EP3997164A1 - Use of phenolically substituted sugar derivatives as stabilisers, plastic composition, method for stabilising plastics and phenolically substituted sugar derivatives - Google Patents

Use of phenolically substituted sugar derivatives as stabilisers, plastic composition, method for stabilising plastics and phenolically substituted sugar derivatives

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Publication number
EP3997164A1
EP3997164A1 EP20737440.6A EP20737440A EP3997164A1 EP 3997164 A1 EP3997164 A1 EP 3997164A1 EP 20737440 A EP20737440 A EP 20737440A EP 3997164 A1 EP3997164 A1 EP 3997164A1
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EP
European Patent Office
Prior art keywords
acid
group
sugar
sugar derivative
agents
Prior art date
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EP20737440.6A
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German (de)
French (fr)
Inventor
Rudolf Pfaendner
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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Publication of EP3997164A1 publication Critical patent/EP3997164A1/en
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    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • 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
    • C08K5/20—Carboxylic acid amides
    • 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
    • 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

Definitions

  • Plastic composition Use of phenolically substituted sugar derivatives as stabilizers.
  • Plastic composition Process for stabilizing plastics such as phenolically substituted sugar derivatives
  • the present invention relates to the use of at least one phenolically substituted sugar derivative as a stabilizer of organic materials, in particular of plastics, against oxidative, thermal and / or actinic degradation.
  • the present invention relates to a corre sponding plastic composition, a method for stabilizing Plastics, a molding compound or a molded part and a phenolically substituted sugar derivative.
  • Organic materials such as plastics are subject to aging processes, which ultimately lead to a loss of the desired properties such as the mechanical parameters.
  • This process known as autoxidation, leads to changes in the polymer chain, such as the molecular weight or the formation of new chemical groups, based on radical chain scission by mechanochemical processes or by UV radiation in the presence of oxygen.
  • Stabilizers are therefore used to prevent or at least delay this aging process.
  • Important representatives of stabilizers are antioxidants that interfere with the radicals formed during autoxidation and thus interrupt the degradation process.
  • primary antioxidants which can react directly with oxygen-containing free radicals or C-radicals
  • secondary antioxidants which react with hydroperoxides formed as intermediates (see C. Kröhnke et al.
  • Antioxidants in Ullmann 's encyclopedia of industrial chemistry Wiley-VCH Verlag, Weinheim 2015.
  • Typical representatives of primary antioxidants are, for example, phenolic antioxidants, amines, but also lactones.
  • Classes of secondary antioxidants are phosphorus compounds such as phosphites and phosphonites, but also organo-sulfur compounds such as sulfides and disulfides.
  • primary and secondary antioxidants are often combined in practice, which leads to a synergistic effect.
  • Phenolic antioxidants generally consist of sterically hindered phenol groups, which are present in the form of esters to increase molecular weight, improve compatibility and reduce volatility.
  • the polyols such as pentaerythritol are used, the 4 alcohol groups of which are fully esterified dig.
  • substitution products are also one of the other They contain a higher number of phenolic antioxidants such as hexasubstituted mannitol or hexasubstituted cyclitol, all of which have in common that, for the reasons mentioned, complete esterification is achieved with the effective structures.
  • phenolic antioxidants are usually combined in a synergistic way with other stabilizers.
  • stabilizers are also known which have both primary and secondary antioxidant structures in one molecule, e.g.
  • the object of the present invention is therefore to provide stabilizers based, at least in part, on renewable raw materials which have a high stabilizing effect.
  • the task is related to a use with the features of patent claim 1, regarding a stabilized plastic composition with the features of patent claim 14, regarding a method for stabilizing plastics with the features of patent claim 17, regarding a molding compound with the features of patent claim 18 , in terms of a stabilizer composition for stabilizing plastics with the features of claim 19 and with respect to the stabilizing we kenden sugar derivatives with the features of claim 20 solved.
  • the respective dependent claims represent advantageous developments.
  • the present invention thus relates to the use of at least one phenolically substituted sugar derivative, the sugar derivative having a base structure derived from a sugar, and at least one substituent according to general formula I
  • R 1 and R 2 are identical or different on each occurrence and are selected from the group consisting of hydrogen and linear or branched alkyl radicals, with the proviso that at least one radical R 1 or R 2 is not hydrogen, an alkylene group with 1 to 18 carbon atoms or a chemical bond,
  • the group X is bound to the terminus shown on the left of the groupings Y shown above, and where the base of the phenolically substituted sugar derivative derived from a sugar has at least 3 unsubstituted hydroxyl groups and / or the base of the phenolic derived from a sugar substituted sugar derivative has at least 4 carbon atoms and at least 2, preferably at least 3 unsubstituted hydroxyl groups, as a stabilizer of organic materials, in particular plastics, against oxidative, thermal and / or actinic degradation.
  • stabilizing in the sense of the present invention is understood that the appropriately equipped organic Ma materials, for example the plastics to which a sugar derivative according to formula I are added, under oxidative, thermal and / or actinic conditions have a longer shelf life, such as retention of mechanical and / or visual properties, compared to molding compounds that are finished without the corresponding additives.
  • the stabilizing effect as defined above, can be achieved with substances which have a basic structure based on renewable raw materials.
  • the base body derived from a sugar is a monosaccharide, an oligosaccharide or a polysaccharide with at least 4 carbons.
  • the phenolic substituted sugar derivative particularly preferably comprises a maximum of 10, preferably a maximum of 5, more preferably a maximum of 3, particularly preferably 1 or 2, substituents according to formula I.
  • the base body derived from a sugar can be at least one alditol, a cyclitol, a sugar acid or an amino sugar with at least 4 carbons.
  • the alditol can have the following empirical formulas
  • the at least one alditol is particularly preferably selected from the group consisting of threitol, erythritol, galactitol, mannitol, ribitol, sorbitol, xylitol, Ara bit, isomalt, lactitol, maltitol, maltotritol and hydrogenated oligo- and polysaccharides with polyol end groups and mixtures thereof , wherein the at least one alditol is preferably selected from the group consisting of erythritol, mannitol, isomalt, maltitol and mixtures thereof.
  • the at least one cyclitol can be selected from the group consisting of inositol (myo, scyllo-, D-chiro-, L-chiro-, muco-, neo-, allo-, epi- and cis-innosite), quercitol, Viscumitol, Bornesitol, Conduritol, Ononitol, Pinitol, Pinpollitol, Ciceritol, Quebrachitol, Quinic acid, Shikimic acid and Valienol, the at least one cyclitol being preferably myo-inositol (myo-inositol).
  • Preferred sugar acids are, for example, aldonic acids, such as in particular allonic acid, altronic acid, gluconic acid, mannonic acid, gulonic acid, idonic acid, galactonic acid, talonic acid, ribonic acid, arabonic acid, xylonic acid, lyxonic acid, erythronic acid or threonic acid or aldaric acids such as mucic acid or glucaric acid, and mixtures and combinations thereof.
  • aldonic acids such as in particular allonic acid, altronic acid, gluconic acid, mannonic acid, gulonic acid, idonic acid, galactonic acid, talonic acid, ribonic acid, arabonic acid, xylonic acid, lyxonic acid, erythronic acid or threonic acid or aldaric acids such as mucic acid or glucaric acid, and mixtures and combinations thereof.
  • the at least one amino sugar is, for example, a mono- or diamino sugar and is particularly preferably selected from the group consisting of 1-amino-l-deoxy-alditols, such as for example 1-amino-1-deoxy-galactitol, 1-amino-1-deoxy-mannitol, 1-amino-1-deoxy-sorbitol, 1-amino-1-deoxy-maltitol or ⁇ , -diamino- ⁇ , -dideoxyalditols such as, for example, 1,6-di-amino-1,6-dideoxy sorbitol.
  • 1-amino-l-deoxy-alditols such as for example 1-amino-1-deoxy-galactitol, 1-amino-1-deoxy-mannitol, 1-amino-1-deoxy-sorbitol, 1-amino-1-deoxy-maltitol or ⁇ , -diamino
  • radicals R 1 and R 2 are identical or different, particularly preferably identical.
  • the radicals R 1 and R 2 can in particular be selected from the group consisting of tert-butyl and methyl.
  • Particularly preferred phenolically substituted sugar derivatives are selected from the group consisting of the following molecules as well as mixtures and combinations thereof.
  • the at least one phenolically substituted sugar derivative can preferably be used in a total amount of 0.01 to 10% by weight, preferably 0.05 to 5% by weight, particularly preferably 0.1 to 3% by weight, based on the plastic.
  • the at least one phenolically substituted sugar derivative is used in combination with a primary and / or secondary antioxidant that differs from the at least one phenolically substituted sugar derivative
  • the at least one antioxidant preferably being selected from the group consisting of from phenolic antioxidants, amines, lactones and mixtures thereof
  • the at least one secondary antioxidant is selected from the group consisting of phosphorus compounds, in particular phosphites and phosphites, organosulfur compounds, in particular sulfides and disulfides, and mixtures thereof.
  • Suitable primary antioxidants are phenolic antioxidants, amines and
  • Lactones Suitable synthetic phenolic antioxidants are for example:
  • Alkylated monophenols such as, for example, 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di -tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methyl-phenol, 2- ( ⁇ -methylcyclohexyl) -4,6-dimethylphenol , 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, linear or branched nonylphenols, such as 2,6-dinonyl- 4-methyl-phenol, 2,4-dimethyl-6- (l'-methylundec-l'-yl) phenol, 2,4-
  • Alkylthiomethylphenols such as 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol;
  • Hydroquinones and alkylated hydroquinones such as, for example, 2,6-di-tert-butyl-4-methyoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4 octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl -4-hydroxyphenyl stearate, bis (3,5-di-tert-butyl-4-hydroxylphenyl) adipate;
  • Hydroxylated thiodiphenyl ethers such as 2,2'-thiobis (6-tert-butyl-4-methyl-phenol), 2,2'-thiobis (4-octylphenol), 4,4'-thiobis (6-tert-butyl- 3-methyl-phenol), 4,4'-thiobis (6-tert-butyl-2-methylphenol), 4,4'-thiobis (3,6-di-sec-amylphenol), 4,4'-bis ( 2,6-dimethyl-4-hydroxyphenyl disulfide;
  • Alkylidenebisphenols such as 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 2,2'-methylenebis [4-methyl- 6- (a-methylcyclohexyl) phenol], 2,2'-methylenebis (4-methyl-6-cyclhexylphenol), 2,2'-methylenebis (6-nonyl-4-methylphenol), 2,2'-methylenebis (4 , 6-di-tert-butylphenol), 2,2'-ethylidenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (6-tert-butyl-4-isobutylphenol), 2,2 ' -Methylene bis [6- (a-methylbenzyl) -4-nonyl- phenol], 2,2'-methylenebis [6- (a, a-dimethylbenzyl) -4-nonyl
  • O-, N- and S-benzyl compounds such as, for example, 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzyl mercapto acetate , Tridecyl-4-hydroxy-3,5-di-tert-butylbenzyl mercaptoacetate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) amine, bis (4-tert-butyl-3-hydroxy-2,6 dimethylbenzyl) dithioterephthalate, bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzyl mercaptoacetate;
  • Hydroxybenzylated malonates such as dioctadecyl-2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, dioctadecyl-2- (3-tert-butyl-4-hydroxy-5-methylbenzyl) malonate, didodecyl mercaptoethyl-2,2-bis (3,5-di-tert-butyl-4-hydroxy-benzyl) malonate, bis [4- (l, l, 3,3-tetramethylbutyl) phenyl] -2,2- bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate;
  • Aromatic hydroxybenzyl compounds such as, for example, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3,5-di-tert- butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) phenol;
  • Triazine compounds such as, for example, 2,4-bis (octylmercapto) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -1, 3,5-triazine, 2-octylmercapto-4,6-bis (3 , 5-di-tert-butyl-4-hydroxyanilino) -l, 3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyphenoxy) -l, 3,5-triazine, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenoxy) -l, 2,3-triazine, 1,3,5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-T ris (4- te / T-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyan
  • Benzyl phosphonates such as dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethl-3,5-di-te / T-butyl-4-hydroxybenzylphosphonate, dioctadecyl
  • Acylaminophenols such as 4-hydroxylauranilide, 4-hydroxystearanilide, octyl-N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate;
  • Esters of ß- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with monohydric or polyhydric alcohols e.g. methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaund canol , 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2
  • Esters of ß- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with mono- or polyhydric alcohols e.g. methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaund canol , 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] o
  • Esters of ß- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid with monohydric or polyhydric alcohols e.g. methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2- Propanediol, neopentyl glycol, Thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6, 7-trioxabicyclo [2.2.2] octane;
  • Esters of (3,5-di-te / T-butyl-4-hydroxyphenyl) acetic acid with mono- or polyvalent alcohols for example methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol , 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane , 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane;
  • Amides of ß- (3,5-di-te / T-butyl-4-hydroxyphenyl) propionic acid such as N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylene diamide, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylene diamide, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylene diamide, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazide, N, N'-bis [2- (3- [3,5-di- te / T-butyl-4-hydroxyphenyl] propionyloxy) ethyl] oxamide (Naugard ® XL-l, ver driven by Sl group);
  • vitamin C Ascorbic acid (vitamin C).
  • Particularly preferred phenolic antioxidants are the following structures:
  • n is an integer in the aforementioned compounds and is between 2 and 10
  • phenolic antioxidants are phenolic antioxidants based on renewable raw materials such as. B. a-, ß-, g-, d-tocopherol and mixtures of these (vitamin E), tocotrienols, tocomonoenols, ubiquinol, hydroxytyrosol, flavonoids and flavonols such as chrysin, quercitin, hes peridin, neohesperidin, naringin, morin , Kaempferol, fisetin, datiscetin, lute olin, apigenin, taxifolin, isoflavones such as genistein, genistin, daidzein, daidzin, formononetin, anthocyanins such as delphinidin and malvidin, curcumin, carnosic acid, carnosol, rosmarinic acid, tannin and carotenoid resverrol with alcoholic groups, such as beta-crypto
  • Further stabilizers are copper-l-halides, for example CuJ, CuBr, optionally in mixtures with alkali halides such as KJ or KBr or Cu (l) complexes, for example with triphenylphosphine.
  • Suitable aminic antioxidants are, for example:
  • Preferred amine antioxidants are: N, N'-di-isopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-bis (1,4-dimethylpentyl) -p -phenylenediamine, N, N'-bis (l-ethyl-3-methylpentyl) -p-phenylenediamine, N, N'-bis (l-methylheptyl) -p-phenylenediamine, N, N'-dicyclohexyl-p- phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N'-bis (2-naphthyl) -p-phenylenediamine, N-isop- ropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N
  • Particularly preferred aminic antioxidants are the structures:
  • n is an integer and is between 3 and 100.
  • aminic antioxidants are hydroxylamines or N-oxides (nitrones), such as, for example, N, N-dialkylhydroxylamines, N, N-dibenzylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-distearylhydroxylamine, N-benzyl-a-phe - nylnitron, N-octadecyl-a-hexadecylnitron, as well as Genox TM EP (Sl Group) according to the formula:
  • R 2 C 14 -C 2 alkyl chains
  • Suitable lactones are benzofuranones and indolinones such as 3- (4- (2-ace- toxyethoxy) 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 -on), 5,7-di-tert-butyl-3- (4-ethoxyphenyl) benzofuran-2-one, 3- (4-acetoxy-3,5-dimethylphenyl) -5,7-di-tert-butyl -benzofuran-2-one, 3- (3,5-dimethyl-4-pivaloyloxyphenyl) -5
  • antioxidants are isoindolo [2, l-A] quinazolines such as e.g.
  • Suitable secondary antioxidants (B) are phosphorus compounds such as phosphites and phosphonites, and organosulfur compounds such as sulphides and disulphides.
  • Suitable phosphites / phosphonites are, for example:
  • Triphenyl phosphite diphenyl alkyl phosphites, phenyl dialkyl phosphites, tri (nonyl phenyl) phosphite, trilauryl phosphites, trioctadecyl phosphite, distearyl penta- erythritol diphosphite, tris- (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-phosphite-di-phosphitol) -tertitol, diisodecylpenta-erythritol -butylphenyl) pentaerythritol diphosphite, bis (2,4-di-cumylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaery
  • Particularly preferred phosphites / phosphonites are:
  • a preferred phosphonite is:
  • Suitable sulfur compounds are, for example, distearyl thiodipropionate, dilauryl thiodipropionate; Ditridecyldithiopropionate, ditetradecylthiodipropionate, 3- (dodecylthio) -, l, l '- [2,2-bis [[3- (dodecylthio) -l-oxopropoxy] methyl] -l, 3-propanediyl] propanoic acid ester.
  • the following structures are preferred:
  • the aforementioned primary and / or secondary antioxidants can there in a total amount (ie as the sum of primary and / or secondary antioxidant), based on the total amount of the at least one phenolically substituted sugar derivative of 0.01 to 5 parts by weight , preferably from 0.02 to 3 parts by weight, particularly preferably from 0.05 to 2 parts by weight.
  • thermoplastic, thermoset or elastomeric polymers 0.04 to 6 parts by weight, preferably 0.06 to 1 part by weight, of the at least one primary antioxidant and / or of the at least one secondary antioxidant are introduced.
  • the plastics are in particular thermoplastic, thermoset or elastomeric polymers.
  • Suitable thermoplastic or thermoset polymers are in particular: a) Polymers made from olefins or diolefins such as polyethylene (LDPE,
  • polystyrene polymethylstyrene, poly-alpha-methylstyrene, polyvinylnaphtha lin, polyvinylbiphenyl, polyvinyltoluene, styrene-butadiene (SB), styrene-butadiene-styrene (SBS), styrene-ethylene-butylene-styrene (SEBS), styrene Ethylene-propylene-styrene, styrene-isoprene, styrene-isoprene-styrene (SIS), styrene-butadiene-acrylonitrile (ABS), styrene-acrylonitrile (SAN), styrene-acrylonitrile-acrylate (ASA), styrene-ethylene, Styrene-maleic anhydride polymers including appropriate graft copopoly
  • halogen-containing polymers such as polyvinyl chloride (PVC), polychloroprene and polyvinylidene chloride (PVDC), copolymers of vinyl chloride and vinylidene chloride or of vinyl chloride and vinyl acetate, chlorinated polyethylene, polyvinylidene fluoride, epichlorohydrin homo and copolymers, especially with ethylene oxide (ECO)
  • PVC polyvinyl chloride
  • PVDC polychloroprene and polyvinylidene chloride
  • PMMA polymethyl methacrylate
  • PMMA polybutyl acrylate
  • polylauryl acrylate polylauryl acrylate
  • polystearyl acrylate polyglycidyl acrylate
  • polyacetals such as polyoxymethylene (POM) or copolymers with e.g.
  • polyphenylene oxides and blends with polystyrene or polyamides h) polymers of cyclic ethers such as polyethylene glycol, polypropylene glycol, polyethylene oxide, polypropylene oxide, polytetrahydrofuran, i) polyurethanes made from hydroxy-terminated polyethers or polyesters and aromatic or aliphatic isocyanates such as 2,4- or 2,6 toluene diisocyanate or methylenediphenyl diisocyanate, especially linear polyurethanes (TPU), polyureas,
  • TPU linear polyurethanes
  • Polyamides such as polyamide-6, 6.6, 6.10, 4.6, 4.10, 6.12, 10.10, 10.12, 12.12, polyamide 11, polyamide 12 and (partially) aromatic polyamides such as polyphthalamides, e.g.
  • terephthalic acid and / or isophthalic acid and aliphatic diamines such as hexamethylenediamine or m-xylylenediamine or from aliphatic dicarboxylic acids such as adipic acid or sebacic acid and aromatic diamines such as 1,4- or 1,3-diaminobenzene, blends of different polyamides such as PA-6 and PA 6.6 or blends of Polyamides and polyolefins such as PA / PP
  • polyimides polyamide-imides, polyetherimides, polyesterimides, poly (ether) ketones, polysulfones, polyether sulfones, polyarylsulfones, polyphenylene sulfides, polybenzimidazoles, polyhydantoins,
  • Polyesters made from aliphatic or aromatic dicarboxylic acids and diols or from hydroxycarboxylic acids such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polypropylene terephthalate (PTT), polyethylene naphthylate (PEN), poly-1,4-dimethylolcyclohexate, polyhydrotha-benzoate Polyhydroxynaphthalate, polylactic acid (PLA), polyhydroxybutyrate (PHB), polyhydroxyvalerate (PHV), polyethylene succinate, polytetramethylene succinate, polycaprolactone m) Polycarbonates, polyester carbonates, and blends such as PC / ABS, PC / PBT, PC / PET / PBT, PC / PA
  • cellulose derivatives such as cellulose nitrate, cellulose acetate, cellulose propionate, cellulose butyrate,
  • Epoxy resins consisting of di- or polyfunctional epoxy compounds in combination with e.g. hardeners based on amines, anhydrides, dicyandiamide, mercaptans, isocyanates or catalytically active hardeners,
  • Phenolic resins such as phenol-formaldehyde resins, urea-formaldehyde resins, melamine-formaldehyde resins,
  • Silicones e.g. based on dimethylsiloxanes, methyl-phenyl-siloxanes or diphenylsiloxanes, e.g. terminated with vinyl groups
  • polymers specified under a) to r) are copolymers, they can be in the form of random (“random”), block or “tape red” structures. Furthermore, the polymers mentioned can be in the form of linear, branched, star-shaped or hyperbranched structures.
  • polymers specified under a) to r) are stereoregular polymers, these can be in the form of isotactic, stereotactic, but also atactic forms or as stereoblock copolymers.
  • the polymers specified under a) to r) can have both amorphous and (partially) crystalline morphologies.
  • polystyrene resins mentioned under a) can also be crosslinked, e.g. crosslinked polyethylene, which is then referred to as X-PE.
  • the present compounds can be used to stabilize chewing Schuken and elastomers are used.
  • This can be natural rubber (NR) or synthetic rubber materials.
  • Polymers made from renewable raw materials such as polylactic acid (PLA), polyhydroxybutyric acid, polyhydroxyvaleric acid or polybutylene succinate are also preferred.
  • the aforementioned polymers can be in the form of fresh goods or as recycled materials.
  • the present invention also relates to a plastic composition containing or consisting of at least one plastic and at least one phenolically substituted sugar derivative, the sugar derivative having a base body derived from a sugar, and at least one substituent according to general formula I.
  • R 1 and R 2 are identical or different on each occurrence and are selected from the group consisting of hydrogen and linear or branched alkyl radicals, with the proviso that at least one radical R 1 or R 2 is not hydrogen,
  • X is an alkylene group with 1 to 18 carbon atoms or a chemical bond
  • Y is a group selected from the group consisting of the following groupings where the grouping X is attached to the terminus shown on the left of the deten groupings Y is bonded, and wherein the base of the phenolically substituted sugar derivative derived from a sugar has at least 3 unsubstituted hydroxyl groups and / or the base of the phenolic substituted sugar derivative derived from a sugar has at least 4 carbon atoms and at least 2, preferably at least 3 unsubstituted ones Has hydroxyl groups.
  • the plastic composition can preferably also contain at least one additive selected from the group consisting of UV absorbers, light stabilizers, metal deactivators, costabilizers, filler deactivators, antiozonants, nucleating agents, anti-nucleating agents, impact strength improvers, plasticizers, lubricants, rheology modifiers, chain extenders, thixotropic agents optical brightening agents, antimicrobial agents, antistatic agents, slip agents, antiblocking agents, coupling agents, crosslinking agents, anti-crosslinking agents, hydrophilizing agents, hydrophobizing agents, adhesion promoters, dispersants, compatibilizers, oxygen scavengers, acid scavengers, propellants, anti-odor agents, anti-odor agents, antifoaming agents, antioxidants Contain fillers, reinforcing agents and mixtures thereof.
  • at least one additive selected from the group consisting of UV absorbers, light stabilizers, metal deactivators, costabilizers, filler deactivators, antio
  • the plastic composition preferably also contains at least one additive selected from the group consisting of a) acid scavengers ("antiacids”) are salts of one, two, three or four-valued metals, preferably alkali, alkaline earth metals, aluminum or zinc, in particular formed with Fatty acids, such as calcium stearate, magnesium stearate, zinc stearate, aluminum stearate, calcium laurate, calcium behenate, calcium lactate, calcium stearoyl-2-lactate, Other classes of suitable acid scavengers are Hydrotalcites, in particular synthetic hydrotalcites based on aluminum, magnesium and zinc, hydrocalumites, zeolites, alkaline earth oxides, in particular calcium oxide and magnesium oxide, and zinc oxide, alkaline earth carbonates, in particular calcium carbonate, magnesium carbonate and dolomite and hydroxides, in particular brucite (magnesium hydroxide),
  • antiacids are salts of one, two, three or four-valued metals, preferably al
  • Suitable light stabilizers are, for example, compounds based on 2- (2 'hydroxyphenyl) benzotriazoles, 2-hydroxybenzophenones, esters of benzoic acids, acrylates, oxamides, and 2- (2-hydroxyphenyl) -l, 3,5-NEN Triazi-.
  • Suitable 2- (2 'hydroxyphenyl) benzotriazoles are for example 2- (2'-hy- roxy-5'-methylphenyl) benzotriazole, 2- (3', 5'-di-tert-butyl-2'-hydroxyphenyl) - benzotriazole , 2- (5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'- (l, l, 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'-te / t-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-4'-octy
  • Suitable 2-hydroxybenzophenones are, for example, 4-hydroxy-, 4-methoxy-, 4-octyloxy-, 4-decyloxy-4-dodecyloxy, 4-benzyloxy, 4,2 ', 4'-trihydroxy- and 2'-hydroxy -4,4'-dimethoxy-derivatives of 2-hydroxybenzophenones.
  • Suitable acrylates are, for example, ethyl a-cyano-ß, ß-diphenyl acrylate, isooctyl-a-cyano-ß, ß-diphenyl acrylate, methyl a-carbomethoxycinnamate, methyl a-cyano-ß-methyl-p-methoxycinnamate, Butyl ⁇ -cyano- ⁇ -methyl-p-methoxycinnamate, methyl- ⁇ -carbomethoxy-p-methoxycinnamate and N- ( ⁇ -carbomethoxy- ⁇ -cyanovinyl) -2-methylindoline.
  • Suitable esters of benzoic acids are, for example, 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis (4-tert-butylbenzoyl) resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl-3,5-di-tert- butyl-4-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di- tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
  • Suitable oxamides are, for example, 4,4'-dioctyloxyoxanilide, 2,2'-diethoxy-oxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'- di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixtures with 2- Ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and p-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.
  • Suitable 2- (2-hydroxyphenyl) -1, 3,5-triazines are, for example, 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-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1, 3,5-triazine, 2- (2- Hydroxy-4-octyloxyphenyl) -4,6-bis (4-methyl-phenyl-1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethyl - phen
  • Suitable metal deactivators are, for example, N, N'-diphenyloxamide, N-
  • metal activators are:
  • Suitable hindered amines are, for example, l, l-bis (2,2,6,6-tetramethyl-
  • 4-piperidyl) succinate bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (l- octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebazate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -n-butyl-3,5-di-tert-butyl -4-hydroxybenzylmalonate, the condensation product of 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensation products of N, N'-bis (2.2 , 6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-tert-octylamino-2,6-di-chloro-1,3,5-triazine, tris (2,2,6,6-tetramethyl-4 -piperidyl) nitrilotriacetate,
  • the structures given above also include the sterically hindered NH, N-alkyl such as N-methyl or N-octyl, the N-alkoxy derivatives such as N-methoxy or N-octyloxy, the cycloalkyl derivatives such as N- cyclohexyloxy and the N- (2-hydroxy-2-methylpropoxy) analogs.
  • Preferred hindered amines also have the following structures:
  • Preferred oligomeric and polymeric hindered amines have the following structures:
  • n 3 to 100 in each case.
  • Suitable dispensing agents are, for example:
  • Polyacrylates for example copolymers with long-chain side groups, polyacrylate block copolymers, alkylamides: for example N, N'-1,2-ethanediylbisoctadecanamide, sorbitan esters, for example monostearyl sorbitan esters, titanates and zirconates, reactive copolymers with functional groups, for example polypropylene-co-acrylic acid, polypro - pylene-co-maleic anhydride, polyethylene-co-glycidyl methacrylate, polystyrene-alt-maleic anhydride-polysiloxanes: e.g.
  • Suitable costabilizers are also polyols, in particular alditols or cyclitols.
  • Polyols are, for example, pentaerythritol, dipentaerythritol, tripentaerythritol, short-chain polyether polyols or short-chain polyester polyols, and hyper-branched polymers / oligomers or dendrimers with alcohol groups, for example
  • the at least one alditol is preferably selected from the group consisting of threitol, erythritol, galactitol, mannitol, ribitol, sorbitol, xylitol, arabitol, isomalt, lactitol, maltitol, altritol, iditol, maltotritol and hydrogenated oligo- and polysaccharides with polyol End groups and mixtures thereof.
  • the at least one preferred alditol is particularly preferably selected from the group consisting of erythritol, mannitol, isomalt, maltitol and mixtures thereof.
  • heptitols and octitols meso-glycero-allo-heptitol, D-glycero-D-altro-heptitol, D-glycero-D-manno-heptitol, meso-glycero-gulo-heptitol, D-glycero D-galacto-heptitol (Perseitol), D-glycero-D-gluco-heptitol, L-glycero-D-gluco heptitol, D-erythro-L-galacto-octitol, D-threo-L-galacto-octitol.
  • the at least one cyclitol can be selected from the group consisting of inositol (myo, scyllo-, D-chiro-, L-chiro-, muco-, neo-, allo-, epi- and cis-inositol), 1,2 , 3,4-tetrahydroxycyclohexane, 1, 2,3,4, 5-pentahydroxycyclohexane, quercitol, viscumitol, bornesitol, conduritol, ononitol, pinitol, pinpollitol, quebrachitol, ciceritol, quinic acid, shikimic acid and valienol, myo being preferred -inositol (myo-inositol).
  • inositol myo, scyllo-, D-chiro-, L-chiro-, muco-, neo-, allo-, epi- and cis-inos
  • Suitable nucleating agents are, for example, talc, alkali or alkaline earth salts of monofunctional and polyfunctional carboxylic acids such as benzoic acid, succinic acid, adipic acid, e.g. sodium benzoate, zinc glycerolate, aluminum hydroxy bis (4-tert-butyl) benzoate, benzylidene sorbitols such as 1, 3: 2,4-bis (benzylidene) sorbitol or l, 3: 2,4-bis (4-methylbenzylidene) sorbitol, 2,2 '-me- Thylen-bis- (4,6-di-tert-butylphenyl) phosphate, as well as trisamides and diamides such as trimesic acid tri-cyclohexylamides, trimesic acid tri (4-methylcyclohexyl amide), trimesic acid tri (tert-butyl amide), N, N ' , N "
  • Suitable anti-nucleation agents are azine dyes such as nigrosine.
  • Suitable flame retardants are, for example: a) Inorganic flame retardants such as Al (OH) 3, Mg (OH) 2, AIO (OH), MgCC> 3, sheet silicates such as montmorillonite or sepiolite, unmodified or organically modified, double salts such as Mg- Al silicates, POSS (Polyhedral Oligomeric Silsesquioxane) compounds, huntite, hydromagnite or halloysite as well as Sb2Ü3, Sb 2 0s, M0O3, zinc stannate, zinc hydroxystannate,
  • Inorganic flame retardants such as Al (OH) 3, Mg (OH) 2, AIO (OH), MgCC> 3, sheet silicates such as montmorillonite or sepiolite, unmodified or organically modified, double salts such as Mg- Al silicates, POSS (Polyhedral Oligomeric Silsesquioxane) compounds, huntite, hydromagnite or halloysite as well as Sb
  • Nitrogen-containing flame retardants such as melamine, melamine, melam, melon, melamine derivatives, melamine condensation products or melamine salts, benzoguanamine, polyisocyanurates, allantoin, phosphacenes, in particular melamine cyanurate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, such as melamine phosphate phosphate, melamine polyphosphate, melamine polyphosphate, melamine polyphosphate, melamine polyphosphate, melamine polyphosphate, melamine polyphosphate, melamine polyphosphate, melamine polyphosphate, melamine polyphosphate, melamine polyphosphate, melamine polyphosphate, melamine polyphosphate, for example, melamine polyphosphate, for example melamine condensation products or melamine condensation products , Melamine zinc phosphate, melamine magnesium phosphate and the corresponding pyrophosphates and polyphosphates, poly-
  • Radical formers such as alkoxyamines, hydroxylamine esters, azo compounds, dicumyl or polycumyl, hydroxyimides and their derivatives such as hydroxyimide esters or hydroxyimide ethers
  • Phosphorus-containing flame retardants such as red phosphorus, phosphates such as resorcinol diphosphate, bisphenol A diphosphate and their oligomers, triphenyl phosphate, ethylenediamine diphosphate, phosphinates such as salts of hypophosphorous acid and its derivatives such as alkyl phosphine phosphine or aluminum phosphine phosphine salts such as zinc phosphine or diethyl phosphine salts , Aluminum phosphite, aluminum phosphonate, phosphonate esters, oligomeric and polymeric derivatives of methane phosphonic acid, 9,10-dihydro-9-oxa-10-phosphorylphenanthrene-10-oxide (DOPO) and their substituted compounds,
  • DOPO 9,10-dihydro-9-oxa-10-phosphorylphenanthrene-10-oxide
  • Halogen-containing flame retardants based on chlorine and bromine such as polybrominated diphenyloxides, such as decabromodiphenyloxide, tris (3-bromo-2,2-bis (bromomethyl) propyl phosphate, tris (tribromoneopentyl) phosphate, tetrabromophthalic acid, l, 2-bis (tribromophenoxy) ethane, hexabromocyclododecane, brominated diphenylethane, tris (2,3-dibromopropyl) isocyanurate, ethylene bis (tetrabromophthalimide), tetrabromobisphenol A, brominated polystyrene, brominated polybutadiene - Rol-brominated polybutadiene copolymers, brominated polyphenylene ether, brominated epoxy resin, polypentabromobenzyl acrylate, possibly in combination with Sb2Ü3
  • Sulfur-containing compounds such as elemental sulfur, disulfides and polysulfides, thiuram sulfide, dithiocarbamates, mercaptobenzothiazole and sulfenamides,
  • antidrip agents such as polytetrafluoroethylene
  • Silicon-containing compounds such as polyphenylsiloxanes
  • Carbon modifications such as carbon nanotubes (CNT) or graphs, as well as combinations or mixtures thereof.
  • Suitable azo compounds is for example in M. Aubert et. al. Macromol. Be. Closely. 2007, 292, 707-714 or in WO 2008101845, the production of hydrazones and azines in M. Aubert et al., Pol. Adv. Technol. 2011, 22, 1529-1538, the preparation of triazenes in W. Pawelec et al., Pol. Degr. Rod. 2012, 97, 948-954.
  • the synthesis of iminoxytriazines is described in WO 2014/064064.
  • radical formers to be used are selected from the group consisting of
  • R 3 represents hydrogen or an optionally substituted alkyl, cycloalkyl, aryl, heteroaryl or acyl radical, in particular a C1 to C4 alkyl radical,
  • R 4 represents an alkoxy, aryloxy, cycloalkoxy, aralkoxy or acyloxy radical
  • Z represents hydrogen or an optionally substituted alkyl, cycloalkyl, aryl, heteroaryl or acyl radical, where the two radicals Z can also form a closed ring, which is optionally replaced by ester, ether, amine, Amide, carboxy or urethane groups can be substituted,
  • R 5 denotes an alkyl, cycloalkyl or aryl radical
  • R 6 is identical or different on each occurrence and denotes a linear or branched alkyl radical
  • R 7 is identical or different on each occurrence and denotes hydrogen or a linear or branched alkyl radical
  • R 8 is identical or different on each occurrence and denotes an alkyl, alkoxy, aryloxy, cycloalkyloxy, aralkoxy or acyloxy radical,
  • R 7 has the meaning given above, is preferably methyl, d) and / or polycumyl according to the structural formula shown below
  • R 7 has the meaning given above, is preferably methyl, and 2 ⁇ n ⁇ 100.
  • N-alkoxyamines of the structure indicated are: 1-cyclohexyloxy-2,2,6,6-tetramethyl-4-octadecylaminopiperidine; Bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate; 2,4-bis [(l-cyclohexyloxy- 2.2.6.6-Tetramethylpiperidin-4-yl) butylamino] -6- (2-hydroxyethylamino-S-triazine; bis (l-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) adipate; 2, 4-bis [(l-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -6-chloro-S-triazine; l- (2-hydroxy-2-methylpropoxy) -4- Hydroxy-2,2,6,6-te
  • n 1-15, such as, for example, disterarylhydroxylamine.
  • RI and R2 are preferably identical or different and are selected from linear or branched C1-C6-alkyl and / or aryl;
  • Ri alkyl
  • R2 alkyl
  • M Al or Zn.
  • a particularly preferred example of a phosphinate are the commercially available Exolit OP (RTM) products from Clariant SE.
  • phosphorus-containing flame retardants are metal salts of hypophosphorous acid with a structure according to the formula
  • Met is a metal selected from groups I, II, III and IV of the Periodic Table of the Elements, and n is a number from 1 to 4 which corresponds to the charge of the corresponding metal ion Met.
  • Met n + is Na + ,
  • phosphorus-containing flame retardants are phosphonates or phosphonic acid diaryl esters with a structure according to the following formula:
  • Corresponding structures can also be in the form of phosphonate oligomers, polymers and copolymers.
  • Linear or branched phosphonate oligomers and polymers are known from the prior art.
  • branched phosphonate oligomers and polymers reference is made to US patents US
  • Phophonate are for example under the trade name Nofia (RTM) from FRX Polymers available.
  • phosphorus-containing flame retardants are compounds based on oxaphosphorine oxide and their derivatives with, for example, the following structures:
  • Products based on oxophosphorine oxide are, for example, on the market under the trade name Ukanol (RTM) from Schill und Seilacher GmbH. Further compounds can for example according to the patent specifications WO 2013020696, WO 2010135398, W003070736, W02006084488, WO
  • phosphorus-containing flame retardants are cyclic phosphonates with a structure according to one of the following formulas:
  • a 1 and A 2 independently represent a substituted or unsubstituted, straight-chain or branched alkyl group with 1 to 4 carbon atoms, substituted or unsubstituted benzyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl and where A 3 and A 4 are independently methyl or ethyl and A 5 is a straight-chain or branched alkyl group having 1 to 4 carbon atoms or a phenyl or benzyl group, each of which can have up to 3 methyl groups.
  • Cyclic phosphonates are, for example, from Thor GmbH under the
  • phosphacenes especially polymeric phosphacenes.
  • SPB-100 commercially available from Otsuka Chemicals under the name SPB-100, for example.
  • Nitrogen-containing flame retardants are phosphacenes, especially polymeric phosphacenes.
  • SPB-100 commercially available from Otsuka Chemicals under the name SPB-100, for example.
  • Preferred nitrogen-containing flame retardants are melamine polyphosphate, melamine cyanurate, melamine metal phosphates, poly- [2,4- (piperazin-1,4-yl) -6-
  • Particularly preferred flame retardants are halogen-free and are the following compounds:
  • Suitable fillers and reinforcing materials are, for example, synthetic or natural materials such as calcium carbonate, silicates, glass fibers, glass spheres (solid or hollow), talc, mica, kaolin, barium sulfate, metal oxides and metal hydroxides, carbon black, graphite, carbon nanotubes, graphene, wood flour or fibers from natural products such as cellulose or synthetic fibers.
  • Further suitable fillers are hydrotalcites or zeolites or sheet silicates such as montmorillonite, bentonite, beidelite, mica, hectorite, saponite, ver miculite, ledikite, magadite, lllite, kaolinite, wollastonite, attapulgite.
  • Suitable pigments can be of an inorganic or organic nature.
  • Inorganic pigments are, for example, titanium dioxide, zinc oxide, zinc sulfide, iron oxide, ultramarine, carbon black, organic pigments are, for example, anthraquinones, anthanthrones, benzimidazolones, quinacridones, diketopyrrolopyrroles, dioxazines, indanthrones, isoindolinones, azo compounds, perylenes, phthalocyanines or azo compounds Pyranthrones.
  • Further suitable pigments are effect pigments based on metal or pearlescent pigments based on metal oxide.
  • Suitable lubricants and processing aids are, for example, polyethylene waxes, polypropylene waxes, salts of fatty acids such as calcium stearate, zinc stearate or salts of montan waxes, amide waxes such as erucic acid amide or oleic acid amides, fluoropolymers, silicones or neoalkoxy titanates and zirconates.
  • Suitable optical brighteners are, for example, bisbenzoxazoles, phenylcuma rine or bis (styryl) biphenyls and especially optical brighteners of the formulas:
  • Suitable filler deactivators are, for example, polysiloxanes, polyacrylates, in particular block copolymers such as polymethacrylic acid-polyalkylene oxide or polyglycidyl (meth) acrylates and their copolymers, e.g. with styrene, and epoxides e.g. of the following structures:
  • Suitable antistatic agents are, for example, ethoxylated alkylamines, fatty acid esters, alkyl sulfonates and polymers such as polyether amides.
  • Suitable antiozonants are the above-mentioned amines such as N, N'-diisopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-bis (1,4-dimethylpentyl) -p-phenylenediamine, N, N'-dicyclohexyl-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p- phenylenediamine, N- (1-methylheptyl) -N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine
  • Suitable rheology modifiers e.g. for the production of controlled rheology polypropylene (CR-PP) are, for example, peroxides, alkoxyamine esters, oxyimidesulfonic acid esters and in particular the following structures:
  • Suitable additives for increasing the molecular weight of polycondensation polymers are diepoxides, bis-oxazolines, bis-oxazolones, bis-oxazines, diisocyanates, dianhydrides, bis-acyllactams, bis-maleimides, dicyanates, carbodiimides.
  • Other suitable chain extenders are polymeric compounds such.
  • Suitable additives for increasing the electrical conductivity are, for example, the aforementioned antistatic agents, soot and carbon compounds such as carbon nanotubes and graphene, metal powder such as copper powder and conductive polymers such as Polypyrroles, polyanilines and polythiophenes.
  • Suitable additives for increasing the thermal conductivity are, for example, aluminum nitrides and boron nitrides.
  • Suitable infrared-active additives are, for example, aluminum silicates, hydrotalcites or dyes such as phthalocyanines or anthraquinones.
  • Suitable mold release agents are, for example, silicones, soaps and waxes such as montan waxes.
  • Suitable impact modifiers are, for example, ethylene copolymers with acrylates, methacrylates and / or ethylenically unsaturated carboxylic acids, which can be completely or partially neutralized, for example with zinc, or copolymers of ethylene, propylene and dienes, and core-shell particles, for example of polybutyl acrylate and polymethyl methacrylate.
  • Compatibilizers or compatibilizers are used, for example, in thermodynamically immiscible blends or also in recycled mixtures and contain structural elements of the respective blend components that are mixed.
  • Suitable compatibilizers for polyolefin mixtures are, for example, olefin block copolymers consisting of ethylene, propylene and alpha-olefins such as, for example. 1-octene.
  • compatibilizers especially for compatibilizing polar, such as PET or polyamides, and non-polar, such as PP or PE polymers are, for example, polypropylene-g-maleic anhydride, polyethylene-g-maleic anhydride, polypropylene-g-acrylic acid, polyethylene-g-acrylic acid, poly (ethylene-co-maleic anhydride), SBS-g-maleic anhydride or SEBS-g-maleic anhydride.
  • Suitable crosslinking agents are, for example, peroxides such as dialkyl peroxides, alkylaryl peroxides, peroxyesters, peroxycarbonates, diacylproxides, peroxyketals, silanes such as, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltris (2-methoxyethimoxy) silane, 3-methoxyethylethyltrisylane, vinyldoxymethyltris (2-methoxyethimoxy) silane, 3-methoxyethyl-tri-methoxy-tri-methoxy-methyl propane or ethylene-vinylsilane copolymers.
  • peroxides such as dialkyl peroxides, alkylaryl peroxides, peroxyesters, peroxycarbonates, diacylproxides, peroxyketals
  • silanes such as, for example, vinyltrimethoxysilane, vinyltriethoxysilane,
  • Suitable prodegradants are additives that break down a polymer in Accelerate or control the environment in a targeted manner.
  • Examples are transition metal fatty acid esters, for example of manganese or iron, which accelerate oxidative and / or photooxidative degradation, for example of polyolefins, or enzymes which induce hydrolytic degradation, for example of aliphatic polyesters.
  • Suitable chemical blowing agents include azo compounds such as azodicarbonamide, sulfonyl semicarbazides such as p-Toluolsulfonylsemi- carbazide, tetrazoles such as 5-phenyltetrazole, hydrazides such as p-Toluolsulfonylhydra- zid, 4,4 '-Oxibis (benzenesulfonyl) hydrazide, N-nitroso compounds such as N, N' -Di- nitrosopentamethylenetetramine or carbonates such as sodium hydrogen carbonate or zinc carbonate.
  • azo compounds such as azodicarbonamide
  • sulfonyl semicarbazides such as p-Toluolsulfonylsemi- carbazide
  • tetrazoles such as 5-phenyltetrazole
  • hydrazides such as p
  • Suitable slip agents are, for example, amide waxes such as erucic acid amide or oleic acid amide.
  • Suitable antiblocking agents are, for example, silica, talc or zeolites.
  • Suitable anti-fogging additives are, for example, ethoxylated sorbitan esters, ethoxylated fatty acid alcohols or ethoxylated alkylamine esters.
  • Suitable biocides are, for example, quaternary ammonium salts or silver salts, colloidal silver or silver complexes or natural product derivatives such as Chitosan
  • Suitable aldehyde scavengers are amines, hydroxylamines, polyvinyl alcohol, zeolites or cyclodextrins
  • suitable formaldehyde scavengers are melamine derivatives such as benzoguanamine or urea derivatives such as allantoin.
  • Suitable odor-binding or odor-preventing substances are silicates such as calcium silicate, zeolites or salts of hydroxy fatty acids such as zinc cricene enolate.
  • Suitable marking agents are, for example, fluorescent dyes or rare earths.
  • the present invention further relates to a method for stabilizing plastics against oxidative, thermal and / or actinic degradation, in which at least one phenolically substituted sugar derivative, the sugar derivative having a base substance derived from a sugar, and at least one substituent according to general formula I.
  • R 1 and R 2 are identical or different on each occurrence and are selected from the group consisting of hydrogen and linear or branched alkyl radicals, with the proviso that at least one radical R 1 or R 2 is not hydrogen,
  • X is an alkylene group with 1 to 18 carbon atoms or a chemical bond
  • Y is a group selected from the group consisting of the following groupings where the group X is bound to the terminus shown on the left of the groupings Y shown above, and where the base of the phenolically substituted sugar derivative derived from a sugar has at least 3 unsubstituted hydroxyl groups and / or the base of the phenolically substituted one derived from a sugar Sugar derivative has at least 4 carbon atoms and at least 2, preferably at least 3 unsubstituted hydroxyl groups, is incorporated into a plastic.
  • the phenolic substituted sugar derivative according to the general formula I reference is made to the statements made above.
  • the additive according to the invention which can be present as a powder, liquid, oil, compacted, on a carrier material, as granules, solution or flakes, is preferably mixed with the polymer to be stabilized, the polymer matrix is transferred into the melt and then cooled.
  • a carrier material as granules, solution or flakes
  • these can be added to the polymers separately, in the form of liquids, powders, granules or compacted products or together with the additive composition according to the invention as described above.
  • additive composition and any additional additives are incorporated into the plastic by customary processing methods, the polymer being melted and mixed with the additive composition according to the invention and any further additives, preferably by mixers, kneaders and extruders.
  • Preferred processing machines are extruders such as single-screw extruders, twin-screw extruders, planetary roller extruders, ring extruders, co-kneaders, which are preferably equipped with vacuum degassing. Processing can take place under air or, if necessary, under inert gas conditions.
  • additive compositions according to the invention can be produced and introduced in the form of so-called masterbatches or concentrates which, for example, contain 10-90% of the compositions according to the invention in a polymer.
  • the invention further relates to a molding compound or a molded part, producible from a plastic composition according to the invention as described above, in particular in the form of injection molded parts, foils, films, lacquers, coatings, foams, fibers, cables, pipes, profiles, hollow bodies pern, ribbons, membranes, e.g. geomembranes, lubricants, colorants and / or adhesives that are manufactured via extrusion, injection molding, blow molding, calendering, pressing processes, spinning processes and / or rotomoulding, e.g. for the electrical industry, for the construction industry, for Transport industry, for medical applications, for household and electrical appliances, for vehicle parts, for consumer goods, for packaging, for furniture and / or for textiles.
  • Another area of application are paints, paints and coatings, as well as fats and oils.
  • oils and fats they can be based on mineral oils, vegetable fats or animal fats or oils, fats or waxes based on e.g. synthetic esters.
  • Vegetable oils and fats are, for example, palm oil, olive oil, rapeseed oil, linseed oil, soybean oil, sunflower oil, castor oil, animal fats are, for example, fish oils or beef tallow.
  • the compounds according to the invention can also be used as stabilizers for lubricants, hydraulic oils, motor oils, turbine oils, gear oils, metal processing fluids or as lubricating greases.
  • These mineral or synthetic lubricants are primarily based on hydrocarbons.
  • antioxidants according to the invention can be used to stabilize monomers in order to prevent premature polymerization or oxidation if necessary, e.g. for styrene or acrylates or for the stabilization of polyols in polyurethane synthesis.
  • the present invention also relates to a stabilizer composition for stabilizing plastics against oxidative, thermal and / or actinic degradation, consisting of at least one phenolic substituted sugar derivative, the sugar derivative having a base derived from a sugar, and at least one substituent according to the general formula I.
  • a stabilizer composition for stabilizing plastics against oxidative, thermal and / or actinic degradation consisting of at least one phenolic substituted sugar derivative, the sugar derivative having a base derived from a sugar, and at least one substituent according to the general formula I.
  • R 1 and R 2 are identical or different on each occurrence and are selected from the group consisting of hydrogen and linear or branched alkyl radicals, with the proviso that at least one radical R 1 or R 2 is not hydrogen,
  • X is an alkylene group with 1 to 18 carbon atoms or a chemical bond
  • Y is a group selected from the group consisting of the following groupings where the group X is bound to the terminus shown on the left of the groupings Y shown above, and where the base of the phenolically substituted sugar derivative derived from a sugar has at least 3 unsubstituted hydroxyl groups and / or the base of the phenol derived from a sugar Lisch substituted sugar derivative has at least 4 carbon atoms and at least 2, preferably at least 3 unsubstituted hydroxyl groups, and at least one primary antioxidant and / or at least one secondary antioxidant.
  • the present invention relates to a phenolically substituted sugar derivative, the sugar derivative having a base structure derived from a sugar, as well as at least one substituent according to formula I in general
  • R 1 and R 2 are identical or different on each occurrence and are selected from the group consisting of hydrogen and linear or branched alkyl radicals, with the proviso that at least one radical R 1 or R 2 is not hydrogen,
  • X is an alkylene group with 1 to 18 carbon atoms or a chemical bond
  • Y is a group selected from the group consisting of the following groupings
  • the group X is bound to the terminus shown on the left of the groupings Y shown above, and where the base of the phenolically substituted sugar derivative derived from a sugar has at least 3 unsubstituted hydroxyl groups and / or the base of the phenol derived from a sugar Lisch substituted sugar derivative has at least 4 carbon atoms and at least 2, preferably at least 3 unsubstituted hydroxyl groups.
  • a commercially available polypropylene (Moplen HP 500N, Lyondell Basell Industries) was homogenized in a powder-powder mixture with the specified stabilizers and in a twin-screw microextruder (MC 5, manufacturer DSM) for 30 minutes at 200 ° C and 90 revolutions per minute and recorded the decrease in force.
  • the force is a direct measure of the molecular weight of polypropylene; the lower the decrease, the higher the stabilization effect.
  • a further improvement in the processing stability is achieved by adding 0.1% primary antioxidant (pentaerythritol tetrakis [3- (3rd)) to 0.2% of the 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid ester of mannitol , 5-di-tert-butyl-4-hydroxyphenyl) propionate) or 0.1% secondary antioxidant (tris- (2,4-di-tert-butylphenyl) phosphite) can be added.
  • primary antioxidant penentaerythritol tetrakis [3- (3rd)
  • secondary antioxidant tris- (2,4-di-tert-butylphenyl) phosphite
  • the monofunctional derivatives with more than 80% monosubstitution are obtained by transesterifying 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid methyl ester with erythritol, myo-inositol and sorbitol.
  • Recycled polyolefin consisting of a PE / PP mixture, 210 ° C

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Abstract

The present invention relates to the use of at least one phenolically substituted sugar derivative as a stabiliser of organic materials, in particular plastics, against oxidative, thermal and/or actinic degradation. The present invention also relates to a corresponding plastic composition, to a method for stabilising plastics, to a moulding compound or a moulded part as well as a phenolically substituted sugar derivative.

Description

Verwendung von phenolisch substituierten Zuckerderivaten als Stabilisatoren. Kunststoffzusammensetzung. Verfahren zur Stabilisierung von Kunststoffen so wie phenolisch substituierte Zuckerderivate Die vorliegende Erfindung betrifft die Verwendung mindestens eines pheno- lisch substituierten Zuckerderivates als Stabilisator von organischen Materia lien, insbesondere von Kunststoffen, gegen oxidativen, thermischen und/oder aktinischen Abbau. Zudem betrifft die vorliegende Erfindung eine entspre chende Kunststoffzusammensetzung, ein Verfahren zur Stabilisierung von Kunststoffen, eine Formmasse bzw. ein Formteil sowie ein phenolisch substitu iertes Zuckerderivat. Use of phenolically substituted sugar derivatives as stabilizers. Plastic composition. Process for stabilizing plastics such as phenolically substituted sugar derivatives The present invention relates to the use of at least one phenolically substituted sugar derivative as a stabilizer of organic materials, in particular of plastics, against oxidative, thermal and / or actinic degradation. In addition, the present invention relates to a corre sponding plastic composition, a method for stabilizing Plastics, a molding compound or a molded part and a phenolically substituted sugar derivative.
Organische Materialien wie Kunststoffe unterliegen Alterungsvorgängen, die letztendlich zu einem Verlust der erwünschten Eigenschaften wie z.B. der me chanischen Kennwerte führen. Dieser Autoxidation genannte Vorgang führt ausgehend von radikalischen Kettenspaltungen durch mechanochemische Pro zesse oder durch UV-Strahlung in Gegenwart von Sauerstoff zu Veränderungen der Polymerkette, wie z.B. im Molekulargewicht oder der Bildung neuer chemi scher Gruppen. Um diese Alterung zu verhindern oder zumindest zu verzögern werden deshalb Stabilisatoren eingesetzt. Wichtige Vertreter von Stabilisato ren sind Antioxidantien, die mit den bei der Autoxidation gebildeten Radikalen interferieren und damit den Abbauprozess unterbrechen. Man unterscheidet im Allgemeinen zwischen primären Antioxidantien, die direkt mit sauerstoffhal tigen freien Radikalen oder C-Radikalen reagieren können und sekundären An tioxidantien, die mit intermediär gebildeten Hydroperoxiden reagieren (s. C. Kröhnke et al. Antioxidants in Ullmann's encyclopedia of industrial chemistry, Wiley-VCH Verlag, Weinheim 2015). Typische Vertreter von primären Antioxi dantien sind beispielsweise phenolische Antioxidantien, Amine aber auch Lac- tone. Klassen von sekundären Antioxidantien sind Phosphorverbindungen wie z.B. Phosphite und Phosphonite, aber auch Organo-Schwefelverbindungen wie z.B. Sulfide und Disulfide. Üblicherweise werden in der Praxis häufig primäre und sekundäre Antioxidantien kombiniert, was zu einer synergistischen Wir kung führt. Organic materials such as plastics are subject to aging processes, which ultimately lead to a loss of the desired properties such as the mechanical parameters. This process, known as autoxidation, leads to changes in the polymer chain, such as the molecular weight or the formation of new chemical groups, based on radical chain scission by mechanochemical processes or by UV radiation in the presence of oxygen. Stabilizers are therefore used to prevent or at least delay this aging process. Important representatives of stabilizers are antioxidants that interfere with the radicals formed during autoxidation and thus interrupt the degradation process. A general distinction is made between primary antioxidants, which can react directly with oxygen-containing free radicals or C-radicals, and secondary antioxidants, which react with hydroperoxides formed as intermediates (see C. Kröhnke et al. Antioxidants in Ullmann 's encyclopedia of industrial chemistry , Wiley-VCH Verlag, Weinheim 2015). Typical representatives of primary antioxidants are, for example, phenolic antioxidants, amines, but also lactones. Classes of secondary antioxidants are phosphorus compounds such as phosphites and phosphonites, but also organo-sulfur compounds such as sulfides and disulfides. Usually, primary and secondary antioxidants are often combined in practice, which leads to a synergistic effect.
Da manche der heute eingesetzten Stabilisatoren auch Nachteile aufweisen können (z.B. Hydrolysestabilität von Phosphiten und Freisetzung von Phenol, Geruch bei schwefelhaltigen Stabilisatoren, Verfärbungen bei Aminen etc.) wird nach wie vor nach neuen Stabilisatorlösungen gesucht. Since some of the stabilizers used today can also have disadvantages (e.g. hydrolysis stability of phosphites and the release of phenol, odor of sulfur-containing stabilizers, discoloration of amines, etc.), new stabilizer solutions are still being sought.
Phenolische Antioxidantien bestehen in der Regel aus sterisch gehinderten Phenolgruppen, die zur Molekulargewichtserhöhung, besseren Verträglichkeit und reduzierten Flüchtigkeit in Form von Estern vorliegen. Zur Erhöhung der Wirksamkeit und zu einer hohen Konzentration von Phenolgruppen bei gleich zeitig geringer Konzentration unwirksamer Bestandteile eines Moleküls wur- den Polyole wie z.B. Pentaerythrit eingesetzt, deren 4 Alkoholgruppen vollstän dig verestert werden. Pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxy- phenyl)propionat, z.B. unter dem Handelsnamen Irganox™ 1010 erhältlich hat sich dadurch zu einem der wichtigsten Standardstabilisatoren entwickelt. Grundsätzlich sind auch Substitutionsprodukte, die noch eine höhere Zahl an phenolischen Antioxidantien beinhalten wie z.B. hexasubstituiertes Mannitol oder hexasubstituiertes Cyclitol bekannt. Allen diesen Strukturen gemeinsam ist, dass aus den gesagten Gründen eine vollständige Veresterung mit den wirk samen Strukturen erreicht wird. Phenolic antioxidants generally consist of sterically hindered phenol groups, which are present in the form of esters to increase molecular weight, improve compatibility and reduce volatility. To increase the effectiveness and to achieve a high concentration of phenol groups with a simultaneous low concentration of ineffective components of a molecule, the polyols such as pentaerythritol are used, the 4 alcohol groups of which are fully esterified dig. Pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, available for example under the trade name Irganox ™ 1010, has become one of the most important standard stabilizers. In principle, substitution products are also one of the other They contain a higher number of phenolic antioxidants such as hexasubstituted mannitol or hexasubstituted cyclitol, all of which have in common that, for the reasons mentioned, complete esterification is achieved with the effective structures.
Wie bereits erwähnt werden üblicherweise phenolische Antioxidantien in sy nergistischer Weise mit anderen Stabilisatoren kombiniert. In Ausnahmefällen sind jedoch auch Stabilisatoren bekannt, die in einem Molekül sowohl primäre als auch sekundäre Antioxidans-Strukturen aufweisen wie z.B. As already mentioned, phenolic antioxidants are usually combined in a synergistic way with other stabilizers. In exceptional cases, however, stabilizers are also known which have both primary and secondary antioxidant structures in one molecule, e.g.
In einer eigenen Anmeldung (WO 2019063550) wurde gefunden, dass Kombi nationen von Alditolen oder Cyclitolen mit primären oder sekundären Antioxi dantien insbesondere geeignet sind Kunststoff-Rezyklate zu stabilisieren. Auch hier ist es erfindungsgemäß vorteilhaft Mischungen unterschiedlicher Stabilisa toren einzusetzen. In a separate application (WO 2019063550) it was found that combinations of alditols or cyclitols with primary or secondary antioxidants are particularly suitable for stabilizing recycled plastics. Here, too, it is advantageous according to the invention to use mixtures of different stabilizers.
Aufgabe der vorliegenden Erfindung ist es daher, Stabilisatoren auf, zumindest anteilig, nachwachsender Rohstoffbasis anzugeben, die eine hohe Stabilisie rungswirkung aufzeigen. The object of the present invention is therefore to provide stabilizers based, at least in part, on renewable raw materials which have a high stabilizing effect.
Die Aufgabe wird bezüglich einer Verwendung mit den Merkmalen des Pa tentanspruchs 1, bezüglich einer stabilisierten Kunststoffzusammensetzung mit den Merkmalen des Patentanspruchs 14, bezüglich eines Verfahrens zur Stabi lisierung von Kunststoffen mit den Merkmalen des Patentanspruchs 17, bezüg lich einer Formmasse mit den Merkmalen des Patentanspruchs 18, bezüglich einer Stabilisator-Zusammensetzung zur Stabilisierung von Kunststoffen mit den Merkmalen des Patentanspruchs 19 sowie bezüglich der stabilisierend wir kenden Zuckerderivate mit den Merkmalen des Patentanspruchs 20 gelöst. Die jeweilig abhängigen Patentansprüche stellen dabei jeweils vorteilhafte Weiter bildungen dar. The task is related to a use with the features of patent claim 1, regarding a stabilized plastic composition with the features of patent claim 14, regarding a method for stabilizing plastics with the features of patent claim 17, regarding a molding compound with the features of patent claim 18 , in terms of a stabilizer composition for stabilizing plastics with the features of claim 19 and with respect to the stabilizing we kenden sugar derivatives with the features of claim 20 solved. The respective dependent claims represent advantageous developments.
Die vorliegende Erfindung betrifft somit die Verwendung mindestens eines phenolisch substituierten Zuckerderivates, wobei das Zuckerderivat einen von einem Zucker abgeleiteten Grundkörper aufweist, sowie mindestens einen Substituenten gemäß allgemeiner Formel I The present invention thus relates to the use of at least one phenolically substituted sugar derivative, the sugar derivative having a base structure derived from a sugar, and at least one substituent according to general formula I
Formel I wobei R1 und R2 bei jedem Auftreten gleich oder verschieden sind und ausge wählt sind aus der Gruppe bestehend aus Wasserstoff und linearen oder ver zweigten Alkylreste, mit der Maßgabe, dass mindestens ein Rest R1 oder R2 nicht Wasserstoff ist, eine Alkylengruppe mit 1 bis 18 Kohlenstoffatomen oder eine chemische Bindung,Formula I where R 1 and R 2 are identical or different on each occurrence and are selected from the group consisting of hydrogen and linear or branched alkyl radicals, with the proviso that at least one radical R 1 or R 2 is not hydrogen, an alkylene group with 1 to 18 carbon atoms or a chemical bond,
eine Gruppierung ausgewählt aus der Gruppe bestehend aus den nachfolgenden Gruppierungen a grouping selected from the group consisting of the following groupings
wobei die Gruppierung X an den links dargestellten Terminus der oben abgebil deten Gruppierungen Y gebunden ist, und wobei der von einem Zucker abge leiteten Grundkörper des phenolisch substituierten Zuckerderivates mindes tens 3, unsubstituierte Hydroxygruppen aufweist und/oder der von einem Zu cker abgeleitete Grundkörper des phenolisch substituierten Zuckerderivates mindestens 4 Kohlenstoffatome und mindestens 2, vorzugsweise mindestens 3 unsubstituierte Hydroxygruppen aufweist, als Stabilisator von organischen Ma terialien, insbesondere Kunststoffen gegen oxidativen, thermischen und/oder aktinischen Abbau. where the group X is bound to the terminus shown on the left of the groupings Y shown above, and where the base of the phenolically substituted sugar derivative derived from a sugar has at least 3 unsubstituted hydroxyl groups and / or the base of the phenolic derived from a sugar substituted sugar derivative has at least 4 carbon atoms and at least 2, preferably at least 3 unsubstituted hydroxyl groups, as a stabilizer of organic materials, in particular plastics, against oxidative, thermal and / or actinic degradation.
Als„Stabilisator" bzw.„stabilisierend" im Sinne der vorliegenden Erfindung wird dabei verstanden, dass die entsprechend ausgerüsteten organischen Ma terialien, beispielsweise die Kunststoffe, die mit einem Zuckerderivat gemäß Formel I versetzt sind, unter oxidativen, thermischen und/oder aktinischen Be dingungen eine längere Haltbarkeit wie z.B. Erhalt der mechanischen und/oder visuellen Eigenschaften aufweisen, verglichen mit Formmassen, die ohne die entsprechenden Additive ausgerüstet sind. Überraschenderweise konnte erfin dungsgemäß festgestellt werden, dass die stabilisierende Wirkung, wie voran stehend definiert, mit Substanzen erzielbar ist, die ein auf nachwachsenden Rohstoffen basierendes Grundgerüst aufweisen. As "stabilizer" or "stabilizing" in the sense of the present invention is understood that the appropriately equipped organic Ma materials, for example the plastics to which a sugar derivative according to formula I are added, under oxidative, thermal and / or actinic conditions have a longer shelf life, such as retention of mechanical and / or visual properties, compared to molding compounds that are finished without the corresponding additives. Surprisingly, it could be established according to the invention that the stabilizing effect, as defined above, can be achieved with substances which have a basic structure based on renewable raw materials.
Insbesondere ist hierbei der von einem Zucker abgeleitete Grundkörper ein Monosaccharid, ein Oligosaccharid oder ein Polysaccharid mit mindestens 4 Kohlenstoffen. In particular, the base body derived from a sugar is a monosaccharide, an oligosaccharide or a polysaccharide with at least 4 carbons.
Besonders bevorzugt umfasst das phenolisch substituierte Zuckerderivat maxi mal 10, bevorzugt maximal 5, weiter bevorzugt maximal 3, besonders bevor zugt 1 oder 2 Substituenten gemäß Formel I. The phenolic substituted sugar derivative particularly preferably comprises a maximum of 10, preferably a maximum of 5, more preferably a maximum of 3, particularly preferably 1 or 2, substituents according to formula I.
Insbesondere kann der von einem Zucker abgeleitete Grundkörper mindestens ein Alditol, ein Cyclitol, eine Zuckersäure oder ein Aminozucker mit mindestens 4 Kohlenstoffen sein. In particular, the base body derived from a sugar can be at least one alditol, a cyclitol, a sugar acid or an amino sugar with at least 4 carbons.
Beispielsweise kann das Alditol die nachfolgenden Summenformeln For example, the alditol can have the following empirical formulas
HOCH [CH(OH)]nCH OH, HIGH [CH (OH)] n CH OH,
Ri-OCH2[CH(OH)]nCH2OH, oder Ri-OCH 2 [CH (OH)] n CH 2 OH, or
HOCH2[CH(OH)]n[CH(ORi)]CH2OH mit n = 2-6, bevorzugt n = 3-5 aufweisen, wobei Ri ein gegebenenfalls substitu ierter Zuckerrest ist. Besonders bevorzugt ist das mindestens eine Alditol ausgewählt aus der Gruppe bestehend aus Threit, Erythrit, Galactit, Mannit, Ribit, Sorbit, Xylit, Ara bit, Isomalt, Lactit, Maltit, Maltotritol und hydrierte Oligo- und Polysaccharide mit Polyol-Endgruppen und Mischungen hiervon, wobei das mindestens eine Alditol vorzugsweise ausgewählt ist aus der Gruppe bestehend aus Erythrit, Mannit, Isomalt, Maltit und Mischungen hiervon. HOCH 2 [CH (OH)] n [CH (ORi)] CH 2 OH with n = 2-6, preferably n = 3-5, where Ri is an optionally substituted sugar residue. The at least one alditol is particularly preferably selected from the group consisting of threitol, erythritol, galactitol, mannitol, ribitol, sorbitol, xylitol, Ara bit, isomalt, lactitol, maltitol, maltotritol and hydrogenated oligo- and polysaccharides with polyol end groups and mixtures thereof , wherein the at least one alditol is preferably selected from the group consisting of erythritol, mannitol, isomalt, maltitol and mixtures thereof.
Das mindestens eine Cyclitol kann ausgewählt sein aus der Gruppe bestehend aus Inositol (myo, scyllo-, D-chiro-, L-chiro-, muco-, neo-, allo-, epi- und cis-lno- sit), Quercitol, Viscumitol, Bornesitol, Conduritol, Ononitol, Pinitol, Pinpollitol, Ciceritol, Quebrachitol, Chinasäure, Shikimisäure und Valienol wobei das min destens eine Cyclitol vorzugsweise myo-lnosit (myo-lnositol) ist. The at least one cyclitol can be selected from the group consisting of inositol (myo, scyllo-, D-chiro-, L-chiro-, muco-, neo-, allo-, epi- and cis-innosite), quercitol, Viscumitol, Bornesitol, Conduritol, Ononitol, Pinitol, Pinpollitol, Ciceritol, Quebrachitol, Quinic acid, Shikimic acid and Valienol, the at least one cyclitol being preferably myo-inositol (myo-inositol).
Bevorzugte Zuckersäuren sind beispielsweise Aldonsäuren, wie insbesondere Allonsäure, Altronsäure, Gluconsäure, Mannonsäure, Gulonsäure, Idonsäure, Galaktonsäure, Talonsäure, Ribonsäure, Arabonsäure, Xylonsäure, Lyxonsäure, Erythronsäure oder Threonsäure oder Aldarsäuren wie Schleimsäure oder Glucarsäure sowie Mischungen und Kombinationen hiervon. Preferred sugar acids are, for example, aldonic acids, such as in particular allonic acid, altronic acid, gluconic acid, mannonic acid, gulonic acid, idonic acid, galactonic acid, talonic acid, ribonic acid, arabonic acid, xylonic acid, lyxonic acid, erythronic acid or threonic acid or aldaric acids such as mucic acid or glucaric acid, and mixtures and combinations thereof.
Für den Fall, dass ein Aminozucker das Grundgerüst der erfindungsgemäßen Verbindung gemäß Formel I bildet, ist der mindestens eine Aminozucker bei spielsweise ein Mono- oder Diaminozucker und besonders bevorzugt ausge wählt aus der Gruppe bestehend aus 1-Amino-l-deoxy-alditolen, wie z.B. 1- Amino-l-deoxy-galactit, 1-Amino-l-deoxy-mannit, 1-Amino-l-deoxy-sorbit, 1- Amino-l-deoxy-maltit oder a, -Diamino-a, -dideoxyalditolen, wie z.B. 1,6-Di- amino-l,6-dideoxysorbit. In the event that an amino sugar forms the basic structure of the compound according to the invention according to formula I, the at least one amino sugar is, for example, a mono- or diamino sugar and is particularly preferably selected from the group consisting of 1-amino-l-deoxy-alditols, such as for example 1-amino-1-deoxy-galactitol, 1-amino-1-deoxy-mannitol, 1-amino-1-deoxy-sorbitol, 1-amino-1-deoxy-maltitol or α, -diamino-α, -dideoxyalditols such as, for example, 1,6-di-amino-1,6-dideoxy sorbitol.
Die Reste R1 und R2 sind dabei gleich oder verschieden, insbesondere bevorzugt gleich. Die Reste R1 und R2 können insbesondere ausgewählt sein aus der Gruppe bestehend aus tert.-Butyl und Methyl. The radicals R 1 and R 2 are identical or different, particularly preferably identical. The radicals R 1 and R 2 can in particular be selected from the group consisting of tert-butyl and methyl.
Besonders bevorzugte phenolisch substituierte Zuckerderivate sind ausgewählt aus der Gruppe bestehend aus den nachfolgenden Molekülen sowie Mischungen und Kombinationen hiervon. Particularly preferred phenolically substituted sugar derivatives are selected from the group consisting of the following molecules as well as mixtures and combinations thereof.
Das mindestens eine phenolisch substituierte Zuckerderivat kann bevorzugt in einer Gesamtmenge von 0,01 bis 10 Gew.%, bevorzugt 0,05 bis 5 Gew%, beson ders bevorzugt von 0,1 bis 3 Gew%, bezogen auf den Kunststoff eingesetzt wer den. The at least one phenolically substituted sugar derivative can preferably be used in a total amount of 0.01 to 10% by weight, preferably 0.05 to 5% by weight, particularly preferably 0.1 to 3% by weight, based on the plastic.
Insbesondere ergeben sich hohe stabilisierende Wirkungen, wenn das mindes tens eine phenolisch substituierte Zuckerderivat in Kombination mit einem sich vom mindestens einen phenolisch substituierten Zuckerderivat unterscheiden den primären und/oder sekundären Antioxidans verwendet wird, wobei bevor zugt das mindestens eine Antioxidans ausgewählt ist aus der Gruppe bestehend aus phenolischen Antioxidantien, Aminen, Lactonen und Mischungen hiervon, und das mindestens eine sekundäre Antioxidans ausgewählt ist aus der Gruppe bestehend aus Phosphorverbindungen, insbesondere Phosphiten und Phos- phoniten, Organo-Schwefelverbindungen, insbesondere Sulfiden und Disulfi- den, sowie Mischungen hiervon. In particular, there are high stabilizing effects when the at least one phenolically substituted sugar derivative is used in combination with a primary and / or secondary antioxidant that differs from the at least one phenolically substituted sugar derivative, the at least one antioxidant preferably being selected from the group consisting of from phenolic antioxidants, amines, lactones and mixtures thereof, and the at least one secondary antioxidant is selected from the group consisting of phosphorus compounds, in particular phosphites and phosphites, organosulfur compounds, in particular sulfides and disulfides, and mixtures thereof.
Geeignete primäre Antioxidantien sind phenolische Antioxidantien, Amine undSuitable primary antioxidants are phenolic antioxidants, amines and
Lactone Geeignete synthetische phenolische Antioxidantien sind beispielsweise: Lactones Suitable synthetic phenolic antioxidants are for example:
Alkylierte Monophenole, wie z.B. 2,6-Di-tert-butyl-4-methylphenol, 2-tert- Butyl-4,6-dimethylphenol, 2,6-Di-tert-butyl-4-ethylphenol, 2,6-Di-tert-butyl-4- n-butylphenol, 2,6-Di-tert-butyl-4-isobutylphenol, 2,6-Dicyclopentyl-4-methyl- phenol, 2-(a-Methylcyclohexyl)-4,6-dimethylphenol, 2,6-Dioctadecyl-4-me- thylphenol, 2,4,6-Tricyclohexylphenol, 2,6-Di-tert-butyl-4-methoxymethyl- phenol, lineare oder verzweigte Nonylphenole, wie z.B. 2,6-Dinonyl-4-methyl- phenol, 2,4-Dimethyl-6-(l'-methylundec-l'-yl)phenol, 2,4-Dimethyl-6-(l'-me- thylheptadec-l'-yl)phenol, 2,4-Dimethyl-6-(l'-methyltridec-l'-yl)phenol und Mischungen hiervon; Alkylated monophenols, such as, for example, 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di -tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methyl-phenol, 2- (α-methylcyclohexyl) -4,6-dimethylphenol , 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, linear or branched nonylphenols, such as 2,6-dinonyl- 4-methyl-phenol, 2,4-dimethyl-6- (l'-methylundec-l'-yl) phenol, 2,4-dimethyl-6- (l'-methylheptadec-l'-yl) phenol, 2,4-dimethyl-6- (l'-methyltridec-l'-yl) phenol and mixtures thereof;
Alkylthiomethylphenole, wie z.B. 2,4-Dioctylthiomethyl-6-tert-butylphenol, 2,4-Dioctylthiomethyl-6-methylphenol, 2,4-Dioctylthiomethyl-6-ethylphenol, 2,6-Didodecylthiomethyl-4-nonylphenol; Alkylthiomethylphenols such as 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol;
Hydrochinone und alkylierte Hydrochinone, wie z.B. 2,6-Di-tert-butyl-4-me- thyoxyphenol, 2,5-Di-tert-butylhydrochinon, 2,5-Di-tert-amylhydrochinon, 2,6- Diphenyl-4-octadecyloxyphenol, 2,6-Di-tert-butylhydrochinon, 2,5-Di-tert- butyl-4-hydroxyanisol, 3,5-Di-tert-butyl-4-hydroxyanisol, 3,5-Di-tert-butyl-4- hydroxyphenylstearat, Bis(3,5-di-tert-butyl-4-hydroxylphenyl)adipat; Hydroquinones and alkylated hydroquinones, such as, for example, 2,6-di-tert-butyl-4-methyoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4 octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl -4-hydroxyphenyl stearate, bis (3,5-di-tert-butyl-4-hydroxylphenyl) adipate;
Hydroxylierte Thiodiphenylether, wie z.B. 2,2'-Thiobis(6-tert-butyl-4-methyl- phenol), 2,2'-Thiobis(4-octylphenol), 4,4'-Thiobis(6-tert-butyl-3-methyl- phenol), 4,4'-Thiobis(6-tert-butyl-2-methylphenol), 4,4'-Thiobis(3,6-di-sec- amylphenol), 4,4'-Bis(2,6-dimethyl-4-hydroxyphenyl)disulfid; Hydroxylated thiodiphenyl ethers, such as 2,2'-thiobis (6-tert-butyl-4-methyl-phenol), 2,2'-thiobis (4-octylphenol), 4,4'-thiobis (6-tert-butyl- 3-methyl-phenol), 4,4'-thiobis (6-tert-butyl-2-methylphenol), 4,4'-thiobis (3,6-di-sec-amylphenol), 4,4'-bis ( 2,6-dimethyl-4-hydroxyphenyl disulfide;
Alkylidenbisphenole, wie z.B. 2,2'Methylenbis(6-tert-butyl-4-methylphenol), 2,2'-Methylenbis(6-tert-butyl-4-ethylphenol), 2,2'-Methylenbis[4-methyl-6-(a- methylcyclohexyl)phenol], 2,2'-Methylenbis(4-methyl-6-cyclhexylphenol), 2,2'- Methylenbis(6-nonyl-4-methylphenol), 2,2'-Methylenbis(4,6-di-tert- butylphenol), 2,2'-Ethylidenbis(4,6-di-tert-butylphenol), 2,2'-Ethylidenbis(6- tert-butyl-4-isobutylphenol), 2,2'-Methylenbis[6-(a-methylbenzyl)-4-nonyl- phenol], 2,2'-Methylenbis[6-(a,a-dimethylbenzyl)-4-nonylphenol], 4,4'-Methy- lenbis(2,6-di-tert-butylphenol, 4,4'-Methylenbis(6-tert-butyl-2-methylphenol), l,l-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butan, 2,6-Bis(3-tert-butyl-5- methyl-2-hydroxybenzyl)-4-methylphenol, l,l,3-Tris(5-tert-butyl-4-hydroxy-2- methylphenyl)butan, l,l-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n- dodecylmercaptobutan, Ethylenglycol-bis[3,3-bis(3'-tert-butyl-4'-hydroxyphe- nyl)butyrat], Bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadien, Bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphe- nyl]terephthalat, l,l-Bis-(3,5-dimethyl-2-hydroxyphenyl)butan, 2,2-Bis(3,5-di- tert-butyl-4-hydroxyphenyl)propan, 2,2-Bis-(5-tert-butyl-4-hydroxy-2-methyl- phenyl)-4-n-dodecylmercaptobutan, l,l,5,5-Tetra(5-tert-butyl-4-hydroxy-2- methylphenyl)pentan; Alkylidenebisphenols, such as 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 2,2'-methylenebis [4-methyl- 6- (a-methylcyclohexyl) phenol], 2,2'-methylenebis (4-methyl-6-cyclhexylphenol), 2,2'-methylenebis (6-nonyl-4-methylphenol), 2,2'-methylenebis (4 , 6-di-tert-butylphenol), 2,2'-ethylidenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (6-tert-butyl-4-isobutylphenol), 2,2 ' -Methylene bis [6- (a-methylbenzyl) -4-nonyl- phenol], 2,2'-methylenebis [6- (a, a-dimethylbenzyl) -4-nonylphenol], 4,4'-methylenebis (2,6-di-tert-butylphenol, 4,4'-methylenebis (6-tert-butyl-2-methylphenol), l, l-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis (3-tert-butyl-5-methyl- 2-hydroxybenzyl) -4-methylphenol, l, l, 3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, l, l-bis (5-tert-butyl-4-hydroxy-2 -methylphenyl) -3-n-dodecylmercaptobutane, ethylene glycol bis [3,3-bis (3'-tert-butyl-4'-hydroxyphenyl) butyrate], bis (3-tert-butyl-4-hydroxy-5 -methylphenyl) dicyclopentadiene, bis [2- (3'-tert-butyl-2'-hydroxy-5'-methylbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate, 1,1-bis- (3 , 5-dimethyl-2-hydroxyphenyl) butane, 2,2-bis (3,5-di-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (5-tert-butyl-4-hydroxy- 2-methyl-phenyl) -4-n-dodecylmercaptobutane, 1,1,5-tetra (5-tert-butyl-4-hydroxy-2-methylphenyl) pentane;
O-, N- und S-Benzyl-Verbindungen, wie z.B. 3,5,3',5'-Tetra-tert-butyl-4,4'- dihydroxydibenzylether, Octadecyl-4-hydroxy-3,5-dimethylbenzylmercapto- acetat, Tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetat, Tris(3,5-di- tert-butyl-4-hydroxybenzyl)amin, Bis(4-tert-butyl-3-hydroxy-2,6-dimethyl- benzyl)dithioterephthalat, Bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfid, lsooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetat; O-, N- and S-benzyl compounds, such as, for example, 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzyl mercapto acetate , Tridecyl-4-hydroxy-3,5-di-tert-butylbenzyl mercaptoacetate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) amine, bis (4-tert-butyl-3-hydroxy-2,6 dimethylbenzyl) dithioterephthalate, bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzyl mercaptoacetate;
Hydroxybenzylierte Malonate, wie z.B. Dioctadecyl-2,2-bis(3,5-di-tert-butyl-2- hydroxybenzyl)malonat, Dioctadecyl-2-(3-tert-butyl-4-hydroxy-5-methyl- benzyl)malonat, Didodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxy- benzyl)malonat, Bis[4-(l,l,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert- butyl-4-hydroxybenzyl)malonat; Hydroxybenzylated malonates, such as dioctadecyl-2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, dioctadecyl-2- (3-tert-butyl-4-hydroxy-5-methylbenzyl) malonate, didodecyl mercaptoethyl-2,2-bis (3,5-di-tert-butyl-4-hydroxy-benzyl) malonate, bis [4- (l, l, 3,3-tetramethylbutyl) phenyl] -2,2- bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate;
Aromatische Hydroxybenzylverbindungen, wie z.B. l,3,5-Tris(3,5-di-tert-butyl- 4-hydroxybenzyl)-2,4,6-trimethylbenzol, l,4-Bis(3,5-di-tert-butyl-4-hydroxy- benzyl)-2,3,5,6-tetramethylbenzol, 2,4,6-Tris(3,5-di-tert-butyl-4-hydroxy- benzyl)phenol; Aromatic hydroxybenzyl compounds, such as, for example, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3,5-di-tert- butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) phenol;
Triazinverbindungen, wie z.B. 2,4-Bis(octylmercapto)-6-(3,5-di-tert-butyl-4- hydroxyanilino)-l,3,5-triazin, 2-Octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hyd- roxyanilino)-l,3,5-triazin, 2-Octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxy- phenoxy)-l,3,5-triazin, 2,4,6-Tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-l,2,3- triazin, l,3,5-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurat, 1,3,5-T ris(4- te/T-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurat, 2,4,6-Tris(3,5-di-tert- butyl-4-hydroxphenylethyl)-l,3,5-triazin, l,3,5-Tris(3,5-di-te/T-butyl-4-hydroy- phenylpropionyl)hexahydro-l,3,5-triazin, l,3,5-Tris(3,5-dicyclohexyl-4-hydro- xybenzyl)isocyanurat; Triazine compounds, such as, for example, 2,4-bis (octylmercapto) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -1, 3,5-triazine, 2-octylmercapto-4,6-bis (3 , 5-di-tert-butyl-4-hydroxyanilino) -l, 3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyphenoxy) -l, 3,5-triazine, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenoxy) -l, 2,3-triazine, 1,3,5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-T ris (4- te / T-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxphenylethyl) -1, 3,5-triazine, l , 3,5-Tris (3,5-di-te / T-butyl-4-hydroxyphenylpropionyl) hexahydro-1,3,5-triazine, 1,3,5-tris (3,5-dicyclohexyl-4 hydroxybenzyl isocyanurate;
Benzylphosphonate, wie z.B. Dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphos- phonat, Dietyhl-3,5-di-te/T-butyl-4-hydroxybenzylphosphonat, Dioctadecyl-Benzyl phosphonates, such as dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethl-3,5-di-te / T-butyl-4-hydroxybenzylphosphonate, dioctadecyl
3.5-di-te/T-butyl-4-hydroxybenzylphosphonat, Dioctadecyl-5-te/T-butyl-4-hyd- roxy-3-methylbenzylphosphonat, das Calciumsalz des Monoethylesters der3.5-di-te / T-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-te / T-butyl-4-hydroxy-3-methylbenzylphosphonate, the calcium salt of the monoethyl ester of
3.5-Di-tert-butyl-4-hydroxybenzylphosphonsäure; 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid;
Acylaminophenole, wie z.B.4-Hydroxylauranilid, 4-Hydroxystearanilid, Octyl-N- (3,5-di-tert-butyl-4-hydroxyphenyl)carbamat; Acylaminophenols such as 4-hydroxylauranilide, 4-hydroxystearanilide, octyl-N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate;
Ester der ß-(3,5-Di-tert-butyl-4-hydroxyphenyl)propionsäure mit ein- oder mehrwertigen Alkoholen, z.B. Methanol, Ethanol, n-Octanol, i-Octanol, Octade- canol, 1,6-Hexandiol, 1,9-Nonandiol, Ethylenglycol, 1,2-Propandiol, Neopen- tylglycol, Thiodiethylenglycol, Diethylenglycol, Triethylenglycol, Pentaerythri- tol, Tris(hydroxyethyl)isocyanurat, N,N'-Bis(hydroxyethyl)oxamid, 3-Thiaunde- canol, 3-Thiapentadecanol, Trimethylhexandiol, Trimethylolpropan, 4-Hydro- xymethyl-l-phospha-2,6,7-trioxabicyclo[2.2.2]octan; Esters of ß- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with monohydric or polyhydric alcohols, e.g. methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaund canol , 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane;
Ester der ß-(5-tert-Butyl-4-hydroxy-3-methylphenyl)propionsäure mit ein- oder mehrwertigen Alkoholen, z.B. Methanol, Ethanol, n-Octanol, i-Octanol, Octade- canol, 1,6-Hexandiol, 1,9-Nonandiol, Ethylenglycol, 1,2-Propandiol, Neopen- tylglycol, Thiodiethylenglycol, Diethylenglycol, Triethylenglycol, Pentaerythri- tol, Tris(hydroxyethyl)isocyanurat, N,N'-bis(hydroxyethyl)oxamid, 3-Thiaunde- canol, 3-Thiapentadecanol, Trimethylhexandiol, Trimethylolpropan, 4-Hydro- xymethyl-l-phospha-2,6,7-trioxabicyclo[2.2.2]octan, 3,9-Bis[2-{3-(3-tert-butyl- 4-hydroxy-5-methylphenyl)propionyloxy}-l,l-dimethylethyl]-2,4,8,10-tetrao- xaspiro[5.5]undecan; Esters of ß- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with mono- or polyhydric alcohols, e.g. methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaund canol , 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane, 3,9-bis [2- {3- (3-tert-butyl - 4-hydroxy-5-methylphenyl) propionyloxy} -1, l-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane;
Ester der ß-(3,5-Dicyclohexyl-4-hydroxyphenyl)propionsäure mit ein- oder mehrwertigen Alkoholen, z.B. Methanol, Ethanol, Octanol, Octadecanol, 1,6- Hexandiol, 1,9-Nonandiol, Ethylenglycol, 1,2-Propandiol, Neopentylglycol, Thiodiethylenglycol, Diethylenglycol, Triethylenglycol, Pentaerythritol, Tris- (hydroxyethyl)isocyanurat, N,N'-bis(hydroxyethyl)oxamid, 3-Thiaundecanol, 3- Thiapentadecanol, Trimethylhexandiol, Trimethylolpropan, 4-Hydroxymethyl- l-phospha-2,6,7-trioxabicyclo[2.2.2]octan; Esters of ß- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid with monohydric or polyhydric alcohols, e.g. methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2- Propanediol, neopentyl glycol, Thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6, 7-trioxabicyclo [2.2.2] octane;
Ester der (3,5-Di-te/T-butyl-4-hydroxyphenyl)essigsäure mit ein- oder mehrwer tigen Alkoholen, z.B. Methanol, Ethanol, Octanol, Octadecanol, 1,6-Hexandiol, 1,9-Nonandiol, Ethylenglycol, 1,2-Propandiol, Neopentylglycol, Thiodiethylen glycol, Diethylenglycol, Triethylenglycol, Pentaerythritol, Tris(hydroxyethyl)iso- cyanurat, N,N'-bis(hydroxyethyl)oxamid, 3-Thiaundecanol, 3-Thiapentadeca- nol, Trimethylhexandiol, Trimethylolpropan, 4-Hydroxymethyl-l-phospha- 2,6,7-trioxabicyclo[2.2.2]octan; Esters of (3,5-di-te / T-butyl-4-hydroxyphenyl) acetic acid with mono- or polyvalent alcohols, for example methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol , 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane , 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane;
Amide der ß-(3,5-Di-te/T-butyl-4-hydroxyphenyl)propionsäure, wie z.B. N,N'- Bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylendiamid, N,N'- Bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylendiamid, N,N'- Bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylendiamid, N,N'- Bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazid, N,N'-Bis[2-(3-[3,5-di- te/T-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamid (Naugard®XL-l, ver trieben durch Sl group ); Amides of ß- (3,5-di-te / T-butyl-4-hydroxyphenyl) propionic acid, such as N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylene diamide, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylene diamide, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylene diamide, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazide, N, N'-bis [2- (3- [3,5-di- te / T-butyl-4-hydroxyphenyl] propionyloxy) ethyl] oxamide (Naugard ® XL-l, ver driven by Sl group);
Ascorbinsäure (Vitamin C). Ascorbic acid (vitamin C).
Besonders bevorzugte phenolische Antioxidantien sind die folgenden Struktu ren: Particularly preferred phenolic antioxidants are the following structures:
wobei in den zuvor genannten Verbindungen n eine ganze Zahl ist und bei zwi schen 2 und 10 liegt where n is an integer in the aforementioned compounds and is between 2 and 10
Weitere bevorzugte phenolische Antioxidantien sind auf nachwachsenden Roh stoffen basierende phenolische Antioxidantien wie z. B. a-, ß-, g-, d-Tocopherol und Mischungen aus diesen (Vitamin E), Tocotrienole, Tocomonoenole, Ubichi- nol, Hydroxytyrosol, Flavonoide and Flavonole wie z.B. Chrysin, Quercitin, Hes peridin, Neohesperidin, Naringin, Morin, Kaempferol, Fisetin, Datiscetin, Lute olin, Apigenin, Taxifolin, Isoflavone wie z.B. Genistein, Genistin, Daidzein, Daidzin, Formononetin, Anthocyane, wie z.B. Delphinidin und Malvidin, Cur- cumin, Carnosolsäure, Carnosol, Rosmarinsäure, Tannin und Resveratrol sowie Carotenoide mit alkoholischen Gruppen ,wie z.B. beta-Cryptoxanthin, Lutein, Zeaxanthin oder Astaxanthin Other preferred phenolic antioxidants are phenolic antioxidants based on renewable raw materials such as. B. a-, ß-, g-, d-tocopherol and mixtures of these (vitamin E), tocotrienols, tocomonoenols, ubiquinol, hydroxytyrosol, flavonoids and flavonols such as chrysin, quercitin, hes peridin, neohesperidin, naringin, morin , Kaempferol, fisetin, datiscetin, lute olin, apigenin, taxifolin, isoflavones such as genistein, genistin, daidzein, daidzin, formononetin, anthocyanins such as delphinidin and malvidin, curcumin, carnosic acid, carnosol, rosmarinic acid, tannin and carotenoid resverrol with alcoholic groups, such as beta-cryptoxanthin, lutein, zeaxanthin or astaxanthin
Weitere Stabilisatoren insbesondere für Polyamide sind Kupfer-l-halogenide z.B. CuJ, CuBr, ggf. In Mischungen mit Alkalihalogeniden wie KJ oder KBr bzw. Cu-(l)-Komplexe zum Beispiel mit Triphenylphosphin. Geeignete aminische Antioxidantien sind beispielsweise: Further stabilizers, especially for polyamides, are copper-l-halides, for example CuJ, CuBr, optionally in mixtures with alkali halides such as KJ or KBr or Cu (l) complexes, for example with triphenylphosphine. Suitable aminic antioxidants are, for example:
N,N'-Di-isopropyl-p-phenylendiamin, N,N'-Di-sec-butyl-p-phenylendiamin, N,N'-Bis(l,4-dimethylpentyl)-p-phenylendiamin, N,N'-Bis(l-ethyl-3-methyl- pentyl)-p-phenylendiamin, N,N'-Bis(l-methylheptyl)-p-phenylendiamin, N,N'- Dicyclohexyl-p-phenylendiamin, N,N'-Diphenyl-p-phenylendiamin, N,N'- Bis(2-naphthyl)-p-phenylendiamin, N-lsopropyl-N'-phenyl-p-phenylendiamin, N-(l,3-Dimethylbutyl)-N'-phenyl-p-phenylen-diamin, N-(1-Methylheptyl)-N'- phenyl-p-phenylendiamin, N-Cyclohexyl-N'-phenyl-p-phenylendiamin, 4-(p- Toluolsulfamoyl)diphenylamin, N,N'-Dimethyl-N,N'-di-sec-butyl-p-phenylen- diamin, Diphenylamin, N-Allyldiphenylamin, 4-lsopropoxydiphenylamin, N- Phenyl-l-naphthylamin, N-(4-tert-Octylphenyl)-l-naphthylamin, N-Phenyl-2- naphthylamin, octyliertes Diphenylamin, z.B. p,p'-Di-tert-octyldiphenylamin, 4-n-Butylaminophenol, 4-Butyrylaminophenol, 4-Nonanoylaminophenol, 4- Dodecanoylaminophenol, 4-Octadecanoylamino-phenol, Bis(4-methoxyphe- nyl)amin, 2,6-Di-tert-butyl-4-dimethylaminomethyl-phenol, 2,4'-Diami- nodiphenylmethan, 4,4'-Diaminodiphenylmethan, N,N,N',N'-Tetra-methyl- 4,4'-diaminodiphenylmethan, l,2-Bis[(2-methyl-phenyl)amino]ethan, 1,2- Bis(phenylamino)propan, (o-Tolyl)biguanid, Bis[4-(l',3'-dimethylbutyl)phe- nyl]amin, tert- octyliertes N-Phenyl-l-naphthylamin, ein Gemisch aus mono- und dialkylierten tert-Butyl/tert-Octyldiphenylaminen, ein Gemisch aus mono- und dialkylierten Nonyldiphenylaminen, ein Gemisch aus mono- und dialkylierten Dodecyldiphenylaminen, ein Gemisch aus mono- und dialkylier ten Isopropyl/lsohexyl-diphenylaminen, ein Gemisch aus mono- und dialky lierten tert-Butyldiphenylaminen, 2,3-Dihydro-3,3-dimethyl-4H-l,4-benzothi- azin, Phenothiazin, ein Gemisch aus mono- und dialkylierten tert-Butyl/tert- Octylphenothiazinen, ein Gemisch aus mono- und dialkylierten tert- Octylphe- nothiazinen, N-Allylphenothiazin, N,N,N',N'-Tetraphenyl-l,4-diaminobut-2- en sowie Mischungen oder Kombinationen hiervon. N, N'-di-isopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-bis (1,4-dimethylpentyl) -p-phenylenediamine, N, N ' -Bis (l-ethyl-3-methyl-pentyl) -p-phenylenediamine, N, N'-bis (l-methylheptyl) -p-phenylenediamine, N, N'-dicyclohexyl-p-phenylenediamine, N, N'- Diphenyl-p-phenylenediamine, N, N'- bis (2-naphthyl) -p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl- p-phenylenediamine, N- (1-methylheptyl) -N'- phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4- (p-toluenesulfamoyl) diphenylamine, N, N'- Dimethyl-N, N'-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N- (4-tert-octylphenyl) -l-naphthylamine , N-phenyl-2-naphthylamine, octylated diphenylamine, e.g. p, p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis ( 4-methoxyphenyl) amine, 2,6-di-tert-butyl-4-dimethylaminomethyl-phen ol, 2,4'-diamino diphenyl methane, 4,4'-diaminodiphenyl methane, N, N, N ', N'-tetra-methyl-4,4'-diaminodiphenyl methane, 1,2-bis [(2-methyl- phenyl) amino] ethane, 1,2-bis (phenylamino) propane, (o-tolyl) biguanide, bis [4- (l ', 3'-dimethylbutyl) phenyl] amine, tert-octylated N-phenyl-l -naphthylamine, a mixture of mono- and dialkylated tert-butyl / tert-octyldiphenylamines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl / isohexyl-diphenylamines a mixture of mono- and dialkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a mixture of mono- and dialkylated tert-butyl / tert-octylphenothiazines , a mixture of mono- and dialkylated tert-octylphenothiazines, N-allylphenothiazine, N, N, N ', N'-tetraphenyl-1,4-diaminobut-2-ene and mixtures or combinations thereof.
Bevorzugte aminische Antioxidantien sind: N,N'-Di-isopropyl-p-phenylendia- min, N,N'-Di-sec-butyl-p-phenylendiamin, N,N'-Bis(l,4-dimethylpentyl)-p-phe- nylendiamin, N,N'-Bis(l-ethyl-3-methylpentyl)-p-phenylendiamin, N,N'-Bis(l- methylheptyl)-p-phenylendiamin, N,N'-Dicyclohexyl-p-phenylendiamin, N,N'- Diphenyl-p-phenylendiamin, N,N'-Bis(2-naphthyl)-p-phenylendiamin, N-Isop- ropyl-N'-phenyl-p-phenylendiamin, N-(l,3-Dimethylbutyl)-N'-phenyl-p-pheny- len-diamin, N-(l-Methylheptyl)-N'-phenyl-p-phenylendiamin, N-Cyclohexyl-N'- phenyl-p-phenylendiamin Preferred amine antioxidants are: N, N'-di-isopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-bis (1,4-dimethylpentyl) -p -phenylenediamine, N, N'-bis (l-ethyl-3-methylpentyl) -p-phenylenediamine, N, N'-bis (l-methylheptyl) -p-phenylenediamine, N, N'-dicyclohexyl-p- phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N'-bis (2-naphthyl) -p-phenylenediamine, N-isop- ropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N- (l-methylheptyl) -N'-phenyl-p-phenylenediamine , N-cyclohexyl-N'-phenyl-p-phenylenediamine
Besonders bevorzugte aminische Antioxidantien sind die Strukturen: Particularly preferred aminic antioxidants are the structures:
wobei n eine ganze Zahl ist und zwischen 3 und 100 liegt. where n is an integer and is between 3 and 100.
Weitere bevorzugte aminische Antioxidantien sind Hydroxylamine bzw. N- oxide (Nitrone), wie z.B. N,N-Dialkylhydroxylamine, N,N-Dibenzylhydroxyla- min, N,N-Dilaurylhydroxylamin, N,N-Distearylhydroxylamin, N-Benzyl-a-phe- nylnitron, N-Octadecyl-a-hexadecylnitron, sowie Genox™ EP (Sl Group) ge mäß der Formel: Further preferred aminic antioxidants are hydroxylamines or N-oxides (nitrones), such as, for example, N, N-dialkylhydroxylamines, N, N-dibenzylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-distearylhydroxylamine, N-benzyl-a-phe - nylnitron, N-octadecyl-a-hexadecylnitron, as well as Genox ™ EP (Sl Group) according to the formula:
Ri Ri
R2— N— *-0 R 2 - N - * -0
LH3 LH3
Ri, R2 = C14-C2 alkyl chains Geeignete Lactone sind Benzofuranone und Indolinone wie z.B. 3-(4-(2-ace- toxyethoxy)-phenyl]-5,7-di-tert-butyl-benzofuran-2-on, 5,7-di-tert-butyl-3- [4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-on, 3,3'-bis[5,7-di-tert-butyl- 3-(4-(2-hydroxyethoxy]phenyl )benzofuran-2-on), 5,7-di-tert-butyl-3-(4- ethoxyphenyl )benzofuran-2-on, 3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di- tert-butyl-benzofuran-2-on, 3-(3,5-dimethyl-4-pivaloyloxyphenyl )-5,7-di- tert-butyl-benzofuran-2-on, 3-(3,4-dimethylphenyl)-5,7-di-tert-butyl-ben- zofuran-2-on, 3-(2,3-di- methylphenyl)-5,7-di-tert-butyl-benzofuran-2-on sowie Lactone, die zusätzlich Phosphitgruppen beinhalten wie z.B. Ri, R 2 = C 14 -C 2 alkyl chains Suitable lactones are benzofuranones and indolinones such as 3- (4- (2-ace- toxyethoxy) 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 -on), 5,7-di-tert-butyl-3- (4-ethoxyphenyl) benzofuran-2-one, 3- (4-acetoxy-3,5-dimethylphenyl) -5,7-di-tert-butyl -benzofuran-2-one, 3- (3,5-dimethyl-4-pivaloyloxyphenyl) -5,7-di-tert-butyl-benzofuran-2-one, 3- (3,4-dimethylphenyl) -5.7 -di-tert-butyl-benzofuran-2-one, 3- (2,3-dimethylphenyl) -5,7-di-tert-butyl-benzofuran-2-one and lactones which also contain phosphite groups such as e.g.
Eine weitere geeignete Gruppe von Antioxidantien sind lsoindolo[2,l-A]chi- nazoline wie z.B. Another suitable group of antioxidants are isoindolo [2, l-A] quinazolines such as e.g.
Geeignete sekundäre Antioxidantien (B) sind Phosphorverbindungen wie z.B. Phosphite und Phosphonite, und Organo-Schwefelverbindungen wie z.B. Sul fide und Disulfide. Suitable secondary antioxidants (B) are phosphorus compounds such as phosphites and phosphonites, and organosulfur compounds such as sulphides and disulphides.
Geeignete Phosphite/Phosphonite sind beispielsweise: Suitable phosphites / phosphonites are, for example:
Triphenylphosphit, Diphenylalkylphosphite, Phenyldialkylphosphite, Tri(nonyl- phenyl)phosphit, Trilaurylphosphite, Trioctadecylphosphit, Distearylpenta- erythritoldiphosphit, Tris-(2,4-di-tert-butylphenyl)phosphit, Diisodecylpenta- erythritoldiphosphit, Bis(2,4-di-tert-butylphenyl)pentaerythritoldiphosphit, Bis(2,4-di-cumylphenyl)pentaerythritoldiphosphit, Bis(2,6-di-tert-butyl-4-me- thylphenyl)pentaerythritoldiphosphit, Diisodecyloxypentaerythritoldiphosphit, Bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritoldiphosphit, Bis(2,4,6- tris(te/t-butylphenyl)pentaerythritoldiphosphit, Tristearylsorbitoltriphosphit, Tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylendiphosphonit, 6-lsooctyloxy- 2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-l,B,2-dioxaphosphocin, Bis(2,4-di- tert-butyl-6-methylphenyl)methylphosphit, Bis(2,4-di-tert-butyl-6-methylphe- nyl)ethylphosphit, 6-Fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-Triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tri (nonyl phenyl) phosphite, trilauryl phosphites, trioctadecyl phosphite, distearyl penta- erythritol diphosphite, tris- (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-phosphite-di-phosphitol) -tertitol, diisodecylpenta-erythritol -butylphenyl) pentaerythritol diphosphite, bis (2,4-di-cumylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis (2,4-di-tert-butyl -6-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tris (te / t-butylphenyl) pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, 6-isooctyloxy - 2,4,8,10-tetra-tert-butyl-12H-dibenz [d, g] -l, B, 2-dioxaphosphocin, bis (2,4-di-tert-butyl-6-methylphenyl) methylphosphite, Bis (2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz [d, g] -
1.3.2-dioxaphosphocin, 2,2'2"-Nitrilo[triethyltris(3,3",5,5'-tetra-tert-butyl- l,l'-biphenyl-2,2'-diyl)phosphit], 2-Ethylhexyl(3,3',5,5'-tetra-tert-butyl-l,l'- biphenyl-2,2'-diyl))phosphit, 5-Butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1.3.2-dioxaphosphocin, 2,2'2 "-nitrilo [triethyltris (3,3", 5,5'-tetra-tert-butyl-l, l'-biphenyl-2,2'-diyl) phosphite], 2-ethylhexyl (3,3 ', 5,5'-tetra-tert-butyl-l, l'-biphenyl-2,2'-diyl)) phosphite, 5-butyl-5-ethyl-2- (2, 4,6-tri-tert-butylphenoxy) -
1.3.2-dioxaphosphiran. 1.3.2-dioxaphosphirane.
Besonders bevorzugte Phosphite/Phosphonite sind: Particularly preferred phosphites / phosphonites are:
wobei n= 3-100 bedeutet. where n = 3-100.
Ein bevorzugtes Phosphonit ist: A preferred phosphonite is:
Geeignete Schwefelverbindungen sind beispielsweise Distearylthiodipropio- nat, Dilaurylthiodipropionat; Ditridecyldithiopropionat, Ditetradecylthio- dipropionat, 3-(dodecylthio)-, l,l'-[2,2-bis[[3-(dodecylthio)-l-oxopropoxy]me- thyl]-l,3-propandiyl]propansäureester. Bevorzugt sind die folgenden Struktu ren: Suitable sulfur compounds are, for example, distearyl thiodipropionate, dilauryl thiodipropionate; Ditridecyldithiopropionate, ditetradecylthiodipropionate, 3- (dodecylthio) -, l, l '- [2,2-bis [[3- (dodecylthio) -l-oxopropoxy] methyl] -l, 3-propanediyl] propanoic acid ester. The following structures are preferred:
Die zuvorgenannten primären und/oder sekundären Antioxidantien können da bei in einer Gesamtmenge (d. h. als Summe aus primärem und/oder sekundä rem Antioxidans), bezogen auf die Gesamtmenge des mindestens einen phe- nolisch substituierten Zuckerderivates von 0,01 bis 5 Gew. -Teilen, bevorzugt von 0,02 bis 3 Gew. -Teilen, besonders bevorzugt von 0,05 bis 2 Gew. -Teilen eingesetzt werden. The aforementioned primary and / or secondary antioxidants can there in a total amount (ie as the sum of primary and / or secondary antioxidant), based on the total amount of the at least one phenolically substituted sugar derivative of 0.01 to 5 parts by weight , preferably from 0.02 to 3 parts by weight, particularly preferably from 0.05 to 2 parts by weight.
Insbesondere hat es sich als vorteilhaft erwiesen, wenn bezogen auf 91 bis 99,94 Gew. -Teile, bevorzugt 98,5 bis 99,91 Gew. -Teile des Kunststoffs In particular, it has proven to be advantageous if, based on 91 to 99.94 parts by weight, preferably 98.5 to 99.91 parts by weight, of the plastic
(A) 0,02 bis 3 Gew. -Teile, bevorzugt 0,03 bis 0,5 Gew. -Teile des mindes tens einen phenolisch substituierten Zuckerderivates, und(A) 0.02 to 3 parts by weight, preferably 0.03 to 0.5 parts by weight, of the at least one phenolic substituted sugar derivative, and
(B) 0,04 bis 6 Gew. -Teile, bevorzugt 0,06 bis 1 Gew. -Teile des mindes tens einen primären Antioxidans und/oder des mindestens einen se kundären Antioxidans eingebracht werden. Bei den Kunststoffen handelt es sich insbesondere um thermoplastische, duro- mere oder elastomere Polymere. Geeignete thermoplastische oder duromere Polymere sind insbesondere: a) Polymeren aus Olefinen oder Diolefinen wie z.B. Polyethylen (LDPE,(B) 0.04 to 6 parts by weight, preferably 0.06 to 1 part by weight, of the at least one primary antioxidant and / or of the at least one secondary antioxidant are introduced. The plastics are in particular thermoplastic, thermoset or elastomeric polymers. Suitable thermoplastic or thermoset polymers are in particular: a) Polymers made from olefins or diolefins such as polyethylene (LDPE,
LLDPE, VLDPE, ULDPE, MDPE, HDPE, UHMWPE), Metallocen-PE (m-PE), Polypropylen, Polyisobutylen, Poly-4-methyl-penten-l, Polybutadien, Po lyisopren, wie z.B. auch Naturkautschuk (NR), Polycycloocten, Polyalky- len-Kohlenmonoxid-Copolymere, sowie Copolymere in Form von statisti schen oder Blockstrukturen wie z.B. Polypropylen-Polyethylen (EP), EPM oder EPDM mit z.B. 5-Ethyliden-2-Norbornen als Comonomer, Ethylen- Vinylacetat (EVA), Ethylen-Acrylester, wie z.B. Ethylen-Butylacrylat, Ethy- len-Acrylsäure und deren Salze (lonomere), sowie Terpolymere wie z.B. Ethylen-Acrylsäure-Glycidyl(meth)acrylat, Pfropfpolymere wie z.B. Polyp- ropylen-graft-Maleinsäureanhydrid, Polypropylen-graft-Acrylsäure, Po- lyethylen-graft -Acrylsäure, Polyethylen-Polybutylacrylat-graft-Malein- säureanhydrid sowie Blends wie z.B. LDPE/LLDPE oder auch langketten verzweigte Polypropylen-Copolymere die mit alpha-Olefinen als Como- nomere hergestellt werden wie z.B. mit 1-Buten, 1-Hexen, 1-Octen oder 1-Octadecen LLDPE, VLDPE, ULDPE, MDPE, HDPE, UHMWPE), metallocene-PE (m-PE), polypropylene, polyisobutylene, poly-4-methyl-pentene-1, polybutadiene, polyisoprene, such as natural rubber (NR), polycyclooctene , Polyalkylene-carbon monoxide copolymers, and copolymers in the form of statistical or block structures such as polypropylene-polyethylene (EP), EPM or EPDM with, for example, 5-ethylidene-2-norbornene as comonomer, ethylene-vinyl acetate (EVA), ethylene Acrylic esters, such as ethylene-butyl acrylate, ethylene-acrylic acid and their salts (ionomers), and terpolymers such as ethylene-acrylic acid-glycidyl (meth) acrylate, graft polymers such as polypropylene-graft-maleic anhydride, polypropylene-graft Acrylic acid, polyethylene-graft-acrylic acid, polyethylene-polybutyl acrylate-graft-maleic anhydride and blends such as LDPE / LLDPE or long-chain branched polypropylene copolymers which are produced with alpha-olefins as comonomers such as, for example, 1-butene , 1-hexene, 1-octene or 1-octadecene
b) Polystyrol, Polymethylstyrol, Poly-alpha-methylstyrol, Polyvinylnaphtha lin, Polyvinylbiphenyl, Polyvinyltoluol, Styrol-Butadien (SB), Styrol-Buta- dien-Styrol (SBS), Styrol-Ethylen-Butylen-Styrol (SEBS), Styrol-Ethylen- Propylen-Styrol, Styrol-Isopren, Styrol-Isopren-Styrol (SIS), Styrol-buta- dien-acrylnitril (ABS), Styrol-acrylnitril (SAN), Styrol-acrylnitril-acrylat (ASA), Styrol-Ethylen, Styrol-Maleinsäureanhydrid-Polymere einschl. ent sprechender Pfropfcopolymere wie z.B. Styrol auf Butadien, Maleinsäu reanhydrid auf SBS oder SEBS, sowie Pfropfcopolymere aus Methylme- thacrylat, Styrol-Butadien und ABS (MABS), sowie hydrierte Polystyrol- Derivate wie z.B. Polyvinylcyclohexan b) Polystyrene, polymethylstyrene, poly-alpha-methylstyrene, polyvinylnaphtha lin, polyvinylbiphenyl, polyvinyltoluene, styrene-butadiene (SB), styrene-butadiene-styrene (SBS), styrene-ethylene-butylene-styrene (SEBS), styrene Ethylene-propylene-styrene, styrene-isoprene, styrene-isoprene-styrene (SIS), styrene-butadiene-acrylonitrile (ABS), styrene-acrylonitrile (SAN), styrene-acrylonitrile-acrylate (ASA), styrene-ethylene, Styrene-maleic anhydride polymers including appropriate graft copolymers such as styrene on butadiene, maleic anhydride on SBS or SEBS, and graft copolymers made from methyl methacrylate, styrene-butadiene and ABS (MABS), and hydrogenated polystyrene derivatives such as polyvinylcyclohexane
c) halogenenthaltenden Polymeren wie z.B. Polyvinylchlorid (PVC), Poly- chloropren und Polyvinylidenchlorid (PVDC), Copolymere aus Vinylchlorid und Vinylidenchlorid oder aus Vinylchlorid und Vinylacetat, chloriertes Polyethylen, Polyvinylidenfluorid, Epichlorhydrin-Homo und Copolymere insbes. mit Ethylenoxid (ECO) d) Polymeren von ungesättigten Estern wie z.B. Polyacrylate und Polyme- thacrylate wie Polymethylmethacrylat (PMMA), Polybutylacrylat, Po- lylaurylacrylat, Polystearylacrylat, Polyglycidylacrylat, Polyglycidylme- thacrylat, Polyacrylnitril, Polyacrylamide, Copolymere wie z.B. Polyacryl- nitril-Polyalkylacrylat, c) halogen-containing polymers such as polyvinyl chloride (PVC), polychloroprene and polyvinylidene chloride (PVDC), copolymers of vinyl chloride and vinylidene chloride or of vinyl chloride and vinyl acetate, chlorinated polyethylene, polyvinylidene fluoride, epichlorohydrin homo and copolymers, especially with ethylene oxide (ECO) d) Polymers of unsaturated esters such as polyacrylates and polymethacrylates such as polymethyl methacrylate (PMMA), polybutyl acrylate, polylauryl acrylate, polystearyl acrylate, polyglycidyl acrylate, polyglycidyl methacrylate, polyacrylonitrile, polyacrylamides, copolymers such as polyacrylonitrile
e) Polymeren aus ungesättigten Alkoholen und Derivaten, wie z.B. Polyvi nylalkohol, Polyvinylacetat, Polyvinylbutyral, Polyallylphthalat, Polyal lylmelamin e) Polymers of unsaturated alcohols and derivatives, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyallyl phthalate, polyalyl melamine
f) Polyacetalen, wie z.B. Polyoxymethylen (POM) oder Copolymere mit z.B. f) polyacetals such as polyoxymethylene (POM) or copolymers with e.g.
Butanal, Butanal,
g) Polyphenylenoxiden und Blends mit Polystyrol oder Polyamiden, h) Polymeren von cyclischen Ethern wie z.B. Polyethylenglycol, Polypropy- lenglycol, Polyethylenoxid, Polypropylenoxid, Polytetrahydrofuran, i) Polyurethanen, aus hydroxyterminierten Polyethern oder Polyestern und aromatischen oder aliphatischen Isocyanaten wie z.B. 2,4- oder 2,6 Toluy- lendiisocyanat oder Methylendiphenyldiisocyanat insbesondere auch li neare Polyurethane (TPU), Polyharnstoffen, g) polyphenylene oxides and blends with polystyrene or polyamides, h) polymers of cyclic ethers such as polyethylene glycol, polypropylene glycol, polyethylene oxide, polypropylene oxide, polytetrahydrofuran, i) polyurethanes made from hydroxy-terminated polyethers or polyesters and aromatic or aliphatic isocyanates such as 2,4- or 2,6 toluene diisocyanate or methylenediphenyl diisocyanate, especially linear polyurethanes (TPU), polyureas,
j) Polyamiden wie z.B. Polyamid-6, 6.6, 6.10, 4.6, 4.10, 6.12, 10.10, 10.12, 12.12, Polyamid 11, Polyamid 12 sowie (teil-)aromatische Polyamide wie z.B. Polyphthalamide, z.B. hergestellt aus Terephthalsäure und/oder Isophthalsäure und aliphatischen Diaminen wie z.B. Hexamethylendiamin oder m-Xylylendiamin oder aus aliphatischen Dicarbonsäuren wie z.B. Adipinsäure oder Sebazinsäure und aromatischen Diaminen wie z.B. 1,4- oder 1,3- Diaminobenzol, Blends von unterschiedlichen Polyamiden wie z.B. PA-6 und PA 6.6 bzw. Blends von Polyamiden und Polyolefinen wie z.B. PA/PP j) Polyamides such as polyamide-6, 6.6, 6.10, 4.6, 4.10, 6.12, 10.10, 10.12, 12.12, polyamide 11, polyamide 12 and (partially) aromatic polyamides such as polyphthalamides, e.g. made from terephthalic acid and / or isophthalic acid and aliphatic diamines such as hexamethylenediamine or m-xylylenediamine or from aliphatic dicarboxylic acids such as adipic acid or sebacic acid and aromatic diamines such as 1,4- or 1,3-diaminobenzene, blends of different polyamides such as PA-6 and PA 6.6 or blends of Polyamides and polyolefins such as PA / PP
k) Polyimiden, Polyamid-imiden, Polyetherimiden, Polyesterimiden, Poly- (ether)ketonen, Polysulfonen, Polyethersulfonen, Polyarylsulfonen, Poly- phenylensulfiden, Polybenzimidazolen, Polyhydantoinen, k) polyimides, polyamide-imides, polyetherimides, polyesterimides, poly (ether) ketones, polysulfones, polyether sulfones, polyarylsulfones, polyphenylene sulfides, polybenzimidazoles, polyhydantoins,
L) Polyestern aus aliphatischen oder aromatischen Dicarbonsäuren und Di olen oder aus Hydroxy-Carbonsäuren wie z.B. Polyethylenterephthalat (PET), Polybutylenterephthalat (PBT), Polypropylenterephthalat (PTT), Polyethylennaphthylat (PEN), Poly-l,4-dimethylolcyclohexanterephtha- lat, Polyhydroxybenzoat, Polyhydroxynaphthalat, Polymilchsäure (PLA), Polyhydroxybutyrat (PHB), Polyhydroxyvalerat (PHV), Polyethylensuc- cinat, Polytetramethylensuccinat, Polycaprolacton m) Polycarbonaten, Polyestercarbonaten, sowie Blends wie z.B. PC/ABS, PC/PBT, PC/PET/PBT, PC/PA L) Polyesters made from aliphatic or aromatic dicarboxylic acids and diols or from hydroxycarboxylic acids such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polypropylene terephthalate (PTT), polyethylene naphthylate (PEN), poly-1,4-dimethylolcyclohexate, polyhydrotha-benzoate Polyhydroxynaphthalate, polylactic acid (PLA), polyhydroxybutyrate (PHB), polyhydroxyvalerate (PHV), polyethylene succinate, polytetramethylene succinate, polycaprolactone m) Polycarbonates, polyester carbonates, and blends such as PC / ABS, PC / PBT, PC / PET / PBT, PC / PA
n) Cellulosederivaten wie z.B. Cellulosenitrat, Celluloseacetat, Cellu losepropionat, Cellulosebutyrat, n) cellulose derivatives such as cellulose nitrate, cellulose acetate, cellulose propionate, cellulose butyrate,
o) Epoxidharzen, bestehend aus di- oder polyfunktionellen Epoxidverbin dungen in Kombination mit z.B. Härtern auf der Basis von Aminen, An hydriden, Dicyandiamid, Mercaptanen, Isocyanaten oder katalytisch wir kenden Härtern, o) Epoxy resins, consisting of di- or polyfunctional epoxy compounds in combination with e.g. hardeners based on amines, anhydrides, dicyandiamide, mercaptans, isocyanates or catalytically active hardeners,
p) Phenolharzen wie z.B. Phenol-Formaldehyd-Harze, Harnstoff-Formalde- hyd-Harze, Melamin-Formaldehydharze, p) Phenolic resins such as phenol-formaldehyde resins, urea-formaldehyde resins, melamine-formaldehyde resins,
q) ungesättigten Polyesterharzen aus ungesättigten Dicarbonsäuren und Di olen mit Vinylverbindungen z.B. Styrol, Alkydharze, q) unsaturated polyester resins made from unsaturated dicarboxylic acids and diols with vinyl compounds e.g. styrene, alkyd resins,
r) Silikonen, z.B. auf der Basis von Dimethylsiloxanen, Methyl-Phenyl-siloxa- nen oder Diphenylsiloxanen z.B. Vinylgruppen terminiert r) Silicones, e.g. based on dimethylsiloxanes, methyl-phenyl-siloxanes or diphenylsiloxanes, e.g. terminated with vinyl groups
s) sowie Mischungen, Kombinationen oder Blends aus zwei oder mehr der zuvor genannten Polymere. s) and also mixtures, combinations or blends of two or more of the aforementioned polymers.
Sofern es sich bei den unter a) bis r) angegebenen Polymeren um Copolymere handelt, können diese in Form von statistischen („random"), Block- oder„tape red" Strukturen vorliegen. Weiterhin können die genannten Polymeren in Form von linearen, verzweigten, sternförmigen oder hyperverzweigten Strukturen vorliegen. If the polymers specified under a) to r) are copolymers, they can be in the form of random (“random”), block or “tape red” structures. Furthermore, the polymers mentioned can be in the form of linear, branched, star-shaped or hyperbranched structures.
Sofern es sich bei den unter a) bis r) angegebenen Polymeren um stereoregu läre Polymere handelt, können diese in Form von isotaktischen, stereotakti schen, aber auch ataktischen Formen oder als Stereoblockcopolymere vorlie gen. If the polymers specified under a) to r) are stereoregular polymers, these can be in the form of isotactic, stereotactic, but also atactic forms or as stereoblock copolymers.
Weiterhin können die unter a) bis r) angegebenen Polymere sowohl amorphe als auch (teil-) kristalline Morphologien aufweisen. Furthermore, the polymers specified under a) to r) can have both amorphous and (partially) crystalline morphologies.
Ggf. können die unter a) genannten Polyolefine auch vernetzt vorliegen, z.B. vernetztes Polyethylen, das dann als X-PE bezeichnet wird. If necessary, the polyolefins mentioned under a) can also be crosslinked, e.g. crosslinked polyethylene, which is then referred to as X-PE.
Weiterhin können die vorliegenden Verbindungen zur Stabilisierung von Kaut- schuken und Elastomeren eingesetzt werden. Hier kann es sich um Naturkaut schuk (NR) oder synthetische Kautschukmaterialien handeln. Furthermore, the present compounds can be used to stabilize chewing Schuken and elastomers are used. This can be natural rubber (NR) or synthetic rubber materials.
Weiterhin bevorzugt sind insbesondere Polymere aus nachwachsenden Roh stoffen wie z.B. Polymilchsäure (PLA), Polyhydroxybuttersäure, Polyhydroxyva- leriansäure oder Polybutylensuccinat. Polymers made from renewable raw materials such as polylactic acid (PLA), polyhydroxybutyric acid, polyhydroxyvaleric acid or polybutylene succinate are also preferred.
Die zuvorgenannten Polymere können als Frischware oder auch als Rezyklate vorliegen. The aforementioned polymers can be in the form of fresh goods or as recycled materials.
Die vorliegende Erfindung betrifft zudem eine Kunststoffzusammensetzung, enthaltend oder bestehend aus mindestens einen Kunststoff, sowie mindes tens ein phenolisch substituiertes Zuckerderivat, wobei das Zuckerderivat ei nen von einem Zucker abgeleiteten Grundkörper aufweist, sowie mindestens einen Substituenten gemäß allgemeiner Formel I The present invention also relates to a plastic composition containing or consisting of at least one plastic and at least one phenolically substituted sugar derivative, the sugar derivative having a base body derived from a sugar, and at least one substituent according to general formula I.
Formel I wobei R1 und R2 bei jedem Auftreten gleich oder verschieden sind und ausge wählt sind aus der Gruppe bestehend aus Wasserstoff und linearen oder ver zweigten Alkylreste, mit der Maßgabe, dass mindestens ein Rest R1 oder R2 nicht Wasserstoff ist, Formula I where R 1 and R 2 are identical or different on each occurrence and are selected from the group consisting of hydrogen and linear or branched alkyl radicals, with the proviso that at least one radical R 1 or R 2 is not hydrogen,
X eine Alkylengruppe mit 1 bis 18 Kohlenstoffatomen oder eine chemische Bindung, X is an alkylene group with 1 to 18 carbon atoms or a chemical bond,
Y eine Gruppierung ausgewählt aus der Gruppe bestehend aus den nachfolgenden Gruppierungen wobei die Gruppierung X an den links dargestellten Terminus der oben abgebil- deten Gruppierungen Y gebunden ist, und wobei der von einem Zucker abge leiteten Grundkörper des phenolisch substituierten Zuckerderivates mindes tens 3 unsubstituierte Hydroxygruppen aufweist und/oder der von einem Zu cker abgeleitete Grundkörper des phenolisch substituierten Zuckerderivates mindestens 4 Kohlenstoffatome und mindestens 2, vorzugsweise mindestens 3 unsubstituierte Hydroxygruppen aufweist. Y is a group selected from the group consisting of the following groupings where the grouping X is attached to the terminus shown on the left of the deten groupings Y is bonded, and wherein the base of the phenolically substituted sugar derivative derived from a sugar has at least 3 unsubstituted hydroxyl groups and / or the base of the phenolic substituted sugar derivative derived from a sugar has at least 4 carbon atoms and at least 2, preferably at least 3 unsubstituted ones Has hydroxyl groups.
Bezüglich der phenolisch substituierten Zuckerderivate gemäß Formel I wird auf die zuvorstehenden Ausführungsformen verwiesen, die uneingeschränkt auch für die erfindungsgemäße Kunststoffzusammensetzung Geltung besitzen. With regard to the phenolic substituted sugar derivatives according to formula I, reference is made to the above embodiments, which also apply without restriction to the plastic composition according to the invention.
Bevorzugt kann die Kunststoffzusammensetzung zusätzlich mindestens einen Zusatzstoff enthalten, welcher ausgewählt ist aus der Gruppe bestehend aus UV-Absorbern, Lichtstabilisatoren, Metalldesaktivatoren, Costabilisatoren, Füllstoffdesaktivatoren, Antiozonantien, Nukleierungsmitteln, Antinukleie rungsmitteln, Schlagzähigkeitsverbesserern, Weichmachern, Gleitmitteln, Rhe ologiemodifikatoren, Thixotropiemitteln, Kettenverlängerern, optischen Auf hellern, antimikrobiellen Wirkstoffen, Antistatika, Slipmitteln, Antiblockmit teln, Kopplungsmitteln, Vernetzungsmitteln, Antivernetzungsmitteln, Hydro- philisierungsmitteln, Hydrophobisierungsmitteln, Haftvermittlern, Dispergier mitteln, Kompatibilisatoren, Sauerstofffängern, Säurefängern, Treibmitteln, Prodegradantien, Entschäumungsmitteln, Geruchsfängern, Markierungsmit teln, Antifoggingmitteln, Füllstoffen, Verstärkungsstoffen und Mischungen hiervon enthalten. The plastic composition can preferably also contain at least one additive selected from the group consisting of UV absorbers, light stabilizers, metal deactivators, costabilizers, filler deactivators, antiozonants, nucleating agents, anti-nucleating agents, impact strength improvers, plasticizers, lubricants, rheology modifiers, chain extenders, thixotropic agents optical brightening agents, antimicrobial agents, antistatic agents, slip agents, antiblocking agents, coupling agents, crosslinking agents, anti-crosslinking agents, hydrophilizing agents, hydrophobizing agents, adhesion promoters, dispersants, compatibilizers, oxygen scavengers, acid scavengers, propellants, anti-odor agents, anti-odor agents, antifoaming agents, antioxidants Contain fillers, reinforcing agents and mixtures thereof.
Nachfolgend sind mögliche Zusatzstoffe gelistet, die allerdings nicht abschlie ßend zu verstehen sind. Possible additives are listed below, but they are not to be understood as exhaustive.
Bevorzugt enthält die Kunststoffzusammensetzung zusätzlich mindestens ei nen Zusatzstoff ausgewählt aus der Gruppe bestehend aus a) Säurefängern, („Antiacids") sind Salze von ein, zwei, drei oder vierwer tigen Metallen, vorzugsweise Alkali-, Erdalkalimetalle, Aluminium oder Zink, insbesondere gebildet mit Fettsäuren, wie z.B. Calciumstearat, Magnesiumste- arat, Zinkstearat, Aluminiumstearat, Calciumlaurat, Calciumbehenat, Calcium lactat, Calciumstearoyl-2-lactat. Weitere Klassen geeigneter Säurefänger sind Hydrotalcite, insbesondere synthetische Hydrotalcite auf Aluminium-, Magne sium- und Zinkbasis, Hydrocalumite, Zeolithe, Erdalkalioxide, insbesondere Cal ciumoxid und Magnesiumoxid sowie Zinkoxid, Erdalkalicarbonate, insbeson dere Calciumcarbonat, Magnesiumcarbonat und Dolomit sowie Hydroxide, ins besondere Brucit (Magnesiumhydroxid), The plastic composition preferably also contains at least one additive selected from the group consisting of a) acid scavengers ("antiacids") are salts of one, two, three or four-valued metals, preferably alkali, alkaline earth metals, aluminum or zinc, in particular formed with Fatty acids, such as calcium stearate, magnesium stearate, zinc stearate, aluminum stearate, calcium laurate, calcium behenate, calcium lactate, calcium stearoyl-2-lactate, Other classes of suitable acid scavengers are Hydrotalcites, in particular synthetic hydrotalcites based on aluminum, magnesium and zinc, hydrocalumites, zeolites, alkaline earth oxides, in particular calcium oxide and magnesium oxide, and zinc oxide, alkaline earth carbonates, in particular calcium carbonate, magnesium carbonate and dolomite and hydroxides, in particular brucite (magnesium hydroxide),
b) Lichtstabilisatoren, vorzugsweise Lichtstabilisatoren aus der Gruppe der gehinderten Amine, b) light stabilizers, preferably light stabilizers from the group of hindered amines,
c) Dispergiermitteln, sowie c) dispersants, as well as
d) Mischungen hiervon. d) mixtures thereof.
Geeignete Lichtstabilisatoren sind beispielsweise Verbindungen auf der Basis von 2-(2'-Hydroxyphenyl)benzotriazolen, 2-Hydroxybenzophenonen, Estern von Benzoesäuren, Acrylaten, Oxamiden und 2-(2-Hydroxyphenyl)-l,3,5-Triazi- nen. Suitable light stabilizers are, for example, compounds based on 2- (2 'hydroxyphenyl) benzotriazoles, 2-hydroxybenzophenones, esters of benzoic acids, acrylates, oxamides, and 2- (2-hydroxyphenyl) -l, 3,5-NEN Triazi-.
Geeignete 2-(2'-Hydroxyphenyl)benzotriazole sind beispielsweise 2-(2'-Hyd- roxy-5'methylphenyl)benzotriazol, 2-(3',5'-Di-tert-butyl-2'-hydroxyphenyl)- benzotriazol, 2-(5'-tert-Butyl-2'-hydroxy-phenyl)benzotriazol, 2-(2'-Hydroxy-5'- (l,l,3,3-tetramethylbutyl)phenyl)benzotriazol, 2-(3',5'-Di-tert-butyl-2'-hydro- xyphenyl)-5-chlorobenzotriazol, 2-(3'-tert-Butyl-2'-hydroxy-5'-methylphenyl-5- chlorobenzotriazol, 2-(3'-sec-Butyl-5'-te/t-butyl-2'-hydroxy-phenyl)benzotria- zol, 2-(2'-Hydroxy-4'-octyloxyphenyl)benzotriazol, 2-(3',5'-Di-tert-amyl-2'-hyd- roxyphenyl)benzotriazol, 2-(3',5'-Bis(a,a-dimethylbenzyl)-2'-hydroxyphe- nyl)benzotriazol, 2-(3'-tert-Butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phe- nyl)-5-chlorobenzotriazol, 2-(3'-te/t-Butyl-5'-[2-(2-ethylhexyloxy)carbonyl- ethyl]-2'-hydroxyphenyl)-5-chlorobenzotriazol, 2-(3'-tert-Butyl-2'-hydroxy-5'- (2-methoxycarbonylethyl)phenyl)-5-chlorobenzotriazol, 2-(3'-tert-Butyl-2'- hydroxy-5'-(2-methoxycarbonylethyl)phenyl)benzotriazol, 2-(3'-tert-Butyl-2'- hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)benzotriazol, 2-(3'-tert-Butyl-5'- [2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)benzotriazol, 2-(3'-Dode- cyl-2'-hydroxy-5'-methylphenyl)benzotriazol, 2-(3'-tert-Butyl-2'-hydroxy-5'-(2- isooctyloxycarbonylethyl)phenylbenzotriazol, 2,2'-Methylenbis[4-(l,l,3,3-tet- ramethylbutyl)-6-benzotriazol-2-ylphenol]; das Produkt der Umesterung von 2- [3'-tert-Butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazol mit Polyethylenglycol 300; [R— CH2CH2— COO— CH2CH2+2 wobei R = 3 '-tert- Butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl, 2-[2'-Hydroxy-3'-(a,a-dime- thylbenzyl)-5'-(l,l,3,3-tetramethylbutyl)phenyl]benzotriazol, 2-[2'-hydroxy-3'- (l,l,3,3-tetramethylbutyl)-5'-(a,a-dimethylbenzyl)phenyl]benzotriazol. Suitable 2- (2 'hydroxyphenyl) benzotriazoles are for example 2- (2'-hy- roxy-5'-methylphenyl) benzotriazole, 2- (3', 5'-di-tert-butyl-2'-hydroxyphenyl) - benzotriazole , 2- (5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'- (l, l, 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'-te / t-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) benzotriazole, 2- (3 ', 5'-Di-tert-amyl-2'-hydroxyphenyl) benzotriazole, 2- (3 ', 5'-bis (a, a-dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole, 2- (3'-tert -Butyl-2'-hydroxy-5 '- (2-octyloxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-te / t-butyl-5' - [2- (2-ethylhexyloxy) carbonyl- ethyl] -2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'- (2-methoxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-tert -Butyl-2'-hydroxy-5 '- (2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3'-th rt-butyl-2'-hydroxy-5 '- (2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-5'- [2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-isooctyloxycarbonylethyl) phenylbenzotriazole, 2 , 2'-methylenebis [4- (l, l, 3,3-tetramethylbutyl) -6-benzotriazol-2-ylphenol]; the product of the transesterification of 2- [3'-tert-butyl-5 '- (2-methoxycarbonylethyl) -2'-hydroxyphenyl] -2H-benzotriazole with polyethylene glycol 300; [R— CH2CH2— COO— CH2CH2 + 2 where R = 3 '-tert- Butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl, 2- [2'-hydroxy-3 '- (a, a-dimethylbenzyl) -5' - (l, l, 3.3 -tetramethylbutyl) phenyl] benzotriazole, 2- [2'-hydroxy-3'- (1,1,3,3-tetramethylbutyl) -5 '- (a, a-dimethylbenzyl) phenyl] benzotriazole.
Geeignete 2-Hydroxybenzophenone sind beispielsweise 4-Hydroxy-, 4-Me- thoxy-, 4-Octyloxy-, 4-Decyloxy- 4-Dodecyloxy, 4-Benzyloxy, 4,2',4'-Trihydroxy- und 2'-Hydroxy-4,4'-dimethyoxy-Derivate der 2-Hydroxybenzophenone. Suitable 2-hydroxybenzophenones are, for example, 4-hydroxy-, 4-methoxy-, 4-octyloxy-, 4-decyloxy-4-dodecyloxy, 4-benzyloxy, 4,2 ', 4'-trihydroxy- and 2'-hydroxy -4,4'-dimethoxy-derivatives of 2-hydroxybenzophenones.
Geeignete Acrylate sind beispielsweise Ethyl-a-cyano-ß,ß-diphenylacrylat, lsooctyl-a-cyano-ß,ß-diphenylacrylat, Methyl-a-carbomethoxycinnamat, Me- thyl-a-cyano-ß-methyl-p-methoxycinnamat, Butyl-a-cyano-ß-methyl-p-me- thoxycinnamat, Methyl-a-carbomethoxy-p-methoxycinnamat und N-(ß-carbo- methoxy-ß-cyanovinyl)-2-methylindolin. Suitable acrylates are, for example, ethyl a-cyano-ß, ß-diphenyl acrylate, isooctyl-a-cyano-ß, ß-diphenyl acrylate, methyl a-carbomethoxycinnamate, methyl a-cyano-ß-methyl-p-methoxycinnamate, Butyl α-cyano-β-methyl-p-methoxycinnamate, methyl-α-carbomethoxy-p-methoxycinnamate and N- (β-carbomethoxy-β-cyanovinyl) -2-methylindoline.
Geeignete Ester von Benzoesäuren sind beispielsweise 4-tert-Butylphenylsa- licylat, Phenylsalicylat, Octylphenylsalicylat, Dibenzoylresorcinol, Bis(4-tert- butylbenzoyl)resorcinol, Benzoylresorcinol, 2,4-Di-tert-butylphenyl-3,5-di-tert- butyl-4-hydroxybenzoat, Hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoat, Octa- decyl-3,5-di-tert-butyl-4-hydroxybenzoat, 2-Methyl-4,6-di-tert-butylphenyl- 3,5-di-tert-butyl-4-hydroxybenzoat. Suitable esters of benzoic acids are, for example, 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis (4-tert-butylbenzoyl) resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl-3,5-di-tert- butyl-4-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di- tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
Geeignete Oxamide sind beispielsweise 4,4'-Dioctyloxyoxanilid, 2,2'-diethoxy- oxanilid, 2,2'-Dioctyloxy-5,5'-di-tert-butoxanilid, 2,2'-didodecyloxy-5,5'-di-tert- butoxanilid, 2-Ethoxy-2'-ethyloxanilid, N,N'-Bis(3-dimethylaminopropyl)oxa- mid, 2-Ethoxy-5-tert-butyl-2'-ethoxanilid und seine Mischungen mit 2-Ethoxy- 2'-ethyl-5,4'-di-tert-butoxanilid, Mischungen von o- und p-Methoxy-disubstitu- ierten Oxaniliden und Mischungen von o- und p-Ethoxy-disubstituierten Oxani- liden. Suitable oxamides are, for example, 4,4'-dioctyloxyoxanilide, 2,2'-diethoxy-oxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'- di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixtures with 2- Ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and p-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.
Geeignete 2-(2-Hydroxyphenyl)-l,3,5-Triazine sind beispielsweise 2,4,6-T ris(2- hydroxy-4-octyloxyphenyl)-l,3,5-triazin, 2-(2-Hydroxy-4-octyloxyphenyl)-4,6- bis(2,4-dimethylphenyl)-l,3,5-triazin, 2-(2,4-Dihydroxyphenyl)-4,6-bis(2,4-di- methylphenyl)-l,3,5-triazin, 2,4-Bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-di- methylphenyl)-l,3,5-triazin, 2-(2-Hydroxy-4-octyloxyphenyl)-4,6-bis(4-methyl- phenyl-l,3,5-triazin, 2-(2-Hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethyl- phenyl)-l,3,5-triazin, 2-(2-Hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethyl- phenyl)-l,3,5-triazin, 2-[2-Hydroxy-4-(2-hydroxy-3-butyloxypropoxy)-phenyl]- 4,6-bis(2,4-dimethyl)-l,3,5-triazin, 2-[2-Hydroxy-4-(2-hydroxy-3-octyloxypro- pyloxy)phenyl]-4,6-bis(2,4-dimethyl)-l,3,5-triazin, 2-[4-(Dodecyloxy/Tridecy-Suitable 2- (2-hydroxyphenyl) -1, 3,5-triazines are, for example, 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-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1, 3,5-triazine, 2- (2- Hydroxy-4-octyloxyphenyl) -4,6-bis (4-methyl-phenyl-1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethyl - phenyl) -1, 3,5-triazine, 2- (2-hydroxy-4-tridecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, 2- [2 -Hydroxy-4- (2-hydroxy-3-butyloxypropoxy) phenyl] - 4,6-bis (2,4-dimethyl) -1, 3,5-triazine, 2- [2-hydroxy-4- (2nd -hydroxy-3-octyloxypropyloxy) phenyl] -4,6-bis (2,4-dimethyl) -1, 3,5-triazine, 2- [4- (dodecyloxy / tridecy-
5 loxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-l,3,5- triazin, 2-[2-Hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4- dimethylphenyl-l,3,5-triazin, 2-(2-Hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-5 loxy-2-hydroxypropoxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3- dodecyloxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl-1,3,5-triazine, 2- (2-hydroxy-4-hexyloxy) phenyl-4,6-diphenyl-
1.3.5-triazin, 2-(2-Hydroxy-4-methoxyphenyl)-4,6-diphenyl-l,3,5-triazin, 2,4,6- Tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-l,3,5-triazin, 2-(2-Hyd-1.3.5-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2,4,6-tris [2-hydroxy-4- (3-butoxy -2-hydroxypropoxy) phenyl] -l, 3,5-triazine, 2- (2-hyd-
10 roxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-l,3,5-triazin, 2-{2-Hydroxy-4-[3-(2- ethylhexyl-l-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis(2,4-dimethylphenyl-10 roxyphenyl) -4- (4-methoxyphenyl) -6-phenyl-1,3,5-triazine, 2- {2-hydroxy-4- [3- (2-ethylhexyl-1-oxy) -2-hydroxypropyloxy] phenyl} -4,6-bis (2,4-dimethylphenyl-
1.3.5-triazin. 1.3.5-triazine.
Geeignete Metalldeaktivatoren sind beispielsweise N,N'-Diphenyloxamid, N-Suitable metal deactivators are, for example, N, N'-diphenyloxamide, N-
15 Salicylal-N'-salicyloylhydrazin, N,N'-Bis(salicyloyl)hydrazin, N,N'-Bis(3,5-di-tert- butyl-4-hydroxyphenylpropionyl)hydrazin, 3-Salicyloylamino-l,2,4-triazol, Bis(benzyliden)oxalyldihydrazid, Oxanilid, Isophthaloyldihydrazid, Sebacoylbis- phenylhydrazid, N,N'-Diacetyladipoyldihydrazid, N,N'-Bis(salicyloyl)oxylyldi- hydrazid, N,N'-Bis(salicyloyl)thiopropionyldihydrazid. 15 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, bis (benzylidene) oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenyl hydrazide, N, N'-diacetyladipoyl dihydrazide, N, N'-bis (salicyloyl) oxylyldihydrazide, N, N'-bis (salicyloyl) dihydrazide-picyloyl
20 20th
Besonders bevorzugt als Metalldaktivatoren sind: Particularly preferred as metal activators are:
2525th
BOBO
Geeignete gehinderte Amine sind beispielsweise l,l-Bis(2,2,6,6-tetramethyl-Suitable hindered amines are, for example, l, l-bis (2,2,6,6-tetramethyl-
4-piperidyl)succinat, Bis(l,2,2,6,6-pentamethyl-4-piperidyl)sebazat, Bis(l- octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebazat, Bis(l, 2,2,6, 6-pentamethyl- 4-piperidyl)-n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonat, das Konden sationsprodukt aus l-(2-Hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperi- din und Succinsäure, lineare oder zyklische Kondensationsprodukte von N,N'- Bis(2,2,6,6-tetramethyl-4-piperidyl )hexamethylendiamin und 4-tert-Octyla- mino-2,6-di-chloro-l,3,5-triazin, Tris(2 ,2,6,6-tetramethyl-4-piperidyl)nitrilot- riacetat, Tetrakis(2 ,2,6,6-tetra-methyl-4-piperidyl)-l,2,3,4-butantetracar- boxylat, l,l'-(l,2-Ethandiyl)-bis(3,3,5,5-tetramethylpiperazinon), 4-Benzoyl- 2,2,6,6-tetramethylpiperidin, 4-Stearyloxy-2,2,6,6-tetramethylpiperidin, line are oder zyklische Kondensationsprodukte aus N,N'-Bis(2,2,6,6-tetramethyl- 4-piperidyl)hexamethylendiamin und 4-Morpholino-2,6-dichloro-l,3,5-triazin das Reaktionsprodukt von 7,7,9,9-Tetramethyl-2-cycloundecyl-l-oxa-3,8-di- aza-4-oxospiro-[4,5]decan und Epichlorhydrin. 4-piperidyl) succinate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (l- octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebazate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -n-butyl-3,5-di-tert-butyl -4-hydroxybenzylmalonate, the condensation product of 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensation products of N, N'-bis (2.2 , 6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-tert-octylamino-2,6-di-chloro-1,3,5-triazine, tris (2,2,6,6-tetramethyl-4 -piperidyl) nitrilotriacetate, tetrakis (2, 2,6,6-tetra-methyl-4-piperidyl) -l, 2,3,4-butanetetracarboxylate, l, l '- (l, 2-ethanediyl) bis (3,3,5,5-tetramethylpiperazinon), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, linear or cyclic condensation products from N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine the reaction product of 7,7,9,9-tetramethyl -2-cycloundecyl-1-oxa-3,8-di-aza-4-oxospiro- [4,5] decane and epichlorohydrin.
Umfasst in den oben angegebenen Strukturen sind dabei jeweils auch die ste risch gehinderten N-H, N-alkyl wie N-methyl oder N-octyl, die N-alkoxy-Deri- vate wie N-methoxy oder N-octyloxy, die Cycloalkylderivate wie N-cyclohexy- loxy und die N-(2-hydroxy-2-methylpropoxy) Analoga. The structures given above also include the sterically hindered NH, N-alkyl such as N-methyl or N-octyl, the N-alkoxy derivatives such as N-methoxy or N-octyloxy, the cycloalkyl derivatives such as N- cyclohexyloxy and the N- (2-hydroxy-2-methylpropoxy) analogs.
Bevorzugte gehinderte Amine weisen weiterhin die folgenden Strukturen auf: Preferred hindered amines also have the following structures:
Bevorzugte oligomere und polymere gehinderte Amine weisen die folgenden Strukturen auf: Preferred oligomeric and polymeric hindered amines have the following structures:
Bei den zuvor genannten Verbindungen bedeutet n jeweils 3 bis 100. In the compounds mentioned above, n is 3 to 100 in each case.
Ein weiterer geeigneter Lichtstabilisator ist Hostanox NOW (Hersteller: Clari- ant SE) mit der folgenden allgemeinen Struktur: Another suitable light stabilizer is Hostanox NOW (manufacturer: Clariant SE) with the following general structure:
Geeignete Dispereiermittel sind beispielsweise: Suitable dispensing agents are, for example:
Polyacrylate, z.B. Copolymere mit langkettigen Seitengruppen, Polyacrylat- Blockcopolymere, Alkylamide: z.B. N,N'-l,2-Ethandiylbisoctadecanamid Sorbi- tanester, z.B. Monostearylsorbitanester, Titanate und Zirconate, reaktive Co polymere mit funktionellen Gruppen z.B. Polypropylen-co-Acrylsäure, Polypro- pylen-co-Maleinsäureanhydrid, Polyethylen-co-Glycidylmethacrylat, Polysty- rol-alt-Maleinsäureanhydrid-Polysiloxane: z.B. Dimethylsilandiol-Ethylenoxid Copolymer, Polyphenylsiloxan Copolymer, Amphiphile Copolymere: z.B. Poly- ethylen-block-Polyethylenoxid, Dendrimere, z.B. hydroxylgruppenhaltige Den- drimere der folgenden Strukturen: Geeignete Costabilisatoren sind weiterhin Polyole insbesondere Alditole oder Cyclitole. Polyole sind z.B. Pentaerythrit, Dipentaerythrit, Tripentaerythrit, kurzkettige Polyetherpolyole oder kurzkettige Polyesterpolyole, sowie hyper verzweigte Polymere/Oligomere oder Dendrimere mit Alkoholgruppen z.B. Polyacrylates, for example copolymers with long-chain side groups, polyacrylate block copolymers, alkylamides: for example N, N'-1,2-ethanediylbisoctadecanamide, sorbitan esters, for example monostearyl sorbitan esters, titanates and zirconates, reactive copolymers with functional groups, for example polypropylene-co-acrylic acid, polypro - pylene-co-maleic anhydride, polyethylene-co-glycidyl methacrylate, polystyrene-alt-maleic anhydride-polysiloxanes: e.g. dimethylsilanediol-ethylene oxide copolymer, polyphenylsiloxane copolymer, amphiphilic copolymers: e.g. polyethylene-block-group-polyethylene denoxide, dendrimers, e.g. drimere of the following structures: Suitable costabilizers are also polyols, in particular alditols or cyclitols. Polyols are, for example, pentaerythritol, dipentaerythritol, tripentaerythritol, short-chain polyether polyols or short-chain polyester polyols, and hyper-branched polymers / oligomers or dendrimers with alcohol groups, for example
Vorzugsweise wird das mindestens eine Alditol ausgewählt aus der Gruppe be stehend aus Threit, Erythrit, Galactit, Mannit, Ribit, Sorbit, Xylit, Arabit, Isomalt, Lactit, Maltit, Altritol, Iditol, Maltotritol und hydrierte Oligo- und Polysaccha ride mit Polyol-Endgruppen und Mischungen hiervon. Besonders bevorzugt ist das mindestens eine bevorzugte Alditol ausgewählt aus der Gruppe bestehend aus Erythrit, Mannit, Isomalt, Maltit und Mischungen hiervon. The at least one alditol is preferably selected from the group consisting of threitol, erythritol, galactitol, mannitol, ribitol, sorbitol, xylitol, arabitol, isomalt, lactitol, maltitol, altritol, iditol, maltotritol and hydrogenated oligo- and polysaccharides with polyol End groups and mixtures thereof. The at least one preferred alditol is particularly preferably selected from the group consisting of erythritol, mannitol, isomalt, maltitol and mixtures thereof.
Beispiele für weitere geeignete Zuckeralkohole sind Heptitole und Octitole: meso-glycero-allo-Heptitol, D-glycero-D-altro-Heptitol, D-glycero-D-manno- Heptitol, meso-glycero-gulo-Heptitol, D-glycero-D-galacto-Heptitol (Perseitol), D-glycero-D-gluco-Heptitol, L-glycero-D-gluco Heptitol, D-erythro-L-galacto- Octitol, D-threo-L-galacto-Octitol. Insbesondere kann das mindestens eine Cyclitol ausgewählt sein aus der Gruppe bestehend aus Inositol (myo, scyllo-, D-chiro-, L-chiro-, muco-, neo-, allo-, epi- und cis-lnosit), 1,2,3,4-tetrahydroxycyclohexan, 1, 2,3,4, 5-pentahyd- roxycyclohexan, Quercitol, Viscumitol, Bornesitol, Conduritol, Ononitol, Pinitol, Pinpollitol, Quebrachitol, Ciceritol, Chinasäure, Shikimisäure und Valienol, be vorzugt ist dabei myo-lnosit (myo-lnositol). Examples of other suitable sugar alcohols are heptitols and octitols: meso-glycero-allo-heptitol, D-glycero-D-altro-heptitol, D-glycero-D-manno-heptitol, meso-glycero-gulo-heptitol, D-glycero D-galacto-heptitol (Perseitol), D-glycero-D-gluco-heptitol, L-glycero-D-gluco heptitol, D-erythro-L-galacto-octitol, D-threo-L-galacto-octitol. In particular, the at least one cyclitol can be selected from the group consisting of inositol (myo, scyllo-, D-chiro-, L-chiro-, muco-, neo-, allo-, epi- and cis-inositol), 1,2 , 3,4-tetrahydroxycyclohexane, 1, 2,3,4, 5-pentahydroxycyclohexane, quercitol, viscumitol, bornesitol, conduritol, ononitol, pinitol, pinpollitol, quebrachitol, ciceritol, quinic acid, shikimic acid and valienol, myo being preferred -inositol (myo-inositol).
Geeignete Nukleierungsmittel sind beispielsweise Talkum, Alkali oder Erdalka lisalze von mono- und polyfunktionellen Carbonsäuren wie z.B. Benzoesäure, Bernsteinsäure, Adipinsäure, z.B. Natriumbenzoat, Zinkglycerolat, Alumi- niumhydroxy-bis(4-tert-butyl)benzoat, Benzylidensorbitole wie z.B. 1, 3:2,4- Bis(Benzyliden)sorbitol oder l,3:2,4-Bis(4-Methylbenzyliden)sorbitol, 2,2'-Me- thylen-bis-(4,6-di-tert-butylphenyl)phosphat, sowie Trisamide und Diamide wie z.B. Trimesinsäuretricyclohexylami, Trimesinsäuretri(4-methylcyclohexylamid), Trimesinsäure tri(tert.butylamid), N,N',N"-l,3,5-Benzoltriyltris(2,2-dimethyl- propanamid) oder 2,6-Naphthalindicarbosäuredicyclohexylamid. Suitable nucleating agents are, for example, talc, alkali or alkaline earth salts of monofunctional and polyfunctional carboxylic acids such as benzoic acid, succinic acid, adipic acid, e.g. sodium benzoate, zinc glycerolate, aluminum hydroxy bis (4-tert-butyl) benzoate, benzylidene sorbitols such as 1, 3: 2,4-bis (benzylidene) sorbitol or l, 3: 2,4-bis (4-methylbenzylidene) sorbitol, 2,2 '-me- Thylen-bis- (4,6-di-tert-butylphenyl) phosphate, as well as trisamides and diamides such as trimesic acid tri-cyclohexylamides, trimesic acid tri (4-methylcyclohexyl amide), trimesic acid tri (tert-butyl amide), N, N ' , N " -l, 3,5-benzene triyl tris (2,2-dimethyl propanamide) or 2, 6-naphthalenedicarboxylic acid dicyclohexylamide.
Geeignete Antinukleierungsmittel sind Azinfarbstoffe wie z.B. Nigrosin. Suitable anti-nucleation agents are azine dyes such as nigrosine.
Geeignete Flammschutzmittel sind beispielsweise: a) Anorganische Flammschutzmittel wie z.B. AI(OH)3, Mg(OH)2, AIO(OH), MgCC>3, Schichtsilikate wie z.B. Montmorillonit oder Sepiolit, nicht oder organisch modifiziert, Doppelsalze, wie z.B. Mg-Al-Silikate, POSS-(Po- lyhedral Oligomeric Silsesquioxane) Verbindungen, Huntit, Hydromagne- sit oder Halloysit sowie Sb2Ü3, Sb20s, M0O3, Zinkstannat, Zinkhydroxyst- annat, Suitable flame retardants are, for example: a) Inorganic flame retardants such as Al (OH) 3, Mg (OH) 2, AIO (OH), MgCC> 3, sheet silicates such as montmorillonite or sepiolite, unmodified or organically modified, double salts such as Mg- Al silicates, POSS (Polyhedral Oligomeric Silsesquioxane) compounds, huntite, hydromagnite or halloysite as well as Sb2Ü3, Sb 2 0s, M0O3, zinc stannate, zinc hydroxystannate,
b) Stickstoffhaltige Flammschutzmittel wie z.B. Melamin, Meiern, Melam, Melon, Melaminderivate, Melaminkondensationsprodukte oder Mela minsalze, Benzoguanamin, Polyisocyanurate, Allantoin, Phosphacene, insbesondere Melamincyanurat, Melaminphosphat, Dimelaminphos- phat, Melaminpyrophosphat, Melaminpolyphosphat, Melamin-Metall- Phosphate wie z.B. Melaminaluminumphosphat, Melaminzinkphosphat, Melaminmagnesiumphopsphat, sowie die entsprechenden Pyrophos- phate und Polyphosphate, Poly-[2,4-(piperazin-l,4-yl)-6-(morpholin-4- yl)-l,3,5-triazin], Ammoniumpolyphosphat, Melaminborat, Melaminhyd- robromid, b) Nitrogen-containing flame retardants, such as melamine, melamine, melam, melon, melamine derivatives, melamine condensation products or melamine salts, benzoguanamine, polyisocyanurates, allantoin, phosphacenes, in particular melamine cyanurate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, such as melamine phosphate phosphate, melamine polyphosphate, melamine polyphosphate, melamine polyphosphate, melamine polyphosphate, melamine polyphosphate, melamine polyphosphate, melamine polyphosphate, for example, melamine polyphosphate, for example melamine condensation products or melamine condensation products , Melamine zinc phosphate, melamine magnesium phosphate and the corresponding pyrophosphates and polyphosphates, poly- [2,4- (piperazin-1,4-yl) -6- (morpholin-4- yl) -l, 3,5-triazine], ammonium polyphosphate, melamine borate, melamine hydrobromide,
c) Radikalbildner, wie z.B. Alkoxyamine, Hydroxylaminester, Azoverbindun gen, Dicumyl oder Polycumyl, Hydroxyimide und deren Derivate wie z.B. Hydroxyimidester oder Hydroxyimidether c) Radical formers, such as alkoxyamines, hydroxylamine esters, azo compounds, dicumyl or polycumyl, hydroxyimides and their derivatives such as hydroxyimide esters or hydroxyimide ethers
d) Phosphorhaltige Flammschutzmitteln wie z.B. roter Phosphor, Phosphate wie z.B. Resorcindiphosphat, Bisphenol-A-diphosphat und ihre Oligo mere, Triphenylphosphat, Ethylendiamindiphosphat, Phosphinate wie z.B. Salze der hypophosphorigen Säure und Ihrer Derivate wie Alkylphos- phinatsalzen z.B. Diethylphosphinataluminium oder Diethylphosphinat- Zink oder Aluminiumphosphinat, Aluminiumphosphit, Aluminiumphos- phonat, Phosphonatester, oligomere und polymere Derivate der Methan- phosphonsäure, 9,10-Dihydro-9-oxa-10-phosphorylphenanthren-10-oxid (DOPO) und deren substituierte Verbindungen, d) Phosphorus-containing flame retardants such as red phosphorus, phosphates such as resorcinol diphosphate, bisphenol A diphosphate and their oligomers, triphenyl phosphate, ethylenediamine diphosphate, phosphinates such as salts of hypophosphorous acid and its derivatives such as alkyl phosphine phosphine or aluminum phosphine phosphine salts such as zinc phosphine or diethyl phosphine salts , Aluminum phosphite, aluminum phosphonate, phosphonate esters, oligomeric and polymeric derivatives of methane phosphonic acid, 9,10-dihydro-9-oxa-10-phosphorylphenanthrene-10-oxide (DOPO) and their substituted compounds,
e) Halogenhaltige Flammschutzmittel auf Chlor- und Brombasis wie z.B. po- lybrominierte Diphenyloxide, wie z.B. Decabromdiphenyloxid,Tris(3- bromo-2,2-bis(bromomethyl)propyl-phosphat, Tris(tribromneopen- tyl)phosphat, Tetrabromphthalsäure, l,2-Bis(tribromphenoxy)ethan, He- xabromcyclododecan, bromiertes Diphenylethan, Tris-(2,3-dibrompro- pyl)isocyanurat, Ethylen-bis(tetrabromophthalimid), Tetrabromo-bi- sphenol A, bromiertes Polystyrol, bromiertes Polybutadien bzw, Polysty- rol-bromiertes Polybutadien-Copolymere, bromierter Polypheny- lenether, bromiertes Epoxidharz, Polypentabrombenzylacrylat, ggf. in Kombination mit Sb2Ü3 und/oder Sb20s, e) Halogen-containing flame retardants based on chlorine and bromine such as polybrominated diphenyloxides, such as decabromodiphenyloxide, tris (3-bromo-2,2-bis (bromomethyl) propyl phosphate, tris (tribromoneopentyl) phosphate, tetrabromophthalic acid, l, 2-bis (tribromophenoxy) ethane, hexabromocyclododecane, brominated diphenylethane, tris (2,3-dibromopropyl) isocyanurate, ethylene bis (tetrabromophthalimide), tetrabromobisphenol A, brominated polystyrene, brominated polybutadiene - Rol-brominated polybutadiene copolymers, brominated polyphenylene ether, brominated epoxy resin, polypentabromobenzyl acrylate, possibly in combination with Sb2Ü3 and / or Sb 2 0s,
f) Borate wie z.B. Zinkborat oder Calciumborat, ggf. auf Trägermaterial wie z.B. Silica f) Borates such as zinc borate or calcium borate, possibly on a carrier material such as silica
g) Schwefelhaltige Verbindungen wie z.B. elementarer Schwefel, Disulfide und Polysulfide, Thiuramsulfid, Dithiocarbamate, Mercaptobenzthiazol und Sulfenamide, g) Sulfur-containing compounds such as elemental sulfur, disulfides and polysulfides, thiuram sulfide, dithiocarbamates, mercaptobenzothiazole and sulfenamides,
h) Antidrip-Mitteln wie z.B. Polytetrafluorethylen, h) antidrip agents such as polytetrafluoroethylene,
i) Siliciumhaltige Verbindungen wie z.B. Polyphenylsiloxane, i) Silicon-containing compounds such as polyphenylsiloxanes,
j) Kohlenstoffmodifikationen wie z.B.Carbon-Nanoröhren (CNT) oder Gra phen, sowie Kombinationen oder Mischungen hieraus. Besonders geeignete Flammschutzmittel sind Radikalbildner bevorzugt ausge wählt aus der Gruppe bestehend aus N-Alkoxyaminen, -C-C- Radikalbildnern, Radikalbildnern mit Azogruppen (-N=N-), Radikalbildnern mit Hydrazingruppen (-NH-HN-), Radikalbildnern mit Hydrazongruppen (>C=N-NH-), Radikalbildnern mit Azingruppen (>C=N-N=C<), Radikalbildnern mit Triazengruppen (-N=N-N<) oder aus Iminoxytriazinen. j) Carbon modifications such as carbon nanotubes (CNT) or graphs, as well as combinations or mixtures thereof. Particularly suitable flame retardants are radical formers preferably selected from the group consisting of N-alkoxyamines, -CC- radical formers, radical formers with azo groups (-N = N-), radical formers with hydrazine groups (-NH-HN-), radical formers with hydrazone groups (> C = N-NH-), radical formers with azine groups (> C = NN = C <), radical formers with triazene groups (-N = NN <) or from iminoxytriazines.
Die Herstellung geeigneter Azoverbindungen ist beispielsweise in M. Aubert et. al. Macromol. Sei. Eng. 2007, 292, 707-714 oder in WO 2008101845, die Herstellung von Hydrazonen und Azinen in M. Aubert et al., Pol. Adv. Technol. 2011, 22, 1529-1538, die Herstellung von Triazenen in W. Pawelec et al., Pol. Degr. Stab. 2012, 97, 948-954 beschrieben. Die Synthese von Iminoxytriazinen ist in WO 2014/064064 beschrieben. The preparation of suitable azo compounds is for example in M. Aubert et. al. Macromol. Be. Closely. 2007, 292, 707-714 or in WO 2008101845, the production of hydrazones and azines in M. Aubert et al., Pol. Adv. Technol. 2011, 22, 1529-1538, the preparation of triazenes in W. Pawelec et al., Pol. Degr. Rod. 2012, 97, 948-954. The synthesis of iminoxytriazines is described in WO 2014/064064.
Insbesondere zu verwendende Radikalbildner sind dabei ausgewählt aus der Gruppe bestehend aus In particular, radical formers to be used are selected from the group consisting of
a) N-Alkoxyaminen gemäß der nachfolgend abgebildeten Strukturformel a) N-alkoxyamines according to the structural formula shown below
wobei in which
R3 für Wasserstoff oder einen gegebenenfalls substituierter Alkyl-, Cycloal- kyl-, Aryl-, Heteroaryl- oder Acyl-Rest steht, insbesondere ein CI bis C4- Alkylrest ist, R 3 represents hydrogen or an optionally substituted alkyl, cycloalkyl, aryl, heteroaryl or acyl radical, in particular a C1 to C4 alkyl radical,
R4 für einen Alkoxy-, Aryloxy-, Cycloalkoxy-, Aralkoxy- oder Acyloxy-Rest steht,R 4 represents an alkoxy, aryloxy, cycloalkoxy, aralkoxy or acyloxy radical,
Z für Wasserstoff oder einen gegebenenfalls substituierter Alkyl-, Cycloal- kyl-, Aryl-, Heteroaryl- oder Acyl-Rest steht, wobei die beiden Reste Z auch einen geschlossenen Ring bilden können, der ggf. durch Ester-, Ether-, Amin, Amid, Carboxy- oder Urethangruppen substituiert sein kann, Z represents hydrogen or an optionally substituted alkyl, cycloalkyl, aryl, heteroaryl or acyl radical, where the two radicals Z can also form a closed ring, which is optionally replaced by ester, ether, amine, Amide, carboxy or urethane groups can be substituted,
E für einen Alkoxy-, Aryloxy- Cycloalkyloxy-, Aralkoxy oder Acyloxyrest steht, b) Azo-Verbindungen gemäß der nachfolgend abgebildeten Strukturfor meln E stands for an alkoxy, aryloxy, cycloalkyloxy, aralkoxy or acyloxy radical, b) Azo compounds according to the structural formulas shown below
wobei in which
R5 einen Alkly-, Cycloalkyl- oder Arylrest bedeutet, R 5 denotes an alkyl, cycloalkyl or aryl radical,
R6 bei jedem Auftreten gleich oder verschieden ist und einen linearen oder verzweigten Alkylrest bedeutet, R 6 is identical or different on each occurrence and denotes a linear or branched alkyl radical,
R7 bei jedem Auftreten gleich oder verschieden ist und Wasserstoff oder einen linearen oder verzweigten Alkylrest bedeutet, und R 7 is identical or different on each occurrence and denotes hydrogen or a linear or branched alkyl radical, and
R8 bei jedem Auftreten gleich oder verschieden ist und einen Alkyl, Alkoxy-, Aryloxy- Cycloalkyloxy-, Aralkoxy oder Acyloxyrest bedeutet, R 8 is identical or different on each occurrence and denotes an alkyl, alkoxy, aryloxy, cycloalkyloxy, aralkoxy or acyloxy radical,
c) Dicumyl gemäß der nachfolgend abgebildeten Strukturformel c) Dicumyl according to the structural formula shown below
wobei R7 die zuvor angegebene Bedeutung aufweist, bevorzugt Methyl ist, d) und/oder Polycumyl gemäß der nachfolgend abgebildeten Strukturfor mel where R 7 has the meaning given above, is preferably methyl, d) and / or polycumyl according to the structural formula shown below
wobei R7 die zuvor angegebene Bedeutung aufweist, bevorzugt Methyl ist, und 2 < n < 100. where R 7 has the meaning given above, is preferably methyl, and 2 <n <100.
Typische Beispiele für die zuvor genannten N-Alkoxyamine der angegebenen Struktur sind dabei: l-Cyclohexyloxy-2,2,6,6-Tetramethyl-4-Octadecylaminopiperidin; Bis(l-Octyl- oxy-2,2,6,6-Tetramethylpiperidin-4-yl) Sebacat; 2,4-Bis[(l-Cyclohexyloxy- 2.2.6.6-Tetramethylpiperidin-4-yl)Butylamino]-6-(2-Hydroxyethylamino-S-Tria- zin; Bis(l-Cyclohexyloxy-2,2,6,6-Tetramethylpiperidin-4-yl) Adipat; 2,4-Bis[(l- Cyclohexyloxy-2,2,6,6-Tetramethylpiperidin-4-yl)Butylamino]-6-Chloro-S-Tria- zin; l-(2-Hydroxy-2-Methylpropoxy)-4-Hydroxy-2,2,6,6-Tetramethylpiperidin; l-(2-Hydroxy-2-Methylpropoxy)-4-Oxo-2,2,6,6-Tetramethylpiperidin; l-(2- Hydroxy-2-Methylpropoxy)-4-Octadecanoyloxy-2,2,6,6-Tetramethylpiperidin; Bis(l-(2-Hydroxy-2-Methylpropoxy)-2,2,6,6-Tetramethylpiperidin-4-yl) Se- bacat; Bis(l-(2-Hydroxy-2-Methylpropoxy)-2,2,6,6-Tetramethylpiperidin-4-yl) Adipat; 2,4-Bis{N-[l-(2-Hydroxy-2-Methylpropoxy)-2,2,6,6-Tetramethylpiperi- din-4-yl]-N-Butylamino}-6-(2-Hydroxyethylamino)-S-Triazin); 4-Piperidinol,Typical examples of the aforementioned N-alkoxyamines of the structure indicated are: 1-cyclohexyloxy-2,2,6,6-tetramethyl-4-octadecylaminopiperidine; Bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate; 2,4-bis [(l-cyclohexyloxy- 2.2.6.6-Tetramethylpiperidin-4-yl) butylamino] -6- (2-hydroxyethylamino-S-triazine; bis (l-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) adipate; 2, 4-bis [(l-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -6-chloro-S-triazine; l- (2-hydroxy-2-methylpropoxy) -4- Hydroxy-2,2,6,6-tetramethylpiperidine; 1- (2-hydroxy-2-methylpropoxy) -4-oxo-2,2,6,6-tetramethylpiperidine; 1- (2-hydroxy-2-methylpropoxy) - 4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine; bis (l- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl) sebacate; bis (l- (2-Hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl) adipate; 2,4-bis {N- [1- (2-hydroxy-2-methylpropoxy) -2.2 , 6,6-tetramethylpiperidin-4-yl] -N-butylamino} -6- (2-hydroxyethylamino) -S-triazine); 4-piperidinol,
2.2.6.6-Tetramethyl-l-(undecyloxy)-4,4'-carbonat; das Reaktionsprodukt von 2,4-Bis[(l-Cyclohexyloxy-2,2,6,6-Tetramethylpiperidin-4-yl)Butylamino]-6- Chloro-S-Triazin mit N,N'-Bis(3-Aminopropylethylendiamin); die Oligomer-Ver- bindung, welche das Kondensationsprodukt ist von 4,4'-Hexamethylen-Bis- (amino-2,2,6,6-Tetramethylpiperidin) und 2,4-Dichloro-6-[(l-Cyclohexyloxy-2.2.6.6-tetramethyl-1- (undecyloxy) -4,4'-carbonate; the reaction product of 2,4-bis [(l-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -6-chloro-S-triazine with N, N'-bis (3-aminopropylethylenediamine) ; the oligomer compound, which is the condensation product of 4,4'-hexamethylene bis (amino-2,2,6,6-tetramethylpiperidine) and 2,4-dichloro-6 - [(l-cyclohexyloxy-
2.2.6.6-Tetramethyl-4-yl)Butylamino]-S-Triazin, an den Enden verschlossen mit 2-Chloro-4,6-Bis(Dibutylamino)-S-Triazin; aliphatische Hydroxylamin wie z.B. 2.2.6.6-Tetramethyl-4-yl) butylamino] -S-triazine, closed at the ends with 2-chloro-4,6-bis (dibutylamino) -S-triazine; aliphatic hydroxylamine such as e.g.
in denen n = 1-15 ist, wie z.B. Disterarylhydroxylamin. in which n = 1-15, such as, for example, disterarylhydroxylamine.
Die oben genannten Verbindungen sind teilweise kommerzielle Produkte und werden unter den folgenden Handelsnamen gehandelt: FLAMESTAB NOR 116 (RTM), TINUVIN NOR 371 (RTM), IRGATEC CR 76 (RTM) von BASF SE, Hostavin NOW (RTM) von Clariant oder ADK Stab LA 81 (RTM) von Adeka. Dicumyl und Polycumyl sind Handelsprodukte, die z.B. von United Initiators erhältlich sind. a) Phosphorhaltige Flammschutzmittel z.B. Phosphinate der folgenden Struktu ren: Some of the above-mentioned compounds are commercial products and are traded under the following trade names: FLAMESTAB NOR 116 (RTM), TINUVIN NOR 371 (RTM), IRGATEC CR 76 (RTM) from BASF SE, Hostavin NOW (RTM) from Clariant or ADK Stab LA 81 (RTM) from Adeka. Dicumyl and Polycumyl are commercial products available, for example, from United Initiators. a) Phosphorus-containing flame retardants, e.g. phosphinates of the following structures:
wobei bevorzugt RI und R2 identisch oder verschieden sind und ausgewählt sind aus linearem oder verzweigtem Cl-C6-Alkyl und/oder Aryl; M ausgewählt ist aus der Gruppe bestehend aus Mg, Ca, AI, Sb, Sn, Ge, Ti, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K, Zn und/oder einem protonierten Stickstoff-Base, vorzugsweise Calcium-Ionen, Magnesium-Ionen, Aluminium-Ionen, und/oder Zink-Ionen; und m = 1-4, bevorzugt 2 oder 3, ist; n = 1-4, bevorzugt 1 oder 3, ist; x = 1-4, bevorzugt 1 oder 2, ist. In einer besonders bevorzugten Ausführungsform ist Ri = Alkyl, R2 = Alkyl und M = AI oder Zn. where RI and R2 are preferably identical or different and are selected from linear or branched C1-C6-alkyl and / or aryl; M is selected from the group consisting of Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K, Zn and / or a protonated nitrogen base, preferably calcium ions, magnesium ions, aluminum ions, and / or zinc ions; and m = 1-4, preferably 2 or 3; n = 1-4, preferably 1 or 3; x = 1-4, preferably 1 or 2. In a particularly preferred embodiment, Ri = alkyl, R2 = alkyl and M = Al or Zn.
Ein besonders bevorzugtes Beispiel für ein Phosphinat sind die kommerziell erhältlichen Produkte Exolit OP (RTM) von Clariant SE. A particularly preferred example of a phosphinate are the commercially available Exolit OP (RTM) products from Clariant SE.
Weitere bevorzugte phosphorhaltige Flammschutzmittel sind Metallsalze der hypophosphorigen Säure mit einer Struktur gemäß der Formel Further preferred phosphorus-containing flame retardants are metal salts of hypophosphorous acid with a structure according to the formula
wobei Met ein Metall ist, ausgewählt aus den Gruppen I, II, III und IV des Peri odensystems der Elemente, und n eine Zahl von 1 bis 4 ist, die der Ladung des entsprechenden Metall-Ions Met entspricht. Metn+ ist beispielsweise Na+, where Met is a metal selected from groups I, II, III and IV of the Periodic Table of the Elements, and n is a number from 1 to 4 which corresponds to the charge of the corresponding metal ion Met. For example, Met n + is Na + ,
Ca2+, Mg2+, Zn2+, Ti4+ oder Al3+, wobei Ca2+, Zn2+ und Al3+ besonders bevorzugt sind. Ca 2+ , Mg 2+ , Zn 2+ , Ti 4+ or Al 3+ , with Ca 2+ , Zn 2+ and Al 3+ being particularly preferred.
Die oben genannten Salze der hypophosphorigen Säure sind teilweise kom merziell erhältlich z.B. unter der Bezeichnung Phoslite (RTM) von Italmatch Chemicals. Some of the above-mentioned salts of hypophosphorous acid are commercially available, e.g. under the name Phoslite (RTM) from Italmatch Chemicals.
Eine weitere bevorzugte Gruppe von phosphorhaltigen Flammschutzmitteln sind Phosphonate oder Phosphonsäurediarylester einer Struktur gemäß der folgenden Formel: Another preferred group of phosphorus-containing flame retardants are phosphonates or phosphonic acid diaryl esters with a structure according to the following formula:
wobei Rs, und Rio = H, Alkyl, vorzugsweise C1-C4 sind, Rg= C1-C4 alkyl u = l-5st und v = l-5ist. where Rs, and Rio = H, alkyl, preferably C1-C4, Rg = C1-C4 alkyl, u = 1-5st and v = 1-5.
Entsprechende Strukturen können auch in der Form von Phosphonat-Oligo- meren, Polymeren und Co-Polymeren vorliegen. Linear oder verzweigte Phos- phonat-Oligomere und Polymere sind aus dem Stand der Technik bekannt. Für verzweigte Phosphonat-Oligomere und Polymere wird auf die US-Patente USCorresponding structures can also be in the form of phosphonate oligomers, polymers and copolymers. Linear or branched phosphonate oligomers and polymers are known from the prior art. For branched phosphonate oligomers and polymers, reference is made to US patents US
2 716 101, US 3 326 852, US 4 328 174, US 4 331 614, US 4 374 971, USUS 2,716,101, US 3,326,852, US 4,328,174, US 4,331,614, US 4,374,971, US
4 415 719, US 5 216 113, US 5 334 692, US 3 442 854, US 6 291 630 Bl, US 6 861 499 B2 und US 7816486 B2 verwiesen. Für Phosphonat-Oligomere wird auf die US-Patentanmeldungen US 2005/0020800 Al, US 2007/0219295 Al und US 2008/0045673 Al verwiesen. In Bezug auf lineare Phosphonat-Oligo mere und Polymere wird auf die US-Patent-Dokumente , US 3 946 093, US4 415 719, US 5 216 113, US 5 334 692, US 3 442 854, US 6 291 630 B1, US 6 861 499 B2 and US 7816486 B2 are referred to. For phosphonate oligomers, reference is made to US patent applications US 2005/0020800 A1, US 2007/0219295 A1 and US 2008/0045673 A1. With respect to linear phosphonate oligomers and polymers, see US Patent Documents, US 3,946,093, US
3 919 363, US 6 288 210 Bl, US 2 682 522 und US 2 891 915 verwiesen. 3,919,363, US 6,288,210 B1, US 2,682,522 and US 2,891,915 are referred to.
Phophonate sind beispielsweise unter dem Handelsnamen Nofia (RTM) von FRX Polymers erhältlich. Phophonate are for example under the trade name Nofia (RTM) from FRX Polymers available.
Eine weitere bevorzugte Gruppe von phosphorhaltigen Flammschutzmitteln sind Verbindungen auf Basis von Oxaphosphorinoxid und deren Derivate mit beispielsweise den folgenden Strukturen: Another preferred group of phosphorus-containing flame retardants are compounds based on oxaphosphorine oxide and their derivatives with, for example, the following structures:
wobei M ein Metall ist, ausgewählt aus der zweiten, dritten, zwölften oder dreizehnten Gruppe des Periodensystems der Elemente ist, x = 2 oder 3 ist, n > 10 ist, m= 0-25 ist, R = H, Halogen oder ein aliphatischer oder aromatischer Rest mit 1-32 C-Atomen ist und Ri = H, C1-C6 alkyl oder phenyl ist. where M is a metal selected from the second, third, twelfth or thirteenth group of the Periodic Table of the Elements, x = 2 or 3, n> 10, m = 0-25, R = H, halogen or an aliphatic or an aromatic radical with 1-32 carbon atoms and Ri = H, C1-C6 alkyl or phenyl.
Produkte auf der Basis von Oxophosphorinoxid sind beispielsweise unter dem Handelsnamen Ukanol (RTM) von Schill und Seilacher GmbH im Handel. Wei tere Verbindungen können beispielsweise gemäß der Patentschriften WO 2013020696, WO 2010135398, W003070736, W02006084488, WO Products based on oxophosphorine oxide are, for example, on the market under the trade name Ukanol (RTM) from Schill und Seilacher GmbH. Further compounds can for example according to the patent specifications WO 2013020696, WO 2010135398, W003070736, W02006084488, WO
2006084489, W02011000019, WO2013068437, WO2013072295 hergestellt werden. 2006084489, W02011000019, WO2013068437, WO2013072295.
Weitere geeignete phosphorhaltige Flammschutzmittel sind zyklische Phos- phonate einer Struktur gemäß einer der folgenden Formeln: Further suitable phosphorus-containing flame retardants are cyclic phosphonates with a structure according to one of the following formulas:
wobei A1 und A2 unabhängig voneinander eine substituierte oder nicht substi tuierte, geradkettige oder verzweigte Alkylgruppe mit 1 bis 4 Kohlenstoffato- men, substituiertes oder nicht substituiertes Benzyl, substituiertes oder nicht substituiertes Phenyl, substituiertes oder nicht substituiertes Naphthyl dar stellten und wobei A3 und A4 unabhängig voneinander Methyl oder Ethyl sind und A5 eine geradkettige oder verzweigte Alkylgruppe mit 1 bis 4 Kohlenstoff atomen oder eine Phenyl- oder Benzylgruppe ist, die jeweils bis zu 3 Methyl- gruppen aufweisen kann, ist. Zyklische Phosphonate sind beispielsweise von der Fa. Thor GmbH unter dem where A 1 and A 2 independently represent a substituted or unsubstituted, straight-chain or branched alkyl group with 1 to 4 carbon atoms, substituted or unsubstituted benzyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl and where A 3 and A 4 are independently methyl or ethyl and A 5 is a straight-chain or branched alkyl group having 1 to 4 carbon atoms or a phenyl or benzyl group, each of which can have up to 3 methyl groups. Cyclic phosphonates are, for example, from Thor GmbH under the
Handelsnamen Aflammit (RTM) im Handel oder können gemäß EP 2450401 hergestellt werden. Trade names Aflammit (RTM) are commercially available or can be produced in accordance with EP 2450401.
Weitere synergistische phosphorhaltige Flammschutzmittel sind Phos- phacene, insbes. polymere Phosphacene. Ein entsprechendes Produkt ist z.B. unter der Bezeichnung SPB-100 von Otsuka Chemicals im Handel. b) Stickstoffhaltige Flammschutzmittel Further synergistic phosphorus-containing flame retardants are phosphacenes, especially polymeric phosphacenes. A corresponding product is commercially available from Otsuka Chemicals under the name SPB-100, for example. b) Nitrogen-containing flame retardants
Bevorzugte Stickstoffhaltige Flammschutzmittel sind Melaminpolyphosphat, Melamincyanurat, Melamin-Metall-Phosphate, Poly-[2,4-(piperazin-l,4-yl)-6-Preferred nitrogen-containing flame retardants are melamine polyphosphate, melamine cyanurate, melamine metal phosphates, poly- [2,4- (piperazin-1,4-yl) -6-
(morpholin-4-yl)-l,3,5-triazin] und Ammoniumpolyphosphat. Diese Verbin dungen sind kommerzielle Produkte und unter den Handelsnamen Melapur (RTM) von BASF SE, Budit (RTM) von Budenheim Chemische Fabrik, Exolit (RTM) von Clariant, Safire (RTM) von Huber Chemicals oder MCA PPM Triazine von MCA Technologies GmbH erhältlich. c) Bevorzugte schwefelhaltige Flammschutzmittel sind beispielsweise die folgenden Verbindungen (morpholin-4-yl) -1, 3,5-triazine] and ammonium polyphosphate. These compounds are commercial products and are available under the trade names Melapur (RTM) from BASF SE, Budit (RTM) from Budenheim Chemische Fabrik, Exolit (RTM) from Clariant, Safire (RTM) from Huber Chemicals or MCA PPM Triazine from MCA Technologies GmbH . c) Preferred sulfur-containing flame retardants are, for example, the following compounds
Ganz besonders bevorzugte Flammschutzmittel sind halogenfrei und sind die folgenden Verbindungen: Particularly preferred flame retardants are halogen-free and are the following compounds:
AI(OH)3 , Mg(OH)2, Al (OH) 3 , Mg (OH) 2,
n=2-20 mit n = 3 bis 100 n mit jeweils R= Alkyl, Phenyl und n = 3 bis 20 n = 2-20 with n = 3 to 100 n with each R = alkyl, phenyl and n = 3 to 20
Geeignete Füllstoffe und Verstärkungsstoffe sind beispielsweise synthetische oder natürliche Materialien wie z.B. Calciumcarbonat, Silikate, Glasfasern, Glas kugeln (massiv oder hohl), Talkum, Glimmer, Kaolin, Bariumsulfat, Metalloxide und Metallhydroxide, Ruß, Graphit, Kohlenstoffnanoröhrchen, Graphen, Holz mehl oder Fasern von Naturprodukten wie z.B. Cellulose oder synthetische Fa sern. Weitere geeignete Füllstoffe sind Hydrotalcite oder Zeolithe oder Schicht silikate wie z.B. Montmorillonit, Bentonit, Beidelit, Mica, Hectorit, Saponit, Ver miculit, Ledikit, Magadit, lllit, Kaolinit, Wollastonit, Attapulgit. Suitable fillers and reinforcing materials are, for example, synthetic or natural materials such as calcium carbonate, silicates, glass fibers, glass spheres (solid or hollow), talc, mica, kaolin, barium sulfate, metal oxides and metal hydroxides, carbon black, graphite, carbon nanotubes, graphene, wood flour or fibers from natural products such as cellulose or synthetic fibers. Further suitable fillers are hydrotalcites or zeolites or sheet silicates such as montmorillonite, bentonite, beidelite, mica, hectorite, saponite, ver miculite, ledikite, magadite, lllite, kaolinite, wollastonite, attapulgite.
Geeignete Pigmente können anorganischer oder organischer Natur sein. Anor ganische Pigmente sind beispielsweise Titandioxid, Zinkoxid, Zinksulfid, Eisen oxid, Ultramarin, Ruß, organische Pigmente sind beispielsweise Anthrachinone, Anthanthrone, Benzimidazolone, Chinacridone, Diketopyrrolopyrrole, Dio- xazine, Indanthrone, Isoindolinone, Azo-Verbindungen, Perylene, Phthalocya- nine oder Pyranthrone. Weitere geeignete Pigmente sind Effektpigmente auf Metallbasis oder Perlglanzpigmente auf Metalloxid-Basis. Suitable pigments can be of an inorganic or organic nature. Inorganic pigments are, for example, titanium dioxide, zinc oxide, zinc sulfide, iron oxide, ultramarine, carbon black, organic pigments are, for example, anthraquinones, anthanthrones, benzimidazolones, quinacridones, diketopyrrolopyrroles, dioxazines, indanthrones, isoindolinones, azo compounds, perylenes, phthalocyanines or azo compounds Pyranthrones. Further suitable pigments are effect pigments based on metal or pearlescent pigments based on metal oxide.
Geeignete Gleitmittel und Verarbeitungshilfsmittel sind beispielsweise Po lyethylenwachse, Polypropylenwachse, Salze von Fettsäuren wie z.B. Calci- umstearat, Zlnkstearat oder Salze von Montanwachsen, Amidwachse wie z.B. Erucasäureamid oder Ölsäureamide, Fluorpolymere, Silikone oder Neoalkoxy- titanate- und Zirkonate. Suitable lubricants and processing aids are, for example, polyethylene waxes, polypropylene waxes, salts of fatty acids such as calcium stearate, zinc stearate or salts of montan waxes, amide waxes such as erucic acid amide or oleic acid amides, fluoropolymers, silicones or neoalkoxy titanates and zirconates.
Geeignete Optische Aufheller sind beispielsweise Bisbenzoxazole, Phenylcuma rine oder Bis(styryl)biphenyle und insbesondere optische Aufheller der For meln: Suitable optical brighteners are, for example, bisbenzoxazoles, phenylcuma rine or bis (styryl) biphenyls and especially optical brighteners of the formulas:
Geeignete Füllstoffdeaktivatoren sind beispielsweise Polysiloxane, Polyacrylate insbesondere Blockcopolymere wie Polymethacrylsäure-polyalkylenoxid oder Polyglycidyl(meth)acrylate und deren Copolymere z.B. mit Styrol sowie Epoxide z.B. der folgenden Strukturen: Suitable filler deactivators are, for example, polysiloxanes, polyacrylates, in particular block copolymers such as polymethacrylic acid-polyalkylene oxide or polyglycidyl (meth) acrylates and their copolymers, e.g. with styrene, and epoxides e.g. of the following structures:
Geeignete Antistatika sind beispielsweise ethoxylierte Alkylamine, Fettsäurees ter, Alkylsulfonate und Polymere wie z.B. Polyetheramide. Suitable antistatic agents are, for example, ethoxylated alkylamines, fatty acid esters, alkyl sulfonates and polymers such as polyether amides.
Geeignete Antiozonantien sind die oben genannten Amine wie z.B. N,N'-Di- isopropyl-p-phenylendiamin, N,N'-Di-sec-butyl-p-phenylendiamin, N,N'- Bis(l,4-dimethylpentyl)-p-phenylendiamin, N,N'-Dicyclohexyl-p-phenylendia- min, N-lsopropyl-N'-phenyl-p-phenylendiamin, N-(l,3-Dimethylbutyl)-N'-phe- nyl-p-phenylen-diamin, N-(l-Methylheptyl)-N'-phenyl-p-phenylendiamin, N- Cyclohexyl-N'-phenyl-p-phenylendiamin Suitable antiozonants are the above-mentioned amines such as N, N'-diisopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-bis (1,4-dimethylpentyl) -p-phenylenediamine, N, N'-dicyclohexyl-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p- phenylenediamine, N- (1-methylheptyl) -N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine
Geeignete Rheologiemodifikatoren z.B. für die Herstellung von Controlled rhe- ology Polypropylen (CR-PP) sind beispielsweise Peroxide, Alkoxyaminester, Oxyimidsulfonsäureester und insbesondere die folgenden Strukturen: Suitable rheology modifiers e.g. for the production of controlled rheology polypropylene (CR-PP) are, for example, peroxides, alkoxyamine esters, oxyimidesulfonic acid esters and in particular the following structures:
Geeignete Additive zum Molekulargewichtsaufbau von Polykondensationspo lymeren (Kettenverlängerer) sind Diepoxide, Bis-Oxazoline, Bis-Oxazolone, Bis- Oxazine, Diisocyanate, Dianhydride, Bis-Acyllactame, Bis-Maleimide, Dicya- nate, Carbodiimide. Weitere geeignete Kettenverlängerer sind polymere Ver bindungen wie z. B. Polystyrol-Polyacrylat-Polyglycidyl(meth)acrylat- Copoly mere, Polystyrol-Maleinsäureanhydrid-Copolymere und Polyethylen-Malein- säureanhydrid-Copolymere. Suitable additives for increasing the molecular weight of polycondensation polymers (chain extenders) are diepoxides, bis-oxazolines, bis-oxazolones, bis-oxazines, diisocyanates, dianhydrides, bis-acyllactams, bis-maleimides, dicyanates, carbodiimides. Other suitable chain extenders are polymeric compounds such. B. polystyrene-polyacrylate-polyglycidyl (meth) acrylate copolymers, polystyrene-maleic anhydride copolymers and polyethylene-maleic anhydride copolymers.
Geeignete Additive zur Erhöhung der elektrischen Leitfähigkeit sind beispiels weise die erwähnten Antistatika, Ruß und Kohlenstoffverbindungen wie Koh- lenstoff-Nanoröhrchen und Graphen, Metallpulver wie z.B. Kupferpulver und leitfähige Polymere wie bsp. Polypyrrole, Polyaniline und Polythiophene. Geig- nete Additive zur Erhöhung der thermischen Leitfähigkeit sind beispielsweise Aluminumnitride und Bornitride. Suitable additives for increasing the electrical conductivity are, for example, the aforementioned antistatic agents, soot and carbon compounds such as carbon nanotubes and graphene, metal powder such as copper powder and conductive polymers such as Polypyrroles, polyanilines and polythiophenes. Suitable additives for increasing the thermal conductivity are, for example, aluminum nitrides and boron nitrides.
Geeignete Infrarot-aktive Additive sind beispielsweise Aluminumsilikate, Hyd rotalcite oder Farbstoffe wie Phthalocyanine oder Anthrachinone. Suitable infrared-active additives are, for example, aluminum silicates, hydrotalcites or dyes such as phthalocyanines or anthraquinones.
Geeignete Entformungshilfsmittel sind beispielsweise Silikone, Seifen und Wachse wie z.B. Montanwachse. Suitable mold release agents are, for example, silicones, soaps and waxes such as montan waxes.
Geeignete Schlagzähigkeitsverbesserer sind z.B. Ethylen-Copolymere mit Ac- rylaten, Methacrylaten und/oder ethylenisch ungesättigten Carbonsäuren, die ganz oder teilweise z.B. mit Zink neutralisiert sein können oder Copolymere aus Ethylen, Propylen und Dienen, sowie Kern-Schale-Partikel z.B. aus Polybutylac- rylat und Polymethylmethacrylat. Suitable impact modifiers are, for example, ethylene copolymers with acrylates, methacrylates and / or ethylenically unsaturated carboxylic acids, which can be completely or partially neutralized, for example with zinc, or copolymers of ethylene, propylene and dienes, and core-shell particles, for example of polybutyl acrylate and polymethyl methacrylate.
Kompatibilisatoren oder Verträglichkeitsmacher werden beispielsweise bei thermodynamisch nicht mischbaren Blends oder auch bei Rezyklatmischungen eingesetzt und enthalten Strukturelemente der jeweiligen Blendkomponenten, die gemischt werden. Geeignete Kompatibilisatoren für Polyolefin-Mischungen sind beispielsweise Olefin-Blockcopolymere, bestend aus Ethylen, Propylen und alpha-Olefinen wie z:B. 1-Octen. Andere Kompatibilisatoren insbesondere zur Kompatibilisierung von polaren, wie PET oder Polyamide und unpolaren, wie PP oder PE Polymeren sind beispielsweise Polypropylen-g- Maleinsäurean hydrid, Polyethylen-g-Maleinsäureanhydrid, Polypropylen-g-Acrylsäure, Po- lyethylen-g-Acrylsäure, Poly(ethylen-co-maleinsäureanhydrid), SBS-g-Malain- säureanhydrid oder SEBS-g-Maleinsäureanhydrid. Compatibilizers or compatibilizers are used, for example, in thermodynamically immiscible blends or also in recycled mixtures and contain structural elements of the respective blend components that are mixed. Suitable compatibilizers for polyolefin mixtures are, for example, olefin block copolymers consisting of ethylene, propylene and alpha-olefins such as, for example. 1-octene. Other compatibilizers, especially for compatibilizing polar, such as PET or polyamides, and non-polar, such as PP or PE polymers are, for example, polypropylene-g-maleic anhydride, polyethylene-g-maleic anhydride, polypropylene-g-acrylic acid, polyethylene-g-acrylic acid, poly (ethylene-co-maleic anhydride), SBS-g-maleic anhydride or SEBS-g-maleic anhydride.
Geeignete Vernetzungsmittel sind beispielsweise Peroxide wie Dialkylperoxide, Alkyl-aryl-peroxide, Peroxyester, Peroxycarbonate, Diacylproxide, Peroxyke- tale, Silane wie z.B. Vinyltrimethoxysilan, Vinyltriethoxysilan, Vinyltriacetoxy- silan, Vinyltris(2-methoxyethoxy)silan, 3-Methacryloyloxypropyltrimethoxy- silan, Vinyldimethoxymethylsilan oder Ethylen-Vinylsilan-Copolymere. Suitable crosslinking agents are, for example, peroxides such as dialkyl peroxides, alkylaryl peroxides, peroxyesters, peroxycarbonates, diacylproxides, peroxyketals, silanes such as, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltris (2-methoxyethimoxy) silane, 3-methoxyethylethyltrisylane, vinyldoxymethyltris (2-methoxyethimoxy) silane, 3-methoxyethyl-tri-methoxy-tri-methoxy-methyl propane or ethylene-vinylsilane copolymers.
Geeignete Prodegradantien sind Additive, die einen Abbau eines Polymeren in der Umwelt gezielt beschleunigen oder kontrollieren. Beispiele sind Übergangs metallfettsäureester, z.B. von Mangan oder Eisen, die einen oxidativen und/o der photooxidativen Abbau z.B. von Polyolefinen beschleunigen oder Enzyme, die einen hydrolytischen Abbau z.B. von aliphatischen Polyestern induzieren. Suitable prodegradants are additives that break down a polymer in Accelerate or control the environment in a targeted manner. Examples are transition metal fatty acid esters, for example of manganese or iron, which accelerate oxidative and / or photooxidative degradation, for example of polyolefins, or enzymes which induce hydrolytic degradation, for example of aliphatic polyesters.
Geeignete chemische Treibmittel sind beispielsweise Azoverbindungen wie Azodicarbonsäurediamid, Sulfonylsemicarbazide wie p-Toluolsulfonylsemi- carbazid, Tetrazole wie 5-Phenyltetrazol, Hydrazide wie p-Toluolsulfonylhydra- zid, 4,4'-Oxibis(benzolsulfonyl)hydrazid, N-Nitrosoverbindungen wie N,N'-Di- nitrosopentamethylentetramin oder Carbonate wie z.B. Natriumhydrogencar bonat oder Zinkcarbonat. Suitable chemical blowing agents include azo compounds such as azodicarbonamide, sulfonyl semicarbazides such as p-Toluolsulfonylsemi- carbazide, tetrazoles such as 5-phenyltetrazole, hydrazides such as p-Toluolsulfonylhydra- zid, 4,4 '-Oxibis (benzenesulfonyl) hydrazide, N-nitroso compounds such as N, N' -Di- nitrosopentamethylenetetramine or carbonates such as sodium hydrogen carbonate or zinc carbonate.
Geeignete Slip-Agents sind beispielsweise Amidwachse wie Erucasäureamid o- der Ölsäureamid. Suitable slip agents are, for example, amide waxes such as erucic acid amide or oleic acid amide.
Geeignete Antiblock-Mittel sind beispielsweise Silica, Talk oder Zeolithe. Suitable antiblocking agents are, for example, silica, talc or zeolites.
Geeignete Antifogging-Additive sind beispielsweise ethoxylierte Sorbitanester, ethoxylierte Fettsäurealkohole oder ethoxylierte Alkylaminester. Suitable anti-fogging additives are, for example, ethoxylated sorbitan esters, ethoxylated fatty acid alcohols or ethoxylated alkylamine esters.
Geeignete Biozide sind beispielsweise quaternäre Ammoniumsalze oder Silber- salze, kolloidales Silber oder Silberkomplexe oder auch Naturstoffderivate wie bsp. Chitosan Suitable biocides are, for example, quaternary ammonium salts or silver salts, colloidal silver or silver complexes or natural product derivatives such as Chitosan
Geeignete Aldehyd-Scavenger sind Amine, Hydroxylamine, Polyvinylalkohol, Zeolithe oder Cyclodextrine, geeignete Formaldehyd-Scavenger sind Melamin derivate wie z.B. Benzoguanamin oder Harnstoffderivate wie Allantoin. Suitable aldehyde scavengers are amines, hydroxylamines, polyvinyl alcohol, zeolites or cyclodextrins, suitable formaldehyde scavengers are melamine derivatives such as benzoguanamine or urea derivatives such as allantoin.
Geeignete geruchsbindende oder geruchsverhindernde Substanzen sind Sili kate wie Calciumsilikat, Zeolithe oder Salze von Hydroxyfettsäuren wie z.B. Zin- kriceneolat. Suitable odor-binding or odor-preventing substances are silicates such as calcium silicate, zeolites or salts of hydroxy fatty acids such as zinc cricene enolate.
Geeignete Markierungsmittel sind beispielsweise Fluoreszenzfarbstoffe oder seltene Erden. Weiter betrifft die vorliegende Erfindung ein Verfahren zur Stabilisierung von Kunststoffen gegen oxidativen, thermischen und/oder aktinischen Abbau, bei dem mindestens ein phenolisch substituiertes Zuckerderivat, wobei das Zucker derivat einen von einem Zucker abgeleiteten Grundkörper aufweist, sowie min destens einen Substituenten gemäß allgemeiner Formel I Suitable marking agents are, for example, fluorescent dyes or rare earths. The present invention further relates to a method for stabilizing plastics against oxidative, thermal and / or actinic degradation, in which at least one phenolically substituted sugar derivative, the sugar derivative having a base substance derived from a sugar, and at least one substituent according to general formula I.
Formel I wobei R1 und R2 bei jedem Auftreten gleich oder verschieden sind und ausge wählt sind aus der Gruppe bestehend aus Wasserstoff und linearen oder ver zweigten Alkylreste, mit der Maßgabe, dass mindestens ein Rest R1 oder R2 nicht Wasserstoff ist, Formula I where R 1 and R 2 are identical or different on each occurrence and are selected from the group consisting of hydrogen and linear or branched alkyl radicals, with the proviso that at least one radical R 1 or R 2 is not hydrogen,
X eine Alkylengruppe mit 1 bis 18 Kohlenstoffatomen oder eine chemische Bindung, X is an alkylene group with 1 to 18 carbon atoms or a chemical bond,
Y eine Gruppierung ausgewählt aus der Gruppe bestehend aus den nachfolgenden Gruppierungen wobei die Gruppierung X an den links dargestellten Terminus der oben abgebil deten Gruppierungen Y gebunden ist, und wobei der von einem Zucker abge leiteten Grundkörper des phenolisch substituierten Zuckerderivates mindes tens 3 unsubstituierte Hydroxygruppen aufweist und/oder der von einem Zu cker abgeleitete Grundkörper des phenolisch substituierten Zuckerderivates mindestens 4 Kohlenstoffatome und mindestens 2, vorzugsweise mindestens 3 unsubstituierte Hydroxygruppen aufweist, in einen Kunststoff eingearbeitet wird. Bezüglich des phenolisch substituierten Zuckerderivates gemäß der allgemei nen Formel I wird auf die zuvor gemachten Ausführungen verwiesen. Y is a group selected from the group consisting of the following groupings where the group X is bound to the terminus shown on the left of the groupings Y shown above, and where the base of the phenolically substituted sugar derivative derived from a sugar has at least 3 unsubstituted hydroxyl groups and / or the base of the phenolically substituted one derived from a sugar Sugar derivative has at least 4 carbon atoms and at least 2, preferably at least 3 unsubstituted hydroxyl groups, is incorporated into a plastic. With regard to the phenolic substituted sugar derivative according to the general formula I, reference is made to the statements made above.
Bevorzugt wird das erfindungsgemäße Additiv, das als Pulver, Flüssigkeit, ÖL, kompaktiert, auf einem Trägermaterial, als Granulat, Lösung oder Schuppen vorliegen kann mit dem zu stabilisierenden Polymeren gemischt, die Polymer matrix in die Schmelze überführt und anschließend abgekühlt. Alternativ hierzu ist es ebenso möglich, das Additiv in einem schmelzflüssigen Zustand in eine Polymerschmelze einzubringen. The additive according to the invention, which can be present as a powder, liquid, oil, compacted, on a carrier material, as granules, solution or flakes, is preferably mixed with the polymer to be stabilized, the polymer matrix is transferred into the melt and then cooled. As an alternative to this, it is also possible to introduce the additive in a molten state into a polymer melt.
Für den Fall, dass der Polymerzusammensetzung weitere Bestandteile zugefügt werden, können diese separat, in Form von Flüssigkeiten, Pulvern, Granulaten oder kompaktierten Produkten oder zusammen mit der erfindungsgemäßen Additivzusammensetzung wie zuvor beschrieben den Polymeren zugesetzt werden. In the event that further constituents are added to the polymer composition, these can be added to the polymers separately, in the form of liquids, powders, granules or compacted products or together with the additive composition according to the invention as described above.
Die Einarbeitung der oben beschriebenen Additivzusammensetzung und ggf. der zusätzlichen Additive in den Kunststoff erfolgt durch übliche Verarbeitungs methoden, wobei das Polymere aufgeschmolzen und mit der erfindungsgemä ßen Additivzusammensetzung und den ggf. weiteren Zusätzen gemischt wird, vorzugsweise durch Mischer, Kneter und Extruder. Als Verarbeitungsmaschinen bevorzugt sind Extruder wie z.B. Einschneckenextruder, Zweischneckenextru der, Planetwalzenextruder, Ringextruder, Co-Kneter, die vorzugsweise mit ei ner Vakuumentgasung ausgestattet sind. Die Verarbeitung kann dabei unter Luft oder ggf. unter Inertgasbedingungen erfolgen. The above-described additive composition and any additional additives are incorporated into the plastic by customary processing methods, the polymer being melted and mixed with the additive composition according to the invention and any further additives, preferably by mixers, kneaders and extruders. Preferred processing machines are extruders such as single-screw extruders, twin-screw extruders, planetary roller extruders, ring extruders, co-kneaders, which are preferably equipped with vacuum degassing. Processing can take place under air or, if necessary, under inert gas conditions.
Weiterhin können die erfindungsgemäßen Additivzusammensetzungen in Form von sogenannten Masterbatchen oder Konzentraten, die beispielsweise 10-90 % der erfindungsgemäßen Zusammensetzungen in einem Polymeren enthal ten, hergestellt und eingebracht werden. Furthermore, the additive compositions according to the invention can be produced and introduced in the form of so-called masterbatches or concentrates which, for example, contain 10-90% of the compositions according to the invention in a polymer.
Die Erfindung betrifft desweiteren eine Formmasse oder ein Formteil, herstell bar aus einer wie voranstehend beschriebenen erfindungsgemäßen Kunststoff zusammensetzung insbesondere in Form von Spritzgussteilen, Folien, Filmen, Lacken, Beschichtungen, Schäumen, Fasern, Kabeln, Rohren, Profilen, Hohlkör- pern, Bändchen, Membranen, z.B. Geomembranen, Schmierstoffen, Farbmit teln und/oder Klebstoffen, die über Extrusion, Spritzguss, Blasformen, Kaland rieren, Pressverfahren, Spinnprozesse und/oder Rotomoulding hergestellt wer den z.B. für die Elektroindustrie, für die Bauindustrie, für die Transportindust rie, für medizinische Anwendungen, für Haushalts- und Elektrogeräte, für Fahr zeugteile, für Konsumartikel, für Verpackungen, für Möbel, und/oder für Texti lien. Ein weiterer Einsatzbereich sind Lacke, Farben und Beschichtungen (Coatings), sowie Fette und Öle. The invention further relates to a molding compound or a molded part, producible from a plastic composition according to the invention as described above, in particular in the form of injection molded parts, foils, films, lacquers, coatings, foams, fibers, cables, pipes, profiles, hollow bodies pern, ribbons, membranes, e.g. geomembranes, lubricants, colorants and / or adhesives that are manufactured via extrusion, injection molding, blow molding, calendering, pressing processes, spinning processes and / or rotomoulding, e.g. for the electrical industry, for the construction industry, for Transport industry, for medical applications, for household and electrical appliances, for vehicle parts, for consumer goods, for packaging, for furniture and / or for textiles. Another area of application are paints, paints and coatings, as well as fats and oils.
Handelt es sich bei den organischen Materialien um Öle und Fette, so können diese auf der Basis von Mineralölen, Pflanzenfetten oder Tierfetten sein oder auch Öle, Fette oder Wachse auf der Basis von z.B. synthetischen Estern. Pflanz liche Öle und Fette sind beispielsweise Palmöl, Olivenöl, Rapsöl, Leinöl, Soja bohnenöl, Sonnenblumenöl, Rizinusöl, Tierfette sind beispielsweise Fischöle o- der Rindertalg. If the organic materials are oils and fats, they can be based on mineral oils, vegetable fats or animal fats or oils, fats or waxes based on e.g. synthetic esters. Vegetable oils and fats are, for example, palm oil, olive oil, rapeseed oil, linseed oil, soybean oil, sunflower oil, castor oil, animal fats are, for example, fish oils or beef tallow.
Die erfindungsgemäßen Verbindungen können weiterhin als Stabilisatoren von Schmierstoffen, Hydraulikölen, Motorenölen, Turbinenölen, Getriebeölen Me tallbearbeitungsflüssigkeiten oder als Schmierfette eingesetzt werden. Diese mineralischen oder synthetischen Schmierstoffe basieren vorwiegend auf Koh lenwasserstoffen. The compounds according to the invention can also be used as stabilizers for lubricants, hydraulic oils, motor oils, turbine oils, gear oils, metal processing fluids or as lubricating greases. These mineral or synthetic lubricants are primarily based on hydrocarbons.
Weiterhin können die erfindungsgemäßen Antioxidantien zur Stabilisierung von Monomeren eingesetzt werden, um ggf. eine vorzeitige Polymerisation o- der Oxidation zu verhindern, z.B. für Styrol oder Acrylate oder für die Stabili sierung von Polyolen bei der Polyurethansynthese. Furthermore, the antioxidants according to the invention can be used to stabilize monomers in order to prevent premature polymerization or oxidation if necessary, e.g. for styrene or acrylates or for the stabilization of polyols in polyurethane synthesis.
Die vorliegende Erfindung betrifft zudem eine Stabilisator-Zusammensetzung zur Stabilisierung von Kunststoffen gegen oxidativen, thermischen und/oder aktinischen Abbau, bestehend aus mindestens einem phenolisch substituierten Zuckerderivat, wobei das Zuckerderivat einen von einem Zucker abgeleiteten Grundkörper aufweist, sowie mindestens einen Substituenten gemäß allgemei ner Formel I Formel I wobei R1 und R2 bei jedem Auftreten gleich oder verschieden sind und ausge wählt sind aus der Gruppe bestehend aus Wasserstoff und linearen oder ver zweigten Alkylreste, mit der Maßgabe, dass mindestens ein Rest R1 oder R2 nicht Wasserstoff ist, The present invention also relates to a stabilizer composition for stabilizing plastics against oxidative, thermal and / or actinic degradation, consisting of at least one phenolic substituted sugar derivative, the sugar derivative having a base derived from a sugar, and at least one substituent according to the general formula I. Formula I where R 1 and R 2 are identical or different on each occurrence and are selected from the group consisting of hydrogen and linear or branched alkyl radicals, with the proviso that at least one radical R 1 or R 2 is not hydrogen,
X eine Alkylengruppe mit 1 bis 18 Kohlenstoffatomen oder eine chemische Bindung, X is an alkylene group with 1 to 18 carbon atoms or a chemical bond,
Y eine Gruppierung ausgewählt aus der Gruppe bestehend aus den nachfolgenden Gruppierungen wobei die Gruppierung X an den links dargestellten Terminus der oben abgebil deten Gruppierungen Y gebunden ist, und wobei der von einem Zucker abge leiteten Grundkörper des phenolisch substituierten Zuckerderivates mindes tens 3 unsubstituierte Hydroxygruppen aufweist und/oder der von einem Zu cker abgeleitete Grundkörper des pheno-lisch substituierten Zuckerderivates mindestens 4 Kohlenstoffatome und mindestens 2, vorzugsweise mindestens 3 unsubstituierte Hydroxygruppen aufweist, und mindestens einem primären Antioxidans und/oder mindestens einem sekundären Antioxidans. Y is a group selected from the group consisting of the following groupings where the group X is bound to the terminus shown on the left of the groupings Y shown above, and where the base of the phenolically substituted sugar derivative derived from a sugar has at least 3 unsubstituted hydroxyl groups and / or the base of the phenol derived from a sugar Lisch substituted sugar derivative has at least 4 carbon atoms and at least 2, preferably at least 3 unsubstituted hydroxyl groups, and at least one primary antioxidant and / or at least one secondary antioxidant.
Schließlich betrifft die vorliegende Erfindung ein phenolisch substituiertes Zu ckerderivat, wobei das Zuckerderivat einen von einem Zucker abgeleiteten Grundkörper aufweist, sowie mindestens einen Substituenten gemäß allgemei ner Formel I Finally, the present invention relates to a phenolically substituted sugar derivative, the sugar derivative having a base structure derived from a sugar, as well as at least one substituent according to formula I in general
Formel I wobei R1 und R2 bei jedem Auftreten gleich oder verschieden sind und ausge wählt sind aus der Gruppe bestehend aus Wasserstoff und linearen oder ver zweigten Alkylreste, mit der Maßgabe, dass mindestens ein Rest R1 oder R2 nicht Wasserstoff ist, Formula I where R 1 and R 2 are identical or different on each occurrence and are selected from the group consisting of hydrogen and linear or branched alkyl radicals, with the proviso that at least one radical R 1 or R 2 is not hydrogen,
X eine Alkylengruppe mit 1 bis 18 Kohlenstoffatomen oder eine chemische Bindung, X is an alkylene group with 1 to 18 carbon atoms or a chemical bond,
Y eine Gruppierung ausgewählt aus der Gruppe bestehend aus den nachfolgenden Gruppierungen Y is a group selected from the group consisting of the following groupings
wobei die Gruppierung X an den links dargestellten Terminus der oben abgebil deten Gruppierungen Y gebunden ist, und wobei der von einem Zucker abge leiteten Grundkörper des phenolisch substituierten Zuckerderivates mindes tens 3 unsubstituierte Hydroxygruppen aufweist und/oder der von einem Zu cker abgeleitete Grundkörper des pheno-lisch substituierten Zuckerderivates mindestens 4 Kohlenstoffatome und mindestens 2, vorzugsweise mindestens 3 unsubstituierte Hydroxygruppen aufweist. where the group X is bound to the terminus shown on the left of the groupings Y shown above, and where the base of the phenolically substituted sugar derivative derived from a sugar has at least 3 unsubstituted hydroxyl groups and / or the base of the phenol derived from a sugar Lisch substituted sugar derivative has at least 4 carbon atoms and at least 2, preferably at least 3 unsubstituted hydroxyl groups.
Bezüglich der speziellen und bevorzugten Ausführungsform des erfindungsge mäßen phenolisch substituierten Zuckerderivates wird auf die voranstehenden gemachten Ausführungen verwiesen. With regard to the special and preferred embodiment of the phenolically substituted sugar derivative according to the invention, reference is made to the statements made above.
Die vorliegende Erfindung wird anhand dem nachfolgenden Ausführungsbei spiel näher beschrieben, ohne die Erfindung hierauf zu beschränken. Ausführungsbeispiel The present invention is described in more detail with reference to the following Ausführungsbei, game without restricting the invention thereto. Embodiment
Zur Prüfung der Wirkung der erfindungsgemäßen Stabilisatoren wurde ein han delsübliches Polypropylen (Moplen HP 500N, Lyondell Basell Industries) in einer Pulver-Pulver Mischung mit den angegebenen Stabilisatoren homogenisiert und in einem Doppelschnecken-Microextruder (MC 5, Hersteller DSM) über 30 Minuten bei 200 °C und 90 Umdrehungen pro Minute im Kreislauf geführt und die Abnahme der Kraft aufgezeichnet. Die Kraft ist ein direktes Maß für das Mo lekulargewicht von Polypropylen, je geringer die Abnahme, desto höher die Sta bilisierungswirkung. To test the effect of the stabilizers according to the invention, a commercially available polypropylene (Moplen HP 500N, Lyondell Basell Industries) was homogenized in a powder-powder mixture with the specified stabilizers and in a twin-screw microextruder (MC 5, manufacturer DSM) for 30 minutes at 200 ° C and 90 revolutions per minute and recorded the decrease in force. The force is a direct measure of the molecular weight of polypropylene; the lower the decrease, the higher the stabilization effect.
Der Zusatz von 0.1 bis 0.3 % eines 3-(3,5-Di-tert-butyl-4-hydroxyphenyl)propi- onsäureesters von Mannit (> 90 % monosubstituiert), hergestellt durch Umes terung des 3-(3,5-Di-te/t-butyl-4-hydroxyphenyl)propionsäuremethylesters mit Mannit, führt im Vergleich zu einem Polypropylen ohne Zusatz oder zu einem Polypropylen, das nur Mannit enthält, zu einer erhöhten Verarbeitungsstabili sierung, d.h. zu einer höheren Restkraft. Eine weitere Verbesserung der Verar beitungsstabilität wird erreicht indem zu 0.2 % des 3-(3,5-Di-tert-butyl-4-hyd- roxyphenyl)propionsäureesters von Mannit 0.1 % primäres Antioxidans (Pen- taerythritol-tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionat) oder 0.1 % sekundäres Antioxidans (Tris-(2,4-di-tert-butylphenyl)phosphit) zugegeben werden. The addition of 0.1 to 0.3% of a 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid ester of mannitol (> 90% monosubstituted), produced by transesterification of the 3- (3,5-di -te / t-butyl-4-hydroxyphenyl) propionic acid methyl ester with mannitol, leads to increased processing stabilization, ie to a higher residual force, compared to a polypropylene without addition or to a polypropylene that contains only mannitol. A further improvement in the processing stability is achieved by adding 0.1% primary antioxidant (pentaerythritol tetrakis [3- (3rd)) to 0.2% of the 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid ester of mannitol , 5-di-tert-butyl-4-hydroxyphenyl) propionate) or 0.1% secondary antioxidant (tris- (2,4-di-tert-butylphenyl) phosphite) can be added.
In analoger Weise werden durch Umesterung von 3-(3,5-Di-tert-butyl-4-hydro- xyphenyl)propionsäuremethylesters mit Erythrit, myo-lnosit und Sorbit die mo nofunktionellen Derivate mit mehr als 80 % Monosubstitution erhalten. In an analogous manner, the monofunctional derivatives with more than 80% monosubstitution are obtained by transesterifying 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid methyl ester with erythritol, myo-inositol and sorbitol.
Der 3-(3,5-Di-tert-butyl-4-hydroxyphenyl)propionsäureesters von Mannit (> 90 % monosubstituiert) wurde weiterhin bei den angegebenen Verarbeitungstem peraturen den folgenden Polymeren in einer Konzentration von 0,2 % zugege ben, 30 Minuten verarbeitet und der Kraftverlauf bestimmt: The 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid ester of mannitol (> 90% monosubstituted) was also added to the following polymers at the specified processing temperatures in a concentration of 0.2%, 30 minutes processed and the force curve determined:
HDPE, 230 °C HDPE, 230 ° C
LLDPE, 200 °C LLDPE, 200 ° C
Polystyrol, 230 °C Polystyrene, 230 ° C
ABS, 230 °C ABS, 230 ° C
PC/ABS, 250 °C PET, 260 °C (myo-lnosit-Derivat) PC / ABS, 250 ° C PET, 260 ° C (myo-inositol derivative)
PA-6.6, 260 °C (myo-lnosit-Derivat) PA-6.6, 260 ° C (myo-inositol derivative)
Polyolefin-Rezyklat, bestehend aus einer PE/PP-Mischung, 210 °C Recycled polyolefin, consisting of a PE / PP mixture, 210 ° C
In allen Fällen lässt sich durch einen konstanten Kraftverlauf über die Prüfzeit eine Stabilisierungswirkung mit den erfindungsgemäßen Zusätzen im Gegen satz zu den Ausgangspolymeren ohne Zusatz nachweisen. In all cases, a stabilizing effect with the additives according to the invention in contrast to the starting polymers without additives can be demonstrated by a constant force profile over the test time.

Claims

Patentansprüche Claims
1. Verwendung mindestens eines phenolisch substituierten Zuckerderiva tes, wobei das Zuckerderivat einen von einem Zucker abgeleiteten Grundkörper aufweist, sowie mindestens einen Substituenten gemäß allgemeiner Formel I 1. Use of at least one phenolically substituted sugar derivative, the sugar derivative having a basic structure derived from a sugar, and at least one substituent according to general formula I.
Formel I Formula I.
wobei in which
R1 und R2 bei jedem Auftreten gleich oder verschieden sind und ausgewählt sind aus der Gruppe bestehend aus Wasserstoff und linearen oder verzweigten Alkylreste, mit der Maßgabe, dass mindestens ein Rest R1 oder R2 nicht Wasserstoff ist,R 1 and R 2 are identical or different on each occurrence and are selected from the group consisting of hydrogen and linear or branched alkyl radicals, with the proviso that at least one radical R 1 or R 2 is not hydrogen,
X eine Alkylengruppe mit 1 bis 18 Kohlenstoffatomen oder eine chemische Bindung, X is an alkylene group with 1 to 18 carbon atoms or a chemical bond,
Y eine Gruppierung ausgewählt aus der Gruppe bestehend aus den nachfolgenden Gruppierungen Y is a group selected from the group consisting of the following groupings
H H H H
wobei die Gruppierung X an den links dargestellten Terminus der oben abgebildeten Gruppierungen Y gebunden ist, und wobei der von einem Zucker abgeleiteten Grundkörper des pheno lisch substituierten Zuckerderivates mindestens 3 unsubstituierte Hy droxygruppen aufweist und/oder der von einem Zucker abgeleitete Grundkörper des phenolisch substituierten Zuckerderivates mindes- tens 4 Kohlenstoffatome und mindestens 2, vorzugsweise mindestens 3 unsubstituierte Hydroxygruppen aufweist, where the group X is bound to the terminus shown on the left of the groupings Y shown above, and where the sugar-derived base of the phenolic substituted sugar derivative has at least 3 unsubstituted hydroxyl groups and / or the base of the sugar-derived phenolic substituted sugar derivative at least - has at least 4 carbon atoms and at least 2, preferably at least 3 unsubstituted hydroxyl groups,
als Stabilisator von organischen Materialien, insbesondere Kunststof fen gegen oxidativen, thermischen und/oder aktinischen Abbau. as a stabilizer of organic materials, especially plastics, against oxidative, thermal and / or actinic degradation.
2. Verwendung nach Anspruch 1, dadurch gekennzeichnet, dass der von einem Zucker abgeleitete Grundkörper ein Monosaccharid, ein Oli gosaccharid oder ein Polysaccharid mit mindestens 4 Kohlenstoffato men darstellt. 2. Use according to claim 1, characterized in that the base body derived from a sugar is a monosaccharide, an oligosaccharide or a polysaccharide with at least 4 carbon atoms.
3. Verwendung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das phenolisch substituierte Zuckerderivat ma ximal 10, bevorzugt maximal 5, weiter bevorzugt maximal 3, besonders bevorzugt 1 oder 2 Substituenten gemäß Formel I umfasst. 3. Use according to one of the preceding claims, characterized in that the phenolically substituted sugar derivative comprises a maximum of 10, preferably a maximum of 5, more preferably a maximum of 3, particularly preferably 1 or 2, substituents according to formula I.
4. Verwendung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der von einem Zucker abgeleitete Grundkörper mindestens ein Alditol, ein Cyclitol, eine Zuckersäure oder ein Amino zucker mit mindestens 4 Kohlenstoffatomen ist. 4. Use according to one of the preceding claims, characterized in that the basic body derived from a sugar is at least one alditol, a cyclitol, a sugar acid or an amino sugar with at least 4 carbon atoms.
5. Verwendung nach vorhergehendem Anspruch, dadurch gekennzeich net, dass das mindestens eine Alditol die Summenformel 5. Use according to the preceding claim, characterized in that the at least one alditol has the empirical formula
HOCH [CH(OH)]nCH OH, HIGH [CH (OH)] n CH OH,
Ri-OCH2[CH(OH)]nCH2OH, oder Ri-OCH 2 [CH (OH)] n CH 2 OH, or
HOCH2[CH(OH)]n[CH(ORi)]CH2OH HIGH 2 [CH (OH)] n [CH (ORi)] CH 2 OH
mit n = 2-6, bevorzugt n = 3-5 aufweist, wobei Ri ein gegebenenfalls substituierter Zuckerrest ist. with n = 2-6, preferably n = 3-5, where Ri is an optionally substituted sugar residue.
6. Verwendung nach einem der beiden vorhergehenden Ansprüche, dadurch gekennzeichnet, dass 6. Use according to one of the two preceding claims, characterized in that
das mindestens eine Alditol ausgewählt ist aus der Gruppe bestehend aus Threit, Erythrit, Galactit, Mannit, Ribit, Sorbit, Xylit, Arabit, Isomalt, Lactit, Maltit, Maltotritol und hydrierte Oligo- und Polysaccharide mit Polyol-Endgruppen und Mischungen hiervon, wobei das mindestens eine Alditol vorzugsweise ausgewählt ist aus der Gruppe bestehend aus Erythrit, Mannit, Isomalt, Maltit und Mischungen hiervon, das mindestens eine Cyclitol ausgewählt ist aus der Gruppe bestehend aus Inositol, Quercitol, Viscumitol, Bornesitol, Conduritol, Ononitol, Pinitol, Pinpollitol, Ciceritol, Quebrachitol, Chinasäure, Shikimisäure und Valienol wobei das mindestens eine Cyclitol vorzugsweise myo- Inosit ist, the at least one alditol is selected from the group consisting of threitol, erythritol, galactitol, mannitol, ribitol, sorbitol, xylitol, arabitol, isomalt, lactitol, maltitol, maltotritol and hydrogenated oligo- and polysaccharides with polyol end groups and mixtures thereof, the at least an alditol is preferably selected from the group consisting of erythritol, mannitol, isomalt, maltitol and mixtures thereof, the at least one cyclitol is selected from the group consisting of inositol, quercitol, viscumitol, bornesitol, conduritol, ononitol, pinitol, pinpollitol, ciceritol, Quebrachitol, quinic acid, shikimic acid and valienol, the at least one cyclitol preferably being myo-inositol,
die mindestens eine Zuckersäure eine Aldonsäure, wie Allonsäure, Alt- ronsäure, Gluconsäure, Mannonsäure, Gulonsäure, Idonsäure, Galak- tonsäure, Talonsäure, Ribonsäure, Arabonsäure, Xylonsäure, Lyxonsäu- re, Erythronsäure oder Threonsäure oder Aldarsäuren wie Schleimsäu re oder Glucarsäure sowie Mischungen und Kombinationen hiervon ist, und/oder the at least one sugar acid is an aldonic acid such as allonic acid, altronic acid, gluconic acid, mannonic acid, gulonic acid, idonic acid, galactonic acid, talonic acid, ribonic acid, arabonic acid, xylonic acid, lyxonic acid, erythronic acid or threonic acid or aldaric acids such as mucic acid and mixtures or glucaric acid and combinations thereof, and / or
der mindestens eine Aminozucker ein Mono- oder Diaminozucker ist und insbesondere ausgewählt ist aus der Gruppe bestehend aus 1- Amino-l-deoxy-alditolen, wie z.B. 1-Amino-l-deoxy-galactit, 1-Amino- 1-deoxy-mannit, 1-Amino-l-deoxy-sorbit, 1-Amino-l-deoxy-maltit o- der a,(j-Diamino-a,(j-dideoxyalditolen, wie z.B. l,6-Diamino-l,6- dideoxysorbit. the at least one amino sugar is a mono- or diamino sugar and is in particular selected from the group consisting of 1-amino-1-deoxy-alditols, such as, for example, 1-amino-1-deoxy-galactitol, 1-amino-1-deoxy-mannitol , 1-amino-l-deoxy-sorbitol, 1-amino-l-deoxy-maltitol or a, (j-diamino-a, (j-dideoxyalditols, such as l, 6-diamino-1,6-dideoxysorbitol .
7. Verwendung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass R1 und R2 gleich oder verschieden sind und aus gewählt sind aus der Gruppe bestehend aus tert.-Butyl und Methyl. 7. Use according to any one of the preceding claims, characterized in that R 1 and R 2 are identical or different and are selected from the group consisting of tert-butyl and methyl.
8. Verwendung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das phenolisch substituierte Zuckerderivat aus gewählt ist aus der Gruppe bestehend aus den nachfolgenden Molekü len 8. Use according to one of the preceding claims, characterized in that the phenolically substituted sugar derivative is selected from the group consisting of the following molecules
sowie Mischungen und Kombinationen hiervon. as well as mixtures and combinations thereof.
9. Verwendung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das mindestens eine phenolisch substituierte Zu ckerderivat in einer Gesamtmenge von 0,01 bis 10 Gew.-%, bevorzugt 0,05 bis 5 Gew.-%, besonders bevorzugt von 0,1 bis 3 Gew.-%, bezogen auf den Kunststoff eingesetzt wird. 9. Use according to one of the preceding claims, characterized in that the at least one phenolically substituted sugar derivative in a total amount of 0.01 to 10 wt .-%, preferably 0.05 to 5 wt .-%, particularly preferably 0, 1 to 3% by weight, based on the plastic, is used.
10. Verwendung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das mindestens eine phenolisch substituierte Zu ckerderivat in Kombination mit einem sich vom mindestens einen phe nolisch substituierten Zuckerderivat unterscheidenden primären und/oder sekundären Antioxidans verwendet wird, wobei bevorzugt das mindestens eine ausgewählt ist aus der Gruppe bestehend aus phenolischen Antioxidantien, Aminen, Lactonen und Mischungen hier von, und 10. Use according to one of the preceding claims, characterized in that the at least one phenolically substituted sugar derivative is used in combination with a primary and / or secondary antioxidant which differs from the at least one phenolically substituted sugar derivative, the at least one preferably being selected from the group consisting of phenolic antioxidants, amines, lactones and mixtures here of, and
das mindestens eine sekundäre Antioxidans ausgewählt ist aus der Gruppe bestehend aus Phosphorverbindungen, insbesondere Phosphi- ten und Phosphoniten, Organo-Schwefelverbindungen, insbesondere Sulfiden und Disulfiden, sowie Mischungen hiervon. the at least one secondary antioxidant is selected from the group consisting of phosphorus compounds, in particular phosphites and phosphonites, organosulfur compounds, in particular sulfides and disulfides, and mixtures thereof.
11. Verwendung nach vorhergehendem Anspruch, dadurch gekennzeich net, dass das mindestens eine primäre und/oder sekundäre Antioxi dans in einer Gesamtmenge, bezogen auf die Gesamtmenge des min destens einen phenolisch substituierten Zuckerderivates von 0,01 bis 5 Gew. -Teilen, bevorzugt von 0,02 bis 3 Gew. -Teilen, besonders bevor zugt von 0,05 bis 2 Gew. -Teilen eingesetzt wird. 11. Use according to the preceding claim, characterized in that the at least one primary and / or secondary antioxidant in a total amount, based on the total amount of the min least one phenolic substituted sugar derivative of 0.01 to 5 parts by weight, preferably of 0.02 to 3 parts by weight, particularly before given from 0.05 to 2 parts by weight. Is used.
12. Verwendung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass bezogen auf 91 bis 99,94 Gew. -Teile, bevorzugt 98,5 bis 99,91 Gew. -Teile des Kunststoffs 12. Use according to one of the preceding claims, characterized in that based on 91 to 99.94 parts by weight, preferably 98.5 to 99.91 parts by weight of the plastic
(A) 0,02 bis 3 Gew. -Teile, bevorzugt 0,03 bis 0,5 Gew. -Teile des min destens einen phenolisch substituierten Zuckerderivates, und (A) 0.02 to 3 parts by weight, preferably 0.03 to 0.5 parts by weight of the min least one phenolically substituted sugar derivative, and
(B) 0,04 bis 6 Gew. -Teile, bevorzugt 0,06 bis 1 Gew. -Teile des mindes tens einen primären Antioxidans und/oder des mindestens einen sekundären Antioxidans (B) 0.04 to 6 parts by weight, preferably 0.06 to 1 part by weight, of the at least one primary antioxidant and / or of the at least one secondary antioxidant
eingebracht werden. be introduced.
13. Verwendung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der Kunststoff ein Thermoplast ist und insbeson dere ausgewählt ist aus der Gruppe bestehend aus 13. Use according to one of the preceding claims, characterized in that the plastic is a thermoplastic and is in particular selected from the group consisting of
a) Polymeren aus Olefinen oder Diolefinen, wie z.B. Polyethylen, ins besondere LDPE, LLDPE, VLDPE, ULDPE, MDPE, HDPE und UHMWPE, Metallocen-PE (m-PE), Polypropylen, Poylisobutylen, Poly-4-methyl-penten-l, Polybutadien, Polyisopren, Polycyclooc- ten, Polyalkylen-Kohlenmonoxid-Copolymeren, sowie entspre chenden Copolymeren in Form von statistischen oder Blockstruktu ren wie z.B. Polypropylen-Polyethylen (EP), EPM oder EPDM, Ethyl- en-Vinylacetat (EVA), Ethylen-Acrylester, wie z.B. Ethylen- Butylacrylat, Ethylen-Acrylsäure-Glycidylacrylat, und entsprechen den Propfpolymeren wie z.B. Polypropylen-g-Maleinsäureanhydrid, Polypropylen-g-Acrylsäure und Polyethylen-g-Acrylsäure, b) Polystyrol, Polymethylstyrol, Polyvinylnaphthalin, Styrol-Butadien (SB), Styrol-Butadien-Styrol (SBS), Styrol-Ethylen-Butylen-Styrol (SEBS), Styrol-Ethylen-Propylen-Styrol, Styrolisopren, Styrol- Isopren-Styrol (SIS), Styrol-butadien-acrylnitril (ABS), Styrol- acrylnitril-acrylat (ASA), Styrol-Ethylen, Styrol-Maleinsäure- an ydrid-Polymeren einschließlich entsprechenden Pfropfcopoly meren wie z.B. Styrol auf Butadien, Maleinsäureanhydrid auf SBS oder SEBS, sowie Pfropfcopolymeren aus Methylmethacrylat, Sty rol-Butadien und ABS (MABS), a) Polymers made from olefins or diolefins, such as polyethylene, in particular LDPE, LLDPE, VLDPE, ULDPE, MDPE, HDPE and UHMWPE, metallocene PE (m-PE), polypropylene, polyisobutylene, poly-4-methyl-pentene-1 , Polybutadiene, polyisoprene, polycyclooc- ten, polyalkylene-carbon monoxide copolymers, as well as corresponding copolymers in the form of random or block structures such as polypropylene-polyethylene (EP), EPM or EPDM, ethylene-vinyl acetate (EVA), ethylene Acrylic esters, such as ethylene-butyl acrylate, ethylene-acrylic acid-glycidyl acrylate, and correspond to graft polymers such as polypropylene-g-maleic anhydride, polypropylene-g-acrylic acid and polyethylene-g-acrylic acid, b) polystyrene, polymethylstyrene, polyvinylnaphthalene, styrene-butadiene ( SB), styrene-butadiene-styrene (SBS), styrene-ethylene-butylene-styrene (SEBS), styrene-ethylene-propylene-styrene, styrene isoprene, styrene Isoprene-styrene (SIS), styrene-butadiene-acrylonitrile (ABS), styrene-acrylonitrile-acrylate (ASA), styrene-ethylene, styrene-maleic acid an ydride polymers including corresponding graft copolymers such as styrene on butadiene, maleic anhydride on SBS or SEBS, as well as graft copolymers made of methyl methacrylate, styrene butadiene and ABS (MABS),
c) Polymeren von ungesättigten Estern wie z.B. Polyacrylate und Po- lymethacrylate wie Polymethylmethacrylat (PMMA), Polybutylac- rylat, Polylaurylacrylat, Polystearylacrylat, Polyacrylnitril, Polyac rylamide, und entsprechenden Copolymeren wie z.B. Polyacryl- nitril-Polyalkylacrylat, c) Polymers of unsaturated esters such as polyacrylates and polymethacrylates such as polymethyl methacrylate (PMMA), polybutyl acrylate, polylauryl acrylate, polystearyl acrylate, polyacrylonitrile, polyacrylamides, and corresponding copolymers such as polyacrylonitrile-polyalkyl acrylate,
d) Polymeren aus ungesättigten Alkoholen und Derivaten, wie z.B. Po lyvinylalkohol, Polyvinylacetat, Polyvinylbutyral, d) Polymers made from unsaturated alcohols and derivatives, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral,
e) Polyacetalen, wie z.B. Polyoxymethylen (POM), und entsprechen den Copolymeren, wie z.B. Copolymere mit Butanal, e) Polyacetals, such as polyoxymethylene (POM), and correspond to copolymers, such as copolymers with butanal,
f) Polyphenylenoxiden und Blends von diesen mit Polystyrol oder Po lyamiden, f) Polyphenylene oxides and blends of these with polystyrene or polyamides,
g) Polymeren von cyclischen Ethern wie z.B. Polyethylenglycol, Polyp- ropylenglycol, Polyethylenoxid, Polypropylenoxid, g) Polymers of cyclic ethers such as polyethylene glycol, polypropylene glycol, polyethylene oxide, polypropylene oxide,
h) Polyurethanen aus hydroxyterminierten Polyethern oder Polyes tern und aromatischen oder aliphatischen Isocyanaten, insbeson dere lineare Polyurethane, Polyharnstoffen, h) Polyurethanes made from hydroxy-terminated polyethers or polyesters and aromatic or aliphatic isocyanates, in particular linear polyurethanes, polyureas,
i) Polyamiden wie z.B. Polyamid-6, 6.6, 6.10, 4.6, 4.10, 6.12, 12.12, Polyamid 11, Polyamid 12 sowie (teil-)aromatische Polyamide wie z.B. Polyphthalamide, z.B. hergestellt aus Terephthalsäure und/oder Isophthalsäure und aliphatischen Diaminen oder aus aliphatischen Dicarbonsäuren wie z.B. Adipinsäure oder Sebazin- säure und aromatischen Diaminen wie z.B. 1,4- oder 1,3- Diaminobenzol, i) Polyamides such as polyamide-6, 6.6, 6.10, 4.6, 4.10, 6.12, 12.12, polyamide 11, polyamide 12 and (partially) aromatic polyamides such as polyphthalamides, e.g. made from terephthalic acid and / or isophthalic acid and aliphatic diamines or from aliphatic dicarboxylic acids such as adipic acid or sebacic acid and aromatic diamines such as 1,4- or 1,3-diaminobenzene,
j) Polyimiden, Polyamid-imiden, Polyetherimiden, Polyesterimiden, Poly(ether)ketonen, Polysulfonen, Polyethersulfonen, Polyarylsul- fonen, Polyphenylensulfid, Polybenzimidazolen, Polyhydantoinen, k) Polyestern aus aliphatischen oder aromatischen Dicarbonsäuren und Diolen oder aus Hydroxy-Carbonsäuren wie z.B. Polyethylen- terephthalat (PET), Polybutylenterephthalat (PBT), Polypropylen- terphthalat, Polyethylennaphthylat, Poly-1,4- dimethylocyclohexanterphthalat, Polyhydroxybenzoat, Polyhydro- xynaphthalat, Polymilchsäure, j) polyimides, polyamide-imides, polyetherimides, polyesterimides, poly (ether) ketones, polysulfones, polyether sulfones, polyarylsulfones, polyphenylene sulfide, polybenzimidazoles, polyhydantoins, k) Polyesters from aliphatic or aromatic dicarboxylic acids and diols or from hydroxycarboxylic acids such as, for example, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polypropylene terephthalate, polyethylene naphthylate, poly-1,4-dimethylocyclohexane phthalate, polyhydroxybenzoilchthalate, polyhydroxy phthalic acid ,
L) Polycarbonaten, Polyestercarbonaten, sowie Blends von diesen wie z.B. PC/ABS, PC/PBT, PC/P ET/P BT, L) Polycarbonates, polyester carbonates and blends of these such as PC / ABS, PC / PBT, PC / P ET / P BT,
m) Cellulosederivaten, wie z.B. Cellulosenitrat, Celluloseacetat, Cellu losepropionat, Cellulosebutyrat, m) cellulose derivatives, such as cellulose nitrate, cellulose acetate, cellulose propionate, cellulose butyrate,
n) sowie Mischungen, Kombinationen oder Blends aus zwei oder mehr der zuvor genannten Polymere, n) and mixtures, combinations or blends of two or more of the aforementioned polymers,
wobei die genannten Polymere als Frischware oder als Recyklate vor liegen können. wherein the polymers mentioned can be available as fresh goods or as recycled materials.
14. Kunststoffzusammensetzung, enthaltend oder bestehend aus 14. Plastic composition containing or consisting of
mindestens einen Kunststoff, sowie at least one plastic, as well
mindestens ein phenolisch substituiertes Zuckerderivat, wobei das Zu ckerderivat einen von einem Zucker abgeleiteten Grundkörper auf weist, sowie mindestens einen Substituenten gemäß allgemeiner For mel I at least one phenolically substituted sugar derivative, the sugar derivative having a base substance derived from a sugar, and at least one substituent according to general formula I
Formel I Formula I.
wobei in which
R1 und R2 bei jedem Auftreten gleich oder verschieden sind und ausgewählt sind aus der Gruppe bestehend aus Wasserstoff und linearen oder verzweigten Alkylreste, mit der Maßgabe, dass mindestens ein Rest R1 oder R2 nicht Wasserstoff ist, X eine Alkylengruppe mit 1 bis 18 Kohlenstoffatomen oder eine chemische Bindung, R 1 and R 2 are identical or different on each occurrence and are selected from the group consisting of hydrogen and linear or branched alkyl radicals, with the proviso that at least one radical R 1 or R 2 is not hydrogen, X is an alkylene group with 1 to 18 carbon atoms or a chemical bond,
Y eine Gruppierung ausgewählt aus der Gruppe bestehend aus den nachfolgenden Gruppierungen Y is a group selected from the group consisting of the following groupings
H H H H
wobei die Gruppierung X an den links dargestellten Terminus der oben abgebildeten Gruppierungen Y gebunden ist, und wobei der von einem Zucker abgeleiteten Grundkörper des pheno- lisch substituierten Zuckerderivates mindestens 3 unsubstituierte Hyd roxygruppen aufweist und/oder der von einem Zucker abgeleitete Grundkörper des phenolisch substituierten Zuckerderivates mindes tens 4 Kohlenstoffatome und mindestens 2, vorzugsweise mindestens 3 unsubstituierte Hydroxygruppen aufweist. where the group X is bound to the terminus shown on the left of the groupings Y shown above, and where the sugar-derived base of the phenolically substituted sugar derivative has at least 3 unsubstituted hydroxyl groups and / or the base of the phenolically substituted sugar derivative derived from a sugar has at least 4 carbon atoms and at least 2, preferably at least 3, unsubstituted hydroxyl groups.
15. Kunststoffzusammensetzung nach vorhergehendem Anspruch, 15. Plastic composition according to the preceding claim,
dadurch gekennzeichnet, dass die Kunststoffzusammensetzung zusätz lich mindestens einen Zusatzstoff enthält, welcher ausgewählt ist aus der Gruppe bestehend aus UV-Absorbern, Lichtstabilisatoren, Metall desaktivatoren, Costabilisatoren, Füllstoffdesaktivatoren, Antiozonan- tien, Nukleierungsmitteln, Antinukleierungsmitteln, Schlagzähigkeits verbesserern, Weichmachern, Gleitmitteln, Rheologiemodifikatoren, Thixotropiemitteln, Kettenverlängerern, optischen Aufhellern, antimik robiellen Wirkstoffen, Antistatika, Slipmitteln, Antiblockmitteln, Kopp lungsmitteln, Vernetzungsmitteln, Antivernetzungsmitteln, Hydrophili- sierungsmitteln, Hydrophobisierungsmitteln, Haftvermittlern, Disper giermitteln, Kompatibilisatoren, Sauerstofffängern, Säurefängern, Treibmitteln, Prodegradantien, Entschäumungsmitteln, Geruchsfän gern, Markierungsmitteln, Antifoggingmitteln, Füllstoffen, Verstär kungsstoffen und Mischungen hiervon. characterized in that the plastic composition additionally contains at least one additive selected from the group consisting of UV absorbers, light stabilizers, metal deactivators, costabilizers, filler deactivators, antiozonants, nucleating agents, antinucleating agents, impact strength improvers, plasticizers, lubricants, rheology modifiers , Thixotropic agents, chain extenders, optical brighteners, antimicrobial agents, antistatic agents, slip agents, antiblocking agents, coupling agents, crosslinking agents, anti-crosslinking agents, hydrophilicizing agents, hydrophobizing agents, adhesion promoters, dispersing agents, compatibilizers, defoaming agents, defoaming agents, propellants, acid scavengers , Marking agents, anti-fogging agents, fillers, reinforcing agents and mixtures thereof.
16. Kunststoffzusammensetzung nach einem der beiden vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Kunststoffzusammen- Setzung zusätzlich mindestens einen Zusatzstoff enthält, welcher aus gewählt ist aus der Gruppe bestehend aus 16. Plastic composition according to one of the two preceding claims, characterized in that the plastic together Settlement additionally contains at least one additive which is selected from the group consisting of
a) Säurefängern, vorzugsweise Salze von ein, zwei, drei oder vierwer tigen Metallen, vorzugsweise Alkali-, Erdalkalimetalle, Aluminium oder Zink, insbesondere gebildet mit Fettsäuren, wie z.B. Calci- umstearat, Magnesiumstearat, Zinkstearat, Aluminiumstearat, Cal- ciumstearat, Calciumlactat, Calciumstearoyl-2-lactat, Hydrotalcite, insbesondere synthetische Hydrotalciten auf Aluminium-, Magne sium- und Zinkbasis, Hydrocalumite, Zeolithe, Erdalkalioxide, insbe sondere Calciumoxid und Magnesiumoxid, Erdalkalicarbonate, ins besondere Calciumcarbonat, Magnesiumcarbonat und Dolomit, und Hydroxide, insbesondere Brucit, a) Acid scavengers, preferably salts of one, two, three or four-valent metals, preferably alkali, alkaline earth metals, aluminum or zinc, in particular formed with fatty acids such as calcium stearate, magnesium stearate, zinc stearate, aluminum stearate, calcium stearate, calcium lactate, Calcium stearoyl-2-lactate, hydrotalcites, especially synthetic hydrotalcites based on aluminum, magnesium and zinc, hydrocalumites, zeolites, alkaline earth oxides, in particular special calcium oxide and magnesium oxide, alkaline earth metal carbonates, in particular calcium carbonate, magnesium carbonate and dolomite, and hydroxides, in particular brucite,
b) Lichtstabilisatoren, vorzugsweise Lichtstabilisatoren aus der Grup pe der gehinderten Amine, b) light stabilizers, preferably light stabilizers from the group of hindered amines,
c) Dispergiermitteln, sowie c) dispersants, as well as
d) Mischungen hiervon. d) mixtures thereof.
17. Verfahren zur Stabilisierung von Kunststoffen gegen oxidativen, ther mischen und/oder aktinischen Abbau, bei dem mindestens ein pheno- lisch substituiertes Zuckerderivat, wobei das Zuckerderivat einen von einem Zucker abgeleiteten Grundkörper aufweist, sowie mindestens einen Substituenten gemäß allgemeiner Formel I 17. A method for stabilizing plastics against oxidative, thermal and / or actinic degradation, in which at least one phenolically substituted sugar derivative, the sugar derivative having a base body derived from a sugar, and at least one substituent according to general formula I
Formel I Formula I.
wobei in which
R1 und R2 bei jedem Auftreten gleich oder verschieden sind und ausgewählt sind aus der Gruppe bestehend aus Wasserstoff und linearen oder verzweigten Alkylreste, mit der Maßgabe, dass mindestens ein Rest R1 oder R2 nicht Wasserstoff ist, X eine Alkylengruppe mit 1 bis 18 Kohlenstoffatomen oder eine chemische Bindung, R 1 and R 2 are identical or different on each occurrence and are selected from the group consisting of hydrogen and linear or branched alkyl radicals, with the proviso that at least one radical R 1 or R 2 is not hydrogen, X is an alkylene group with 1 to 18 carbon atoms or a chemical bond,
Y eine Gruppierung ausgewählt aus der Gruppe bestehend aus den nachfolgenden Gruppierungen Y is a group selected from the group consisting of the following groupings
H H H H
wobei die Gruppierung X an den links dargestellten Terminus der oben abgebildeten Gruppierungen Y gebunden ist, und wobei der von einem Zucker abgeleiteten Grundkörper des pheno- lisch substituierten Zuckerderivates mindestens 3 unsubstituierte Hyd roxygruppen aufweist und/oder der von einem Zucker abgeleitete Grundkörper des phenolisch substituierten Zuckerderivates mindes tens 4 Kohlenstoffatome und mindestens 2, vorzugsweise mindestens 3 unsubstituierte Hydroxygruppen aufweist, where the group X is bound to the terminus shown on the left of the groupings Y shown above, and where the sugar-derived base of the phenolically substituted sugar derivative has at least 3 unsubstituted hydroxyl groups and / or the base of the phenolically substituted sugar derivative derived from a sugar has at least 4 carbon atoms and at least 2, preferably at least 3 unsubstituted hydroxyl groups,
in einen Kunststoff eingearbeitet wird. is incorporated into a plastic.
18. Formmasse oder Formteil herstellbar aus einer Kunststoffzusammen setzung nach einem der Ansprüche 14 bis 16, insbesondere in Form von Spritzgussteilen, Folien, Filmen, Lacken, Beschichtungen, Schäu men, Fasern, Kabeln, Rohren, Profilen, Hohlkörpern, Bändchen, Membranen, z.B. Geomembranen, Schmierstoffen, Farbmitteln und/oder Klebstoffen, die über Extrusion, Spritzguss, Blasformen, Ka landrieren, Pressverfahren, Spinnprozesse und/oder Rotomoulding hergestellt werden z.B. für die Elektroindustrie, für die Bauindustrie, für die Transportindustrie, für medizinische Anwendungen, für Haus halts- und Elektrogeräte, für Fahrzeugteile, für Konsumartikel, für Ver packungen, für Möbel, und/oder für Textilien. 18. Molding compound or molded part can be produced from a plastic composition according to one of claims 14 to 16, in particular in the form of injection molded parts, foils, films, paints, coatings, foams, fibers, cables, pipes, profiles, hollow bodies, tapes, membranes, for example Geomembranes, lubricants, colorants and / or adhesives that are manufactured via extrusion, injection molding, blow molding, Ka landrieren, pressing processes, spinning processes and / or rotomoulding, e.g. for the electrical industry, for the construction industry, for the transport industry, for medical applications, for households - and electrical devices, for vehicle parts, for consumer articles, for packaging, for furniture and / or for textiles.
19. Stabilisator-Zusammensetzung zur Stabilisierung von Kunststoffen ge gen oxidativen, thermischen und/oder aktinischen Abbau, bestehend aus 19. Stabilizer composition for stabilizing plastics against oxidative, thermal and / or actinic degradation, consisting of
mindestens einem phenolisch substituierten Zuckerderivat, wobei das Zuckerderivat einen von einem Zucker abgeleiteten Grundkörper auf- weist, sowie mindestens einen Substituenten gemäß allgemeiner For mel I at least one phenolically substituted sugar derivative, the sugar derivative having a base body derived from a sugar has, and at least one substituent according to general formula I
Formel I Formula I.
wobei in which
R1 und R2 bei jedem Auftreten gleich oder verschieden sind und ausgewählt sind aus der Gruppe bestehend aus Wasserstoff und linearen oder verzweigten Alkylreste, mit der Maßgabe, dass mindestens ein Rest R1 oder R2 nicht Wasserstoff ist,R 1 and R 2 are identical or different on each occurrence and are selected from the group consisting of hydrogen and linear or branched alkyl radicals, with the proviso that at least one radical R 1 or R 2 is not hydrogen,
X eine Alkylengruppe mit 1 bis 18 Kohlenstoffatomen oder eine chemische Bindung, X is an alkylene group with 1 to 18 carbon atoms or a chemical bond,
Y eine Gruppierung ausgewählt aus der Gruppe bestehend aus den nachfolgenden Gruppierungen Y is a group selected from the group consisting of the following groupings
H H H H
wobei die Gruppierung X an den links dargestellten Terminus der oben abgebildeten Gruppierungen Y gebunden ist, und wobei der von einem Zucker abgeleiteten Grundkörper des pheno- lisch substituierten Zuckerderivates mindestens 3 unsubstituierte Hyd roxygruppen aufweist und/oder der von einem Zucker abgeleitete Grundkörper des phenolisch substituierten Zuckerderivates mindes tens 4 Kohlenstoffatome und mindestens 2, vorzugsweise mindestens 3 unsubstituierte Hydroxygruppen aufweist, where the group X is bound to the terminus shown on the left of the groupings Y shown above, and where the sugar-derived base of the phenolically substituted sugar derivative has at least 3 unsubstituted hydroxyl groups and / or the base of the phenolically substituted sugar derivative derived from a sugar has at least 4 carbon atoms and at least 2, preferably at least 3 unsubstituted hydroxyl groups,
und and
mindestens einem primären Antioxidans und/oder mindestens einem sekundären Antioxidans. at least one primary antioxidant and / or at least one secondary antioxidant.
20. Phenolisch substituiertes Zuckerderivat, wobei das Zuckerderivat einen von einem Zucker abgeleiteten Grundkörper aufweist, sowie mindes tens einen Substituenten gemäß allgemeiner Formel I 20. Phenolically substituted sugar derivative, the sugar derivative having a base structure derived from a sugar, and at least one substituent according to general formula I
Formel I Formula I.
wobei in which
R1 und R2 bei jedem Auftreten gleich oder verschieden sind und ausgewählt sind aus der Gruppe bestehend aus Wasserstoff und linearen oder verzweigten Alkylreste, mit der Maßgabe, dass mindestens ein Rest R1 oder R2 nicht Wasserstoff ist,R 1 and R 2 are identical or different on each occurrence and are selected from the group consisting of hydrogen and linear or branched alkyl radicals, with the proviso that at least one radical R 1 or R 2 is not hydrogen,
X eine Alkylengruppe mit 1 bis 18 Kohlenstoffatomen oder eine chemische Bindung, X is an alkylene group with 1 to 18 carbon atoms or a chemical bond,
Y eine Gruppierung ausgewählt aus der Gruppe bestehend aus den nachfolgenden Gruppierungen Y is a group selected from the group consisting of the following groupings
H H H H
wobei die Gruppierung X an den links dargestellten Terminus der oben abgebildeten Gruppierungen Y gebunden ist, und wobei der von einem Zucker abgeleiteten Grundkörper des pheno lisch substituierten Zuckerderivates mindestens 3 unsubstituierte Hyd roxygruppen aufweist und/oder der von einem Zucker abgeleitete Grundkörper des phenolisch substituierten Zuckerderivates mindes tens 4 Kohlenstoffatome und mindestens 2, vorzugsweise mindestens 3 unsubstituierte Hydroxygruppen aufweist. where the group X is bound to the terminus shown on the left of the groupings Y shown above, and where the sugar-derived base of the phenolically substituted sugar derivative has at least 3 unsubstituted hydroxy groups and / or the base of the phenolically substituted sugar derivative derived from a sugar at least has at least 4 carbon atoms and at least 2, preferably at least 3, unsubstituted hydroxyl groups.
EP20737440.6A 2019-07-08 2020-07-07 Use of phenolically substituted sugar derivatives as stabilisers, plastic composition, method for stabilising plastics and phenolically substituted sugar derivatives Pending EP3997164A1 (en)

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