Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
  • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
  • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
• • 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
  • C07D211/92—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
  • 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
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/48—Stabilisers against degradation by oxygen, light or heat

Definitions

• the present invention relates to novel polyalkylpiperidine group-containing acetic acid and 3-aminoacrylic acid derivatives I
• R 1 is hydrogen, C 1 -C 1 -alkyl, formyl, C 2 - to
• R 3 is hydrogen, -C ⁇ to C ß alkyl or a radical of the formula -CO-OR 4 and
• R 4 Ci to C 20 alkyl, C 5 to Cs cycloalkyl, C 7 to
• R 2 cyano, a radical of the formula -CO-R 5 or -CO-OR 5 or a group of the formula
• R 5 is C-- to -C 2 alkyl, C 5 - to Cs-cycloalkyl, benzyl, phenyl or tolyl,
• X represents 0, NH or NR ⁇ , where
• R 6 means Ci to -C 2 alkyl
• R 7 is phenyl which groups 2 alkyl substituted by one to three C ⁇ ⁇ to C ⁇ , C ⁇ ⁇ C ⁇ to groups 2 alkoxy groups, halogen atoms, cyano groups, hydroxyl groups, phenyl groups or groups of the formula -CO-OR 5, -CO-R 5 , -CO-NHR 5 , -0-CO-R 5 or -NH-CO-R 5 may be substituted, a five- or six-membered unsaturated or saturated heterocyclic ring with up to three heteroatoms from the group nitrogen, oxygen and sulfur be additionally comprising benzo- fused and up C ⁇ pen 2 -Alkylgrup- by one to three C ⁇ ⁇ pen C ⁇ ⁇ to C ⁇ 2 alkoxy groups, halogen atoms, Cyanogrup ⁇ , hydroxyl groups, phenyl groups, phenoxy groups or C to C 2 alkoxycarbonyl groups substituted can, or - in the event that at least one variable X is
• the invention relates to compounds I stabilized against the action of light, oxygen and heat, organic material, in particular stabilized plastics and paints.
• organic material especially plastics and paints
• This destruction is usually manifested in yellowing, discoloration, cracking or embrittlement of the material. Satisfactory protection against the destruction of organic material by light, oxygen and heat should therefore be achieved with light stabilizers and stabilizers.
• DE-A 38 05 786 (2) relates to 3- (polyalkylpiperidinylamino) acrylic acid polyalkylpiperidinyl esters. These compounds are recommended as stabilizers for organic material, especially synthetic polymers.
• R 1 , R 3 to R 6 , R 8 as substituents on the phenyl nucleus and on heterocyclic rings and as an alcohol radical in alkoxycarbonyl groups, which are known as Ci to C 4 , C 1 to C 4 , C 4 ⁇ to C 12 - and C ⁇ ⁇ to C 2 o-alkyl radicals are suitable, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-amyl, iso-amyl, sec.-amyl, tert.-amyl, neopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethyl hexyl, n-nonyl, iso-nonyl, n-
• Suitable straight-chain or branched C 2 -C 6 -alkanoyl for R 1 are acetyl in particular, but also propionyl, butyryl, isobutyryl, pentanoyl and hexanoyl.
• C ⁇ ⁇ to C ⁇ 2 alkoxy groups for R 1 and as substituents on the phenyl nucleus and on heterocyclic rings are especially C ⁇ ⁇ to C 4 alkoxy groups such as methoxy, ethoxy, n-propoxy, iso-propoxy , n-butoxy, iso-butoxy, sec-butoxy and tert-butoxy, but also n-pentoxy, n-hexoxy, iso-hexoxy, n-heptoxy, iso-heptoxy, n-octoxy, 2-ethylhexoxy, iso-octoxy, n-nonoxy, n-decoxy, n-undecoxy and n-dodecoxy.
• C 5 - to C 6 ⁇ cycloalkoxy groups for R 1 are especially cyclopentoxy and cyclohexoxy.
• R 3 is preferably C 1 -C 4 -alkoxycarbonyl, such as especially methoxycarbonyl and ethoxycarbonyl or in particular hydrogen.
• Suitable C 5 - to Ca-cycloalkyl radicals for R 4 and R 5 are especially C 5 - to C ß- cycloalkyl such as cyclopentyl and cyclohexyl, but also cycloheptyl, cyclooctyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, ethylcyclohexyl and dimethylcyclohexyl .
• Suitable C 7 - to C ⁇ 8 -aralkyl radicals for R 4 are, for example, naphthylmethyl, diphenylmethyl or methylbenzyl, but in particular C 7 - to cin-phenylalkyl such as 1-phenylethyl, 2-phenylethyl, 1-phenylpropyl, 2-phenylpropyl , 3-phenylpropyl, 2-phenylprop-2-yl, 4-phenylbutyl, 2,2-dimethyl-2-phenylethyl, 5-phenylamyl, 10-phenyldecyl, 12-phenyldodecyl or especially benzyl.
• Suitable tolyl radicals are ortho-, meta and especially p-tolyl.
• the degree of alkoxylation n in the polyoxyethylene and polyoxypropylene radicals for R 4 is preferably 1 to 10, in particular 2 to 7, very particularly preferably 3 to 5.
• Halogen atoms are to be understood as fluorine, iodine, but especially bromine and especially chlorine. '
• substituted phenyl radicals occur as radicals R 7 and R 9 , the preferred degree of substitution is 2 or in particular 1.
• Monosubstituted phenyl radicals are ortho-, meta- or preferably para-substituted, doubly substituted phenyl radicals often have a 2,4- Substitution patterns and triply substituted phenyl radicals are often used
• the structure I includes both the respective E with respect to the spatial position of the substituents on the CC double bond in the compounds I. - as well as the Z isomers. Mixtures of both isomers can of course also occur.
• R 2 denotes cyano or C bis ⁇ to C 4 alkoxycarbonyl.
• R 9 is phenyl which is substituted by one or two Cteil ⁇ to C 4 alkyl groups, C ⁇ ⁇ to C 4 Alkoxy groups, chlorine atoms, cyano groups, hydroxyl groups or C ⁇ ⁇ to C 4 ⁇ alkoxycarbonyl groups can be substituted, or a six-membered unsaturated or saturated heterocyclic ring with up to three nitrogen atoms, which additionally benzanelliert and by one or two C ⁇ ⁇ to C 4 -alkyl groups, C ⁇ ⁇ to C 4 ⁇ alkoxy groups, chlorine atoms, cyano groups, hydroxy groups or C ⁇ ⁇ to C 4 ⁇ alkoxycarbonyl groups can be substituted.
• Pyridine, pyrimidine, pyridazine, pyrazine and 1,3,5-triazine are particularly suitable as heterocyclic rings for R 9 .
• polyalkylpiperidine groups according to the invention containing the acetic acid and 3-aminoacrylic acid derivatives I can be prepared by methods known per se.
• the reaction is conveniently carried out in a suitable polar organic solvent such as an alcohol, e.g. n-propanol, n-butanol, ethylene glycol, diethylene glycol, ethylene glycol monomethyl ether or cyclohexanol.
• a suitable polar organic solvent such as an alcohol, e.g. n-propanol, n-butanol, ethylene glycol, diethylene glycol, ethylene glycol monomethyl ether or cyclohexanol.
• Carboxylic acid amides such as dimethylformamide or excess trialkyl orthoformate are also suitable as solvents. If the starting compounds used already form a liquid mixture, an additional solvent can be dispensed with.
• Lewis acids such as boric acid, AICI3, ZrCl 4 , TiCl4 or, above all, ZnCl 2 can also be used as catalysts for the reaction in the amounts customary for this.
• the 3-aminoacrylic acid alkyl esters prepared in this way can be easily converted into the corresponding derivatives I containing polyalkylpiperidine groups.
• This is advantageously done by transesterification with, for example, 2,2,6,6-tetramethyl-4-piperidinol in an inert organic solvent such as toluene or xylene in the presence of a catalyst such as tetrabutyl orthotitanate, phenothiazine, lithium amide or dibutyltin acetate.
• polyalkylpiperidinyl-substituted a ides of the formula I is advantageously carried out by reacting the above-mentioned alkyl cyanoacetates, malonalkyl esters or alkyl acetoacetates with triacetone diamine and, if desired, subsequent reaction with aromatic or heterocyclic amines of the formula R 7 -NH 2 or R 7 - NHR 6 as described above.
• radical R 1 in the compounds I denotes an acrylic acid ester group
• compounds I in which R 1 is hydrogen are advantageously reacted with acetylenecarboxylic acid derivatives such as propiolic acid esters or acetylenedicarboxylic acid esters to prepare such compounds.
• the compounds I according to the invention are outstandingly suitable for stabilizing organic material against the action of light, oxygen and heat. They are also effective as metal deactivators. They are added to the organic material to be stabilized in a concentration of 0.01 to 5% by weight, preferably 0.02 to 2% by weight, based on the organic material, before, during or after its production.
• Organic material means, for example, cosmetic preparations such as ointments and lotions, pharmaceutical formulations such as pills and suppositories, photographic recording materials, in particular photographic emulsions, or precursors for plastics and lacquers, but especially plastics and lacquers themselves.
• the present invention also relates to organic material, in particular plastics and lacquers, which is stabilized against the action of light, oxygen and heat and which contains the compounds I in the concentrations indicated above.
• the organic material stabilized by the compounds I according to the invention may optionally contain further additives, e.g. B. antioxidants, light stabilizers, metal deactivators, antistatic agents, flame retardants, pigments and fillers.
• further additives e.g. B. antioxidants, light stabilizers, metal deactivators, antistatic agents, flame retardants, pigments and fillers.
• Antioxidants and light stabilizers which can be added in addition to the compounds I according to the invention are, for. B. Compounds based on sterically hindered phenols or sulfur or phosphorus containing CoStabili ⁇ sators.
• phenolic antioxidants examples include 2,6-di-tert-butyl-4-methylph.enol, n-octa-decyl- ⁇ - (3,5-di-tert-butyl-4-hydroxyphenyl) - propionate, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane.
• phosphorus-containing antioxidants examples include tris (nonylphenyl) phosphite, distearylpentaerythritol diphosphite, tris (2,4-di-tert-butyl-phenyl) phosphite, tris (2-tert-butyl-4-methylphenyl) -phosphite, bis- (2,4-di-tert-butylphenyl) pentaerythritol diphosphite and tetrahis (2,4-di-tert-butylphenyl) -4,4'-biphenylene diphosphite.
• sulfur-containing antioxidants are dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, pentaerythritol tetris (ß-laurylthiopropionate) and pentaerythritol tetris (ß-hexylthiopropionate).
• antioxidants and light stabilizers that can be used together with the compounds I according to the invention are, for. B. 2- (2 r -hydroxyphenyl) benzotriazoles,
• 2-hydroxybenzophenones aryl esters of hydroxybenzoic acids, ⁇ -cyanocinnamic acid derivatives, benzimidazolecarboxylic acid anilides, nickel compounds or oxalic acid dianilides.
• a particularly good stabilization is obtained if at least one further light stabilizer from the class of sterically hindered amines is added to the compounds I in the usual concentration.
• Examples of further sterically hindered amines are: bis- (2,2,6,6-tetramethylpiperidyl) sebacate, bis- (1,2,2,6,6-pentamethylpiperidyl) sebacate, the condensation product of l-Hydroxyethyl-2,2, 6, 6-tetramethyl-4-hydroxypiperidine and succinic acid, the condensation product of N, N '- (2,2,6, 6-tetramethylpiperidyl) -hexamethylene diamine and 4-tert-octylamino -2, 6-dichloro-l, 3,5-triazine, tris (2,2, 6, 6-tetramethylpiperidyl) nitrilotriacetate, tetrakis (2,2,6, 6-tetramethyl-4-piperidyl) -1,2,3,4-butane-tetra- carboxylic acid, 1,1 '- (1,2-ethanediyl) -bis- (3,3,5,5-tetramethyl
• plastics which can be stabilized by the compounds I according to the invention are:
• Polymers of mono- and diolefins such as. B. low or high density polyethylene, polypropylene, linear poly-1-butene, polyisoprene, polybutadiene and copolymers of mono- or diolefins or mixtures of the above-mentioned polymers;
• Copolymers of mono- or diolefins with other vinyl monomers such as.
• Polystyrene and copolymers of styrene or ⁇ -methylstyrene with dienes and / or acrylic derivatives such as.
• ABS acrylonitrile-butadiene-styrene
• MBS methyl methacrylate-butadiene-styrene
• Halogen-containing polymers such as. B. 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 acrylic derivatives or acetals e.g. B. polyvinyl alcohol and polyvinyl acetate;
• lacquer coatings can be stabilized with the compounds I according to the invention, for. B. Industrial paints. Among these, stove enamels, among them in turn vehicle paints, preferably two-coat paints, are particularly noteworthy.
• the compounds I 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 preferably used to stabilize polyurethanes, polyesters, polystyrene, polyolefins such as ethylene or propylene polymers, polyamides, and ABS and SAN polymers, in particular molding compositions thereof, and of lacquer coatings, in particular from acid-curing lacquers .
• Another preferred area of application is the stabilization of fibers made of polypropylene and polyamide.
• 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 conventional 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 non-volatile and, above all, bring about a long protection period for the materials treated with them.
• the invention is further illustrated by the examples below.
• the manufacturing conditions have not been optimized.
• Example 1 Analogously to Example 1, using the corresponding aromatic or heterocyclic amines, the products listed in Table 1 were prepared from N- (2,2,6,6-tetramethyl-piperidin-4-yl) -cyanoacetic acid amide. The melting points and the spectroscopic data of the products are also given in Table 1.
• Example 15a Analogously to Example 15a, the products listed in Table 2 were prepared from the compounds of Examples 2, 3, 5, 6, 7, 9, 10, 11, 12 and 13 and ethyl propiolate. The melting points and the spectroscopic data of the products are also given in Table 2.
• Example 26 Analogously to Example 26, using the corresponding aromatic or heterocyclic amines, the products listed in Table 3 were prepared from 2,2,6,6-tetramethyl-4-piperidinyl esters of cyanoacetate. The melting points and the spectroscopic data of the products are also given in Table 3.
• Example 15a Analogously to Example 15a, the products listed in Table 4 were prepared from the compounds of Examples 26, 27, 28, 29 and 30 and ethyl propiolate. The melting points and the spectroscopic data of the products are also given in Table 4.

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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)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Hydrogenated Pyridines (AREA)
• Paints Or Removers (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Plural Heterocyclic Compounds (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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• 1992
  • 1992-04-07 DE DE4211603A patent/DE4211603A1/de not_active Withdrawn
• 1993
  • 1993-03-24 TW TW082102219A patent/TW230779B/zh active
  • 1993-03-26 EP EP93908853A patent/EP0635005A1/de not_active Withdrawn
  • 1993-03-26 WO PCT/EP1993/000739 patent/WO1993020051A1/de not_active Application Discontinuation
  • 1993-03-26 US US08/313,107 patent/US5624981A/en not_active Expired - Fee Related
  • 1993-03-26 JP JP5517062A patent/JPH07505374A/ja active Pending

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