US3847930A - Hydroxyaryl-tetramenthyl-dehydropiperidines - Google Patents

Hydroxyaryl-tetramenthyl-dehydropiperidines Download PDF

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US3847930A
US3847930A US00310181A US31018172A US3847930A US 3847930 A US3847930 A US 3847930A US 00310181 A US00310181 A US 00310181A US 31018172 A US31018172 A US 31018172A US 3847930 A US3847930 A US 3847930A
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butyl
parts
dehydro
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tetramethylpiperidine
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D Randell
M Smith
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Novartis Corp
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Ciba Geigy Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/92—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with a hetero atom directly attached to the ring nitrogen atom
    • C07D211/94—Oxygen atom, e.g. piperidine N-oxide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/02—Preparation by ring-closure or hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D211/08—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms
    • C07D211/18—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D211/20—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms with hydrocarbon radicals, substituted by singly bound oxygen or sulphur atoms
    • C07D211/22—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms with hydrocarbon radicals, substituted by singly bound oxygen or sulphur atoms by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/68—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
    • C07D211/70—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3435—Piperidines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
    • C09K15/30—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing heterocyclic ring with at least one nitrogen atom as ring member

Definitions

  • the present invention relates to new piperidine derivatives and in particular to new 4-(4'-hydroxyaryl)-3,4-dehydro-2,2,6,6-tetramethyl piperidines, which are useful stabilisers for polymers.
  • R R R and R in formula II being the same or different and each being hydrogen, a straightor branched chain alkyl residue having from 1 to 9, preferably 1 to 4 carbon atoms, a cycloalkyl residue having from 5 to 14, preferably 6 to 8 carbon atoms, an aralkyl residue having from 7 to 14, preferably 7 to 9 carbon atoms, or an aryl or alkaryl residue each having from 6 to 14, preferably 6 to 10 carbon atoms
  • Y is hydrogen, 0, a straightor branched alkyl residue having from 1 to 12 carbon atoms, an alkenyl or alkynyl residue having from 3 to 12 carbon atoms or an aralkyl residue having from 7 to 12 carbon atoms
  • Z is hydrogen, an alkyl or substituted alkyl residue having from 1 to carbon atoms, an alkenyl or alkynyl residue having from 2 to 20 carbon atoms, a cycloaliphatic residue having from 5 to 12 carbon atoms
  • each of the substituents R R R and R may be other than hydrogen, for instance, they may each be methyl, it is preferred in general, that at least two of these substituents are hydrogen.
  • R and/or R are non-bulky substituents for instance a hydrogen atom, methyl or ethyl groups.
  • the other substituent is preferably hydrogen.
  • Y may also be a methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, n-hexyl, noctyl, n-dodecyl, allyl, a-methallyl, l0-undecenyl, benzyl, a-methylbenzyl, p-methylbenzyl or an a-naphthylmethyl residue.
  • particularly preferred substituents Y are 0 and straightor branched alkyl groups having from 1 to 4 carbon atoms, the most preferred substituents Y being 0, hydrogen and methyl residues.
  • alkyl or substituted alkyl residues Z are methyl, ethyl, n-propyl, n-butyl, sec-butyl, t-butyl, nhexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl eicosyl, fi-hydroxyethyl and fi-cyanoethyl residues.
  • Preferred alkyl and substituted alkyl groups Z are those having from 1 to 12 carbon atoms.
  • Z is an alkenyl residue having from 3 to 20 carbon atoms
  • examples of such residues are allyl, met- 3,4-Dehydro-4- 4'-n-butyloxyphenyl)-1-butyl-2,2,6,6-
  • the compounds of formula I in which Y is other than 0 are isolated from the reaction mixture conveniently as their acid salts, and the free compounds may be liberated from the salts by treating the salts with the stoichiometric proportion of a base such as sodium hydroxide or sodium carbonate required to liberate the free compound of formula I. If desired, the compound of formula I may then be further purified by conventional techniques.
  • the present invention also provides a process in which a compound of formula I, wherein X has the formula II or III and Z is hydrogen, is produced comprising reacting the corresponding 2,2,6,6-tet:ramethylpiperidine-4-one or an inorganic or organic acid salt thereof with either a-naphthol or a phenolic compound having the formula:
  • the reaction is effected in the presence of an acidic catalyst such as sulphuric acid, p-toluene sulphonic acid or, preferably, hydrogen chloride, although other catalysts such as sulphur compounds, for instance mercaptans, may also be present, and in the presence of a solvent inert under the reaction conditions, for instance methanol, ethanol or 2-methoxy-ethanol.
  • an acidic catalyst such as sulphuric acid, p-toluene sulphonic acid or, preferably, hydrogen chloride
  • sulphur compounds for instance mercaptans
  • the reaction is conveniently carried out at any temperature within the range of from 0 C. to the reflux temperature of the reaction mixture, or at higher temperature under pressure.
  • the reactants may be employed in molar ratios of from 5:1 to 1:5 preferably from 3:1 to 1:3, especially in molar ratios of approximately 1:1.
  • Compounds of formula I in which Z is the group COZ where Z is as hereinbefore defined may be conveniently prepared by reacting a compound of formula I in which Z is hydrogen with an esterification agent such as an acid, an acid chloride, an acid ester or an acid anhydride or an agent capable of forming a urethane grouping with the compound of formula I, such as an alkyl, alkenyl, aralkyl or aryl isocyanate.
  • the reaction is preferably conducted in a solvent inert under the reaction conditions such as benzene, toluene or xylene.
  • Compounds of formula I in which Y is as hereinbefore defined and Z is not hydrogen may be conveniently produced by reacting compounds of formula I in which Z is hydrogen with an alkali metal such as sodium or potassium followed by reaction with an alkylating, alkenylating, alkynylating or aralkylating agent such as an alkyl, alkenyl, alkynyl or aralkyl halide.
  • the reaction is preferably conducted in a solvent inert under the reaction conditions such as benzene, toluene or xylene.
  • Examples of suitable compounds of formula V are phenol o-cresol, 2,6-xylenol, 2,3-xylenol, 2,5-xylenol, 3,5-xylenol, 2,3,6-trimethylphenol, 2,3,5,6-tetr'amethyl phenol, o-ethylphenol, m-ethylphenol, 2-ethyl-3-methylphenol, 2:6-diethyl phenol, o-n-propylphenol, 2:6-di-npropylphenol, o-isopropylphenol, m-isopropyl phenol, 2,6-di-isopropyl phenol, o-sec.
  • butyl phenol 2,6-di-sec. butyl phenol, o-t-butyl phenol, m-t-butyl phenol, 2-tbutyl-S-methyl phenol, 2-t-butyl-6-methyl phenol, 3-tbutyl-S-methyl phenol, 2,5-di-t-butyl phenol, 2,6-dit-butyl phenol, o-sec. amyl phenol, 2,6-di-sec.
  • amyl phenol o-(1,1-dimethylpropyl) phenol, 2,6-di-(1,1- dimethylpropyl) phenol, o-(1,1-dimethylbutyl) phenol, 2,6-di-(1,1-dimethylbutyl) phenol, o-2-octyl phenol, o-cyclohexyl phenol, o-(l-methyloyclohexyl) phenol, o-benzyl phenol, o-(u,d-dimethylbenzyl phenol) and o-phenyl phenol.
  • the present invention still further provides a composi tion comprising an organic material and a stabilising amount of a compound having the Formula I as hereinbefore defined.
  • the stabilisers of the invention provide effective light and/or heat stabilisation, especially for lowand high-density polyethylene and polypropylene and polystyrene as well as polymers of butene-l, pentene-l, 3-methylbutene-1, hexene-l, 4-methylpentene-1, 4-methylhexene-1 and 4,4-dimethyl-pentene-1, and also coand ter-polymers of olefines, particularly of ethylene or propylene.
  • organic materials susceptible to degradation by the effects of light and the properties of which are improved by the incorporation therein of a compound of Formula I include natural and synthetic polymeric materials, for instance natural and synthetic rubbers, the latter including, for example, homo-, coand ter-polyrners of acrylonitrile, butadiene and styrene.
  • Specific synthetic polymers include polyvinyl chloride, polyvinylidene chloride and vinyl chloride co-polymers, polyvinyl acetate as well as condensation polymers derived from ether, ester (derived from carboxylic sulphonic or carbonic acids), amide or urethane groupings. These polymers can, for instance, form the basis of surface coating media such as paints and lacquers having an oil or resin, for instance an alkyd or polyamide resin, base.
  • the amount of the compound of formula I which is incorporated into the organic material in order to achieve maximal protection against degradation by light varies according to the properties of the organic material treated and according to the severity of the light radiation and to the length of exposure. However, for most purposes it is sufiicient to use an amount of the compound of formula I within the range of from 0.01% to by weight, more preferably within the range of from 0.1% to 2% by weight based on the weight of untreated organic material.
  • the compounds of formula I may be incorporated into the polymeric material by any of the known techniques for compounding additives with a polymer.
  • the compound of formula I and the polymer may be compounded in an internal mixer.
  • the compound of formula I may be added as a solution or slurry in a suitable solvent or dispersant, for instance an inert organic solvent such as methanol, ethanol or acetone to powdered polymer and the whole mixed intimately in a mixer, and the solvent subsequently removed.
  • the compound of formula I may be added to the polymer during the preparation of the latter, for instance at the latex stage of polymer production, to provide pre-stabilised polymer material.
  • the composition of the invention may contain one or more further additives, especially those used in polymer formulations, such as antioxidants of the phenol or amine type, U.V. absorbers and light protectants, phosphite stabilisers, peroxide decomposers, polyamide stabilisers, basic co-stabilisers, polyvinyl chloride stabilisers, nucleation agents, plasticizers, lubricants, emulsifiers, anti-static agents, fiame-protectants, pigments, carbon black, asbestos, glass fibers, kaolin and talc.
  • further additives especially those used in polymer formulations, such as antioxidants of the phenol or amine type, U.V. absorbers and light protectants, phosphite stabilisers, peroxide decomposers, polyamide stabilisers, basic co-stabilisers, polyvinyl chloride stabilisers, nucleation agents, plasticizers, lubricants, emulsifiers, anti-static agents, fiame-protectants, pigment
  • the present invention therefore includes binary, tertiary and multi-cornponent compositions containing the stabiliser of formula I together with one or more functional additives for polymers.
  • Suitable antioxidants are those of the bindered phenol type such as those selected from the following groups:
  • Illustrative examples of the compounds shown above are di-n-octadecyl a-(3,S-di-t-buty1-4-hydroxybenzyl) malonate di-n-octadecyl a-(3 t butyl-4-hydroxy-5-methyl-benzyl) malonate which is disclosed in the Netherlands Pat.
  • Phenolic compounds having the general formula Q-R are 2,6-di-t-butyl-p-cresol 2-methyl-4,6-di-t-butylpheno1 and the like. 2,6-di-Octadecyl-p-cresol (3) Phenolic compounds having the formula Illustrative examples of the compounds shown are: 2,2-methylene-bis (6-t-butyl-4-methylphenol) 2,2'-methylene-bis(6-t butyl-4-ethylphenol) 4,4'-butylidene-bis(2,6-di-t-butylphenol) 4,4'-(2-buty1idene)-bis(2-t-butyl-5-methylphenol) 2,2'-methylene-bis 6- (2-t-methylcyclohexyl) -4-methylphenol 2,2'-methylene-bis(3-t-butyl-5-ethylphenol) 4,4'-methylene-bis (3 ,
  • Phenolic compounds having the formula Illustrative examples of such compounds are 2,S-di-t-butylhydroquinone 2,6-di-t-butylhydroquinone 2,5-di-t-butyl-4-hydroxyanisole (5) Phenolic compounds having the formula QSQ.
  • Such compounds are 4,4'-thiobis-(Z-t-butyl-S-methylphenol) 4,4-thiobis-(2-t-butyl-6-methylphenol) 2,2'-thiobis-(6-t-butyl-4-methylphenol) 4,4'-thiobis-(2-methyl-5-t-butylphenol) (6)
  • Phenolic compounds having the formula Illustrative examples of such compounds are octadecyl-(3,S-dimethyl-4-hydroxybenzylthio)acetate dodecyl- (3,5 -di-t-butyl-4-hydroxybenzylthio -propionate (7)
  • T is hydrogen R or Q as defined above.
  • Illustrative examples of such compounds are 1,1,3-tris(3,5-dimethyl-4-hydroxyphenyl)-propane 1, 1,3-tris 5-t-butyl-4-hydroxy-2-methylphenyl) -butane 1,1,5,5-tetrakis-(3'-t-buty1-4'-hydroxy-6-methylphenyl)- n-pentane (8)
  • Phenolic compounds having the formula (5H; CH2 B 1 Q 2 CH3 B 7 l C 3 H213 wherein B B and B are hydrogen, methyl or Q, provided that when B and B are Q then B is hydrogen or methyl and when B is Q then B and B are hydrogen or methyl.
  • Illustrative examples of such compounds are Di-n-octadecyl 3,5-di-t-butyl-4-hydroxybenzylphosph0nate Di-n-octadecyl 3-t-butyl-4-hydroxy-5-methylbenzylphosphonate Di-n-octadecyl 1-(3,S-di-t-butyl-4-hydroxyphenyl)- ethanephosphonate Di-n-tetradecyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate Di-n-hexadecyl 3,5 -di-t-butyl-4-hydroxybenzylphosphonate Di-n-docosyl-3,5-di-t-butyl-4-hydroxybenzylphosph0nate Di-n-octadecyl 3,5-di-t-butyl-4-hydroxybenzyl
  • the preferred antioxidants consist of the hindered phenols in groups 1, 8, 9, 10, 11, 12 and 13 as mentioned above.
  • the most preferred hindered phenols are those of groups 1, 9, 11, 12 and 13.
  • antioxidants are those of the aminoaryl series for instance aniline and naphthylamine derivatives as well as their heterocyclic derivatives such as:
  • phenyl-l-naphthylamine phenyl-Z-naphthylamine N,N-diphenyl-p-phenyldiamine N,N'-di-sec.butyl-p-phenylenediamine 6Ethoxy-2,2,4-trimethyl-1,Z-dihydroquinoline 6-Dodecyl-2,2,4-trimethyl-1,2-dihydroquinoline Monoand di-octyliminodibenzyl and polymerised 2,2,4-triniethyl-1,2-dihydroquinoline.
  • Ultraviolet absorbers and light protectants include (a) 2-(2'-hydroxyphenyl)benzotriazoles, for instance methyl; 3,5-di-t-butyl; 5'-t-butyl; 5-chloro-3,5-di-t-bu tyl; 5-chloro-3'-t-butyl-5'-methyl; 3'-sec.butyl-5-tert.butyl; 3'-[a-methylbenzyl]-5'-methyl-; 3[a-methylbenzyl)-5'-methyl-5-chloro-; 4'-octoxy-; 3',5'-dit-arnyl; 3'- methyl-5'-carbomethoxyethyl; 5 chloro-3',5'-di-t-amyl derivatives.
  • 2-(2'-hydroxyphenyl)benzotriazoles for instance methyl; 3,5-di-t-butyl; 5'-t-butyl; 5-chloro-3,
  • Aryl esters from optionally substituted benzoic acids such as phenylsalicylate, octylphenylsalicylate, dibenzoyl resorcinol, bis-(4-tert.butylbenzoyl) resorcinol, benzoylresorcinol and 3,S-di-tert.butyl-4-hydroxy-benzoic acid-2,4-di-tert.butyl phenyl ester and -octadecyl ester and -2-methyl-4, 6-di-tert.butyl phenyl ester.
  • benzoic acids such as phenylsalicylate, octylphenylsalicylate, dibenzoyl resorcinol, bis-(4-tert.butylbenzoyl) resorcinol, benzoylresorcinol and 3,S-di-tert.butyl-4-hydroxy-benzoic
  • (f) Acrylates, for instance a-Cyan0-fl,[3-diphenylacrylic acid ethylor iso-octyl ester a-carbomethoxy-cinnamic acid methylor butyl ester and N-(fi-carbomethoxy-vinyl)-2-methyl indoline.
  • Nickel compounds such as nickel complexes of 2,2-
  • thiobis-(4-tert. octylphenol) for instance the 1:1 and 1:2 complexes, optionally having other ligands such as n-butylamine, triethanolamine or N-cyclohexyl-diethanolamine; nickel complexes of bis-(4-tert.
  • octylphenyl) sulphone such as the 2:1 complex, optionally having other ligands such as Z-ethylcaproic acid; nickel dibutyl dithiocarbamates; nickel salts of 4-hydroxy-3,5- di-tert.butylbenzylphosphonic acid mono-alkyl esters such as the methyl-, ethylor butyl esters; the nickel complex of 2-hydroxy-4-rnethyl-phenyl-undecylketonoxime; and nickel-3,5-di-tert.buty1-4-hydroxy benzoate, and
  • Phosphite stabilisers include triphenyl phosphite, diphenylalkyl phosphites, phenyl dialkyl phosphites, trinonylphenyl phosphite, trilauryl phosphite, trioctadecylphosphite, 3,9'-di-isodecyloxy-2,4,8,IO-tetraoxo 3,9 diphosphaspiro-(5,5)-undecane and tri-(4-hydroXy-3,5-ditert.butylphenyl phosphite.
  • Peroxide-decomposing compounds for polyolefin include esters of B-thiodipropionic acids, for instance the 1auryl-, stearyl-, myristylor tridecyl esters, salts of mercaptobenzimidazoles such as the zinc salt and diphenylthiourea.
  • Suitable polyamide stabilisers include copper salts in combination with iodides and/ or further phosphorus compounds and salts of bivalent manganese.
  • Basic co-stabilisers are, for example, polyvinylpyrrolidone, melamine, benzoguanamine, tn'allyl cyanurate, dicyandiamide, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali and alkaline earth salts of higher saturated or unsaturated fatty acids such as calcium stearate.
  • Polyvinyl chloride stabilisers include orgauotin compounds, organo lead compounds and Ba/Cd salts of fatty acids.
  • nucleation agents examples include 4-tert.butyl benzoic acid, adipic acid and diphenylacetic acid.
  • any further additive is advantageously employed in a proportion within 13 the range of from 0.01% to by Weight, based on the weight of untreated polymeric material.
  • the compounds of formula I provide very effective stabiliser packages in polyolefine formulations.
  • ttitlamethylpipefidine tetramethylpiperidine hydrochloride 5.00 parts of triacetonamine hydrochloride and 4.90 parts of phenol were dissolved in 80 parts ethanol by warming. The solution was heated to reflux and dry hydrogen chloride gas bubbled through for 48 hours. After allowing the mixture to stand for 12 hours at 20 C., the solid precipitate was removed by filtration and washed with 20 parts of chilled ethanol. The solid was dissolved in 200 parts of water by warming and this solution made alkaline by the addition of 10% aqueous sodium carbonate solution.
  • the solution was extracted with ether 15 three times and the aqueous phase discarded.
  • the ethereal phase was dried and evaporated to dryness to yield a low melting point residue.
  • the residue was dissolved in hot ethanol and treated with aqueous hydrochloric acid until the hydrochloride started to crystallise. After allowing the solution to cool to room temperature the salt was separated by filtration and recrysallised again from eth-.
  • EXAMPLE 15 3,4Dehydro-4-(3,5-dimethyl-4'-hydroxyphenyl) 2,2,6,G-tetramethylpiperidine-l-oxyl 10.0 Parts by weight of 3,4-dehydro-4-(3',5'-dimethyl- 4'-hydroxyphenyl) 2,2,6,6 tetramethylpiperidine and 0.8 parts by weight of benzyl trimethylammonium chloride were dissolved in parts by weight of sodium tungstate in a little water. Approximately 10 parts by weight of water was added, care being taken to maintain solution. 13 Parts by weight of 30% hydrogen peroxide was dis solved in 16 parts by weight of methanol and this solution added dropwise with stirring to the amine solution.
  • EXAMPLE 18 4-(4-Acetyloxy-3',5'-dimethylphenyl)-3,4-dehydro- 2,2,6,6-tetramethylpiperidine 20 Parts of 4-(3',5'-dimethyl-4-hydroxyphenyl)-3,4-dehydro-2,2,6,6-tetramethy1piperidine were converted to the 17 hydrochloride salt and treated with acetic anhydride as in Example 17.
  • EXAMPLE 20 4-(3',5'-Dimethy1-4'-octanoyloxyphenyl)-3,4dehydro- 2,2,6,6-tetramethylpiperidine 5 Parts of 4-(3,5'-dimethyl-4-hydroxyphenyl)-3,4-dehydro-2,2,6,6-tetramethylpiperidine were dissolved in 250 parts of xylene and heated to reflux whilst stirred. 1.6 parts of octanoyl chloride dissolved in a small amount of xylene were added to the refluxing solution dropwise. The solution was heated at reflux overnight, allowed to cool and filtered.
  • EXAMPLE 21 4- (4'-Benzoyloxyphenyl) -3,4-dehydro-2,2,6,6- tetramethylpiperidine 5 Parts of 4(4'-hydroxyphenyl)-3,4-dehydro-2,2,6,6- tetramethylpiperidine were dissolved in 70 parts of aqueous sodium hydroxide and shaken vigorously with 10 parts of benzoyl chloride. The alkalinity of the solution was maintained by further additions of sodium hydroxide solution. The precipitate was separated and dissolved in hot water. This solution was basified by the addition of aqueous sodium carbonate solution. The precipitate was separated, dissolved in ether and the ethereal solution washed with 10% sodium hydroxide solution and water. The organic phase was dried over magnesium sulphate and evaporated under reduced pressure. The residue was crystallised from a methanol-water mixture to yield 1.1 parts of the desired product melting at 9193 C. and having the following elemental analysis.
  • EXAMPLE 22 4[4(3,5"-di-t-butyl-4"-hydroxybenzoyloxy)phenyl]- 3,4-dehydro-2,2,6,6-tetramethylpiperidine 3.4 Parts of 4-(4'-hydroxyphenyl)3,4-dehydro-2,2,6,6- tetramethylpiperidine were intimately mixed with 8 parts of 3,5-di-t-butyl-4-hydroxybenzoyl chloride. The mixture was heated to 150 and stirred vigorously. Heating was then continued at 120 for 30 minutes. The mixture was cooled, treated with ether and separated. The solid filter was dissolved in a methanol-water mixture and treated with an aqueous sodium carbonate solution.
  • EXAMPLES 24 TO 26 38 Parts of polypropylene were homogenised with 0.76 part of n-octadecyl-fi-(4'-hydroxy-3', '-t-butylphenyl)pripionate in a kneading machine over a period of 3 minutes at 200 C. 0.19 parts of the product of one of Examples 4, 6 and 12 was then added and homogenisation continued for another 7 minutes.
  • This composition was compression moulded with films of 0.1 mm. thickness at 260 C. for 6 minutes, and the films so obtained were then quenched in cold water.
  • a section measuring 44 mm. by mm. was separated from the 0.1 mm. annealed foil and exposed to light irridation in a fademeter device consisting of a circu lar bank of 28 alternate sunlight and blacklight lamps.
  • the sunlight lamps were 2 feet long, 20 watt fluorescent lamps characterised by a peak emission of 3000 Angstrom units; the blacklight lamps were 2 feet long, 40 watt ultraviolet lamps characterised by a peak emission of 3,500 Angstrom units.
  • the sample was rotated concentrically about the bank of lamps so that the radiation therefrom was uniformly distributed over the section under test.
  • the exposed sample was examined periodically and the time at which the sample reached 50% of the initial elongation was noted.
  • R and R are selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, sec-butyl, t-butyl, 1,1-dimethylpropyl, 1,1-dimethy1butyl, 2-octyl, cyclohexyl,
  • a compound according to Claim 1 which is 3,4- dehydro 4 (4 hydroxy phenyl)-2,2,6,6-tetramethylpiperidine.
  • a compound according to Claim 1 which is 3,4- dehydro 4 (3 t butyl 4' hydroxyphenyl) 2,2,6,6- tetramethylpiperidine.
  • a compound according to Claim 1 which is 3,4- dehydro 4 (3'5' di isdpropyl 4' hydroxyphenyl)- 2,2,6,6-tetramethylpiperidine.

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  • Polymers & Plastics (AREA)
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  • Hydrogenated Pyridines (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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US00310181A 1971-11-30 1972-11-28 Hydroxyaryl-tetramenthyl-dehydropiperidines Expired - Lifetime US3847930A (en)

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US4061616A (en) * 1973-06-15 1977-12-06 Sankyo Company Limited Stabilization of synthetic polymers
US4110304A (en) * 1973-04-19 1978-08-29 Ciba-Geigy Corporation Stabilizer system and its use for stabilizing styrene polymers
US4175197A (en) * 1974-09-06 1979-11-20 Eli Lilly And Company 1,3,4-Trisubstituted-4-aryl-1,4,5,6-tetra-hydropyridines
US4263202A (en) * 1977-07-15 1981-04-21 Ciba-Geigy Corporation Novel metal complexes
US4504628A (en) * 1982-02-01 1985-03-12 The Dow Chemical Company Polymerizable UV light stabilizers from isocyanatoalkyl esters of unsaturated carboxylic acids
US5998518A (en) * 1996-10-16 1999-12-07 Ciba Specialty Chemcials Corporation Phenyl Glycidyl ether hals
US20040085490A1 (en) * 2000-08-30 2004-05-06 Ji Li Liquid crystal mixture
TWI776033B (zh) * 2018-06-27 2022-09-01 日商東京應化工業股份有限公司 化學增幅型正型感光性樹脂組成物、感光性乾膜、感光性乾膜的製造方法、經圖型化的抗蝕膜的製造方法、附有模板的基板之製造方法、鍍敷成形物的製造方法及含氮雜環化合物
CN115477607A (zh) * 2022-10-14 2022-12-16 泰兴市锐容新材料科技合伙企业(有限合伙) 一种光稳定剂中间体及其制备方法

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US4141883A (en) * 1975-05-28 1979-02-27 Sankyo Company, Limited Stabilization of synthetic polymers by penta-or-hexa-substituted 4-piperidinol derivatives
JPS5578033A (en) * 1978-12-08 1980-06-12 Adeka Argus Chem Co Ltd Stabilized synthetic resin composition
US4322522A (en) * 1980-07-08 1982-03-30 Akzona Incorporated Polyester/polyether segmented copolymers stabilized against degradation by UV light via copolymerization with analogs of 2,2,6,6-tetramethylpiperidine derivatives
FR2508908A1 (fr) * 1981-07-06 1983-01-07 Sandoz Sa Nouvelles polyalkylpiperidines utilisables comme stabilisants de matieres organiques polymeres, et leur preparation
JPS5852655U (ja) * 1981-10-01 1983-04-09 赤井電機株式会社 テ−プレコ−ダにおけるテ−プ駆動制御装置
JPS5852656U (ja) * 1981-10-01 1983-04-09 赤井電機株式会社 テ−プレコ−ダにおけるテ−プ駆動制御装置
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JPS5929662A (ja) * 1982-08-12 1984-02-16 Mitsui Petrochem Ind Ltd ４−（２，４−ジヒドロキシフエニル）ピペリジン類およびその製法
ATE102666T1 (de) * 1988-06-14 1994-03-15 Ciba Geigy Ag Verfahren zum fotochemischen stabilisieren von ungefaerbten und gefaerbten polypropylenfasern.
EP1367114A1 (en) * 2002-04-11 2003-12-03 Clariant International Ltd. Active matrix liquid crystal device and smectic liquid crystal mixture
US6824707B2 (en) 2001-10-23 2004-11-30 Clariant International Ltd. Active matrix liquid crystal device and smectic liquid crystal mixture
ITMI20080739A1 (it) 2008-04-23 2009-10-24 3V Sigma Spa Ammine stericamente impedite oligomeriche e loro uso come stabilizzanti per polimeri
ITMI20080747A1 (it) * 2008-04-24 2009-10-25 3V Sigma Spa Miscele di ammine stericamente impedite per la stabilizzazione di polimeri
IT1399477B1 (it) 2010-03-15 2013-04-19 3V Sigma Spa Miscele di ammine stericamente impedite per la stabilizzazione di polimeri
ITMI20110802A1 (it) 2011-05-10 2012-11-11 3V Sigma Spa Miscele di ammine stericamente impedite per la stabilizzazione di polimeri
IT201700073726A1 (it) 2017-06-30 2018-12-30 3V Sigma Spa Ammine impedite polimeriche
IT201700078234A1 (it) 2017-07-11 2019-01-11 3V Sigma Spa Ammine impedite

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US2498430A (en) * 1945-05-21 1950-02-21 Hoffmann La Roche 1-methyl-4-p-methoxyphenyl-4-propionoxy-piperidine hydrochloride
US3431232A (en) * 1965-11-26 1969-03-04 Sankyo Co Piperidine n-oxide polyolefin stabilizers
GB1194402A (en) * 1966-06-15 1970-06-10 Sankyo Co 2,2,5,5-Tetrasubstituted-4-Oxoimidazolidine Nitroxide and Process for Preparing the Same
US3534048A (en) * 1966-06-15 1970-10-13 Sankyo Co 2,2-dimethyl-4,4,6,6-tetrasubstituted-piperidine-1-oxide derivatives
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US3503982A (en) * 1966-08-24 1970-03-31 Sankyo Co 2,2-dimethyl-6,6 disubstituted-4-substituted aminopiperidine-1-oxides
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US3542729A (en) * 1968-03-19 1970-11-24 Sankyo Co Stabilization of synthetic polymers
US3734883A (en) * 1970-04-16 1973-05-22 Ciba Geigy Corp Stabilizing organic material with piperidone azines
US3733326A (en) * 1971-03-10 1973-05-15 Sankyo Co Inhibition of the polymerization of vinyl monomers
GB1403942A (en) * 1973-04-05 1975-08-28 Ciba Geigy Ag Piperidine derivatives

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4110304A (en) * 1973-04-19 1978-08-29 Ciba-Geigy Corporation Stabilizer system and its use for stabilizing styrene polymers
US4123418A (en) * 1973-04-19 1978-10-31 Ciba-Geigy Corporation Stabilizer system for stabilizing styrene polymers
US4061616A (en) * 1973-06-15 1977-12-06 Sankyo Company Limited Stabilization of synthetic polymers
US4175197A (en) * 1974-09-06 1979-11-20 Eli Lilly And Company 1,3,4-Trisubstituted-4-aryl-1,4,5,6-tetra-hydropyridines
US4263202A (en) * 1977-07-15 1981-04-21 Ciba-Geigy Corporation Novel metal complexes
US4504628A (en) * 1982-02-01 1985-03-12 The Dow Chemical Company Polymerizable UV light stabilizers from isocyanatoalkyl esters of unsaturated carboxylic acids
US5998518A (en) * 1996-10-16 1999-12-07 Ciba Specialty Chemcials Corporation Phenyl Glycidyl ether hals
US20040085490A1 (en) * 2000-08-30 2004-05-06 Ji Li Liquid crystal mixture
US6958176B2 (en) 2000-08-30 2005-10-25 Ji Li Liquid crystal mixture
US20060011886A1 (en) * 2000-08-30 2006-01-19 Ji Li Liquid crystal mixture
US9388338B2 (en) * 2000-08-30 2016-07-12 Merck Patent Gmbh Liquid crystal mixture
TWI776033B (zh) * 2018-06-27 2022-09-01 日商東京應化工業股份有限公司 化學增幅型正型感光性樹脂組成物、感光性乾膜、感光性乾膜的製造方法、經圖型化的抗蝕膜的製造方法、附有模板的基板之製造方法、鍍敷成形物的製造方法及含氮雜環化合物
CN115477607A (zh) * 2022-10-14 2022-12-16 泰兴市锐容新材料科技合伙企业(有限合伙) 一种光稳定剂中间体及其制备方法
CN115477607B (zh) * 2022-10-14 2024-05-24 肖尖 一种光稳定剂中间体及其制备方法

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NL7216277A (enrdf_load_html_response) 1973-06-04
DE2258086A1 (de) 1973-06-07
AT317555B (de) 1974-09-10
JPS4865181A (enrdf_load_html_response) 1973-09-08
FR2162058B1 (enrdf_load_html_response) 1975-03-28
FR2162059B1 (enrdf_load_html_response) 1976-04-23
US4038280A (en) 1977-07-26
CA986115A (en) 1976-03-23
ES409081A1 (es) 1976-03-16
IT971343B (it) 1974-04-30
NL7216276A (enrdf_load_html_response) 1973-06-04
AT318925B (de) 1974-11-25
FR2162058A1 (enrdf_load_html_response) 1973-07-13
GB1395159A (en) 1975-05-21
DE2257998A1 (de) 1973-06-14
CA984845A (en) 1976-03-02
FR2162059A1 (enrdf_load_html_response) 1973-07-13
IT971344B (it) 1974-04-30
CH586251A5 (enrdf_load_html_response) 1977-03-31
JPS4876787A (enrdf_load_html_response) 1973-10-16
ES409077A1 (es) 1976-05-01
JPS569554B2 (enrdf_load_html_response) 1981-03-02

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