Use of dieugenol, eugenol oligomers and / or eugenol polymers for stabilizing organic materials, stabilized plastic compositions, stabilizer compositions, and methods for stabilizing organic materials

Abstract

Organic materials, such as plastics, are subject to aging processes that ultimately result in the loss of desired properties, such as mechanical properties. This process, called autoxidation, is caused by radical chain scission by mechanochemical processes or UV radiation in the presence of oxygen, leading to changes in polymer chains, such as molecular weight or the formation of new chemical groups. Stabilizers are therefore used to prevent or at least slow this aging process. Important stabilizers are antioxidants, which block the free radicals formed during autoxidation and thus interrupt the degradation process. A distinction is generally made between primary antioxidants, which can react directly with oxygen-containing free radicals or C radicals, and secondary antioxidants, which react with the intermediately formed hydroperoxides (see C. Krohnke et al., Antioxidants in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH Verlag, Weinheim 2015). Typical examples of primary antioxidants are phenolic antioxidants, amines, and certain lactones (benzofuranones). Classes of secondary antioxidants include phosphorus compounds such as phosphite esters and phosphonites, as well as organic sulfur compounds such as sulfides and disulfides in the form of long-chain alkyl derivatives. Primary and secondary antioxidants are usually used in combination, often in practice, to achieve a synergistic effect.

Description

[Technical Field]

[0001] Organic materials, such as plastics, are subject to aging processes that ultimately result in the loss of desired properties, such as mechanical properties. This process, called autoxidation, is caused by radical chain scission by mechanochemical processes or UV radiation in the presence of oxygen, leading to changes in polymer chains, such as molecular weight or the formation of new chemical groups. Stabilizers are therefore used to prevent or at least slow this aging process. Important stabilizers are antioxidants, which block the free radicals formed during autoxidation and thus interrupt the degradation process. A distinction is generally made between primary antioxidants, which can react directly with oxygen-containing free radicals or C radicals, and secondary antioxidants, which react with the intermediately formed hydroperoxides (see C. Krohnke et al., Antioxidants in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH Verlag, Weinheim 2015). Typical examples of primary antioxidants are phenolic antioxidants, amines, and certain lactones (benzofuranones). Classes of secondary antioxidants include phosphorus compounds such as phosphite esters and phosphonites, as well as organic sulfur compounds such as sulfides and disulfides in the form of long-chain alkyl derivatives. Primary and secondary antioxidants are usually used in combination, often in practice, to achieve a synergistic effect.

[0002] Plastics made from fossil raw materials such as crude oil or natural gas are now being supplemented or replaced by plastics based on sustainable raw materials, with the corresponding monomers being produced by biochemical processes. Therefore, it is necessary to search for additives that are also based on sustainable raw materials. Since stabilizers, especially antioxidants, are used in virtually all plastics, there is a need for efficient stabilizers made from particularly sustainable raw materials.

[0003] Basically, primary antioxidants made from sustainable raw materials are known, and are sometimes used in plastics. Tocopherol (vitamin E) is a typical example. Like conventional antioxidants, tocopherol has a sterically hindered phenolic structure and can be used alone or in combination with secondary antioxidants (e.g., S. Al-Malaika, Macromol. Symp. 2001, 176, 107). Tocopherol can be isolated from natural sources, such as wheat germ oil, sunflower oil, or olive oil. Further known phenolic antioxidants made from natural substances that have been considered for use in plastics are, for example: -Quercetin (B.Kirschweng et al.,Melt stabilization of PE with natural antioxidants:Comparison of rutin and quercetin,Eur.Pol.J.2018, 103,228-237) -Dihydromyrecitin (B. Kirschweng et al., Melt stabilization of polyethylene with dihydromyrecitin, a natural antioxidant, Pol. Degr. Stab. 2016, 133, 192-200) - Derivatives of rosmarinic acid (see K. Doudin et al., New genre of antioxidants from renewable natural resources: Synthesis and characterization of rosemary plant-derived antioxidants and their performance in polyolefins, Pol. Degr. Stab. 2016, 130, 126-134, annex) -Tannins (WJGrigsby et al., Esterification of condensed tannins and their impact on the properties of poly(lactic acid), Polymers s (2013)344-360) -curcumin (D. Tatraaljai et al. Processing stabilization of PE with a natural antioxidant, curcumin, European Polymer Journal 49 (2013) 1196-1203) and -Silymarin and silibinin (B. Kirschweng et al., Melt stabilization of polyethylene with natural antioxidants: comparison of a natural extract and its main components. Journal of Thermal Analysis and Calorimetry https: / / doi.or g / 10.1007 / s10973-020-09709-5). -Catechins from tea and coffee extract (O. Olejnik, A. Masek, Bio-Based Packaging Materials Containing Substances Derived from Coffee and Tea Plants, Materials 2020, 13, 5719)

[0004] WO2020 / 083740 describes the improved use of natural phenols through synergistic compositions consisting of polyphenols and alditols or cyclitols.

[0005] However, some of the natural phenols already considered as stabilizers in plastics also have drawbacks, such as undesirable strong coloring (e.g., curcumin), mixtures of different and varying compositions (e.g., rosemarin and other plant extracts, silymarin), insufficient long-term effectiveness (e.g., tocopherol), and / or volatility.

[0006] Dieugenol (oligomer, polymer, copolymer) has not previously been used as a stabilizer for thermoplastic resins. Document WO 2019 / 092359 A1, or rather Goswinus HM de Kruijff et al. Green Chem., 2019, 21, 481.5-4823, describes its use as a raw material for epoxy resins. However, in this case, the phenolic groups essential for its antioxidant effect are either epoxidized or reactively transformed during the crosslinking reaction of the epoxy resin.

[0007] Therefore, there is a need for effective stabilizers based on sustainable raw materials and that do not have these drawbacks. Summary of the Invention

[0008] This problem is solved by using dieugenol, eugenol oligomers and / or eugenol polymers to stabilize organic materials, in particular against oxidative, thermal and / or photodegradation. Claim 12 relates to a correspondingly stabilized plastic composition. Claim 14 specifies a stabilizer composition. Claim 16 specifies a method for the stabilization of organic materials. The dependent claims relate to advantageous embodiments.

[0009] The oligomer or polymer may also be a cooligomer or copolymer containing other suitable monomers. To achieve the antioxidant effect, it is essential that the phenolic groups in the polymers and oligomers, or copolymers and cooligomers, remain active components and are not inactivated during the polymer synthesis by reactions such as condensation and conversion to ester or ether groups. Eugenol end groups, which are used in polycarbonates for further reaction and synthesis of polysiloxane copolymers, as described in, for example, WO 2019 / 228783 or WO 2020 / 094553, are therefore not included in the present invention, since these polymers do not contain free phenolic groups.

[0010] The natural-based raw material eugenol for making dieugenol and eugenol oligomers and polymers is obtained not only from Kolb's oil but also by biotechnological processes based on biomass, e.g. wood. [ka]

[0011] Dieugenol

[0012] Dieugenol can be produced from eugenol by oxidative coupling, for example electrochemically (GHM de Kruijff et al., Green Chem. 2019, 21, 4815-4823) according to FA Marques et al., Tetrahedron Letters 1998, 39, 943-946, M. Ogata et al., Biol. Pharm. Bull. 2005, 28, 1120-1 122), or enzymatically by Laccase (A. Llevot et al., Polym. Chem. 2015, 6, 7693-7700).

[0013] It has surprisingly been found that eugenol or its derivatives have a stabilizing effect on organic materials, especially plastics.

[0014] The eugenol cooligomers and / or eugenol copolymers preferably comprise or are formed from repeating units A and B. wherein repeat unit A has the formula: [ka] and B is at least one repeating unit derived from a radiation-, anionic-, cationic- or coordination-polymerizable monomer, in particular ethylene, propylene, butadiene, isoprene, styrene or a styrene derivative such as, for example, alpha-methylstyrene, an acrylic acid ester such as, for example, ethyl, propyl, or butyl acrylate, lauryl acrylate, or stearyl acrylate, a methacrylic acid ester such as, for example, methyl methacrylate, ethyl, or hydroxyethyl methacrylate, lauryl or stearyl methacrylate, acrylonitrile, and mixtures and combinations thereof. Preferred radiation-polymerizable monomers B are, in particular, styrene, n-butyl acrylate, or methyl methacrylate.

[0015] The eugenol oligomer or polymer is obtained in the absence of comonomer B.

[0016] The use according to the invention of the cooligomers and copolymers is furthermore distinguished in particular by the following: the molar ratio of repeat units A to the sum of all repeat units is between 3% and 99.99%, preferably between 25...% and 99...%, and / or The total number of repeating units A is 3 to 100, and the total number of all repeating units B is 1 to 100.

[0017] Here, oligomer or copolymer is understood to mean a compound containing up to 10 repeating units A or A and B; polymer or copolymer is understood to mean a compound containing more than 10 repeating units A or A and B.

[0018] Crosslinked structures may also be present in copolymers, obtained by adding to the polymerizable composition di-, tri- or higher functional monomers such as divinylbenzene or pentaerythritol tetraacrylate, as well as dieugenol.

[0019] Oligomers or cooligomas are preferably used, and dieugenol is even more preferred.

[0020] Here, polymers or oligomers can be produced by polymerization reaction via the allyl groups of eugenol, with the phenolic groups remaining largely unchanged in the oligomeric or polymeric structure.

[0021] For example, polymers or oligomeric eugenols can be synthesized electrochemically from eugenol. Allyl compounds can, in principle, be polymerized by radical, controlled radical, anionic, cationic, or coordination polymerization (see, for example, A. Matsumoto, "Polymerization of Multiallyl Monomers," Progress of Polymer Science, 2001, 26, 189-257). Polymerization methods are known to those skilled in the art and can be inferred from relevant works, such as Ullmann's Encyclopedia of Industrial Chemistry, Polymerization Processes, Wiley 2015. For radical, controlled radical, cationic, anionic, or coordination polymerization, the phenolic groups must first be protected by known methods, such as acetyl groups, which can then be removed by hydrolysis after polymerization or copolymerization. For radical polymerization using allyl groups, oligomeric structures are generally preferred. The copolymers are obtained by polymerizing eugenol bearing protective groups together with other polymerizable monomers, such as styrene, styrene derivatives, acrylic esters or methacrylic esters, by one of the methods described.

[0022] Additionally, oligomeric and polymeric eugenol can be synthesized by, for example, copper-catalyzed or enzymatic oxidative CC ligation. [ka] Then, the following polymer structures are obtained, where n=3 to 100, preferably 3 to 10:

[0023] Radical, anionic, cationic or coordination polymerization can also be used to obtain oligomeric and polymeric eugenols having the formula: [ka]

[0024] Here, n has the meaning described above.

[0025] Here, oligomer is understood to mean a compound containing up to 10 repeating units (n=3 to 10), and polymer is understood to mean a compound containing more than 10 repeating units.

[0026] Eugenol oligomers or polymers can also be prepared, for example, by ZnO-catalyzed reactions (J.E. Weinberg et al., Journal of Dental Research (1972), 51, 1055-61), where polymerization also occurs primarily via the allylic groups, while the phenolic groups are largely preserved. A further possibility for the preparation of eugenol (co)polymers is constituted by eugenol-formaldehyde polymer novolacs (M. Shibata et al., React. Funct. Polym. 2013, 73, 1086).

[0027] All methods previously described for the preparation of eugenol or dieugenol polymers or copolymers can also be used for the purposes of the present invention and are therefore encompassed by the present invention.

[0028] Dieugenol is very particularly preferred, since in addition to the phenolic group the allyl group likewise contributes to the stabilizing effect.

[0029] Preferred embodiments provide stabilization of plastics, coatings, lubricants, hydraulic oils, engine oils, turbine oils, transmission oils, metalworking fluids, chemicals, or monomers.

[0030] Very particular preference is given to using them to stabilise plastics.

[0031] Dieugenol, eugenol oligomers and / or eugenol polymers are preferably used in the organic material in a weight ratio of 0.01 to 10.00% by weight, preferably 0.02 to 5.00% by weight, more preferably 0.05 to 3.00% by weight, particularly preferably 0.10 to 2.00% by weight.

[0032] Preferred plastics to be stabilized here are selected from the group consisting of: a) Polymers 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, also polyisoprene, such as natural rubber (NR), polycyclooctene, polyalkylene-carbon monoxide copolymers, and also polymers from polyolefins, such as polypropylene-polyethylene (EP), EPM or EPDM with 5-ethylidene-2-norbornene as a comonomer, ethylene-vinyl acetate (EVA), such as ethylene butyl acrylate, ethylene acrylic acid and Copolymers in the form of random or block structures, such as ethylene acrylic esters, including their salts (ionomers), and graft polymers, such as ethylene acrylic acid glycidyl (meth)acrylate, polypropylene-grafted maleic anhydride, polypropylene-grafted acrylic acid, polyethylene-grafted acrylic acid, polyethylene-polybutylacrylate-grafted maleic anhydride, and terpolymers, such as blends, such as LDPE / LLDPE, or long-chain branched polypropylene copolymers produced with alpha-olefins, such as 1-butene, 1-hexene, 1-octene or 1-octadecene, as comonomers. b) polystyrene, polymethylstyrene, polyalphamethylstyrene, 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 the corresponding graft copolymers, such as styrene on butadiene, maleic anhydride on SBS or SEBS, and graft copolymers of methyl methacrylate, styrene-butadiene and ABS (MABS), and hydrogenated polystyrene derivatives, such as polyvinylcyclohexane, c) halogen-containing polymers such as, for example, polyvinyl chloride (PVC), polychloroprene and polyvinylidene chloride (PVDC), copolymers of vinyl chloride and vinylidene chloride or vinyl chloride and vinyl acetate, chlorinated polyethylene, polyvinylidene fluoride, epichlorohydrin homo- and copolymers, especially with ethylene oxide (ECO); d) polymers of unsaturated esters, such as polyacrylate, polymethacrylates such as polymethyl methacrylate (PMMA), polybutyl acrylate, polylauryl acrylate, polystearyl acrylate, polyglycidyl methacrylate, polyacrylonitrile, polyacrylamide, copolymers such as 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, such as butanal, polyphenylene oxide, polystyrene or blends with polyamides; g) cyclic ether polymers such as polyethylene glycol, polypropylene glycol, polyethylene oxide, polypropylene oxide, polytetrahydrofuran; h) polyphenylene oxide, and polystyrene and / or polyamides and blends thereof; i) polyurethanes, especially linear polyurethanes (TPUs), polyureas, made from hydroxy-terminated polyethers or polyesters and aromatic or aliphatic isocyanates, such as, for example, 2,4- or 2,6-tolylene diisocyanate or methylene diphenyl diisocyanate; 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 made from, for example, terephthalic acid and / or isophthalic acid and aliphatic diamines, such as hexamethylenediamine or m-xylylenediamine, or from aliphatic dicarboxylic acids, such as adipic acid or sebacic acid, and aromatic diamines, such as 1,4- or 1,3-diaminobenzene; blends of different polyamides, such as PA-6 and PA6.6, or blends of polyamides and polyolefins, such as PA / PP; k) polyimides, polyamide-imides, polyetherimides, polyesterimides, poly(ether)ketones, polysulfones, polyethersulfones, polyarylsulfones, polyphenylene sulfides, polybenzimidazoles, polyhydantoins, 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 (PPT), polyethylene naphthylate (PEN), poly 1,4-dimethylolcyclohexane terephthalate, polyhydroxybenzoates, polyhydroxynaphthalates, polylactic acid (PLA), polyhydroxybutyric acid (PHB), polyhydroxyvalerate (PHV), polyethylene succinate, polytetramethylene succinate, polycaprolactone, m) Polycarbonate, polyester carbonate and blends such as PC / ABS, PC / PBT, PC / PET / PBT, PC / PA, etc. 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 based, for example, on amines, anhydrides, dicyandiamide, mercaptans, isocyanates or catalytically active hardeners; p) phenolic resins such as phenol formaldehyde resins, urea formaldehyde resins, melamine formaldehyde resins, etc. q) unsaturated polyester resins from unsaturated dicarboxylic acids and diols with vinyl compounds, such as styrene alkyd resins, r) silicones based, for example, on dimethylsiloxane, methyl-phenylsiloxane or diphenylsiloxane, for example, terminated with vinyl groups; s) and mixtures, combinations, or blends of two or more of the foregoing polymers.

[0033] When the polymers identified in a) to r) are copolymers, they can exist in the form of random, block or tapered structures.

[0034] Furthermore, the polymers mentioned can exist in the form of linear, branched, star or hyperbranched structures.

[0035] When the polymers specified by a) through r) are stereoregular polymers, they can exist as stereoblock copolymers in isotactic and stereotactic forms as well as in atactic form.

[0036] Furthermore, the polymers identified in a) through r) can have both amorphous and (partially) crystalline morphologies.

[0037] Optionally, the polyolefins mentioned under a) can also be crosslinked, for example crosslinked polyethylene, which is then called X-PE.

[0038] Furthermore, the compounds of the invention can be used to stabilize rubbers and elastomers, which may be natural rubber (NR) or synthetic rubber materials such as, for example, chloroprene (CR), polybutadiene (BR), styrene-butadiene (SBR), polyisoprene (IR), butyl rubber (IIR), nitrile rubber (NBR), hydrogenated nitrile rubber (HNBR), polyester or polyether urethane rubber, or silicone rubber.

[0039] Apart from new goods, the plastics can also be recycled plastics from industrial collections, such as production waste, or from household or recyclable collections.

[0040] Further preferred are polymers, especially those produced wholly or partly from sustainable raw materials, such as polylactic acid (PLA), polybutylene succinate (PBS), polybutylene succinate-co-adipate) (PBSA), poly(butylene adipate) (PBA), poly(hexamethylene succinate), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polypropylene terephthalate (PPT), polyethylene furanoate (poly(ethylene-2,5-furandicarboxylate)) (PEF), poly 3-hydroxybutyrate, poly 4-hydroxybutyrate, poly 3-hydroxyvalerate, and the like.

[0041] More preferably, the organic material, especially the plastic, comprises at least one additional additive selected from the group consisting of primary and / or secondary antioxidants, in particular phosphites, phosphonites, thiols, phenolic antioxidants, sterically hindered amines, hydroxylamines, and mixtures or combinations thereof, UV absorbers, light stabilizers, hydroxylamine stabilizers, benzofuranone stabilizers, nucleating agents, impact modifiers, plasticizers, die lubricants, rheology modifiers, chain extenders, processing aids, pigments, dyes, optical brighteners, antibacterial agents, antistatic agents, slip agents, antiblocking agents, coupling agents, dispersants, compatibilizers, oxygen scavengers, acid scavengers, co-stabilizers, marking agents, and antifogging agents, in particular secondary antioxidants, which are added to the plastic during use, with phosphites, phosphonites, acid scavengers, hindered amines, and / or combinations thereof being particularly preferred.

[0042] In the above-mentioned embodiments, it is advantageous if the at least one additive is contained or added in an amount of 0.01 to 9.99 wt. %, preferably 0.01 to 4.98 wt. %, particularly preferably 0.02 to 2.00 wt. %, based on the total of dieugenol, eugenol oligomer and / or eugenol polymer, organic material and at least one additive.

[0043] The present invention further relates to organic materials, in particular plastic compositions containing dieugenol, eugenol oligomers, and / or eugenol polymers as stabilizers.

[0044] Particularly advantageously, the organic material, and in particular the plastic composition, has the following composition: 0.01 to 10.00 wt. %, preferably 0.02 to 5.00 wt. %, more preferably 0.05 to 3.00 wt. %, and particularly preferably 0.10 to 2.00 wt. % of dieugenol, eugenol oligomers, and / or eugenol polymers, 99.99 to 90.00 wt. %, preferably 99.89 to 95.00 wt. %, more preferably 97.00 to 99.95 wt. %, particularly preferably 99.90 to 98.00 wt. % of at least one organic material, preferably selected from the group consisting of plastics, coatings, lubricants, hydraulic oils, engine oils, turbine oils, transmission oils, metalworking fluids, chemicals, or monomers, and 0 to 9.99% by weight, preferably 0 to 4.98% by weight, particularly preferably 0.02 to 2.00% by weight, of at least one additive, Here, the components are added up to 100% by weight.

[0045] The plastic compositions can be in the form of injection molded parts, foils or films, foams, fibers, cables and pipes, sections, hollow bodies, ribbons, membranes, e.g., geomembranes, or adhesives, produced, for example, by extrusion, injection molding, blow molding, calendering, pressing, spinning, or rotoforming, for the electrical and electronics industry, the construction industry, the transport industry (automotive, aviation, marine, rail), medical applications, household and electrical appliances, vehicle parts, consumer products, packaging, furniture, textiles, etc. Furthermore, they are also used in paints, colorants, coatings, etc.

[0046] The at least one additive is preferably selected from the group consisting of primary and / or secondary antioxidants, in particular the primary and / or secondary antioxidants are 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 stabilizers, benzofuranone stabilizers, nucleating agents, toughening agents, plasticizers, die lubricants, rheology modifiers, chain extenders, processing aids, pigments, dyes, optical brighteners, antimicrobial active agents, antistatic agents, slip agents, antiblocking agents, coupling agents, dispersants, compatibilizers, oxygen scavengers, acid scavengers, co-stabilizers, marking agents, anti-fogging agents, in particular secondary antioxidants; the at least one additive is preferably selected from the group consisting of secondary antioxidants, in particular selected from the group consisting of phosphites, phosphonites, and thiols, polyols, acid scavengers, and at least one co-stabilizer selected from the group consisting of sterically hindered amines.

[0047] The present invention also relates to stabilizer compositions consisting of or including dieugenol, eugenol oligomers, eugenol co-polymers, eugenol polymers and / or eugenol copolymers, and mixtures and combinations thereof, and at least one secondary antioxidant selected from the group consisting of phosphites, phosphonites, or thiols, and / or at least one co-stabilizer selected from the group consisting of polyols, acid scavengers, or sterically hindered amines, and mixtures and combinations thereof.

[0048] Thus, new stabilizer compositions and new methods for the stabilization of plastics based on sustainable raw materials become possible, which are highly effective, environmentally friendly and have a favorable cost structure.

[0049] With regard to specific embodiments of dieugenol, eugenol oligomers, eugenol co-polymers, eugenol polymers and / or eugenol copolymers, reference is made to the above descriptions.

[0050] In the stabilizer composition, dieugenol, oligoeugenol or polyeugenol and the at least one secondary antioxidant and / or co-stabilizer are preferably present in a weight ratio of 100:1 to 1:100, preferably 10:1 to 1:10, particularly preferably 4:1 to 1:4.

[0051] The present invention further relates to methods in which dieugenol, eugenol oligomers and / or eugenol polymers are incorporated into organic materials to stabilize the organic materials, especially against oxidative, thermal and / or photodegradation.

[0052] In a preferred embodiment, the composition comprises a secondary antioxidant, in particular a phosphite / phosphonite or a thio compound.

[0053] Suitable phosphites include triphenyl phosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite, tri(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol phosphite, tris-(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythrityl phosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol phosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol phosphite, Bis(2,4-dicumylphenyl)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), tristearyl sorbitan triphosphite, tetramethyl ... Rakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12Hdibenz[d,g]-1,3,2-dioxaphosposine, bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyldi Benz[d,g]-1,3,2-dioxaphosphinate, 2,2'2''-nitrilo[triethyltris(3,3'',5,5'-tetra-tert-butyl-1,1'-biphenyl-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-butylphenoxy)-1,3,2-dioxaphosphirane.

[0054] Particularly preferred phosphites / phosphonites include: [ka] [ka] n=3-100.

[0055] Very particular preference is given to using the phosphite tris-(2,4-di-tert-butylphenyl) phosphite as secondary antioxidant, where n=3-100.

[0056] Very particular preference is given to using the phosphite tris-(2,4-di-tert-butylphenyl) phosphite as secondary antioxidant.

[0057] Suitable secondary antioxidants are also organic sulfur compounds, such as sulfides and disulfides, such as 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: [ka]

[0058] The additives may also be selected from the group consisting of primary antioxidants, UV absorbers, light stabilizers, metal deactivators, filler deactivators, antiozonants, nucleating agents, antinucleating agents, impact modifiers, plasticizers, die lubricants, rheology modifiers, thixotropic agents, chain extenders, processing aids, mold release agents, flame retardants, pigments, dyes, optical brighteners, antimicrobial agents, antistatic agents, slip agents, antiblocking agents, coupling agents, crosslinking agents, anticrosslinking agents, hydrophilizing agents, hydrophobizing agents, adhesion promoters, dispersants, compatibilizers, oxygen scavengers, acid scavengers, foaming agents, degradation additives, antifoaming agents, deodorizing agents, marking agents, antifogging agents, fillers, and reinforcing agents.

[0059] In a preferred embodiment, the composition specifically comprises an acid scavenger.

[0060] Suitable scavenger agents ("antacids") are salts of monovalent, divalent, trivalent, or tetravalent metals, preferably alkali metals, alkaline earth metals, aluminum, or zinc, especially salts formed with fatty acids, such as calcium stearate, magnesium stearate, zinc stearate, aluminum stearate, calcium laurate, calcium behenate, calcium lactate, calcium stearoyl dilactate, etc. A further class of suitable scavenger agents is hydrolactites, especially synthetic hydrolactites based on aluminum, magnesium, and zinc, hydrocalumites, zeolites, alkaline earth oxides, especially calcium oxide, magnesium oxide, and zinc oxide, alkaline earth carbonates, especially calcium carbonate, magnesium carbonate, dolomite, and hydroxides, especially brookite (magnesium hydroxide).

[0061] Suitable further primary antioxidants are phenolic antioxidants, amines, lactones.

[0062] Suitable phenolic antioxidants are, for example: alkylated monophenols such as 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-methylphenol, 2-(alpha-methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, for example 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6-(1'-methylundec-1'-yl) ... linear or branched nonylphenols such as 2,4-dimethyl-6-(1'-methylheptadec-1'-yl)phenol and 2,4-dimethyl-6-(1'-methyltridec-1'-yl)phenol, and mixtures thereof; alkylthiomethylphenols such as 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, and 2,6-didodecylthiomethyl-4-nonylphenol; and 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2.Hydroquinones and alkylated hydroquinones such as 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 hydroxyphenyl) adipate; tocopherols such as α-, β-, γ-, δ-tocopherol, and mixtures thereof (vitamin E); 2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-2-methylphenol), phenol), 4,4'-thiobis(3,6-di-sec-amylphenol), 4,4'-bis(2,6-dimethyl-4-hydroxyphenyl) disulfide; hydroxylated thiodiphenyl ethers such as 2,2'methylenebis(6-tert-butyl-4-methylphenol), 2,2'-methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-(alpha-methylcyclohexyl)phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-nonyl-4-methylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-ethyldenebis(4.6-di-tert-butylphenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis[6-(alpha-methylbenzyl)-4-nonylphenol], 2,2'-methylenebis[6-(alpha,alpha-dimethylbenzyl)-4-nonylphenol], 4,4'-methylenebis(2,6-di-tert-butylphenol, 4,4'-methylenebis(6-tert-butyl-2-methylphenol), 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-methylphenyl)-3-nododecylmercaptobutane, ethylene glycol-bis[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl) butyrate], bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene, bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate, 1,1-bis(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis-(5-tert-butyl-4-hydroxy-2-methyl alkylidene bisphenols such as 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzyl mercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzyl mercaptoacetate, tris(3.O-, N- and S-benzyl compounds such as bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)amine, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isoctyl-3,5-di-tert-butyl-4-hydroxybenzyl mercaptoacetate; for example, dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate, dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl) ... Hydroxybenzylated malonates such as decyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, dodecylmercaptoethyl-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; for example, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6 -trimethylbenzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol; for example, 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxybenzyl)- xyanilino)-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.Triazine compounds such as 4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexahydro-1,3,5-triazine, and 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate; benzyl phosphonates such as diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid; for example 4-hydroxylauranyl Acylaminophenols such as octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate; β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid and monohydric or polyhydric alcohols, such as 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-cyaundecanol, 3-cyapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]Esters of octane; β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with monohydric or polyhydric alcohols, such as 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-cyaundecanol, 3-cyapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane, 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy- 5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxspiro[5·5]undecane esters; β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, such as methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.Esters of 2-octane; esters of (3,5-di-tert-butyl-4-hydroxyphenyl)acetic acid with monohydric or polyhydric alcohols, such as methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, and thiodiethylene glycol; diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane; and amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, such as N,N'-. Bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide, N,N'-bis[2-(3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide (Naugard® XL-1, sold by Uniroyal); ascorbic acid (vitamin C).

[0063] A particularly preferred phenolic antioxidant has the following structure: [ka] [ka] [ka] [ka] 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).Further particularly preferred phenolic antioxidants are based on sustainable raw materials, such as tocopherol (vitamin E), tocotrienols, tocomonoenol, carotenoids, hydroxytyrosol, flavonols such as chrysin, quercetin, hesperidin, neohesperidin, naringin, morin, camphor oil, anthocyanins such as fisetin, delphinidin and malvidin, curcumin, carnosic acid, carnosol, rosmarinic acid and resveratrol.

[0064] Suitable aminic antioxidants include, for example:

[0065] N,N'-diisopropyl-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-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-argyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamines, such as p,p'-di-tert- Octyldodiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylaminomethyl-phenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N,N,N''-tetramethyl-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, mixtures of mono- and di-alkylated tert-butyl / tert-octyldodiphenylamines, mixtures of mono- and di-alkylated nonyldiphenylamines, mixtures of mono- and di-alkylated dodecyldiphenylamines, mono- and di-alkylated isopropyl / isohexyldiphenylamines mixtures of mono- and di-alkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, mixtures of mono- and di-alkylated tert-butyl / tert-octylphenothiazines, mixtures of mono- and di-alkylated tert-octylphenothiazines, N-allylphenothiazine, N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene and mixtures or combinations thereof.

[0066] Preferred amine antioxidants are: N,N'-diisopropyl-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-phenylenediamine, N,N'-dicyclohexyl-p-phenylenediamine, N,N'-bis(1-methylheptyl) ... 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, and N-cyclohexyl-N'-phenyl-p-phenylenediamine.

[0067] A particularly preferred amine antioxidant has the following structure: [ka]

[0068] More preferred amine antioxidants are hydroxylamines or N-oxides (nitrones), e.g., N,N-dialkylhydroxylamine, N,N-dibenzylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-distearylhydroxylamine, N-benzyl-alpha-phenylnitrone, N-octadecyl-alpha-hexadecylnitrone, Genox EP (SI Group), and the like, according to the formula: [ka]

[0069] Suitable lactones are, for example, 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-acetoxyethoxy)phenyl]benzofuran-2-one, 3,3′-bis[5,7-di-tert-butyl-3-(4-(2-hydroxyethoxy)phenyl]benzofuran-2-one], 3,3′-bis[5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one], 3,3′-bis[5,7-di-tert-butyl-3-(4-acetoxyethoxy)phenyl] ... benzofuranones and indolinones such as 3-(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, which additionally have a phosphite group, for example [ka] [ka] and other lactones.

[0070] Further suitable groups of antioxidants include, for example: [ka] and isoindole[2,1-A]quinazonyl compounds such as:

[0071] Suitable costabilizers are furthermore polyols, in particular alditols or cyclitols, such as pentaerythritol, dipentaerythritol, tripentaerythritol, short-chain polyether polyols or short-chain polyester polyols, and also highly branched polymers / oligomers or dendrimers containing alcohol groups, such as: [ka] Branched polymers / oligomers or dendrimers containing alcohol groups, such as: [ka]

[0072] The at least one alditol is preferably selected from the group consisting of threitol, erythritol, galactitol, mannitol, ribitol, sorbitol, xylitol, arabitol, isomalt, lactitol, maltitol, altitol, iditol, maltotritol, hydrogenated oligo- and polysaccharides with polyol end groups, and mixtures thereof. The at least one preferred alditol is particularly preferably selected from the group comprising erythritol, mannitol, isomaltol, maltitol, and mixtures thereof.

[0073] Further examples of suitable sugar alcohols are the heptitols and octitols: mesoglyceroalloheptitol, D-glycero-D-altroheptitol, D-glycero-D-mannoheptitol, mesoglycero-glo-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.

[0074] The at least one cyclitol may in particular be selected from the group consisting of inositol (myo-, schiro-, D-tyro-, L-tyro-, muco-, neo-, allo-, epi- and cis-inositol), 1,2,3,4-tetrahydroxycyclohexane, 1,2,3,4,5-pentahydroxycyclohexane, quercitol, biscumitol, bornesitol, conduritol, ononitol, pinitol, pinpollitol, quebrachitol, cisceritol, quinic acid, shikimic acid, valienol, where myo-inositol (myo-inositol) is preferred.

[0075] Suitable light stabilizers are, for example, compounds based on 2-(2'-hydroxyphenyl)benzotriazoles, 2-hydroxybenzophenones, esters of benzoic acid, acrylates, oxamides and 2-(2-hydroxyphenyl)-1,3,5-triazine.

[0076] Suitable 2-(2'-hydroxyphenyl)benzotriazoles include, for example, 2-(2'-hydroxy-5'methylphenyl)benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'-tert-butyl-2'-hydroxy-phenyl)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'-hydroxy-phenyl)benzotriazole, 2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole, 2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)benzotriazole, 2-(3',5'-bis(α,α-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxyphenyl)benzotriazole 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-methoxycarbonylethyl)phenyl)benzotriazole, -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 transesterification product of 2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazole with polyethylene glycol 300, [R-CH2CH2-COO-CH2CH2-]-2, where R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl, 2-[2'-hydroxy-3'-(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,

[0077] Suitable 2-hydroxybenzophenones are, for example, the 4-hydroxy-, 4-methoxy-, 4-octyloxy-, 4-dodecyloxy-, 4-benzyloxy-, 4,2',4'-trihydroxy- and 2'-hydroxy-4,4'-dimethyoxy derivatives of 2-hydroxybenzophenone.

[0078] Suitable acrylates are, for example, ethyl-α-cyano-β,β-diphenylacrylate, isoctyl-α-cyano-β,β-diphenylacrylate, methyl-α-carbomethoxycinnamate, methyl-α-cyano-β-methyl-p-methoxycinnamate, butyl-α-cyano-β-methyl-p-methoxycinnamate, methyl-α-carbomethoxy-p-methoxycinnamate, N-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline.

[0079] Suitable esters of benzoic acid 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.

[0080] Suitable oxamides are, for example, 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxide, N,N'-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and p-methoxy-disubstituted oxanilides, and mixtures of o- and p-ethoxy-disubstituted oxanilides.

[0081] Suitable 2-(2-hydroxyphenyl)-1,3,5-triazines include, 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)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy 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-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine; 2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropoxy]phenyl}-4,6-bis(2,4-dimethylphenyl-1,3,5-triazine).

[0082] Suitable metal deactivators are, for example, N,N'-diphenyloxamide, N-salicylal-N'-salicyloylhydrazine, N,N'-bis(salicyloyl)hydrazine, N,N'-bis(3,5-di-tertbutyl-4-hydroxyphenylpropionyl)hydrazine, 3-salicyloylamine-1,2,4-triazole, bis(benzylidene)oxylylhydrazide, oxanilhydride. Isophthaloyl dihydrazide, sebacoyl-bis-phenylhydrazide, N,N'-diacetyladipoyl dihydrazide, N,N'-bis(salicyloyl)oxylyl dihydrazide, N,N'-bis(salicyloyl)thiopropionyl dihydrazide, tris[2-tert-butyl-4thio(2'-methyl-4'-hydroxy-5'-tert-butyl)-phenyl-5-methyl]phenyl phosphite.

[0083] Particularly preferred metal deactivators are: [ka]

[0084] Suitable hindered amines include, 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)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-n-butyl-3,5-di-tert-butyl-4-hydroxy Condensation products of benzylmalonic acid, 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine and linear or Cyclic condensation products, tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate, tetrakis(2,2,6,6-tetramethyl-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)hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, reaction products of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxspiro-[4,5]decane and epichlorohydrin.

[0085] Also included within the structures recited herein above are sterically hindered NH, N-alkyl derivatives such as N-methyl or N-octyl, N-alkoxy derivatives such as N-methoxy or N-octyloxy, cycloalkyl derivatives such as N-cyclohexyloxy, N-(2-hydroxy-2-methylpropionyl) analogs, and the like.

[0086] Also preferred hindered amines have the following structure: [ka] [ka] [ka] [ka]

[0087] Preferred oligomeric and polymeric hindered amines have the following structure: [ka] [ka] [ka]

[0088] In the above compounds, n is 3 to 100.

[0089] A further suitable light stabilizer is Hostanox NOW (manufacturer: Clariant SE) which has the following general structure: [ka]

[0090] Suitable dispersants are, for example: polyacrylates, for example copolymers with long chain side groups, polyacrylate block copolymers, alkylamides, for example N,N'-1,2-ethanediylbisooctadecaneamidosorbitan esters, for example monostearyl sorbitan esters, titanates and zirconates, reactive copolymers with functional groups, for example polypropylene-co-acrylic acid, polypropylene-co-maleic anhydride, polyethylene-co-glycidyl methacrylate, polystyrene-alto-maleic anhydride-polysiloxanes, for example dimethylsilanediol-ethylene oxide copolymers, polyphenylsiloxane copolymers, amphiphilic copolymers, for example polyethylene-block-polyethylene oxide, dendrimers, for example dendrimers consisting of hydroxyl groups.

[0091] Suitable antinuclear agents are, for example, azine dyes such as nigrosine.

[0092] Suitable flame retardants are in particular inorganic flame retardants, such as, for example, AI(OH)3, Mg(OH)2, AlO(OH), MgCO3, sheet silicates, such as, for example, montmorillonite or sepiolite, unmodified or organically modified double salts, such as, for example, Mg-Al silicates, polyhedral oligomeric silsesquioxanes (POSS), silsesquioxanes), huntite hydromagnesite or halloysite and Sb2O3, Sb2O5, MoO3, zinc stannate, zinc hydroxystannate, and other nitrogen-containing flame retardants, such as melamine, melem, melon, melamine derivatives, melamine condensation products or melamine salts, benzoguanamine, polyisocyanurates, allantoin, phosphacenes, in particular melamine cyanurate, melamine phosphate, dimelamine phosphate, melamine prophosphate, melamine polyphosphates, such as aluminum melamine phosphate, zinc melamine phosphate, magnesium melamine phosphate, and the corresponding pyrophosphates and polyphosphates, poly-[2,4-(piperazin-1,4-yl)-6-(morpholin-4-yl)-1,3,5-triazine], ammonium polyphosphate, melamine metal phosphates, such as melamine borate and melamine bromide, in radical form. flame retardants, such as alkoxyamines, hydroxylamine esters, azo compounds, triazine compounds, disulfides, polysulfides, thiols, thiuram sulfides, dithiocarbamates, mercaptobenthazoles, sulfenamides, sulfenimides, dicumyl or polycumyl, hydroxyimides and their derivatives, such as hydroxyimide esters or hydroxyimide ethers, phosphorus-containing flame retardants, such as red phosphorus, phosphates, such as resorcinol diphosphate, bisphenol A diphosphate, and their oligomers, triphenyl phosphate, ethylenediamine diphosphate, hypophosphorous acid and, for example, aluminum diethylphosphinate or zinc diethylphosphinate or aluminum phosphinate, aluminum phosphite, aluminum phosphonate, phosphonic acid esters, oligomeric and polymeric derivatives of methanephosphonic acid,Alkyl phosphinates such as 10-dihydro-9-oxa-10-phosphorylphenanthrene-10-oxide (DOPO) and their derivatives such as substituted compounds thereof, halogenated flame retardants based on chlorine and bromine, such as polybrominated diphenyl oxides, for example, decabromodiphenyl oxide, tris(3-bromo-2,2-bis(bromomethyl)propyl)phosphate, tris(tribromonopentyl)phosphate, tetrabromophthalic acid, 1,2-bis(tribromophenoxy)ethane, hexabromocyclodecane, diphenyl bromide, tris(2,3-dibromopropyl)isocyanurate, ethylene-bis-(tetrabromophthalimide), tetrabromobisphenol A, brominated polystyrene, brominated polybutadiene or polystyrene-brominated polybutadiene copolymer, brominated polyphenylene ether, brominated epoxy resins, polypentabromobenzyl acrylate. Anti-drip agents such as, for example, elemental sulfur, disulfides and polysulfides, thiuram sulfides, dithiocarbamates, mercaptobenzothiazoles and sulfenamides, sulfur-containing compounds on silica, for example, borates, for example, zinc borate or calcium borate, optionally on a carrier material, for example, carbon nanotubes (CNTs), expandable graphite or graphene, and combinations or mixtures thereof, for example, polyphenylsiloxanes, carbon modifications, for example, polytetrafluoroethylene, silicon-containing compounds, etc.

[0093] The following compounds, which are halogen-free, are very particularly preferred flame retardants:

[0094] Al(OH)3, Mg(OH)2, [ka] [ka] [ka] Suitable plasticizers are, for example, phthalates, adipates, esters of citric acid, esters of 1,2-cyclohexanedicarboxylic acid, trimellitates, isopropyl esters, phosphate esters, epoxides, such as, for example, epoxidized soybean oil, or aliphatic polyesters.

[0095] Suitable die lubricants and processing aids are, for example, polyethylene waxes, polypropylene waxes, salts of fatty acids such as, for example, calcium stearate, zinc stearate, or salts of montan wax, amide waxes such as, for example, erucamide or oleamide, fluoropolymers, silicones, or neoalkoxy titanates and zirconates.

[0096] Suitable pigments may be inorganic or organic. Inorganic pigments include, for example, titanium dioxide, zinc oxide, zinc sulfide, iron oxide, ultramarine, and carbon black. Organic pigments include, for example, anthraquinone, anthrone, benzimidazolone, quinacridone, diketopyrrolopyrrole, dioxazines, indanthrone, isoindolinone, azo compounds, perylene, phthalocyanine, and pyranthrone. Further suitable pigments include metal-based effect pigments or metal oxide-based pearl gloss pigments.

[0097] Suitable optical brighteners are, for example, bis-benzoxazoles, phenylcoumarins, or bis(styryl)biphenyls, in particular those of the formula [ka] It is an optical brightener.

[0098] Suitable filler deactivators are, for example, polysiloxanes, polyacrylates, in particular block copolymers such as polymethacrylic acid polyalkylene oxides or polyglycidyl (meth)acrylates and copolymers thereof, such as styrene and epoxides, for example of the following structure: [ka]

[0099] Suitable antistatic agents are, for example, ethoxylated alkylamines, fatty acid esters, alkyl sulfonates, and polymers such as, for example, polyetheramides.

[0100] Suitable antiozonants are, for example, the above-mentioned amines, such as N,N'-diisopropyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine, N,N'-dicyclohexyl-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine, and N-cyclohexyl-N'-phenyl-p-phenylenediamine.

[0101] Suitable rheology modifications, such as the preparation of controlled rheology polypropylene (CR-PP), include, for example, peroxides, alkoxyaminoesters, oximidosulfonic acid esters, especially those having the following structure: [ka]

[0102] Suitable nucleating agents are talcum, alkali or alkaline earth salts of mono- and polyfunctional carboxylic acids, such as benzoic acid, succinic acid, adipic acid, for example, trisamides and dimides, such as sodium benzoate, zinc glycerate, aluminum hydroxy-bis(4-tert-butyl)benzoate, 2,2'-methylene-bis-(4,6-di-tert-butylphenyl)phosphate, and, for example, trimesic acid tricyclohexylamide, trimesic acid tri(4-methylcyclohexylamide), trimesic acid tri(tert-butylamide), N,N',N"-1,3,5-benzoltriyltris(2,2-dimethyl-propanamide) or 2,6-naphthalenedicarboxylic acid cyclohexylamide.

[0103] Suitable additives (chain extenders) for the linear molecular weight structure of polycondensation polymers are diepoxides, bisoxazolines, bisoxazolones, bisoxazines, diisocyanates, dianhydrides, bisacyllactams, bismaleimides, dicyanates, carbodiimides. Further suitable chain extenders are polymeric compounds such as polystyrene-polyacrylate-polyglycidyl (meth)acrylate copolymers, polystyrene-maleic anhydride copolymers, and polyethylene-maleic anhydride copolymers.

[0104] Suitable additives for increasing electrical conductivity include, for example, the above-mentioned antistatic agents, carbon compounds such as black carbon, carbon nanotubes, and graphene, metal powders such as copper powder, and conductive polymers such as polypyrrole, polyaniline, polythiopene, etc. Suitable additives for increasing thermal conductivity include, for example, aluminum nitride and boron nitride.

[0105] Suitable infrared-active additives are, for example, aluminum silicates, hydrotalcites, or dyes such as phthalocyanines or anthraquinones.

[0106] Suitable crosslinking agents are, for example, peroxides such as dialkyl peroxides, alkylaryl peroxides, peroxyesters, peroxycarbonates, diacyloxides, peroxyketals, silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltris(2-methoxyethoxy)silane, 3-methacryloyloxypropyltriethoxysilane, vinyldimethoxymethylsilane or ethylene-vinylsilane copolymers.

[0107] Suitable prodegradants are additives that specifically promote or control the degradation of polymers in the environment, such as enzymes that induce the hydrolysis of transition metal fatty acid esters of, for example, manganese or iron, which promote the oxidative and / or photooxidative degradation of polyolefins, or aliphatic polyesters.

[0108] Suitable chemical blowing agents include, for example, azo compounds such as azodicarboxylic acid diamide, sulfonyl semicarbazides such as p-toluenesulfonyl semicarbazide, tetrazoles such as 5-phenyltetrazole, hydrazides such as p-toluenesulfonyl hydrazide and 4,4′-oxybis(benzenesulfonyl)hydrazide, N-nitroso compounds such as N,N′-dinitrosopentamethylenetetramine, and carbonates such as sodium bicarbonate and zinc carbonate.

[0109] Suitable slip agents are, for example, amide waxes such as erucamide or oleamide.

[0110] Suitable antiblocking agents are, for example, silica, talc, or zeolites.

[0111] Suitable anti-fog additives are, for example, ethoxylated sorbitan esters, ethoxylated fatty acid alcohols or ethoxylated alkylamine esters.

[0112] Suitable biocides are, for example, quaternary ammonium or silver salts, colloidal silver or silver complexes, or natural product derivatives such as chitosan.

[0113] Suitable aldehyde scavengers are amines, hydroxylamines, polyvinyl alcohols, zeolites or cyclodextrins, suitable formaldehyde scavengers are, for example, melamine derivatives such as benzoguanamine or urea derivatives such as allantoin.

[0114] Suitable odor-binding or odor-controlling substances are silicates such as calcium silicate, zeolites or salts of hydroxy fatty acids, such as zinc ricenoleate.

[0115] Suitable markers are, for example, fluorescent dyes or rare earths.

[0116] Suitable additives for increasing the thermal conductivity of plastics are, for example, inorganic fillers such as boron nitride, aluminum nitride, aluminum oxide, aluminum silicate, silicon carbide, but also carbon nanotubes (CNTs).

[0117] Suitable impact modifiers are usually selected for the particular recycle and are chosen from the group of functionalized or non-functionalized polyolefins such as ethylene copolymers, such as EPDM or maleic anhydride or styrene-acrylonitrile modified EPDM, glycidyl methacrylate modified ethylene-acrylate copolymers, or core-shell polymers based on ionomers, such as MBS (methacrylate-butadiene-styrene copolymer) or acrylic ester-polymethyl methacrylate, for example styrene-block copolymers (styrene-butadiene (SB), styrene-butadiene-styrene (SBS), optionally hydrated (SEBS) or modified with maleic anhydride (SEBS-g-MAH), thermoplastic polyurethanes, copolyesters or copolyamide-based thermoplastic elastomers (TPE).

[0118] Suitable release agents are, for example, silicones, soaps, and waxes, such as montan wax.

[0119] Stabilization methods:

[0120] The additives according to the invention, i.e., dieugenol, eugenol oligomers and / or eugenol polymers, which may be present as powders, liquids, oils, compacts, on carrier materials, granules, solutions or flakes, are preferably mixed with the polymer to be stabilized; the polymer matrix is ​​melted and then cooled. Alternatively, it is also possible to introduce the additives into the polymer melt in the molten state.

[0121] If further components are added to the polymer composition, these may be added to the polymer in the form of a liquid, powder, granules or compressed product, either separately or together with the additive composition according to the invention as described above.

[0122] The additive composition and optionally further additives are incorporated into plastics by conventional processing methods, where the polymer is melted and mixed with the additive composition according to the invention and optionally further additives, preferably using mixers, kneaders and extruders. Preferred processing machines include extruders such as single-screw extruders, twin-screw extruders, planetary gear extruders, ring extruders, and co-kneaders, preferably equipped with a vacuum degassing device. Processing can be carried out in air or, optionally, under inert gas conditions.

[0123] The additive compositions according to the invention can also be prepared in the form of so-called masterbatches or concentrates, which contain, for example, 10 to 90% of the composition according to the invention, and incorporated into polymers.

[0124] The present invention will now be described in more detail with reference to the following embodiments, without limiting the invention to the illustrative examples.

[0125] Embodiments:

[0126] To test the effectiveness of the stabilizer of the present invention, commercially available polypropylene (Moplen HP 500N, Lyondell Basell Industries) was homogenized with a powder-powder mixture of 0.10% dieugenol (Test 1), 0.25% dieugenol (Test 2), and 0.5% dieugenol (Test 3). The mixture was then circulated in a twin-screw microextruder (MC5, DSM) at 200°C and 90 rpm for 30 minutes, and the force reduction was recorded. This force is an index directly linked to the molecular weight of the polypropylene; the smaller the force reduction, the greater the stabilizing effect.

[0127] Compared to polypropylene without additives, higher concentrations of dieugenol achieve improved processing stability, ie, produce greater residual strength.

[0128] Similarly, further improvements in processing stability were obtained by combining 0.25% dieugenol with 0.25% secondary antioxidant (tris-(2,4-di-tertbutylphenyl)phosphite).

[0129] Similarly, a combination of 0.25% dieugenol and 0.25% methionine in the form of a sulfur-containing secondary antioxidant provided further improvement in processing stability.

[0130] Similarly, the processing stability of polyethylene, polystyrene, polyamide-6, and post-consumer recycled polypropylene was improved by adding 0.25% eugenol.

[0131] To test for improved long-term stability, polypropylene granules containing 0.25% dieugenol were stored in a circulating air oven at 135°C compared to base-stabilized polypropylene (containing 0.05% antioxidant). The change in MVR (Melt Volume Rate) was measured to determine the time until polymer degradation occurred. Compared to the comparative example, the long-term stability after 100 hours was improved to more than 300 hours.

Claims

1. Use of dieugenol, eugenol oligomers, eugenol co-oligomers, eugenol polymers and / or eugenol copolymers for stabilizing plastics, the plastics comprising: a) polymers from olefins or diolefins, and copolymers and terpolymers in the form of random or block structures; b) polystyrene, polymethylstyrene, polyalphamethylstyrene, 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 the corresponding graft copolymers, and methyl methacrylate, graft copolymers of styrene-butadiene and ABS (MABS), and hydrogenated polystyrene derivatives; c) halogen-containing polymers, copolymers of vinyl chloride and vinylidene chloride or vinyl chloride and vinyl acetate, chlorinated polyethylene, polyvinylidene fluoride, epichlorohydrin homo- and copolymers; d) polymers of unsaturated esters; e) polymers of unsaturated alcohols and derivatives; f) polyacetals or copolymers with butanal, blends with polyphenylene oxide, polystyrene or polyamides; g) cyclic ether polymers; h) polyphenylene oxide and its blends with polystyrene and / or polyamide; i) polyurethanes, polyureas made from hydroxy-terminated polyethers or polyesters and aromatic or aliphatic isocyanates; j) polyamides and (partially) aromatic polyamides, blends of different polyamides or blends of polyamides and polyolefins; k) polyimides, polyamide-imides, polyetherimides, polyesterimides, poly(ether)ketones, polysulfones, poly-ethersulfones, polyarylsulfones, polyphenylene sulfides, polybenzimidazoles, polyhydantoins; l) polyesters made from aliphatic or aromatic dicarboxylic acids and diols or from hydroxycarboxylic acids; m) polycarbonates, polyester carbonates, and blends; n) cellulose derivatives, o) epoxy resins consisting of difunctional or polyfunctional epoxy compounds; p) phenolic resin, q) unsaturated polyester resins from unsaturated dicarboxylic acids and diols with vinyl compounds, and s) mixtures, combinations, or blends of two or more of the foregoing polymers The use of any one of the following:

2. 2. The use of claim 1, wherein the dieugenol has the following structure: 【Chemical 1】 。

3. The eugenol oligomer or the eugenol polymer has one of the following formulas: 【Chemistry 2】 3. The use according to claim 1 or 2, wherein n is an integer from 3 to 100.

4. The eugenol co-oligomer and / or the eugenol copolymer comprises or is formed from repeating units A and B: The repeat unit A has the formula: 【Chemistry 3】 and B is at least one repeat unit derived from a radioactive, anionic, cationic or coordinatively polymerizable monomer, and mixtures thereof and combinations thereof.

5. the molar ratio of repeat units A to the sum of all repeat units is from 3% to 99.99%, and / or the sum of all repeating units A is 3 to 100, and the sum of all repeating units B is 1 to 100; 5. The use according to claim 4.

6. The use according to any one of claims 1 to 5, wherein the dieugenol, the eugenol oligomer, the eugenol co-oligomer, the eugenol polymer and / or the eugenol copolymer are contained in the plastic in a weight ratio of 0.01 to 10.00% by weight.

7. 2. The use according to claim 1, wherein the plastic comprises and / or is added to the plastic during use at least one additional additive selected from the group consisting of primary and / or secondary antioxidants.

8. 8. The use according to claim 7, wherein the at least one further additive is contained or added in an amount of 0.01 to 9.99% by weight, based on the total of the dieugenol, the eugenol oligomer, the eugenol co-oligomer, the eugenol polymer and / or the eugenol copolymer, the plastic and the at least one additive.

9. A plastic composition comprising dieugenol, eugenol oligomers, eugenol co-oligomers, eugenol polymers and / or eugenol copolymers as a stabilizer, said plastic comprising: a) polymers from olefins or diolefins, and copolymers and terpolymers in the form of random or block structures; b) polystyrene, polymethylstyrene, polyalphamethylstyrene, 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 the corresponding graft copolymers, and methyl methacrylate, graft copolymers of styrene-butadiene and ABS (MABS), and hydrogenated polystyrene derivatives; c) halogen-containing polymers, copolymers of vinyl chloride and vinylidene chloride or vinyl chloride and vinyl acetate, chlorinated polyethylene, polyvinylidene fluoride, epichlorohydrin homo- and copolymers; d) polymers of unsaturated esters; e) polymers of unsaturated alcohols and derivatives; f) polyacetals or copolymers with butanal, blends with polyphenylene oxide, polystyrene or polyamides; g) cyclic ether polymers; h) polyphenylene oxide and its blends with polystyrene and / or polyamide; i) polyurethanes, polyureas made from hydroxy-terminated polyethers or polyesters and aromatic or aliphatic isocyanates; j) polyamides and (partially) aromatic polyamides, blends of different polyamides or blends of polyamides and polyolefins; k) polyimides, polyamide-imides, polyetherimides, polyesterimides, poly(ether)ketones, polysulfones, poly-ethersulfones, polyarylsulfones, polyphenylene sulfides, polybenzimidazoles, polyhydantoins; l) polyesters made from aliphatic or aromatic dicarboxylic acids and diols or from hydroxycarboxylic acids; m) polycarbonates, polyester carbonates, and blends; n) cellulose derivatives, o) epoxy resins consisting of difunctional or polyfunctional epoxy compounds; p) phenolic resin, q) unsaturated polyester resins from unsaturated dicarboxylic acids and diols with vinyl compounds, and s) mixtures, combinations, or blends of two or more of the foregoing polymers A plastic composition selected from the group consisting of:

10. 0.01 to 10.00 wt. % of dieugenol, eugenol oligomers, eugenol co-oligomers, eugenol polymers and / or eugenol copolymers, 99.99 to 90.00 wt. % plastic, and 0 to 9.99 wt. % of at least one additive; Including, Ingredients are added up to 100% by weight The plastic composition of claim 9.

11. the at least one additive is selected from the group consisting of primary and / or secondary antioxidants; The plastic composition of claim 10.

12. Dieugenol, eugenol oligomers, eugenol co-oligomers, eugenol polymers and / or eugenol copolymers, and mixtures and combinations thereof; and at least one secondary antioxidant selected from the group consisting of a phosphite, a phosphonite, or a thiol, and / or at least one co-stabilizer selected from the group consisting of a polyol, an acid scavenger, or a sterically hindered amine, and mixtures and combinations thereof; A stabilizer composition comprising or consisting of:

13. 13. The stabilizer composition of claim 12, wherein the dieugenol, oligoeugenol, or polyeugenol and the at least one secondary antioxidant and / or co-stabilizer are present in a weight ratio of 100:1 to 1:

100.

14. 1. A method for stabilizing a plastic in which dieugenol, eugenol oligomers, eugenol co-oligomers, eugenol polymers and / or eugenol copolymers are incorporated into said plastic, said plastic comprising: a) polymers from olefins or diolefins, and copolymers and terpolymers in the form of random or block structures; b) polystyrene, polymethylstyrene, polyalphamethylstyrene, 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 the corresponding graft copolymers, and methyl methacrylate, graft copolymers of styrene-butadiene and ABS (MABS), and hydrogenated polystyrene derivatives; c) halogen-containing polymers, copolymers of vinyl chloride and vinylidene chloride or vinyl chloride and vinyl acetate, chlorinated polyethylene, polyvinylidene fluoride, epichlorohydrin homo- and copolymers; d) polymers of unsaturated esters; e) polymers of unsaturated alcohols and derivatives; f) polyacetals or copolymers with butanal, blends with polyphenylene oxide, polystyrene or polyamides; g) cyclic ether polymers; h) polyphenylene oxide and its blends with polystyrene and / or polyamide; i) polyurethanes, polyureas made from hydroxy-terminated polyethers or polyesters and aromatic or aliphatic isocyanates; j) polyamides and (partially) aromatic polyamides, blends of different polyamides or blends of polyamides and polyolefins; k) polyimides, polyamide-imides, polyetherimides, polyesterimides, poly(ether)ketones, polysulfones, poly-ethersulfones, polyarylsulfones, polyphenylene sulfides, polybenzimidazoles, polyhydantoins; l) polyesters made from aliphatic or aromatic dicarboxylic acids and diols or from hydroxycarboxylic acids; m) polycarbonates, polyester carbonates, and blends; n) cellulose derivatives, o) epoxy resins consisting of difunctional or polyfunctional epoxy compounds; p) phenolic resin, q) unsaturated polyester resins from unsaturated dicarboxylic acids and diols with vinyl compounds, and s) mixtures, combinations, or blends of two or more of the foregoing polymers The method is selected from the group consisting of:

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