EP4127045A1 - Utilisation de sels d'acide hydroxycinnamique pour la stabilisation de matériaux organiques, matériau organique stabilisé, procédé de stabilisation de matériaux organiques, stabilisateurs spécifiques et compositions stabilisantes - Google Patents

Utilisation de sels d'acide hydroxycinnamique pour la stabilisation de matériaux organiques, matériau organique stabilisé, procédé de stabilisation de matériaux organiques, stabilisateurs spécifiques et compositions stabilisantes

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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
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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
Application number
EP21716104.1A
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German (de)
English (en)
Inventor
Rudolf Pfaendner
Jannik MAYER
Elke Metzsch-Zilligen
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Original Assignee
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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Publication of EP4127045A1 publication Critical patent/EP4127045A1/fr
Pending legal-status Critical Current

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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
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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

L'invention concerne l'utilisation de sels d'acide hydroxycinnamique spécifiques pour la stabilisation de matières organiques. L'invention concerne également un matériau organique correspondant stabilisé par incorporation d'un sel d'acide hydroxycinnamique spécifique et un procédé de stabilisation de matériaux organiques. De plus, l'invention concerne un sel d'aluminium spécifique d'un acide hydroxycinnamique approprié en tant que stabilisant organique. L'invention concerne en outre une composition stabilisante comprenant un sel d'acide hydroxycinnamique correspondant.
EP21716104.1A 2020-03-27 2021-03-25 Utilisation de sels d'acide hydroxycinnamique pour la stabilisation de matériaux organiques, matériau organique stabilisé, procédé de stabilisation de matériaux organiques, stabilisateurs spécifiques et compositions stabilisantes Pending EP4127045A1 (fr)

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DE102020203988.7A DE102020203988A1 (de) 2020-03-27 2020-03-27 Verwendung von Hydroxyzimtsäuresalzen zur Stabilisierung von organischen Materialien, stabilisiertes organisches Material, Verfahren zur Stabilisierung von organischen Materialien, spezifische Stabilisatoren sowie Stabilisatorzusammensetzungen
PCT/EP2021/057775 WO2021191364A1 (fr) 2020-03-27 2021-03-25 Utilisation de sels d'acide hydroxycinnamique pour la stabilisation de matériaux organiques, matériau organique stabilisé, procédé de stabilisation de matériaux organiques, stabilisateurs spécifiques et compositions stabilisantes

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KR20220161385A (ko) 2022-12-06
DE102020203988A1 (de) 2021-09-30
US20230119120A1 (en) 2023-04-20
CN115803380A (zh) 2023-03-14
JP2023518876A (ja) 2023-05-08

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