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EP0874821A1 - Copolymeres renfermant de la tetramethylpiperidine - Google Patents

Copolymeres renfermant de la tetramethylpiperidine

Info

Publication number
EP0874821A1
EP0874821A1 EP96939088A EP96939088A EP0874821A1 EP 0874821 A1 EP0874821 A1 EP 0874821A1 EP 96939088 A EP96939088 A EP 96939088A EP 96939088 A EP96939088 A EP 96939088A EP 0874821 A1 EP0874821 A1 EP 0874821A1
Authority
EP
European Patent Office
Prior art keywords
tetramethylpiperidine
alkyl
hydrogen
radicals
copolymers according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP96939088A
Other languages
German (de)
English (en)
Inventor
Alfred Krause
Alexander Aumüller
Hubert Trauth
Albin Berger
Andreas Deckers
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP0874821A1 publication Critical patent/EP0874821A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
    • 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
    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/57—Compounds covalently linked to a(n inert) carrier molecule, e.g. conjugates, pro-fragrances

Definitions

  • the present invention relates to copolymers containing tetramethylpiperidine
  • R 2 hydrogen, C 1 -C 12 alkyl, COOR 7 , COR 8 , CONR 8 R 9 or CN,
  • R 3 is hydrogen, methyl, ethyl or propyl
  • R 4 is hydrogen, straight-chain or branched Ci-C 2 n-alkyl, where every third C atom of the chain can be replaced by oxygen or NR 6 , C 3 -C 8 cycloalkyl, phenyl, or a radical of the formulas
  • R 5 is hydrogen, methyl, ethyl or propyl
  • R 6 is hydrogen, or Ci-C ⁇ -alkyl
  • R 7 is hydrogen, C ⁇ ⁇ to C ⁇ - alkyl, C 5 - to C ⁇ -cycloalkyl, C 3 - to Cs-alkenyl or phenyl, which by one to three C ⁇ ⁇ to C 4 alkyl radicals, C ⁇ ⁇ to C 4 alkoxy radicals , Ci to C 4 alkoxycarbonyl groups, halogen atoms, hydroxyl groups, phenoxy groups, phenyl groups, tolyl groups or
  • Xylyl radicals can be substituted
  • R 9 is hydrogen, C 1 to C 2 alkyl, C 5 to Cs cycloalkyl or phenyl, which is substituted by one to three C 1 to C 4 alkyl radicals, C 1 to C 4 alkoxy radicals, C 1 to C 4 alkoxycarbonyl groups ,
  • Halogen atoms, hydroxyl groups, phenoxy groups, phenyl radicals, tolyl radicals or xylyl radicals can be substituted
  • R 10 is hydrogen or methyl
  • A is a bridge member of the formula
  • r means 0 to 100
  • the invention further relates to processes for the preparation of the compounds, the use of the copolymers as light stabilizers and stabilizers and organic material which is stabilized against the action of light, oxygen and heat and which contains the copolymers.
  • Organic material especially plastics and lacquers, is very quickly destroyed by light, oxygen and heat, which can be seen, for example, in yellowing, discoloration, embrittlement or cracking. This destruction is to be prevented with light stabilizers and stabilizers and the organic material is to be largely protected from these damaging influences.
  • tetramethylpiperidine structure compounds with hindered amine units such as the tetramethylpiperidine structure have proven to be particularly suitable. Tetramethylpiperidine compounds with several piperidine residues have proven to be particularly advantageous, e.g. dimeric or polymeric structures, since these can diffuse out of the stabilized organic material only with difficulty and therefore have particularly long-lasting protective effects.
  • Oxygen is preferred as the bridge member X.
  • the group COOR 7 is preferred as the radical R 1 .
  • the radical R 2 is preferably hydrogen or COOR 7 .
  • the radicals R 3 and R 5 are preferably hydrogen or methyl.
  • R 4 is preferably hydrogen, methyl, phenyl or a radical of the formulas
  • R 6 is preferably hydrogen, methyl or ethyl.
  • R 7 is preferably C 1 -C 4 alkyl, particularly preferably ethyl.
  • R 2 , R 4 , R 6 , R 7 , R 8 , R 9 , RH and R 12 are, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl.
  • the radicals R 2 , R 4 , R 6 , R 7 , R 8 and R 9 are furthermore n-pentyl, isopentyl, sec. -Pentyl, tert. -Pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl and 2-ethylhexyl.
  • R 2 , R 4 , R 2 and R 9 are furthermore n-nonyl, iso-nonyl, n-decyl, n-undecyl and n-dodecyl.
  • Cycloalkyl radicals such as, in particular, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl and ethylcyclohexyl are also suitable as radicals R 4 , R 7 , R 8 and R 9 .
  • the radical R 4 can also mean cyclopropyl and cyclobutyl.
  • C 3 -C 5 alkenyl radicals are also suitable as the radical R 7 , especially allyl, methallyl, crotyl, pentenyl, 1,3- and 2,4-pentadienyl.
  • the copolymers according to the invention contain the tetramethylpiperidine residue as an effective stabilizer unit. This is particularly easy to access and has particularly advantageous properties. However, other tetraalkylpiperidine residues show very similar properties, in which one or more of the methyl residues are replaced by other alkyl residues such as ethyl, propyl, butyl or each because two adjacent methyl radicals are linked to form a cyclic radical.
  • the copolymers preferably have an average molecular weight (weight average) between 1000 and 50,000 daltons, particularly preferably between 1000 and 25,000 daltons.
  • copolymers according to the invention can advantageously be prepared by polymer-analogous reactions.
  • a copolymer is exposed, for example
  • R 13 is hydrogen, methyl, ethyl, propyl, butyl or dimethyl aminoethyl
  • component Ia is derived from an acrylic ester in which the alcohol radical R 13 can preferably be methyl or ethyl, but also hydrogen or dimethylaminoethyl.
  • the polymer-analogous reaction is carried out in a manner known per se, preferably by azeotropic esterification or amidation, the water of reaction formed or the alcohol R 13 OH released being removed from the reaction mixture by distillation.
  • azeotropic esterification or amidation an inert, high-boiling entrainer is added to the starting material mixture, which is distilled off together with the water or alcohol.
  • the entrainer can then be separated from the water, for example, and returned to the reaction mixture. In this case, a relatively small addition of entrainer of 50-200% by weight based on the expected amount of water is sufficient. Without recycling, an up to 30-fold excess of entraining agent is generally added, and the entraining agent can also be added continuously.
  • toluene As entrainer e.g. Toluene, xylene, cyclohexane, methyl cyclohexane or even commercially available mixtures of aromatic hydrocarbons into consideration, toluene is preferably used.
  • entrainer e.g. Toluene, xylene, cyclohexane, methyl cyclohexane or even commercially available mixtures of aromatic hydrocarbons into consideration, toluene is preferably used.
  • the distillation temperature depends both on the boiling point of the entrainer or azeotrope and on the reaction pressure.
  • the distillation can be carried out at normal pressure, but distillation is preferably carried out under reduced pressure of, for example, 50-400 mbar.
  • the temperature is generally between 100 and 250 ° C, particularly preferably 150 ° -200 ° C.
  • the polymer-analogous reaction can also be carried out in the melt, for example in a kneader or extruder.
  • the choice of temperature depends primarily on the melting point of the starting polymer.
  • the reaction is generally carried out at 80-300 ° C., preferably at 120-250 ° C., distillation under reduced pressure being advantageous, for example at 50-400 mbar.
  • the reaction in the melt can also be carried out continuously or batchwise.
  • the reaction is preferably carried out in the presence of a catalyst.
  • Suitable catalysts are, for example, protonic acids such as p-toluenesulfonic acid, sulfuric acid, phosphoric acid, Lewis acids such as tetraalkyl titanates or organotin compounds or basic compounds such as alkaline earth metal hydroxides and carbonates as well as lithium and sodium amide.
  • copolymers according to the invention are outstandingly suitable for stabilizing organic material against the action of light, oxygen and heat, in particular when acidic liquids or gases are exposed at the same time.
  • Organic material means, for example, cosmetic preparations such as ointments and lotions, pharmaceutical formulations such as tablets and suppositories, photographic recording materials, in particular photographic emulsions or precursors for plastics and lacquers, but especially plastics and lacquers.
  • the present invention also relates to organic material stabilized against the action of light, oxygen and heat, in particular plastics and paints, containing 0.01 to 5% by weight, preferably 0.02 to 1% by weight. based on the total weight of the organic material, one or more copolymers according to the invention.
  • the organic material stabilized by the copolymers according to the invention may optionally contain further additives, for example antioxidants, light stabilizers, metal deactivators, antistatic agents, flame retardants, pigments and fillers.
  • antioxidants, light stabilizers, metal deactivators, antistatic agents, flame retardants, pigments and fillers are, for example, compounds based on sterically hindered phenols or costabilizers containing sulfur or phosphorus.
  • phenolic antioxidants examples include 2,6-di-tert-butyl-4-methylphenol, n-octadecyl- ⁇ - (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1, 1, 3-tris- (2-methy- 1-4-hydroxy-5-tert-butyl-phenyl) -butane, 1,3, 5-trimethyl-2, 4,6-tris- (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris - [ß- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ethyl] isocyanurate, 1,3, 5-tris- (2,6-dimethyl-3-hydroxy-4 -tert.-butylbenzyl) isocyanurate and pentaeryth
  • Examples of phosphorus-containing antioxidants are tris (nonylphenyl) phosphite, distearylpentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2-tert-butyl-4-methylphenyl) -phosphite.
  • sulfur-containing antioxidants are dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, pentarythritol tetrakis ( ⁇ -lauryl thiopropionate) and pentaerythritol tetrakis ( ⁇ -hexylthiopropionate).
  • antioxidants and light stabilizers which can be used together with the copolymers according to the invention are e.g. 2- (2'-hydroxyphenyl) benzotriazoles, 2-hydroxybenzophenones, aryl esters of hydroxybenzoic acids, ⁇ -cyanocinnamic acid derivatives, benzimidazolecarboxylic acid anilides, nickel compounds or oxalic acid dianilides.
  • plastics which can be stabilized by the copolymers according to the invention are:
  • Polymers of mono- and diolefins such as, for example, low or high density polyethylene, polypropylene, linear polybutene-1, polyisoprene, polybutadiene and copolymers of mono- or diolefins or mixtures of the polymers mentioned; Copolymers of mono- or diolefins with other vinyl monomers, such as, for example, ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylate copolymers, ethylene-vinyl acetate copolymers or ethylene-acrylic acid copolymers;
  • Polystyrene and copolymers of styrene or ⁇ -methylstyrene with dienes and / or acrylic derivatives such as Styrene-butadiene, styrene-acrylonitrile (SAN), styrene-ethyl methacrylate, styrene-butadiene-ethyl acrylate, styrene-acrylonitrile-methacrylate, acrylonitrile-butadiene-styrene (ABS) or methyl methacrylate-butadiene-styrene (MBS);
  • SAN styrene-acrylonitrile
  • ABS acrylonitrile-butadiene-styrene
  • MVS methyl methacrylate-butadiene-styrene
  • Halogen-containing polymers e.g. Polyvinyl chloride, polyvinyl fluoride, polyvinylidene fluoride and their copolymers;
  • Polymers derived from ⁇ , ⁇ -unsaturated acids and their derivatives such as polyacrylates, polymethacrylates, polyacrylamides and polyacrylonitriles;
  • Polymers derived from unsaturated alcohols and amines or from their acyl derivatives or acetals e.g. Polyvinyl alcohol and polyvinyl acetate;
  • Polyurethanes Polyamides, polyureas, polyesters, polycarbonates, polysulfones, polyether sulfones and polyether ketones.
  • Coatings can also be stabilized with the copolymers according to the invention, e.g. Industrial paints.
  • stove enamels in particular vehicle paints, preferably two-coat paints, are particularly noteworthy.
  • Another area of use is e.g. Paints for exterior painting of buildings, other structures or technical equipment.
  • copolymers according to the invention can be added to the lacquer in solid or dissolved form. Their good solubility in coating systems is of particular advantage.
  • the compounds I according to the invention are notable for good compatibility with the customary types of plastics and for good solubility and excellent compatibility in the customary coating systems. As a rule, they have no or only a very slight intrinsic color, are stable at the usual plastics and lacquer processing temperatures and are not volatile and, above all, bring about a long protection period for the materials treated with them.
  • Example e
  • Copolymers had different molecular weights. As a measure of their size, the viscosity at 120 ° C was determined, which is also shown in Table 1.
  • Example 3 0.1% by weight of the copolymers containing tetramethylpiperidine according to Example 3 and Example 17 (comparative sample) were incorporated by extrusion once in low-density polyethylene.
  • the granules obtained were processed into 250 ⁇ m thick films. Pieces of these films were subjected to a rapid weathering test (device: Xenotest 1200). The time until embrittlement (cracking) of the test specimens was measured.

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • Dermatology (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Paints Or Removers (AREA)
  • Hydrogenated Pyridines (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Copolymères renfermant de la tétraméthylpipéridine, comprenant 1 à 100 % en moles de motifs monomères, identiques ou différents, de formule générale (I) (R?1=COOR7, COR8, CONR8R9, CN; R2¿=H, alkyle en C¿1?-C12, COOR?7, COR8, CONR8R9, CN; R3¿=H, méthyle, éthyle, propyle; R6=H, alkyle en C¿1?-C8; R?7¿=H, alkyle en C¿1?-C8, cycloalkyle en C5-C8, alcényle en C3-C5, phényle substitué ou non; R?8 et R9¿=H, alkyle en C¿1?-C12, cycloalkyle en C5-C8, phényle substitué ou non; X=oxygène, soufre, NR?6¿), ainsi que d'autres monomères. L'invention concerne en outre un procédé de production des copolymères précités, leur utilisation comme agents de protection contre la lumière ou stabilisants, ainsi qu'une matière organique renfermant lesdits copolymères.
EP96939088A 1995-11-29 1996-11-18 Copolymeres renfermant de la tetramethylpiperidine Withdrawn EP0874821A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19544404A DE19544404A1 (de) 1995-11-29 1995-11-29 Tetramethylpiperidinhaltige Copolymere
DE19544404 1995-11-29
PCT/EP1996/005068 WO1997019922A1 (fr) 1995-11-29 1996-11-18 Copolymeres renfermant de la tetramethylpiperidine

Publications (1)

Publication Number Publication Date
EP0874821A1 true EP0874821A1 (fr) 1998-11-04

Family

ID=7778647

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96939088A Withdrawn EP0874821A1 (fr) 1995-11-29 1996-11-18 Copolymeres renfermant de la tetramethylpiperidine

Country Status (6)

Country Link
US (1) US5973040A (fr)
EP (1) EP0874821A1 (fr)
JP (1) JP2000501132A (fr)
AU (1) AU7627096A (fr)
DE (1) DE19544404A1 (fr)
WO (1) WO1997019922A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6366340B1 (en) * 1995-08-18 2002-04-02 Hitachi, Ltd. Electron exposure apparatus
SG91852A1 (en) * 1998-12-21 2002-10-15 Toyo Boseki Hindered amine compound, resin composition, polyurethane fiber and production method and use thereof

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS53282A (en) * 1976-06-24 1978-01-05 Nippon Paint Co Ltd Thermosetting resin, method of preparing same, and coating composition containing same as main component
EP0000496B1 (fr) * 1977-07-19 1982-05-19 Ciba-Geigy Ag Polymères acryliques substitués par des noyaux N-hétérocycliques et leur utilisation comme agent contre la dégradation par la lumière
US4413096A (en) * 1981-04-13 1983-11-01 Ciba-Geigy Corporation α-Olefin copolymers containing pendant hindered amine groups
US4450224A (en) * 1983-07-06 1984-05-22 Eastman Kodak Company Polymeric mordants
DE4139606A1 (de) * 1991-11-30 1993-06-03 Basf Ag Polyalkylpiperidingruppen enthaltende (beta)-aminoacrylsaeureester-derivate
DE4140304A1 (de) * 1991-12-06 1993-06-09 Basf Ag, 6700 Ludwigshafen, De N-((beta)-carbonyl- und (beta)-cyanovinyl)-2,2,6,6- tetramethylpiperidin-derivate
DE4211603A1 (de) * 1992-04-07 1993-10-14 Basf Ag Polyalkylpiperidin-Gruppen enthaltende Essigsäure- und 3-Aminoacrylsäure-Derivate

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9719922A1 *

Also Published As

Publication number Publication date
DE19544404A1 (de) 1997-06-05
US5973040A (en) 1999-10-26
JP2000501132A (ja) 2000-02-02
WO1997019922A1 (fr) 1997-06-05
AU7627096A (en) 1997-06-19

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