Classifications

• • 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
  • C07—ORGANIC CHEMISTRY
  • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
  • C07B63/00—Purification; Separation; Stabilisation; Use of additives
  • C07B63/04—Use of additives
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/10—Homopolymers or copolymers of propene
  • C08L23/12—Polypropene
• • 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
• • 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
  • C09D7/65—Additives macromolecular
• • 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
• • 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
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K2201/00—Specific properties of additives
  • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2201/00—Properties
  • C08L2201/08—Stabilised against heat, light or radiation or oxydation
• • 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
  • C09K15/20—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing nitrogen and oxygen

Definitions

• the invention relates to a mixture composed of oligomeric and monomeric compounds of HALS type, to a process for their preparation, and also to their use as stabilizers for organic material.
• Organic material in particular plastics and paints, is known to decompose very rapidly, especially via exposure to light. This decomposition is usually apparent from yellowing, discoloration, cracking, or embrittlement of the material. Light stabilizers and other stabilizers are therefore intended to achieve satisfactory prevention of decomposition of organic material via light, oxygen, and heat.
• HALS Hindered Amine Light Stabilizers
• WO 94/12544 describes maleimide- ⁇ -olefin copolymers which have HALS groups as substituents, features of these copolymers being not only the lack of any tendency toward migration within the material to be protected but also good compatibility with the usual types of plastic, and good solubility, and excellent compatibility in the usual paint systems.
• the object is achieved via a mixture of the oligomeric HALS described above with certain low-molar-mass (M ⁇ 1000 g/mol) HALS.
• the inventive mixture firstly has increased, synergistic stabilizing action and secondly exhibits improved storage properties and improved transport properties, because, unlike the oligomeric compounds alone, it has no tendency toward caking on storage.
• the inventive mixture does not therefore need to be diluted with diluents, such as fumed silica, silicates, alkaline earth metal stearates, or talc.
• the invention therefore provides a mixture, comprising
• the inventive mixtures are used for stabilization of organic material, in particular of polymers, with respect to the effect of light.
• the average molecular weight of the oligomers (A) is generally from 1000 to 50 000, preferably from 1500 to 10 000, in particular from 2000 to 5000.
• the molecular weights given are number-average molecular weights.
• the average number of repeat units is from 3 to 100, preferably from 4 to 30, in particular from 5 to 10.
• the radical R 1 is preferably H, C 1 -C 6 -alkyl, formyl, acyl, C 1 -C 6 -alkoxy, or benzyl, particularly preferably H, methyl, formyl, acyl or benzyl, in particular H.
• the radical R 2 is a mixture composed of C 14 -C 28 -alkyl groups, preferably C 16 -C 24 -alkyl groups, in particular C 18 -C 22 -alkyl groups, and the units on which the copolymer is based are therefore C 16 -C 30 ⁇ -olefins, preferably C 18 -C 26 ⁇ -olefins, in particular C 20 -C 24 ⁇ -olefins.
• R 2 is preferably linear alkyl groups.
• a mixture of alkyl groups for R 2 means that, when a statistical average is taken across the entire number of all of the copolymer molecules present, two particular alkyl groups whose number of carbon atoms is not permitted to differ by more than two respectively make up at least 30%, preferably respectively make up at least 40%, of this mixture.
• two particular alkyl groups whose number of carbon atoms is not permitted to differ by more than two respectively make up at least 30%, preferably respectively make up at least 40%, of this mixture.
• 3 particular alkyl groups e.g.
• octadecyl, eicosyl, and docosyl where two of these groups whose number of carbon atoms differs by 2 make up more than 40% of the mixture, and the third group makes up from 3 to 18% of the mixture; other alkyl groups having somewhat fewer than 18 or somewhat more than 22 carbon atoms can be present in the mixture here; their amounts being very small, usually less than 2%.
• radicals R 3 and R 4 are preferably C 1 -C 4 -alkyl, particularly preferably methyl, and the meaning of all of the radicals R 3 and R 4 is in particular respectively methyl.
• Alkyl radicals that can be used and are claimed in the form of C 1 -C 6 (for R 3 and R 4 ) and C 1 -C 18 (for R′′) are branched, and in particular straight-chain members of the group, and therefore especially methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-amyl, isoamyl, sec-amyl, tert-amyl, neopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, 2-propylheptyl, n-nonyl, isononyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, isotridecyl, n-tetrade
• Straight-chain or branched C 2 -C 6 -alkanoyl that can be used for R 1 is especially acetyl, but also propionyl, butyryl, isobutyryl, pentanoyl, and hexanoyl.
• C 6 -C 8 -alkoxy groups such as n-hexoxy, isohexoxy, n-octoxy, 2-ethylhexoxy, and isooctoxy, but also methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, n-nonoxy, n-decoxy, n-undecoxy, and n-dodecoxy.
• C 6 -C 8 -alkoxy groups such as n-hexoxy, isohexoxy, n-octoxy, 2-ethylhexoxy, and isooctoxy, but also methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, n-nonoxy, n-dec
• C 5 -C 6 -cycloalkoxy groups for R 1 are especially cyclopentoxy and cyclohexoxy.
• C 5 -C 8 -cycloalkyl radicals that can be used for R′′ are especially cyclopentyl and cyclohexyl, but also cycloheptyl, cyclooctyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, ethylcyclohexyl, and dimethylcyclohexyl.
• C 7 -C 18 -aralkyl radicals for R′′ are naphthylmethyl, diphenylmethyl, or methylbenzyl, but in particular C 7 -C 18 -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 preferably benzyl.
• C 7 -C 18 -aralkyl radicals for R′′ are naphthylmethyl, diphenylmethyl, or methylbenzyl, but in particular C 7 -C 18 -phenylalkyl, such as 1-phenylethyl, 2-phenylethyl, 1-phenylpropyl, 2-phenylprop
• Tolyl radicals that can be used are ortho-, meta-, and preferably p-tolyl.
• oligomeric component A An oligomer having the repeat unit (Ia) whose number-average molar mass is from 3000 to 4000 g/mol is particularly preferred as oligomeric component A
• a compound of this type is obtainable as Uvinul® 5050 H from BASF Aktiengesellschaft, Ludwigshafen, Germany.
• the compounds can be prepared by the methods given in WO 94/12544.
• n and n are preferably a natural number from 4 to 10, particularly preferably 6 or 8, and especially preferably m is the number 6 and n is the number 8.
• the compounds (IIa), (IIIa), and (IIIb) are particularly preferred as compounds of component (B)
• the compound (IIa) is particularly preferred as component B.
• the compounds of the formula III are not commercially obtainable, they can be prepared by methods that are known and familiar to the person skilled in the art, for example via esterification of sebacic esters with 2,2,6,6-tetraalkylpiperidin-4-ol derivatives.
• the ratio by weight of components (A) and (B) in the inventive mixtures is generally from 5:1 to 1:5, preferably from 2:1 to 1:2, particularly preferably from 1.2:1 to 1:1.2, and particular preference is given to a mixture whose ratio by weight is about 1:1.
• inventive mixtures can be prepared by processes that are known and familiar to the person skilled in the art.
• Component (B) can preferably be added to a melt of component (A), and the mixture can be homogenized, and converted to the desired form, for example pastilles, and allowed to cool.
• the invention therefore also provides a respective process for preparation of the inventive mixtures.
• the combination (a) is particularly preferred.
• the inventive mixtures have excellent suitability for use as stabilizers for stabilization of organic material (preferably not of living organic material) with respect to exposure to light, oxygen, and heat. They are added at a concentration of from 0.01 to 5% by weight, preferably from 0.02 to 1% by weight, based on the organic material, to the organic materials to be stabilized, prior to, during, or after their preparation.
• the inventive mixture can be added to the organic material to be protected in the form of a prefabricated mixture of components (A) and (B), but another possibility is separate addition of components (A) and (B) to the material to be protected, in which case the mixture is not produced until the components are present within the material to be protected. In the event of separate addition of components (A) and (B), this can take place simultaneously or non-simultaneously, and the sequence here is not generally significant.
• organic material examples include cosmetic preparations, such as ointments and lotions, pharmaceutical formulations, such as pills and suppositories, photographic recording material, such as photographic emulsions, or precursors for plastics and paints, but in particular plastics and paints themselves.
• the invention also provides an organic material stabilized with respect to exposure to light, oxygen, and heat, in particular a plastic or paint, where the material comprises an inventive mixture, preferably at the concentrations given above.
• any of the known apparatus and methods for mixing to incorporate stabilizers or other additives into polymers can be used for mixing of the inventive mixture, particularly with plastics.
• inventive mixture, or the organic material to be stabilized via the mixture optionally also comprises at least one further light stabilizer and/or other (co)stabilizers.
• suitable light stabilizers and other (co)stabilizers are those selected from the groups a) to s):
• the group a) of the 4,4-diarylbutadienes includes, for example, compounds of the formula (aa)
• the compounds are known from EP-A 916 335.
• the R 5 and/or R 6 substituents are preferably C 1 -C 8 -alkyl and C 5 -C 8 -cycloalkyl.
• the group b) of the cinnamates includes, for example, 2-isoamyl 4-methoxycinnamate, 2-ethylhexyl 4-methoxycinnamate, methyl ⁇ -(methoxycarbonyl)cinnamate, methyl ⁇ -cyano- ⁇ -methyl-p-methoxycinnamate, butyl ⁇ -cyano- ⁇ -methyl-p-methoxycinnamate and methyl ⁇ -(methoxycarbonyl)-p-methoxycinnamate.
• the group c) of the benzotriazoles includes, for example, 2-(2′-hydroxyphenyl)benzotriazoles, such as 2-(2′-hydroxy-5′-methylphenyl)benzotriazole, 2-(3′,5′-di(tert-butyl)-2′-hydroxyphenyl)benzotriazole, 2-(5′-(tert-butyl)-2′-hydroxyphenyl)benzotriazole, 2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3′,5′-di(tert-butyl)-2′-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3′-(tert-butyl)-2′-hydroxy-5′-methylphenyl)-5-chlorobenzotriazole, 2-(3′-(sec-butyl)-5′-(tert-butyl)-2′-hydroxyphenyl)benzotri
• the group d) of the hydroxybenzophenones includes, for example, 2-hydroxybenzophenones, such as 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2,2′,4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2-hydroxy-4-(2-ethylhexyloxy)benzophenone, 2-hydroxy-4-(n-octyloxy)benzophenone, 2-hydroxy-4-methoxy-4′-methylbenzophenone, 2-hydroxy-3-carboxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its sodium salt, and 2,2′-dihydroxy-4,4′-dimethoxybenzophenone-5,5′-disulfonic acid and its sodium
• the group e) of the diphenylcyanoacrylates includes, for example, ethyl 2-cyano-3,3-diphenylacrylate, which, for example, is obtainable commercially as Uvinul® 3035 from BASF Aktiengesellschaft, Ludwigshafen, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, which, for example, is obtainable commercially as Uvinul® 3039 from BASF Aktiengesellschaft, Ludwigshafen, and 1,3-bis[(2′-cyano-3′,3′-diphenylacryloyl)oxy]-2,2-bis ⁇ [(2′-cyano-3′,3′-diphenylacryloyl)oxy]methyl ⁇ propane, which, for example, is obtainable commercially as Uvinul® 3030 from BASF Aktiengesellschaft, Ludwigshafen.
• the group f) of the oxamides includes, for example, 4,4′-dioctyloxyoxanilide, 2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di(tert-but)oxanilide, 2,2′-didodecyloxy-5,5′-di(tert-but)oxanilide, 2-ethoxy-2′-ethyloxanilide, N,N′-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-(tert-butyl)-2′-ethoxanilide and its mixture with 2-ethoxy-2′-ethyl-5,4′-di(tert-but)oxanilide, and also mixtures of ortho- and para-methoxy-disubstituted oxanilides and mixtures of ortho- and para-ethoxy-disubstituted o
• the group g) of the 2-phenyl-1,3,5-triazines includes, for example, 2-(2-hydroxyphenyl)-1,3,5-triazines, such as 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-propyl-oxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4
• the group h) of the antioxidants comprises, for example:
• the group i) of the nickel compounds includes, for example, nickel complexes of 2,2′-thiobis[4-(1,1,3,3-tetramethylbutyl)phenols], such as the 1:1 or 1:2 complex, if appropriate with additional ligands, such as n-butylamine, triethanolamine, or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of monoalkyl 4-hydroxy-3,5-di-tert-butylbenzylphosphonates, e.g. the methyl or ethyl ester, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphenyl undecyl ketoxime, nickel complex of 1-phenyl-4-lauroyl-5-hydroxypyrazole, if appropriate with additional ligands.
• additional ligands such as n-butylamine, triethanolamine, or N-cyclohexyldiethanolamine, nickel dibutyl
• the group j) of the sterically hindered amines includes, for example, 4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-benzyl-4-hydroxy-2,2,6,6-tetramethylpiperidine, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) (n-butyl)(3,5-di(tert-butyl)-4-hydroxybenzyl)malonate ((n-butyl)(3,5-di(tert-butyl)-4-hydroxy
• the group k) of the metal deactivators includes, for example, N,N′-diphenyloxamide, N-salicylal-N′-salicyloylhydrazine, N,N′-bis(salicyloyl)hydrazine, N,N′-bis(3,5-di(tert-butyl)-4-hydroxyphenylpropionyl)hydrazine, 3-salicyloylamino-1,2,4-triazole, the bis(benzylidene) derivative of oxalic dihydrazide, oxanilide, isophthalic dihydrazide, sebacic bisphenylhydrazide, N,N′-diacetyladipic acid dihydrazide, N,N′-bis(salicyloyl)oxalic acid dihydrazide or N,N′-bis(salicyloyl)thiopropionic dihydrazide.
• the group I) of the phosphites and phosphonites includes, for example, triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di(tert-butyl)phenyl)phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di(tert-butyl)phenyl)pentaerythritol diphosphite, bis(2,6-di(tert-butyl)-4-methylphenyl)pentaerythritol diphosphite, diisodecyloxy pentaerythri
• the group m) of the hydroxylamines includes, for example, N,N-dibenzyl-hydroxylamine, N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine, N,N-dilauryl-hydroxylamine, N,N-ditetradecylhydroxylamine, N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N-methyl-N-octadecylhydroxylamine and N,N-dialkylhydroxyl-amine from hydrogenated tallow fatty amines.
• the group n) of the nitrones includes, for example, N-benzyl- ⁇ -phenylnitrone, N-ethyl- ⁇ -methylnitrone, N-octyl- ⁇ -heptylnitrone, N-lauryl- ⁇ -undecylnitrone, N-tetradecyl- ⁇ -tridecylnitrone, N-hexadecyl- ⁇ -pentadecylnitrone, N-octadecyl- ⁇ -heptadecylnitrone, N-hexadecyl- ⁇ -heptadecylnitrone, N-octadecyl- ⁇ -pentadecylnitrone, N-heptadecyl- ⁇ -heptadecylnitrone, N-octadecyl- ⁇ -hexadecylnitrone, N-methyl- ⁇ -heptadecylnitro
• the group o) of the amine oxides includes, for example, amine oxide derivatives as disclosed in U.S. Pat. Nos. 5,844,029 and 5,880,191, didecylmethylamine oxide, tridecylamine oxide, tridodecylamine oxide and trihexadecylamine oxide.
• the group p) of the benzofuranones and indolinones includes, for example, those disclosed in U.S. Pat. Nos. 4,325,863, 4,338,244, 5,175,312, 5,216,052 or 5,252,643, in DE-A-4316611, in DE-A-4316622, in DE-A-4316876, in EP-A-0589839 or in EP-A-0591102 or 3-[4-(2-acetoxyethoxy)phenyl]-5,7-di(tert-butyl)benzofuran-2-one, 5,7-di(tert-butyl)-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one, 3,3′-bis[5,7-di(tert-butyl)-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one], 5,7-di(tert-butyl)-3-(4-ethoxypheny
• the group q) of the thiosynergists includes, for example, dilauryl thiodipropionate or distearyl thiodipropionate.
• the group r) of the peroxide-destroying compounds includes, for example, esters of ⁇ -thiodipropionic acid, e.g. the lauryl, stearyl, myristyl or tridecyl ester, mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide or pentaerythritol tetrakis( ⁇ -dodecylmercaptopropionate).
• esters of ⁇ -thiodipropionic acid e.g. the lauryl, stearyl, myristyl or tridecyl ester
• mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole zinc dibutyldithiocarbamate
• dioctadecyl disulfide dioctadecyl disulfide or
• the group s) of the basic costabilizers includes, for example, melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, the alkali metal and alkaline earth metal salts of higher fatty acids, e.g. calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate, and potassium palmitate, antimony pyrocatecholate or zinc pyrocatecholate.
• higher fatty acids e.g. calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate, and potassium palmitate, antimony pyrocatecholate or zinc pyrocatecholate.
• the plastic can moreover comprise other additives and added materials.
• Suitable additives of group t) that can be used are the conventional added materials, e.g.
• pigments, dyes, nucleating agents, fillers or reinforcing agents, antifogging agents, biocides, and antistatic agents are examples of pigments, dyes, nucleating agents, fillers or reinforcing agents, antifogging agents, biocides, and antistatic agents.
• Suitable pigments are inorganic pigments, such as titanium dioxide in its three crystalline forms: rutile, anatase, or brookite, ultramarine blue, iron oxides, bismuth vanadates, or carbon black, and also the class of the organic pigments, for example compounds from the class of the phthalocyanines, perylenes, azo compounds, isoindolines, quinophthalones, diketopyrrolopyrroles, quinacridones, dioxazines, indanthrones.
• inorganic pigments such as titanium dioxide in its three crystalline forms: rutile, anatase, or brookite, ultramarine blue, iron oxides, bismuth vanadates, or carbon black
• class of the organic pigments for example compounds from the class of the phthalocyanines, perylenes, azo compounds, isoindolines, quinophthalones, diketopyrrolopyrroles, quinacridones, diox
• Dyes are any of the colorants which dissolve completely in the plastic used or are present in molecularly dispersed form and therefore can be used to provide high-transparency, non-diffusion coloring of polymers.
• Other dyes are organic compounds which fluoresce in the visible portion of the electromagnetic spectrum, e.g. fluorescent dyes.
• Suitable nucleating agents comprise, for example, inorganic substances, such as talc, metal oxides, such as titanium dioxide or magnesium oxide, phosphates, carbonates, or sulfates, preferably of alkaline earth metals; organic compounds, such as mono- or polycarboxylic acids, and also their salts, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate, or sodium benzoate; polymeric compounds, such as ionic copolymers (“ionomers”).
• Suitable fillers or reinforcing materials comprise, for example, calcium carbonate, silicates, talc, mica, kaolin, barium sulfate, metal oxides, metal hydroxides, carbon black, graphite, wood flour, and flours or fibers composed of other natural products, and synthetic fibers.
• Other examples of fibrous or pulverulent fillers that can be used are carbon fibers or glass fibers in the form of glass textiles, glass mats, or glass silk rovings, chopped glass, glass beads, and also wollastonite. Glass fibers can be incorporated in the form of short glass fibers or else in the form of continuous-filament fibers (rovings).
• Suitable antistatic agents are amine derivatives, such as N,N-bis-(hydroxyalkyl)alkylamines or -alkyleneamines, polyethylene glycol esters and polyethylene glycol ethers, ethoxylated carboxylic esters and ethoxylated carboxamides, and glycerolmono- and distearates, and also mixtures of these.
• plastics which can be stabilized via the inventive mixtures are:
• polymers of mono- and diolefins e.g. low- and high-density polyethylene, polypropylene, linear poly-1-butene, polyisoprene, polybutadiene, and also copolymers of mono- or diolefins, and mixtures of the polymers mentioned;
• copolymers of mono- or diolefins with other vinyl monomers e.g. ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylate copolymers, ethylene-vinyl acetate copolymers, or ethylene-acrylic acid copolymers;
• polystyrene and also copolymers of styrene or a-methylstyrene with dienes and/or with acrylic derivatives, e.g. 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
• halogenated polymers e.g. polyvinyl chloride, polyvinyl fluoride, polyvinylidene fluoride, and also their copolymers;
• polymers which derive from ⁇ , ⁇ -unsaturated acids and from their derivatives, e.g. polyacrylates, polymethacrylates, polyacrylamides, and polyacrylonitriles;
• polymers which derive from unsaturated alcohols and amines and, respectively, from their acrylic derivatives or acetals, e.g. polyvinyl alcohol and polyvinyl acetate;
• polyurethanes polyamides, polyureas, polyesters, polycarbonates, polysulfones, polyether sulfones, and polyether ketones.
• inventive mixtures to stabilize paint coatings, e.g. industrial paints.
• paint coatings e.g. industrial paints.
• these may be especially highlighted: stoved finishes, and among these in turn vehicle finishes, preferably two-layer finishes.
• Examples of another application sector are paints for exterior painting of buildings, of other structures, or of industrial apparatus.
• inventive mixtures can be in solid or dissolved form when they are added to the paint. Their good solubility in paint systems is a particular advantage here.
• inventive mixtures are preferably used for stabilization of polyamides, and also of ABS polymers and of SAN polymers, in particular of molding compositions derived therefrom, and of paint coatings.
• Another preferred application sector is stabilization of low- and high-density polyethylene, and also of polypropylene and polyamide, including, for example, stabilization of fibers derived therefrom.
• poly ⁇ 3-(eicosyltetracosyl)-1-[2,2,6,6-tetramethylpiperidin-4-yl]pyrrolidine-2,5-dione ⁇ (CAS No. 152261-33-1; HALS Ia), and also the mixture prepared in example 1, were stored separately at 40° C. in plastic bags. The specimens were assessed visually after 20 h.
• HALS IVa Polymer composed of 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-dispiro[5.1.11.2]heneicosan-21-one and epichlorohydrin (CAS No. 202483-55-4); HALS IVb: 2,2,4,4-tetramethyl-7-oxa-3,20-diazadispiro[5.1.11.2]heneicosan-21-one (CAS No. 64338-16-5).
• Stretched (1:5) tapes composed of polypropylene with various stabilizers were produced and weathered to DIN EN ISO 4892-2.
• the ultimate tensile strength of the specimens was tested at regular intervals.
• the specimen was regarded as decomposed as soon as residual ultimate tensile strength was smaller than or equal to 50% of the initial ultimate tensile strength.
• HALS Ia poly ⁇ 3-(eicosyltetracosyl)-1-[2,2,6,6-tetramethylpiperidin-4-yl]-pyrrolidine-2,5-dione ⁇ (CAS No. 152261-33-1); HALS IIa: N,N′-bisformyl-N,N′-bis(2,2,6,6-tetramethyl-4-piperidinyl)hexa-methylenediamine (CAS No. 124172-53-8); HALS V: polymer of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinylethanol and dimethyl butanedioate

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Life Sciences & Earth Sciences (AREA)
• Wood Science & Technology (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Applications Claiming Priority (3)

Related Parent Applications (1)

Related Child Applications (1)

Publications (1)

Family

ID=37771058

Family Applications (3)

Family Applications After (2)

Country Status (9)

Cited By (2)

Families Citing this family (3)

Citations (3)

Family Cites Families (4)

• 2007
  • 2007-01-12 BR BRPI0707120-5A patent/BRPI0707120A2/pt not_active IP Right Cessation
  • 2007-01-12 CN CN2007800023251A patent/CN101370865B/zh active Active
  • 2007-01-12 MX MX2008008407A patent/MX277096B/es active IP Right Grant
  • 2007-01-12 AT AT07703822T patent/ATE432315T1/de active
  • 2007-01-12 DE DE502007000786T patent/DE502007000786D1/de active Active
  • 2007-01-12 WO PCT/EP2007/050281 patent/WO2007082842A1/fr active Application Filing
  • 2007-01-12 US US12/160,724 patent/US20100160502A1/en not_active Abandoned
  • 2007-01-12 EP EP07703822A patent/EP1976925B1/fr active Active
  • 2007-01-12 JP JP2008549878A patent/JP5393157B2/ja active Active
• 2013
  • 2013-05-01 US US13/874,619 patent/US9475918B2/en active Active
• 2016
  • 2016-09-19 US US15/268,846 patent/US20170002178A1/en not_active Abandoned

Patent Citations (3)

Also Published As

Similar Documents

Legal Events