EP4127045A1 - Use of hydroxycinnamic acid salts for stabilising organic materials, stabilised organic material, method for stabilising organic materials, specific stabilisers and stabiliser compositions - Google Patents
Use of hydroxycinnamic acid salts for stabilising organic materials, stabilised organic material, method for stabilising organic materials, specific stabilisers and stabiliser compositionsInfo
- Publication number
- EP4127045A1 EP4127045A1 EP21716104.1A EP21716104A EP4127045A1 EP 4127045 A1 EP4127045 A1 EP 4127045A1 EP 21716104 A EP21716104 A EP 21716104A EP 4127045 A1 EP4127045 A1 EP 4127045A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- styrene
- group
- tert
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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Classifications
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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
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/40—Unsaturated compounds
- C07C59/58—Unsaturated compounds containing ether groups, groups, groups, or groups
- C07C59/64—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/203—Solid polymers with solid and/or liquid additives
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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
- C08K5/0008—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
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- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
Definitions
- the present invention relates to the use of specific hydrocinnamic acid salts for stabilizing organic materials.
- the invention also relates to an organic material correspondingly stabilized by the incorporation of a specific hydroxycinnamic acid salt and to a method for stabilizing organic materials.
- the present invention also relates to a stabilizer composition which contains a corresponding hydroxycinnamic acid salt.
- 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 in the molecular weight or the formation of new chemical groups, based on radical chain cleavages through mechanochemical processes or through 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, which interfere with the radicals formed during autoxidation and thus interrupt the breakdown process.
- primary antioxidants which can react directly with oxygen-containing free radicals or C-radicals
- secondary antioxidants which react with intermediate hydroperoxides (see C.
- plastics made from fossil raw materials such as crude oil or natural gas are being supplemented or replaced by plastics based on renewable raw materials using biochemical processes.
- the question of sustainability then also arises for the primary and secondary antioxidants used for this (and for plastics made from fossil raw materials).
- primary antioxidants from renewable raw materials are known, some of which are also used in plastics.
- a typical example are tocopherols (vitamin E).
- tocopherols have a sterically hindered phenol structure and can be used alone or in combination with secondary antioxidants (for example S. Al-Malaika, Macromol. Symp. 2001, 176, 107-117).
- Tocopherols can be isolated from natural substances such as wheat germ oil, sunflower oil or olive oil, for example.
- phenols with an antioxidant effect in plastics are, for example, quercetin (B. Kirschweng et al., Eur. Pol. J. 2018, 103, 228-237), dihydromyricetin (B. Kirschweng et al., Pol. Degr. Stab. 2016, 133, 192-200), derivatives of rosmarinic acid (K. Doudin et al., Pol. Degr. Stab. 2016, 130, 126-134) or also tannin (WJ Grigsby et al., Polymers 2013, 5, 344-360 ).
- quercetin B. Kirschweng et al., Eur. Pol. J. 2018, 103, 228-237
- dihydromyricetin B. Kirschweng et al., Pol. Degr. Stab. 2016, 133, 192-200
- derivatives of rosmarinic acid K. Doudin et al., Pol. Degr. Stab. 2016, 130, 126
- Ferulic acid and its salts are used, for example, in the cosmetics industry or as active pharmaceutical ingredients (e.g. FR 2907338, CN 101181256, DE 1957433), the production of the salts is known in principle (e.g. AT 317184).
- CN 107629310 layered compounds with light stabilizers are synthesized, which can contain sodium cinnamate as possible light stabilizers and which can be used in plastics or coatings.
- ester derivatives of ferulic acid (AF Reano et al., ACS Sustainable Chemistry and Engineering 4 (2015), 6562-6571, AF Reano et al., ACS Sustainable Chemistry and Engineering 3 (2015), 3486-3496), oligomers and Polymers of ferulic acid (US 2016257846) and caffeic acid (V. Ambrogi et al. Biomacromolecules 15 (2014), 302-310).
- these derivatives are relatively laboriously produced by enzymatic syntheses.
- ferulic acid derivatives in the form of ester compounds are isosorbide esters (US20070189990) and cholestanyl esters (WO2018153917).
- the present invention thus relates to the use of a compound or mixtures of several compounds according to general formula I whereby
- R 1 , R 2 and R 3 are each independently selected from the group consisting of hydroxyl, linear or branched alkoxy groups having 1 to 6 carbon atoms and hydrogen, with the proviso that at least one of the radicals R 1 , R 2 and R 3 is a Hydroxyrest is M is selected from the group consisting of metals, and n is an integer from 1 to 4, for stabilizing organic materials, in particular against oxidative, thermal and / or actinic degradation.
- cosmetics are not counted among the organic materials.
- a metal salt of a hydroxycinnamic acid in which at least one phenol group has steric hindrance is used as a stabilizer.
- the compounds according to the invention according to formula I act as stabilizers and, based on renewable raw materials, have a high level of effectiveness, environmental friendliness and a favorable cost structure.
- a preferred embodiment provides that the invention relates to the stabilization of plastics, coatings, lubricants, hydraulic oils, engine oils, turbine oils, gear oils, metal working fluids, chemicals or monomers.
- plastics in the form of injection molded parts, foils or films, foams, fibers, cables and pipes, profiles, hollow bodies, tapes, membranes such as geomembranes, or adhesives that are manufactured via extrusion, injection molding, blow molding, calendering, pressing processes, spinning processes, rotomoulding are for example for the electrical and electronics industry, construction industry, transport industry (car, airplane, ship, train), for medical applications, for household and electrical appliances, vehicle parts, consumer goods, packaging, furniture, textiles.
- Another area of application are paints, paints and coatings as well as the stabilization of oils and fats.
- radicals R 1 , R 2 and R 3 are each a hydroxy radical, two of the radicals R 1 , R 2 and R 3 are hydroxy and one of the radicals R 1 , R 2 and R 3 is hydrogen or a linear one or branched alkoxy group of 1 to 6 Carbon atoms, one of the radicals R 1 , R 2 and R 3 is a hydroxy radical and two of the radicals R 1 , R 2 and R 3 are a linear or branched alkoxy group with 1 to 6 carbon atoms, or one of the radicals R 1 , R 2 and R each 3 represent a hydroxy group, a linear or branched alkoxy group having 1 to 6 carbon atoms and hydrogen.
- the compound according to general formula I is selected from the group consisting of the following compounds: where M and n are as defined above.
- the hydroxycinnamic acid salts used according to the invention are thus derived from the following hydroxycinnamic acids: a) Ferulic acid b) isoferulic acid c) caffeic acid d) sinapic acid
- the metals M are selected from the group consisting of alkali metals, alkaline earth metals, aluminum and zinc
- Preferred alkali metals here are lithium, sodium and potassium, with sodium being particularly preferred.
- Preferred alkaline earth metals are, in particular, magnesium and calcium.
- a further preferred embodiment of the present invention provides that the compound according to general formula I or, in the case of a mixture of several compounds according to general formula I, all of the compounds according to general formula I in a proportion by weight of 0.01 to 10.00 wt. %, preferably from 0.02 to 5.00% by weight, particularly preferably from 0.05 to 2.00% by weight, is contained in the organic material.
- Thermoplastic and thermoset polymers are for example: a) Polymers made from olefins or diolefins such as polyethylene (LDPE, 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, as well as copolymers in the form of random or block structures such as polypropylene-polyethylene (EP), EPM or EPDM with e.g.
- olefins or diolefins such as polyethylene (LDPE, LLDPE, VLDPE, ULDPE, MDPE, HDPE, UHMWPE), metallocene PE (m-PE), polypropylene, polyisobutylene, poly-4- methyl-pen
- EVA ethylene-vinyl acetate
- ethylene-acrylic esters such as, for example, ethylene-butyl acrylate, ethylene-acrylic acid and their salts (ionomers), as well as 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 1-butene, 1-hexene, 1-octene or 1-octadecene b) polystyrene, polymethylstyrene, poly-alpha-methyls
- Polyesters 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-dimethylolcyclohexane terephthalate, polyhydroxaphthalate , 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) Cellulose derivatives such as cellulose nitrate, cellulose acetate,
- epoxy resins consisting of di- or polyfunctional epoxy compounds in combination with e.g. hardeners based on amines, anhydrides, dicyandiamide, mercaptans, isocyanates or catalytic
- phenolic resins such as phenol-formaldehyde resins, urea
- Formaldehyde resins melamine-formaldehyde resins
- unsaturated polyester resins made from unsaturated dicarboxylic acids and diols with vinyl compounds e.g. styrene, alkyd resins, allyl resins r) silicones, e.g. based on dimethylsiloxanes, methylphenylsiloxanes or diphenylsiloxanes, e.g. terminated with vinyl groups
- vinyl compounds e.g. styrene, alkyd resins, allyl resins r
- silicones e.g. based on dimethylsiloxanes, methylphenylsiloxanes or diphenylsiloxanes, e.g. terminated with vinyl groups
- 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.
- polymers specified under a) to r) can have both amorphous and (partially) crystalline morphologies.
- the polyolefins mentioned under a) can also be present in crosslinked form, for example crosslinked polyethylene, which is then referred to as X-PE.
- the present compounds can also be used to stabilize rubbers and elastomers.
- This can be natural rubber (NR) or synthetic rubber materials such as NR (Natural Rubber), chloroprene (CR), polybutadiene (BR), styrene-butadiene (SBR), polyisoprene (IR), butyl rubber (IIR), nitrile rubber (NBR ), hydrogenated nitrile rubber (HNBR), polyester or polyether urethane rubber, silicone rubber.
- NR Natural Rubber
- CR chloroprene
- BR polybutadiene
- SBR styrene-butadiene
- IR polyisoprene
- IR butyl rubber
- NBR nitrile rubber
- HNBR hydrogenated nitrile rubber
- polyester or polyether urethane rubber silicone rubber.
- the plastics can be recycled plastics e.g. B. from industrial collections such as production waste or plastics from household or recyclable material collections.
- Preferred plastics are thermoplastics and, in particular, plastics that are used in packaging such as food packaging, in particular polyolefins, polystyrene, polyesters and polyamides.
- Polypropylene homo- and copolymers, and also polyethylene in the form of LDPE, LLDPE, HDPE, MDPE, VLDPE and polyethylene terephthalate (PET), homo- and copolymers are very particularly preferred.
- aliphatic polyesters from renewable raw materials which are essentially produced from aliphatic dicarboxylic acids and aliphatic diols, from hydroxycarboxylic acids or lactones, such as polylactic acid (PLA), polyglycolic acid (PGA), polyhydroxybutyric acid (PHB), polyhydroxyvaleric acid (PHV), polyhydroxyvaleric acid (PHV).
- PESu polybutylene succinate (PBS), polyethylene adipate poly (butylene succinate-co-adipate) (PBSA) or polycaprolactone (PCL).
- the plastics can in particular in the form of injection molded parts, foils or films, foams, fibers, cables and pipes, profiles, hollow bodies, tapes, membranes, such as geomembranes, or adhesives that are produced via extrusion, injection molding, blow molding, calendering, Pressing processes, spinning processes, rotomoulding are produced e.g. for the electrical and electronics industry, construction industry, transport industry (car, aircraft, ship, train), for medical applications, for household and electrical appliances, vehicle parts, consumer goods, packaging, furniture, textiles. Another area of application are paints, paints and coatings as well as the stabilization of oils and fats.
- the plastic has at least one further additive selected from the group consisting of primary and / or secondary antioxidants, in particular primary and / or secondary antioxidants selected from the group consisting of phosphites, phosphonites, Thiols, phenolic antioxidants, sterically hindered amines, hydroxylamines and mixtures or combinations thereof, UV absorbers, light stabilizers, hydroxylamine-based stabilizers, benzofuranone-based stabilizers, nucleating agents, impact strength improvers, plasticizers, lubricants, rheology modifiers, pigments, color extenders, chain extenders substances, optical brighteners, antimicrobial agents, antistatic agents, slip agents, antiblocking agents, coupling agents, dispersants, compatibilizers, oxygen scavengers, acid scavengers, costabilizers, markers gsstoff as well as anti-fogging agents is added to the plastic during use and / or contains.
- primary and / or secondary antioxidants selected from the group consisting of
- Suitable primary antioxidants (A) 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- (1'-methylundec-1'-yl) phenol, 2,4-d
- Alkylthiomethylphenols such as 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol,
- Hydroquinones and alkylated hydroquinones such as 2,6-di-tert-butyl-4-methyoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone,
- Tocopherols such as ⁇ -, ⁇ -, ⁇ -, d-tocopherol and mixtures of these (vitamin E);
- 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-methylphenol), 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-methylcyclohexylphenol], 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'-methylenebis [6- ( ⁇ -methylbenzyl) -4-nonylphenol], 2,2'-methylenebis [6- (a, a-dimethylbenzyl) -4-nonylphenol], 4,4'-
- 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 dimethyl benzyl) dithioterephthalate, bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, iso-octyl-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, didodecylmercaptoethyl-2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, bis [4- (1,1,3,3-tetramethylbutyl) phenyl] -2,2- bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate;
- Aromatic hydroxybenzyl compounds such as 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 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) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,3 , 5-triazine, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenoxy) - 1,2,3-triazine, 1,3,5-tris (3,5-di- tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-
- Benzyl phosphonates such as dimethyl 2,5-di-tert-butyl-4-hydroxybenzyl phosphonate, Dietyhl-3,5-di-tert-butyl-4-hydroxybenzyl phosphonate, di-octadecyl-3,5-di-tert- butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert- butyl 4-hydroxy-B-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid;
- 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-thiaundecanol 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane,
- Esters of ß- (5-tert-butyl-4-hydroxy-3-methylphenyl) 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-thiaundecanol, 3-thiapentadecanol, , Trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane, 3,9-
- 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, trimethylolxymethyl- 1-phosphymethyl 2,6,7-trioxabicyclo [2.2.2] octane;
- Esters of (3,5-di-tert-butyl-4-hydroxyphenyl) acetic 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-
- monohydric or polyhydric alcohols e.g. methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1, 2-propane
- Amides of ß- (3,5-di-tert-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-tert-butyl-4-hydroxyphenyl] propionyloxy) ethyl] oxamide (Naugard ® XL-1, sold by Uniroyal);
- vitamin C Ascorbic acid (vitamin C).
- Particularly preferred phenolic antioxidants are the following structures: Very particularly preferred phenolic antioxidants are octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate and pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate
- phenolic antioxidants are based on renewable raw materials such as.
- vitamin E tocopherols
- tocotrienols tocomonoenols
- carotenoids hydroxytyrosol
- flavonols such as chrysin, quercitin, hesperidin, neohesperidin, naringin, morin, kaempferol, fisetin, anthocyanins such as delphinidin and
- Suitable aminic antioxidants are, for example: N, N'-di-isopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-bis (1,4-dimethylpentyl) -p- phenylenediamine, N, N'-bis (1-ethyl-3-methyl-pentyl) -p-phenylenediamine, N, N'-bis (1-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
- p, p'-di-tert-octyldiphenylamine 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4- dodecanoylaminophenol, 4- Octadecanoylaminophenol, bis (4-methoxyphe nyl) amine, 2,6-di-tert-butyl-4-dimethylaminomethyl-phenol, 2,4'-di-aminodiphenyl methane, 4,4'-diaminodiphenyl methane, N, N, N ', N'-tetra-methyl- 4,4'-diaminodiphenylmethane, 1,2-bis [(2-methyl-phenyl) amino] ethane, 1,2-bis (phenylamino) propane, (o-tolyl) biguanide, bis [4- (1 ', 3 '-dimethylbutyl) - phenyl]
- Preferred aminic 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 (1-ethyl-3-methylpentyl) -p- phenylenediamine, N, N'-bis (1-methylheptyl) -p-phenylenediamine, N, N'-
- aminic antioxidants are hydroxylamines or N- oxides (nitrones), such as N, N-dialkylhydroxylamine, N, N-dibenzylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-distearylhydroxylamine, N-benzyl- ⁇ -phenyl nitrone, N-octadecyl- ⁇ -hexadecyl nitrone, as well Genox EP (Sl Group) according to the formula:
- Suitable lactones are benzofuranones and indolinones such as 3- (4- (2-acetoxyethoxy) -phenyl] -5,7-di-tert-butyl-benzofuran-2-one, 5,7-di-tert-butyl 3- [4- (2-stearoyloxyethoxy) phenyl] benzofuran-2-one, 3,3'-bis [5,7-di-tert-butyl-3- (4- (2-hydroxyethoxy] phenyl) benzofuran-2-one ), 5,7-di-tert-butyl-3- (4-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-benzo
- antioxidants are isoindolo [2,1- A] quinazoline such as
- Suitable secondary antioxidants are in particular phosphites or phosphonites such as e.g.
- Triphenyl phosphite diphenyl alkyl phosphites, phenyl dialkyl phosphites, tri (nonyl phenyl) phosphite, trilauryl phosphites, trioctadecyl phosphite, distearyl penterythritol diphosphite, tris- (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-phosphite-di-phosphite-tertiary -butylphenyl) pentaerythritol diphosphite, bis (2,4-di-cumylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyloxypentaeryth
- Particularly preferred phosphites / phosphonites are:
- a preferred phosphonite is:
- the phosphite tris (2,4-di-tert-butylphenyl) phosphite is very particularly preferably used as a secondary antioxidant.
- Suitable secondary antioxidants are also organosulfur compounds such as sulfides and disulfides, for example distearyl thiodipropionate, dilauryl thiodipropionate; Ditridecyldithiopropionate, ditetradecylthiodipropionate, 3- (dodecylthio) -1,1 '- [2,2-bis [[3- (dodecylthio) -1-oxopropoxy] methyl] -1,3-propanediyl] propanoic acid ester.
- organosulfur compounds such as sulfides and disulfides, for example distearyl thiodipropionate, dilauryl thiodipropionate; Ditridecyldithiopropionate, ditetradecylthiodipropionate, 3- (dodecylthio) -1,1 '- [2,2-bis [[
- organosulfur compounds are sulfur-containing ones
- Amino acids in particular cystine, cystine or methionine are amino acids in particular cystine, cystine or methionine.
- Suitable acid scavengers are salts of one, two, three or tetravalent metals, preferably alkali metals, 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 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
- 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 hyperbranched 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-inositol is preferred ( myo-inositol).
- inositol myo, scyllo-, D-chiro-, L-chiro-, muco-, neo-, allo-, epi- and cis-inosi
- 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) -1,3,5-triazines.
- Suitable 2- (2 'hydroxyphenyl) benzotriazoles are for example 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3', 5'-di-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5 '- (1,1,3,3-tetramethylbutyl) phenyl) benzotriazole, 2- (3' , 5'-di-tert-butyl-2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl-5-chlorobenzotriazole, 2- (3'- sec-butyl-5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) benzotriazole, 2- (3
- 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-hydroxybenzo- phenones.
- Suitable acrylates are, for example, ethyl ⁇ -cyano-ß, ß-diphenyl acrylate, isooctyl- ⁇ -cyano-ß, ß-diphenyl acrylate, methyl ⁇ -carbomethoxycinnamate, methyl ⁇ -cyano-ß-methyl-p-methoxycinnamate, butyl ⁇ -cyano-ß-methyl-p-methoxycinnamate, methyl- ⁇ -carbomethoxy-p-methoxycinnamate and N- (ß-carbomethoxy-ß-cyanovinyl) -2-methylindoline.
- Suitable esters of benzoic acids are, for example, 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis (4-tert-butylbenzoyl) resorcinol, benzoylresorcinol, 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-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) oxalyldihydrazide, oxanilide, isophthaloyldihydrazide, sebacoylbisphenylhydrazide, N, N'-diacetyladipoyldihydrazide, N, N'-bis (salicyloyl) hydrazide, salicyloyl) N, N'-bis (salicyloyl) thiopropionyl dihydrazide
- Suitable hindered amines are, for example, 1,1-bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1 - octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebazate, bis (1, 2,2,6, 6-pentamethyl-4-piperidyl) -n-butyl-3,5-di-tert- butyl 4-hydroxybenzyl malonate, the
- the structures indicated 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 is in each case from 3 to 100.
- Suitable light stabilizer is Hostanox NOW (manufacturer: Clariant SE) with the following general structure: where R is -OC (O) -C 15 H 31 or -OC (O) -C 17 H 35 .
- Suitable dispensing agents are, for example:
- Polyacrylates e.g. copolymers with long-chain side groups, polyacrylate block copolymers, alkylamides: e.g. N, N'-1,2-ethanediylbisoctadecanamide, sorbitan esters, e.g. monostearyl sorbitan esters, titanates and zirconates, reactive copolymers with functional groups e.g. B. polypropylene-co-acrylic acid, polypropylene-co-maleic anhydride, polyethylene-co-glycidyl methacrylate, polystyrene-old maleic anhydride-polysiloxanes: e.g. dimethylsilanediol
- Ethylene oxide copolymer, polyphenylsiloxane copolymer, amphiphilic copolymers e.g. E.g., polyethylene-block-polyethylene oxide, dendrimers, e.g., hydroxyl-containing dendrimers.
- Suitable anti-nucleating agents are azine dyes such as nigrosine.
- Suitable flame retardants are in particular a) Inorganic flame retardants such as Al (OH) 3 , Mg (OH) 2 , AIO (OH), MgCO 3 , sheet silicates such as montmorillonite or sepiolite, not modified or organically modified, double salts such as Mg-Al- Silicates, POSS (Polyhedral Oligomeric Silsesquioxane) compounds, huntite, hydromagnesite or halloysite as well as Sb 2 O 3 , Sb 2 O 5 , MoO 3 , zinc stannate, zinc hydroxystannate, b) nitrogen-containing flame retardants such as melamine, melem, melam, melon, melamine derivatives, Melamine condensation products or melamine salts, benzoguanamine, polyisocyanurates, allantoin, phosphacenes, in particular melamine cyan
- Particularly preferred flame retardants are halogen-free and are the following compounds:
- Suitable plasticizers are, for example, phthalic acid esters, adipic acid esters, esters of citric acid, esters of 1,2-cyclohexanedicarboxylic acid, trimellitic acid esters, isosorbide esters, phosphate esters, epoxides such as epoxidized soybean oil or aliphatic polyesters.
- 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 pigments can be inorganic or organic in 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, azoanthrones, perylenes, phthaloneocyanines or.
- Further suitable pigments are effect pigments based on metal or pearlescent pigments based on metal oxide.
- Suitable optical brighteners are, for example, bisbenzoxazoles, phenylcoumarins or bis (styryl) biphenyls and in particular 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, for example with styrene, and epoxides, for example of the following structures:
- Suitable antistatic agents are, for example, ethoxylated alkyl amines, fatty acid esters, alkyl sulfonates and polymers such as polyether amides.
- Suitable antiozonants are the above-mentioned amines such as N, N'-di-isopropyl-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 for example for the production of controlled rheology polypropylene (CR-PP), are, for example, peroxides, alkoxyamine esters, oxyimide sulfonic acid esters and in particular the following structures:
- Suitable nucleating agents are talc, alkali or alkaline earth salts of mono- and polyfunctional carboxylic acids such as. Benzoic acid, succinic acid, adipic acid, for example sodium benzoate, Zinkglycerolat, aluminum hydroxy-bis (4-tert-butyl) benzoate, 2,2 '-methylene-bis- (4,6-di-tert-butylphenyl) phosphate, and tris-amides and Diamides such as trimesic acid tri-cyclohexylamide, trimesic acid tri (4-methylcyclohexylamide), trimesic acid tri (tert-butylamide), N, N ' , N " -1,3,5-benzenetriyltris (2,2-dimethylpropanamide) or 2,6-naphthalenedicarboxylic acid dicyclohexylamide .
- Chain extenders are diepoxides, bis-oxazolines, bis-oxazolones, bis-oxazines, diisocyanates, dianhydrides, bis-acyl lactams, bis-maleimides, dicyanates, carbodiimides.
- Other suitable chain extenders are polymeric compounds such.
- Suitable additives for increasing 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 e.g. 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.
- the additives according to the invention can also be used to stabilize oils, fats and chemical products.
- the organic materials are oils and fats, these can be based on mineral oils, vegetable fats or animal fats or oils, fats or waxes based on, for example, 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 working fluids or as lubricating greases. These mineral or synthetic lubricants are mainly based on hydrocarbons. Chemical products are used, for example, to stabilize polyols in polyurethane production or of monomers such as styrene, acrylic ester or methacrylic ester for transport and storage.
- the additives described above and optionally the 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 the optionally further additives, preferably using a mixer, kneader or extruder.
- 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 contain, for example, 10-90% of the stabilizers or compositions according to the invention in a polymer.
- additives described above are particularly suitable as possible additives.
- secondary antioxidants are particularly preferred, in particular selected from the group consisting of phosphites, phosphonites and thiols, costabilizers selected from the group consisting of polyols, acid scavengers and sterically hindered amines or mixtures and combinations thereof.
- the at least one additive is present in an amount of 0.01 to 80% by weight, preferably 0.01 to 9.99% by weight, more preferably 0.01 to 4.98% by weight. -%, particularly preferably from 0.02 to 2.00% by weight, based on the totality of the at least one compound according to formula I, the organic material and the at least one additive, is contained or added.
- the present invention also relates to an organic material, in particular a plastic composition, containing at least one Compound according to general formula I or a mixture of several compounds according to general formula I as a stabilizer where R 1 , R 2 , R 3 M and n are as defined above.
- the organic material has the following composition:
- the invention also relates to a method for stabilizing organic materials, in particular against oxidative, thermal and / or actinic degradation, in which one or more compounds according to general formula I
- the present invention also relates to compounds according to general formula I.
- R 1 , R 2 and R 3 are each independently selected from the group consisting of hydroxyl, linear or branched alkoxy groups having 1 to 6 carbon atoms and hydrogen, with the proviso that at least one of the radicals R 1 , R 2 and R 3 is a Is hydroxy and M is aluminum and n is 3.
- Another aspect of the present invention relates to a stabilizer composition, comprising or consisting of a) a compound or mixtures of several compounds according to general formula I.
- R 1 , R 2 and R 3 , M and n are as defined above (component A), and b) at least one secondary antioxidant selected from the group consisting of phosphites, phosphonites or thiols, at least one costabilizer selected from Group consisting of polyols, acid scavengers or sterically hindered amines and mixtures and combinations thereof (component B).
- component A and component B are present in the stabilizer composition in a weight ratio of 100: 1 to 1: 100, preferably 10: 1 to 1:10, particularly preferably 4: 1 to 1: 4 .
- A) Preparation of the hydroxycinnamic acid salts according to the invention Al) Synthesis of sodium ferulate (NaFa) First, 12.00 g (1.00 eq., 61.80 mmol) of ferulic acid (1) are dissolved in 620 mL of methanol in a beaker. Then 2.47 g (1.00 eq., 61.80 mmol) sodium hydroxide are dissolved in 60 mL distilled water and the resulting NaOH solution is added dropwise to the ferulic acid solution via a dropping funnel. When the addition is complete, the pale yellow solution is poured into 1.5 l of acetone.
- the yellow precipitate which separates out is filtered off, washed 3 times with 200 mL acetone each time and finally dried for two days at 80 ° C. in a vacuum drying cabinet. 10.51 g of a yellow, finely powdered precipitate are obtained. The yield is 78.66%.
- DSDTP distearyl thiodipropionate
- Phosphite tris (2,4-di-tert-butylphenyl) phosphite
- the additives according to the invention show a clear stabilizing effect, since less degradation of the polymer takes place over the duration of the experiment.
- Oxidation induction time (OIT) The oxidation induction time is a standardized test, which in one
- Differential calorimeter is performed. This method allows a determination of the thermal stability of the material to be examined. The time between melting and the start of decomposition is determined under isothermal conditions (here 220 ° C). A nitrogen atmosphere is present until the material to be examined melts, then synthetic air is added. Table 4 summarizes the additive combinations incorporated and investigated into commercial polypropylene (Moplen HP 500N, Lyondell Basell Industries) using a co-rotating twin-screw laboratory extruder (Process 11, Thermo Fisher Scientific) with an extrusion temperature of 200 ° C.
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Abstract
The invention relates to the use of specific specific hydroycinnamic acid salts for stabilising organic materials. The invention also relates to a corresponding organic material stabilised by incorporating a specific hydroxycinnamic acid salt, and to a method for stabilising organic materials. In addition, a specific aluminium salt of a hydoxycinnamic acid suitable as an organic stabiliser is described. The invention further relates to a stabilizer composition comprising a corresponding hydroxycinnamic acid salt.
Description
Verwendung von Hydroxyzimtsäuresalzen zur Stabilisierung von organischenUse of hydroxycinnamic acid salts to stabilize organic
Materialien, stabilisiertes organisches Material. Verfahren zur Stabilisierung von organischen Materialien, spezifische Stabilisatoren sowieMaterials, stabilized organic material. Process for stabilizing organic materials, specific stabilizers as well
Stabilisatorzusammensetzungen Stabilizer compositions
Die vorliegende Erfindung betrifft die Verwendung von spezifischen Hydroyzimtsäuresalzen zur Stabilisierung von organischen Materialien. Die Erfindung betrifft zudem ein entsprechend durch Einarbeitung eines spezifischen Hydroxyzimtsäuresalzes stabilisiertes organisches Material sowie ein Verfahren zurStabilisierung von organischen Materialien. Daneben wird ein
spezifisches Aluminiumsalz einer Hydoxyzimtsäure beschrieben, das sich als organischer Stabilisator eignet. Des Weiteren betrifft die vorliegende Erfindung eine Stabilisator-Zusammensetzung, die ein entsprechendes Hydroxyzimtsäuresalz beinhaltet. The present invention relates to the use of specific hydrocinnamic acid salts for stabilizing organic materials. The invention also relates to an organic material correspondingly stabilized by the incorporation of a specific hydroxycinnamic acid salt and to a method for stabilizing organic materials. Next to it is a specific aluminum salt of a hydoxycinnamic acid described, which is suitable as an organic stabilizer. The present invention also relates to a stabilizer composition which contains a corresponding hydroxycinnamic acid salt.
Organische Materialien wie Kunststoffe unterliegen Alterungsvorgängen, die letztendlich zu einem Verlust der erwünschten Eigenschaften wie z.B. der mechanischen Kennwerte führen. Dieser Autoxidation genannte Vorgang führt ausgehend von radikalischen Kettenspaltungen durch mechanochemische Prozesse oder durch UV-Strahlung in Gegenwart von Sauerstoff zu Veränderungen der Polymerkette, wie z.B. im Molekulargewicht oder der Bildung neuer chemischer Gruppen. Um diese Alterung zu verhindern oder zumindest zu verzögern werden deshalb Stabilisatoren eingesetzt. Wichtige Vertreter von Stabilisatoren 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 sauerstoffhaltigen freien Radikalen oder C- Radikalen reagieren können und sekundären Antioxidantien, 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 Antioxidantien sind beispielsweise phenolische Antioxidantien, Amine aber auch Lactone. Klassen von sekundären Antioxidantien sind Phosphorverbindungen wie z.B. Phosphite und Phosphonite, aber auch Organo-Schwefelverbindungen wie z.B. Thioester und Disulfide. Üblicherweise werden in der Praxis häufig primäre und sekundäre Antioxidantien kombiniert, was zu einer synergistischen Wirkung 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 in the molecular weight or the formation of new chemical groups, based on radical chain cleavages through mechanochemical processes or through 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, which interfere with the radicals formed during autoxidation and thus interrupt the breakdown 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 intermediate hydroperoxides (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 organosulfur compounds such as thioesters and disulfides. Usually, in practice, primary and secondary antioxidants are often combined, which leads to a synergistic effect.
In zunehmendem Maße werden Kunststoffe aus fossilen Rohstoffen wie Erdöl oder Erdgas durch Kunststoffe auf der Basis von nachwachsenden Rohstoffen gewonnen über biochemische Prozesse ergänzt bzw. ersetzt. Die Frage der Nachhaltigkeit stellt sich dann auch für die dafür (und für Kunststoffe aus fossilen Rohstoffen) eingesetzten primären und sekundären Antioxidantien. Es besteht daher der Bedarf an Stabilisatoren basierend auf nachwachsenden und verfügbaren Rohstoffen mit hoher Wirksamkeit, niedriger Flüchtigkeit und Kompatibilität mit polymeren Substraten.
Grundsätzlich sind primäre Antioxidantien aus nachwachsenden Rohstoffen bekannt, die auch vereinzelt in Kunststoffen eingesetzt werden. Ein typisches Beispiel sind Tocopherole (Vitamin E). Tocopherole weisen wie übliche Antioxidantien eine sterisch gehinderte Phenolstruktur auf und können allein oder in Kombination mit sekundären Antioxidantien eingesetzt werden (z.B. S. Al-Malaika, Macromol. Symp. 2001, 176, 107-117). Tocopherole können z.B. aus Naturstoffen wie z.B. Weizenkeimöl, Sonnenblumenöl oder Olivenöl isoliert werden. Increasingly, plastics made from fossil raw materials such as crude oil or natural gas are being supplemented or replaced by plastics based on renewable raw materials using biochemical processes. The question of sustainability then also arises for the primary and secondary antioxidants used for this (and for plastics made from fossil raw materials). There is therefore a need for stabilizers based on renewable and available raw materials with high effectiveness, low volatility and compatibility with polymeric substrates. In principle, primary antioxidants from renewable raw materials are known, some of which are also used in plastics. A typical example are tocopherols (vitamin E). Like customary antioxidants, tocopherols have a sterically hindered phenol structure and can be used alone or in combination with secondary antioxidants (for example S. Al-Malaika, Macromol. Symp. 2001, 176, 107-117). Tocopherols can be isolated from natural substances such as wheat germ oil, sunflower oil or olive oil, for example.
Weitere bekannte in Kunststoffen antioxidativ wirkende Phenole sind z.B. Quercetin (B. Kirschweng et al., Eur. Pol. J. 2018, 103, 228-237), Dihydromyricetin (B. Kirschweng et al., Pol. Degr. Stab. 2016, 133, 192-200), Derivate der Rosmarinsäure (K. Doudin et al., Pol. Degr. Stab. 2016, 130, 126- 134) oder auch Tannin (W.J. Grigsby et al., Polymers 2013, 5, 344-360). Other known phenols with an antioxidant effect in plastics are, for example, quercetin (B. Kirschweng et al., Eur. Pol. J. 2018, 103, 228-237), dihydromyricetin (B. Kirschweng et al., Pol. Degr. Stab. 2016, 133, 192-200), derivatives of rosmarinic acid (K. Doudin et al., Pol. Degr. Stab. 2016, 130, 126-134) or also tannin (WJ Grigsby et al., Polymers 2013, 5, 344-360 ).
Weiterhin sind auch Derivate der Ferulasäure (A.F. Reano et al., ACS Sustainable Chemistry and Engineering 4 (2015), 6562-6571) und der Caffeesäure (V. Ambrogi et al., Biomacromolecules 15 (2014), 302-310) bekannt. Furthermore, derivatives of ferulic acid (A.F. Reano et al., ACS Sustainable Chemistry and Engineering 4 (2015), 6562-6571) and of caffeic acid (V. Ambrogi et al., Biomacromolecules 15 (2014), 302-310) are known.
Die meisten der natürlichen Phenole erfordern jedoch einen hohen Aufwand bei der Isolierung, der Aufreinigung oder der Herstellung von anwendbaren Folgeprodukten. Most of the natural phenols, however, require a great deal of effort in isolation, purification or the production of applicable secondary products.
Ferulasäure und ihre Salze werden beispielsweise in der Kosmetikindustrie oder als pharmazeutischer Wirkstoffe eingesetzt (z.B. FR 2907338, CN 101181256, DE 1957433), die Herstellung der Salze ist grundsätzlich bekannt (z.B. AT 317184). In CN 107629310 werden Schichtverbindungen mit Lichtschutzmitteln synthetisiert, die als mögliche Lichtschutzmittel Natrium Cinnamat beispielhaft enthalten können und die in Kunststoffen oder Coatings eingesetzt werden können. Ferulic acid and its salts are used, for example, in the cosmetics industry or as active pharmaceutical ingredients (e.g. FR 2907338, CN 101181256, DE 1957433), the production of the salts is known in principle (e.g. AT 317184). In CN 107629310, layered compounds with light stabilizers are synthesized, which can contain sodium cinnamate as possible light stabilizers and which can be used in plastics or coatings.
Weiterhin sind auch Esterderivate der Ferulasäure (A.F. Reano et al., ACS Sustainable Chemistry and Engineering 4 (2015), 6562-6571, A.F. Reano et al., ACS Sustainable Chemistry and Engineering 3 (2015), 3486-3496), Oligomere und Polymere der Ferulasäure (US 2016257846) und der Caffeesäure (V.
Ambrogi et al. Biomacromolecules 15 (2014), 302-310) bekannt. Diese Derivate werden jedoch verhältnismäßig aufwändig durch enzymatische Synthesen hergestellt. Ebenfalls bekannte Ferulasäurederivate in Form von Esterverbindungen sind Isosorbidester (US20070189990) und Cholestanylester (WO2018153917). Furthermore, ester derivatives of ferulic acid (AF Reano et al., ACS Sustainable Chemistry and Engineering 4 (2015), 6562-6571, AF Reano et al., ACS Sustainable Chemistry and Engineering 3 (2015), 3486-3496), oligomers and Polymers of ferulic acid (US 2016257846) and caffeic acid (V. Ambrogi et al. Biomacromolecules 15 (2014), 302-310). However, these derivatives are relatively laboriously produced by enzymatic syntheses. Also known ferulic acid derivatives in the form of ester compounds are isosorbide esters (US20070189990) and cholestanyl esters (WO2018153917).
Ausgehend hiervon war es Aufgabe der vorliegenden Erfindung, nachhaltige Antioxidantien für organische Materialien insbesondere Polymere auf der Basis von nachwachsenden Rohstoffen mit hoher Wirksamkeit, hoher Thermostabilität und geringer Flüchtigkeit zur Verfügung zu stellen. Starting from this, it was the object of the present invention to provide sustainable antioxidants for organic materials, in particular polymers based on renewable raw materials, with high effectiveness, high thermal stability and low volatility.
Diese Aufgabe wird bezüglich der Verwendung einer in Patentanspruch 1 definierten Verbindung der allgemeinen Formel I zur Stabilisierung von organischen Materialien, insbesondere gegen oxidativen, thermischen und/oder actinischen Abbau gelöst. Des Weiteren wird die Aufgabe mit einem organischen Material gemäß Patentanspruch 11 gelöst. Die Erfindung betrifft zudem ein Verfahren zur Stabilisierung von organischen Materialien, wie in Patentanspruch 14 angegeben. Spezifische Zimtsäuresalze, die als Stabilisatoren Verwendung finden, sind in Patentanspruch 15 definiert. Des Weiteren betrifft die vorliegende Erfindung eine Stabilisator- Zusammensetzung gemäß Patentanspruch 16. Die jeweiligen abhängigen Patentansprüche stellen dabei vorteilhafte Weiterbildungen dar. This object is achieved with regard to the use of a compound of the general formula I defined in claim 1 for stabilizing organic materials, in particular against oxidative, thermal and / or actinic degradation. Furthermore, the object is achieved with an organic material according to patent claim 11. The invention also relates to a method for stabilizing organic materials, as specified in claim 14. Specific cinnamic acid salts which are used as stabilizers are defined in claim 15. Furthermore, the present invention relates to a stabilizer composition according to claim 16. The respective dependent claims represent advantageous developments.
Gemäß einem ersten Aspekt betrifft die vorliegende Erfindung somit die Verwendung einer Verbindung oder Mischungen mehrerer Verbindungen gemäß allgemeiner Formel I
wobei According to a first aspect, the present invention thus relates to the use of a compound or mixtures of several compounds according to general formula I whereby
R1, R2 und R3 jeweils unabhängig voneinander ausgewählt sind aus der Gruppe bestehend aus Hydroxy, linearen oder verzweigten Alkoxygruppen mit 1 bis 6 Kohlenstoffatomen und Wasserstoff, mit der Maßgabe, dass mindestens einer der Reste R1, R2 und R3 ein Hydroxyrest ist,
M ausgewählt ist aus der Gruppe bestehend aus Metallen, und n eine ganze Zahl von 1 bis 4 ist, zur Stabilisierung von organischen Materialien, insbesondere gegen oxidativen, thermischen und/oder actinischen Abbau. R 1 , R 2 and R 3 are each independently selected from the group consisting of hydroxyl, linear or branched alkoxy groups having 1 to 6 carbon atoms and hydrogen, with the proviso that at least one of the radicals R 1 , R 2 and R 3 is a Hydroxyrest is M is selected from the group consisting of metals, and n is an integer from 1 to 4, for stabilizing organic materials, in particular against oxidative, thermal and / or actinic degradation.
Erfindungsgemäß werden Kosmetika nicht zu den organischen Materialien gezählt. According to the invention, cosmetics are not counted among the organic materials.
Erfindungsgemäß wird somit ein Metallsalz einer Hydroxyzimtsäure, bei der zumindest eine Phenolgruppe eine sterische Hinderung aufweist, als Stabilisator eingesetzt. According to the invention, a metal salt of a hydroxycinnamic acid in which at least one phenol group has steric hindrance is used as a stabilizer.
Überraschenderweise wurde gefunden, dass die erfindungsgemäßen Verbindungen gemäß Formel I als Stabilisatoren wirken und auf Basis nach- wachsender Rohstoffe eine hohe Wirksamkeit, Umweltfreundlichkeit und eine günstige Kostenstruktur aufweisen. It has surprisingly been found that the compounds according to the invention according to formula I act as stabilizers and, based on renewable raw materials, have a high level of effectiveness, environmental friendliness and a favorable cost structure.
Eine bevorzugte Ausführungsform sieht vor, dass die Erfindung die Stabilisierung von Kunststoffen, Beschichtungen, Schmiermitteln, Hydraulikölen, Motorenölen, Turbinenölen, Getriebeölen, Metallbearbeitungs- flüssigkeiten, Chemikalien oder Monomeren betrifft. Beispielsweise Kunststoffe in Form von Spritzgussteilen, Folien oder Filmen, Schäumen, Fasern, Kabeln und Rohren, Profilen, Hohlkörpern, Bändchen, Membranen, wie z.B. Geomembranen, oder Klebstoffen, die über Extrusion, Spritzguss, Blasformen, Kalandrieren, Pressverfahren, Spinnprozesse, Rotomoulding hergestellt werden z.B. für die Elektro- und Elektronikindustrie, Bauindustrie, Transportindustrie (Auto, Flugzeug, Schiff, Bahn), für medizinische Anwendungen, für Haushalts- und Elektrogeräte, Fahrzeugteile, Konsumartikel, Verpackungen, Möbel, Textilien. Ein weiterer Einsatzbereich sind Lacke, Farben und Beschichtungen (Coatings) sowie die Stabilisierung von Ölen und Fetten. A preferred embodiment provides that the invention relates to the stabilization of plastics, coatings, lubricants, hydraulic oils, engine oils, turbine oils, gear oils, metal working fluids, chemicals or monomers. For example, plastics in the form of injection molded parts, foils or films, foams, fibers, cables and pipes, profiles, hollow bodies, tapes, membranes such as geomembranes, or adhesives that are manufactured via extrusion, injection molding, blow molding, calendering, pressing processes, spinning processes, rotomoulding are for example for the electrical and electronics industry, construction industry, transport industry (car, airplane, ship, train), for medical applications, for household and electrical appliances, vehicle parts, consumer goods, packaging, furniture, textiles. Another area of application are paints, paints and coatings as well as the stabilization of oils and fats.
Eine bevorzugte Ausführungsform sieht vor, dass die Reste R1, R2 und R3 jeweils ein Hydroxyrest, zwei der Reste R1, R2 und R3 ein Hydroxyrest und einer der Reste R1, R2 und R3 Wasserstoff oder eine lineare oder verzweigte Alkoxygruppe mit 1 bis 6
Kohlenstoffatomen, einer der Reste R1, R2 und R3 ein Hydroxyrest und zwei der Reste R1, R2 und R3 eine lineare oder verzweigte Alkoxygruppe mit 1 bis 6 Kohlenstoffatomen, oder je einer der Reste R1, R2 und R3 ein Hydroxyrest, eine lineare oder verzweigte Alkoxygruppe mit 1 bis 6 Kohlenstoffatomen und Wasserstoff darstellen. A preferred embodiment provides that the radicals R 1 , R 2 and R 3 are each a hydroxy radical, two of the radicals R 1 , R 2 and R 3 are hydroxy and one of the radicals R 1 , R 2 and R 3 is hydrogen or a linear one or branched alkoxy group of 1 to 6 Carbon atoms, one of the radicals R 1 , R 2 and R 3 is a hydroxy radical and two of the radicals R 1 , R 2 and R 3 are a linear or branched alkoxy group with 1 to 6 carbon atoms, or one of the radicals R 1 , R 2 and R each 3 represent a hydroxy group, a linear or branched alkoxy group having 1 to 6 carbon atoms and hydrogen.
Gemäß einer besonders bevorzugten Ausführungsform ist die Verbindung gemäß allgemeiner Formel I ausgewählt aus der Gruppe bestehend aus den nachfolgenden Verbindungen:
wobei M und n wie voranstehend definiert sind. According to a particularly preferred embodiment, the compound according to general formula I is selected from the group consisting of the following compounds: where M and n are as defined above.
Gemäß dieser bevorzugten Ausführungsform leiten sich die erfindungsgemäß verwendeten Hydroxyzimtsäuresalze somit von den nachfolgenden Hydroxyzimtsäuren ab: a) Ferulasäure
b) Isoferulasäure
c) Kaffeesäure
d) Sinapinsäure
According to this preferred embodiment, the hydroxycinnamic acid salts used according to the invention are thus derived from the following hydroxycinnamic acids: a) Ferulic acid b) isoferulic acid c) caffeic acid d) sinapic acid
Insbesondere sind die Metalle M dabei ausgewählt aus der Gruppe bestehend aus Alkalimetallen, Erdalkalimetallen, Aluminium und Zink In particular, the metals M are selected from the group consisting of alkali metals, alkaline earth metals, aluminum and zinc
Bevorzugte Alkalimetalle sind hierbei Lithium, Natrium und Kalium, wobei Natrium besonders bevorzugt ist. Bevorzugte Erdalkalimetalle sind insbesondere Magnesium und Calcium. Preferred alkali metals here are lithium, sodium and potassium, with sodium being particularly preferred. Preferred alkaline earth metals are, in particular, magnesium and calcium.
Eine weiter bevorzugte Ausführungsform der vorliegenden Erfindung sieht vor, dass die Verbindung gemäß allgemeiner Formel I oder im Falle einer Mischung mehrerer Verbindungen gemäß allgemeiner Formel I die Gesamtheit aller Verbindungen gemäß allgemeiner Formel I zu einem Gewichtsanteil von 0,01 bis 10,00 Gew.-%, bevorzugt von 0,02 bis 5,00 Gew.-%, besonders bevorzugt von 0,05 bis 2,00 Gew.-% im organischen Material enthalten ist. A further preferred embodiment of the present invention provides that the compound according to general formula I or, in the case of a mixture of several compounds according to general formula I, all of the compounds according to general formula I in a proportion by weight of 0.01 to 10.00 wt. %, preferably from 0.02 to 5.00% by weight, particularly preferably from 0.05 to 2.00% by weight, is contained in the organic material.
Insbesondere eignet sich die vorliegende Erfindung zur Stabilisierung von thermoplastischen, elastomeren oder duromeren Polymeren. Thermoplastische und duromere Polymere sind beispielsweise: a) Polymeren aus Olefinen oder Diolefinen wie z.B. Polyethylen (LDPE, LLDPE, VLDPE, ULDPE, MDPE, HDPE, UHMWPE), Metallocen-PE (m-PE), Polypropylen, Polyisobutylen, Poly-4-methyl-penten-1, Polybutadien, Polyisopren, wie z.B. auch Naturkautschuk (NR), Polycycloocten, Polyalkylen-Kohlenmonoxid-Copolymere, sowie Copolymere in Form von statistischen 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, Ethylen-Acrylsäure und deren Salze (lonomere), sowie
Terpolymere wie z.B. Ethylen-Acrylsäure-Glycidyl(meth)acrylat, Pfropf- polymere wie z.B. Polypropylen-graft-Maleinsäureanhydrid, Poly- propylen-graft -Acrylsäure, Polyethylen-graft-Acrylsäure, Polyethylen- Polybutylacrylat-graft-Maleinsäureanhydrid sowie Blends wie z.B. LDPE/LLDPE oder auch langkettenverzweigte Polypropylen-Copolymere die mit alpha-Olefinen als Comonomere hergestellt werden wie z.B. mit 1-Buten, 1-Hexen, 1-Octen oder 1-Octadecen b) Polystyrol, Polymethylstyrol, Poly-alpha-methylstyrol, Polyvinyl- naphthalin, Polyvinylbiphenyl, Polyvinyltoluol, Styrol-Butadien (SB), Styrol-Butadien-Styrol (SBS), Styrol-Ethylen-Butylen-Styrol (SEBS), Styrol- Ethylen-Propylen-Styrol, Styrol-Isopren, Styrol-Isopren-Styrol (SIS), Styrol-butadien-acrylnitril (ABS), Styrol-acrylnitril (SAN), Styrol-acrylnitril- acrylat (ASA), Styrol-Ethylen, Styrol-Maleinsäureanhydrid-Polymere einschl. entsprechender Pfropfcopolymere wie z.B. Styrol auf Butadien, Maleinsäureanhydrid auf SBS oder SEBS, sowie Pfropfcopolymere aus Methylmethacrylat, Styrol-Butadien und ABS (MABS), sowie hydrierte Polystyrol-Derivate wie z.B. Polyvinylcyclohexan c) halogenenthaltenden Polymeren wie z.B. Polyvinylchlorid (PVC), Polychlorpren 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 Polymethacrylate wie Polymethylmethacrylat (PMMA), Polybutylacrylat, Polylaurylacrylat, Polystearylacrylat, Polyglycidylacrylat, Polyglycidyl- methacrylat, Polyacrylnitril, Polyacrylamide, Copolymere wie z.B. Polyacrylnitril-Polyalkylacrylat, e) Polymeren aus ungesättigten Alkoholen und Derivaten, wie z.B. Polyvinylalkohol, Polyvinylacetat, Polyvinylbutyral, Polyallylphthalat, Polyallylmelamin
f) Polyacetalen, wie z.B. Polyoxymethylen (POM) oder Copolymere mit z.B. Butanal, g) Polyphenylenoxiden und Blends mit Polystyrol oder Polyamiden, h) Polymeren von cyclischen Ethern wie z.B. Polyethylenglycol, Polypropylenglycol, Polyethylenoxid, Polypropylenoxid, Polytetra- hydrofuran, i) Polyurethanen, aus hydroxyterminierten Polyethern oder Polyestern und aromatischen oder aliphatischen Isocyanaten wie z.B. 2,4- oder 2,6 Toluylendiisocyanat oder Methylendiphenyldiisocyanat insbesondere auch lineare Polyurethane (TPU), Polyharnstoffen, 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 k) Polyimiden, Polyamid-imiden, Polyetherimiden, Polyesterimiden, Poly- (ether)ketonen, Polysulfonen, Polyethersulfonen, Polyarylsulfonen, Poly- phenylensulfiden, Polybenzimidazolen, Polyhydantoinen, The present invention is particularly suitable for stabilizing thermoplastic, elastomeric or thermosetting polymers. Thermoplastic and thermoset polymers are for example: a) Polymers made from olefins or diolefins such as polyethylene (LDPE, 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, as well as copolymers in the form of random or block structures such as polypropylene-polyethylene (EP), EPM or EPDM with e.g. 5- Ethylidene-2-norbornene as comonomer, ethylene-vinyl acetate (EVA), ethylene-acrylic esters, such as, for example, ethylene-butyl acrylate, ethylene-acrylic acid and their salts (ionomers), as well as 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 1-butene, 1-hexene, 1-octene or 1-octadecene b) polystyrene, polymethylstyrene, poly-alpha-methylstyrene, polyvinylnaphthalene , 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 corresponding graft copolymers such as styrene on butadiene, maleic anhydride on SBS or SEBS, as well as Pfropfcopol ymers made from methyl methacrylate, styrene-butadiene and ABS (MABS), and hydrogenated polystyrene derivatives such as polyvinylcyclohexane c) halogen-containing polymers such as polyvinyl chloride (PVC), polychlorprene and polyvinylidene chloride (PVDC), copolymers made from vinyl chloride and vinylidene chloride or from vinyl chloride and vinyl acetate, chlorinated polyethylene, polyvinylidene fluoride, epichlorohydrin homo and copolymers, in particular 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, polyacrylate acrylate, polyglycidyl acrylate, polyacrylate acrylate, polystearyl acrylate, polyglycidyl acrylate Copolymers, such as, for example, polyacrylonitrile-polyalkyl acrylate, e) polymers of unsaturated alcohols and derivatives, such as, for example, polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyallyl phthalate, polyallyl melamine f) polyacetals, such as polyoxymethylene (POM) or copolymers with, for example, butanal, 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, from hydroxy-terminated polyethers or polyesters and aromatic or aliphatic isocyanates such as 2,4- or 2,6 tolylene diisocyanate or methylenediphenyl diisocyanate, especially linear polyurethanes (TPU), polyureas, 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, for example 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 n polyamides such as PA-6 and PA 6.6 or blends of polyamides and polyolefins such as PA / PP 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 Diolen oder aus Hydroxy-Carbonsäuren wie z.B. Polyethylenterephthalat (PET), Polybutylenterephthalat (PBT), Polypropylenterephthalat (PTT), Polyethylennaphthylat (PEN), Poly-1,4-dimethylolcyclohexantereph- thalat, Polyhydroxybenzoat, Polyhydroxynaphthalat, Polymilchsäure (PLA), Polyhydroxybutyrat (PHB), Polyhydroxyvalerat (PHV), Polyethylensuccinat, Polytetramethylensuccinat, Polycaprolacton
m) Polycarbonaten, Polyestercarbonaten, sowie Blends wie z.B. PC/ABS, PC/PBT, PC/PET/PBT, PC/PA n) Cellulosederivaten wie z.B. Cellulosenitrat, Celluloseacetat,L) Polyesters 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-dimethylolcyclohexane terephthalate, polyhydroxaphthalate , 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) Cellulose derivatives such as cellulose nitrate, cellulose acetate,
5 Cellulosepropionat, Cellulosebutyrat, o) Epoxidharzen, bestehend aus di- oder polyfunktionellen Epoxid- verbindungen in Kombination mit z.B. Härtern auf der Basis von Aminen, Anhydriden, Dicyandiamid, Mercaptanen, Isocyanaten oder katalytisch5 Cellulose propionate, cellulose butyrate, o) epoxy resins, consisting of di- or polyfunctional epoxy compounds in combination with e.g. hardeners based on amines, anhydrides, dicyandiamide, mercaptans, isocyanates or catalytic
10 wirkenden Härtern, p) Phenolharzen wie z.B. Phenol-Formaldehyd-Harze, Harnstoff-10 active hardeners, p) phenolic resins such as phenol-formaldehyde resins, urea
Formaldehyd-Harze, Melamin-Formaldehydharze, Formaldehyde resins, melamine-formaldehyde resins,
15 q) ungesättigten Polyesterharzen aus ungesättigten Dicarbonsäuren und Diolen mit Vinylverbindungen z.B. Styrol, Alkydharze, Allylharze r) Silikonen, z.B. auf der Basis von Dimethylsiloxanen, Methyl-Phenyl- siloxanen oder Diphenylsiloxanen z.B. Vinylgruppen terminiert 15 q) unsaturated polyester resins made from unsaturated dicarboxylic acids and diols with vinyl compounds e.g. styrene, alkyd resins, allyl resins r) silicones, e.g. based on dimethylsiloxanes, methylphenylsiloxanes or diphenylsiloxanes, e.g. terminated with vinyl groups
20 s) sowie Mischungen, Kombinationen oder Blends aus zwei oder mehr der zuvor genannten Polymere. 20 s) and mixtures, combinations or blends of two or more of the aforementioned polymers.
Sofern es sich bei den unter a) bis r) angegebenen Polymeren um CopolymereIf the polymers specified under a) to r) are copolymers
25 handelt, können diese in Form von statistischen („random"), Block- oder „tapered" Strukturen vorliegen. Weiterhin können die genannten Polymeren in Form von linearen, verzweigten, sternförmigen oder hyperverzweigten Strukturen vorliegen. 25 acts, these can be in the form of statistical ("random"), block or "tapered" structures. Furthermore, the polymers mentioned can be in the form of linear, branched, star-shaped or hyperbranched structures.
BO Sofern es sich bei den unter a) bis r) angegebenen Polymeren um stereoreguläre Polymere handelt, können diese in Form von isotaktischen, stereotaktischen, aber auch ataktischen Formen oder als Stereoblock- copolymere vorliegen. BO 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.
35 Weiterhin können die unter a) bis r) angegebenen Polymere sowohl amorphe als auch (teil-) kristalline Morphologien aufweisen.
Ggf. können die unter a) genannten Polyolefine auch vernetzt vorliegen, z.B. vernetztes Polyethylen, das dann als X-PE bezeichnet wird. Furthermore, the polymers specified under a) to r) can have both amorphous and (partially) crystalline morphologies. If necessary, the polyolefins mentioned under a) can also be present in crosslinked form, for example crosslinked polyethylene, which is then referred to as X-PE.
Weiterhin können die vorliegenden Verbindungen zur Stabilisierung von Kautschuken und Elastomeren eingesetzt werden. Hier kann es sich um Naturkautschuk (NR) oder synthetische Kautschukmaterialien wie z.B. NR (Natural Rubber), Chloropren (CR), Polybutadien (BR), Styrol-Butadien (SBR), Polyisopren (IR), Butylkautschuk (IIR), Nitrilkautschuk (NBR), hydrierter Nitrilkautschuk (HNBR), Polyester- oder Polyether-Urethan-Kautschuk, Silikonkautschuk handeln. The present compounds can also be used to stabilize rubbers and elastomers. This can be natural rubber (NR) or synthetic rubber materials such as NR (Natural Rubber), chloroprene (CR), polybutadiene (BR), styrene-butadiene (SBR), polyisoprene (IR), butyl rubber (IIR), nitrile rubber (NBR ), hydrogenated nitrile rubber (HNBR), polyester or polyether urethane rubber, silicone rubber.
Außer um Neuware kann es sich bei den Kunststoffen um rezyklierte Kunststoffe z. B. aus Industriesammlungen wie z.B. Produktionsabfälle oder um Kunststoffe aus Haushalts- oder Wertstoffsammlungen handeln. In addition to new goods, the plastics can be recycled plastics e.g. B. from industrial collections such as production waste or plastics from household or recyclable material collections.
Bevorzugt sind als Kunststoffe thermoplastische Kunststoffe und insbesondere Kunststoffe, die in Verpackungen wie z.B. Lebensmittelverpackungen eingesetzt werden, insbesondere Polyolefine, Polystyrol, Polyester und Polyamide. Ganz besonders bevorzugt sind Polypropylen Homo- und Copolymere, sowie Polyethylen in Form von LDPE, LLDPE, HDPE, MDPE, VLDPE und Polyethylenterephthalat (PET), Homo- und Copolymere. Preferred plastics are thermoplastics and, in particular, plastics that are used in packaging such as food packaging, in particular polyolefins, polystyrene, polyesters and polyamides. Polypropylene homo- and copolymers, and also polyethylene in the form of LDPE, LLDPE, HDPE, MDPE, VLDPE and polyethylene terephthalate (PET), homo- and copolymers are very particularly preferred.
Weiterhin insbesondere bevorzugt sind aliphatische Polyester aus nachwachsenden Rohstoffen, die im Wesentlichen aus aliphatischen Dicarbonsäuren und aliphatischen Diolen, aus Hydroxycarbonsäuren oder Lactonen hergestellt werden wie z.B. Polymilchsäure (PLA), Polyglycolsäure (PGA), Polyhydroxybuttersäure (PHB), Polyhydroxyvaleriansäure (PHV), Polyethyelnsuccinat (PESu) Polybutylensuccinat (PBS), Polyethylenadipat Poly(butylensuccinat-co-adipat) (PBSA) oder Polycaprolacton (PCL). Also particularly preferred are aliphatic polyesters from renewable raw materials, which are essentially produced from aliphatic dicarboxylic acids and aliphatic diols, from hydroxycarboxylic acids or lactones, such as polylactic acid (PLA), polyglycolic acid (PGA), polyhydroxybutyric acid (PHB), polyhydroxyvaleric acid (PHV), polyhydroxyvaleric acid (PHV). PESu) polybutylene succinate (PBS), polyethylene adipate poly (butylene succinate-co-adipate) (PBSA) or polycaprolactone (PCL).
Die Kunststoffe können erfindungsgemäß insbesondere in Form von Spritzgussteilen, Folien oder Filmen, Schäumen, Fasern, Kabeln und Rohren, Profilen, Hohlkörper, Bändchen, Membranen, wie z.B. Geomembranen, oder Klebstoffen, die über Extrusion, Spritzguss, Blasformen, Kalandrieren,
Pressverfahren, Spinnprozesse, Rotomoulding hergestellt werden z.B. für die Elektro- und Elektronikindustrie, Bauindustrie, Transportindustrie (Auto, Flugzeug, Schiff, Bahn), für medizinische Anwendungen, für Haushalts- und Elektrogeräte, Fahrzeugteile, Konsumartikel, Verpackungen, Möbel, Textilien vorliegen. Ein weiterer Einsatzbereich sind Lacke, Farben und Beschichtungen (Coatings) sowie die Stabilisierung von Ölen und Fetten.. According to the invention, the plastics can in particular in the form of injection molded parts, foils or films, foams, fibers, cables and pipes, profiles, hollow bodies, tapes, membranes, such as geomembranes, or adhesives that are produced via extrusion, injection molding, blow molding, calendering, Pressing processes, spinning processes, rotomoulding are produced e.g. for the electrical and electronics industry, construction industry, transport industry (car, aircraft, ship, train), for medical applications, for household and electrical appliances, vehicle parts, consumer goods, packaging, furniture, textiles. Another area of application are paints, paints and coatings as well as the stabilization of oils and fats.
Eine weitere vorteilhafte Ausführungsform der erfindungsgemäßen Verwendung zeichnet sich dadurch aus, dass der Kunststoff mindestens ein weiterer Zusatzstoff, ausgewählt aus der Gruppe bestehend aus primären und/oder sekundären Antioxidantien, insbesondere primären und/oder sekundären Antioxidantien ausgewählt aus der Gruppe bestehend aus Phosphiten, Phosphoniten, Thiolen, phenolischen Antioxidantien, sterisch gehinderten Aminen, Hydroxylaminen sowie Mischungen oder Kombinationen hiervon, UV-Absorbern, Lichtstabilisatoren, Hydroxylamin basierten Stabilisatoren, Benzofuranon basierten Stabilisatoren, Nukleierungsmitteln, Schlagzähigkeitsverbesserern, Weichmachern, Gleitmitteln, Rheologiemodi- fikatoren, Kettenverlängerern, Verarbeitungshilfsmitteln, Pigmenten, Farb- stoffen, optischen Aufhellern, antimikrobiellen Wirkstoffen, Antistatika, Slip- mitteln, Antiblockmitteln, Kopplungsmitteln, Dispergiermitteln, Kompatibilisatoren, Sauerstofffängern, Säurefängern, Costabilisatoren, Markierungsmitteln sowie Antifoggingmitteln bei der Verwendung dem Kunststoff zugesetzt wird und/oder enthält. Another advantageous embodiment of the use according to the invention is characterized in that the plastic has at least one further additive selected from the group consisting of primary and / or secondary antioxidants, in particular primary and / or secondary antioxidants selected from the group consisting of phosphites, phosphonites, Thiols, phenolic antioxidants, sterically hindered amines, hydroxylamines and mixtures or combinations thereof, UV absorbers, light stabilizers, hydroxylamine-based stabilizers, benzofuranone-based stabilizers, nucleating agents, impact strength improvers, plasticizers, lubricants, rheology modifiers, pigments, color extenders, chain extenders substances, optical brighteners, antimicrobial agents, antistatic agents, slip agents, antiblocking agents, coupling agents, dispersants, compatibilizers, oxygen scavengers, acid scavengers, costabilizers, markers gsmittel as well as anti-fogging agents is added to the plastic during use and / or contains.
Geeignete primäre Antioxidantien (A) sind phenolische Antioxidantien, Amine und Lactone Suitable primary antioxidants (A) are phenolic antioxidants, amines and lactones
Geeignete synthetische phenolische Antioxidantien sind beispielsweise: 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-(α-Methylcyclohexyl)-4,6-dimethylphenol, 2,6-Dioctadecyl-4- methylphenol, 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-(1'-methylundec-1'-yl)phenol, 2,4-Dimethyl-6-(1'-
methylheptadec-1'-yl)phenol, 2,4-Dimethyl-6-(1'-methyltridec-1'-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- (1'-methylundec-1'-yl) phenol, 2,4-dimethyl-6- (1'- methylheptadec-1'-yl) phenol, 2,4-dimethyl-6- (1'-methyltridec-1'-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,Alkylthiomethylphenols such as 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol,
2.6-Didodecylthiomethyl-4-nonylphenol; 2,6-didodecylthiomethyl-4-nonylphenol;
Hydrochinone und alkylierte Hydrochinone, wie z.B. 2,6-Di-tert-butyl-4- methyoxyphenol, 2,5-Di-tert-butylhydrochinon, 2,5-Di-tert-amylhydrochinon,Hydroquinones and alkylated hydroquinones such as 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-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; 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;
Tocopherole, wie z.B. a-, ß-, y-, d-Tocopherol und Mischungen aus diesen (Vitamin E); Tocopherols such as α-, β-, γ-, d-tocopherol and mixtures of these (vitamin E);
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-methylphenol), 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- methylcyclohexyßphenol], 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-(α-methylbenzyl)-4-nonyl- phenol], 2,2'-Methylenbis[6-(a,a-dimethylbenzyl)-4-nonylphenol], 4,4'-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-methylcyclohexylphenol], 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'-methylenebis [6- (α-methylbenzyl) -4-nonylphenol], 2,2'-methylenebis [6- (a, a-dimethylbenzyl) -4-nonylphenol], 4,4'-
Methylenbis(2,6-di-tert-butylphenol, 4,4'-Methylenbis(6-tert-butyl-2-methyl- phenol), 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butan, 2,6-Bis(3-tert- butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-Tris(5-tert-butyl-4- hydroxy-2-methylphenyl)butan, 1,1-bis(5-tert-butyl-4-hydroxy-2-methyl- phenyl)-3-n-dodecylmercaptobutan, Ethylenglycol-bis[3,3-bis(3'-tert-butyl-4'- hydroxyphenyl)butyrat], Bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclo- pentadien, Bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4- methylphenyl]terephthalat, 1,1-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-methylphenyl)-4-n-dodecylmercaptobutan, 1,1,5,5-Tetra(5-tert-butyl-4- hydroxy-2-methylphenyl)pentan; Methylenebis (2,6-di-tert-butylphenol, 4,4'-methylenebis (6-tert-butyl-2-methyl-phenol), 1,1-bis (5-tert-butyl-4-hydroxy-2- methylphenyl) butane, 2,6-bis (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl ) butane, 1,1-bis (5-tert-butyl-4-hydroxy-2-methyl-phenyl) -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-methylphenyl) -4-n-dodecyl mercaptobutane, 1,1, 5,5-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, Iso- octyl-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 dimethyl benzyl) dithioterephthalate, bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, iso-octyl-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-(1,1,3,3-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, didodecylmercaptoethyl-2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, bis [4- (1,1,3,3-tetramethylbutyl) phenyl] -2,2- bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate;
Aromatische Hydroxybenzylverbindungen, wie z.B. 1,3,5-Tris(3,5-di-tert-butyl- 4-hydroxybenzyl)-2,4,6-trimethylbenzol, 1,4-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 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)-1,3,5-triazin, 2-Octylmercapto-4,6-bis(3,5-di-tert-butyl-4- hydroxyanilino)-1,3,5-triazin, 2-Octylmercapto-4,6-bis(3,5-di-tert-butyl-4- hydroxyphenoxy)-1,3,5-triazin, 2,4,6-Tris(3,5-di-tert-butyl-4-hydroxyphenoxy)- 1,2,3-triazin, 1,3,5-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurat, 1,3,5- Tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurat, 2,4,6-T ris(3,5-di- tert-butyl-4-hydroxphenylethyl)-1,3,5-triazin, 1,3,5-Tris(3,5-di-tert-butyl-4- hydroyphenylpropionyl)hexahydro-1,3,5-triazin, 1,3,5-Tris(3,5-dicyclohexyl-4- hydroxybenzyl)isocyanurat; Triazine compounds such as 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) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,3 , 5-triazine, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenoxy) - 1,2,3-triazine, 1,3,5-tris (3,5-di- tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris (3,5-di - tert-butyl-4-hydroxphenylethyl) -1,3,5-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroyphenylpropionyl) 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-hydroxybenzyl- phosphonat, Dietyhl-3,5-di-tert-butyl-4-hydroxybenzylphosphonat, Di- octadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonat, Dioctadecyl-5-tert-
butyl-4-hydroxy-B-methylbenzylphosphonat, das Calciumsalz des Mono- ethylesters der 3,5-Di-tert-butyl-4-hydroxybenzylphosphonsäure; Benzyl phosphonates, such as dimethyl 2,5-di-tert-butyl-4-hydroxybenzyl phosphonate, Dietyhl-3,5-di-tert-butyl-4-hydroxybenzyl phosphonate, di-octadecyl-3,5-di-tert- butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert- butyl 4-hydroxy-B-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 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, Octadecanol, 1,6-Hexandiol, 1,9-Nonandiol, Ethylenglycol, 1,2-Propandiol, Neopentylglycol, Thiodiethylenglycol, Diethylenglycol, Triethylenglycol, Pentaerythritol, Tris(hydroxyethyl)isocyanurat, N,N'-Bis(hydroxyethyl)oxamid,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-Thiaundecanol, 3-Thiapentadecanol, Trimethylhexandiol, Trimethylolpropan,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane,
4-Hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octan; 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, Octadecanol, 1,6-Hexandiol, 1,9-Nonandiol, Ethylenglycol, 1,2-Propandiol, Neopentylglycol, Thiodiethylenglycol, Diethylenglycol, Triethylenglycol, Penta- erythritol, Tris(hydroxyethyl)isocyanurat, N,N'-bis(hydroxyethyl)oxamid, 3- Thiaundecanol, 3-Thiapentadecanol, Trimethylhexandiol, Trimethylolpropan, 4-Hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octan, 3,9-Bis[2-{3-(3- tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}- 1,1-dimethylethyl]- 2,4,8,10-tetraoxaspiro[5.5]undecan; Esters of ß- (5-tert-butyl-4-hydroxy-3-methylphenyl) 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-thiaundecanol, 3-thiapentadecanol, , 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} - 1,1-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- 1-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, trimethylolxymethyl- 1-phosphymethyl 2,6,7-trioxabicyclo [2.2.2] octane;
Ester der (3,5-Di-tert-butyl-4-hydroxyphenyl)essigsäure 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-Esters of (3,5-di-tert-butyl-4-hydroxyphenyl) acetic 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, Trimethylhexandiol, Trimethylolpropan, 4-Hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octan; Thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane;
Amide der ß-(3,5-Di-tert-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- tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamid (Naugard®XL-1, vertrieben durch Uniroyal); Amides of ß- (3,5-di-tert-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-tert-butyl-4-hydroxyphenyl] propionyloxy) ethyl] oxamide (Naugard ® XL-1, sold by Uniroyal);
Ascorbinsäure (Vitamin C). Ascorbic acid (vitamin C).
Besonders bevorzugte phenolische Antioxidantien sind die folgenden Strukturen:
Ganz besonders bevorzugte phenolische Antioxidantien sind Octadecyl-3-(3,5- di-tert-butyl-4-hydroxyphenyl)propionat und Pentaerythritol tetrakis(3-(3,5-di- tert-butyl-4-hydroxyphenyl)propionat Particularly preferred phenolic antioxidants are the following structures: Very particularly preferred phenolic antioxidants are octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate and pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate
Weitere besonders bevorzugte phenolische Antioxidantien basieren auf nachwachsenden Rohstoffen wie z. B. Tocopherole (Vitamin E), Tocotrienole, Tocomonoenole, Carotenoide, Hydroxytyrosol, Flavonole wie z.B. Chrysin, Quercitin, Hesperidin, Neohesperidin, Naringin, Morin, Kaempferol, Fisetin, Anthocyane, wie z.B. Delphinidin und Malvidin, Curcumin, Carnosolsäure, Carnosol, Rosmarinsäure und Resveratrol. Other particularly preferred phenolic antioxidants are based on renewable raw materials such as. B. tocopherols (vitamin E), tocotrienols, tocomonoenols, carotenoids, hydroxytyrosol, flavonols such as chrysin, quercitin, hesperidin, neohesperidin, naringin, morin, kaempferol, fisetin, anthocyanins such as delphinidin and malvidin, curcumin, carnosolic acid and resveratrol.
Geeignete aminische Antioxidantien sind beispielsweise: N,N'-Di-isopropyl-p-phenylendiamin, N,N'-Di-sec-butyl-p-phenylendiamin, N,N'-Bis(1,4-dimethylpentyl)-p-phenylendiamin, N,N'-Bis(1-ethyl-3-methyl- pentyl)-p-phenylendiamin, N,N'-Bis(1-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-(1,3-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-1-naphthylamin, N-(4-tert-Octylphenyl)-1-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-methoxy- phenyl)amin, 2,6-Di-tert-butyl-4-dimethylaminomethyl-phenol, 2,4'-Di- aminodiphenylmethan, 4,4'-Diaminodiphenylmethan, N,N,N',N'-Tetra- methyl-4,4'-diaminodiphenylmethan, 1,2-Bis[(2-methyl-phenyl)amino]ethan, 1,2-Bis(phenylamino)propan, (o-Tolyl)biguanid, Bis[4-(1',3'-dimethylbutyl)- phenyl]amin, tert- octyliertes N-Phenyl-1-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 dialkylierten Isopropyl/lsohexyl-diphenylaminen, ein Gemisch aus mono- und dialkylierten tert-Butyldiphenylaminen, 2,3-Dihydro-3,3-dimethyl-4H-1,4-
benzothiazin, Phenothiazin, ein Gemisch aus mono- und dialkylierten tert- Butyl/tert-Octylphenothiazinen, ein Gemisch aus mono- und dialkylierten tert-Octylphenothiazinen, N-Allylphenothiazin, N,N,N',N'-Tetraphenyl-1,4- diaminobut-2-en sowie Mischungen oder Kombinationen hiervon. Suitable aminic antioxidants are, for example: N, N'-di-isopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-bis (1,4-dimethylpentyl) -p- phenylenediamine, N, N'-bis (1-ethyl-3-methyl-pentyl) -p-phenylenediamine, N, N'-bis (1-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) -1-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-methoxyphe nyl) amine, 2,6-di-tert-butyl-4-dimethylaminomethyl-phenol, 2,4'-di-aminodiphenyl methane, 4,4'-diaminodiphenyl methane, N, N, N ', N'-tetra-methyl- 4,4'-diaminodiphenylmethane, 1,2-bis [(2-methyl-phenyl) amino] ethane, 1,2-bis (phenylamino) propane, (o-tolyl) biguanide, bis [4- (1 ', 3 '-dimethylbutyl) - phenyl] amine, tert-octylated N-phenyl-1-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- phenylendiamin, N,N'-Di-sec-butyl-p-phenylendiamin, N,N'-Bis(1,4- dimethylpentyl)-p-phenylendiamin, N,N'-Bis(1-ethyl-3-methylpentyl)-p- phenylendiamin, N,N'-Bis(1-methylheptyl)-p-phenylendiamin, N,N'-Preferred aminic 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 (1-ethyl-3-methylpentyl) -p- phenylenediamine, N, N'-bis (1-methylheptyl) -p-phenylenediamine, N, N'-
Dicyclohexyl-p-phenylendiamin, N,N'-Diphenyl-p-phenylendiamin, N,N'-Bis(2- naphthyl)-p-phenylendiamin, N-lsopropyl-N'-phenyl-p-phenylendiamin, N- (1,3-Dimethylbutyl)-N'-phenyl-p-phenylen-diamin, N-(1-Methylheptyl)-N'- phenyl-p-phenylendiamin, N-Cyclohexyl-N'-phenyl-p-phenylendiamin 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-phenylene-diamine, N- (1-methylheptyl) -N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine
Besonders bevorzugte aminische Antioxidantien sind die Strukturen:
mit n= 3 bis 100 Particularly preferred amine antioxidants are the structures: with n = 3 to 100
Weitere bevorzugte aminische Antioxidantien sind Hydroxylamine bzw. N-
oxide (Nitrone), wie z.B. N,N-Dialkylhydroxylamine, N,N-Dibenzylhydroxyl- amin, N,N-Dilaurylhydroxylamin, N,N-Distearylhydroxylamin, N-Benzyl-α- phenylnitron, N-Octadecyl-α-hexadecylnitron, sowie Genox EP (Sl Group ) gemäß der Formel:
Further preferred aminic antioxidants are hydroxylamines or N- oxides (nitrones), such as N, N-dialkylhydroxylamine, N, N-dibenzylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-distearylhydroxylamine, N-benzyl-α-phenyl nitrone, N-octadecyl-α-hexadecyl nitrone, as well Genox EP (Sl Group) according to the formula:
Geeignete Lactone sind Benzofuranone und Indolinone wie z.B. 3-(4-(2- acetoxyethoxy)-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- benzofuran-2-on, 3-(2,3-di- methylphenyl)-5,7-di-tert-butyl-benzofuran-2-on sowie Lactone, die zusätzlich Phosphitgruppen beinhalten wie z.B.
Suitable lactones are benzofuranones and indolinones such as 3- (4- (2-acetoxyethoxy) -phenyl] -5,7-di-tert-butyl-benzofuran-2-one, 5,7-di-tert-butyl 3- [4- (2-stearoyloxyethoxy) phenyl] benzofuran-2-one, 3,3'-bis [5,7-di-tert-butyl-3- (4- (2-hydroxyethoxy] phenyl) benzofuran-2-one ), 5,7-di-tert-butyl-3- (4-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 that also contain phosphite groups such as
Eine weitere geeignete Gruppe von Antioxidantien sind lsoindolo[2,1-
A]chinazoline wie z.B.
Another suitable group of antioxidants are isoindolo [2,1- A] quinazoline such as
Geeignete sekundäre Antioxidantien sind insbesondere Phosphite oder Phosphonite wie z.B. Suitable secondary antioxidants are in particular phosphites or phosphonites such as e.g.
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- methylphenyl)pentaerythritoldiphosphit, Diisodecyloxypentaerythritoldiphos- phit, Bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritoldiphosphit, Bis(2,4,6- tris(tert-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]-1,3,2-dioxaphosphocin, Bis(2,4-di- tert-butyl-6-methylphenyl)methylphosphit, Bis(2,4-di-tert-butyl-6-methyl- phenyl)ethylphosphit, 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-1,1'-biphenyl-2,2'-diyl)phosphit], 2-Ethylhexyl(3,3',5,5'-tetra-tert-butyl- 1,1'-biphenyl-2,2'-diyl))phosphit, 5-Butyl-5-ethyl-2-(2,4,6-tri-tert-butyl- phenoxy)-1,3,2-dioxaphosphiran. Triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tri (nonyl phenyl) phosphite, trilauryl phosphites, trioctadecyl phosphite, distearyl penterythritol diphosphite, tris- (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-phosphite-di-phosphite-tertiary -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 (tert-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] -1,3,2-dioxaphosphocine, bis (2,4-di-tert-butyl-6-methylphenyl) methylphosphite, bis ( 2,4-di-tert-butyl-6-methyl-phenyl) 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-te rt-butyl-1,1'-biphenyl-2,2'-diyl) phosphite], 2-ethylhexyl (3,3 ', 5,5'-tetra-tert-butyl-1,1'-biphenyl-2, 2'-diyl)) phosphite, 5-butyl-5-ethyl-2- (2,4,6-tri-tert-butyl-phenoxy) -1,3,2-dioxaphosphirane.
Besonders bevorzugte Phosphite/Phosphonite sind:
Particularly preferred phosphites / phosphonites are:
20
wobei n= 3-100 bedeutet. 20th where n = 3-100.
Ein bevorzugtes Phosphonit ist:
A preferred phosphonite is:
Ganz besonders bevorzugt wird das Phosphit Tris-(2,4-di-tert- butylphenyl)phosphit als sekundäres Antioxidans verwendet. The phosphite tris (2,4-di-tert-butylphenyl) phosphite is very particularly preferably used as a secondary antioxidant.
Geeignete sekundäre Antioxidantien sind weiterhin Organo- Schwefelverbindungen wie z.B. Sulfide und Disulfide z.B. Distearylthiodipropionat, Dilaurylthiodipropionat; Ditridecyldithiopropionat, Ditetradecylthiodipropionat, 3-(Dodecylthio)-1,1'-[2,2-bis[[3-(dodecylthio)-1- oxopropoxy]methyl]-1,3-propandiyl]propansäureester. Bevorzugt sind die folgenden Strukturen:
Suitable secondary antioxidants are also organosulfur compounds such as sulfides and disulfides, for example distearyl thiodipropionate, dilauryl thiodipropionate; Ditridecyldithiopropionate, ditetradecylthiodipropionate, 3- (dodecylthio) -1,1 '- [2,2-bis [[3- (dodecylthio) -1-oxopropoxy] methyl] -1,3-propanediyl] propanoic acid ester. The following structures are preferred:
Weitere geeignete Organoschwefelverbindungen sind schwefelhaltigeFurther suitable organosulfur compounds are sulfur-containing ones
Aminosäuren insbesondere Cyste in, Cystin oder Methionin. Amino acids in particular cystine, cystine or methionine.
Geeignete Säurefänger („Antiacids") sind Salze von ein, zwei, drei oder vierwertigen Metallen, vorzugsweise Alkali-, Erdalkalimetalle, Aluminium oder Zink, insbesondere gebildet mit Fettsäuren, wie z.B. Calciumstearat, Magnesiumstearat, Zinkstearat, Aluminiumstearat, Calciumlaurat, Calciumbehenat, Calciumlactat, Calciumstearoyl-2-lactat. Weitere Klassen
geeigneter Säurefänger sind Hydrotalcite, insbesondere synthetische Hydrotalcite auf Aluminium-, Magnesium- und Zinkbasis, Hydrocalumite, Zeolithe, Erdalkalioxide, insbesondere Calciumoxid und Magnesiumoxid sowie Zinkoxid, Erdalkalicarbonate, insbesondere Calciumcarbonat, Magnesiumcarbonat und Dolomit sowie Hydroxide, insbesondere BrucitSuitable acid scavengers ("antiacids") are salts of one, two, three or tetravalent metals, preferably alkali metals, 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 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
(Magnesiumhydroxid), (Magnesium hydroxide),
Geeignete Costabilisatoren sind weiterhin Polyole insbesondere Alditole oder Cyclitole. Polyole sind z.B. Pentaerythrit, Dipentaerythrit, Tripentaerythrit, kurzkettige Polyetherpolyole oder kurzkettige Polyesterpolyole, sowie hyperverzweigte Polymere/Oligomere oder Dendrimere mit Alkoholgruppen z.B.
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 hyperbranched polymers / oligomers or dendrimers with alcohol groups, for example
Vorzugsweise wird das mindestens eine Alditol ausgewählt aus der Gruppe bestehend aus Threit, Erythrit, Galactit, Mannit, Ribit, Sorbit, Xylit, Arabit, Isomalt, Lactit, Maltit, Altritol, Iditol, Maltotritol und hydrierte Oligo- und Polysaccharide 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.
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 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. 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
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- pentahydroxycyclohexan, Quercitol, Viscumitol, Bornesitol, Conduritol, Ononitol, Pinitol, Pinpollitol, Quebrachitol, Ciceritol, Chinasäure, Shikimisäure und Valienol, bevorzugt ist dabei myo-lnosit (myo-lnositol). 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-inositol is preferred ( myo-inositol).
Geeignete Lichtstabilisatoren sind beispielsweise Verbindungen auf der Basis von 2-(2'-Hydroxyphenyl)benzotriazolen, 2-Hydroxybenzophenonen, Estern von Benzoesäuren, Acrylaten, Oxamiden und 2-(2-Hydroxyphenyl)-1,3,5- Triazinen. 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) -1,3,5-triazines.
Geeignete 2-(2'-Hydroxyphenyl)benzotriazole sind beispielsweise 2-(2'- Hydroxy-5'methylphenyl)benzotriazol, 2-(3',5'-Di-tert-butyl-2'-hydroxy- phenyl)benzotriazol, 2-(5'-tert-Butyl-2'-hydroxy-phenyl)benzotriazol, 2-(2'- Hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazol, 2-(3',5'-Di-tert- butyl-2'-hydroxyphenyl)-5-chlorbenzotriazol, 2-(3'-tert-Butyl-2'-hydroxy-5'- methylphenyl-5-chlorbenzotriazol, 2-(3'-sec-Butyl-5'-tert-butyl-2'-hydroxy- phenyl)benzotriazol, 2-(2'-Hydroxy-4'-octyloxyphenyl)benzotriazol, 2-(3',5'-Di- tert-amyl-2'-hydroxyphenyl)benzotriazol, 2-(3',5'-Bis(a,a-dimethylbenzyl)-2'- hydroxyphenyl)benzotriazol, 2-(3'-tert-Butyl-2'-hydroxy-5'-(2-octyloxy- carbonylethyl)phenyl)-5-chlorbenzotriazol, 2-(3'-tert-Butyl-5'-[2-(2-ethyl- hexyloxy)carbonylethyl]-2'-hydroxyphenyl)-5-chlorbenzotriazol, 2-(3 '-tert- Butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chlorbenzotriazol, 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)benzo- triazol, 2-(3'-Dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazol, 2-(3 '-tert- Butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotriazol, 2,2'- Methylenbis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-ylphenol]; das
Produkt der Umesterung von 2-[B'-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'-(α,α-dimethylbenzyl)-5'-(1,1,3,3-tetramethylbutyl)- phenyl]benzotriazol, 2-[2'-hydroxy-3'-(1,1,3,3-tetramethylbutyl)-5'-(α,α- dimethylbenzyl)phenyl]benzotriazol. Suitable 2- (2 'hydroxyphenyl) benzotriazoles are for example 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3', 5'-di-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5 '- (1,1,3,3-tetramethylbutyl) phenyl) benzotriazole, 2- (3' , 5'-di-tert-butyl-2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl-5-chlorobenzotriazole, 2- (3'- sec-butyl-5'-tert-butyl-2'-hydroxyphenyl) 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'-tert-butyl-5 '- [2- (2-ethylhexyloxy) carbonylethyl] -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'-tert-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- (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-ylphenol]; the Product of the transesterification of 2- [B'-tert-butyl-5 '- (2-methoxycarbonylethyl) -2'-hydroxyphenyl] -2H-benzotriazole with polyethylene glycol 300; [R - CH 2 CH 2 - COO - CH 2 CH 2 +2, where R = 3'-tert -butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl, 2- [2'-hydroxy -3 '- (α, α-dimethylbenzyl) -5' - (1,1,3,3-tetramethylbutyl) -phenyl] benzotriazole, 2- [2'-hydroxy-3 '- (1,1,3,3 -tetramethylbutyl) -5 '- (α, α-dimethylbenzyl) phenyl] benzotriazole.
Geeignete 2-Hydroxybenzophenone sind beispielsweise 4-Hydroxy-, 4- Methoxy-, 4-Octyloxy-, 4-Decyloxy- 4-Dodecyloxy, 4-Benzyloxy, 4, 2', 4'- Trihydroxy- und 2'-Hydroxy-4,4'-dimethyoxy-Derivate der 2-Hydroxybenzo- phenone. 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-hydroxybenzo- phenones.
Geeignete Acrylate sind beispielsweise Ethyl-α-cyano-ß,ß-diphenylacrylat, lsooctyl-α-cyano-ß,ß-diphenylacrylat, Methyl-α-carbomethoxycinnamat, Methyl-α-cyano-ß-methyl-p-methoxycinnamat, Butyl-α-cyano-ß-methyl-p- methoxycinnamat, Methyl-α-carbomethoxy-p-methoxycinnamat und N-(ß- carbomethoxy-ß-cyanovinyl)-2-methylindolin. Suitable acrylates are, for example, ethyl α-cyano-ß, ß-diphenyl acrylate, isooctyl-α-cyano-ß, ß-diphenyl acrylate, methyl α-carbomethoxycinnamate, methyl α-cyano-ß-methyl-p-methoxycinnamate, butyl α-cyano-ß-methyl-p-methoxycinnamate, methyl-α-carbomethoxy-p-methoxycinnamate and N- (ß-carbomethoxy-ß-cyanovinyl) -2-methylindoline.
Geeignete Ester von Benzoesäuren sind beispielsweise 4-tert-Butylphenyl- salicylat, 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, dibenzoylresorcinol, bis (4-tert-butylbenzoyl) resorcinol, benzoylresorcinol, 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)- oxamid, 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- disubstituierten Oxaniliden und Mischungen von o- und p-Ethoxy- disubstituierten Oxaniliden. 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)-1,3,5-Triazine sind beispielsweise 2,4,6-Tris(2- hydroxy-4-octyloxyphenyl)-1,3,5-triazin, 2-(2-Hydroxy-4-octyloxyphenyl)-4,6-
bis(2,4-dimethylphenyl)-1,3,5-triazin, 2-(2,4-Dihydroxyphenyl)-4,6-bis(2,4-di- methylphenyl)-1,3,5-triazin, 2,4-Bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-di- methylphenyl)-1,3,5-triazin, 2-(2-Hydroxy-4-octyloxyphenyl)-4,6-bis(4-methyl- phenyl-1,3,5-triazin, 2-(2-Hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethyl- phenyl)-1,3,5-triazin, 2-(2-Hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethyl- phenyl)-1,3,5-triazin, 2-[2-Hydroxy-4-(2-hydroxy-3-butyloxypropoxy)-phenyl]- 4,6-bis(2,4-dimethyl)-1,3,5-triazin, 2-[2-Hydroxy-4-(2-hydroxy-3-octyloxypro- pyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazin, 2-[4-(Dodecyloxy/Tri- decyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)- 1,3,5-triazin, 2-[2-Hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6- bis(2,4-dimethylphenyl-1,3,5-triazin, 2-(2-Hydroxy-4-hexyloxy)phenyl-4,6- diphenyl-1,3,5-triazin, 2-(2-Hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-tri- azin, 2,4,6-Tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazin, 2-(2-Hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazin, 2-{2-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- (2-hydroxy-3-octyloxypropyloxy) phenyl] -4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2- [4- (dodecyloxy / tridecyloxy-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-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] -1,3,5-triazine, 2- ( 2-hydroxyphenyl) -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. Hydroxy-4- [3- (2-ethylhexyl-1-oxy) -2-hydroxypropyloxy] phenyl} -4,6-bis (2,4-dimethylphenyl-1,3,5-triazine.
Geeignete Metalldeaktivatoren sind beispielsweise N,N'-Diphenyloxamid, N- Salicylal-N'-salicyloylhydrazin, N,N'-Bis(salicyloyl)hydrazin, N,N'-Bis(3,5-di-tert- butyl-4-hydroxyphenylpropionyl)hydrazin, 3-Salicyloylamino-1,2,4-triazol, Bis(benzyliden)oxalyldihydrazid, Oxanilid, Isophthaloyldihydrazid, Sebacoylbis- phenylhydrazid, N,N'-Diacetyladipoyldihydrazid, N,N'-Bis(salicyloyl)oxylyldi- hydrazid, N,N'-Bis(salicyloyl)thiopropionyldihydrazid. Suitable metal deactivators are, for example, N, N'-diphenyloxamide, N-salicylal-N'-salicyloylhydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3,5-di-tert-butyl-4- hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis (benzylidene) oxalyldihydrazide, oxanilide, isophthaloyldihydrazide, sebacoylbisphenylhydrazide, N, N'-diacetyladipoyldihydrazide, N, N'-bis (salicyloyl) hydrazide, salicyloyl) N, N'-bis (salicyloyl) thiopropionyl dihydrazide.
Besonders bevorzugt als Metalldaktivatoren sind:
Geeignete gehinderte Amine sind beispielsweise 1,1-Bis(2,2,6,6-tetramethyl- 4-piperidyl)succinat, Bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebazat, Bis(1- octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebazat, Bis(1, 2,2,6, 6-pentamethyl- 4-piperidyl)-n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonat, dasParticularly preferred as metal activators are: Suitable hindered amines are, for example, 1,1-bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1 - octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebazate, bis (1, 2,2,6, 6-pentamethyl-4-piperidyl) -n-butyl-3,5-di-tert- butyl 4-hydroxybenzyl malonate, the
Kondensationsprodukt aus 1-(2-Hydroxyethyl)-2,2,6,6-tetramethyl-4- hydroxypiperidin und Succinsäure, lineare oder zyklische Kondensationsprodukte von N,N'-Bis(2 ,2,6,6-tetramethyl-4-piperidyl )hexamethylendiamin und 4-tert-Octylamino-2,6-di-chlor-1,3,5-triazin, Tris(2 ,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetat, Tetrakis(2 ,2,6,6-tetra-methyl- 4-piperidyl)-1,2,3,4-butantetracarboxylat, 1, 1'-(1,2-Ethandiyl)-bis(3, 3,5,5- tetramethylpiperazinon), 4-Benzoyl-2,2,6,6-tetramethylpiperidin, 4- Stearyloxy-2,2,6,6-tetramethylpiperidin, lineare oder zyklische Kondensationsprodukte aus N,N'-Bis(2,2,6,6-tetramethyl-4-piperidyl)hexa- methylendiamin und 4-Morpholino-2,6-dichlor-1,3,5-triazin das Reaktions- produkt von 7,7,9,9-Tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro- [4,5]decan und Epichlorhydrin. 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) -1,2,3,4-butanetetracarboxylate, 1, 1 '- (1,2-ethanediyl) -bis (3, 3,5,5-tetramethylpiperazinone), 4 -Benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, linear or cyclic condensation products of N, N'-bis (2,2,6,6-tetramethyl-4 -piperidyl) hexamethylene diamine 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 -diaza-4-oxospiro- [4,5] decane and epichlorohydrin.
Umfasst in den oben angegebenen Strukturen sind dabei jeweils auch die sterisch gehinderten N-H, N-alkyl wie N-methyl oder N-octyl, die N-alkoxy- Derivate wie N-methoxy oder N-octyloxy, die Cycloalkylderivate wie N- cyclohexyloxy und die N-(2-hydroxy-2-methylpropoxy) Analoga. The structures indicated 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 case of the compounds mentioned above, n is in each case from 3 to 100.
Ein weiterer geeigneter Lichtstabilisator ist Hostanox NOW (Hersteller: Clariant SE) mit der folgenden allgemeinen Struktur:
wobei R -O-C(O)-C15H31oder-O-C(O)-C17H35 bedeutet.
Geeignete Dispereiermittel sind beispielsweise: Another suitable light stabilizer is Hostanox NOW (manufacturer: Clariant SE) with the following general structure: where R is -OC (O) -C 15 H 31 or -OC (O) -C 17 H 35 . Suitable dispensing agents are, for example:
Polyacrylate, z.B. Copolymere mit langkettigen Seitengruppen, Polyacrylat- Blockcopolymere, Alkylamide: z.B. N,N'-1,2-Ethandiylbisoctadecanamid Sorbitanester, z.B. Monostearylsorbitanester, Titanate und Zirconate, reaktive Copolymere mit funktionellen Gruppen z. B. Polypropylen-co-Acrylsäure, Polypropylen-co-Maleinsäureanhydrid, Polyethylen-co-Glycidylmethacrylat, Polystyrol-alt-Maleinsäureanhydrid-Polysiloxane: z.B. Dimethylsilandiol-Polyacrylates, e.g. copolymers with long-chain side groups, polyacrylate block copolymers, alkylamides: e.g. N, N'-1,2-ethanediylbisoctadecanamide, sorbitan esters, e.g. monostearyl sorbitan esters, titanates and zirconates, reactive copolymers with functional groups e.g. B. polypropylene-co-acrylic acid, polypropylene-co-maleic anhydride, polyethylene-co-glycidyl methacrylate, polystyrene-old maleic anhydride-polysiloxanes: e.g. dimethylsilanediol
Ethylenoxid Copolymer, Polyphenylsiloxan Copolymer, Amphiphile Copolymere: z. B. Polyethylen-block-Polyethylenoxid, Dendrimere, z.B. hydroxylgruppenhaltige Dendrimere. Ethylene oxide copolymer, polyphenylsiloxane copolymer, amphiphilic copolymers: e.g. E.g., polyethylene-block-polyethylene oxide, dendrimers, e.g., hydroxyl-containing dendrimers.
Geeignete Antinukleierungsmittel sind Azinfarbstoffe wie z.B. Nigrosin. Geeignete Flammschutzmittel sind insbesondere a) Anorganische Flammschutzmittel wie z.B. AI(OH)3, Mg(OH)2, AIO(OH), MgCO3, Schichtsilikate wie z.B. Montmorillonit oder Sepiolit, nicht oder organisch modifiziert, Doppelsalze, wie z.B. Mg-Al-Silikate, POSS- (Polyhedral Oligomeric Silsesquioxane) Verbindungen, Huntit, Hydromagnesit oder Halloysit sowie Sb2O3, Sb2O5, MoO3, Zinkstannat, Zinkhydroxystannat, b) Stickstoffhaltige Flammschutzmittel wie z.B. Melamin, Melem, Melam, Melon, Melaminderivate, Melaminkondensationsprodukte oder Melaminsalze, Benzoguanamin, Polyisocyanurate, Allantoin, Phosphacene, insbesondere Melamincyanurat, Melaminphosphat, Dimelaminphosphat, Melaminpyrophosphat, Melaminpolyphosphat, Melamin-Metall-Phosphate wie z.B. Melaminaluminiumphosphat, Melaminzinkphosphat, Melaminmagnesiumphosphat, sowie die entsprechenden Pyrophosphate und Polyphosphate, Poly-[2,4- (piperazin-1,4-yl)-6-(morpholin-4-yl)-1,3,5-triazin], Ammoniumpolyphosphat, Melaminborat, Melaminhydrobromid, c) Radikalbildner, wie z. B. Alkoxyamine, Hydroxylaminester, Azoverbindungen, Triazenverbindungen, Disulfide, Polysulfide, Thiole,
Thiuramsulfide, Dithiocarbamate, Mercaptobenzthiazole Sulfenamide, Sulfenimide d) Dicumyl oder Polycumyl, Hydroxyimide und deren Derivate wie z.B. Hydroxyimidester oder Hydroxyimidether e) Phosphorhaltige Flammschutzmitteln wie z.B. roter Phosphor, Phosphate wie z.B. Resorcindiphosphat, Bisphenol-A-diphosphat und ihre Oligomere, Triphenylphosphat, Ethylendiamindiphosphat, Phosphinate wie z.B. Salze der hypophosphorigen Säure und Ihrer Derivate wie Alkylphosphinatsalzen z.B. Diethylphosphinataluminium oder Diethylphosphinat-Zink oder Aluminiumphosphinat, Aluminiumphosphit, Aluminiumphosphonat, Phosphonatester, oligomere und polymere Derivate der Methanphosphonsäure, 9,10-Dihydro-9-oxa-10-phosphoryl- phenanthren-10-oxid (DOPO) und deren substituierte Verbindungen, f) Halogenhaltige Flammschutzmittel auf Chlor- und Brombasis wie z.B. polybrominierte Diphenyloxide, wie z.B. Decabromdiphenyloxid, Tris(3- bromo-2,2-bis(bromomethyl)propyl-phosphat,Suitable anti-nucleating agents are azine dyes such as nigrosine. Suitable flame retardants are in particular a) Inorganic flame retardants such as Al (OH) 3 , Mg (OH) 2 , AIO (OH), MgCO 3 , sheet silicates such as montmorillonite or sepiolite, not modified or organically modified, double salts such as Mg-Al- Silicates, POSS (Polyhedral Oligomeric Silsesquioxane) compounds, huntite, hydromagnesite or halloysite as well as Sb 2 O 3 , Sb 2 O 5 , MoO 3 , zinc stannate, zinc hydroxystannate, b) nitrogen-containing flame retardants such as melamine, melem, melam, melon, melamine derivatives, Melamine condensation products or melamine salts, benzoguanamine, polyisocyanurates, allantoin, phosphacenes, in particular melamine cyanurate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, melamine polyphosphate, melamine metal phosphates such as melamine aluminum phosphate, melamine zinc phosphate, and the corresponding polyphosphate, polyphosphate, and the corresponding polyphosphate, melamine phosphate, and the corresponding [2,4, melamine phosphate, and (piperazin-1,4-yl) -6- (morpholin-4-yl) -1,3,5-triazine], ammonium polyphosphate, melamine borate, melamine hydrobro mid, c) radical formers, such as. B. alkoxyamines, hydroxylamine esters, azo compounds, triazene compounds, disulfides, polysulfides, thiols, Thiuram sulfides, dithiocarbamates, mercaptobenzothiazoles sulfenamides, sulfenimides d) dicumyl or polycumyl, hydroxyimides and their derivatives such as hydroxyimide esters or hydroxyimide ethers e) phosphorus-containing flame retardants such as red phosphorus, phosphates such as resorcinol diphosphate, triphosphate diphosphate, bisphenosphol-amine and their oligophosphate diphosphate, bisphenophospholene Phosphinates such as salts of hypophosphorous acid and its derivatives such as alkyl phosphinate salts such as diethyl phosphinate aluminum or diethyl phosphinate zinc or aluminum phosphinate, aluminum phosphite, aluminum phosphonate, phosphonate esters, oligomeric and polymeric derivatives of methane phosphonic acid, 9,10-dihydro-9-oxa-10-phosphanthrene 10-oxide (DOPO) and its substituted compounds, f) halogen-containing flame retardants based on chlorine and bromine such as polybrominated diphenyl oxides, such as decabromodiphenyl oxide, tris (3-bromo-2,2-bis (bromomethyl) propyl phosphate,
Tris(tribromneopentyl)phosphat, Tetrabromphthalsäure, 1,2-Bis- (tribromphenoxy)ethan, Hexabromcyclododecan, bromiertes Diphenylethan, Tris-(2,3-dibrompropyl)isocyanurat, Ethylen-bis- (tetrabromophthalimid), Tetrabromo-bisphenol A, bromiertes Polystyrol, bromiertes Polybutadien bzw, Polystyrol-bromiertes Polybutadien- Copolymere, bromierter Polyphenylenether, bromiertes Epoxidharz, Polypentabrombenzylacrylat, ggf. in Kombination mit Sb2O3 und/oder Sb2O5, g) Borate wie z.B. Zinkborat oder Calciumborat, ggf. auf Trägermaterial wie z.B. Silica h) Schwefelhaltige Verbindungen wie z.B. elementarer Schwefel, Disulfide und Polysulfide, Thiuramsulfid, Dithiocarbamate, Mercaptobenzthiazol und Sulfenamide, i) Antidrip-Mitteln wie z.B. Polytetrafluorethylen,
j) Siliciumhaltige Verbindungen wie z.B. Polyphenylsiloxane, k) Kohlenstoffmodifikationen wie z.B. Carbon-Nanoröhren (CNT), Blähgraphit oder Graphen Tris (tribromoneopentyl) phosphate, tetrabromophthalic acid, 1,2-bis- (tribromophenoxy) ethane, hexabromocyclododecane, brominated diphenylethane, tris- (2,3-dibromopropyl) isocyanurate, ethylene-bis- (tetrabromophthalimide), tetrabromo-bisphenylated , brominated polybutadiene or polystyrene-brominated polybutadiene copolymers, brominated polyphenylene ether, brominated epoxy resin, polypentabromobenzyl acrylate, possibly in combination with Sb 2 O 3 and / or Sb 2 O 5 , g) borates such as zinc borate or calcium borate, possibly on a carrier material such as silica h) sulfur-containing compounds such as elemental sulfur, disulfides and polysulfides, thiuram sulfide, dithiocarbamates, mercaptobenzothiazole and sulfenamides, i) antidrip agents such as polytetrafluoroethylene, j) silicon-containing compounds such as polyphenylsiloxanes, k) carbon modifications such as carbon nanotubes (CNT), expandable graphite or graphene
L) sowie Kombinationen oder Mischungen hieraus. L) and combinations or mixtures thereof.
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,
mit jeweils R= Alkyl, Phenyl und mit n= 3 bis 20
where R = alkyl, phenyl and where n = 3 to 20
Geeignete Weichmacher sind beispielsweise Phthalsäureester, Adipinsäureester, Ester der Zitronensäure, Ester der 1,2- Cyclohexandicarbonsäure, Trimellithsäureester, Isosorbidester, Phosphatester, Epoxide wie z.B. epoxidiertes Sojabohnenöl oder aliphatische Polyester. Suitable plasticizers are, for example, phthalic acid esters, adipic acid esters, esters of citric acid, esters of 1,2-cyclohexanedicarboxylic acid, trimellitic acid esters, isosorbide esters, phosphate esters, epoxides such as epoxidized soybean oil or aliphatic polyesters.
Geeignete Gleitmittel und Verarbeitungshilfsmittel sind beispielsweise Polyethylenwachse, Polypropylenwachse, Salze von Fettsäuren wie z.B. Calciumstearat, Zinkstearat oder Salze von Montanwachsen, Amidwachse wie z.B. Erucasäureamid oder Ölsäureamide, Fluorpolymere, Silikone oder Neoalkoxytitanate- 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 Pigmente können anorganischer oder organischer Natur sein. Anorganische Pigmente sind beispielsweise Titandioxid, Zinkoxid, Zinksulfid, Eisenoxid, Ultramarin, Ruß, organische Pigmente sind beispielsweise Anthrachinone, Anthanthrone, Benzimidazolone, Chinacridone, Diketopyrrolopyrrole, Dioxazine, Indanthrone, Isoindolinone, Azo- verbindungen, Perylene, Phthalocyanine oder Pyranthrone. Weitere geeignete Pigmente sind Effektpigmente auf Metallbasis oder Perlglanzpigmente auf Metalloxid-Basis. Suitable pigments can be inorganic or organic in 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, azoanthrones, perylenes, phthaloneocyanines or. Further suitable pigments are effect pigments based on metal or pearlescent pigments based on metal oxide.
Geeignete optische Aufheller sind beispielsweise Bisbenzoxazole, Phenylcumarine oder Bis(styryl)biphenyle und insbesondere optische Aufheller der Formeln:
Suitable optical brighteners are, for example, bisbenzoxazoles, phenylcoumarins or bis (styryl) biphenyls and in particular 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, for example with styrene, and epoxides, for example of the following structures:
Geeignete Antistatika sind beispielsweise ethoxylierte Alkylamine, Fettsäureester, Alkylsulfonate und Polymere wie z.B. Polyetheramide. Suitable antistatic agents are, for example, ethoxylated alkyl amines, 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(1,4-dimethylpentyl)-p-phenylendiamin, N,N'-Dicyclohexyl-p- phenylendiamin, N-lsopropyl-N'-phenyl-p-phenylendiamin, N-(1,3- Dimethylbutyl)-N'-phenyl-p-phenylen-diamin, N-(1-Methylheptyl)-N'-phenyl- p-phenylendiamin, N-Cyclohexyl-N'-phenyl-p-phenylendiamin Suitable antiozonants are the above-mentioned amines such as N, N'-di-isopropyl-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 rheology Polypropylen (CR-PP) sind beispielsweise Peroxide, Alkoxyaminester, Oxyimidsulfonsäureester und insbesondere die folgenden Strukturen:
Suitable rheology modifiers, for example for the production of controlled rheology polypropylene (CR-PP), are, for example, peroxides, alkoxyamine esters, oxyimide sulfonic acid esters and in particular the following structures:
Geeignete Nukleierungsmittel sind Talkum, Alkali oder Erdalkalisalze von mono- und polyfunktionellen Carbonsäuren wie z. B. Benzoesäure, Bernsteinsäure, Adipinsäure, z.B. Natriumbenzoat, Zinkglycerolat, Aluminiumhydroxy-bis(4-tert-butyl)benzoat, 2,2'-Methylen-bis-(4,6-di-tert- butylphenyl)phosphat, sowie Trisamide und Diamide wie z.B. Trimesinsäuretricyclohexylamid, Trimesinsäuretri(4-methylcyclohexylamid), Trimesinsäure tri(tert.butylamid), N,N',N"-1,3,5-Benzoltriyltris(2,2-dimethyl- propanamid) oder 2,6-Naphthalindicarbosäuredicyclohexylamid.
Geeignete _ Additive _ zum _ Molekulargewichtsaufbau vonSuitable nucleating agents are talc, alkali or alkaline earth salts of mono- and polyfunctional carboxylic acids such as. Benzoic acid, succinic acid, adipic acid, for example sodium benzoate, Zinkglycerolat, aluminum hydroxy-bis (4-tert-butyl) benzoate, 2,2 '-methylene-bis- (4,6-di-tert-butylphenyl) phosphate, and tris-amides and Diamides such as trimesic acid tri-cyclohexylamide, trimesic acid tri (4-methylcyclohexylamide), trimesic acid tri (tert-butylamide), N, N ' , N " -1,3,5-benzenetriyltris (2,2-dimethylpropanamide) or 2,6-naphthalenedicarboxylic acid dicyclohexylamide . Suitable _ additives _ for _ building up the molecular weight of
Polykondensationspolymeren (Kettenverlängerer) sind Diepoxide, Bis- Oxazoline, Bis-Oxazolone, Bis-Oxazine, Diisocyanate, Dianhydride, Bis- Acyllactame, Bis-Maleimide, Dicyanate, Carbodiimide. Weitere geeignete Kettenverlängerer sind polymere Verbindungen wie z. B. Polystyrol-Polyacrylat- Polyglycidyl(meth)acrylat- Copolymere, Polystyrol-Maleinsäureanhydrid- Copolymere und Polyethylen-Maleinsäureanhydrid-Copolymere. Polycondensation polymers (chain extenders) are diepoxides, bis-oxazolines, bis-oxazolones, bis-oxazines, diisocyanates, dianhydrides, bis-acyl lactams, 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 beispielsweise die erwähnten Antistatika, Ruß und Kohlenstoffverbindungen wie Kohlenstoff-Nanoröhrchen und Graphen, Metallpulver wie z.B. Kupferpulver und leitfähige Polymere wie bsp. Polypyrrole, Polyaniline und Polythiophene. Geignete Additive zur Erhöhung der thermischen Leitfähigkeit sind beispielsweise Aluminumnitride und Bornitride. Suitable additives for increasing 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 e.g. 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, Hydrotalcite 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.
Weiterhin können die erfindungsgemäßen Additive zur Stabilisierung von Ölen, Fetten und chemischen Produkten eingesetzt werden. 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. Pflanzliche Öle und Fette sind beispielsweise Palmöl, Olivenöl, Rapsöl, Leinöl, Sojabohnenöl, Sonnenblumenöl, Rizinusöl; Tierfette sind beispielsweise Fischöle oder Rindertalg. Die erfindungsgemäßen Verbindungen können weiterhin als Stabilisatoren von Schmierstoffen, Hydraulikölen, Motorenölen, Turbinenölen, Getriebeölen Metallbearbeitungsflüssigkeiten oder als Schmierfette eingesetzt werden. Diese mineralischen oder synthetischen Schmierstoffe basieren vorwiegend auf Kohlenwasserstoffen. Bei chemischen Produkten handelt es sich z.B. zur Stabilisierung von Polyolen bei der Polyurethanherstellung oder
von Monomeren wie z.B. Styrol, Acrylester oder Methacrylester für Transport und Lagerung. The additives according to the invention can also be used to stabilize oils, fats and chemical products. If the organic materials are oils and fats, these can be based on mineral oils, vegetable fats or animal fats or oils, fats or waxes based on, for example, 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 working fluids or as lubricating greases. These mineral or synthetic lubricants are mainly based on hydrocarbons. Chemical products are used, for example, to stabilize polyols in polyurethane production or of monomers such as styrene, acrylic ester or methacrylic ester for transport and storage.
Die Einarbeitung der oben beschriebenen Additive und ggf. der zusätzlichen Additive in den Kunststoff erfolgt durch übliche Verarbeitungsmethoden, wobei das Polymere aufgeschmolzen und mit der erfindungsgemäßen Additivzusammensetzung und den ggf. weiteren Zusätzen gemischt wird, vorzugsweise durch Mischer, Kneter oder Extruder. Als Verarbeitungsmaschinen bevorzugt sind Extruder wie z.B. Einschneckenextruder, Zweischneckenextruder, Planetwalzenextruder, Ringextruder, Co-Kneter, die vorzugsweise mit einer Vakuumentgasung ausgestattet sind. Die Verarbeitung kann dabei unter Luft oder ggf. unter Inertgasbedingungen erfolgen. The additives described above and optionally the 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 the optionally further additives, preferably using a mixer, kneader or extruder. 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 Stabilisatoren oder Zusammensetzungen in einem Polymeren enthalten, 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 contain, for example, 10-90% of the stabilizers or compositions according to the invention in a polymer.
Als mögliche Zusatzstoffe kommen insbesondere die voranstehend beschriebenen Zusatzstoffe infrage. Besonders bevorzugt sind hierbei beispielsweise sekundäre Antioxidantien, insbesondere ausgewählt aus der Gruppe bestehend aus Phosphiten, Phosphoniten und Thiolen, Costabilisatoren, ausgewählt aus der Gruppe bestehend aus Polyolen, Säurefängern sowie sterisch gehinderten Aminen bzw. Mischungen und Kombinationen hiervon. The additives described above are particularly suitable as possible additives. For example, secondary antioxidants are particularly preferred, in particular selected from the group consisting of phosphites, phosphonites and thiols, costabilizers selected from the group consisting of polyols, acid scavengers and sterically hindered amines or mixtures and combinations thereof.
Hierbei ist es insbesondere bevorzugt, wenn der mindestens eine Zusatzstoff in einer Menge von 0,01 bis 80 Gew.%, bevorzugt von 0,01 bis 9,99 Gew.-%, weiter bevorzugt von 0,01 bis 4,98 Gew.-%, besonders bevorzugt von 0,02 bis 2,00 Gew.-%, bezogen auf die Gesamtheit der mindestens einen Verbindung gemäß Formel I, des organischen Materials und des mindestens einen Zusatzstoffs, enthalten oder zugesetzt wird. It is particularly preferred here if the at least one additive is present in an amount of 0.01 to 80% by weight, preferably 0.01 to 9.99% by weight, more preferably 0.01 to 4.98% by weight. -%, particularly preferably from 0.02 to 2.00% by weight, based on the totality of the at least one compound according to formula I, the organic material and the at least one additive, is contained or added.
Die vorliegende Erfindung betrifft zudem ein organisches Material, insbesondere eine Kunststoffzusammensetzung, enthaltend mindestens eine
Verbindung gemäß allgemeiner Formel I oder eine Mischung mehrerer Verbindungen gemäß allgemeiner Formel I als Stabilisator
wobei R1, R2, R3 M und n wie voranstehend definiert sind. The present invention also relates to an organic material, in particular a plastic composition, containing at least one Compound according to general formula I or a mixture of several compounds according to general formula I as a stabilizer where R 1 , R 2 , R 3 M and n are as defined above.
Sämtliche im Zusammenhang mit der erfindungsgemäßen Verwendung beschriebenen vorteilhaften Ausführungsformen gelten uneingeschränkt ebenso für das organische Material. All of the advantageous embodiments described in connection with the use according to the invention also apply without restriction to the organic material.
In einer bevorzugten Ausführungsform weist das organische Material die nachfolgende Zusammensetzung auf: In a preferred embodiment, the organic material has the following composition:
0,01 bis 10,00 Gew.-%, bevorzugt 0,01 bis 7,50 Gew.-%, weiter bevorzugt von 0,02 bis 5,00 Gew.-%, besonders bevorzugt von 0,050 bis 2,00 Gew.-% einer Verbindung gemäß allgemeiner Formel I oder im Falle einer Mischung mehrerer Verbindungen gemäß allgemeiner Formel I die Gesamtheit aller Verbindungen gemäß allgemeiner Formel I 0.01 to 10.00% by weight, preferably 0.01 to 7.50% by weight, more preferably from 0.02 to 5.00% by weight, particularly preferably from 0.050 to 2.00% by weight. -% of a compound according to general formula I or, in the case of a mixture of several compounds according to general formula I, all of the compounds according to general formula I
99,99 bis 10,00, bevorzugt 99,99 bis 90,00 Gew.-%, bevorzugt 99,89 bis 95,00 Gew.-%, besonders bevorzugt 99,90 bis 98,00 Gew.-% mindestens eines organischen Materials, bevorzugt ausgewählt aus der Gruppe bestehend aus Kunststoffen, Beschichtungen, Schmiermitteln, Hydraulikölen, Motorenölen, Turbinenölen, Getriebeölen, Metallbearbeitungsflüssigkeiten, Chemikalien oder Monomeren, sowie
0 bis 80,00 Gew.-%, bevorzugt 0 bis 9,99 Gew.-%, weiter bevorzugt 0,01 bis 4,98 Gew.-%, besonders bevorzugt 0,02 bis 2,00 Gew.-% mindestens eines Zusatzstoffs, wobei sich die Bestandteile zu 100 Gew.-% addieren. 99.99 to 10.00, preferably 99.99 to 90.00% by weight, preferably 99.89 to 95.00% by weight, particularly preferably 99.90 to 98.00% by weight of at least one organic Materials, preferably selected from the group consisting of plastics, coatings, lubricants, hydraulic oils, motor oils, turbine oils, gear oils, metal working fluids, chemicals or monomers, as well 0 to 80.00% by weight, preferably 0 to 9.99% by weight, more preferably 0.01 to 4.98% by weight, particularly preferably 0.02 to 2.00% by weight, of at least one Additive, the constituents adding up to 100% by weight.
Die Erfindung betrifft zudem ein Verfahren zur Stabilisierung von organischen Materialien, insbesondere gegen oxidativen, thermischen und/oder actinischen Abbau, bei dem eine Verbindung oder mehrere Verbindungen gemäß allgemeiner Formel I
The invention also relates to a method for stabilizing organic materials, in particular against oxidative, thermal and / or actinic degradation, in which one or more compounds according to general formula I
Formel I wobei R1, R2, R3 und M und n wie voranstehend definiert sind, in das organische Material eingearbeitet wird. Formula I where R 1 , R 2 , R 3 and M and n are as defined above, is incorporated into the organic material.
Zudem betrifft die vorliegende Erfindung Verbindungen gemäß allgemeiner Formel I
The present invention also relates to compounds according to general formula I.
Formel I wobei Formula I where
R1, R2 und R3 jeweils unabhängig voneinander ausgewählt sind aus der Gruppe bestehend aus Hydroxy, linearen oder verzweigten Alkoxygruppen mit 1 bis 6 Kohlenstoffatomen und Wasserstoff, mit der Maßgabe, dass mindestens einer der Reste R1, R2 und R3 ein Hydroxyrest ist, und M Aluminium ist, und n 3 ist. R 1 , R 2 and R 3 are each independently selected from the group consisting of hydroxyl, linear or branched alkoxy groups having 1 to 6 carbon atoms and hydrogen, with the proviso that at least one of the radicals R 1 , R 2 and R 3 is a Is hydroxy and M is aluminum and n is 3.
Ein weiterer Aspekt der vorliegenden Erfindung betrifft eine Stabilisator- Zusammensetzung, umfassend oder bestehend aus
a) einer Verbindung oder Mischungen mehrerer Verbindungen gemäß allgemeiner Formel I
Another aspect of the present invention relates to a stabilizer composition, comprising or consisting of a) a compound or mixtures of several compounds according to general formula I.
Formel I wobei R1, R2 und R3, M und n wie voranstehend definiert sind (Komponente A), sowie b) mindestens einem sekundären Antioxidans, ausgewählt aus der Gruppe bestehend aus Phosphiten, Phosphoniten oder Thiolen, mindestens einem Costabilisator ausgewählt aus der Gruppe bestehend aus Polyolen, Säurefängern oder sterisch gehinderten Aminen sowie Mischungen und Kombinationen hiervon (Komponente B). Formula I where R 1 , R 2 and R 3 , M and n are as defined above (component A), and b) at least one secondary antioxidant selected from the group consisting of phosphites, phosphonites or thiols, at least one costabilizer selected from Group consisting of polyols, acid scavengers or sterically hindered amines and mixtures and combinations thereof (component B).
Hierbei ist es insbesondere von Vorteil, wenn in der Stabilisator- Zusammensetzung Komponente A und Komponente B in einem Gewichtsverhältnis von 100 : 1 bis 1: 100, bevorzugt 10 : 1 bis 1 : 10, besonders bevorzugt von 4:1 bis 1:4 vorliegen. It is particularly advantageous if component A and component B are present in the stabilizer composition in a weight ratio of 100: 1 to 1: 100, preferably 10: 1 to 1:10, particularly preferably 4: 1 to 1: 4 .
Die vorliegende Erfindung wird anhand der nachfolgenden Ausführungsformen näher beleuchtet, ohne die vorliegende Erfindung auf die spezifischen Ausführungsbeispiele zu beschränken. The present invention is elucidated in more detail on the basis of the following embodiments, without restricting the present invention to the specific embodiments.
Ausführungsbeispiele: Embodiments:
A) Herstellung der erfindungsgemäßen Hydroxyzimtsäuresalze Al) Synthese des Natriumferulats (NaFa)
In einem Becherglas werden zunächst 12,00 g (1,00 eq., 61,80 mmol) Ferulasäure (1) in 620 mL Methanol gelöst. Anschließend werden 2,47 g (1,00 eq., 61,80 mmol) Natriumhydroxid in 60 mL destilliertem Wasser gelöst und die resultierende NaOH-Lösung über einen Tropftrichter der Ferulasäure- Lösung zugetropft. Nach beendeter Zugabe wird die leicht gelbe Lösung in 1,5 I Aceton gegeben. Der ausfallende, gelbe Niederschlag wird abfiltriert, 3-mal mit je 200 mL Aceton gewaschen und schließlich im Vakuumtrockenschrank zwei Tage bei 80 °C getrocknet. Es werden 10,51 g eines gelben, feinpulvrigen Niederschlags erhalten. Die Ausbeute beträgt 78,66 %. A) Preparation of the hydroxycinnamic acid salts according to the invention Al) Synthesis of sodium ferulate (NaFa) First, 12.00 g (1.00 eq., 61.80 mmol) of ferulic acid (1) are dissolved in 620 mL of methanol in a beaker. Then 2.47 g (1.00 eq., 61.80 mmol) sodium hydroxide are dissolved in 60 mL distilled water and the resulting NaOH solution is added dropwise to the ferulic acid solution via a dropping funnel. When the addition is complete, the pale yellow solution is poured into 1.5 l of acetone. The yellow precipitate which separates out is filtered off, washed 3 times with 200 mL acetone each time and finally dried for two days at 80 ° C. in a vacuum drying cabinet. 10.51 g of a yellow, finely powdered precipitate are obtained. The yield is 78.66%.
A2) Synthese des Aluminiumferulats (AlFa)
A2) Synthesis of aluminum ferulate (AlFa)
Zunächst werden 11,18 g (3,07 eq., 57,57 mmol) Ferulasäure in 50 mL Methanol gelöst. Zu der gelben Lösung werden 57 mL einer 1 M NaOH-Lösung zugegeben. Nachdem die Lösung eine halbe Stunde gerührt hat, wird über einen Tropftrichter eine Lösung aus 2,5 g (1,00 eq., 18,75 mmol) Aluminiumtrichlorid und 2,8 mL destilliertem Wasser zugetropft. Dabei fällt sofort ein weißer Niederschlag aus, der noch eine weitere Stunde gerührt und danach abfiltriert wird. Nach dem dreimaligen Waschen mit je 200 mL destillierten Wasser und 200 mL Aceton sowie dem Trocknen im Vakuumtrockenschrank bei 80 °C über Nacht werden 5,32 g eines weißen, grobkörnigen Feststoffs erhalten. First, 11.18 g (3.07 eq., 57.57 mmol) ferulic acid are dissolved in 50 mL methanol. 57 mL of a 1 M NaOH solution are added to the yellow solution. After the solution has stirred for half an hour, a solution of 2.5 g (1.00 eq., 18.75 mmol) of aluminum trichloride and 2.8 mL of distilled water is added dropwise via a dropping funnel. A white precipitate immediately separates out, which is stirred for a further hour and then filtered off. After washing three times with 200 ml of distilled water and 200 ml of acetone each and drying in a vacuum drying cabinet at 80 ° C. overnight, 5.32 g of a white, coarse-grained solid are obtained.
A3) Synthese des Magnesiumferulats (MgFa)
A3) Synthesis of Magnesium Ferulate (MgFa)
In einem Becherglas werden zunächst 2,5 g (1,00 eq., 42,86 mmol)
Magnesiumhydroxid in 600 mL destillierten Wasser suspendiert. Anschließend werden 16,91 g (2,03 eq., 87,08 mmol) Ferulasäure in 250 mL Methanol unter Erwärmen gelöst und die resultierende leicht gelbe Lösung zur Magnesiumhydroxid-Suspension gegeben. Die Suspension wird über Nacht bei Raumtemperatur gerührt, wobei das Magnesiumhydrovid in Lösung geht. Die resultierende leicht gelbe Lösung wird in 1,5 I Aceton gegeben. Der ausfallende, gelbe Niederschlag wird abfiltriert, 3-mal mit je 200 mL Aceton gewaschen und schließlich im Vakuumtrockenschrank zwei Tage bei 80 °C getrocknet. Es werden2,80 g eines gelben, feinpulvrigen Niederschlags erhalten. Die Ausbeute beträgt 15,90 %. First, 2.5 g (1.00 eq., 42.86 mmol) Magnesium hydroxide suspended in 600 mL of distilled water. Then 16.91 g (2.03 eq., 87.08 mmol) of ferulic acid are dissolved in 250 ml of methanol with heating and the resulting slightly yellow solution is added to the magnesium hydroxide suspension. The suspension is stirred overnight at room temperature, the magnesium hydride going into solution. The resulting slightly yellow solution is poured into 1.5 l of acetone. The yellow precipitate which separates out is filtered off, washed 3 times with 200 mL acetone each time and finally dried for two days at 80 ° C. in a vacuum drying cabinet. 2.80 g of a yellow, finely powdered precipitate are obtained. The yield is 15.90%.
A4) Synthese des Calciumferulats (CaFa)
A4) Synthesis of calcium ferulate (CaFa)
In einem Becherglas werden zunächst 2,00 g (1,00 eq., 26,99 mmol) Calciumhydroxid in 100 mL destillierten Wasser suspendiert. Anschließend werden 10,48 g (2,00 eq., 53,97 mmol) Ferulasäure in 100 mL Methanol unter Erwärmen gelöst und die resultierende leicht gelbe Lösung zur Calciumhydroxid-Suspension gegeben. Die Suspension wird über Nacht bei Raumtemperatur gerührt, wobei das Calciumhydroxid in Lösung geht. Gleichzeitig bleibt ein silberner Rückstand zurück, der abfiltriert wird. Das Filtrat wird in 1,5 I Aceton gegeben. Der ausfallende, gelbe Niederschlag wird abfiltriert, 3-mal mit je 200 mL Aceton gewaschen und schließlich im Vakuumtrockenschrank zwei Tage bei 80 °C getrocknet. Es werden 7,42 g eines gelben, feinpulvrigen Niederschlags erhalten. Die Ausbeute beträgt 64,47 %. First, 2.00 g (1.00 eq., 26.99 mmol) of calcium hydroxide are suspended in 100 mL of distilled water in a beaker. Then 10.48 g (2.00 eq., 53.97 mmol) of ferulic acid are dissolved in 100 ml of methanol with heating and the resulting slightly yellow solution is added to the calcium hydroxide suspension. The suspension is stirred overnight at room temperature, the calcium hydroxide going into solution. At the same time, a silver residue remains, which is filtered off. The filtrate is poured into 1.5 l of acetone. The yellow precipitate which separates out is filtered off, washed 3 times with 200 mL acetone each time and finally dried for two days at 80 ° C. in a vacuum drying cabinet. 7.42 g of a yellow, finely powdered precipitate are obtained. The yield is 64.47%.
B) Anwendungsprüfung B) Application testing
Zur Prüfung der Wirkung der erfindungsgemäßen Stabilisatoren wurde ein handelsübliches Polypropylen (Moplen HP 501N, Lyondell Basell Industries) in einer Pulver-Pulver Mischung mit den in den Tabellen angegebenen Stabilisatoren bzw. Stabilisatorkombinationen homogenisiert und in einem Doppelschnecken-Microextruder (MC 5, Hersteller DSM) über 30 Minuten bei 200 °C und 200 Umdrehungen pro Minute im Kreislauf geführt und die
Abnahme der Kraft aufgezeichnet. Die Kraft ist ein direktes Maß für das Molekulargewicht von Polypropylen, je geringer die Abnahme, desto höher die Stabilisierungswirkung. Tabelle 1: Stabilisierung von Polypropylen
To test the effect of the stabilizers according to the invention, a commercially available polypropylene (Moplen HP 501N, Lyondell Basell Industries) was homogenized in a powder-powder mixture with the stabilizers or stabilizer combinations specified in the tables, and in a twin-screw microextruder (MC 5, manufacturer DSM) circulated for 30 minutes at 200 ° C. and 200 revolutions per minute and the Decrease in force recorded. The force is a direct measure of the molecular weight of polypropylene, the smaller the decrease, the higher the stabilizing effect. Table 1: Stabilization of polypropylene
Tabelle 2: Stabilisierung von Polypropylen
Table 2: Stabilization of polypropylene
Tabelle S: Stabilisierung von Polypropylen
Tabelle 3: Stabilisierung von Polypropylen
Table S: Stabilization of Polypropylene Table 3: Stabilization of polypropylene
DSDTP= Distearylthiodipropionat DSDTP = distearyl thiodipropionate
Phosphit = Tris-(2,4-di-tert-butylphenyl)phosphit Phosphite = tris (2,4-di-tert-butylphenyl) phosphite
Die erfindungsgemäßen Zusätze zeigen eine deutliche Stabilisierungswirkung, da über die Versuchszeit ein geringerer Abbau des Polymeren stattfindet. The additives according to the invention show a clear stabilizing effect, since less degradation of the polymer takes place over the duration of the experiment.
C) Oxidations-Induktionszeit (OIT) Die Oxidations-Induktionszeit ist ein standardisierter Test, welcher in einemC) Oxidation induction time (OIT) The oxidation induction time is a standardized test, which in one
Differenzkalorimeter durchgeführt wird. Diese Methode erlaubt eine Bestimmung der thermischen Stabilität des zu untersuchenden Materials. Es wird dabei die Zeit zwischen dem Schmelzen und dem Beginn der Zersetzung unter isothermen Bedingungen (hier 220 °C) bestimmt. Bis zum Schmelzen des zu untersuchenden Materials liegt dabei eine Stickstoff-Atmosphäre vor, anschließend wird synthetische Luft zugeführt. In Tabelle 4 sind die in handelsübliches Polypropylen (Moplen HP 500N, Lyondell Basell Industries) mittels eines co-rotierenden Doppelschnecken-Laborextruders (Process 11, Thermo Fisher Scientific) mit einer Extrusionstemperatur von 200 °C eingearbeiteten und untersuchten Additivkombinationen zusammengefasst. Differential calorimeter is performed. This method allows a determination of the thermal stability of the material to be examined. The time between melting and the start of decomposition is determined under isothermal conditions (here 220 ° C). A nitrogen atmosphere is present until the material to be examined melts, then synthetic air is added. Table 4 summarizes the additive combinations incorporated and investigated into commercial polypropylene (Moplen HP 500N, Lyondell Basell Industries) using a co-rotating twin-screw laboratory extruder (Process 11, Thermo Fisher Scientific) with an extrusion temperature of 200 ° C.
Tabelle 4: Oxidations-Induktionszeit der in Polypropylen eingearbeiteten Verbindungen.
Table 4: Oxidation induction time of the compounds incorporated in polypropylene.
Es zeigt sich, dass durch den Zusatz von 0.5 % Natriumferulat eine deutliche Steigerung der oxidativen Stabilität von Polypropylen erreicht wird.
It can be seen that the addition of 0.5% sodium ferulate significantly increases the oxidative stability of polypropylene.
Claims
1. Verwendung einer Verbindung oder Mischungen mehrerer Verbindun- gen gemäß allgemeiner Formel I
1. Use of a compound or mixtures of several compounds according to general formula I
Formel I wobei Formula I where
R1, R2 und R3 jeweils unabhängig voneinander ausgewählt sind aus der Gruppe bestehend aus Hydroxy, linearen oder verzweigten Alkoxy- gruppen mit 1 bis 6 Kohlenstoffatomen und Wasserstoff, mit der Maß- gabe, dass mindestens einer der Reste R1, R2 und R3 ein Hydroxyrest ist, R 1 , R 2 and R 3 are each independently selected from the group consisting of hydroxyl, linear or branched alkoxy groups with 1 to 6 carbon atoms and hydrogen, with the proviso that at least one of the radicals R 1 , R 2 and R 3 is a hydroxy radical,
M ausgewählt ist aus der Gruppe bestehend aus Metallen, und n eine ganze Zahl von 1 bis 4 ist, zur Stabilisierung von organischen Materialien, insbesondere gegen oxidativen, thermischen und/oder actinischen Abbau. M is selected from the group consisting of metals, and n is an integer from 1 to 4, for stabilizing organic materials, in particular against oxidative, thermal and / or actinic degradation.
2. Verwendung nach Anspruch 1, zur Stabilisierung von Kunststoffen, Be- schichtungen, Schmiermitteln, Hydraulikölen, Motorenölen, Turbinen- ölen, Getriebeölen, Metallbearbeitungsflüssigkeiten, Chemikalien oder Monomeren. 2. Use according to claim 1, for stabilizing plastics, coatings, lubricants, hydraulic oils, motor oils, turbine oils, gear oils, metal working fluids, chemicals or monomers.
Verwendung nach einem der vorhergehenden Ansprüche, dadurch ge- kennzeichnet, dass die Reste R1, R2 und R3 jeweils ein Hydroxyrest,
zwei der Reste R1, R2 und R3 ein Hydroxyrest und einer der Reste R1, R2 und R3 Wasserstoff oder eine lineare oder verzweigte Alkoxygruppe mit 1 bis 6 Kohlenstoffatomen, einer der Reste R1, R2 und R3 ein Hydroxyrest und zwei der Reste R1, R2 und R3 eine lineare oder verzweigte Alkoxygruppe mit 1 bis 6 Kohlen- stoffatomen, oder je einer der Reste R1, R2 und R3 ein Hydroxyrest, eine lineare oder ver- zweigte Alkoxygruppe mit 1 bis 6 Kohlenstoffatomen und Wasserstoff darstellen. Use according to one of the preceding claims, characterized in that the radicals R 1 , R 2 and R 3 are each a hydroxy radical, two of the radicals R 1 , R 2 and R 3 are hydroxy and one of the radicals R 1 , R 2 and R 3 is hydrogen or a linear or branched alkoxy group with 1 to 6 carbon atoms, one of the radicals R 1 , R 2 and R 3 Hydroxy radical and two of the radicals R 1 , R 2 and R 3 have a linear or branched alkoxy group with 1 to 6 carbon atoms, or one of the radicals R 1 , R 2 and R 3 has a hydroxy radical or a linear or branched alkoxy group Represent 1 to 6 carbon atoms and hydrogen.
4. Verwendung nach einem der vorhergehenden Ansprüche, dadurch ge- kennzeichnet, dass die Verbindung gemäß allgemeiner Formel I ausge- wählt ist aus der Gruppe bestehend aus den nachfolgenden Verbin- dungen:
wobei M und n wie in Anspruch 1 definiert sind. 4. Use according to one of the preceding claims, characterized in that the compound according to general formula I is selected from the group consisting of the following compounds: wherein M and n are as defined in claim 1.
5. Verwendung nach einem der vorhergehenden Ansprüche, dadurch ge- kennzeichnet, dass die Metalle M ausgewählt sind aus der Gruppe be- stehend aus Alkalimetallen, Erdalkalimetallen, Aluminium und Zink.5. Use according to one of the preceding claims, characterized in that the metals M are selected from the group consisting of alkali metals, alkaline earth metals, aluminum and zinc.
6. Verwendung nach einem der vorhergehenden Ansprüche, dadurch ge- kennzeichnet, dass die Verbindung gemäß allgemeiner Formel I oder im Falle einer Mischung mehrerer Verbindungen gemäß allgemeiner Formel I die Gesamtheit aller Verbindungen gemäß allgemeiner Formel I zu einem Gewichtsanteil von 0,01 bis 10,00 Gew.-%, bevorzugt von
0,02 bis 5,00 Gew.-%, besonders bevorzugt von 0,05 bis 2,00 Gew.-% im organischen Material enthalten ist. 6. Use according to one of the preceding claims, characterized in that the compound according to general formula I or, in the case of a mixture of several compounds according to general formula I, all of the compounds according to general formula I in a proportion by weight of 0.01 to 10, 00% by weight, preferably of 0.02 to 5.00% by weight, particularly preferably from 0.05 to 2.00% by weight, is contained in the organic material.
7. Verwendung nach einem der vorhergehenden Ansprüche, zur Stabili- sierung von Kunststoffen, wobei der Kunststoff ausgewählt ist aus der Gruppe bestehend aus a) Polymeren aus Olefinen oder Diolefinen wie z.B. Polyethylen (LDPE, LLDPE, VLDPE, ULDPE, MDPE, HDPE, UHMWPE), Metallocen-PE (m- PE), Polypropylen, Polyisobutylen, Poly-4-methyl-penten-1, Polybu- tadien, Polyisopren, Polycycloocten, Polyalkylen-Kohlenmonoxid- Copolymere, sowie Copolymere in Form von statistischen oder Blockstrukturen wie z.B. Polypropylen-Polyethylen (EP), EPM oder EPDM, Ethylen-Vinylacetat (EVA), Ethylen-Acrylester, wie z.B. Ethy- len-Butylacrylat, Ethylen-Acrylsäure und deren Salze (lonomere), so- wie Terpolymere wie z.B. Ethylen-Acrylsäure-Glycidyl(meth)acrylat, Pfropfpolymere wie z.B. Polypropylen-graft-Maleinsäureanhydrid, Polypropylen-graft -Acrylsäure, Polyethylen-graft-Acrylsäure, Po- lyethylen-Polybutylacrylat-graft-Maleinsäureanhydrid sowie Blends hiervon, b) Polystyrol, Polymethylstyrol, Poly-alpha-methylstyrol, Polyvinyl- naphthalin, Polyvinylbiphenyl, Polyvinyltoluol, Styrol-Butadien (SB), Styrol-Butadien-Styrol (SBS), Styrol-Ethylen-Butylen-Styrol (SEBS), Styrol-Ethylen-Propylen-Styrol, Styrol-Isopren, Styrol-Isopren-Styrol (SIS), Styrol-butadien-acrylnitril (ABS), Styrol-acrylnitril (SAN), Styrol- acrylnitril-acrylat (ASA), Styrol-Ethylen, Styrol-Maleinsäureanhydrid- Polymere einschl. entsprechender Pfropfcopolymere wie z.B. Styrol auf Butadien, Maleinsäureanhydrid auf SBS oder SEBS, sowie Pfropfcopolymere aus Methylmethacrylat, Styrol-Butadien und ABS (MABS), sowie hydrierte Polystyrol-Derivate, c) halogenenthaltenden Polymeren wie z.B. Polyvinylchlorid (PVC), Po- lychloropren und Polyvinylidenchlorid (PVDC), Copolymere aus Vi- nylchlorid und Vinylidenchlorid oder aus Vinylchlorid und Vi- nylacetat, chloriertes Polyethylen, Polyvinylidenfluorid, Epich- lorhydrin-Homo, und Copolymere hiervon,
d) Polymeren von ungesättigten Estern wie z.B. Polyacrylate und Poly- methacrylate wie Polymethylmethacrylat (PMMA), Polybutylacrylat, Polylaurylacrylat, Polystearylacrylat, Polyglycidylacrylat, Polyglyci- dylmethacrylat, Polyacrylnitril, Polyacrylamide, Copolymere wie z.B. Polyacrylnitril-Polyalkylacrylat, e) Polymeren aus ungesättigten Alkoholen und Derivaten, wie z.B. Po- lyvinylalkohol, Polyvinylacetat, Polyvinylbutyral, Polyallylphthalat, Polyallylmelamin, f) Polyacetalen, wie z.B. Polyoxymethylen (POM) oder Copolymere mit z.B. Butanal, g) Polyphenylenoxiden und Blends mit Polystyrol oder Polyamiden, h) Polymeren von cyclischen Ethern wie z.B. Polyethylenglycol, Polyp- ropylenglycol, Polyethylenoxid, Polypropylenoxid, Polytetrahydro- furan, i) Polyurethanen, aus hydroxyterminierten Polyethern oder Polyes- tern und aromatischen oder aliphatischen Isocyanaten insbeson- dere lineare Polyurethane (TPU), Polyharnstoffen, 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 Po- lyamide wie z.B. Polyphthalamide, z.B. hergestellt aus Terephthal- säure und/oder Isophthalsäure und aliphatischen Diaminen oder aus aliphatischen Dicarbonsäuren wie z.B. Adipinsäure oder Seba- zinsäure und aromatischen Diaminen wie z.B. 1,4- oder 1,3- Diami- nobenzol, Blends von unterschiedlichen Polyamiden wie z.B. PA-6 und PA 6.6 bzw. Blends von Polyamiden und Polyolefinen wie z.B. PA/PP k) Polyimiden, Polyamid-imiden, Polyetherimiden, Polyesterimiden, Poly(ether)ketonen, Polysulfonen, Polyethersulfonen, Polyarylsulfo- nen, Polyphenylensulfiden, Polybenzimidazolen, Polyhydantoinen,7. Use according to one of the preceding claims, for stabilizing plastics, the plastic being selected from the group consisting of a) polymers made from olefins or diolefins such as polyethylene (LDPE, LLDPE, VLDPE, ULDPE, MDPE, HDPE, UHMWPE ), Metallocene PE (m-PE), polypropylene, polyisobutylene, poly-4-methyl-pentene-1, polybutadiene, polyisoprene, polycyclooctene, polyalkylene-carbon monoxide copolymers, and copolymers in the form of random or block structures such as polypropylene -Polyethylene (EP), EPM or EPDM, ethylene-vinyl acetate (EVA), ethylene-acrylic ester, such as ethylene-butyl acrylate, ethylene-acrylic acid and its salts (ionomers), as well as 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 thereof, b) polystyrene, polymethylstyrene, poly-alpha-methylstyrene , Polyvinyl naphthalene, polyvinyl biphenyl, polyvinyl toluene, 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 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), as well as hydrogenated polystyrene derivatives, c) halogen-containing polymers such as polyvinyl chloride (PVC), polychloroprene and polyvinylidene chloride (PVDC), copolymers made of Vi - nyl chloride and vinylidene chloride or from vinyl chloride and vinyl acetate, chlorinated polyethylene, polyvinylidene fluoride, epichlorohydrin homo, and copolymers thereof, d) Polymers of unsaturated esters such as, for example, polyacrylates and polymethacrylates such as polymethyl methacrylate (PMMA), polybutyl acrylate, polylauryl acrylate, polystearyl acrylate, polyglycidyl acrylate, polyglycidyl methacrylate, polyacrylonitrile, polyacrylamides, copolymers made from, for example, polyacrylonitrile-unsaturated polymers, and copolymers such as polyacrylonitrile-unsaturated polyacrylonitrile such as polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyallyl phthalate, polyallyl melamine, f) polyacetals such as polyoxymethylene (POM) or copolymers with, for example, butanal, 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, in particular linear polyurethanes (TPU), polyureas, 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, for example 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-diamino benzene, blends of different polyamides such as PA-6 and PA 6.6 or blends of polyamides and polyolefins such as PA / PP 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 Diolen oder aus Hydroxy-Carbonsäuren wie z.B. Polyethylen-
terephthalat (PET), Polybutylenterephthalat (PBT), Polypropylen- terephthalat (PTT), Polyethylennaphthylat (PEN), Poly-1,4-dimethyl- olcyclohexanterephthalat, Polyhydroxybenzoat, Polyhydroxynaph- thalat, Polymilchsäure (PLA), Polyhydroxybutyrat (PHB), Polyhyd- roxy-valerat (PHV), Polyethylensuccinat, Polytetraethylensuccinat, Polycaprolacton, m)Polycarbonaten, Polyestercarbonaten, sowie Blends wie z.B. 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-dimethylolcyclohexane terephthalate, polyhydroxybenzoate, polyhydroxynaphthalate, polylactic acid (PLA), polyhydroxybutyrate (PLA), polyhydroxybutyrate roxy-valerate (PHV), polyethylene succinate, polytetraethylene 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, o) Epoxidharzen, bestehend aus di- oder polyfunktionellen Epoxidver- bindungen in Kombination mit z.B. Härtern auf der Basis von Ami- nen, Anhydriden, Dicyandiamid, Mercaptanen, Isocyanaten oder katalytisch wirkenden Härtern, p) Phenolharzen wie z.B. Phenol-Formaldehyd-Harze, Harnstoff-For- maldehyd-Harze, Melamin-Formaldehydharze, q) ungesättigten Polyesterharzen aus ungesättigten Dicarbonsäuren und Diolen mit Vinylverbindungen, r) Silikonen, s) sowie Mischungen, Kombinationen oder Blends aus zwei oder mehr der zuvor genannten Polymere. PC / ABS, PC / PBT, PC / PET / PBT, PC / PA n) cellulose derivatives such as cellulose nitrate, cellulose acetate, cellulose propionate, cellulose butyrate, o) epoxy resins, consisting of di- or polyfunctional epoxy compounds in combination with hardeners, for example based on amines, anhydrides, dicyandiamide, mercaptans, isocyanates or catalytically active hardeners, p) phenolic resins such as phenol-formaldehyde resins, urea-formaldehyde resins, melamine-formaldehyde resins, q) unsaturated polyester resins made from unsaturated dicarboxylic acids and diols with vinyl compounds, r) silicones, s) and mixtures, combinations or blends of two or more of the aforementioned polymers.
8. Verwendung nach einem der vorhergehenden Ansprüche, dadurch ge- kennzeichnet, dass der Kunststoff mindestens einen weiteren Zusatz- stoff, ausgewählt aus der Gruppe bestehend aus primären und/oder sekundären Antioxidantien, insbesondere primären und/oder sekundä- ren Antioxidantien ausgewählt aus der Gruppe bestehend aus Phosphi- ten, Phosphoniten, Thiolen, phenolischen Antioxidantien, sterisch ge- hinderten Aminen, Hydroxylaminen sowie Mischungen oder Kombina- tionen hiervon, UV-Absorbern, Lichtstabilisatoren, Hydroxylamin ba- sierten Stabilisatoren, Benzofuranon basierten Stabilisatoren, Nukleie- rungsmitteln, Schlagzähigkeitsverbesserern, Weichmachern, Gleitmit-
teln, Rheologiemodifikatoren, Kettenverlängerern, Verarbeitungshilfs- mitteln, Pigmenten, Farbstoffen, optischen Aufhellern, antimikrobiel- len Wirkstoffen, Antistatika, Slipmitteln, Antiblockmitteln, Kopplungs- mitteln, Dispergiermitteln, Kompatibilisatoren, Sauerstofffängern, Säu- refängern, Costabilisatoren, Markierungsmitteln sowie Antifoggingmit- teln, enthält und/oder bei der Verwendung dem Kunststoff zugesetzt wird. 8. Use according to one of the preceding claims, characterized in that the plastic has at least one further additive selected from the group consisting of primary and / or secondary antioxidants, in particular primary and / or secondary antioxidants selected from the group consisting of phosphites, phosphonites, thiols, phenolic antioxidants, sterically hindered amines, hydroxylamines and mixtures or combinations thereof, UV absorbers, light stabilizers, hydroxylamine-based stabilizers, benzofuranone-based stabilizers, nucleating agents, impact strength improvers, Plasticizers, lubricants agents, rheology modifiers, chain extenders, processing aids, pigments, dyes, optical brighteners, antimicrobial agents, antistatic agents, slip agents, antiblocking agents, coupling agents, dispersants, compatibilizers, oxygen scavengers, acid scavengers, costabilizers, antifogging agents, and marking agents contains and / or is added to the plastic during use.
9. Verwendung nach vorhergehendem Anspruch, dadurch gekennzeich- net, dass der mindestens eine Zusatzstoff in einer Menge von 0,01 bis 80 Gew.%, bevorzugt von 0,01 bis 9,99 Gew.-%, weiter bevorzugt von 0,01 bis 4,98 Gew.-%, besonders bevorzugt von 0,02 bis 2,00 Gew.-%, bezogen auf die Gesamtheit der mindestens einen Verbindung gemäß Formel I des organischen Materials und des mindestens einen Zusatz- stoffs, zugesetzt wird oder enthält. . 9. Use according to the preceding claim, characterized in that the at least one additive is in an amount of 0.01 to 80% by weight, preferably 0.01 to 9.99% by weight, more preferably 0.01 up to 4.98% by weight, particularly preferably from 0.02 to 2.00% by weight, based on the totality of the at least one compound according to formula I of the organic material and of the at least one additive, is added or contains . .
10. Verwendung nach einem der vorhergehenden Ansprüche, dadurch ge- kennzeichnet, dass die Verbindung oder Mischungen mehrerer Verbin- dungen gemäß allgemeiner Formel I in Kombination mit einem Costa- bilisator verwendet wird, wobei der Costabilisator ausgewählt ist aus der Gruppe bestehend aus Polyolen, insbesondere Alditolen und/oder Cyclitolen, wie z.B. Pentaerythrit, Dipentaerythrit, Tri pentaerythrit, kurzkettige Polyetherpolyole oder kurzkettige Polyesterpolyole, sowie hyperverzweigte Polymere/Oligomere oder Dendrimere mit Alkohol- gruppen, Threit, Erythrit, Galactit, Mannit, Ribit, Sorbit, Xylit, Arabit, Isomalt, Lactit, Maltit, Altritol, Iditol, Maltotritol und hydrierte Oligo- und Polysaccharide mit Polyol-Endgruppen und Mischungen hiervon10. Use according to one of the preceding claims, characterized in that the compound or mixtures of several compounds according to general formula I is used in combination with a costabilizer, the costabilizer being selected from the group consisting of polyols, in particular Alditols and / or cyclitols, such as pentaerythritol, dipentaerythritol, tri pentaerythritol, short-chain polyether polyols or short-chain polyester polyols, as well as hyperbranched polymers / oligomers or dendrimers with alcohol groups, threitol, erythritol, galactitol, mannitol, ribitol, sorbitol, x , Lactitol, maltitol, altritol, iditol, maltotritol and hydrogenated oligo- and polysaccharides with polyol end groups and mixtures thereof
11. Organisches Material, insbesondere Kunststoffzusammensetzung, ent- haltend mindestens eine Verbindung gemäß allgemeiner Formel I oder eine Mischung mehrerer Verbindungen gemäß allgemeiner Formel I als Stabilisator
Formel I wobei R1, R2, R3 M und n wie in einem der Ansprüche 1, 3 und 5 defi- niert sind. 11. Organic material, in particular plastic composition, containing at least one compound according to general formula I or a mixture of several compounds according to general formula I as a stabilizer Formula I where R 1 , R 2 , R 3, M and n are defined as in one of Claims 1, 3 and 5.
12. Organisches Material nach vorhergehendem Anspruch, mit folgender Zusammensetzung 12. Organic material according to the preceding claim, with the following composition
0,01 bis 10,00 Gew.-%, bevorzugt 0,01 bis 7,50 Gew.-%, weiter bevor- zugt von 0,02 bis 5,00 Gew.-%, besonders bevorzugt von 0,05 bis 2,00 Gew.-% einer Verbindung gemäß allgemeiner Formel I oder im Falle ei- ner Mischung mehrerer Verbindungen gemäß allgemeiner Formel I die Gesamtheit aller Verbindungen gemäß allgemeiner Formel I0.01 to 10.00% by weight, preferably 0.01 to 7.50% by weight, more preferably from 0.02 to 5.00% by weight, particularly preferably from 0.05 to 2% 00% by weight of a compound according to general formula I or, in the case of a mixture of several compounds according to general formula I, all of the compounds according to general formula I
99,99 bis 10,00, bevorzugt 99,99 bis 90,00 Gew.-%, bevorzugt 99,89 bis 95,00 Gew.-%, besonders bevorzugt 99,95 bis 98,00 Gew.-% mindes- tens eines organischen Materials, bevorzugt ausgewählt aus der Gruppe bestehend aus Kunststoffen, Beschichtungen, Schmiermitteln, Hydraulikölen, Motorenölen, Turbinenölen, Getriebeölen, Metallbear- beitungsflüssigkeiten, Chemikalien oder Monomeren, sowie 99.99 to 10.00, preferably 99.99 to 90.00% by weight, preferably 99.89 to 95.00% by weight, particularly preferably 99.95 to 98.00% by weight, at least an organic material, preferably selected from the group consisting of plastics, coatings, lubricants, hydraulic oils, motor oils, turbine oils, gear oils, metal working fluids, chemicals or monomers, as well as
0 bis 80,00 Gew.-%, bevorzugt 0 bis 9,99 Gew.-%, weiter bevorzugt 0,01 bis 4,98 Gew.-%, besonders bevorzugt 0,02 bis 2,00 Gew.-% min- destens eines Zusatzstoffs, wobei sich die Bestandteile zu 100 Gew.-% addieren. 0 to 80.00% by weight, preferably 0 to 9.99% by weight, more preferably 0.01 to 4.98% by weight, particularly preferably 0.02 to 2.00% by weight min- at least one additive, the constituents adding up to 100% by weight.
13. Organisches Material nach vorhergehendem Anspruch, dadurch ge- kennzeichnet, dass der mindestens eine Zusatzstoff ausgewählt aus der Gruppe bestehend aus primären und/oder sekundären Antioxidan- tien, insbesondere primären und/oder sekundären Antioxidantien aus- gewählt aus der Gruppe bestehend aus Phosphiten, Phosphoniten, Thi- olen, phenolischen Antioxidantien, sterisch gehinderten Aminen, Hyd- roxylaminen sowie Mischungen oder Kombinationen hiervon, UV-Ab- sorbern, Lichtstabilisatoren, Hydroxylamin basierten Stabilisatoren, Benzofuranon basierten Stabilisatoren, Nukleierungsmittel, Schlagzä- higkeitsverbesserern, Weichmachern, Gleitmitteln, Rheologiemodifika- toren, Kettenverlängerern, Verarbeitungshilfsmitteln, Pigmenten,
Farbstoffen, optische Aufhellern, antimikrobiellen Wirkstoffen, Antis- tatika, Slipmitteln, Antiblockmitteln, Kopplungsmitteln, Dispergiermit- teln, Kompatibilisatoren, Sauerstofffängern, Säurefängern, Costabilisa- toren, Markierungsmitteln sowie Antifoggingmitteln; insbesondere ausgewählt ist aus der Gruppe bestehend aus einem se- kundären Antioxidans ausgewählt aus der Gruppe bestehend aus Phos- phiten, Phosphoniten und Thiolen, mindestens einem Costabilisator ausgewählt aus der Gruppe bestehend aus Polyolen, Säurefängern so- wie sterisch gehinderten Aminen. 13. Organic material according to the preceding claim, characterized in that the at least one additive selected from the group consisting of primary and / or secondary antioxidants, in particular primary and / or secondary antioxidants selected from the group consisting of phosphites, Phosphonites, thiols, phenolic antioxidants, sterically hindered amines, hydroxylamines and mixtures or combinations thereof, UV absorbers, light stabilizers, hydroxylamine-based stabilizers, benzofuranone-based stabilizers, nucleating agents, impact strength improvers, plasticizers, lubricants, gates, chain extenders, processing aids, pigments, Dyes, optical brighteners, antimicrobial agents, antistatic agents, slip agents, antiblocking agents, coupling agents, dispersants, compatibilizers, oxygen scavengers, acid scavengers, costabilizers, marking agents and anti-fogging agents; is selected in particular from the group consisting of a secondary antioxidant selected from the group consisting of phosphites, phosphonites and thiols, at least one costabilizer selected from the group consisting of polyols, acid scavengers and sterically hindered amines.
14. Verfahren zur Stabilisierung von organischen Materialien, insbeson- dere gegen oxidativen, thermischen und/oder actinischen Abbau, bei dem eine Verbindung oder mehrere Verbindungen gemäß allgemeiner Formel I
14. Process for stabilizing organic materials, in particular against oxidative, thermal and / or actinic degradation, in which one or more compounds according to general formula I
Formel I wobei R1, R2, R3 und M und n wie in einem der Ansprüche 1, 3 und 5 definiert sind, in das organische Material eingearbeitet wird. Formula I wherein R 1 , R 2 , R 3 and M and n are as defined in one of Claims 1, 3 and 5, is incorporated into the organic material.
15. Verbindungen gemäß allgemeiner Formel I
15. Compounds according to general formula I.
Formel I wobei Formula I where
R1, R2 und R3 jeweils unabhängig voneinander ausgewählt sind aus der Gruppe bestehend aus Hydroxy, linearen oder verzweigten Alkoxy-
gruppen mit 1 bis 6 Kohlenstoffatomen und Wasserstoff, mit der Maß- gabe, dass mindestens einer der Reste R1, R2 und R3 ein Hydroxyrest , und R 1 , R 2 and R 3 are each independently selected from the group consisting of hydroxy, linear or branched alkoxy groups with 1 to 6 carbon atoms and hydrogen, with the proviso that at least one of the radicals R 1 , R 2 and R 3 is a hydroxy radical, and
M Aluminium ist, und n 3 ist. M is aluminum and n is 3.
16. Stabilisator-Zusammensetzung, umfassend oder bestehend aus a) einer Verbindung oder Mischungen mehrerer Verbindungen ge- mäß allgemeiner Formel I
16. Stabilizer composition, comprising or consisting of a) a compound or mixtures of several compounds according to general formula I
Formel I wobei R1, R2 und R3, M und n wie in einem der Ansprüche 1, 3 und 5 definiert sind (Komponente A), sowie b) mindestens einem sekundären Antioxidans, ausgewählt aus der Gruppe bestehend aus Phosphiten, Phosphoniten oderThiolen, o- der mindestens einem Costabilisator ausgewählt aus der Gruppe bestehend aus Polyolen, Säurefängern; oder sterisch gehinderten Aminen sowie Mischungen und Kombinationen hiervon (Kompo- nente B). Formula I where R 1 , R 2 and R 3 , M and n are as defined in one of claims 1, 3 and 5 (component A), and b) at least one secondary antioxidant selected from the group consisting of phosphites, phosphonites or thiols , or at least one co-stabilizer selected from the group consisting of polyols, acid scavengers; or sterically hindered amines and mixtures and combinations thereof (component B).
17. Stabilisator-Zusammensetzung nach vorhergehendem Anspruch, dadurch gekennzeichnet, dass Komponente A und Komponente B in ei- nem Gewichtsverhältnis von 100 : 1 bis 1: 100, bevorzugt 10 : 1 bis 1 : 10, besonders bevorzugt von 4 : 1 bis 1 : 4 vorliegen.
17. Stabilizer composition according to the preceding claim, characterized in that component A and component B in a weight ratio of 100: 1 to 1: 100, preferably 10: 1 to 1:10, particularly preferably 4: 1 to 1: 4 are available.
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DE102020203988.7A DE102020203988A1 (en) | 2020-03-27 | 2020-03-27 | Use of hydroxycinnamic acid salts to stabilize organic materials, stabilized organic material, processes for stabilizing organic materials, specific stabilizers and stabilizer compositions |
PCT/EP2021/057775 WO2021191364A1 (en) | 2020-03-27 | 2021-03-25 | Use of hydroxycinnamic acid salts for stabilising organic materials, stabilised organic material, method for stabilising organic materials, specific stabilisers and stabiliser compositions |
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CN114075360B (en) * | 2022-01-10 | 2022-03-25 | 潍坊潍星联合橡塑有限公司 | Chlorinated polyethylene rubber compound and preparation method thereof |
DE102022201632A1 (en) | 2022-02-16 | 2023-08-17 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung eingetragener Verein | Polymeric stabilizers based on syringic acid, vanillic acid, isovanillic acid or 5-hydroxyveratric acid, plastic composition, method for stabilizing a plastic composition and stabilizer composition |
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DE1957433A1 (en) | 1969-11-14 | 1971-05-27 | Pluripharm Sarl | Magnesium trans-cinnamate and trans- - ferulate as cholagogues and cholereties |
AT317184B (en) | 1969-11-19 | 1974-08-12 | Pluripharm Sarl | Process for the production of new cinnamic acid salts |
DE2544014A1 (en) * | 1975-10-02 | 1977-04-14 | Hoechst Ag | POLAR PHENOLIC ANTIOXIDANTS FOR THE STABILIZATION OF PLASTICS |
CN1919202A (en) * | 2005-08-23 | 2007-02-28 | 蔡军 | Pharmaceutical composition of pharmacy acceptable salt of carthamus tinctorius yellow colour and ferulaic acid |
US20070189990A1 (en) | 2006-02-16 | 2007-08-16 | Anthony East | Ultraviolet absorber for cosmetics and polymeric materials |
FR2907338B1 (en) | 2006-10-20 | 2020-01-10 | Greentech | USE OF FERULIC ACID IN THE COSMETIC AND / OR PHARMACEUTICAL FIELD |
CN100574752C (en) | 2007-11-29 | 2009-12-30 | 中山大学 | A kind of pharmaceutical composition of preventing and treating ischemic cerebrovascular and preparation method thereof |
CN103073820A (en) * | 2013-01-18 | 2013-05-01 | 内蒙古科技大学 | Rare earth composite heat stabilizer for PVC |
FR3011841B1 (en) | 2013-10-14 | 2016-09-16 | Agronomique Inst Nat Rech | BIARYL 5-5 PHENOLIC POLYMER, PROCESS FOR PREPARATION AND USES THEREOF |
JP6401578B2 (en) * | 2014-10-31 | 2018-10-10 | アクアス株式会社 | Copper anticorrosion composition and copper anticorrosion method |
WO2017117099A1 (en) * | 2015-12-29 | 2017-07-06 | L'oreal | Stable antioxidant compositions |
US11091611B2 (en) | 2017-02-23 | 2021-08-17 | Sabic Global Technologies B.V. | Polyolefin composition |
CN107629310B (en) | 2017-07-28 | 2020-07-24 | 北京化工大学 | Supermolecule intercalation structure light stabilizer and preparation method thereof |
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