CA1259333A - Substituted aminoxyethyl sulfoxides and sulfones - Google Patents
Substituted aminoxyethyl sulfoxides and sulfonesInfo
- Publication number
- CA1259333A CA1259333A CA000525155A CA525155A CA1259333A CA 1259333 A CA1259333 A CA 1259333A CA 000525155 A CA000525155 A CA 000525155A CA 525155 A CA525155 A CA 525155A CA 1259333 A CA1259333 A CA 1259333A
- Authority
- CA
- Canada
- Prior art keywords
- tert
- butyl
- carbon atoms
- alkyl
- bis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
Abstract
SUBSTITUTED AMINOXYETHYL SULFOXIDES AND SULFONES
Abstract of the Disclosure Substituted dibenzyl aminoxyethyl sulfoxides and sulfones of the formula I
(I) wherein n is 1 or 2, R1 is hydrogen, alkyl of 1 to 36 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenyl, aralkyl of 7 to 9 carbon atoms or said aralkyl substituted by alkyl of 1 to 36 carbon atoms, and R2 is alkyl of 1 to 36 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenyl, aralkyl of 7 to 9 carbon atoms, said aralkyl substi-tuted by alkyl of 1 to 36 carbon atoms or the group
Abstract of the Disclosure Substituted dibenzyl aminoxyethyl sulfoxides and sulfones of the formula I
(I) wherein n is 1 or 2, R1 is hydrogen, alkyl of 1 to 36 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenyl, aralkyl of 7 to 9 carbon atoms or said aralkyl substituted by alkyl of 1 to 36 carbon atoms, and R2 is alkyl of 1 to 36 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenyl, aralkyl of 7 to 9 carbon atoms, said aralkyl substi-tuted by alkyl of 1 to 36 carbon atoms or the group
Description
~Z5~333 3-15686/=lCGC 1170 SUBSTITUTED AMI~OXYETHYL SULFOXIDES AND SULFO~ES
The present invention relates to novel aminoxyethyl sulfoxides and sulfones, to the use thereof and to the organic material stabilized with the aid of said sulfoxides or sulfones against thermal, oxidative and/or light induced degradation.
Organic polymeric materials such as plastics and resins, are subject to thermal, oxidative and photo-degradation. A great variety of stabilizers are known in the art for stabilizing a diversity of substrates. Their effectiveness varies depending upon the causes of degradation and the substrate stabilized. In general, it is diffi-cult to predict which stabilizer will be most effective and most ec~nomical for any one area of application. For example, stabilizer effectiveness in reducing volatility may depend upon preventing bond scission in the substrate molecule. Limiting embrittlement and retaining elasticity in a polymer or rubber may require prevention of excessive crosslinking and/or chain scission. Prevention of discolo~ation may require inhibiting reactions which yield new chromophores or color bodies in the substrate or stabilizer.
Problems of process stability and incompatibility must also be considered.
Various organic hydroxylamine compounds are generally known and some are commercially available. A number of patents disclose nitrogen-substituted hydroxyl-amines as antioxidant stabilizers for various substrates including polyolefins, polyesters and polyurethanes.
U.S. 3,432,57~, 3,644,278, 3,778,4S4, 3,408,422, 3,926,909, 4,316,996 and 4,386,224 are representative of such patents which 9~
basically disclose N,N-dialkyl-, N,N-diaryl- and N,N-diaralkyl hydroxylamine compounds and their color improvement and color stabilizing activity.
U.S. Patent 3,316,299 describes the preparation of R2NOCH2C~z~CH2CH20NRz ( )2 wherein R2N is di-lower-alkylamino (C1 to C8~ or heterocyclic moieties like aziridinyl, pyrrolidinyl, etc. and mentions the use of these compounds as central nervous system depressants in animals.
It has now been determined that the substituted dibenzyl aminoxy-ethyl sulfoxides and sulfones of this invention exhibit a variety of desirable properties which makes them particularly effective and useful as stabilizers. Thus, the compounds serve to protect various substrates such as polyolefins, elastomers and lubricating oils against the adverse effects of oxidative and thermal degradation.
They are most effective as color improvers and process stabilizers in polyolefln compositions which may contain metal salts of fatty acids and which contain a phenolic antioxidant. Thus, they serve to substantially reduce color formation resulting from the presence of the phenolic antioxidant andlor from the processing conditions as well as to directly protect the polymer from said processing conditions. They also prevent the discoloration of polyolefin compositions containing hindered amine light stabilizers or combi-nations of phenolic antioxidants and organic phosphites. In addi-tion, the gas fading that may be experienced upon exposure to the combustion products of natural gas is also significantly reduced.
It is the primary object of this invention to provide sulfoxides and sulione derivatives which exhibit a broad range of i~proved stabili-zation performance characteristics.
Various other objects and advantages of this invention will become evident from the following description thereof.
~5~333 The compounds of this invention correspond to the formula I
.~ CH2_ - NOCH2C~2- 1- R2 (I) .=. 2 ( )n wherein n is 1 or 2, R1 is hydrogen, alkyl of 1 to 36 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenyl, aralkyl of 7 to 9 carbon atoms or said aralkyl substituted by alkyl of 1 to 36 carbon atoms, and R2 is alkyl of 1 to 36 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenyl, aralkyl of 7 to 9 carbon atoms, said aralkyl substi-tuted by alkyl of 1 to 36 carbon atoms or the group ~ CHz - NOCH2CH2-wherein R1 is as defined hereinabove.
Rl and R2 as alkyl of 1 to 36 carbon atoms are for examplemethyl, ethyl, n-propyl, n-butyl, tert-butyl, n-pentyl, n-octyl,
The present invention relates to novel aminoxyethyl sulfoxides and sulfones, to the use thereof and to the organic material stabilized with the aid of said sulfoxides or sulfones against thermal, oxidative and/or light induced degradation.
Organic polymeric materials such as plastics and resins, are subject to thermal, oxidative and photo-degradation. A great variety of stabilizers are known in the art for stabilizing a diversity of substrates. Their effectiveness varies depending upon the causes of degradation and the substrate stabilized. In general, it is diffi-cult to predict which stabilizer will be most effective and most ec~nomical for any one area of application. For example, stabilizer effectiveness in reducing volatility may depend upon preventing bond scission in the substrate molecule. Limiting embrittlement and retaining elasticity in a polymer or rubber may require prevention of excessive crosslinking and/or chain scission. Prevention of discolo~ation may require inhibiting reactions which yield new chromophores or color bodies in the substrate or stabilizer.
Problems of process stability and incompatibility must also be considered.
Various organic hydroxylamine compounds are generally known and some are commercially available. A number of patents disclose nitrogen-substituted hydroxyl-amines as antioxidant stabilizers for various substrates including polyolefins, polyesters and polyurethanes.
U.S. 3,432,57~, 3,644,278, 3,778,4S4, 3,408,422, 3,926,909, 4,316,996 and 4,386,224 are representative of such patents which 9~
basically disclose N,N-dialkyl-, N,N-diaryl- and N,N-diaralkyl hydroxylamine compounds and their color improvement and color stabilizing activity.
U.S. Patent 3,316,299 describes the preparation of R2NOCH2C~z~CH2CH20NRz ( )2 wherein R2N is di-lower-alkylamino (C1 to C8~ or heterocyclic moieties like aziridinyl, pyrrolidinyl, etc. and mentions the use of these compounds as central nervous system depressants in animals.
It has now been determined that the substituted dibenzyl aminoxy-ethyl sulfoxides and sulfones of this invention exhibit a variety of desirable properties which makes them particularly effective and useful as stabilizers. Thus, the compounds serve to protect various substrates such as polyolefins, elastomers and lubricating oils against the adverse effects of oxidative and thermal degradation.
They are most effective as color improvers and process stabilizers in polyolefln compositions which may contain metal salts of fatty acids and which contain a phenolic antioxidant. Thus, they serve to substantially reduce color formation resulting from the presence of the phenolic antioxidant andlor from the processing conditions as well as to directly protect the polymer from said processing conditions. They also prevent the discoloration of polyolefin compositions containing hindered amine light stabilizers or combi-nations of phenolic antioxidants and organic phosphites. In addi-tion, the gas fading that may be experienced upon exposure to the combustion products of natural gas is also significantly reduced.
It is the primary object of this invention to provide sulfoxides and sulione derivatives which exhibit a broad range of i~proved stabili-zation performance characteristics.
Various other objects and advantages of this invention will become evident from the following description thereof.
~5~333 The compounds of this invention correspond to the formula I
.~ CH2_ - NOCH2C~2- 1- R2 (I) .=. 2 ( )n wherein n is 1 or 2, R1 is hydrogen, alkyl of 1 to 36 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenyl, aralkyl of 7 to 9 carbon atoms or said aralkyl substituted by alkyl of 1 to 36 carbon atoms, and R2 is alkyl of 1 to 36 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenyl, aralkyl of 7 to 9 carbon atoms, said aralkyl substi-tuted by alkyl of 1 to 36 carbon atoms or the group ~ CHz - NOCH2CH2-wherein R1 is as defined hereinabove.
Rl and R2 as alkyl of 1 to 36 carbon atoms are for examplemethyl, ethyl, n-propyl, n-butyl, tert-butyl, n-pentyl, n-octyl,
2-ethylhexyl, decyl or dodecyl. Straight-chain or branched alkyl with l to 12 carbon atoms is preferred.
R1 and R2 as cycloalkyl of 5 to 12 carbon atoms are for example cyclopentyl, cyclohexyl or cyclooctyl. A cycloalkyl radical having 5 to 7 carbon atoms is preferred. Cyclopentyl and cyclohexyl are especially preferred.
R1 and ~2 as aralkyl of 7 to 9 carbon ato~s or said aralkyl substi-tuted by alkyl of 1 to 36 carbon atoms may be in part~cular phenyl-alkyl with 7 to 9 carbon atoms where the phenyl ring is optionally ~25~3333 substituted by alkyl of 1 to 36 carbon atoms, preferably methyl.
Examples are benzyl, ~-methylbenzyl, ~,~-dimethylbenzyl, 3,5-di-methylbenzyl and p-nonylbenzyl.
n is 1 and preferably 2.
Compounds of formula I wherein Rl and R2 are independently alkyl of 1 to 12 carbon atoms, cyclopentyl, cyclohexyl, phenyl, benzyl, ~-methylbenzyl or ~,~-dimethylbenzyl are of interest.
Rl is preferably hydrogen.
Compounds of formula I wherein R2 is the group ~ CH2 ~ - NOCH2CH2-wherein R1 is hydrogen, alkyl of 1 to 36 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenyl, aralkyl of 7 to 9 carbon atoms or said aralkyl substituted by alkyl of 1 to 36 carbon atoms are especially preferred.
Preferred examples of compounds of formula I are:
[N,N-(Dibenzyl)amlnoxyethyl]ethyl sulfone [N,N-(Dibenzyl)aminoxyethyl]phenylsulfoxide Bis¦N,N (dibenzyl)aminoxyethyl~sulfone The compounds of formula I can be prepared in analogy to known methods, by reacting the appropriately substituted dibenzyl hydroxylamine with a vinyl sulfoxide or sulfone in a solvent to yield the desired product. The solvent can be for example an aromatic hydrocarbon such as e.g. benzene, toluene, xylene, and the like, or a heterocyclic ether, such as e.g. tetrahydrofuran. The ~2S9333 reaction temperature conveniently ranges from 0 to 80C. The preferred method for preparing the compounds of this invention involves reacting the hydroxylamine with the sulfoxide or sul~one in the presence of a proton acceptor such as for example a tertiary amine including triethylamine or pyridine, or an alkali hydroxida or an alkali a~koxide.
The starting materials needed to prepare the stabilizers of this invention are items of commerce or can be prepared by known methods.
The compounds of the present invention are particularly effective in stabilizing organic materials sub~ect to oxidative, thermal and/or actinic degradation, such as plastics, polymer~ and resins.
In general polymers which can be stabilized include 1. Polymers of monoolefins and diolefins, for example polypro-pylene, polyisobutylene, polybutene-1, polymethylpentene-1, poly-isoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optio-nally can be crosslinked), for example high density polyethylene (HDPE), low density polyethylene (LDPE and linear low denslty polyethylene (LLDPE).
2. Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of differ-ent types of polyethylene (for example LDPE/HDPE).
R1 and R2 as cycloalkyl of 5 to 12 carbon atoms are for example cyclopentyl, cyclohexyl or cyclooctyl. A cycloalkyl radical having 5 to 7 carbon atoms is preferred. Cyclopentyl and cyclohexyl are especially preferred.
R1 and ~2 as aralkyl of 7 to 9 carbon ato~s or said aralkyl substi-tuted by alkyl of 1 to 36 carbon atoms may be in part~cular phenyl-alkyl with 7 to 9 carbon atoms where the phenyl ring is optionally ~25~3333 substituted by alkyl of 1 to 36 carbon atoms, preferably methyl.
Examples are benzyl, ~-methylbenzyl, ~,~-dimethylbenzyl, 3,5-di-methylbenzyl and p-nonylbenzyl.
n is 1 and preferably 2.
Compounds of formula I wherein Rl and R2 are independently alkyl of 1 to 12 carbon atoms, cyclopentyl, cyclohexyl, phenyl, benzyl, ~-methylbenzyl or ~,~-dimethylbenzyl are of interest.
Rl is preferably hydrogen.
Compounds of formula I wherein R2 is the group ~ CH2 ~ - NOCH2CH2-wherein R1 is hydrogen, alkyl of 1 to 36 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenyl, aralkyl of 7 to 9 carbon atoms or said aralkyl substituted by alkyl of 1 to 36 carbon atoms are especially preferred.
Preferred examples of compounds of formula I are:
[N,N-(Dibenzyl)amlnoxyethyl]ethyl sulfone [N,N-(Dibenzyl)aminoxyethyl]phenylsulfoxide Bis¦N,N (dibenzyl)aminoxyethyl~sulfone The compounds of formula I can be prepared in analogy to known methods, by reacting the appropriately substituted dibenzyl hydroxylamine with a vinyl sulfoxide or sulfone in a solvent to yield the desired product. The solvent can be for example an aromatic hydrocarbon such as e.g. benzene, toluene, xylene, and the like, or a heterocyclic ether, such as e.g. tetrahydrofuran. The ~2S9333 reaction temperature conveniently ranges from 0 to 80C. The preferred method for preparing the compounds of this invention involves reacting the hydroxylamine with the sulfoxide or sul~one in the presence of a proton acceptor such as for example a tertiary amine including triethylamine or pyridine, or an alkali hydroxida or an alkali a~koxide.
The starting materials needed to prepare the stabilizers of this invention are items of commerce or can be prepared by known methods.
The compounds of the present invention are particularly effective in stabilizing organic materials sub~ect to oxidative, thermal and/or actinic degradation, such as plastics, polymer~ and resins.
In general polymers which can be stabilized include 1. Polymers of monoolefins and diolefins, for example polypro-pylene, polyisobutylene, polybutene-1, polymethylpentene-1, poly-isoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optio-nally can be crosslinked), for example high density polyethylene (HDPE), low density polyethylene (LDPE and linear low denslty polyethylene (LLDPE).
2. Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of differ-ent types of polyethylene (for example LDPE/HDPE).
3. Copolymers of monoolQfines and diolefines with each other or with other vinyl monomers, such as, for example, ethylene/propylene, linear low density polyethylene (LLDPE) and its mixtures with low density polyethylene (LDPE), propylene/butene-l, ethylene/hexene, ethylene/ethylpentene, ethylene/heptene, ethylene/octene, pro-pylene/isobutylene7 ethylene/butene-1, propylene/butadiene, iso-butylene/isoprene, ethylene/alkyl acrylates, ethylene/alkyl meth-~'~S9333 acrylates, ethylene/vinyl acetate or ethylene/ acrylic acid copoly-mers and their salts (ionomers) and terpolymers of ethylene with propylene and a diene, such as hexadiene, dicyclopentadiene or ethylidene-norbornene; as well as mlxtures of such copolymers and their mixtures with polymers mentioned in 1) above, for example polypropylenelethylene-propylene-copolymers, LDPE/EVA, LDPE/EA~, LLDPEIEVA and LLDPE/EAA.
3a. Hydrocarbon resins (for example Cs-Cg) and hydrogenated modifi-cations thereof (for example tackifiers).
3a. Hydrocarbon resins (for example Cs-Cg) and hydrogenated modifi-cations thereof (for example tackifiers).
4. Polystyrene, poly-(p-methylstyrene), poly-(~-methylstyrene).
5. Copolymers of styrene or ~-methylstyrene with dienes or acrylic derivatives, such as, for example, styrene/butadiene, styrene/
acrylonitrile, styrene/alkyl methacrylate, styrene/maleic anhydride, styrene/butadiene/ethyl acrylate, styrene/acrylonitrile/methyl acrylate; mixtures of high impact strength from styrene copolymers and another polymer, such as, for example, from a polyacrylate, a diene polymer or an ethylene/propylene/diene terpolymer; and block copolymers of styrene, such as, for example, styrene/butadiene/
styrene, styrene/ isoprene/styrene, styrene/ethylene/butylene/
styrene or styrene/ ethylene/propylene/styrene.
acrylonitrile, styrene/alkyl methacrylate, styrene/maleic anhydride, styrene/butadiene/ethyl acrylate, styrene/acrylonitrile/methyl acrylate; mixtures of high impact strength from styrene copolymers and another polymer, such as, for example, from a polyacrylate, a diene polymer or an ethylene/propylene/diene terpolymer; and block copolymers of styrene, such as, for example, styrene/butadiene/
styrene, styrene/ isoprene/styrene, styrene/ethylene/butylene/
styrene or styrene/ ethylene/propylene/styrene.
6. Graft copolymers of styrene or ~-methylstyrene such as, for example, styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene and maleic anhydride or maleimide on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene, styrene and alkyl acrylates or methacrylates on polybutadiene, styrene and acrylonitrile on ethylene/propylene/diene terpolymers, styrene and acrylonitrile on polyacrylates or polymethacrylates, styrene and acrylonitrile on l'~S~333 acrylate/butadiene copolymers, as well as mixtures thereof with the copolymers listed under 5), for instance the copolymer mixtures known as ABS-, MBS-, ASA- or AES-polymers.
7. Halogen-containing polymers, such as polychloroprene, chlori-nated rubbers, chlorinated or sulfochlorinated polyethylene, epichlorohydrine homo- and copolymers, polymers from halogen-con-taining vinyl compounds,as for example, polyvinylchloride, poly-vinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof, as for example, vinyl chloride/vinyli-dene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.
8. Polymers which are derived from a,~-unsaturated acids and derivatives thereof, such as polyacrylates and polymethacrylates, polyacrylamide and polyacrylonitrile.
9. Copolymers from the monomers mentioned under 8) with each other or with other unsaturated monomers, such as, for instance, acrylo-nitrile/butadien, acrylonitrile/alkyl acrylate, acrylonitrile/
alkoxyalkyl acrylate or acrylonitrile/vinyl halogenide copolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.
alkoxyalkyl acrylate or acrylonitrile/vinyl halogenide copolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.
10. Polymers which are derived from unsaturated alcohols and amines, or acyl derivatives thereof or acetals thereof, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinylbutyral, polyallyl phthalate or polyallyl-melamine; as well as their copolymers with olefins mentioned in 1) ~bove.
11. Homopolymers and copolymers of cyclic ethers, such as poly-alkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bis-glycidyl ethers.
~;259333
~;259333
12. Polyacetals, such as polyoxymethylene and those polyoxy-methylenes which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
13. Polyphenylene oxides and sulfides, and mixtures of poly-phenylene oxides with polystyrene or polyamides.
14. Polyurethanes which are derived Erom polyethers, polyesters or polybutadiens with terminal hydroxyl groups on the one side and aliphatic or aromatic polyisocyanates on the other side, as well as precursors thereof (polyisocyanates, polyols or prepolymers).
15. Polyamides and copolyamides which are derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corre-sponding lactams, such as polyamide 4, polyamide 6, polyamide 6/6, 6110, 6/9, 6112 and 416, polyamide 11, polyamide 12, aromatic polyamides obtained by condensation of m-xylene, diamine and adipic acid; polyamides prepared from hexamethylene diamine and isophthalic orland terephthalic acid and optionally an elastomer as modifier, for example poly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide. Further copolymers of the aforemen-tioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, such as for instance, with polyethylene glycol, polypropylene glycol or polytetramethylene glycols. Polyamides or copolyamides modified wlth EPDM or ABS. Polyamides condensed during processing (RIM-polyamide systems).
16. Polyureas, polyimides and polyamide-imides.
17. Polyesters which are derived from dicarboxyllc acids and diols and~or from hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylol-cyclohexane terephthalate, poly-L2,2,-(4-1~5~3333 hydroxyphenyl)-propane] terephthalate and polyhydroxyben~oates as well as block-copolyether-esters derived from polyethers having hydroxyl end groups.
18. Polycarbonates and polyester-carbonates.
19. Polysulfones, polyethersulfones and polyetherketones.
20. Crosslinked polymers which are derived ~rom aldehydes on the one hand and phenols, ureas and melamines on the other hand, such as phenol/formaldehyde resins, urea/formaldehyde resins and melamine/
formaldehyde resins.
formaldehyde resins.
21. Drying and non-drying alkyd resins.
22. Unsaturated polyester resins which are derived from copoly-esters of saturated and unsaturated dicarboxylic acids with poly-hydric alcohols and vinyl compounds as crosslinking agents, and also halogen-containing modifications thereof of low inflammability.
23. Thermosetting acrylic resins, derived from substituted acrylic esters, such as epoxy-acrylates, urethane-acrylates or polyester-acrylates.
24. Alkyd resins, polyester resins or acrylate resins in admixture with melamine resins, urea resins, polyisocyanates or epoxide resins as crosslinking agents.
25. Crosslinked epoxide resins which are derived from polyepoxides, for example from bis~glycidyl ethers or from cycloaliphatic di-epoxides.
1;~59333
1;~59333
26. Natural polymers, such as cellulose, rubber, gelatine and derivatives thereof which are chemically modified in a polymer-homologous manner, such as cellulose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers, such as methyl-cellulose; rosins and their derivatives.
27. Mixtures of polymers as mentioned above, for example PP~EPDM, Polyamide 6/EPDM or ABS, PVC~EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT~ PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPE/HIPS, PP~/PA 6.6 and copolymers, PA/HDPE, PA/PP, P~/PPE.
28. Naturally occurring and synthetic organic materials which are pure monomeric compounds or mixtures of such compounds, for example mineral oils, animal and vegetable fats, oil and waxes, or oils, fats and waxes based on synthetic esters (e.g. phthalates, adipates, phosphates or trimellithates) and also mixtures of synthetic esters with mineral oils in any weight ratios, which materials may be used as plasticizer for polymers or as textile spinning oils, as well as aqueous emulsions of such materials.
29. Aqueous emulsions of natural or synthetic rubber, e.g. natural latex or latices of carboxylated styrene/butadiene copolymers.
Substrates in which the instant compounds are useful are synthetic polymers, in particular polyolefin homopolymers or copolymers.
Substrates in which the instant compounds are particularly useful are polyolefins such as e.g. polyethylene and polypropylene, polystyrene, including impact polystyrene, ABS resin, SBR, isoprene, as well as natural rubber, polyesters, including polyethylene terephthalate and polybutylene terephthalate, including copolymers, and lubricating oils such as those derived from mineral oll.
~Z5~333 In general, the compounds of the present invention can be employed in from about 0.01 to about 5 % by weight o~ the stabilized com-position, although this will vary with the particular substrate and application. An advantageous range is from about 0.5 to about 2 %, and especially 0.1 to about 1 %.
The stabilizers of the instant invention may readily be incorporated into the organic polymers by conventional techniques, at any convenient stage before or during shaping. For example, the stabi-lizer may be mi~ed into the melt or the stabilizer may be mixed with ths 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 stabilized compositions of the invention may optionally also contain for example from about 0.05 to about 5 %, preferably from about 0.1 to about 2.5 % by weight of various conventional addi-tives, such as the following:
1. Antioxidants 1.1. Alkylated monophenols, for example 2,6-di-tert-butyl-4-methyl-phenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethyl-phenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-iso-butylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(~-methylcyclo-hexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, 2,6-di-nonyl-4-methylphenol.
1.2. Alkylated hydroquinones,for example 2,6-di-tert-butyl-4-me-thoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydro-quinone, 2,6-diphenyl-4-octadecyloxyphenol.
~'~5~333 1.3._Hydroxylated thiodiphenyl ethers, for example 2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2' thiobis(4-octylphenol), 4,4'-thio-bls(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-2-methylphenol).
1.4. Alkylidenebispllenols, for example 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'-methylenebis(6-tert-butyl-4-ethyl-phenol), 2,2'-methylenebis[4-~ethyl-6-(~-methylcyclohexyl)phenol~, 2,2'-methyleneb~s(4-~ethyl-6-cyclohexylphenol), 2,2'-methylenebis-(6-nonyl-4-methylphenol), 2,2'-methylenebis(4,6-di-tert-butyl-phenol), 2,2'-ethylidenebis(4,6-di-tert-butylphenol), 2,2'-ethyli-denebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis[6-(~-methylbenzyl)-4-nonylphenoll, 2,2'-methylenebis[6-(~,~-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-methylphenol, 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis-[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-S-methylphenyl~dicyclopentadiene, bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4methylphenyl]
terephthalate.
1.5. Benzyl compounds, for example 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl 3,5-di tert-butyl-4-hydroxybenzyl-mercaptoacetate, 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-dl-tert-butyl-4-hydroxybenzylphospho-nate, calcium salt of monoethyl 3,5-di-tert-butyl-4-hydroxybenzyl-phosphonate, 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)iso-cyanurate.
~;~593~3 1.6. Acylaminophenols, for example anilide of 4-hydroxylauric acid, anilide of 4-hydroxystearic acid, 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino~-s-triazine, octyl N-(3,5-di-tert-butyl 4-hydroxyphenyl)carbamate.
1.7. Esters of ~-(3,5-di-tert-butyl-4-hydroxyPhenYl)proPionic acid with mono- or polyhydric alcohols, e.g. with methanol, diethylene glycol, octadecanol, trie~hylene glycol, l,6-hexanediol, penta-erythritol, 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 acid with mono- o~ polyhydric alcohols, e.g. with methanol, di-ethylene 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 with mono- or polyhydric alcohols, e.g. with methanol, diethylene glycol, octadecanol, trlethylene glycol, 1,6-hexanediol, penta-erythritol, neopentyl glycol, tris(hydroxyethyl) isocyanurateJ
thiodiethylene glycol, N,N'-bis(hydroxyethyl)oxalic acid diamide.
1.10. Amides of ~-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g. N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexa-methylene-diamine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenyl-propionyl)trimethylene-diamine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine.
2. UV absorbers and light 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'-d~-tert-amyl and 3',5'-bis(a,a dimethylbenzyl) derivatives.
~L25~333 2.2 2-H~droxybenzophenones, for example the 4-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 benzoic acids, for example, 4-tert-butylphenyl salicylate, phenyl salicylate, octyl-phenyl 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-hydroxy-benzoate.
2.4. Acrylates, for example ethyl ~-cyano-~,~-diphenylacrylate, lsooctyl ~-cyano-~,~-diphenylacrylate, methyl ~-carbomethoxycinn-amate, methyl ~-cyano-~-methyl-p-methoxy-cinnamate, butyl ~-cyano-~-methyl-p-methoxycinnamate, methyl ~-carbomethoxy-p-methoxy-clnnamate and N-(~-carbomethoxy-~-cyanovinyl)-2-methylindoline.
2.5. Nickel compounds, for example nickel complexes of 2,2'-thio-bis[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or 1:2 complex, with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldi-thiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert-butylbenzyl-phosphonic acid monoalkyl esters, e.g. of the methyl or ethyl ester, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methyl-phenyl undecyl ketoneoxime, nickel complexes of l-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.
2.6. Sterically hindered amines, for example bis(2,2,6,6-tetra-methylpiperidyl) sebacate, bis(l,2,2,6,6-pentamethylpiperidyl~
sebacate, bis(1,2,2,6,6-pentamethylpiperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensation product of 1-hydroxyethyl-2,2,6,5-tetramethyl-4-hydroxypiperidine and succinic acid, the condensation product of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl) nitrilotri-lZS9333 acetate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate, 1,1'-(1,2-ethanediyl)bis(3,3,5,5-tetramethyl-piperazinone).
2 7. Oxallc acid diamides, for example 4,4'-dioctyloxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butyloxanilide, 2,2'-didodecyloxy-S,5'-di-tert-butyloxanilide, 2-ethoxy-2'-ethyloxanilide, ~ bis(3-di-methylaminopropyl)oxalamide, 2-ethoxy-5-tert-butyl-2'-ethylox-anilide and its mixture with 2-etho~y-2'-ethyl-5,4'-di-tert-butylox-anilide and mixtures of ortho- and para-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.
3. Metal deactivators, for example N,N'-diphenyloxalic acid diamide, N-salicylal-N'-salicyloylhydrazine, N,N'-bis(salicyloyl)hydrazine, N,N'-bis(3,5-dl-tert-butyl-4-hydroxyphenylpropionyl)hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalic acid dihydrazide.
_ Phosphites and phosphonites, for example triphenyl phosphite, diphenylalkyl phosphites, phenyld~alkyl phosphites, tris(nonyl-phenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol tri-phosphite, tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylene diphosphonite, 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetra-oxa-3,9-diphosphaspiro[5.5]undecane.
5. Peroxide scavengers, for example esters of B-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis(~-dodecylmercapto)propionate.
i;2S~333 6. Polyamide stabilis_rs, for example, copper salts ln combination with iodides and/or phosphorus compounds and salts of divalent manganese.
7. Basic co-stabilisers, for example, melamine, polyvinylpyrroli-done, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatlves, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids for example Ca stearate, Zn stearate, Mg stearate, ~a ricinoleate and K palmi-tate, antimony pyrocatecholate or zinc pyrocatecholate.
8. ~ucleating agents, for example, 4-tert.butyl-benzoic acid, adipic acid, diphenylacetic acid.
9. Fillers and reinforcing agents, for example, calcium carbonate, silicates, glass fibres, asbestos, talc, ~aolin, mica, barium sulfate, metal oxides and hydroxydes, carbon black, graphite.
10. Other additives, for example, plasticisers, lubricants, emulsi-fiers, pigments, optical brighteners, flameproofing agents, anti-static agents and blowing agents.
While the instant sulfoxides and sulfones can be beneficially used as stabilizers for a variety of substrates, particularly the poly-olefins, both alone and in conjunction with other coadditives, the introduction of the instant sulfoxides and sulfones into polyole-fins, optionally containing various alkali metal, alkaline earth metal and aluminum salts of higher fatty acids (see Additive #7 hereinabove), with hindered phenolir antioxidants provides enhanced and particularly salubrious protection to such substrates in terms of reducing color formation stemming from the presence of the phenols. Such phenolic antioxidants include n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, neopentanetetrayl tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), di-n-octadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, thiodiethylene bis(3,5-di-tert-butyl-~25~3333 4-hydroxyhydrocinnamate), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 3,6-di-oxaoctamethylene bis(3-methyl-5-tert-butyl 4-hydroxyhydrocinnamate), 2,6-di-tert-butyl-p-cresol, 2,2`-ethylidene-bis(4,6-di-tert-butylphenol), l,395-tris(2,6-di-methyl-4-tert-butyl-3-hydroxybenzyl)isocyanurate, 1,1,3-tris(2-methyl-4-hydroxy-5-telt-butylphenyl)butane, 1,3~5-trisl2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)ethyl]isocyanurate, 3,5-bis-t3,5-di-tert-butyl-4-hydroxybenzyl)mesitol, hexamethylene bis-(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 1-(3,5-di-tert-butyl-4-hydroxyanilino)-3,5-bis(octylthio)-s-triazine, N,N'-hexamethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide), calcium bis(ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate), ethylene bis[3,3-bis-(3-tert-butyl-4-hydroxyphenyl)butyrate], octyl 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate, bis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamoyl)hydrazide, and N,~'-bis[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)ethyl~oxamide, and preferably neopentane-tetrayl tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, ~,3,5-tri-methyl-2,4,6-tris(3,5-dl-tert-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 2,6-di-tert-butyl-p-cresol or 2,2'-ethylidene-bis(4,6-di-tert-butylphenol).
Likewise, the instant compounds prevent color formation when hindered amine light stabilizers are present, such hindered amines including bis(l,2,2,6,6-pentamethyl-4-piperidyl)-2-n-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate; bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate; dimethylsuccinate polymer with l-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine; and polymer of 2,4-di-chloro-6-octylamino-s-triazine with N,N'-(2,2,6,6-tetramethyl-4-piperidyl)hexamethylene diamine.
The following examples illustrate the embodiments of this invention.
In these examples, all parts given are by weight unless otherwise specified.
lZS9333 Example I: [N,N-(Dibenzyl)aminoxyethyl]ethyl sulfone A solution of 17.65 g of dibenzylhydroxylamine in 50 ml of tetra-hydrofuran is admixed with 1.0 g of potassium-tert-butoxide, followed by a solution of lO.0 g of ethylvinylsulfone in 50 ml of tetrahy~rofuran. The solution is stirred at room temperature for 12 hours and concentrated under reduced pressure. The residue is partitioned between organic layer and water. The organic layer is washed with water, brine, dried (MgS04) and evaporated to give the cr~de product. Preparative liquid chromatography affords the title compound as a white solid; mp 65-67C.
Anal. Calcd. for C18H23N03S: C, 64.8; H, 7.0; N, 4.2.
Found: C, 65.2; H, 6.9; N, 4Ø
Example II: [N,N-(Dibenzyl)aminoxyethyl]phenylsulfoxide The procedure of Example I is repeated using 21.3 g of dibenzyl-hydroxylamine, 1.12 g of potassium-tert-butoxide and 15.2 g of phenylvinylsulfoxide in tetrahydrofuran to afford the title compound as a pale yellow oil.
Anal. Calcd. for C22H23N02S: C, 72.3;H, 6.3; N, 3.8.
Found: C, 72.4; H, 6.2; N, 3.8.
Example III: Bis[N,N-(dibenzyl~aminoxyethyl]sulfone The procedure of Example I is repeated using 21.25 g of dibenzyl-hydroxylamine, 1.12 g of potassium-tert-butoxide and 5.89 g of vinylsulfone in tetrahydrofuran to afford the title compounds as a thick oil.
Anal. Calcd. for C32H36N204S: C, 70.6; H, 6.7; N, 5.1.
~ound: C, 70.9; H, 6.3; N, 5.1.
125~333 Example IV: Processing of Polypropylene Base Formulation Polypropylene* 100 parts Calcium Stearate 0.10 part *~Profax 6501 from Himont USA
The indicated stabilizers are solvent blended into polypropylene as solutions in methylene chloride and after removal of solvent by evaporation at reduced pressure, the resin is extruded using the following extruder conditions-Temperature ( C?
Cylinder #1 232 Cylinder #2 246 Cylinder 1~3 260 Gate #1 260 Gate #2 260 Gate #3 260 During extrusion, the internal extruder pressure is determined using a pressure transducer. After each of the first, third and fifth extrusions, resln pellets are compression molded into 3.2 mm thick plaques at 193C and specimen yellowness index (Y.I.) determined according to ASTM D1925-63T.
The melt flow rate ~MFR) is determined by ASTM method 1238 condi-tion L. Ths melt flow rate varles inversely as the transducer pr~ssure and both are a measure of the molecular weight for a specific type of polymer.
The results are shown in the following tables.
~259333 Extrusion Temperature 260C
YI Color Additives After Extrusion ~ase Resin 1.8 2.5 3.5 0.1 % Antloxidant A* 4.6 8.9 10.9 0.1 % Antioxidan~ A* ~ 0.05 ~0 Fx. III 1.9 2.9 3.6 Additives MFR After Extrusion (g/10 min) Base Resin 5.0 9.9 0.1 % Aniioxidant A* 2.8 4.8 0.1 % Antioxidant A* ~ 0.05 % Ex. III 2.2 3.8 *Neopentyl tetrakis [3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)-propanoate]
Summarizing, it is seen that this invention provides novel compounds which exhibit effective stabilization activity. Variations may be made in proportions, procedures and materials without departing from the scope of the invention as defined by the following claims.
Substrates in which the instant compounds are useful are synthetic polymers, in particular polyolefin homopolymers or copolymers.
Substrates in which the instant compounds are particularly useful are polyolefins such as e.g. polyethylene and polypropylene, polystyrene, including impact polystyrene, ABS resin, SBR, isoprene, as well as natural rubber, polyesters, including polyethylene terephthalate and polybutylene terephthalate, including copolymers, and lubricating oils such as those derived from mineral oll.
~Z5~333 In general, the compounds of the present invention can be employed in from about 0.01 to about 5 % by weight o~ the stabilized com-position, although this will vary with the particular substrate and application. An advantageous range is from about 0.5 to about 2 %, and especially 0.1 to about 1 %.
The stabilizers of the instant invention may readily be incorporated into the organic polymers by conventional techniques, at any convenient stage before or during shaping. For example, the stabi-lizer may be mi~ed into the melt or the stabilizer may be mixed with ths 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 stabilized compositions of the invention may optionally also contain for example from about 0.05 to about 5 %, preferably from about 0.1 to about 2.5 % by weight of various conventional addi-tives, such as the following:
1. Antioxidants 1.1. Alkylated monophenols, for example 2,6-di-tert-butyl-4-methyl-phenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethyl-phenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-iso-butylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(~-methylcyclo-hexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, 2,6-di-nonyl-4-methylphenol.
1.2. Alkylated hydroquinones,for example 2,6-di-tert-butyl-4-me-thoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydro-quinone, 2,6-diphenyl-4-octadecyloxyphenol.
~'~5~333 1.3._Hydroxylated thiodiphenyl ethers, for example 2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2' thiobis(4-octylphenol), 4,4'-thio-bls(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-2-methylphenol).
1.4. Alkylidenebispllenols, for example 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'-methylenebis(6-tert-butyl-4-ethyl-phenol), 2,2'-methylenebis[4-~ethyl-6-(~-methylcyclohexyl)phenol~, 2,2'-methyleneb~s(4-~ethyl-6-cyclohexylphenol), 2,2'-methylenebis-(6-nonyl-4-methylphenol), 2,2'-methylenebis(4,6-di-tert-butyl-phenol), 2,2'-ethylidenebis(4,6-di-tert-butylphenol), 2,2'-ethyli-denebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis[6-(~-methylbenzyl)-4-nonylphenoll, 2,2'-methylenebis[6-(~,~-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-methylphenol, 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis-[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-S-methylphenyl~dicyclopentadiene, bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4methylphenyl]
terephthalate.
1.5. Benzyl compounds, for example 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl 3,5-di tert-butyl-4-hydroxybenzyl-mercaptoacetate, 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-dl-tert-butyl-4-hydroxybenzylphospho-nate, calcium salt of monoethyl 3,5-di-tert-butyl-4-hydroxybenzyl-phosphonate, 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)iso-cyanurate.
~;~593~3 1.6. Acylaminophenols, for example anilide of 4-hydroxylauric acid, anilide of 4-hydroxystearic acid, 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino~-s-triazine, octyl N-(3,5-di-tert-butyl 4-hydroxyphenyl)carbamate.
1.7. Esters of ~-(3,5-di-tert-butyl-4-hydroxyPhenYl)proPionic acid with mono- or polyhydric alcohols, e.g. with methanol, diethylene glycol, octadecanol, trie~hylene glycol, l,6-hexanediol, penta-erythritol, 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 acid with mono- o~ polyhydric alcohols, e.g. with methanol, di-ethylene 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 with mono- or polyhydric alcohols, e.g. with methanol, diethylene glycol, octadecanol, trlethylene glycol, 1,6-hexanediol, penta-erythritol, neopentyl glycol, tris(hydroxyethyl) isocyanurateJ
thiodiethylene glycol, N,N'-bis(hydroxyethyl)oxalic acid diamide.
1.10. Amides of ~-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g. N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexa-methylene-diamine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenyl-propionyl)trimethylene-diamine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine.
2. UV absorbers and light 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'-d~-tert-amyl and 3',5'-bis(a,a dimethylbenzyl) derivatives.
~L25~333 2.2 2-H~droxybenzophenones, for example the 4-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 benzoic acids, for example, 4-tert-butylphenyl salicylate, phenyl salicylate, octyl-phenyl 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-hydroxy-benzoate.
2.4. Acrylates, for example ethyl ~-cyano-~,~-diphenylacrylate, lsooctyl ~-cyano-~,~-diphenylacrylate, methyl ~-carbomethoxycinn-amate, methyl ~-cyano-~-methyl-p-methoxy-cinnamate, butyl ~-cyano-~-methyl-p-methoxycinnamate, methyl ~-carbomethoxy-p-methoxy-clnnamate and N-(~-carbomethoxy-~-cyanovinyl)-2-methylindoline.
2.5. Nickel compounds, for example nickel complexes of 2,2'-thio-bis[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or 1:2 complex, with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldi-thiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert-butylbenzyl-phosphonic acid monoalkyl esters, e.g. of the methyl or ethyl ester, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methyl-phenyl undecyl ketoneoxime, nickel complexes of l-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.
2.6. Sterically hindered amines, for example bis(2,2,6,6-tetra-methylpiperidyl) sebacate, bis(l,2,2,6,6-pentamethylpiperidyl~
sebacate, bis(1,2,2,6,6-pentamethylpiperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensation product of 1-hydroxyethyl-2,2,6,5-tetramethyl-4-hydroxypiperidine and succinic acid, the condensation product of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl) nitrilotri-lZS9333 acetate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate, 1,1'-(1,2-ethanediyl)bis(3,3,5,5-tetramethyl-piperazinone).
2 7. Oxallc acid diamides, for example 4,4'-dioctyloxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butyloxanilide, 2,2'-didodecyloxy-S,5'-di-tert-butyloxanilide, 2-ethoxy-2'-ethyloxanilide, ~ bis(3-di-methylaminopropyl)oxalamide, 2-ethoxy-5-tert-butyl-2'-ethylox-anilide and its mixture with 2-etho~y-2'-ethyl-5,4'-di-tert-butylox-anilide and mixtures of ortho- and para-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.
3. Metal deactivators, for example N,N'-diphenyloxalic acid diamide, N-salicylal-N'-salicyloylhydrazine, N,N'-bis(salicyloyl)hydrazine, N,N'-bis(3,5-dl-tert-butyl-4-hydroxyphenylpropionyl)hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalic acid dihydrazide.
_ Phosphites and phosphonites, for example triphenyl phosphite, diphenylalkyl phosphites, phenyld~alkyl phosphites, tris(nonyl-phenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol tri-phosphite, tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylene diphosphonite, 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetra-oxa-3,9-diphosphaspiro[5.5]undecane.
5. Peroxide scavengers, for example esters of B-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis(~-dodecylmercapto)propionate.
i;2S~333 6. Polyamide stabilis_rs, for example, copper salts ln combination with iodides and/or phosphorus compounds and salts of divalent manganese.
7. Basic co-stabilisers, for example, melamine, polyvinylpyrroli-done, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatlves, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids for example Ca stearate, Zn stearate, Mg stearate, ~a ricinoleate and K palmi-tate, antimony pyrocatecholate or zinc pyrocatecholate.
8. ~ucleating agents, for example, 4-tert.butyl-benzoic acid, adipic acid, diphenylacetic acid.
9. Fillers and reinforcing agents, for example, calcium carbonate, silicates, glass fibres, asbestos, talc, ~aolin, mica, barium sulfate, metal oxides and hydroxydes, carbon black, graphite.
10. Other additives, for example, plasticisers, lubricants, emulsi-fiers, pigments, optical brighteners, flameproofing agents, anti-static agents and blowing agents.
While the instant sulfoxides and sulfones can be beneficially used as stabilizers for a variety of substrates, particularly the poly-olefins, both alone and in conjunction with other coadditives, the introduction of the instant sulfoxides and sulfones into polyole-fins, optionally containing various alkali metal, alkaline earth metal and aluminum salts of higher fatty acids (see Additive #7 hereinabove), with hindered phenolir antioxidants provides enhanced and particularly salubrious protection to such substrates in terms of reducing color formation stemming from the presence of the phenols. Such phenolic antioxidants include n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, neopentanetetrayl tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), di-n-octadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, thiodiethylene bis(3,5-di-tert-butyl-~25~3333 4-hydroxyhydrocinnamate), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 3,6-di-oxaoctamethylene bis(3-methyl-5-tert-butyl 4-hydroxyhydrocinnamate), 2,6-di-tert-butyl-p-cresol, 2,2`-ethylidene-bis(4,6-di-tert-butylphenol), l,395-tris(2,6-di-methyl-4-tert-butyl-3-hydroxybenzyl)isocyanurate, 1,1,3-tris(2-methyl-4-hydroxy-5-telt-butylphenyl)butane, 1,3~5-trisl2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)ethyl]isocyanurate, 3,5-bis-t3,5-di-tert-butyl-4-hydroxybenzyl)mesitol, hexamethylene bis-(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 1-(3,5-di-tert-butyl-4-hydroxyanilino)-3,5-bis(octylthio)-s-triazine, N,N'-hexamethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide), calcium bis(ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate), ethylene bis[3,3-bis-(3-tert-butyl-4-hydroxyphenyl)butyrate], octyl 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate, bis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamoyl)hydrazide, and N,~'-bis[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)ethyl~oxamide, and preferably neopentane-tetrayl tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, ~,3,5-tri-methyl-2,4,6-tris(3,5-dl-tert-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 2,6-di-tert-butyl-p-cresol or 2,2'-ethylidene-bis(4,6-di-tert-butylphenol).
Likewise, the instant compounds prevent color formation when hindered amine light stabilizers are present, such hindered amines including bis(l,2,2,6,6-pentamethyl-4-piperidyl)-2-n-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate; bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate; dimethylsuccinate polymer with l-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine; and polymer of 2,4-di-chloro-6-octylamino-s-triazine with N,N'-(2,2,6,6-tetramethyl-4-piperidyl)hexamethylene diamine.
The following examples illustrate the embodiments of this invention.
In these examples, all parts given are by weight unless otherwise specified.
lZS9333 Example I: [N,N-(Dibenzyl)aminoxyethyl]ethyl sulfone A solution of 17.65 g of dibenzylhydroxylamine in 50 ml of tetra-hydrofuran is admixed with 1.0 g of potassium-tert-butoxide, followed by a solution of lO.0 g of ethylvinylsulfone in 50 ml of tetrahy~rofuran. The solution is stirred at room temperature for 12 hours and concentrated under reduced pressure. The residue is partitioned between organic layer and water. The organic layer is washed with water, brine, dried (MgS04) and evaporated to give the cr~de product. Preparative liquid chromatography affords the title compound as a white solid; mp 65-67C.
Anal. Calcd. for C18H23N03S: C, 64.8; H, 7.0; N, 4.2.
Found: C, 65.2; H, 6.9; N, 4Ø
Example II: [N,N-(Dibenzyl)aminoxyethyl]phenylsulfoxide The procedure of Example I is repeated using 21.3 g of dibenzyl-hydroxylamine, 1.12 g of potassium-tert-butoxide and 15.2 g of phenylvinylsulfoxide in tetrahydrofuran to afford the title compound as a pale yellow oil.
Anal. Calcd. for C22H23N02S: C, 72.3;H, 6.3; N, 3.8.
Found: C, 72.4; H, 6.2; N, 3.8.
Example III: Bis[N,N-(dibenzyl~aminoxyethyl]sulfone The procedure of Example I is repeated using 21.25 g of dibenzyl-hydroxylamine, 1.12 g of potassium-tert-butoxide and 5.89 g of vinylsulfone in tetrahydrofuran to afford the title compounds as a thick oil.
Anal. Calcd. for C32H36N204S: C, 70.6; H, 6.7; N, 5.1.
~ound: C, 70.9; H, 6.3; N, 5.1.
125~333 Example IV: Processing of Polypropylene Base Formulation Polypropylene* 100 parts Calcium Stearate 0.10 part *~Profax 6501 from Himont USA
The indicated stabilizers are solvent blended into polypropylene as solutions in methylene chloride and after removal of solvent by evaporation at reduced pressure, the resin is extruded using the following extruder conditions-Temperature ( C?
Cylinder #1 232 Cylinder #2 246 Cylinder 1~3 260 Gate #1 260 Gate #2 260 Gate #3 260 During extrusion, the internal extruder pressure is determined using a pressure transducer. After each of the first, third and fifth extrusions, resln pellets are compression molded into 3.2 mm thick plaques at 193C and specimen yellowness index (Y.I.) determined according to ASTM D1925-63T.
The melt flow rate ~MFR) is determined by ASTM method 1238 condi-tion L. Ths melt flow rate varles inversely as the transducer pr~ssure and both are a measure of the molecular weight for a specific type of polymer.
The results are shown in the following tables.
~259333 Extrusion Temperature 260C
YI Color Additives After Extrusion ~ase Resin 1.8 2.5 3.5 0.1 % Antloxidant A* 4.6 8.9 10.9 0.1 % Antioxidan~ A* ~ 0.05 ~0 Fx. III 1.9 2.9 3.6 Additives MFR After Extrusion (g/10 min) Base Resin 5.0 9.9 0.1 % Aniioxidant A* 2.8 4.8 0.1 % Antioxidant A* ~ 0.05 % Ex. III 2.2 3.8 *Neopentyl tetrakis [3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)-propanoate]
Summarizing, it is seen that this invention provides novel compounds which exhibit effective stabilization activity. Variations may be made in proportions, procedures and materials without departing from the scope of the invention as defined by the following claims.
Claims (18)
1. A compound of the formula I
(I) wherein n is 1 or 2, R1 is hydrogen, alkyl of 1 to 36 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenyl, aralkyl of 7 to 9 carbon atoms or said aralkyl substituted by alkyl of 1 to 36 carbon atoms, and R2 is alkyl of 1 to 36 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenyl, aralkyl of 7 to 9 carbon atoms, said aralkyl substi-tuted by alkyl of 1 to 36 carbon atoms or the group wherein R1 is as defined hereinabove.
(I) wherein n is 1 or 2, R1 is hydrogen, alkyl of 1 to 36 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenyl, aralkyl of 7 to 9 carbon atoms or said aralkyl substituted by alkyl of 1 to 36 carbon atoms, and R2 is alkyl of 1 to 36 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenyl, aralkyl of 7 to 9 carbon atoms, said aralkyl substi-tuted by alkyl of 1 to 36 carbon atoms or the group wherein R1 is as defined hereinabove.
2. The compound of claim 1, wherein n is 1.
3. The compound of claim 1, wherein n is 2.
4. The compound of claim 1, wherein R1 and R2 are independently alkyl of 1 to 12 carbon atoms, cyclopentyl, cyclohexyl, phenyl, benzyl, .alpha.-methylbenzyl or .alpha.,.alpha.-dimethylbenzyl.
5. The compound of claim 1, wherein R1 is hydrogen.
6. The compound of claim 1, wherein R2 is the group wherein R1 is as defined in claim 1.
7. [N,N-(Dibenzyl)aminoxyethyl]ethyl sulfone according to claim 3.
8. [N,N-(Dibenzyl)aminoxyethyl]phenylsulfoxide according to claim 2.
9. Bis[N,N-(dibenzyl)aminoxyethyl]sulfone according to claim 3.
10. A composition of matter comprising an organic material subject to oxidative, thermal and/or actinic degradation stabilized with an effective stabilizing amount of a compound of claim 1.
11. The composition of claim 10, wherein the organic material is a synthetic polymer.
12. The composition of claim 11, wherein said synthetic polymer is a polyolefin homopolymer or copolymer.
13. The composition of claim 10, which also contains an effective amount of one or more conventional additives.
14. The composition of claim 13 wherein said conventional additive is a metal salt of a higher fatty acid.
15. The composition of claim 13 wherein said conventional additive is a phenolic antioxidant.
16. The composition of claim 13 wherein said conventional additives are a phenolic antioxidant and a metal salt of a higher fatty acid.
17. The composition of claim 15, wherein said phenolic antioxidant is selected from the group consisting of neopentanetetrayl tetra-kis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 2,6-di-tert-butyl-p-cresol and 2,2'-ethylidene-bis(4,6-di-tert-butylphenol).
18. A method for stabilizing an organic material against oxidative, thermal and/or actinic degradation which comprises incorporating into said organic material an effective stabilizing amount of a compound of claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US80963785A | 1985-12-16 | 1985-12-16 | |
| US809,637 | 1985-12-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1259333A true CA1259333A (en) | 1989-09-12 |
Family
ID=25201845
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000525155A Expired CA1259333A (en) | 1985-12-16 | 1986-12-12 | Substituted aminoxyethyl sulfoxides and sulfones |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0228994B1 (en) |
| JP (1) | JPS62153269A (en) |
| CA (1) | CA1259333A (en) |
| DE (1) | DE3662040D1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007153587A (en) * | 2005-12-07 | 2007-06-21 | Mitsubishi Electric Corp | Brake releasing device of elevator hoisting machine |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3287124A (en) * | 1963-06-26 | 1966-11-22 | Polaroid Corp | Sulfone-hydroxylamines as photographic developers |
| US3316299A (en) * | 1963-08-27 | 1967-04-25 | Upjohn Co | Bis(2-aminooxyethyl)sulfones |
| US3644278A (en) * | 1968-03-04 | 1972-02-22 | Ciba Geigy Corp | Substituted hydroxylamine stabilizers |
-
1986
- 1986-12-10 EP EP19860810582 patent/EP0228994B1/en not_active Expired
- 1986-12-10 DE DE8686810582T patent/DE3662040D1/en not_active Expired
- 1986-12-12 CA CA000525155A patent/CA1259333A/en not_active Expired
- 1986-12-16 JP JP29983086A patent/JPS62153269A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP0228994B1 (en) | 1989-02-08 |
| JPS62153269A (en) | 1987-07-08 |
| EP0228994A1 (en) | 1987-07-15 |
| DE3662040D1 (en) | 1989-03-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5175312A (en) | 3-phenylbenzofuran-2-ones | |
| EP0269570A2 (en) | Compositions stabilized with N-hydroxyiminodiacetic or dipropionic acids or esters thereof | |
| US4906678A (en) | 1,2,2,6,6-Pentamethyl-4-piperidylaminotriazine derivatives and their use as stabilizers | |
| CA1295619C (en) | 1,3,2-oxazaphospholidine stabilizers | |
| CA1336938C (en) | Compositions stabilized with substituted aminoxy silanes | |
| CA1304090C (en) | Compositions stabilized with aminoxy alkylamine derivatives | |
| US4992493A (en) | Piperidine-triazine compounds for use as stabilizers for organic materials | |
| CA1274844A (en) | Substituted aminoxy-propanoates | |
| EP0313517B1 (en) | Aliphatic esters of 1,3,2-oxazaphospholidines | |
| CA1321602C (en) | N,n-bis(hydroxyethyl)hydroxylamine ester stabilizers | |
| CA1274840A (en) | Substituted aminoxy succinates and the use thereof as stabilizers | |
| US4942238A (en) | Unsaturated derivatives of 2,2,6,6-tetramethylpiperidine | |
| AU594139B2 (en) | Substituted aminoxy-propionamides | |
| CA1292227C (en) | Compositions stabilized with substituted amino carbamates and novel substituted amino carbamates | |
| EP0255478A1 (en) | Tris(substituted hydroxyphenyl-thio)trithioorthoesters | |
| US4948889A (en) | Triazine compounds derived from 2,2,6,6-tetramethylpiperidine | |
| CA1276650C (en) | Long chain (4-hydroxyphenyl) propanoate stabilizers | |
| EP0314623B1 (en) | Substituted hydroxylamine ester stabilizers | |
| CA1259333A (en) | Substituted aminoxyethyl sulfoxides and sulfones | |
| CA2026900A1 (en) | Stabilised organic material | |
| EP0263068A1 (en) | Compositions stabilized with substituted benzylhydroxylamines | |
| CA1273357A (en) | Substituted aminoxyethyl phosphonates | |
| CA1273955A (en) | Hydroxylamine derivatives and their use as stabilizers | |
| CA1310971C (en) | Substituted 1,3,4-oxathiazol-2-one stabilizers | |
| GB2179939A (en) | 5-Higher alkyl substituted-2H-benzotriazoles and stabilized compositions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |