tert-butyl-4-hydroxy-benzyl) sulfide, isooctyl 3,5-di-tert-butyl-4-hydroxybenzylmercapto-acetate, bis(4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) dithiolterephthalate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate~
1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, dioctadecyl 3,5-di-tert-butyl-4-hydroxy-: ' . ~ .
2~ 391 benzylphosphonate, calcium salt ofmonoethyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 1,3,5-tris-(3,5-dicyclo-hexyl-4-hydroxybenzyl)isocyanurate.
1.6. Acylaminophenols, for example lauric acid4-hydroxy-anilide, stearic acid 4-hydroxyanilide, 2,4-bis(octyl-mercapto)-6-(3,5-di-tert-butyl-9-hydroxyanilino)-s-trlazine, octylN-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate.
1.7. Esters of~-(3,5-di-tert-butYl-4-hvdroxyphenvl)propionic acid withmono- or polyhydric alcohols, e.g. withmethanol, diethylene glycol, octadecanol, triethylene glycol, 1,6-hexanediol, pentaerythritol, neopentyl glycol, tris-(hydroxyethyl) isocyanurate, thiodiethylene glycol, N,N'-bis(hydroxyethyl)oxalic acid diamide.
1.8. Esters of~-(5-tert-butYl-4-hYdroxY-3-methYlphenyl)-propionic acidwith mono- or polyhydric alcohols, e.g. with methanol, diethylene glycol, octadecanol, triethylene glycol 1,6-hexanediol, pentaerythritol, neopentyl glycol, tris-(hydroxyethyl) isocyanurate, thiodiethylene glycol, N,N'-bis(hydroxyethyl)oxalic acid diamide.
1.9. Esters of~-(3,5-dicYclohexyl-4-hYdroxyphenYl)Propionic acid withmono- or polyhydric alcohols, e.g. with methanol, diethyleneglycol, octadecanol, triethylene glycol, 1,6-hexanediol, pentaerythritol, neopentyl glycol, tris-(hydroxyethyl) isocyanurate, thiodiethylene glycol, N,N'-bis(hydroxyethyl)oxalic acid diamide.
1.10. Amides ofb-(3,5-di-tert-butyl-4-hydroxyphenYl~-ProPionic acid e.g.N,N'-bis(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl)hexamethylene-diamine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)tri-methylene-diamine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine.
2Q~ 8~L
2. UV absorbers and liqht stabilisers 2.1. 2-(2'-Hydroxyphenyl)benzotriazoles, for example the 5'-methyl, 3',5'-di-tert-butyl, 5'-tert-butyl, 5'-(1,1,3,3-tetramethylbutyl), 5-chloro-3',5'-di-tert-butyl, 5-chloro-3'-tert-butyl-5'-methyl, 3'-sec-butyl-5'-tert-butyl, 4'-octoxy, 3',5'-di-tert-amyl and3',5'-bis (a, a- dimethyl-benzyl) derivatives.
.
2.2. 2-Hydroxybenzophenones, for example the4-hydroxy, 4-methoxy, 4-octoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives.
2.3. Esters of substituted and unsubstituted benzoicacids, for example, 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)-resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate and hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate.
2.4. Acrylates, for example ethyl a-cyano-~,~-diphenyl-acrylate, isooctyla-cyano-~ diphenylacrylate, methyl a-carbomethoxycinnamate, methyla-cyano-~-methyl-p-methoxy-cinnamate, butyla-cyano-~-methyl-p-methoxy-cinnamate, methyl a-carbomethoxy-p-methoxycinnamate and N-(~-carbo-methoxy-~-cyanovinyl)-2-methylindoline.
2.5. Nickel comPounds, for example nickel complexesof 2,2'-thio-bis-[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or 1:2 complex, with or without additional ligands such as n-butylamine, triethanolamine orN-cyclohexyldi-ethanolamine, nickel dibutyldithiocarbamate, nickel saltsof 4-hydroxy-3,5-di-tert-butylbenzyl-phosphonicacidmonoalkyl esters, e.g. of the methyl or ethyl ester, nickelcomplexes OI
ketoximes, e.g. of2-hydroxy-4-methyl-phenylundecylketoxime, Z~ 89~
nickel complexesofl-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.
2.6. Sterically hindered amines, for examplebist2,2,6,6-tetramethyl-piperidyl) sebacate, bis(1,2,2,6,6-penta-methylpiperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-piperidyl) n-bu-tyl-3,5-di-tert-butyl-4-hydroxy-benzyl-malonate, the condensation product ofl-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidineand succinic acid, the condensation product ofN,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-tert-octylamino-2,6-dichloro-1,3,5-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane-tetracarboxylate, 1,1'-(1,2-ethane-diyl)bis-(3,3,5,5-tetramethylpiperazinone).
2.7. Oxalic acid diamides, for example4,4'-dioctyloxy-oxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butyloxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butyloxanilide, 2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylamino-propyl)oxalamide, 2-ethoxy-5-tert-butyi-2'-ethyloxanilide anditsmixturewith 2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide and mixtures of ortho- and para-methoxy-disubstitutedoxanilides and mixtures of o- and p-ethoxy-disubsti-tutedoxanilides.
2.8. 2-(2-HydroxY~henYl)-1,3,5-triazines, for example 2,4,6-tris(2- hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxy-phenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxy-phenyl)-9,6-bis(2,4-dimethylphenyl)-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-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.
3. Metal deactivators, for exampleN,N'-diphenyloxalic acid ,~
- .
.
9~
diamide, N-salicylal-N'-salicyloylhydrazine, N,N'-bis(salicyl-oyl)hydrazine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenyl-propionyl)hydrazine, 3-salicyl-oylamino-1,2,4-triazole, bis(benzylidene~oxalodihydrazide.
4. Phosphites and phosphoni~es, for example triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl) phosphite, trilaurylphosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diiso-decyl pentaerythritol diphosphite, bis(2,4-di-tertbutyl-phenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl) 4,4'-bi-phenylene diphosphonite, 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane.
S. Peroxide scavenqers, for example esters of~-thiodi-propionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritoltetrakis(~-dodecyl-mercapto)propionate.
6. PolYamide stabilisers, for example, copper salts in combination with iodides and/orphosphorus compounds andsalts of divalent manganese.
7. Basic co-stabilisers, for example, melamine, polyvinyl-pyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids for example Ca stearate, Zn stearate, Mg stearate, Na ricinoleate and K palmitate, antimony pyrocatecholate or zinc pyrocatecholate.
8. Nucleatinq aqents, for example, 4-tert.butyl-benzoic acid, 26~ 39~.
adipic acid, diphenylacetic acid.
9. Fillers and reinforcinq aqents, for example, calcium carbonate, silicates, glass fibres, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxydes, carbon black, graphite.
10. Other additives, for example, plasticisers, lubricants, emulsifiers, pigments, optical brighteners, flameproofing agents, antistatic agents and blowing agents.
Of particular value in the instant compositions are the benzotriazoles of high molecular weight and low volatility such as2-[2-hydroxy-3,5-di(alpha,alpha-dimethylbenzyl)-phenyl]-2H-benzotriazole, 2-(2-hydroxy-3,5-di-tert-octyl-phenyl)-2H-benzotriazole, 2-(2-hydroxy-3-alpha-alpha-dimethylbenzyl-5-tert-octyl-phenyl)-2H-benzotriazole, 2-(2-hydroxy-3-tert-octyl-5-alpha,alpha-dimethylbenzyl-phenyl)-2H-benzotriazole, 2-(2-hydroxy-3,5-di-tert-amyl-phenyl)-2H-benzotriazole, 2-[2-hydroxy-3-tert-butyl-5-(2-(omega-hydroxy-octa-(ethyleneoxy)carbonyl)-ethyl-phenyl]-2H-benzotriazole and the 5-chloro compoundscorre-sponding toeach of the above namedbenzotriazoles.
Most preferably the benzotriazoles ùseful in the instant compositions are 2-[2-hydroxy-3,5-di(alpha,alpha-dimethyl-benzyl)phenyl]-2H-benzotriazole and2-[2-hydroxy-3-tert-butyl-5-(2-(omega-hydroxy-octa-(ethyleneoxy)-carbonyl)-ethylphenyl]-2H-benzotriazole.
Of particular interest in connection with the stabilization of polyvinyl halides are formulations containing (1) a polyvinyl halide, (2) a thermal stabilizer and (3) an NOR1 hindered amine derivative of the instant invention, prefer-ably a NOR1 derivative wherein R1 is not an acyl group.
Thermal stabilizers are generally known. Includedamong such : ' ~: '~ .' -:: ' : :
..
z~
derivatives are organotin carboxylate compounds characterized by having an oxygen atom bonded directly to thetin atom.Such compounds may be identified as carboxylates oralcoholates containing Sn-ORad, Sn-OOCRad, RadCOO-Sn-O-Sn-OOCRad or Sn-OOCCH=CHCOORad groups wherein "Rad" defines a series of alkyl, cycloalkyl, aryl or aralkylsubstituents. Other organotins include organotin mercaptoestes and organotin mercaptides, the formercontaining groups of Sn-[S(CH2)u-COORad] while the lattercorrespond to thegeneral formula (RadS)-Sn-Rad.
Other categories of thermal stabilizers are barium/cadmium, barium/zinc, calcium/zinc, atimony and lead compounds, including salts of fatty acids.
These formulations can contain optional ingredients such as titanium dioxide, other pigments, fillers, plasticizers, and the like, as well as the UV absorbers and antioxidants noted hereinabove.
The following examples further illustrate the embodiments of the instant invention. All parts given are by weight unless otherwise noted.
Example 1: Liqht Stabilization of Polypropylene Polypropylene powder (Hercules Profax 6501) stabili~ed with 0.2 % octadecyl 3,5-di-tert.butyl-4-hydroxy hydrocinnamate antioxidant is thoroughly blended with 0.1 % of the stabilizer indicated in the table. The blended materials are then milled on a two-roll mill at 182C for 5 minutes, after which time the stabilized polypropylene is sheeted from the mill and allowed to cool. The milled polypropylene is then cut into pieces and compression molded on a hydraulic press at 250C and 175 psi tl.2 x 106 Pa) into 5 mil (0.127 mm) films. The sample is exposed in a fluorescent sunlight/black light chamber until failure. Failure is taken as the hours -891.
required to reach 0.5 carbonyl absorbance by infrared spectroscopy on the exposed films.
Table 1 Stabilizer Hours to Failure none 340 Example 2: This example ill~strates the performance of the instant compounds in polyvinyl chloride formulations. In particular, it illustrates the manner in which the instant compounds minimize the detrimental effect on thermal stability during processing of such formulations, which detrimental effect is encountered with conventional hindered amine light stabilizers.
The following rigid polyvinyl chloride formulations are prepared.
, - .
,.: , ~ , ~, 91.
Parts A B
polyvinyl chloride resin1 100.0 100.0 tin mercaptide2 1.5 tin carboxylate3 - 2.5 methacrylic acid/ester 1.5 1.5 processing aid4 acrylic impact modifier56.0 6.0 paraffin wax 1.0 Q.3 polyethylene wax 0.1 0.1 calcium stearate 1.0 brown pigment6 0.9 0.9 pigment7 0.1 0.1 1 - GEON 103EP-76 from B.F. Goodrich Co.
2 - THERMOLITE T-137 from M&T Chemicals 3 - IRGASTAB T-634 from CIBA-GEIGY Corp.
4 - ACRYLOID K120N from Rohm and Haas 5 - ACRYLOID K323B from Rohm and Haas 6 - CROMOPHTAL BROWN from CIBA-GEIGY Corp.
7 - MONARCH X-3228 from CIBA-GEIGY Corp.
The ingredients are blended together with one part per hundred of the indicated stabilizer Thereafter, 60 gram samples are tested in a Brabender Plasti-Corder at 190C.
Changes in torque are measured over time. Longer times to degradation are indicative of reduced detrimental effects of the light stabilizer on the thermal stability of the PVC
during processing.
:
:
Z~1~()89~.
~ 19 -Table 2 Stabilizer Degradation Time ~min) PVC-A PVC-B
none 24.0 20.0 A 14.5 1~.0 6 23.0 24.5 26.0 23.5 14 25.0 23.5 A = bis(2,2,6,6-tetramethylpiperidin-4-yl)-sebacate Exam~le 3: The polyvinyl chloride formulation B of example 2 is belnded with one part per 100 parts of PVC of the stabi-lizers indicated in ~able 3. The samples are milled on atwo roll mill ~front roll 171C - back roll 165C) for aperiodof three minutes after band formation. The resultingmaterialis then compression molded (temperature 182C, 2 minutes contrapressure, 1 minute pumping pressure, 2 minutes full pressure, cool to 38C) and cut into test plaques (5.1 cm x 5.1 cm). The plaques are exposed in a Xenon ArcWeatherometer at black panel temperature of 60-66C and relative humidityof 25-35 %. Samples are withdrawn at periodic intervals and~
values measured according to ASTMD-1925-63T utilizing an Applied Color System Spectro-SensorII Colorimeter. Higher values are indicative of less stability.
Table 3 Stabilizer none 6.7 6 2.8 7 5.0 21 9.7 , . . . ~:
- : ~ ,:.: ~ ; ., 2~0891.
Example 4: This example illustrates the stabilization performance of the instant compounds in acrylonitrile/-butadiene/styrene polymer.
The ABS polymer (DOW 342EZ) is blended with 4 %, by weight, TiO2-containing pigment and with the indicated amounts of stabilizer, compounded on a two roll mill at 150C/163~C for five minutes and compression molded at 218C to form 5 cm x 5 cm x 0.2 cm test plaques. The plaques are then exposed in the Interior Automative Xenon Arc Weatherometer at 89~C and 100 % relative humidity in the dark cycle. Yellowness Index values and ~E values are determined originally and after 400hoursexposure.
Conc. YI (~E) after hours Stabilizer (% by wt.)0 400 - - 14 43 (15.1) 1 l.0 14 28 (7.3) B/1 0.5/0.5 14 27 (6.4) 9 l.0 14 30 (8.5) B/9 0.5/0.5 14 29 (8.0) Stabilizer B =2-[3,5-di(l,1-dimethylpropyl)-2-hydroxy-phenyl]-benzotri~zole .
- :
Claims (14)
1. A stabilized composition comprising (a) a polyolefin or an organic polymer containing hetero atoms, double bonds or aromatic rings and (b) an effective stabilizing amount of a substituted hindered amine derivative of the formula (A) (A) wherein R is hydxogen or methyl, R1 iS C1-C8alkYl, C2-C18alkenyl, C2-C18alkynyl, C5-C12cyclo-alkyl, C6-Clobicycloalkyl, C5-Cgcycloalkenyl, C6-C1oaryl, C7-Cgaralkyl, C7-Cgaralkyl substituted byC1-C4alkyl or C6-C10aryl, or R1 is wherein D isC1-C18alkyl, C1-C18-alkoxy, phenyl, phenyl substituted byhydroxy, C1-C4alkyl or C1-C4alkoxy, or amino or amino mono- or disubstituted by C1-C12alkyl or phenyl and R2 is hydrogen, C1-C18alkyl optionally interrupted by one or more oxygen atoms, C2-C12alkenyl, C6-C10arYl, C7-C18aralkY
glycidyl, a monovalent acyl radical of an aliphatic, cyclo-aliphatic, araliphatic or aromatic carboxylic acid, or of a carbamic acid.
glycidyl, a monovalent acyl radical of an aliphatic, cyclo-aliphatic, araliphatic or aromatic carboxylic acid, or of a carbamic acid.
2. The composition of claim 1, wherein in component (b) R1 is C1-C18alkyl, C2-C18alkenyl, C5-C12cycloalkyl, C7-Cgaralkyl or C7-Cgaralkyl substituted by alkyl or aryl.
3. The composition according to claim 1 wherein the compound of component (b) is selected from the group consisting of 1,4-diacetoxy-2,2,6,6-tetramethylpiperidine 1-acetoxy-4-hydroxy-2,2,6,6-tetramethylpiperidine (1-acetoxy-2,2,6,6-tetramethylpiperidin-4-yl)-4-hydroxy-3,5-di-tert.butylbenzoate 1,4-di-(2-ethylhexanoyloxy)-2,2,6,6-tetramethylpiperidine 1,4-di-(4-hydroxy-3,5-di-tert-butylbenzoyloxy)-2,2,6,6-tetra-methylpiperidine n-butyl-(4-benzoyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-carbonate 1-carbamoyloxy-4-benzoyloxy-2,2,6,6-tetramethylpiperidine
4-benzoyloxy-1-ethoxy-2,2,6,6-tetramethylpiperidine 1,4-dibenzoyloxy-2,2,6,6-tetramethylpiperidine 4-benzoyloxy-1-(alpha-methylbenzyloxy)-2,2,6,6-tetramethyl-piperidine 1,4-dimethoxy-2,2,6,6-tetramethylpiperidine 4-benzoyloxy-1-methoxy-2,2,6,6-tetramethylpiperidine (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-3,5-di-t.butyl-4-hydroxybenzoate 1-cyclohexyloxy-4-octadecanoyloxy-2,2,6,6-tetramethyl-piperidine 4-benzoyloxy-1-benzyloxy-2,2,6,6-tetramethylpiperidine 4. The composition of claim 1, wherein component (a) is a polyolefin which is a homopolymer or copolymer of an alpha-olefin.
5. The composition of claim 4, wherein the polyolefin is selected from the group consisting of polypropylene, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, poly(butene-1), ethylene/vinyl acetate copolymer, ethylene/-propylene copolymer and copolymers of ethylene or ofpropyl-ene with other alpha-olefins.
6. The composition of claim 5, wherein the polyolerin is polypropylene, high density polyethylene, ethylene/propylene copolymer or a copolymer of ethylene or of propylene with another alpha-olefin.
7. The composition of claim 1, wherein component (a) is polybutadiene, polyisoprene, polystyrene, a styrene copolymer, a styrene graft polymer, a halogen-containing vinyl homo- or copolymer, a polymer derived from an alpha,beta-unsaturated acid, a polymer derived from an unsaturated alcohol or its acyl or acetyl derivative, a polyacetal, a polyurethane, a polycarbonate, a polyamide or a polyester.
8. The composition of claim 7, wherein said organic polymer is polyvinyl chloride, a polyurethane or acrylonitrile/-butadiene/styrene.
9. The composition of claim 8, wherein said organic polymer is polyvinyl chloride containing a thermal stabilizer therein.
10. The composition of claim 1 which additionally contains a phenolic antioxidant.
11. The composition of claim 1, which additionally contains a UV absorber selected from the group consisting of benzo-phenons, benzotriazoles, benzoic acid esters, acrylic acid derivatives, organic nickel compounds and oxanilides.
12. The composition of claim 1 containing 0.01 to 5 % by weight of the compound of formula (A).
13. The composition of claim 1 containing 0.05 to 2 % by weight of the compound of formula (A).
14. A method for stabilizing a polyolefin or an organic polymer containing hetero atoms, double bonds or aromatic rings against oxidative, thermal and actinic degradation which comprises incorporating into said polyolefin an effective stabilizing amount of a compound of formula (A) as defined in claim 1.
FO 7.3/SA/sm*
FO 7.3/SA/sm*
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US25994688A | 1988-10-19 | 1988-10-19 | |
| US25995588A | 1988-10-19 | 1988-10-19 | |
| US259,955 | 1988-10-19 | ||
| US259,946 | 1988-10-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2000891A1 true CA2000891A1 (en) | 1990-04-19 |
Family
ID=26947634
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2000891 Abandoned CA2000891A1 (en) | 1988-10-19 | 1989-10-17 | Polymeric substrates stabilized with n-substituted hindered amines |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0365481A1 (en) |
| JP (1) | JPH02166138A (en) |
| BR (1) | BR8905305A (en) |
| CA (1) | CA2000891A1 (en) |
Families Citing this family (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE68913267T3 (en) * | 1988-09-29 | 1998-06-18 | Sumitomo Chemical Co | Weather resistant thermoplastic resin composition. |
| US5359069A (en) * | 1989-03-21 | 1994-10-25 | Ciba-Geigy Corporation | Non-migrating 1-hydrocarbyloxy hindered amine derivatives as polymer stabilizers |
| US5145893A (en) * | 1989-03-21 | 1992-09-08 | Ciba-Geigy Corporation | Non-migrating 1-hydrocarbyloxy hindered amine derivatives as polymer stabilizers |
| US5216156A (en) * | 1992-05-05 | 1993-06-01 | Ciba-Geigy Corporation | Non-migrating 1-hydrocarbyloxy-2,2,6,6-tetramethylpiperidine 1,3,5-triazine derivatives |
| TW358820B (en) * | 1995-04-11 | 1999-05-21 | Ciba Sc Holding Ag | Synergistic stabilizer mixture |
| JP3661293B2 (en) * | 1996-08-26 | 2005-06-15 | 三井化学株式会社 | Polyolefin composition |
| JP4334033B2 (en) * | 1998-03-23 | 2009-09-16 | アキレス株式会社 | Agricultural vinyl chloride resin film |
| EP1132085A4 (en) * | 1998-11-25 | 2003-04-23 | Daiichi Radioisotope Lab | Drugs and reagents containing n-acyloxylated cycloalkyl compounds as the active ingredient |
| GB0003326D0 (en) * | 1999-02-25 | 2000-04-05 | Ciba Sc Holding Ag | Hydroxy-Substituted N-Alkoxy hindered amines |
| DE60012738T2 (en) * | 1999-07-02 | 2005-08-04 | Ciba Specialty Chemicals Holding Inc. | MONO AND MULTIFUNCTIONAL ALKOXYAMINES FOR THE MANUFACTURE OF FUNCTIONALIZED MACROMERS |
| JP4493131B2 (en) * | 1999-11-04 | 2010-06-30 | 株式会社Ａｄｅｋａ | Rubber composition for tire |
| JP5274743B2 (en) * | 2000-05-19 | 2013-08-28 | チバ ホールディング インコーポレーテッド | Hydroxylamine esters as polymerization initiators |
| JP5051956B2 (en) * | 2001-09-19 | 2012-10-17 | 日本合成化学工業株式会社 | Production method of vinyl acetate polymer and saponified product thereof |
| WO2003087211A2 (en) * | 2002-04-17 | 2003-10-23 | Ciba Specialty Chemicals Holding Inc. | Flame retardant polymer compositions containing hydroxylamine esters |
| PL1601719T3 (en) * | 2003-03-12 | 2006-11-30 | Basf Se | Coating composition comprising hydroxylamine esters |
| US7582690B2 (en) | 2004-11-19 | 2009-09-01 | Eastman Chemical Company | Stabilized aliphatic polyester compositions |
| AU2007224516A1 (en) | 2006-03-16 | 2007-09-20 | Clariant Finance (Bvi) Limited | Modified waxes, a process for their preparation, and their use |
| EP2005453B1 (en) * | 2006-04-11 | 2009-09-09 | Basf Se | Electret materials |
| JP5283153B2 (en) | 2007-10-25 | 2013-09-04 | 株式会社Ａｄｅｋａ | Synthetic resin composition and automotive interior / exterior material |
| EP2270101B1 (en) | 2008-03-10 | 2016-01-13 | Adeka Corporation | Synthetic resin composition, and automotive interior/exterior material comprising the same |
| ES2505492T3 (en) * | 2009-08-11 | 2014-10-10 | Basf Se | Sterically hindered bicyclic or tricyclic alkoxyamines and procedures for their preparation |
| JP5777643B2 (en) * | 2010-03-05 | 2015-09-09 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Sterically hindered amine |
| CN102781917B (en) * | 2010-03-05 | 2016-04-13 | 巴斯夫欧洲公司 | Bulky amine |
| JP5581133B2 (en) * | 2010-07-02 | 2014-08-27 | 日本ポリエチレン株式会社 | Resin composition for solar cell encapsulant, solar cell encapsulant using the same, method for producing the same, and solar cell module |
| EP2514800B2 (en) * | 2011-04-21 | 2018-03-07 | Merck Patent GmbH | Compounds and liquid crystalline medium |
| JP5949388B2 (en) * | 2012-09-24 | 2016-07-06 | 日本ゼオン株式会社 | Resin composition and molded body thereof |
| CN105646935A (en) * | 2014-11-11 | 2016-06-08 | 南通市振兴精细化工有限公司 | Light stabilizer and preparation method thereof |
| CN112126060B (en) * | 2019-06-25 | 2022-05-31 | 北京天罡助剂有限责任公司 | Polymeric high-molecular steric hindrance amine and preparation method thereof |
-
1989
- 1989-10-10 EP EP89810773A patent/EP0365481A1/en not_active Withdrawn
- 1989-10-17 CA CA 2000891 patent/CA2000891A1/en not_active Abandoned
- 1989-10-18 BR BR898905305A patent/BR8905305A/en not_active Application Discontinuation
- 1989-10-19 JP JP27274189A patent/JPH02166138A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP0365481A1 (en) | 1990-04-25 |
| JPH02166138A (en) | 1990-06-26 |
| BR8905305A (en) | 1990-05-22 |
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