EP0000496B1 - Seitenständige N-heterocyclische Ringe tragende Acrylatpolymere und deren Verwendung als Lichtschutzmittel - Google Patents

Seitenständige N-heterocyclische Ringe tragende Acrylatpolymere und deren Verwendung als Lichtschutzmittel Download PDF

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Publication number
EP0000496B1
EP0000496B1 EP78100360A EP78100360A EP0000496B1 EP 0000496 B1 EP0000496 B1 EP 0000496B1 EP 78100360 A EP78100360 A EP 78100360A EP 78100360 A EP78100360 A EP 78100360A EP 0000496 B1 EP0000496 B1 EP 0000496B1
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hydrogen
formula
alkyl
group
methyl
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EP78100360A
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German (de)
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French (fr)
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EP0000496A1 (de
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Friedrich Dr. Karrer
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Novartis AG
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Ciba Geigy AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/10—Spiro-condensed systems
    • 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
    • C07D211/36—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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D211/40—Oxygen atoms
    • C07D211/44—Oxygen atoms attached in position 4
    • C07D211/46—Oxygen atoms attached in position 4 having a hydrogen atom as the second substituent in position 4
    • 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
    • C07D211/36—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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D211/56—Nitrogen atoms
    • C07D211/58—Nitrogen atoms attached in position 4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/52—Amides or imides
    • C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F20/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds

Definitions

  • the present invention relates to acrylate homopolymers and copolymers bearing pendant N-heterocyclic rings and to their use as light stabilizers in organic polymers.
  • R 7 and R 8 are C 1 ⁇ C 12 alkyl, for example methyl, ethyl, isopropyl, n-butyl, isobutyl, t-butyl, isopentyl, n -Octyl or n-dodecyl, R 7 and R 8 are preferred C 1 ⁇ C 4 alkyl.
  • R 7 is as C 3 ⁇ C 8 alkenyl, for example allyl, 2-butenyl or 2-hexenyl.
  • R 7 is as C 7 ⁇ C 8 aralkyl, for example benzyl or ⁇ -phenylethyl.
  • Y means -0- or preferably -0-.
  • the homopolymers characterized by the definition given above are good light stabilizers. Nevertheless, in many cases it is advantageous to modify these homopolymers by copolymerization with at least one compound which has one or more polymerizable double bonds. This enables the properties, such as the solubility or the softening point of the additive, to be influenced in a simple manner.
  • suitable copolymerizable components are styrene, divinylbenzene, 2- or 4-vinylpyridine, compounds from the acrylic acid series, such as esters or amides, which are derived from acrylic acid or methacrylic acid, e.g.
  • Preferred copolymerizable components are styrene, acrylonitrile, acrylic or methacrylic acid esters, vinyl esters, vinyl ethers or acrylic or methacrylamides.
  • Copolymers can also be made from two different piperidyl monomers.
  • Compounds in soft R 1 and R 2 together represent a group of the formula VIII are particularly suitable for copolymerization reactions, be it with other piperidinyl monomers or other above-mentioned polymerizable components.
  • the compound specifically chosen as the co-monomer component plays a minor role, i.e.
  • the connections listed above are largely interchangeable.
  • the measures which must be taken in order to obtain copolymers of similar molecular weight and similar properties are known to the person skilled in the art.
  • copolymers of more than two monomeric components e.g. Terpolymers can be used.
  • the molecular weight of the homo- or copolymers according to the invention is more than 500; however, it can make up to 150,000.
  • Preferred compounds have a molecular weight of 500 to 50,000 and in particular 1000-20,000.
  • the copolymerizable component can be completely absent or up to a 10-fold excess.
  • the molar ratio of the side-containing N-heterocyclic ring-containing compound to the co-component is therefore preferably about 1: 0.001 to 1:10, in particular 1: 0.001 to 1: 5.
  • the amount of the Co component can be very small (eg 0.1% based on the component of the formula 1). This will be the case in particular if the Co component has two polymerizable double bonds, such as divinylbenzene or bisacrylates or bismethacrylates with which branched or crosslinked additives are formed.
  • the monomers which are suitable as starting materials for the polymerization reaction correspond to the general formula IX wherein R 1 , R 2 , R 3 and R 4 have the meaning defined above.
  • R 1 is a group of the formula II in which Y is -0- or -NH and R 5 and R 6 are hydrogen, and R 2 and R 3 are hydrogen or methyl and R 4 is hydrogen
  • the monomers are new and therefore also constitute an object of the invention.
  • the monomers of the formula IX are themselves light stabilizers for organic material.
  • the monomers of the formula IX used for the polymerization are prepared in a manner known per se, for example analogously to that in US Pat. 3,705,166 methods described. For example, it becomes a reactive derivative of an unsaturated carboxylic acid of the formula X. with one of the compounds of the formulas XI, XII, XIII or XIV wherein all the substituents have the meaning defined above, preferably implemented in an inert organic solvent.
  • Reactive derivatives of an unsaturated carboxylic acid are, for example, an acid halide of the formula Xa wherein Hal, bromine or especially chlorine, or an acid anhydride of the formula Xb
  • About one mole of a compound of the formula Xa or Xb is preferably used per mole of one of the compounds of the formulas XI, XII, XIII or XIV.
  • R 2 , R 3 and R 4 in the formulas Xa and Xb correspond to the definition given above.
  • an acid halide of the formula Xa When using an acid halide of the formula Xa, one works in the presence of a base, for example in the presence of a tertiary amine, such as triethylamine, di-isopropylethylamine, N, N-diethylaniline or pyridine; or in the presence of an anhydrous alkali metal or alkaline earth metal carbonate, or alkali metal bicarbonate such as MgCO 3 , NaHCO 3 , Na 2 CO 3 or K 2 CO 3 .
  • a base for example in the presence of a tertiary amine, such as triethylamine, di-isopropylethylamine, N, N-diethylaniline or pyridine; or in the presence of an anhydrous alkali metal or alkaline earth metal carbonate, or alkali metal bicarbonate such as MgCO 3 , NaHCO 3 , Na 2 CO 3 or K 2 CO 3 .
  • Aliphatic hydrocarbons such as hexane or ligroin are suitable, for example; aromatic hydrocarbons such as benzene, toluene or xylene; chlorinated hydrocarbons such as methylene chloride or chloroform; Amides such as hexamethylene phosphoric triamide; or ethers such as dioxane, 1,2-dimethoxyethane, diethyl ether or tetrahydrofuran.
  • the temperature of this reaction is preferably -20 to + 120 ° C, but especially -10 ° C to + 80 ° C.
  • a further process variant consists in that an ester of the formula Xc is used as the reactive derivative of a carboxylic acid of the formula X.
  • R 2 , R 3 and R 4 have the meaning given above and R * C 1 ⁇ C 4 alkyl is used.
  • the reactants of the formulas XI, XII, XIII or XIV, in which m and n are 1 and the other symbols have the meaning given above, can be reacted in approximately stoichiometric amounts or with an excess of Xc.
  • transesterification catalyst e.g. an acid or preferably a base takes place.
  • the temperature is preferably 20-170 ° C, in particular 50-150 ° C.
  • An ion exchange resin can also be used as a catalyst.
  • the compounds of the formula Xc are liquid compounds, a solvent can optionally be dispensed with.
  • the reaction component Xc is optionally before the transesterification reaction with one of the known stabilizers, such as. Hydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-p-cresol, another 2,6-di-tert-butyl-phenyl derivative or phenothiazine.
  • the compounds of the formulas X, Xa, Xb and Xc used as starting materials are compounds known to the person skilled in the art and, if not commercially available, can be prepared in a simple manner.
  • the piperidinyl derivatives used as reactants are also known compounds.
  • the preparation of the compounds of formula XI is, for example, DT-OS 2,352,658 (4-hydroxypiperidine) or in US Pat. 3,684,765 (4-aminopiperidines).
  • the compounds of the formulas XI, XII, XIII and XIV which have different substituents in the piperidyl ring in the 2- and 6-position can be prepared by reacting a ketone of the formula CH 3 ⁇ CO ⁇ CH 2 ⁇ R 6 with ammonia.
  • the pyrimidine formed is, as in Helv. Chim. Acta 30, 114 (1947), hydrolyzed to an amino ketone of formula XV.
  • the compounds of the formula XV are reacted in a second process step with ammonia and a ketone CH 3 ⁇ CO ⁇ CH 2 ⁇ R 6 , as described, for example, in Monthly Chemistry 88, 464 (1957) (R B has the formulas given the above meaning).
  • R B has the formulas given the above meaning.
  • the compounds of the formulas XI and XII, in which R 5 is hydrogen, can be obtained from the pyrimidine thus obtained by hydrolysis.
  • the monomers of the formula IX can be polymerized by known methods, which are described, for example, in Houben-Weyl, 14 (1) 1010-1078 (1962).
  • the reactions known under the names radical and ionic homo- or copolymerization are particularly suitable.
  • the polymerization is controlled in a known manner by initiators and regulators or chain terminators. This makes it possible to obtain polymers of the desired molecular weight.
  • the polyreaction can be carried out in bulk, in solution, in dispersion, in emulsion, in suspension or as a so-called bead polymerization.
  • Per compounds are particularly suitable for radical homo- or copolymerization. Azo compounds and redox systems as initiators. Common organic or inorganic per-compounds include hydroperoxides, dialkyl peroxides, diacyl peroxides, peresters or peroxodisulfates. Examples of per compounds are hydrogen peroxide and potassium peroxodisulfate. Cumene hydroperoxide, di-t-butyl peroxide, ethyl methyl ketone peroxide, cyclohexanone peroxide or dibenzoyl peroxide optionally substituted by chlorine or bromine.
  • Particularly suitable azo compounds are those in which the azo group is bound on both sides to tertiary carbon atoms which, in addition to alkyl groups, also carry nitrile or ester groups. If the polyreaction is triggered by means of a redox system, organic or inorganic per-compounds are suitable as oxidizing agents and either metal ions of low valence or metal-free compounds which can be easily oxidized are suitable as reducing agents. Examples of oxidizing agents are hydrogen peroxide. Peroxidisulfate or diacyl peroxides.
  • the easiest way to control the molecular weight of the polymer is to use a suitable regulator.
  • suitable regulator examples are mercaptans, such as n-butyl mercaptan or dodecyl mercaptan and other organic sulfur compounds, such as diisopropylxanthogen disulfide, and also aliphatic aldehydes and acetals or allyl compounds, such as allyl alcohol.
  • the reaction temperatures are known to the person skilled in the art and, depending on the type of components used, are from -20 ° C. to + 200 ° C., preferably from + 20 ° C. to + 150 ° C., for the radical polymerization.
  • the polymerization is ionic, it can be cationic, but preferably anionic.
  • Suitable initiators are organometallic compounds such as diethyl zinc or diisobutyl zinc, naphthalene sodium, n-amyl sodium, cyclopentadienyl sodium, n-butyllithium or triethyl aluminum.
  • Bases such as alkali metal hydroxides, alcoholates and amides also act as initiators.
  • substances are used in ionic polymerization which react with the growing chain end; these include e.g. Water, alcohols, acids and amines.
  • the temperature in this reaction variant is from -100 ° C to + 200 ° C, preferably -20 ° C to +1 50 ° C and is known to the person skilled in the art for the type of polymer desired in each case.
  • the methods described are basically suitable for both homo- and copolymerization reactions. Depending on the choice of the copolymerization parameters, statistical copolymers or block copolymers are obtained in this way. It is essential for the present invention that only the physical properties such as softening point are added by adding co-monomer components. Solubility, etc. are influenced, but not their usefulness as light stabilizers for organic material. While the copolymerization of two monomers and the associated effects have been investigated particularly well and are known to the person skilled in the art, it is also useful in certain cases to use polymers of three or more polymerizable compounds. Such less known polymers are described, for example, in G.E. Ham, Copolymerization, High Polymers 18 (1964).
  • the compounds of formula 1 can be used as stabilizers for plastics against their damage by the action of oxygen, heat and light.
  • plastics are the polymers listed in DT-OS 2 456 864 on pages 12-14.
  • polyolefins styrene polymers
  • polyamides and of polyurethane for which the compounds of formula 1 are outstandingly suitable, examples being high and low density polyethylene, polypropylene, ethylene-propylene copolymers, polystyrene, styrene-butadiene Acrylonitrile terpolymers, mixtures of polyolefins or styrene polymers, polyurethanes based on polyether or polyester in the form of lacquers, threads, foils, plates, films, elastomers or foams.
  • the homopolymeric or copolymeric stabilizers are added to the plastics in a concentration of 0.05 to 5% by weight, calculated on the material to be stabilized. 0.1 to 2.5% by weight of the compounds, calculated on the material to be stabilized, is preferably incorporated into the latter.
  • the incorporation can take place after the polymerization, for example by mixing the compounds and, if appropriate, further additives into the melt by the methods customary in industry, before or during shaping, or else by applying the dissolved or dispersed ones gated compounds on the polymer, optionally with subsequent evaporation of the solvent.
  • the new compounds can also be added to the plastics to be stabilized in the form of a masterbatch which contains these compounds, for example in a concentration of 2.5 to 25% by weight.
  • the invention therefore also relates to the plastics stabilized by the addition of 0.01 to 5% by weight of a compound of the formula I, which may also contain other known and customary additives.
  • the plastics stabilized in this way can be used in a wide variety of forms, e.g. as foils, fibers, tapes. Profiles or as binders for paints, adhesives or putties.
  • the polymerization solution cooled to 80 ° C., was then poured into 1.3 liters of methanol at ⁇ 20 ° C. over approximately 5 minutes with vigorous turbination (Homorex) and the mixture was slowly warmed to room temperature within approximately 30 minutes. After the methanol solution had been decanted off, the resin-like deposited polymer was dissolved in a little dichloromethane and, as described, reprecipitated by pouring it into methanol. The poly-1,2,2,6,6-pentamethyl-4-methacryloxypiperidine thus purified was dried at 80 ° C. in a vacuum cabinet. The colorless, easily pulverizable polymer obtained has a softening point of ⁇ 190 ° C mol. M n) ⁇ 12,000.
  • the polymerization solution cooled to about 70 ° C., was then poured into 800 ml of methanol pre-cooled to 0 ° C. with vigorous turbination (Ho morex), as a result of which the polymer precipitated out as a fine white powder. After turbinating for a further 30 minutes at room temperature, the copolymer was filtered off, washed well with methanol and dried in a vacuum cabinet at 70.degree. The colorless copolymer thus obtained has a softening point of 110 ° C.
  • the 1-benzyl-2,2,6,6-tetramethyl-4-acryloyloxy-piperidine used as the monomeric component was obtained by reacting 1-benzyl-2,2,6,6-tetramethyl 4-hydroxypiperidine (m.p .: 156 ⁇ 157 ° C) with freshly distilled acrylic acid chloride in pure chloroform at 0 ° to 10 ° C in the presence of 1.1 equivalent of anhydrous triethylamine. Recrystallization from acetonitrile gave the analytically pure monomer with mp: 66 ⁇ 68 ° C.
  • the exposure time up to 50% loss of tensile strength is the measure of the protective effect.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP78100360A 1977-07-19 1978-07-11 Seitenständige N-heterocyclische Ringe tragende Acrylatpolymere und deren Verwendung als Lichtschutzmittel Expired EP0000496B1 (de)

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CH8915/77 1977-07-19
CH891577 1977-07-19

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EP0000496A1 EP0000496A1 (de) 1979-02-07
EP0000496B1 true EP0000496B1 (de) 1982-05-19

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US (2) US4210612A (enrdf_load_stackoverflow)
EP (1) EP0000496B1 (enrdf_load_stackoverflow)
JP (1) JPS5421489A (enrdf_load_stackoverflow)
AU (1) AU517364B2 (enrdf_load_stackoverflow)
BR (1) BR7804636A (enrdf_load_stackoverflow)
CA (1) CA1147097A (enrdf_load_stackoverflow)
DE (1) DE2861843D1 (enrdf_load_stackoverflow)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0010518A1 (de) * 1978-10-13 1980-04-30 Ciba-Geigy Ag Seitenständige N-heterocyclische Ringe tragende Copolymere, deren Verwendung und Verfahren zu deren Herstellung
EP0047605A1 (en) * 1980-09-10 1982-03-17 Carstab Corporation Polyalkylated 4-aminopiperidine derivatives and synthetic polymers containing the same
EP0063544A1 (de) * 1981-04-13 1982-10-27 Ciba-Geigy Ag Alpha-Olefincopolymere mit sterisch gehinderten Aminseitengruppen
GB2145100A (en) * 1981-08-12 1985-03-20 Ciba Geigy Ag Copolymeric polyalkylpiperidines
FR2597336A1 (fr) * 1986-01-10 1987-10-23 Oreal Nouvelles compositions de polymeres derives d'acrylamide substitue par des composes absorbant les radiations ultraviolettes, et leur application notamment dans la realisation de compositions cosmetiques destinees a proteger la peau contre les effets indesires des radiations ultraviolettes.
EP0212439A3 (en) * 1985-08-13 1987-12-23 Hoechst Aktiengesellschaft Polymers and radiosensitive compositions containing them
EP0389420A1 (en) * 1989-03-21 1990-09-26 Ciba-Geigy Ag Ethylenically unsaturated compounds containing 1-hydrocarbyloxy-2,2,6,6-tetramethylpiperidine moieties, and polymers, copolymers and stabilized compositions
FR2644790A1 (fr) * 1989-03-21 1990-09-28 Ciba Geigy Ag Procede pour modifier des copolymeres acryliques et liants pour peintures qui contiennent des copolymeres acryliques modifies
EP0434619A3 (en) * 1989-12-21 1991-11-27 Ciba-Geigy Ag Process for incorporating o-hydroxyphenyl-s-triazin into organic polymers

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* Cited by examiner, † Cited by third party
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DE2861843D1 (en) * 1977-07-19 1982-07-08 Ciba Geigy Ag Acrylic polymers substituted by n-heterocyclic rings and their use as light protection agents
US4413096A (en) * 1981-04-13 1983-11-01 Ciba-Geigy Corporation α-Olefin copolymers containing pendant hindered amine groups
JPS57177053A (en) * 1981-04-23 1982-10-30 Adeka Argus Chem Co Ltd Synthetic resin composition
US4356287A (en) * 1981-07-20 1982-10-26 American Cyanamid Company Novel polymeric light stabilizers for polymers
US4369274A (en) * 1981-07-20 1983-01-18 American Cyanamid Company Hindered amine light stabilizers for polymers
EP0080431B1 (de) * 1981-10-16 1986-09-24 Ciba-Geigy Ag Synergistisches Gemisch von niedermolekularen und hochmolekularen Polyalkylpiperidinen
JPS58160522A (ja) * 1982-03-17 1983-09-24 Honda Motor Co Ltd 多気筒内燃エンジンの電子式燃料噴射制御装置
JPS58160523A (ja) * 1982-03-17 1983-09-24 Honda Motor Co Ltd 多気筒内燃エンジンの電子式燃料噴射制御装置
US4522990A (en) * 1982-04-19 1985-06-11 E. I. Du Pont De Nemours And Company Light stable polymers by anionic polymerization
JPS5962245U (ja) * 1982-10-18 1984-04-24 日本電子機器株式会社 内燃機関の電子制御燃料噴射装置
US4439565A (en) * 1982-11-10 1984-03-27 Ciba-Geigy Corporation Oligomeric esteramides containing pendant hindered amine groups
US5080809A (en) * 1983-01-28 1992-01-14 Phillips Petroleum Company Polymers useful in the recovery and processing of natural resources
US5186257A (en) * 1983-01-28 1993-02-16 Phillips Petroleum Company Polymers useful in the recovery and processing of natural resources
US4577007A (en) * 1983-02-25 1986-03-18 E. I. Du Pont De Nemours And Company Polymers containing resorcinol monobenzoate
US4495325A (en) * 1983-02-25 1985-01-22 E. I. Du Pont De Nemours And Company Polymer-bound ultraviolet stabilizer coating compositions containing cross linkers
US4522971A (en) * 1983-02-25 1985-06-11 E. I. Du Pont De Nemours And Company Polymers containing resorcinol monobenzoate
US4585693A (en) * 1983-02-25 1986-04-29 E. I. Du Pont De Nemours And Company Polymer-bound ultraviolet stabilizer coating compositions containing cross linkers
US4636431A (en) * 1983-02-25 1987-01-13 E. I. Du Pont De Nemours And Company Polymers containing resorcinol monobenzoate
DE3323951A1 (de) * 1983-07-02 1985-01-03 Röhm GmbH, 6100 Darmstadt Acrylatharze als bindemittel fuer farbmittelkonzentrate
US4590252A (en) * 1983-12-16 1986-05-20 E. I. Du Pont De Nemours And Company Light-stable anionically polymerized polymers
US4960593A (en) * 1985-01-30 1990-10-02 Hilmont Incorporated Process for preparing thermally stable olefinic polymers
US5350786A (en) * 1986-06-30 1994-09-27 Enichem Synthesis S.P.A. Process of (co)polymerization of α-olefins in the presence of stabilizers
US5162405A (en) * 1987-12-24 1992-11-10 Elf Atochem North America, Inc. Single-functional and mixtures of multi-functional oligomeric performance additive compositions and their uses
US5013777A (en) * 1987-12-24 1991-05-07 Atochem North America, Inc. Novel single-functional and mixtures of multi-functional oligomeric performance additive compositions and their uses
US4913844A (en) * 1988-01-25 1990-04-03 Hoechst Celanese Corp. Acrylic polymers and copolymers exhibiting nonlinear optical response
US5135986A (en) * 1988-04-15 1992-08-04 Ciba-Geigy Corporation Stabilized styrene copolymers containing elastomer particles
JP2753838B2 (ja) * 1988-10-08 1998-05-20 日本ユニカー株式会社 Ｎ−置換マレイミドで変性されたエチレン−極性コモノマー共重合体
US4975494A (en) * 1988-11-23 1990-12-04 Atochem Of North America, Inc. Polymer bound light stabilizer coating resins
US4927891A (en) * 1988-11-23 1990-05-22 Pennwalt Corporation Polymer bound light stabilizer coating resins
GB8928278D0 (en) * 1989-12-14 1990-02-21 Smith Kline French Lab Compounds
US5189084A (en) * 1989-12-21 1993-02-23 Ciba-Geigy Corporation Process for incorporating o-hydroxyphenyl-s-triazines in organic polymers
JPH03238480A (ja) * 1990-02-16 1991-10-24 Nec Corp 現像器
JP2549183B2 (ja) * 1990-02-26 1996-10-30 三共株式会社 アクリル酸ピペリジルエステル誘導体の製法
JP2546216B2 (ja) * 1991-11-18 1996-10-23 株式会社日本触媒 高耐候性一液架橋型エマルション
TW237471B (enrdf_load_stackoverflow) * 1992-09-03 1995-01-01 Ciba Geigy
TW267179B (enrdf_load_stackoverflow) * 1993-07-13 1996-01-01 Ciba Geigy
US5994264A (en) * 1995-06-07 1999-11-30 American Trim, Llc Transfer printing of metal using protective overcoat
DE19544404A1 (de) * 1995-11-29 1997-06-05 Basf Ag Tetramethylpiperidinhaltige Copolymere
US6166148A (en) * 1996-12-18 2000-12-26 Basf Corporation Durability enhancing agents, method therefore and cured coating compositions containing the same
US6147163A (en) * 1996-12-18 2000-11-14 Basf Corporation Acrylic oligomeric and polymeric durability enhancing agents, method therefore and cured coating compositions containing the same
EP0875544B1 (en) * 1997-04-28 2002-12-11 Seiko Epson Corporation Ink composition capable of realizing light fast image
US5976296A (en) * 1998-04-27 1999-11-02 American Trim, Llc Transfer printing of complex objects
NL1012219C2 (nl) * 1998-06-19 2000-04-13 Ciba Sc Holding Ag Werkwijze voor de polymersitie van overzadigde polyalkylpiperidinen.
SE512919C2 (sv) * 1998-10-15 2000-06-05 Borealis As KOmbinerat ljus- och värmestabiliseringsmedel för polymerer
SG91852A1 (en) * 1998-12-21 2002-10-15 Toyo Boseki Hindered amine compound, resin composition, polyurethane fiber and production method and use thereof
DE69915694T2 (de) 1998-12-23 2004-07-29 Ciba Specialty Chemicals Holding Inc. Polymerstabilisatoren mit einem niedrigpolydispersat
US6737528B2 (en) * 2001-02-22 2004-05-18 Council Of Scientific And Industrial Research Vinylic hindered amine light stabilizers
US6489482B2 (en) * 2001-02-22 2002-12-03 Council Of Scientific And Industrial Research Process for the preparation of novel vinylic hindered amine light stabilizers
US7297409B2 (en) * 2001-10-12 2007-11-20 Sabic Innovative Plastics Ip Bv Multilayer, weatherable compositions and method of manufacture thereof
US6630527B2 (en) 2001-10-19 2003-10-07 General Electric Company UV stabilized, impact modified polyester/polycarbonate blends, articles, and methods of manufacture thereof
US7090926B2 (en) * 2001-11-09 2006-08-15 General Electric Company Multi-layer, weatherable compositions and method of manufacture thereof
WO2008062860A1 (fr) * 2006-11-24 2008-05-29 Mitsubishi Rayon Co., Ltd. Stabilisant pour une résine de polyoléfine et composition de résine de polyoléfine stabilisée
US9663603B2 (en) * 2011-05-31 2017-05-30 Mitsubishi Rayon Co., Ltd. Curable composition and polymer
US11254837B2 (en) 2017-04-25 2022-02-22 Basf Se Coating compositions having covalently bound ultraviolet absorbers
US10840615B2 (en) * 2018-06-28 2020-11-17 Te Connectivity Corporation Connection enclosure assemblies, connector systems and methods for forming an enclosed connection between conductors

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3004957A (en) * 1959-03-12 1961-10-17 Union Carbide Corp Pyridyl acrylates
GB1112439A (en) * 1966-01-13 1968-05-08 Nii Monomerov Dlia Sint Kauchu Aminoalkyl esters of ª‡,ª‰-unsaturated acids and method of preparing these compounds
US3486932A (en) * 1967-03-13 1969-12-30 Calgon C0Rp Electroconductive paper
US3645988A (en) * 1969-06-17 1972-02-29 Dow Chemical Co Pyridyl acrylates and methacrylates and dyeable acrylonitrile copolymers prepared therefrom
US3705166A (en) * 1969-08-15 1972-12-05 Sankyo Co Acrylic acid derivatives of 2,2,6,6-tetramethylpiperidines
US3590045A (en) * 1969-09-25 1971-06-29 Smith Kline French Lab Certain substituted imidazo (4,5-b)pyridines
JPS5855980B2 (ja) * 1975-05-28 1983-12-13 三共株式会社 ゴウセイコウブンシザイリヨウヨウアンテイザイ
JPS5848580B2 (ja) * 1975-05-28 1983-10-29 三共株式会社 ゴウセイコウブンシザイリヨウヨウアンテイザイ
DE2861843D1 (en) * 1977-07-19 1982-07-08 Ciba Geigy Ag Acrylic polymers substituted by n-heterocyclic rings and their use as light protection agents

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0010518A1 (de) * 1978-10-13 1980-04-30 Ciba-Geigy Ag Seitenständige N-heterocyclische Ringe tragende Copolymere, deren Verwendung und Verfahren zu deren Herstellung
EP0047605A1 (en) * 1980-09-10 1982-03-17 Carstab Corporation Polyalkylated 4-aminopiperidine derivatives and synthetic polymers containing the same
EP0063544A1 (de) * 1981-04-13 1982-10-27 Ciba-Geigy Ag Alpha-Olefincopolymere mit sterisch gehinderten Aminseitengruppen
GB2145100A (en) * 1981-08-12 1985-03-20 Ciba Geigy Ag Copolymeric polyalkylpiperidines
EP0212439A3 (en) * 1985-08-13 1987-12-23 Hoechst Aktiengesellschaft Polymers and radiosensitive compositions containing them
US4910119A (en) * 1985-08-13 1990-03-20 Hoechst Aktiengesellschaft Polymeric compounds and radiation-sensitive mixture containing them
FR2597336A1 (fr) * 1986-01-10 1987-10-23 Oreal Nouvelles compositions de polymeres derives d'acrylamide substitue par des composes absorbant les radiations ultraviolettes, et leur application notamment dans la realisation de compositions cosmetiques destinees a proteger la peau contre les effets indesires des radiations ultraviolettes.
BE1004271A4 (fr) * 1986-01-10 1992-10-27 Oreal Compositions cosmetiques destinees a proteger la peau contre les effets indesires des radiations ultraviolettes.
EP0389420A1 (en) * 1989-03-21 1990-09-26 Ciba-Geigy Ag Ethylenically unsaturated compounds containing 1-hydrocarbyloxy-2,2,6,6-tetramethylpiperidine moieties, and polymers, copolymers and stabilized compositions
FR2644790A1 (fr) * 1989-03-21 1990-09-28 Ciba Geigy Ag Procede pour modifier des copolymeres acryliques et liants pour peintures qui contiennent des copolymeres acryliques modifies
EP0434619A3 (en) * 1989-12-21 1991-11-27 Ciba-Geigy Ag Process for incorporating o-hydroxyphenyl-s-triazin into organic polymers

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CA1147097A (en) 1983-05-24
AU517364B2 (en) 1981-07-23
DE2861843D1 (en) 1982-07-08
US4210612A (en) 1980-07-01
EP0000496A1 (de) 1979-02-07
AU3812878A (en) 1980-01-24
US4294949A (en) 1981-10-13
JPS632963B2 (enrdf_load_stackoverflow) 1988-01-21
BR7804636A (pt) 1979-04-17
JPS5421489A (en) 1979-02-17

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