MXPA97009369A - 1.2-bis-stable nitroxid adducts with substitute ethylene and stabilization compositions - Google Patents

Abstract

The present invention relates to 1,2-bis-adducts of hindered nitroxide compounds entable with substituted ethylenes, which propagate the reaction of two equivalents of nitroxyl compounds with an ethylenically unsaturated compound such as styrene or acrylate ester. These adducts are very effective inhibitors to prevent the premature polymerization of ethylenically unsaturated monomers, when these monomers are distilled, processed or stored

Description

1.2-BIS-STABLE NITROXID ADUCTS WITH SUBSTITUTEED ETHYLENE AND STABILIZED COMPOSITIONS The present invention relates to novel 1,2-adducts of stable hindered nitroxyl compounds, with substituted ethylenes, such as are found in ethylenically unsaturated monomers. The adducts are very effective inhibitors to prevent the premature polymerization of vinyl monomers. Many of the industrially important ethylenically unsaturated monomers are highly susceptible to unwanted radical polymerization, which is initiated either thermally or by adventitious impurities. Some examples of these monomers are styrene, acrylic and methacrylic acid, esters of acrylate and methacrylate and acrylonitrile. Premature polymerization may occur during manufacture, purification or storage of the monomer. Many of these monomers are purified by distillation. It is in this operation where premature polymerization is most likely to occur and is the most problematic. Methods to avoid or reduce the amount of this polymerization in this manner are highly convenient since the prevention or mitigation of this premature polymerization increases the yield of the purified monomer and also insures against costly and potentially dangerous uncontrolled polymerization in the plant.

The. Stable hindered organic nitroxyl compounds included in this invention are those nitroxides that are completely substituted on the alpha carbon atoms. See LB Volodarsky et al., Synthetic Chemistry of Stable Nitroxides, (Synthetic Chemistry of Stable Nitroxides), CRC Press, Boca Raton, FL, 1994. Bis-trifiuoromethylnitroxide is a stable nitroxide and its 1,2-bis-adducts with ethylenes, they know See A. E. Tipping et al., J. Fluor. Chem., 69, 163 (1994); R. E. Banks et al., J. Chem. Soc. C, 901 (1966); and R. E. Banks et al., J. Chem. Soc., C, 2777 (1971). 1-Phenyl-1, 2-bis (2,2,6,6-tetramethylpiperidin-1-yloxy) -ethane is a known bis-adduct. G. Moad et al., Polymer Bu. £, 589 (1982) reported this material prepared by the reaction of 1-oxyl-2,2,6,6-tetramethylpiperidine with styrene. No Chemical Abstract number was assigned to this compound nor was a utility assigned to said compounds. It is an object of this invention to provide novel bis-adducts compounds that are formed by the reaction of stable hindered organic nitroxyl compounds with an ethylenically unsaturated monomer. Another object of this invention is to demonstrate the ability of these bis-adducts to prevent or mitigate the premature polymerization of ethylenically unsaturated monomers during distillation and purification.

Yet another objective of this invention is to provide compounds that exhibit effective stabilization efficiency to organic substrates subject to light or thermal induced radiation. The present invention relates to novel 1,2-bis-adducts of formula I or II where Rj. and R2 independently are alkyl of 1 to 4 carbon atoms, or Rj. and R2 together are pentamethylene, preferably Rr and R2, each being methyl; E is aryl with 6 to 10 carbon atoms, or the aryl substituted by alkyl with 1 to 4 carbon atoms or by halogen or E is -COOH or -C00R6, where R6 is alkyl with 1 to 18 carbon atoms or hydroxyalkyl with 2 to 8 carbon atoms, or E is -CN, preferably E is -COOH, -CN or -COORβ, wherein * is alkyl with 1 to 4 carbon atoms, more preferably butyl; R3, R4 and R5 are independently alkyl with 1 to 4 carbon atoms, preferably methyl; and T is a group required to complete a 5-, 6- or 7-membered ring or a 1,1,3,3-tetramethylisoindoline moiety, the T group can also be substituted by hydroxyl, by oxo, by acetamido, by - ORβ wherein R8 is alkyl having 1 to 18 carbon atoms, or where -O-CO-R ,, where R "is alkyl having 1 to 17 carbon atoms or phenyl, preferably R9 is alkyl with 1 to 11 carbon atoms or phenyl, with the proviso that the compound of formula I is not l-phenyl-1,2-bis (2,2,6,6-tetramethylpiperidine-1 iloxy) ethane or 1-phenyl-1,2-bis (1,1,3,3-tetramethyl-isoindolin-2-yloxy) ethane. The compounds 1-phenyl-1,2-bis (2,2,6,6-tetramethylpiperidin-1-yloxy) ethane and l-phenyl-1,2-bis (1,1,3,3-tetramethyl-isoindoline- 2-yloxy) ethane are the 1,2-bis-adduct of 1-oxyl-2,2,6,6-tetramethylpiperidine and styrene and the 1,2-bis-adduct of 2-oxyl-1, l, 3, 3-tetramethylisoindoline and styrene. Preferably, T is a group required to complete a 5-, 6- or 7-membered ring or a 1,1,3,3-tetramethyl isoindoline moiety, wherein the T group is unsubstituted or substituted by hydroxyl, by oxo , by acetamido or by -0-C0-R9, where - <; is alkyl with 1 to 11 carbon atoms or phenyl. The following compounds are most preferred: (a) 1,2-bis-adduct of l-oxyl-2,2,6,6-tetramethyl-4-benzoyloxypiperidine and styrene; (b) 1, 2-bis-adduct of l-oxyl-2,2,6,6-tetramethyl-4-benzoyloxypiperidine and 4-chlorostyrene; (c) 1, 2-bis-adduct of l-oxyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and styrene; (d) 1, 2-bis-adduct of l-oxyl-2,2,6,6-tetramethyl-4-oxopiperidine and styrene; (e) 1, 2-bis-adduct of l-oxyl-2,2,6,6-tetramethyl-4-benzoyloxypiperidine and butyl acrylate; (f) 1, 2-bis-adduct of l-oxyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and butyl acrylate, or (g) 1,2-bis-l-oxyl adduct 2,2,6,6-tetramethyl-4-acetamido-piperidine and styrene. Formula I represents stable ring nitroxides adducts with cyclic 5-, 6- and 7-members.

Formula II represents adducts of stable acyclic nitroxides. The compounds of the formula I and II can be prepared according to standard procedures. Another aspect of the present invention is the use of the bis-adducts of the formulas I and II as effective inhibitors against the premature polymerization of ethylenically unsaturated monomers. The monomers are any that have at least one carbon-carbon double bond capable of undergoing polymerization induced by free radicals. These monomers are well known in the trade and comprise a wide variety of structural types. Typical examples of these monomers are vinyl aromatic hydrocarbons such as styrene, α-methylstyrene and divinylbenzene; dienes such as butadiene and isoprene; halogenated monomers such as vinyl chloride, chloroprene, vinylidene chloride, vinylidene fluoride and vinyl fluoride; unsaturated acids such as acrylic acid, methacrylic acid and crotonic acid; unsaturated esters such as the acrylates and methacrylates exemplified by butyl acrylate, methyl methacrylate, ethyl acrylate and methyl acrylate; unsaturated nitriles such as acrylonitrile and methacrylonitrile; unsaturated ethers such as methyl vinyl ether; and miscellaneous vinyl monomers such as vinyl pyridines, diethyl vinylphosphonate and sodium styrene sulfonate.

A further objective of the present invention is a monomer composition stabilized against premature polymerization, comprising: (a) an ethylenically unsaturated monomer, and (b) an effective stabilizing amount of a compound of formula I or II as described above. Preferably, the ethylenically unsaturated monomer is selected from the group consisting of vinyl aromatic hydrocarbons; the dienes; the halogenated vinyl monomers; unsaturated acids; the unsaturated esters; the unsaturated nitriles; the unsaturated ethers; and miscellaneous vinyl monomers which are vinyl pyridines, diethyl vinylphosphonate and sodium styrene sulfonate. Particularly preferred is a composition wherein the monomer is "-methylstyrene, divinylbenzene, butadiene, isoprene, vinyl chloride, chloroprene, vinylidene chloride, vinylidene fluoride, vinyl fluoride, acrylic acid, methacrylic acid, crotonic acid, butyl acrylate. , methyl acrylate, ethyl acrylate, methyl acrylate, acrylonitrile, methacrylonitrile or methyl vinyl ether. Particularly preferred is a composition wherein the monomer is acrylic acid, methacrylic acid, butyl acrylate, ethyl acrylate or acrylonitrile. Styrene and substituted vinyl aromatics are not among the most preferred monomers.

The amount of effective stabilizer of component (b) is 1 to 10,000 ppm by weight based on the weight of the component monomer (a). Preferably, the amount of component (b) is 10 to 1,000 ppm by weight based on the component monomer (a). Activated polymerization inhibitor mixtures can be introduced into the monomer to be protected by any conventional method. It can be added just upstream of the desired application point by any convenient means. In addition, this mixture can be injected separately into the distillation stream together with the monomer feed feed or through separate entry points that provide efficient distribution of the activated inhibitor mixture. Since the inhibitor is gradually depleted during operation, it is generally necessary to maintain the appropriate amount of the activated inhibitor mixture in the distillation system by adding additional inhibitor during the course of the distillation process. This addition can be carried out either on a continuous basis or by intermittently charging fresh inhibitor to the distillation system, if the concentration of the inhibitor is to be maintained above the minimum required level. A further object of the present invention is the use of bis-adducts of formulas I and II as effective inhibitors against the premature polymerization of ethylenically unsaturated monomers.

The bis adducts of formula I or II can be prepared according to standard methods of organic chemistry. The starting materials, ie the N-oxyses, are partially commercial compounds or can be prepared according to the methods of the prior art. The present invention also relates to a stabilized composition comprising (a) an organic material subject to the harmful effects of heat, oxygen or actinic radiation, and (b) an effective stabilizing amount of a compound of the formula I or II as described previously. The organic material is preferably a polymer, especially a polyolefin such as polypropylene or polyethylene, or a polymer, copolymer or blend of polymers containing at least one polymer or polymer component of significant ethylenic unsaturation. Examples of the latter are polymers selected from the group consisting of ABS, HIPS, emulsion SBR, PP / EPDM, PP / NBR, PP / NR, ABS / PC, ABS / nylon, @ ABS / PVC, ABS / polyester, ABS / SMA, ABS / polysulfone, ASA / PC, acetal / elastomer, polyester / elastomer, nylon / elastomer, PPO / NR, EPDM / NBR and EPDM / olefin. In general, polymers that can be stabilized include: 1. Polymers of monoolefins and diol-ethines, for example polyethylene (which can optionally be interlaced) polypropylene, polyisobutylene, polybutene-1, polymethylpentene-1, polyisoprene or polybutadiene, as well as cycloolefin polymers, for example of cyclopentene or norbornene. Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene with polyisobutylene. Copolymers of monoolefins and diolefins with one another or with other vinyl monomers, such as, for example, ethylene / propylene or, propylene / butene-1, propylene / isobutylene, ethylene / butene-1, propylene / butadiene, isobutylene / isoprene copolymers, ethylene / alkyl acrylates, ethylene / alkyl methacrylates, ethylene / vinyl acetate or ethylene / acrylic acid and its salts (ionomers) and terpolymers of ethylene with propylene and a diene, such as hexadiene, dicyclopentadiene or ethylidene-norbornene. Polystyrene, poly- (c-methylstyrene). Copolymers of styrene or methylstyrene with dienes or acrylic derivatives, such as, for example, styrene / butadiene, styrene / acrylonitrile, styrene / ethyl methacrylate, styrene / butadiene / ethyl acrylate, styrene / acrylonitrile / methyl acrylate; blends with high impact strength of styrene copolymers and another polymer, such as, for example, of a polyacrylate, a diene polymer or an ethylene / propylene / diene terpolymer; and styrene block polymers, such as, for example, styrene / butadiene / styrene, / isoprene / styrene, / e t i n e / b u t i l e n o / e s t i r e n o or styrene / ethylene / propylene / styrene. Styrene graft copolymers such as, for example, styrene in polybutadiene, styrene and acrylonitrile in polybutadiene, styrene and alkyl acrylates or methacrylates in polybutadiene, styrene and acrylonitrile in ethylene / propylene / diene terpolymers, styrene and acrylonitrile in polyacrylates or polymethacrylates, styrene and acrylonitrile in acrylate / butadiene copolymers, as well as their mixtures with the copolymers listed under 5), for example mixtures of copolymers known as ABS-, MBS-, ASA- or AES-polymers. Halogen-containing polymers, such as polychloroprene, chlorinated rubbers, chlorinated or sulfo-chlorinated polyethylene, homo and poly-epichlorohydrin solvents, polymers from halogen-containing vinyl compounds, such as, for example, polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof, such as, for example, vinyl chloride / vinylidene chloride copolymers, vinyl chloride / vinyl acetate, vinylidene chloride / vinyl acetate or vinyl fluoride / vinyl ether copolymers. 8. Polymers derived from α, β-unsaturated acids and their derivatives, such as polyacrylates and polymethacrylates, polyacrylamide and polyacrylonitrile. 9. Copolymers of the monomers mentioned under 8) with each other or with other unsaturated monomers, such as for example copolymers of acrylonitrile / butadiene, acrylonitrile / alkyl acrylate, acrylonitrile / alkoxyalkyl acrylate or acrylonitrile / vinyl halide or terpolymers of acrylonitrile / alkyl methacrylate / butadiene. 10. Polymers derived from unsaturated alcohols and amines or their acyl derivatives or their acetals, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine. 11. Homopolymers and copolymers of cyclic ethers, such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or their copolymers with bis-glycidyl ethers. 12. Polyacetals such as polyoxyethylene and those polyoxymethylenes containing ethylene oxide as comonomers. 13. Polyphenylene oxides and sulphides and mixtures of polyphenylene oxides with polystyrene. 14. Polyurethanes derived from polyethers, polyesters or polybutadienes with terminal hydroxyl groups on one side and aliphatic or aromatic polyisocyanates on the other side, as well as their precursors (polyisocyanates, polyols or prepolymers). Polyamides and copolyamides which are derived from diamines and dicarboxylic acids and / or aminocarboxylic acids or the corresponding lactams such as polyamide 4, polyamide 6, polyamide 6/6, polyamide 6/10, polyamide 11, polyamide 12, poly-2,4 , 4-trimethylhexamethylene terephthalamide, poly-p-phenylene terephthalamide or poly-phenylene isophthalamide, as well as their copolymers with polyethers, such as for example with polyethylene glycol, polypropylene glycol or polytetramethylene glycols. Polyureas, polyimides and polyamide-imides. Polyesters which are derived from dicarboxylic acids and diols and / or hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly-l, 4-dimethylol-cyclohexane terephthalate, poly- [2,2- (4-hydroxyphenyl ) -propane terephthalate and polyhydroxybenzoates as well as block copolyether-esters derived from polyethers having hydroxyl end groups. Polycarbonates Polysulfones, polyethersulfones and polyether ketones. Interlaced polymers derived from aldehydes on the one hand and phenols, ureas and melamines on the other side, such as phenol / formaldehyde resins, urea / aldehyde resins and melamine / formaldehyde resins. 21. Alkuldic resins for drying and non-drying. 22. Unsaturated polyester resins which are derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents and also their halogen-containing modifications of low flammability. 23. Acrylic thermoset resins, derived from substituted acrylic esters, such as epoxyacrylates, urethane-acrylates or polyester acrylates. 24. Alkyd resins, polyester resins or acrylate resins in admixture with melamine resins, urea resins, polyisocyanates or epoxy resins as entanglement agents. 25. Interlaced epoxy resins which are derived from polyepoxides, for example from bisglycidyl ethers or from cycloaliphatic diepoxides. 26. Natural polymers, such as cellulose, rubber, gelatin and its derivatives that are chemically modified into a homologous form of polymer, such as cellulose acetates, cellulose propionates and cellulose butyrates, or cellulose ethers, such as methyl cellulose .

Polymer mixtures as mentioned above, for example PP / EPDM, Polyamide 6 / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBTP / ABS. Organic materials of natural and synthetic origin which are pure monomeric compounds or mixtures of these compounds, for example mineral oils, animal and vegetable oils, waxes and oils or oils, fats and waxes based on synthetic esters (for example, phthalates, adipates, phosphates) or trimellitates) and also mixtures of synthetic esters with mineral oils in any proportions by weight, the materials of which can be used as plasticizers for polymers or as textile spinning agents, as well as aqueous emulsions of these materials. Aqueous emulsions of natural or synthetic rubber, for example natural latex or latices of carboxylated styrene / -butadiene copolymers. Polysiloxanes such as the mild hydrophilic polysiloxanes described, for example, in U.S. Pat. No. 4,259,467; and the hard polyorganosiloxanes described, for example, in U.S. Pat. No. 4,355,147. Polyketimines in combination with unsaturated acrylic polyacetoacetate resins or with unsaturated acrylic resins. Unsaturated acrylic resins include urethane acrylates, polyether acrylates, vinyl or acrylic copolymers with secondary unsaturated groups and the acrylated melamines. The polyketimines are prepared from polyamines and ketones in the presence of an acid catalyst. 32. Radiation curable compositions containing ethylenically unsaturated monomers or oligomers and a polyunsaturated aliphatic oligomer. 33. Epoxymelamine resins such as light-stable epoxy resins entangled by a melamine resin of high functional coefficient solid content by epoxy such as LSE-4103 (Monsanto). In general, the compounds of the present invention employ from about 1 to about 20% by weight of the stabilized composition, although this will vary with the particular substrate and application. An advantageous range is approximately 1 to 5%; preferably 1.5 to 2.5%. The resulting stabilized compositions of the present invention can optionally also contain from about 0.01 to about 5%, preferably about 0.025 to about 2%, and especially from about 0.1 to about 1% by weight of various conventional additives, such as the materials listed below or their mixtures. Other compositions of special interest include those which additionally contain a UV absorbent selected from the group consisting of the benzophenones, benzotriazoles, cyanoacrylic acid derivatives, hydroxyaryl-triazines, organic nickel compounds and oxanilides. Preferred UV absorbers are selected from the group consisting of 2- [2-hydroxy-3,5-di- (, a-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- [2-hydroxy-3- (a, a -dimethylbenzyl) -5-octylphenyl] -2H-benzotriazole, 2- (2-hydroxy-3,5-di-tert-amylphenyl) -2H-benzotriazole, 2- [2-hydroxy-3-tert-butyl-5- (omega-hydroxy-octa (ethylene-oxy) carboni1) ethylphenyl] -2H-benzotriazole, 2- [2-hydroxy-3-tert-butyl-5- (2-octyloxycarbonylethyl) phenyl] -2H-benzotriazole, 4.4 1-dioctyloxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butyloxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butyloxanilide, 2-ethoxy-2'-ethyloxanilide, , 6-bis (2,4-dimethylphenyl) -4- (2-hydroxy-4-octyloxyphenyl-s-triazine, 2,6-bis (2,4-dimethylphenyl) -4- (2,4-dihydroxyphenyl) - s-triazine, 2,4-bis (2,4-dihydroxyphenyl) -6- (4-chlorophenyl) -s-triazine, 2,6-bis (2,4-dimethylphenyl) -4- [2-hydroxy-4] - (2-hydroxy-3-dodecyloxypropan-oxy) phenyl] -s-triazine and 2,2'-dihydroxy-4,4'-dimethoxy-benzophenone Additional compositions of interest include those containing n additionally an effective stabilizing amount of a phenolic antioxidant; those which additionally contain a hindered amine derivative; or which additionally contain a phosphite or phosphonite stabilizer. Compositions of special interest also include those where the organic material ßß a high solids enamel used for an industrial finish; it is used as a coil coating; It is used as a penetrating wood finish or used as a film-forming wood finish. When the present compounds also contain a reactive functional group, the compounds can be chemically bonded either by condensation or addition reaction of free radicals to the polymeric substrate. This provides a non-migratable, non-sublimable, UV absorbing stabilizer. These reactive functional groups include hydroxy, amino, amido, carboxyl and ethylenically unsaturated portions. The various organic materials useful in the present invention are described in detail later in this application as well as the various co-additives whose concomitant use with the present compounds is often highly beneficial. The resulting stabilized polymer compositions of the invention can optionally also contain from about 0.01 to about 5%, preferably from about 0.025 to about 2%, and especially from about 0.1 to about 1% by weight of various conventional additives such as materials listed below or their mixtures. 1. AntiQxJdanfres 1.1. Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol 2-tert-butyl-4,6-dimethylphenol 2,6-di-tert-butyl-4-ethylphenol 2,6-di-ter- butyl-4-n-butylphenol 2,6-di-tert-butyl-4-y-butylphenol 2,6-di-cyclopentyl-4-methylphenol 2- (a-methylcyclohexyl) -4,6-dimethylphenol 2, 6 di-octadecyl-4-methylphenol 2,4,6-tri-cyclohexylphenol 2,6-di-tert-butyl-4-methoxymethylphenol 1.2. Alkylated Hydroquinones, for example 2, 6-di-tert-butyl-4-methoxyphenol 2, 5-di-tert-butyl-hydroquinone 2,5-di-tert-amyl-hydroquinone 2,6-diphenyl-4-octadecyloxyphenol 1.3 . Hydroxylated thiodiphenyl ethers. for example, 2,2'-thio-bis- (6-tert-butyl-4-methylphenol) 2,2'-thio-bis- (4-octylphenol) 4,4'-thio-bis- (6-ter- butyl-3-methylphenol) 4,4'-thio-bis- (6-tert-butyl-2-methylphenol) 1.4- Alkylidene-bisphenols. for example, 2,2'-methylene-bis- (6-tert-butyl-4-methylphenol) 2,2'-methylene-bis- (6-tert-butyl-4-ethylphenol) 2,2'-methylene-bis - [4-Methyl-6- (a-methylcyclohexyl) -phenol] 2,2'-methylene-bis- (4-methyl-6-cyclohexylphenol) 2, 2 * -methylene-bis- (6-nonyl-4-methylphenol) 2,2'-methylene-bis- [6- (a -methylbenzyl) -4-nonylphenol] 2,2'-methylene-bis- [6- (, -dimethylbenzyl) -4-nonylphenol] 2,2'-methylene-bis- (4,6-di-tert-butylphenol) 2, 2'-ethylidene-bis- (4,6-di-tert-butylphenol) 2,2'-ethylidene-bis- (6-tert-butyl-4-isobutylphenol) 4, 4'-methylene-bis- ( 2,6-di-tert-butylphenol) 4,4'-methylene-bis- (6-tert-butyl-2-methylphenol) 1,1-bis- (5-tert-butyl-4-hydroxy-2-methylphenyl) ) -butane, 2,6-di- (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-dodesyl ercaptobutane, ethylene glycol bis- [3, 3-bis- (3 '-ter -butyl-4 '-hydroxyphenyl) -butyrate] di- (3-tert-butyl-4-hydroxy-5-methylphenyl) -dicyclopentadiene di- [2- (3'-tert-butyl-2'-hydroxy-5' -methyl-benzyl) -6-tert-butyl-4-ethylphenyl] terephthalate. 1.5. Benzyl Compounds Example 1, 3, 5-tri- (3, 5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene di- (3, 5-di-tert-butyl-4-) hydroxybenzyl) sulfide, isooctyl ester of 3,5-di-tert-butyl-4-hydroxybenzyl mercaptoacetic acid bis- (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithiol terephthalate l, 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 ester of acid 3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid calcium salt of 3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid monoethyl ester 1.6. Acyl inophenols. for example, anuided 4-hydroxy-lauric acid of 4-hydroxy-stearic acid 2, 4-bis-octylmercapto-6- (3,5-tert-butyl-4-hydroxyanilino) -s-triazine octyl-N- ( 3, 5-di-tert-butyl-4-hydroxyphenyl) -carbamate 1.7. Esters of ß-f 3,5-di-tert-butyl-4-hydroxyphenin-propionic acid with monohydric or polyhydric alcohols, for example methanol diethylene glycol octadecanol triethylene glycol 1,6-hexanediol pentaerythritol neopentyl glycol tris-hydroxyethyl isocyanurate thiodiethylene glycol diamine di-hydroxyethyl oxalic acid 1.8. Esters of ß- (5-tert-butyl-4-hydroxy-3-methylphenyl) -propionic acid with monohydric or polyhydric alcohols, for example methanol diethylene glycol octadecanol triethylene glycol 1,6-hexanediol pentaerythritol neopentyl glycol tris-hydroxyethyl isocyanurate thiodiethylene glycol diamide of di-hydroxyethyl oxalic acid 1.9. Amides of ß-f 3,5-di-tert-butyl-4-hydroxyphenyl-propionic acid, for example, N, N'-di- (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -hexamethylenediamine N, N '-di- (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -trimethylenediamine N, N'-di- (3, 5-di-tert-butyl-4-hydroxyphenylpropionyl) -hydrazine 2. UV absorbers and light stabilizers 2.1. 2-f2'-Hydroxyphenyl) -benzotriazoles. for example, the derivatives 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-, 3', 5'-bis- (a, -dimethylbenzyl), 3'-a-cumyl-5'-tert-octyl, 3'-tert-butyl 1- 5'- (2- (omega-hydroxy-octa- (ethyleneoxy) carbonyl-ethyl) -3'-dodecyl-5'-methyl-y3'-tert-butyl-1-5 '- (2-octyloxycarbonyl) ethyl- and 2.2-2-Hydroxy-benzophenones, for example, the derivatives 4-hydroxy-, 4-methoxy-, 4-octoxy, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy, 4.2 ' , 4'-trihydroxy- and 2'-hydroxy-4,4-dimethoxy 2,3-esters of optionally substituted benzoic acids, for example, phenyl salicylate, 4-tert-butylphenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis- (4) -tert-butyl-benzoyl) resorcinol, benzoylresorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid, 2,4-di-tert-butylphenyl ester and hexadecyl ester of 3,5-di-ter- Butyl-4-hydroxybenzoic acid. 2. 4. Acrylates. for example, ethyl ester or isooctyl ester of a-cyano-β, β-diphenylacrylic acid, methyl ester of -carbomethoxy-cinnamic acid, methyl ester or butyl ester of a-cyano-β-methyl-p-methoxy-cinnamic acid, methyl ester of -carbomethoxy-p-methoxy-cinnamic acid, N- (β-carbomethoxy-β-cyanovinyl) -2-methyl-indoline. 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, optionally with additional ligands such as n-butylamine, triethanolamine or N -cyclohexyl-diethanolamine, nickel dibutyldithiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic monoalkyl esters, such as methyl, ethyl or butyl ester, ketoximes nickel complexes such as 2-hydroxy -4-methyl-phenyl undecyl ketoxime, nickel complexes of l-phenyl-4-lauroyl-5-hydroxy-pyrazole, optionally with additional ligands. 2t6- Sterically hindered amines, for example bis- (2, 2,6,6-tetramethylpiperidyl) sebacate, bis- (1,2,2,6,6-pentamethyl-piperidyl) sebacate, bis- (1,2,2 , 6,6-pentan-methyl-piperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzyl malonic acid ester, condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl- 4-hydroxypiperidine and succinic acid, condensation product of N, N '- (2,2,6,6-tetramethylpiperidyl) -hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-s-triazine, ris- (2 , 2,6,6-tetramethylpiperidyl) -nitrile-triacetate, tetrakis- (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butantetracarboxylate, 1,1 '(1,2- ethanediyl) -bis- (3, 3,5, 5-tetramethylpiperazinone). 2.7. Diamides of oxalic acid f for example, 4,4'-di-octyloxy-oxanilide, 2,2'-di-octyloxy-5, 5'-di-tert-butyl-oxanilide, 2,2'-di-dodecyloxy- 5, 5 '-di-tert-butyl-oxanilide, 2-ethoxy-2'-ethyl-oxanilide, N, N * -bis (3-dimethylaminopropyl) -oxalamide, 2-ethoxy-5-tert-butyl-2' ethyloxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide and mixtures of ortho- and para-ethoxy oxanilides as well as o- and p-ethoxy disubstituted. 2.8. Hydroxyphenyl-s-triazines. for example 2,6-bis- (2,4-dimethylphenyl) -4- (2-hydroxy-4-octyloxyphenyl) -s-triazine; 2,6-bis- (2,4-dimethylphenyl) -4- (2,4-dihydroxyphenyl) -s-triazine; 2,4-bis (2,4-dihydroxyphenyl) -6- (4-chlorophenyl) -s-triazine; 2,4-bis [2-hydroxy-4- (2-hydroxyethoxy) phenyl] -6- (4-chlorophenyl) -s-triazine; 2, 4-bis [2-hydroxy-4- (2-hydroxy-4- (2-hydroxyethoxy) phenyl] -6- (2,4-di-ethylphenyl) -s-triazine; 2,4-bis [2- hydroxy-4- (2-hydroxyethoxy) phenyl] -6- (4-bromophenyl) -s-triazine; 2,4-bis [2-hydroxy-4- (2-acetoxyethoxy) phenyl] -6- (4-chlorophenyl) ) -s-triazine, 2, 4-bis (2,4-dihydrosxyphenyl) -6- (2,4-dimethylphenyl) -s-triazine 3. Metal deactivators r eg N, N'- acid diamide diphenyloxalic, N-salicylal-N'-salicyloylhydrazine, N, N'-bis-salicylollhidrazine, N, N'-bis- (3,5-di-tert-butyl-4-hydroxyphenyl-propionyl) -hydrazine, 3-sa1iciloi 1amino -1, 2,4-triazole, bis-benzylidene-oxalic acid dihydrazide. 4. Phosphites and phosphonites. for example, triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tri- (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, di-stearyl pentaerythritol diphosphite, tris- (2,4-di-tert-butylphenyl) phosphite, isodecylpentaerythritol diphosphite, di- (2, 4-di-tert-butyldenyl) pentaerythritol diphosphite, tristearyl-sorbitol triphosphite, tetrakis- (2,4-di-tert-butylphenyl) 4,4'-diphenylenediphosphonite. 5. Peroxide destroying compounds, for example, ß-thiodipropionic acid esters, for example lauryl, stearyl, myristyl or tridecyl steres, mercapto-benzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc dibutyl-dithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis- (ß-dodecyl-mercapto) -propionate. 6. Hydroxylamines, for example N, N-dibenzylhydroxylamine, N, N-diethylhydroxylamine, N, N-dioctylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-ditetradecylhydroxylamine, N, N-dihexadecylhydroxylamine, N, N-dioctadecylhydroxylamine, N hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N, N-dialkylhydroxylamine derived from hydrogenated tallow amine. 7. Nitrones. for example, N-benzyl-alpha-phenyl nitrona, N-ethyl-alpha-methyl nitrone, N-octyl-alpha-heptyl, N-Iauryl-alpha-undecyl nitrone, N-tetradecyl-alpha-tridecyl nitrone, N-hexadecyl -alpha-pentadecyl nitrone, N-octadecyl-alpha-heptadecylnitrona, N-hexadecyl-alpha-heptadecyl nitrone, N-octadecyl-alpha-pentadecyl nitrone, N-heptadecyl-alpha-heptadecyl nitrone, N-octadecyl-alpha-hexadecyl nitrone, Nitrona derived from N, N-dialkylhydroxylamine derived from hydrogenated tallow amine. 8. Polyamide stabilizers. for example copper salts, in combination with the iodides and / or phosphorus compounds and salts of divalent manganese. 9. Basic co-stabilizers, 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 stearate Ca, Zn stearate, Mg stearate, Na ricinoleate and K palmitate, Antimony pyrocatechol or zinc pyrocatechol. 10. Nucleating agents, for example 4-tert-butyl-benzoic acid, adipic acid, diphenylacetic acid. 11. Fillers and reinforcing agents, for example, calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite. Other additives, for example, plasticizers, lubricants, emulsifiers, pigments, optical brighteners, flame retardants, anti-static agents, blowing agents and thiosynthetists such as dilauryl thiodipropionate or distearyl thiodipropionate.

The phenolic antioxidant of particular interest is selected from the group consisting of n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, neopentantetrayl tetrakis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 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-ter- butyl-4-hydroxyhydrocinnamate), 1, 3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 3,6-dioxaoctamethylene bis (3-methyl- 5-tert-butyl-4-hydroxyhydrocinnamate), 2,6-di-tert-butyl-p-cresol, 2,2'-ethylidene-bis (4,6-di-tert-butylphenol), 1,3,5 -tris (2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl) isocyanurate, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5 -tris [2- (3,5-di-tert-butyl-4-hydroxyhydrocinnamoxy) ethyl] isocyanurate, 3,5-di- (3,5-di-tert-butyl-4-hydroxybenzyl) mesitol, hexamethylene bis ( 3, 5-di-tert-butyl-4-hydroxyhydrocinnamate), l- (3,5-di-tert-butyl-4-hydroxyanilino) -3,5-di (octylthio) -s-triazine, N, N'-hexamethylene-bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamamide), calcium bis (ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate), ethylenebis [3,3-di] (3-tert-butyl-4-hydroxyphenyl) butyrate], octyl 3,5-di-tert-butyl-4-hydroxybenzylmercapto-acetate, bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl) hydrazide, and N, N'-bis [2- (3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy) -ethyl] -oxamide. A more preferred phenolic antioxidant is neopentantetrail tetrakis (3,5-di-tert-butyl-4-hydroxyhydrazinamate), n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, 1, 3,5-tri -methyl-2,4,6-tris (3,5-di-tert-butyl 1-4 -hydro-benzyl) benzene, l, 3,5-tris (3,5-di-tert-butyl 1) -4-hydroxy-benzyl) isocyanurate, 2,6-di-tert-butyl-p-cresol or 2,2'-ethylidene-bis (4,6-di-tert-butylphenol). The hindered amine compound of particular interest is selected from the group consisting of bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (1,2,2,6,6-pentamethylpiperidin-4-yl). ) sebacate, di (1, 2, 2, 6, 6-pentamethylpiperidin-4-yl) (3,5-di-tert-butyl-4-hydroxybenzyl) butylmalonate, 4-benzoyl-2, 2,6,6- tetramethyl-piperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triaza-spiro [4.5] decan-2 4 -dione, tris (2,2,6,6-tetramethylpiperidin-4-yl) nitriltriacetate, 1,2-bis (2,2,6,6-tetramethyl-3-oxopiperazin-4-yl) ethane, 2,2 , 4,4-tetramethyl-7-oxa-3, 20-diaza-2l-oxodiespiro [5.1.11.2] henoicosane, polycondensation product of 2,4-dichloro-6-ter-octylamino-s-triazine and 4.4 '-hexamethylenebis (amino-2,2,6,6-tetramethyl-piperidine), polycondensation product of l- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, product of polycondensation of 4,4 'hexamethylenebis- (amino-2,2,6,6-tetramethylpiperidine) and 1,2-d ibromoethane, tetrakis (2,2,6,6-tetramethylpiperidin-4-yl) 1,2,3,4-butantetracarboxylate, tetrakis (1, 2,2,6,6-pentamethylpiperidin-4-yl) 1,2, 3,4-butantetracarboxylate, polycondensation product of 2,4-dichloro-6-morpholin-s-triazine and 4,4'-hexamethylenebis (amino-2,2,6,6-tetramethylpiperidine), N, N ', NM , N »'-tetrakis [(4,6-bis (butyl-1-1, 2,2,6,6-pentamethyl-piperidin-4-yl) -amino-s-triazin-2-yl] -1, 10 -diamin-4, 7-diazadecane, [2,2,6,6-tetramethyl-piperidin-4-i 1 / β, β, β *, β * -tetramethyl-3, 9- (2, 4, 8, 10-tetraoxa-spiro [5.5] -undecan) diethyl] 1,2,3,4-butantetracarboxylate mixed, [1,2,2,6,6-pentamethylpiperidin-4-yl / β, β, β, β * - tetramethyl-3, 9- (2, 4, 8, 10-tetraoxaespir or [5.5] undecan) dieti 1] 1,2,3, 4-butantetracarboxylate mixed, octamethylene bis (2,2,6, 6-tetra- methylpiperidin-4-car oxylate), 4,4'-ethylenebis (2,2,6,6-tetramethylpiperazin-3-one), N-2, 2,6,6-tetramethylpiperidin-4-yl-n-dodecyl succinimide, Nl, 2,2,6,6-pentamethylpiperidin- 4-yl-n-dodecyl succinimide, Nl-acetyl-2, 2,6,6-tetramethylpiperidin-4-yl-n-dodecyl succinimide, l-acetyl-3-dodecyl-7,7,9,9-tetramethyl-3, 8-triazaspiro [4.5] decan-2,4-dione, di- (1-octyloxy-2, 2,6,6-tetramethylpiperidin-4-yl) sebacate, di- (1-cyclohexyloxy-2, 2.6, 6-tetramethylpiperidin-4-yl) succinate, l-octyloxy-2,2,6-tetramethyl-4-hydroxy-piperidine, poly. { [6-tert-octylamino-s-triazin-2,4-diyl] [2- (1-cyclohexyloxy-2, 2,6,6-tetramethylpiperidin-4-yl) imino-hexamethylene [4- (1-cyclohexyloxy) 2, 2, 6, 6-tetramethylpiperidin-4-yl) imino], and 2, 4, 6-tris [N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) -n- Butylaminol-s-triazine. A most preferred hindered amine compound is bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, di (1, 2, 2, 6, 6-pentamethylpiperidin-4-yl) (3, 5-di-tert-butyl-4-hydroxybenzyl) -butylmalonate, polycondensation product of l- (2-hydroxyethyl) -2,2,6, 6-tetramethyl-4-hydroxypiperidine and succinic acid, the polycondensation product of 2,4-dichloro-6-ter-octylamino-s-triazine and 4,4'-hexamethylenebis (amino-2,2,6,6-tetramethyl) -piperidine), N, N ', N ", N" "- tetrakis [(4,6-bis (butyl- (1,2, 2,6,6-pentamethyl-piperidin-4-yl) amino) -s -triazin-2-yl] -1, 10-diamino-4,7-diazadecane, di- (1-octyloxy-2, 2,6,6-tetramethylpiperidin-4-yl) sebacate, di- (1-cyclohexyloxy) 2, 2,6,6-tetramethylpiperidin-4-yl) succinate, l-octyloxy-2,2,6,6-methyl-4-hydroxy-piperidine, poly- { [6-tert-octylamino-s- triazin-2, 4-diyl] [2- (1-hydrohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) imino-hexamethylene- [4- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin- 4-yl) imino], or 2,4,6-tris [N- (1-cyclohexyloxy-2, 2,6,6-tetramethylpiperidin-4-yl) -n-butylamino] -s-triazine. The following examples are intended to illustrate in the present invention. Example 1 1,2-Bis-adduct of l-Oxyl-2,2,6,6-tetramethyl-4-benzoyloxypiperidine and styrene A deoxygenated solution of 10 g of l-oxyl-2,6,6,6-tetramethyl- 4-benzoyloxypiperidine in 120 L of styrene is heated at 100 ° C for 24 hours. The unreacted styrene is then removed under reduced pressure. The title compound is isolated from the residue by chromatography and purified by crystallization from hexane / ethyl acetate to give 5.3 g of adduct product which melts at 175-176 ° C.

Example 2 1,2-Bis-adduct of l-Oxyl-2, 2,6,6-tetramethyl-4-benzoyloxypiperidine and 4-chlorostyrene When the procedure of Example 1 is followed, an equivalent amount of 4-chlorostyrene is replaced by styrene, the title compound is obtained after purification by chromatography as a white solid that melts at 76-78 ° C. Example 3 1,2-Bis-adduct of l-Oxyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and Styrene When the procedure of Example 1 is followed, an equivalent amount of l-oxyl-2,2, 6,6-tetramethyl-4-hydroxy-piperidine is replaced by l-oxyl-2,2,6,6-tetramethyl-4-benzoyloxypiperidine, the title compound is obtained after purification by chromatography as a white solid that melts at 104 ° C. -108 ° C. Example 4 1,2-Bis-adduct of l-Oxyl-2,2,6,6-tetra-methylpiperidine and styrene When the procedure of Example 1 is followed, an equivalent amount of l-oxyl-2,2,6, 6-tetramethylipiperidine is replaced by l-oxyl-2, 2,6,6-tetramethyl-4-benzoyloxypiperidine, the title compound is obtained after purification by chromatography as a colorless oil. Example 5 1,2-Bis-adduct of l-Oxyl-2, 2,6,6-tetramethyl-4-oxopiperidine and Styrene When the procedure of Example 1 is followed, an equivalent amount of l-oxyl-2, 2, 6,6-tetramethyl-4-oxopiperidine is replaced by l-oxyl-2,2,6,6-tetramethyl-4-benzoyloxy-piperidine, the title compound is obtained after purification by chromatography as a colorless waxy solid. Example 6 1, 2-Bis-adduct of 2-Oxyl-1, 3,3-tetra-methyliso-indoline and Styrene When the procedure of Example 1 is followed, an equivalent amount of 2-oxyl-1, 1, 3,3-tetramethylisoindoline is replaced by l-oxyl-2, 2,6,6-tetramethyl-4-benzoyloxypiperidine, the title compound is obtained after purification by chromatography as a white solid that melts at 138-139 ° C. Example 7 1,2-Bis-adduct of l-Oxyl-2,2,6,6-tetramethyl-4-benzoyloxypiperidine and Butyl Acrylate A deoxygenated solution of 30 g of l-oxyl-2,6,6,6-tetramethyl -4-benzoyloxypiperidine in 50 L of butyl acrylate is heated at 130 ° C for 22 hours. The unreacted butyl acrylate is then removed under reduced pressure. The title compound is isolated from the residue by chromatography to give 9.0 g of adduct product as a colorless oil. Example 8 1,2-Bis-adduct of l-Oxyl-2, 2,6,6-tetramethyl-4-hydroxypiperidine and Butyl Acrylate When the procedure of Example 7 is followed, an equivalent amount of l-oxyl-2,2 , 6,6-tetramethyl-4-hydroxy-piperidine is replaced by l-oxyl-2,2,6,6-tetramethyl-4-benzoyloxypiperidine, the title compound is obtained after purification by chromatography as a white solid which melts 115-117 ° C. EXAMPLES 9-15 Commercial grain styrene is released from the storage stabilizer ter-butylcatechol when washed with IN aqueous sodium hydroxide followed by distillation under reduced pressure. A 300-mL three-necked flask equipped with a thermometer, condenser, rubber stopper and magnetic stir bar is charged with 100 g of styrene (purified as described above) without inhibitor (Example 9) or loaded in separate experiments are 200 mg of various test compounds of this invention in Examples 10-15. An oxygen-free atmosphere is established by five consecutive evacuations and filled with nitrogen, followed by spraying the styrene solution with pure nitrogen for 15 minutes. The vessel is immersed in a thermostatically controlled oil bath and mechanically stirred at 120 ° C. Small aliquots are periodically removed and analyzed for polymer content. The amount of polystyrene formed is then determined by refractive index measurements, calibrated with authentic polystyrene in styrene solutions of known concentrations.

The results are illustrated in Table 1 below. Table 1 Percent of polymer formed after heating Compound Example 30 min. 60 min. 90 min. Example N? T 9 none 3.7 8.4 - 10 1 0.0 0.5 2.8 11 2 0.0 0.8 3.8 12 3 0.0 0.2 1.6 13 4 0.0 0.0 1.0 14 5 0.1 0.1 1.9 15 6 0.0 0.2 1.3 It is clear from these data that each of the compounds present adducts of Examples 10-15 provides much superior inhibition efficiency, to avoid or mitigate the premature polymerization of the styrene monomer, as compared to the non-inhibited styrene sample of Example 9. Example 16 1,2-Bis-1-xyl-2, 2,6,6-tetramethyl adduct -4- Acetamidopiperidine and Styrene When the procedure of Example 1 is followed, an equivalent amount of l-oxyl-2,2,6,6-tetramethyl-4-acetamido piperidine is replaced by l-oxyl-2,2,6 , 6-tetramethyl-4-benzoyloxypiperidine, the title compound is obtained after purification by chromatography. Example 17 Light Stabilization of ABS / Polycarbonate Mixtures A 50/50 mixture of ABS (containing a hindered amine stabilizing compound of the formula I) and polycarbonate is prepared by formulating the mixed resin pellets in a mini-Brabender extruder. Injection-molded Izod bars of 3.2 mm (125 mils) are then prepared for light stability evaluation, under Xenon Arc Weathering exposure tests with Xenon Automotive interior arc standard indoor dew-point exposure and exposure. The ABS / Polycarbonate mixture containing the present stabilizing compound of formula I shows improved light stabilization compared to control polymer which has no hindered amine compound present. Example 18 Stabilization of Polypropylene Fibers When a polypropylene fiber contains a stabilizing compound of formula I, it exhibits superior light and thermal stability compared to an unstabilized polypropylene fiber.

Claims (19)

1. CLAIMS 1. A compound of formula I or II wherein R x and R 2 independently are alkyl of 1 to 4 carbon atoms, or R x and R 2 together are pentamethylene, preferably R x and R a, each are methyl; E is aryl with 6 to 10 carbon atoms, or the aryl substituted by alkyl with 1 to 4 carbon atoms or by halogen or E is -COOH or -COORs, where e is alkyl with 1 to 18 carbon atoms or hydroxyalkyl with 2 to 8 carbon atoms, or E is -CN, R3, R * and RB, are independently alkyl with 1 to 4 carbon atoms, and T is a group required to complete a ring of 5-, 6- or 7- members or a 1,1,3,3-tetramethylisoindoline portion, the group T may also be unsubstituted or substituted by hydroxyl, by oxo, by acetamido, by -0R8 wherein R8 is alkyl with 1 to 18 carbon atoms, or by -0-C0-R9, wherein R9 is alkyl having 1 to 17 carbon atoms or phenyl, with the proviso that the compound of formula I is not i-phenyl-1,2-bis (2.2, 6,6-tetramethylpiperidin-1-yloxy) ethane or 1-phenyl-1,2-bis (1,1,3,3-tetramethyl-isoindolin-2-yloxy) ethane.
2. 2. A compound according to claim 1, characterized in that R-, and R2 each are methyl.
3. 3. A compound according to claim 1, characterized in that E is -COOH, -CN or -COORβ, where e, is alkyl with 1 to 4 carbon atoms.
4. 4. A compound according to claim 3, characterized in that Re is butyl.
5. 5. A compound according to claim 1, characterized in that each of R3, R * and Rs is methyl.
6. 6. A compound according to claim 1, characterized in that T is a group required to complete a 5-, 6- or 7- membered ring or a 1,1,3,3-tetraethylisoindoline moiety, wherein the group T is unsubstituted or substituted by hydroxyl, oxo, acetamido or by -0-CO-R ,, where R is alkyl having 1 to 11 carbon atoms or phenyl.
7. 7. A compound according to claim 1, characterized in that it is: (a) 1,2-bis-adduct of l-oxyl-2, 2,6,6-tetramethyl-4-benzoyloxy-piperidine and styrene; (b) 1,2-bis-adduct of l-oxyl-2,2,6,6-tetramethyl-4-benzoyloxy-piperidine and 4-chlorostyrene; (c) 1,2-bis-adduct of 1-oxyl-2,2,6,6-tetramethyl-4-hydroxy-piperidine and styrene; (d) 1,2-bis-adduct of l-oxyl-2,2,6,6-tetramethyl-4-oxopiperidine and styrene; (e) 1,2-bis-adduct of l-oxyl-2,2,6,6-tetramethyl-4-benzoyloxy-piperidine and butyl acrylate; (f) 1,2-bis-adduct of 1-oxyl-2,2,6,6-tetramethyl-4-hydroxy-piperidine and butyl acrylate, or (g) 1,2-bis-adduct of l-oxyl- 2, 2, 6, 6-tetramethyl-4-acetamido-piperidine and styrene.
8. 8. A stabilized composition against premature polymerization comprising a. an ethylenically unsaturated monomer, and b. an effective stabilizing amount of a compound of formula I or II according to claim 1.
9. 9. A composition according to claim 8, characterized in that the ethylenically unsaturated monomer is selected from the group consisting of vinyl aromatic hydrocarbons; the dienes; halogenated monomers; unsaturated acids; the unsaturated esters; the unsaturated nitriles; the unsaturated ethers; and vinyl monomers and miscellaneous which are vinyl pyridines, diethyl vinylphosphonate and sodium styrene sulfonate.
10. 10. A composition according to claim 9, characterized in that the monomer is α-methylstyrene, divinylbenzene, butadiene, isoprene, vinyl chloride, chloroprene, vinylidene chloride, vinylidene fluoride, vinyl fluoride, acrylic acid, methacrylic acid, crotonic acid , butyl acrylate, methyl methacrylate, ethyl acrylate, methyl acrylate, acrylonitrile, methacrylonitrile or methyl vinyl ether.
11. 11. A composition according to claim 10, characterized in that the monomer is acrylic acid, methacrylic acid, butyl acrylate, ethyl acrylate or acrylonitrile.
12. 12. A composition according to claim 8, characterized in that the amount of effective stabilizer of component (b) is from 1 to 10,000 ppm by weight based on the monomer weight of component (a).
13. 13. A stabilized composition characterized in that it comprises: (a) an organic material subject to the harmful effects of heat, oxygen or actinic radiation, and (b) an effective stabilizing amount of a compound of formula I or II according to claim 1
14. 14. A composition according to the claim 13, characterized in that component (a) is a polymer.
15. 15. A composition according to the claim 14, characterized in that the polymer is a polyolefin.
16. 16. A composition according to claim 15, characterized in that the polyolefin is polypropylene or polyethylene.
17. 17. A composition according to claim 13, characterized in that the component (a) is a polymer, copolymer or mixture of polymers containing at least one polymer or a polymer component with significant ethylenic unsaturation.
18. 18. A composition according to claim 17, characterized in that the polymers of component (a) are polymers selected from the group consisting of ABS, HIPS, SBR emulsion, PP / EPDM, PP / NBR, PP / NR, ABS / PC , ABS / nylon, ABS / PVC, ABS / polyester, ABS / SMA, ABS / polysulfone, ASA / PC, acetal / elastomer, polyester / elastomer, nylon / elastomer, PPO / NR, EPDM / NBR and EPDM / olefin.
19. 19. Use of bis-adducts of formulas I and II according to claim 1, as effective inhibitors against the premature polymerization of ethylenically unsaturated monomers.