Stabilizer composition for stabilizing plastics by combining tannin and hydrotalcite, method for stabilization, and stabilized plastic composition

Abstract

Plastics are subject to aging processes that ultimately lead to a loss of desired properties such as mechanical characteristics. This process, known as autoxidation, starts from radical chain scission through mechanochemical processes or through UV radiation in the presence of oxygen and leads to changes in the polymer chain, such as changes in molecular weight and / or the formation of new chemical groups. Stabilizers are therefore used to prevent or at least delay this aging. Antioxidants, particularly sterically hindered phenols, are an important group of stabilizers. In addition to the predominantly used synthetic phenols, a number of natural substances are also known that are increasingly used as stabilizers in polymers, either directly or in modified form.

Description

[0001] Plastics are subject to aging processes that ultimately lead to a loss of desired properties, such as mechanical characteristics. This process, called autoxidation, originates from radical chain scission through mechanochemical processes or UV radiation in the presence of oxygen, resulting in changes to the polymer chain, such as in molecular weight and / or the formation of new chemical groups. Stabilizers are used to prevent or at least delay this aging. An important group of stabilizers are antioxidants, particularly sterically hindered phenols. In addition to the predominantly used synthetic phenols, a number of natural substances are also known to be increasingly used as stabilizers in polymers, either directly or in modified form.

[0002] Examples of the direct application of isolated natural substances as stabilizers in plastics include tocopherols / vitamin E (e.g., S. Al-Malaika, Learning from mother nature: exploiting a biological antioxidant for the melt stabilisation of polymers, Macromol. Symp. 2001, 176, 107-117), quercetin (B. Kirschweng et al., Melt stabilisation of PE with natural antioxidants: Comparison of rutin and quercetin, Eur. Pol. J. 2018, 103, 228-237), dihydromyricetin (B. Kirschweng et al., Melt stabilisation of polyethylene with dihydromyrecitin, a natural antioxidant, Pol. Degr. Stab. 2016, 133, 192-200), and curcumin (D. Tatraaljai et al., Processing stabilisation of PE with a natural antioxidant, curcumin, European Polymer Journal). 2013, 49, 1196-1203), silymarin and sylibine (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 2021, 145, 67-75), Catechin von Tee- und Kaffeeextrakten (O. Olejnik, A. Masek, Bio-Based packaging materialscontaining substances derived from coffee and tea plants, Materials 2020, 13, 5719) oder auch Gallussäure (L. Quiles-Carrillo et al., On the use of gallic acid as a potential natural antioxidant and ultraviolet light stabilizer in cast-extruded bio-based high-density polyethylene films, Polymers 2020, 12, 31).

[0003] Modifizierte Naturstoffe als Antioxidantien sind z.B. als Derivate der Rosmarinsäure (K. Doudin et al., New genre of antioxidants from renewable natural resources: Synthesis and characterisation of rosemary plant-derived antioxidants and their performance in polyolefins, Pol. Degr. Stab. 2016, 130, 126-134), von Tannin (W.J. Grigsby et al., Esterification of condensed tannins and their impact on the properties of poly (lactic acid), Polymers 2013, 5, 344-360), von Ferulasäure (L.F. Longe et al. Improved processability and antioxidant behavior of poly(3-hydroxybutyrate) in presence of ferulic acid-based additives, Bioengineering 2022, 9, 100) und von Sinapinsäure (J. Mayer et al. Antioxidant activity of biogenic cinnamic acid derivatives in polypropylene, Polymers 2023, 15, 3621) bekannt.

[0004] However, due to their natural origin, unmodified antioxidants often have deficiencies which, while usually not negatively affecting their antioxidant effect, do impair other important product properties such as color, migration, or emissions.

[0005] This applies in particular to tannins that are industrially isolated from tree bark or grapes by aqueous or alcoholic extraction. The object of the present invention was therefore to develop improved tannin-containing stabilizer compositions that do not exhibit the aforementioned disadvantages.

[0006] The use of tannins as antioxidants in plastics is generally known and described, for example, in the following publications: - Nanni et al., A comparative study of different winemaking by-products derived additives on oxidation stability, mechanical and thermal properties of polypropylene, Polymer Degradation and Stability 2018, 149, 9-18 - Nanni et al., Thermal and UV aging of polypropylene stabilized by wine seeds waste and their extracts, Polymer Degradation and Stability 2019, 165, 49-59 - K.J. Olejar et al., Enhanced antioxidant activity of polyolefin films integrated with grape tannins, J. Sci. Food Agric. 2016, 96, 2825-2831 J. H. Bridson et al., Polymeric flavonoids processed with co-polymers as UV and thermal stabilisers for polyethylene films, Polymer Degradation and Stability, 2015, 122, 18-24

[0007] Nächster Stand der Technik ist die eigene Anmeldung WO 2020 / 083740, die Stabilisatorkombinationen aus Polyphenolen, z.B. Tannin, mit Alditolen beansprucht.

[0008] The use of tannins in polymer processing, however, leads to significant discoloration, which considerably limits their application. Furthermore, commercially available tannins contain low molecular weight components that negatively affect the thermal stability of the polymer and can lead to migration and emissions. Surprisingly, it has now been found that combinations of tannins with hydrotalcites exhibit a significantly lower tendency to discolor. The thermal stability of the tannins can also be improved by pretreatment.

[0009] The object of the present invention is to provide, starting from the prior art, a possibility for stabilizing polymers in which the thermal stability of the polymers can be positively influenced and a significantly lower tendency to discolor results.

[0010] This problem is disclosed with respect to a stabilizer composition for stabilizing polymers according to claim 1, with respect to a use of the stabilizer composition according to claim 8, with respect to a method for stabilizing polymers according to claim 9, and with respect to a composition according to claim 12. The respective dependent claims represent advantageous embodiments. Claim 17 relates to a molded part or a molded body produced from a composition according to the invention.

[0011] According to a first aspect, the present invention thus relates to a stabilizer composition consisting of at least one tannin and at least one hydrotalcite or mixtures thereof.

[0012] Tannins are polyphenols of varying composition, characterized, for example, by the following representative formula and exhibiting a molecular weight distribution:

[0013] In a particular embodiment, a commercially available tannin is pretreated under vacuum at temperatures between 50 and 200 °C, preferably between 80 and 150 °C, for a period of 10 minutes to 10 hours, preferably 1 to 3 hours. During this process, the low molecular weight fractions of the products decrease and are removed by vacuum. This can be analytically verified by gel permeation chromatography and leads to a product with improved thermal stability, possibly also due to condensation reactions during this process.

[0014] According to a preferred embodiment, the at least one tannin has a molecular weight of 500 to 10,000 g / mol, preferably 1,000 to 5,000. Typically, the molecular weights of commercial products are in the range of 500–5,000.

[0015] In particular, it is advantageous if the at least one tannin is thermally pretreated, the thermal pretreatment preferably taking place at temperatures between 50 and 200 °C, preferably between 80 and 150 °C and / or over a period of 10 minutes to 10 hours, preferably 1 to 3 hours.

[0016] The thermal pretreatment can be carried out under reduced pressure compared to normal pressure, preferably at pressures between 0.01 and 100 mbar, particularly preferably between 0.1 and 10 mbar.

[0017] Preferably, the at least one hydrotalcite is selected from the group consisting of compounds of the general formula (M 2+ ) 1-x · (M3+ ) x · (OH)2 · (A n - ) x / n · m H2O where M 2+ one or more of the metals from the group Mg, Ca, Zn or Sr, M 3+ Al or B A an anion with valence n, preferably OH-, ClO 4- , HCO 3- , CH3COO-, C6H5COO - , CO3 2- , SO4 1- , HSO4 - , n 1 or 2 is, 0 < x < 0.5 is, and m is a number from 0 to 20.

[0018] Particularly preferred hydrotalcites are selected from the group consisting of Al2O3 · 6 MgO · CO2 · 12 H2O, Mg 4,5 Al2(OH) 13 · CO3 · 3.5 H2O, 4 MgO · Al2O3 · CO2 · 9 H2O, 4 MgO · Al2O3 · CO2 · 6 H2O, ZnO · 3 MgO · Al2O3 · CO2 · 8-9 H2O, ZnO · 3 MgO · Al2O3 · CO2 · 5-6 H2O, Ca4Al2(OH) 12 CO3 · 5 H2O and Mg6Al2(OH) 16 · CO3 · 4 H2O.

[0019] In particular, it is advantageous if at least one hydrotalcite is used in anhydrous form.

[0020] For example, the weight ratio of the totality of the at least one tannin to the totality of the at least one hydrotalcite can be 10:1 to 1:10, preferably 5:1 to 1:5, particularly preferably 3:1 to 1:3.

[0021] According to a further aspect, the present invention also relates to the use of the stabilizer composition described above for stabilizing polymers, in particular against oxidative, thermal or actinic degradation.

[0022] Furthermore, the present invention relates to a method for stabilizing polymers in which a stabilizer composition described above is added to or blended with a polymer.

[0023] In the above-described process according to the invention, or in its use, it is advantageous if the stabilizer composition is used or added in a weight ratio of 0.01 to 10 wt.%, preferably 0.05 to 5 wt.%, particularly preferably 0.1 to 3 wt.% based on the polymer.

[0024] In particular, the polymer is selected from the group consisting of a) Polymers made from olefins or diolefins such as polyethylene (LDPE, LLDPE, VLDPE, ULDPE, MDPE, HDPE, UHMWPE), metallocene-PE (m-PE), polypropylene, polyisobutylene, poly-4-methylpentene-1, polybutadiene, polyisoprene, such as natural rubber (NR), polycyclooctene, polyalkylene-carbon monoxide copolymers, as well as copolymers in the form of statistical or block structures such as polypropylene-polyethylene (EP), EPM or EPDM with, for example, 5-ethylidene-2-norbornene as a comonomer, ethylene vinyl acetate (EVA), ethylene acrylates such as 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 polybutylacrylate graft-maleic anhydride, and blends such as LDPE / LLDPE or long-chain branched polypropylene copolymers produced with alpha-olefins as comonomers, such as...with 1-butene, 1-hexene, 1-octene or 1-octadecene. b) Polystyrene, polymethylstyrene, poly-alpha-methylstyrene, polyvinylnaphthalene, polyvinylbiphenyl, polyvinyltoluene, styrene-butadiene (SB), styrene-butadiene-styrene (SBS), styrene-ethylene-butylene-styrene (SEBS), styrene-ethylene-propylene-styrene, styrene-isoprene, styrene-isoprene-styrene (SIS), styrolutadiene acrylonitrile (ABS), styrene-acrylonitrile (SAN), styrene-acrylonitrile acrylate (ASA), styrene-ethylene, styrene-maleic anhydride polymers including corresponding graft copolymers such as styrene on butadiene, maleic anhydride on SBS or SEBS, as well as graft copolymers of methyl methacrylate, styrene-butadiene and ABS (MABS), and hydrogenated Polystyrene derivatives such as polyvinylcyclohexane, c) Polymers of unsaturated esters such as polyacrylates and polymethacrylates like polymethyl methacrylate (PMMA), polybutyl acrylate, polylauryl acrylate, polystearyl acrylate, polyglycidyl acrylate, polyglycidyl methacrylate, polyacrylonitrile, polyacrylamides, copolymers such as polyacrylonitrile-polyalkyl acrylate, d) Polymers made from unsaturated alcohols and derivatives, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyallyl phthalate, polyallyl melamine, e) Polyacetals, such as polyoxymethylene (POM) or copolymers with, for example, butanal, f) Polyphenylene oxides and blends with polystyrene or polyamides, g) Polymers of cyclic ethers such as polyethylene glycol, polypropylene glycol, polyethylene oxide, polypropylene oxide, polytetrahydrofuran, h) Polyurethanes, made from hydroxy-terminated polyethers or polyesters and aromatic or aliphatic isocyanates such as 2,4- or 2,6-toluene diisocyanate or methylene diphenyl diisocyanate, in particular also linear polyurethanes (TPU), polyureas, i) Polyamides such as polyamide-6, 6.6, 6.10, 4.6, 4.10, 6.12, 10.10, 10.12, 12.12, polyamide 11, polyamide 12, and (partially) aromatic polyamides such as polyphthalamides, e.g., produced from terephthalic acid and / or isophthalic acid and aliphatic diamines such as hexamethylenediamine or m-xylylenediamine, or from aliphatic dicarboxylic acids such as adipic acid or sebacic acid and aromatic diamines such as 1,4- or 1,3-diaminobenzene, blends of different polyamides such as PA-6 and PA 6.6, or blends of polyamides and polyolefins such as PA / PP. j) polyimides, polyamidimides, polyetherimides, polyesterimides, poly(ether) ketones, polysulfones, polyethersulfones, polyarylsulfones, polyphenylene sulfides, polybenzimidazoles, polyhydantoins, k) Polyesters made from aliphatic or aromatic dicarboxylic acids and diols or from hydroxycarboxylic acids such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polypropylene terephthalate (PTI), polyethylene naphthylate (PEN), poly-1,4-dimethylolcyclohexane terephthalate, polyhydroxybenzoate, polyhydroxynaphthalate, polylactic acid (PLA), polyhydroxybutyrate (PHB), polyhydroxyvalerate (PHV), polyethylene succinate, polytetramethylene succinate, polycaprolactone, l) Polycarbonates, polyester carbonates, and blends such as PC / ABS, PC / PBT, PC / PET / PBT, PC / PA, m) Cellulose derivatives such as cellulose nitrate, cellulose acetate, cellulose propionate, cellulose butyrate, n) Epoxy resins consisting of di- or polyfunctional epoxy compounds in combination with, for example, hardeners based on amines, anhydrides, dicyandiamide, mercaptans, isocyanates or catalytically acting hardeners, o) Phenolic resins such as phenol-formaldehyde resins, urea-formaldehyde resins, melamine-formaldehyde resins, p) unsaturated polyester resins made from unsaturated dicarboxylic acids and diols with vinyl compounds, e.g., styrene, alkyd resins, q) Silicones, e.g. based on dimethylsiloxanes, methylphenylsiloxanes or diphenylsiloxanes, e.g. vinyl groups terminated, r) as well as mixtures, combinations or blends of two or more of the aforementioned polymers.

[0025] If the polymers listed under a) to q) are copolymers, they can exist in the form of random, block, or tapered structures. Furthermore, the polymers mentioned can exist in the form of linear, branched, star-shaped, or hyperbranched structures.

[0026] If the polymers listed under a) to q) are stereoregular polymers, they can be in the form of isotactic, stereotactic, but also atactic forms or as stereoblock copolymers.

[0027] The polyolefins mentioned under a) may also be cross-linked, e.g. cross-linked polyethylene, which is then referred to as X-PE.

[0028] Besides new goods, the plastics can be recycled plastics, e.g. from industrial collections such as production waste, or plastics from household or recycling collections.

[0029] Furthermore, the present invention relates to a composition containing or consisting of at least one polymer and a stabilizer composition according to the invention as described above.

[0030] It is preferred that the stabilizer composition is contained in a weight ratio of 0.01 to 10 wt.%, preferably of 0.05 to 5 wt.%, particularly preferably of 0.1 to 3 wt.% based on the at least one polymer.

[0031] For example, the composition may contain at least one additive selected from the group consisting of secondary antioxidants, UV absorbers, light stabilizers, metal deactivators, filler deactivators, antiozonants, nucleating agents, antinucleating agents, impact enhancers, plasticizers, lubricants, rheology modifiers, thixotropic agents, chain extenders, processing aids, demolding aids, flame retardants, pigments, dyes, optical brighteners, antimicrobial agents, antistatic agents, slip agents, antiblocking agents, coupling agents, crosslinking agents, anticrosslinking agents, hydrophilizing agents, hydrophobizing agents, hydrolysis stabilizers, adhesion promoters, dispersants, compatibilizers, oxygen scavengers, acid scavengers, blowing agents, degradation additives, defoaming agents, odor neutralizers, marking agents, antifogging agents, fillers, and reinforcing agents.

[0032] Primary antioxidants act as hydrogen donors and radical scavengers, thereby interrupting the radical auto-oxidation process in polymers. Suitable primary antioxidants include phenolic antioxidants, (partially) aromatic amines, hydroxylamines, and lactones.

[0033] Suitable synthetic phenolic antioxidants include, for example: Alkylierte Monophenole, wie z.B. 2,6-Di-tert-butyl-4-methylphenol, 2-tert-Butyl-4,6-dimethylphenol, 2,6-Di-tert-butyl-4-ethylphenol, 2,6-Di-tert-butyl-4-n-butylphenol, 2,6-Di-tert-butyl-4-isobutylphenol, 2,6-Dicyclopentyl-4-methylphenol, 2-(a-Methylcyclohexyl)-4,6-dimethylphenol, 2,6-Dioctadecyl-4-methylphenol, 2,4,6-Tricyclohexylphenol, 2,6-Di-tert-butyl-4-methoxymethylphenol, lineare oder verzweigte Nonylphenole, wie z.B. 2,6-Dinonyl-4-methylphenol, 2,4-Dimethyl-6-(l'-methylundec-l'-yl)phenol, 2,4-Dimethyl-6-(l'-methylheptadec-l'-yl)phenol, 2,4-Dimethyl-6-(I'-methyltridec-I'-yl)phenol und Mischungen hiervon; Alkylthiomethylphenole, wie z.B. 2,4-Dioctylthiomethyl-6-tert-butylphenol, 2,4-Dioctylthiomethyl-6-methylphenol, 2,4-Dioctylthiomethyl-6-ethylphenol, 2,6-Didodecylthiomethyl-4-nonylphenol; Hydrochinone und alkylierte Hydrochinone, wie z.B.2,6-Di-tert-butyl-4-me-thyoxyphenol, 2,5-Di-tert-butylhydroquinone, 2,5-Di-tert-amylhydroquinone, 2,6-Diphenyl-4-octadecyloxyphenol, 2,6-Di-tert-butylhydroquinone, 2,5-Di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis(3,5-di-tert-butyl-4-hydroxylphenyl) adipate; Tocopherols, such as α-, β-, γ-, β-tocopherol and mixtures thereof (vitamin E); hydroxylated thiodiphenyl ethers, such as 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), 4,4'-thiobis(3,6-di-sec-amylphenol), 4,4'-bis(2,6-dimethyl-4-hydroxyphenyl)disulfide; alkylidenebisphenols, such as 2,2'Methylenbis(6-tert-butyl-4-methylphenol), 2,2'-Methylenbis(6-tert-butyl-4-ethylphenol), 2,2'-Methylenbis[4-methyl-6-(a-methylcyclohexyl)phenol], 2,2'-Methylenbis(4-methyl-6-cyclhexylphenol), 2,2'-Methylenbis(6-nonyl-4-methylphenol), 2,2'-Methylenbis(4,6-di-tert-butylphenol), 2,2'-Ethylidenbis(4,6-di-tert-butylphenol), 2,2'-Ethylidenbis(6-tert-butyl-4-isobutylphe-nol), 2,2'-Methylenbis[6-(a-methylbenzyl)-4-nonyl-phenol], 2,2'-Methylenbis[6-(a,a-dimethylbenzyl)-4-nonylphenol], 4,4'-Methy-lenbis(2,6-di-tert-butylphenol, 4,4'-Methylenbis(6-tert-butyl-2-methyl-phe-nol),I,I-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butan, 2,6-Bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, I,I,3-Tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butan, I,I-bis(5-tert-butyl-4-hydroxy-2-methylphe-nyl)-3-n-dodecylmercaptobutan, Ethylenglycol-bis[3,3-bis(3'-tert-butyl-4'-hyd-roxyphenyl)butyrat], Bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopenta-dien,Bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methyl-phenyl]terephthalat, I,I-Bis-(3,5-dimethyl-2-hydroxyphenyl)butan, 2,2-Bis(3,5-di-tert-butyl-4-hydroxyphenyl)propan, 2,2-Bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutan, 1,1,5,5-Tetra(5-tert-butyl-4-hyd-roxy-2-methylphenyl)pentan; O-, N-und S-Benzyl-Verbindungen, wie z.B. 3,5,3',5'-Tetra-tert-butyl-4,4'-dihyd-roxydibenzylether, Octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetat, Tridecyl-4-hydroxy-3,5-di-tert-butylbenzyl-mercaptoacetat, Tris(3,5-di-tert-butyl-4-hydroxybenzyl)amin, Bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-dithioterephthalat, Bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfid, Isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetat; Hydroxybenzylierte Malonate, wie z.B., Dioctadecyl-2,2-bis(3,5-di-tert-butyl-2- hydroxybenzyl)-malonat, Dioctadecyl-2-(3-tert-butyl-4-hydroxy-5-methyl-benzyl)malonat, Didodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxy-benzyl)malonat, Bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malonat; Aromatische Hydroxybenzylverbindungen, wie z.B. 1,3,5-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzol, 1,4-Bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzol, 2,4,6-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol; Triazinverbindungen, wie z.B.2,4-Bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazin, 2-Octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hyd-roxyanilino)-1,3,5-triazin, 2-Octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxy-phenoxy)-1,3,5-triazin, 2,4,6-Tris(3,5-di-tert-butyl-4-hydroxyphe-noxy)-1,2,3-triazin, 1,3,5-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurat, 1,3,5-Tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurat, 2,4,6-Tris(3,5-di-tert-butyl-4-hydroxphenylethyl)-1,3,5-tria-zin, 1,3,5-Tris(3,5-di-tert-butyl-4-hydroy-phenylpropionyl)hexahydro-1,3,5-triazin, 1,3,5-Tris(3,5-dicyclohexyl-4-hydro-xybenzyl)isocyanurat; Benzylphosphonate, wie z.B. Dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphos-phonat, Dietyhl-3,5-di-tert-butyl-4-hydroxybenzylphosphonat, Dioctadecyl- 3.5-di-tert-butyl-4-hydroxybenzylphosphonat, Di-octadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonat, das Calciumsalz des Monoethylesters der3.5-Di-tert-butyl-4-hydroxybenzylphosphonsäure;. acylaminophenols such as 4-hydroxylauranilide, 4-hydroxystearanilide, octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate; Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, e.g. methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, Diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-I-phospha-2,6,7-trioxabicyclo[2.2.2]octane; Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or polyhydric alcohols, e.g.Methanol, Ethanol, n-Octanol, i-Octanol, Octade-canol, 1,6-Hexandiol, 1,9-Nonandiol, Ethylenglycol, 1,2-Propandiol, Neopen-tylglycol, Thiodiethylenglycol, Diethylenglycol, Triethylenglycol, Pentaerythri-tol, Tris(hydroxyethyl)isocyanurat, N,N'-bis(hydroxyethyl)oxamid, 3-Thiaunde-canol, 3-Thiapentadecanol, Trimethylhexandiol, Trimethylolpropan,4-Hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octan, 3,9-Bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,l-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecan; Ester der β-(3,5-Dicyclohexyl-4-hydroxyphenyl)propionsäure mit ein-oder mehrwertigen Alkoholen, z.B.Methanol, Ethanol, Octanol, Octadecanol, 1,6-Hexandiol, 1,9-Nonandiol, Ethylenglycol, 1,2-Propandiol, Neopentylglycol, Thiodiethylenglycol, Diethylenglycol, Triethylenglycol, Pentaerythritol, Tris-(hydroxyethyl)isocyanurat, N,N'-bis(hydroxyethyl)oxamid, 3-Thiaundecanol, 3-Thiapentadecanol, Trimethylhexandiol, Trimethylolpropan, 4-Hydroxymethyl-l-phospha-2,6,7-trioxabicyclo[2.2.2]octan; Ester der (3,5-Di-tert-butyl-4-hydroxyphenyl)essigsäure mit ein-oder mehrwer-tigen Alkoholen, z.B. Methanol, Ethanol, Octanol, Octadecanol, 1,6-Hexandiol, 1,9-Nonandiol, Ethylenglycol, 1,2-Propandiol, Neopentylglycol, Thiodiethylen-glycol, Diethylenglycol, Triethylenglycol, Pentaerythritol, Tris(hydroxyethyl)iso-cyanurat, N,N'-bis(hydroxyethyl)oxamid, 3-Thiaundecanol, 3-Thiapentadeca-nol, Trimethylhexandiol, Trimethylolpropan,4-Hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octan;. 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)hexamethylenediamide, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, 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, distributed by SI Group); Vitamin C

[0034] Particularly favored phenolic antioxidants are:

[0035] Other particularly favored phenolic antioxidants are based on renewable raw materials such as tocopherols (vitamin E), tocotrienols, tocomonoenols, carotenoids, hydroxytyrosol, flavonols such as chrysin, quercetin, hesperidin, neohesperidin, naringin, morin, kaempferol, fisetin, anthocyanins such as delphinidin and malvidin, curcumin, carnosic acid, carnosol, rosmarinic acid, resveratrol and tannins.

[0036] Suitable amine antioxidants include, for example: N,N'-Di-isopropyl-p-phenylendiamin, N,N'-Di-sec-butyl-p-phenylendiamin, N,N'-Bis(1,4-dimethyl-pentyl)-p-phenylendiamin, N,N'-Bis(1-ethyl-3-methylpentyl)-p-phenylendiamin, N,N'-Bis(1-methyl-heptyl)-p-phenylendiamin, N,N'-Dicyclohexyl-p-phenylendiamin, N,N'-Diphenyl-p-phenylendiamin, N,N'-Bis(2-naphthyl)-p-phenylendiamin, N-Isopropyl-N'-phenyl-p-phenylendiamin, N-(1,3-Dimethyl-butyl)-N'-phenyl-p-phenylen-diamin, N-(1-Methylheptyl)-N'phenyl-p-phenylendiamin, N-Cyclohexyl-N'-phenyl-p-phenylendiamin, 4-(p-Toluolsulfamoyl)diphenylamin, N,N'-Dimethyl-N,N'-di-sec-butyl-p-phenylendiamin, Diphenylamin, N-Allyldiphenylamin, 4-Isopropoxydiphenylamin, N-Phenyl-1-naphthylamin, N-(4-tert-Octylphenyl)-1-naphthylamin, N-Phenyl-2-naphthylamin, octyliertes Diphenylamin, z.B. p,p'-Di-tert-octyldiphenylamin, 4-n-Butylaminophenol, 4-Butyrylaminophenol, 4-Nonanoylaminophenol, 4-Dodecanoylaminophenol, 4-Octadecanoylamino-phenol, Bis(4-methoxyphenyl)amin, 2,6-Di-tert-butyl-4-dimethylaminomethyl-phenol, 2,4'-Diaminodiphenylmethane, 4,4'-Diaminodiphenylmethane, N,N,N',N'-Tetra-methyl-4,4'-diaminodiphenylmethane, 1,2-Bis[(2-methyl-phenyl)amino]ethane, 1,2-Bis(phenylamino)propane, (o-Tolyl)biguanide, Bis[4-(1',3'-dimethylbutyl)phenyl]amine, tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- and dialkylated tert-butyl / tert-octyldiphenylamines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl / isohexyldiphenylamines, a mixture of mono- and dialkylated tert-butyldiphenylamines 2,3-Dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a mixture of mono- and dialkylated tert-butyl / tert-octylphenothiazines, a mixture of mono- and dialkylated tert-octylphenothiazines, N-allylphenothiazine, N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene, and mixtures or combinations thereof.

[0037] Preferred amine antioxidants are: N,N'-Di-isopropyl-p-phenylenediamine, N,N'-Di-secbutyl-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-Methy'lheptyl)-N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'phenyl-p-phenylenediamine.

[0038] Particularly favored amine antioxidants are the following structures:

[0039] Preferred hydroxylamines or N-oxides (nitrons) are, for example, N,N-dialkylhydroxylamines, N,N-dibenzylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-distearylhydroxylamine, N-benzyl-α-phenylnitrone, N-octadecyl-α-hexadecylnitrone, and Genox EP (SI Group) according to the formula:

[0040] Suitable lactones are benzofuranones and indolinones 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-ethoxy-phenyl)benzofuran-2-one, 3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one, 3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one, 3-(3,4-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one, 3-(2,3-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one, and lactones that additionally contain phosphite groups, such as...

[0041] One particularly favored lactone has the following structure:

[0042] Another suitable group of antioxidants are isoindolo[2,1-A]quinazolines such as e.g.

[0043] Secondary antioxidants primarily act as hydroperoxide decomposers in the stabilization of plastics.

[0044] Geeignete sekundäre Antioxidantien sind insbesondere Phosphite oder Phosphonite wie z.B. Triphenylphosphit, Diphenylalkylphosphite, Phenyldialkylphosphite, Tri(nonylphenyl)phosphit, Trilaurylphosphite, Trioctadecylphosphit, Distearylpentaerythritoldiphosphit, Tris-(2,4-di-tert-butylphenyl)phosphit, Diisodecylpentaerythritoldiphosphit, Bis(2,4-di-tert-butylphenyl)pentaerythritoldiphosphit, Bis(2,4-di-cumylphenyl)pentaerythritol-diphosphit, Bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol-diphosphit, Diisodecyloxypentaerythritoldiphosphit, Bis(2,4-di-tert-butyl-6 methylphenyl)pentaerythritoldiphosphit, Bis(2,4,6-tris(tert-butylphenyl)pentaerythritol-diphosphit, Tristearylsorbitoltri phosphit, Tetrakis(2,4-di-tert- butylphenyl)-4,4'-biphenylendiphosphonit, 6-Isooctyloxy-2,4,8, 10-tetra-tert-butyl-12 H-dibenz[d,g]-1,3,2-dioxaphosphocin, Bis(2,4-di-tert-butyl-6-methylphenyl)methylphosphit, Bis-(2,4-di-tert-butyl-6-methylphenyl)-ethylphosphit, 6-Fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin, 2,2'2''-nitrilo[triethyltris(3,3'',5,5'-tetra-tert-butyl-1, 1'-biphenyl-2,2'-diyl)phosphite], 2-Ethyl-hexyl(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,,2-dioxaphosphiran.,

[0045] Particularly favored phosphites are: with n = 1 to 100

[0046] With n = 3 to 100

[0047] A preferred phosphonite is [missing information]. Suitable secondary antioxidants also include sulfur compounds such as distearylthiodipropionate, dilaurylthiodipropionate, ditridecyldithiopropionate, ditetradecylthiodipropionate, and 3-(dodecylthio)-1,1'-[2,2-bis[[3-(dodecylthio)-1-oxopropoxy]methyl]-1,3-propanediyl]propanoic acid esters. The following structures are preferred:

[0048] Other suitable secondary antioxidants include sulfites: Preferably, inorganic sulfites, disulfites or thiosulfates of a mono-, di-, tri- or tetravalent metal are used, wherein the metal is preferably an alkali metal, an alkaline earth metal, aluminium and / or zinc, and wherein the inorganic sulfite is used particularly in its anhydrous form. Suitable salts include, in particular, sodium sulfite, potassium sulfite, lithium sulfite, calcium sulfite, magnesium sulfite, aluminum sulfite, and zinc sulfite. Thiosulfates, such as sodium thiosulfate, are also suitable.

[0049] Suitable fillers and reinforcing materials include synthetic or natural materials such as calcium carbonate, silicates, glass fibers, glass beads (solid or hollow), talc, mica, kaolin, barium sulfate, metal oxides and hydroxides, carbon black, graphite, carbon nanotubes, graphene, wood flour, or fibers from natural products such as cellulose or synthetic fibers. Other suitable fillers include hydrotalcites or zeolites or layered silicates such as montmorillonite, bentonite, beidelite, mica, hectorite, saponite, vermiculite, ledikite, magadite, illite, kaolinite, wollastonite, and attapulgite.

[0050] Suitable acid scavengers (“antiacids”) are salts of monovalent, divalent, trivalent, or tetravalent metals, preferably alkali metals, alkaline earth metals, aluminum, or zinc, particularly those formed with fatty acids, such as calcium stearate, magnesium stearate, zinc stearate, aluminum stearate, calcium laurate, calcium behenate, calcium lactate, and calcium stearoyl-2-lactate. Other classes of suitable acid scavengers include hydrocalumites, zeolites, alkaline earth oxides, particularly calcium oxide and magnesium oxide, as well as zinc oxide, alkaline earth carbonates, particularly calcium carbonate, magnesium carbonate, and dolomite, and hydroxides, particularly brucite (magnesium hydroxide).

[0051] Suitable costabilizers also include polyols, especially alditols or cyclitols. Examples of polyols are pentaerythritol, dipentaerythritol, tripentaerythritol, short-chain polyether polyols or polyester polyols, as well as hyperbranched polymers / oligomers or dendrimers with alcohol groups.

[0052] Preferably, the at least one alditol is 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. Particularly preferably, the at least one preferred alditol is selected from the group consisting of erythritol, mannitol, isomalt, maltitol, and mixtures thereof.

[0053] Examples of other suitable sugar alcohols are heptitols and octitols: meso-glycero-allo-heptitol, D-glycero-D-altro-heptitol, D-glycero-D-manno-heptitol, meso-glycero-gulo-heptitol, D-glycero-Dgalacto-heptitol (Perseitol), D-glycero-D-gluco-heptitol, L-glycero-D-gluco heptitol, D-erythro-L-galacto-octitol, D-threo-L-galacto-octitol.

[0054] In particular, at least one cyclitol may 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, condudtol, ononitol, pinitol, pinpollitol, quebrachitol, ciceritol, quinic acid, shikimic acid and valienol, preferably myo-inositol (myo-inositol).

[0055] Other suitable costabilizers are ester and ether derivatives of the aforementioned alditols or cyclitols, such as the following compounds:

[0056] Suitable UV absorbers include compounds based on 2-(2'-hydroxyphenyl)benzotriazoles, 2-hydroxybenzophenones, esters of benzoic acids, acrylates, oxamides and 2-(2-hydroxyphenyl)-1,3 ,5-triazines.

[0057] Geeignete 2-(2'-Hydroxyphenyl)benzotriazole sind beispielsweise 2-(2'-Hydroxy-5'methylphenyl)benzotriazol, 2-(3', 5'-Di-tert-butyl-2'-hydroxyphenyl)-benzotriazol, 2-(5'-tert- Butyl-2'-hydroxy-phenyl)benzotriazol, 2-(2'-Hydroxy-5'-(1, 1,3,3-tetramethylbutyl)phenyl)benzotriazol, 2-(3', 5'-Di-tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazol, 2-(3'''-tert-Butyl-2'-hydroxy-5'-methylphenyl-5-chlorobenzotriazol, 2-(3'-sec-Butyl-5'-tert-butyl-2'-hydroxy-phenyl)benzotriazol, 2-(2'-Hydroxy-4'-octyloxyphenyl)benzotriazol, 2-(3',5'-Di-tert-amyl-2'-hydroxyphenyl)benzotriazol, 2-(3',5'-Bis(a,a-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazol, 2-(3'-tert-Butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)-5-chlorobenzotriazol, 2-(3'-tert-B utyl-5'-[2-(2-ethylhexyloxy)-carbonylethyl]-2'-hydroxyphenyl)-5-chlorobenzotriazol, 2-(3'-tert-Butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chlorobenzotriazol, 2-(3'-tert-Butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)benzotriazol,2-(3'-tert-Butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)benzotriazol, 2-(3'-tert-Butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)benzotri azol, 2-(3'-Dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazol, 2-(3'-tert-Butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotriazol, 2,2'-Methylenbis[ 4-(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-ylphenol]; das Produkt der Umesterung von 2-[3'-tert-Butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazol mit Polyethylenglycol 300; [R-CH2CH2-COO-CH2CH2]2, wobei R = 3'-tert-Butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl, 2-[2'-Hydroxy-3'-(a,a-dimethylbenzyl)-5'-(1,1,3,3-tetramethylbutyl)-phenyl]benzotriazol, 2-[2'-hydroxy-3'-(1, 1,3,3-tetramethylbutyl)-5'-(a,a-dimethylbenzyl)phenyl]benzotriazol.,

[0058] Geeignete 2-Hydroxybenzophenone sind beispielsweise 4-Hydroxy-, 4-Methoxy-, 4-Octyloxy-, 4-Decyloxy-4-Dodecyloxy, 4-Benzyloxy, 4,2',4'-Trihydroxy- und 2'-Hydroxy-4,4'- dimethyoxy-Derivate der 2-Hydroxybenzophenone.

[0059] Geeignete Acrylate sind beispielsweise Ethyl-a-cyano-β,β-diphenylacrylat, Isooctyl-a-cyano- β,β-diphenylacrylat, Methyl-a-carbomethoxycinnamat, Methyl-a-cyano-β-methyl-p-methoxycinnamat, Butyl-a-cyano-β-methyl-p-methoxycinnamat, Methyl-a-carbomethoxy-p- methoxycinnamat und N-(β-carbomethoxy-β-cyanovinyl)-2-methylindolin.

[0060] Suitable esters of benzoic acids include, 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, and 2-methyl-4,6-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate.

[0061] Suitable oxamides include, 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'-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.

[0062] Geeignete 2-(2-Hydroxyphenyl)-1,3,5-Triazine sind beispielsweise 2,4,6-Tris(2-hydroxy-4-octyloxyphenyl)-1 ,3,5-triazin, 2-(2-Hydroxy-4-octyloxyphenyl)-4, 6-bis(2 ,4-dimethylphenyl)-1,3,5-triazin, 2-(2,4-Dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin, 2,4-Bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3, 5-triazin, 2-(2-Hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl-1,3, 5-triazin, 2-(2-Hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3, 5-triazin, 2-(2-Hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3, 5-triazin, 2-[2-Hydroxy-4-(2-hydroxy-3-butyloxypropoxy)-phenyl]-4,6-bis(2,4-dimethyl) 1,3,5-triazin, 2-[2-Hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]-4, 6-bis(2,4-dimethyl)-1,3, 5-triazin, 2-[4-(Dodecyloxy / Tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4, 6-bis(2,4-dimethylphenyl)-1,3, 5-triazin, 2-[2-Hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl-1 ,3,5-triazin, 2-(2-Hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1 ,3,5-triazin, 2-(2-Hydroxy-4-methoxyphenyl)-4, 6-diphenyl-1,3,5-triazin, 2,4,6-Tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1, 3,5-triazin, 2-(2-Hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1, 3,5-triazin, 2-{2-Hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4, 6-bis(2,4-dimethylphenyl-1,3, 5-triazin.,

[0063] Geeignete Metallde(s)aktivatoren sind beispielsweise N,N'-Diphenyloxamid, N-Salicylal-N'-ssalicyloylhydrazin, N,N'-Bis(salicyloyl)hydrazin, N,N'-Bis(3, 5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazin, 3-Salicyloylamino-1,2,4-triazol, Bis- (benzyliden)oxalyldihydrazid, Oxanilid, Isophthaloyldihydrazid, Sebacoylbisphenylhydrazid, N,N'-Diacetyladipoyldihydrazid, N,N'-Bis(salicyloyl)oxylyldihydrazid, N,N'-Bis(salicyloyl)thiopropionyldihydrazid, Tris [2-tert-butyl-4-thio (2'-methyl-4'-hydroxy-5'-tert- butyl)-phenyl-5-methyl] phenylphosphit.

[0064] Besonders bevorzugt als Metalldesaktivatoren sind:

[0065] 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)sebazate, 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-hydroxybenzylmalonate, the condensation product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensation products of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine, and 4-tert-Octylamino-2,6-dichloro-1,3,5-triazine, 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-tetramethyl-piper-azinone), 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 is the reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro-[4,5]decane and epichlorohydrin.

[0066] The structures listed 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.

[0067] Particularly favored hindered amines are the following:

[0068] Preferred oligomeric and polymeric hindered amines exhibit the following structures:

[0069] With n = 2 to 100, preferably 2 to 10

[0070] With n = 2 to 100, preferably 3 to 20

[0071] With n = 3 to 200, preferably 5 to 100

[0072] With n = 1 to 100, preferably 2 to 10, or

[0073] Another suitable light stabilizer is Hostanox NOW (manufacturer: Clariant SE) with the following general structure: where R -OC(O)-C 15 H 31 or -OC(O)-C 17 H 35 means.

[0074] Compatibilizers are used, for example, in thermodynamically immiscible blends or recycled material mixtures and contain structural elements of the respective blend components being mixed. Suitable compatibilizers for polyolefin mixtures include olefin block copolymers consisting of ethylene, propylene, and alpha-olefins such as 1-octene. Other compatibilizers, especially for compatibilizing polar polymers such as PET or polyamides and nonpolar polymers such as PP or PE, often contain reactive groups derived from, for example, maleic anhydride, acrylic acid, glycidyl acrylate, or glycidyl methacrylate, and include, for example, polypropylene-g-maleic anhydride, polyethylene-g-maleic anhydride, polypropylene-g-acrylic acid, polyethylene-g-acrylic acid, poly(ethylene-co-maleic anhydride), SBS-g-maleic anhydride, SEBS-g-maleic anhydride, and polyethylene-polyacrylate-polyglycidyl methacrylate. Suitable dispersing agents include, for example:

[0075] 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., polypropylene-co-acrylic acid, polypropylene-co-maleic anhydride, polyethylene-co-glycidyl methacrylate; polystyrene-alt-maleic anhydride polysiloxanes: e.g., dimethylsilanediol-ethylene oxide copolymer, polyphenylsiloxane copolymer; amphiphilic copolymers: e.g., polyethylene block-polyethylene oxide; dendrimers, e.g., dendrimers containing hydroxyl groups. Suitable flame retardants are in particular a) Inorganic flame retardants such as Al(OH)3, Mg(OH)2, AlO(OH), MgCO3; layered silicates such as montmorillonite or sepiolite, unmodified or organically modified; double salts such as Mg-Al silicates, POSS (Po-Iyhedral Oligomeric Silsesquioxane) compounds, huntite, hydromagnesite or halloysite; as well as Sb2O3, Sb2O5, MoO3, zinc stannate, zinc hydroxystannate, b) Nitrogen-containing flame retardants such as melamine, melem, melam, melon, melamine derivatives, melamine condensation products or melamine salts, benzoguanamine, polyisocyanurates, allantoin, phosphacenes, in particular melamine cyanurate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, melamine polyphosphate, melamine metal phosphates such as melamine aluminum phosphate, melamine zinc phosphate, melamine magnesium phosphate, as well as the corresponding pyrophosphates and polyphosphates, poly-[2,4-(piperazine-1,4-yl)-6-(morpholin-4-yl)-1,3,5-triazine], ammonium polyphosphate, melamine borate, melamine hydrobromide, c) Radical initiators, such as alkoxyamines, hydroxylamine esters, azo compounds, sulfenamides, sulfenimides, dicumyl or polycumyl, hydroxyimides and their derivatives such as hydroxyimide esters or hydroxyimide ethers d) Phosphorus-containing flame retardants such as red phosphorus, phosphates such as resorcinol diphosphate, bisphenol A diphosphate and their oligomers, triphenyl phosphate, ethylenediamine diphosphate, phosphinates such as salts of hypophosphorous acid and its derivatives such as alkyl phosphinate salts e.g. diethylphosphinate aluminum or diethylphosphinate zinc or aluminum phosphinate, aluminum phosphite, aluminum phosphonate, phosphonate esters, oligomeric and polymeric derivatives of methanephosphonic acid, 9,10-dihydro-9-oxa-10-phosphorylphenanthrene-10-oxide (DOPO) and their substituted compounds, e) Halogen-containing flame retardants based on chlorine and bromine, such as polybrominated diphenyl oxides, e.g., decabromodiphenyl oxide, tris(3-bromo-2,2-bis(bromomethyl)propyl phosphate, tris(tribromoneopentyl) phosphate, tetrabromophthalic acid, 1,2-bis(tribromphenoxy)ethane, hexabromocyclododecane, brominated diphenylethane, tris-(2,3-dibromopropyl)isocyanurate, ethylene bis-(tetrabromophthalimide), tetrabromobisphenol A, brominated polystyrene, brominated polybutadiene or polystyrene-brominated polybutadiene copolymers, brominated polyphenylene ether, brominated epoxy resin, polypentabromenzyl acrylate, possibly in combination with Sb₂O₃ and / or Sb₂O₅, f) Borates such as zinc borate or calcium borate, possibly on a carrier material such as silica g) Sulfur-containing compounds such as elemental sulfur, disulfides and polysulfides, thiuram sulfide, dithiocarbamates, mercaptobenzthiazole and sulfenamides, h) Anti-drip agents such as polytetrafluoroethylene, i) Silicon-containing compounds such as polyphenylsiloxanes, j) Carbon modifications such as carbon nanotubes (CNTs), expandable graphite or graphene k) as well as combinations or mixtures thereof. Particularly suitable flame retardants are:

[0076] Radical initiators preferably selected from the group consisting of N-alkoxyamines, -CC- radical initiators, radical initiators with azo groups (-N=N-), radical initiators with hydrazine groups (-NH-HN-), radical initiators with hydrazone groups (>C=N-NH-), radical initiators with azine groups (>C=NN=C<), radical initiators with triazine groups (-N=NN<) or from iminoxytriazines.

[0077] The preparation of suitable azo compounds is described, for example, in M. Aubert et al., Macromol. Sci. Eng. 2007, 292, 707-714 or in WO 2008101845; the preparation of hydrazones and azines in M. Aubert et al., Pol. Adv. Technol. 2011, 22, 1529-1538; and the preparation of triazenes in W. Pawelec et al., Pol. Degr. Stab. 2012, 97, 948-954. The synthesis of iminoxytriazines is described in WO 2014 / 064064.

[0078] In particular, the radical initiators to be used are selected from the group consisting of a) N-Alkoxyamines according to the structural formula shown below, wherein R 3 for hydrogen or an optionally substituted alkyl, cycloalkyl, aryl heteroaryl or acyl group, in particular a Cl, up to C4 alkyl group, R 4 stands for an alkoxy, aryloxy, cycloalkoxy, aralkoxy or acyloxy residue, Z represents hydrogen or an optionally substituted alkyl, cycloalkyl, aryl heteroaryl or acyl residue, wherein the two residues Z may also form a closed ring which may optionally be substituted by ester, ether, amine, amide, carboxy or urethane groups, E stands for an alkoxy, aryloxy, cycloalkyloxy, aralkoxy or acyloxy residue, b) Azo compounds according to the structural formulas shown below R 5 -N=N · R 5 or where R 5 means an alkyl, cycloalkyl or aryl residue, R 6 is the same or different in each occurrence and signifies a linear or branched alkyl group, R 7 is the same or different in each occurrence and signifies hydrogen or a linear or branched alkyl group, and R 8is the same or different in each occurrence and represents an alkyl, alkoxy, aryloxy-cycloalkyloxy, aralkoxy or acyloxy residue, c) Dicumyl according to the structural formula shown below, where R 7 the meaning given above, preferably methyl, d) and / or polycumyl according to the structural formula shown below, where R 7 the meaning given above, preferably methyl, and 2 <n < 100.

[0079] Typical examples of the aforementioned N-alkoxyamines of the given structure are: 1-Cyclohexyloxy-2,2,6,6-tetramethyl-4-octadecylaminopiperidine: bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate; 2,4-Bis[(1-Cyclohexyloxy-2,2,6,6-Tetramethylpiperidin-4-yl)butylamino]-6-(2-Hydroxyethylamino-S-triazine; Bis(1-Cyclohexyloxy-2,2,6,6-Tetramethylpiperidin-4-yl) adipate; 2,4-Bis[(1-Cyclohexyloxy-2,2,6,6-Tetramethylpiperidin-4-yl)Butylamino]-6-chlor-S-Triazin; 1-(2-Hydroxy-2-Methylpropoxy)-4-Hydroxy-2,2,6,6-Tetramethylpiperidin; 1-(2-Hydroxy-2-Methylpropoxy)-4-Oxo-2,2,6,6-Tetramethylpiperidin; 1-(2-Hydroxy-2-Methylpropoxy)-4-Octadecanoyloxy-2,2,6,6-tetramethylpiperidin; Bis(1-(2-Hydroxy-2-Methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)sebacat; Bis(1 -(2-Hydroxy-2-Methylpropoxy)-2,2,6,6-Tetramethylpiperidin-4-yl)adipat; 2,4-Bis{N-[1-(2-Hydroxy-2-Methylpropoxy)-2,2,6,6-Tetramethylpiperidin-4-yl]-N-Butylamino}-6-(2-Hydroxyethylamino)-S-Triazin); 4-Piperidinol, 2,2,6,6-Tetramethyl-1-(undecyloxy)-4,4'-carbonat; das Reaktionsprodukt von 2,4-Bis[(1-Cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-6-chlor-S-triazin mit N,N'-Bis(3-Aminopropylethylendiamin);the oligomeric compound which is the condensation product of 4,4'-hexamethylene-bis(amino-2,2,6,6-tetramethylpiperidine) and 2,4-dichloro-6-[(1-cyclohexyloxy-2,2,6,6-tetramethyl-4-yl)butylamino]-S-triazine, sealed at the ends with 2-chloro-4,6-bis(dibutylamino)-S-triazine; aliphatic hydroxylamines such as disterarylhydroxylamine; as well as compounds of the following formulas, or where n = 1-15;

[0080] The compounds mentioned above are partly commercial products and are traded under the following trade names: FLAMESTAB NOR 116 (RTM), TINUVIN NOR 371 (RTM), IRGATEC CR 76 (RTM) from BASF SE, Hostavin NOW (RTM) from Clariant, or ADK Stab LA 81 (RTM) from Adeka. Dicumyl and polycumyl are commercial products available, for example, from United Initiators. b) Phosphorus-containing flame retardants, e.g., phosphinates, of the following structures: wherein preferably R1 and R2 are identical or different and are selected from linear or branched C1-C6 alkyl and / or aryl; M is selected from the group consisting of Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K, Zn and / or a protonated nitrogen base, preferably calcium ions, magnesium ions, aluminum ions, and / or zinc ions; and m = 1-4, preferably 2 or 3; n = 1-4, preferably 1 or 3; x = 1-4, preferably 1 or 2. In a particularly preferred embodiment, R1 = alkyl, R2 = alkyl, and M = Al or Zn.

[0081] A particularly favored example of a phosphinate is the commercially available product Exolit OP (RTM) from Clariant SE.

[0082] Other preferred phosphorus-containing flame retardants are metal salts of hypophosphorous acid with a structure according to the formula where Met is a metal selected from groups I, II, III and IV of the periodic table of elements, and n is a number from 1 to 4 corresponding to the charge of the corresponding metal ion Met. n+ For example, Na + , Ca 2+ , Mg 2+ , Zn 2+ , Ti 4+ or Al 3+ , where Ca 2+ , Zn 2+ and Al 3+ are especially preferred.

[0083] The above-mentioned salts of hypophosphorous acid are partly commercially available, e.g. under the name Phoslite (RTM) from Italmatch Chemicals.

[0084] Another preferred group of phosphorus-containing flame retardants are phosphonates or phosphonic acid diaryls of a structure according to the following formula: where R8, and R 10= H, alkyl, preferably C1-C4 are, R9=C1-C4 alkyl u = 1-5st and v = 1-5ist.

[0085] Corresponding structures can also exist in the form of phosphonate oligomers, polymers, and copolymers. Linear or branched phosphonate oligomers and polymers are known from the prior art. For branched phosphonate oligomers and polymers, reference is made to US patents US 2,716,101, US 3,326,852, US 4,328,174, US 4,331,614, US 4,374,971, US 4,415,719, US 5,216,113, US 5,334,692, US 3,442,854, US 6,291,630 B1, US 6,861,499 B2, and US 7816,486 B2. For phosphonate oligomers, reference is made to US patent applications US 2005 / 0020800 A1, US 2007 / 0219295 A1 and US 2008 / 0045673 A1. Regarding linear phosphonate oligomers and polymers, reference is made to US patent documents US 3,946,093, US 3,919,363, US 6,288,210 B1, US 2,682,522 and US 2,891,915.

[0086] Phophonates are available, for example, under the trade name Nofia (RTM) from FRX Polymers.

[0087] Another preferred group of phosphorus-containing flame retardants are compounds based on oxaphosphorine oxide and their derivatives with, for example, the following structures: where M is a metal selected from the second, third, twelfth or thirteenth group of the periodic table of elements, x = 2 or 3, n ≥ 10, m = 0-25, R = H, halogen or an aliphatic or aromatic residue with 1-32 C atoms, and R1 = H, C1-C6 alkyl or phenyl.

[0088] Products based on oxophosphorine oxide are available, for example, under the trade name Ukanol (RTM) from Schill und Seilacher GmbH. Further compounds can be produced, for example, according to patent specifications WO 2013020696, WO 2010135398, W003070736, WO2006084488, WO 2006084489, WO 2011000019, WO 2013068437, and WO 2013072295.

[0089] Other suitable phosphorus-containing flame retardants are cyclic phosphonates of a structure according to one of the following formulas: where A 1 and A 2 independently represented a substituted or unsubstituted, straight-chain or branched alkyl group with 1 to 4 carbon atoms, substituted or unsubstituted benzyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, and wherein A 3 and A 4 Methyl or ethyl are independent of each other and

[0090] A 5 a straight-chain or branched alkyl group with 1 to 4 carbon atoms, or a phenyl or benzyl group, each of which may have up to 3 methyl groups.

[0091] Cyclic phosphonates are available, for example, from Thor GmbH under the trade name Aflammit (RTM) or can be manufactured according to EP 2450401.

[0092] Other synergistic phosphorus-containing flame retardants are phosphacenes, especially polymeric phosphacenes. A corresponding product is available commercially, for example, under the name SPB-100 from Otsuka Chemicals. a) Nitrogen-containing flame retardants Preferred nitrogen-containing flame retardants are melamine polyphosphate, melamine cyanurate, melamine metal phosphates, poly-[2,4-(piperazine-1,4-yl)-6-(morpholin-4-yl)-1,3,5-triazine], and ammonium polyphosphate. These compounds are commercial products and are available under the trade names Melapur (RTM) from BASF SE, Budit (RTM) from Budenheim Chemische Fabrik, Exolit (RTM) from Clariant, Safire (RTM) from Huber Chemicals, or MCA PPM Triazine from MCA Technologies GmbH. c) Preferred sulfur-containing flame retardants include, for example, the following compounds

[0093] Particularly preferred flame retardants are halogen-free and include the following compounds: Al(OH)3, Mg(OH)2 n=1-100 with n= 2-20n=2-20 with n=3-100 n=1-3n= 3-100with R= Alkyl, Phenyl and n = 3-20

[0094] Suitable lubricants and processing aids include, 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 erucamide or oleamide, fluoropolymers, silicones or neoalkoxy titanates and zirconates.

[0095] Suitable pigments can be inorganic or organic. Examples of inorganic pigments include titanium dioxide, zinc oxide, zinc sulfide, iron oxide, ultramarine, and carbon black. Examples of organic pigments include anthraquinones, anthanthrones, benzimidazolones, quinacridones, diketopyrrolopyrroles, dioxazines, indanthrones, isoindolinones, azo compounds, perylenes, phthalocyanines, and pyranthrones. Other suitable pigments include metal-based effect pigments and metal oxide-based pearlescent pigments.

[0096] Suitable optical brighteners include, for example, bisbenzoxazoles, phenylcoumarins or bis(styryl)biphenyls, and in particular optical brighteners of the following formulas:

[0097] Suitable filler deactivators include, for example, polysiloxanes, polyacrylates, especially block copolymers such as polymethacrylic acid-polyalkylene oxide or polyglycidyl(meth)acrylates and their copolymers, e.g. with styrene, as well as epoxides, e.g. of the following structures:

[0098] Suitable antistatic agents include, for example, ethoxylated alkylamines, fatty acid esters, alkyl sulfonates and polymers that form a co-continuous network with the polymer matrix, such as polyetheramides, polyesteramides, polyetheresteramides or polyether block copolymers, possibly with the addition of ionically conductive metal salts.

[0099] Suitable antiozonants are the amines mentioned above, such as N,N'-diisopropyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine, N,N'-dicyclohexyl-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine

[0100] Suitable rheology modifiers, e.g., for the production of controlled rheology polypropylene (CR-PP), include peroxides, alkoxyamine esters, oxyimide sulfonic acid esters, and in particular the following structures:

[0101] Suitable additives for increasing the molecular weight of polycondensation polymers (chain extenders) include diepoxides, bis-oxazolines, bis-oxazolones, bis-oxazines, diisocyanates, dianhydrides, Bs-acyl lactams, bis-maleimides, dicyanates, carbodiimides, and polycarbodiimides. Other suitable chain extenders are polymeric compounds such as polystyrene-polyacrylate-polyglycidyl(meth)acrylate copolymers, polystyrene-maleic anhydride copolymers, and polyethylene-maleic anhydride copolymers.

[0102] Suitable additives for increasing electrical conductivity include, for example, the aforementioned antistatic agents, carbon black and carbon compounds such as carbon nanotubes and graphene, metal powders such as copper powder and conductive polymers such as polypyrroles, polyanilines and polythiophenes.

[0103] Suitable infrared-active additives include, for example, aluminum silicates, hydrotalcites, or dyes such as phthalocyanines or anthraquinones.

[0104] Suitable crosslinking agents include, for example, peroxides such as dialkyl peroxides, alkyl aryl peroxides, peroxy esters, peroxy carbonates, diacyl peroxides, peroxy ketals, silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltris(2-methoxyethoxy)silane, 3-methacryloyloxypropyltrimethoxysilane, vinyldimethoxymethylsilane or ethylene-vinylsilane copolymers.

[0105] Suitable prodegradants are additives that selectively accelerate or control the degradation of a polymer in the environment. Examples include transition metal fatty acid esters, e.g., of manganese or iron, which accelerate oxidative and / or photooxidative degradation of, for example, polyolefins, or enzymes that induce hydrolytic degradation of, for example, aliphatic polyesters.

[0106] 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-phenyltetrazol, hydrazides such as p-toluenesulfonyl hydrazide, 4,4'-oxibis(benzenesulfonyl)hydrazide, N-nitroso compounds such as N,N'-dinitrosopentamethylenetetramine or carbonates such as sodium hydrogen carbonate or zinc carbonate.

[0107] Suitable slip agents include, for example, amide waxes such as erucamide or oleamide.

[0108] Suitable antiblocking agents include silica, talc, or zeolites.

[0109] Suitable antifogging additives include, for example, ethoxylated sorbitan esters, ethoxylated fatty acid alcohols, or ethoxylated alkylamine esters.

[0110] Suitable biocides include, for example, quaternary ammonium salts or silver salts, colloidal silver or silver complexes, or natural product derivatives such as chitosan.

[0111] Suitable aldehyde scavengers are amines, hydroxylamines, polyvinyl alcohol, zeolites or cyclodextrins; suitable formaldehyde scavengers are melamine derivatives such as benzoguanamine or urea derivatives such as allantoin.

[0112] Suitable odor-binding or odor-preventing substances are silicates such as calcium silicate, zeolites or salts of hydroxy fatty acids such as zinc riceneolate.

[0113] Suitable marking agents include, for example, fluorescent dyes or rare earth elements.

[0114] Suitable nucleating agents are talc, alkali or alkaline earth salts of mono- and polyfunctional carboxylic acids such as benzoic acid, succinic acid, adipic acid, e.g. sodium benzoate, zinc glycerolate, aluminum hydroxybis(4-tert-butyl)benzoate, 2,2'-methylene-bis-(4,6-di-tert-butylphenyl)phosphate, as well as triamides and diamides such as trimesic acid tricyclohexylamide, trimesic acid tri(4-methylcyclohexylamide), trimesic acid tri(tert-butylamide), N,N',N''-1,3,5-benzenetriyltris(2,2-dimethyl-propanamide) or 2,6-naphthalenedicarboic acid dicyclohexylamide.

[0115] Suitable transparency improvers (clarifiers) include, in particular, sorbitol derivatives such as, for example,

[0116] Suitable antinuclear agents are azine dyes such as nigrosine or ionic liquids,

[0117] Suitable additives for increasing the thermal conductivity of recycled plastics include, for example, inorganic fillers such as boron nitride, aluminum nitride, aluminum oxide, aluminum silicate, silicon carbide, and also carbon nanotubes (CNTs).

[0118] Suitable impact improvers are usually selected for the specific recyclate and are, for example, from the group of functionalized or non-functionalized polyolefins, such as ethylene copolymers like EPDM or maleic anhydride or styrene-acrylonitrile-modified EPDM, glycidyl methacrylate-modified ethylene-acrylate copolymers or ionomers, core-shell polymers e.g. based on MBS (methacrylate-butadiene-styrene copolymer) or acrylic ester polymethyl methacrylate, thermoplastic elastomers (TPE) e.g. based on styrene block copolymers (styrene-butadiene (SB), styrene-butadiene-styrene (SBS) possibly hydrogenated (SEBS) or modified by maleic anhydride (SEBS-g-MAH), thermoplastic polyurethanes, copolyesters or copolyamides.

[0119] Suitable plasticizers include, for example, esters of phthalic acid, terephthalic acid, adipic acid, 1,2-cyclohexanedicarboxylic acid, trimellitic acid, citric acid or phosphoric acid such as benzyl butyl phthalate (BBP), butyl nonyl phthalate (BNP), didecyl phthalate (DDP), diisobutyl adipate (DIBA), diisodecyl adipate (DIDA), dioctyl terephthalate (DOTP), diisotridecyl phthalate (DTDP), tributyl-O-acetyl citrate (TBAC), triethyl-O-acetyl citrate (TOAC), tetrahydrofurfuryl oleate (THFO), triisooctyl trimellitate (TIOTM), tributyl phosphate (TBP) as well as epoxidized soybean oil (ESO) or epoxidized linseed oil (ELO).

[0120] Suitable demolding aids include silicones, soaps and waxes such as montan waxes.

[0121] Preferably, the additive according to the invention, which can be in the form of a powder, liquid, oil, compacted on a carrier material, as granules, solution, or flakes, is mixed with the polymer to be stabilized, the polymer matrix is ​​transferred into the melt, and then cooled. Alternatively, it is also possible to introduce the additive into a polymer melt in a molten state.

[0122] Furthermore, the additive compositions according to the invention can be produced and introduced in the form of so-called masterbatches or concentrates, which contain, for example, 10-90% of the compositions according to the invention in a polymer or a polymer recyclate.

[0123] In a further preferred embodiment, the compositions contain secondary antioxidants, in particular phosphites / phosphonites, sulfites, acid scavengers, costabilizers based on polyols and / or light stabilizers from the group of hindered amines (HALS).

[0124] In the aforementioned embodiment, it is advantageous if the at least one additive is contained or added in an amount of 0.01 to 80 wt.%, preferably 0.01 to 9.99 wt.%, more preferably 0.01 to 4.98 wt.%, and particularly preferably 0.02 to 2.00 wt.%, based on the entirety of the at least one compound according to general formula I or II, or, in the case of a mixture of several compounds according to general formula I and / or II, the entirety of all compounds according to general formula I and / or II, the plastic and the at least one additive.

[0125] The composition is particularly preferably made up of (A) 99.9 to 50 wt.% of a plastic (B) 0.005 - 3.0 wt.%, preferably 0.01 - 1.0 wt.%, particularly preferred 0.02 - 0.50 wt.% of at least one tannin (C) 0.005 - 3.0 wt.%, preferably 0.01 to 1.0 wt.%, particularly preferably 0.02 - 0.5 wt.% of at least one hydrotalcite, (D) 0 - 3.0 wt.%, preferably 0.02 - 2.0%, particularly preferably 0.05 - 1.0 wt.% of a primary and / or secondary antioxidant, (E) 0 - 50 wt.% of at least one additive, wherein components (A) to (E) add up to 100 wt.%.

[0126] Particularly preferred is the at least one polymer selected from the group consisting of polyolefins, in particular polyethylenes or polypropylenes.

[0127] Furthermore, the present invention relates to a molded part or a molded body, producible from a composition described above according to the invention, in particular foils or films, foams, fibers, cables and tubes, profiles, hollow bodies, tapes, membranes, such as geomembranes, or adhesives, which are produced by extrusion, injection molding, blow molding, calendering, pressing processes, spinning processes, rotomoulding, e.g. for the electrical and electronics industry, construction industry, transport industry (car, aircraft, ship, railway), for medical applications, for household and electrical appliances, vehicle parts, consumer goods, packaging, furniture, textiles.

[0128] Stabilizers for plastics in the form of injection-molded parts, foils or films, foams, fibers, cables and tubes, profiles, hollow bodies, tapes, membranes, such as geomembranes, or adhesives, which are produced by extrusion, injection molding, blow molding, calendering, compression molding, spinning processes, rotomoulding, e.g. - for packaging, e.g., for food, detergents, cosmetics, adhesives in the form of films, bottles, bags, screw-top containers - Storage and transport containers such as boxes, crates, barrels, buckets, pallets - Automotive, railway, aircraft, ship and machine parts such as bumpers, trim parts, instrument and functional parts, upholstery - Construction applications such as profiles, construction films, cable ducts, house cladding, noise barriers, drainage channels, profile boards, floor coverings - Road and landscaping applications such as beacon bases, posts, barriers, geotextiles, - Electrical and electronic applications such as housing parts and accessories for televisions, computers, mobile phones, washing machines, dishwashers, coffee machines, drills, connectors, storage media - Cable insulation - Pipes for e.g. water, gas, wastewater, irrigation, drainage pipes - Hygiene products such as diapers - Furniture and textile applications, such as curtains and upholstery, worktops - Household, leisure and sporting goods such as balls, tennis rackets, skis, flower pots, rain barrels, clothes hangers - Agricultural applications such as mulch, tunnel or perforated films, plant pots - Pharmaceutical and plant protection applications, such as the encapsulation of active ingredients and biologically active substances - In medical technology for the production of suture material, dressing material, orthoses and prostheses.

[0129] The present invention will be explained in more detail with reference to the following examples, without reducing the invention to the examples. Examples of implementation: Pretreatment:

[0130] A commercially available tannin (Jiurui 93%, manufactured by Jiurui Biology and Chemistry Co. Ltd., Hunan, China) was pretreated under vacuum at 50 mbar and 60 °C for 48 hours. Thermal stability was determined by thermogravimetric analysis (TGA), and molecular weight by gel permeation chromatography. The pretreated tannins exhibit improved thermal stability and a monomodal distribution. The results of these investigations are tabulated below as the mass average of the molar mass (Mmol). W ), the temperature at 5% mass loss (T m5% ) and the percentage mass residue at 800 °C (m³) r800°C ) listed. Table 1 Key figure Jiurui 93% untreated Jiurui 93% pretreated M W [g / mol] 1,5545*10 3 1,6131*10 3 T m5% [°C] 108 249 M r800°C [%] 22,1 22,7

[0131] To test the effect of the stabilizers according to the invention, a commercially available polypropylene (Moplen HP 500N, LyondellBasell Industries) was homogenized in a powder-powder mixture with the stabilizers according to the invention and processed in a 16 mm twin-screw extruder (Thermo Scientific HAAKE PolyLab OS System, L / D ratio 25) at a maximum temperature of 235 °C, a throughput of 2 kg / h, and 200 revolutions per minute. The melt volume flow rate (MVR) was then determined according to ISO 1133:2022. The resulting color of the samples was determined after the production of injection-molded test specimens (Babyplast 6 / 10P) using the yellowness index with a spectro-guide sphere gloss from BYK according to DIN EN ISO 11664:2020. Table 1: MVR [g / 10min] 230 YI Comparative example 1 0.025% tannin 17,5 7,9 Comparative example 2 0.05% tannin 16,3 11,9 Example according to the invention 1 0.025% tannin0.050% hydrotalcite 17,1 5,2

[0132] With increasing tannin concentration, a distinct discoloration occurs, detectable by the yellowness index. The composition according to the invention leads to improved stabilization with a simultaneous reduction in discoloration.

[0133] In a further series of experiments (Table 2), compositions according to the invention were extruded five times under the processing conditions mentioned above, and the MVR was determined after the 1st, 3rd, and 5th extrusions. The composition according to the invention showed a very good stabilizing effect, which can be increased by the further addition of vitamin E. Table 2: MVR [g / 10min] 230°C / 2.16 kg after 1st extrusion MVR [g / 10min] 230°C / 2.16 kg after 3rd extrusion MVR [g / 10min] 230°C / 2.16 kg after 5th extrusion Comparative example 3 Without addition 18,7 21,3 24,1 Comparative example 4 0.05% hydrotalcite 17,0 19,3 21,8 Example 2 according to the invention 0.025% tannin + 0.05% hydrotalcite 16,1 17,5 19,9 Example according to the invention 3 0.025% tannin + 0.005% vitamin E + 0.05% hydrotalcite 15,6 15,8 16,1 Example according to the invention 3 0.025% tannin + 0.01% vitamin E + 0.05% hydrotalcite 15,5 15,6 15,8

[0134] Hycite 713 (Clariant SE, Muttenz, CH) was used as hydrotalcite. Vitamin E was obtained from Alfa Aesar.

[0135] All examples also contain 0.1% calcium stearate. QUOTES INCLUDED IN THE DESCRIPTION

[0000] This list of documents cited by the applicant was automatically generated and is included solely for the reader's convenience. The list is not part of the German patent or utility model application. The DPMA accepts no liability for any errors or omissions. Cited patent literature

[0000] WO 2020 / 083740

[0007] WO 2008101845

[0077] WO 2014 / 064064

[0077] US 2 716 101

[0085] US 3 326 852

[0085] US 4 328 174

[0085] US 4 331 614

[0085] US 4 374 971

[0085] US 4 415 719

[0085] US 5 216 113

[0085] US 5 334 692

[0085] US 3 442 854

[0085] US 6 291 630 B1

[0085] US 6 861 499 B2

[0085] US 7816486 B2

[0085] US 2005 / 0020800 A1

[0085] US 2007 / 0219295 A1

[0085] US 2008 / 0045673 A1

[0085] US 3 946 093

[0085] US 3 919 363

[0085] US 6 288 210 B1

[0085] US 2 682 522

[0085] US 2 891 915

[0085] WO 2013020696

[0088] WO 2010135398

[0088] WO 2006084488

[0088] WO 2006084489

[0088] WO 2011000019

[0088] WO 2013068437

[0088] EP 2450401

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[0077]

Claims

[1] Stabiliser composition consisting of at least one tannin and at least one hydrotalcite or mixtures thereof. [2] Stabilizer composition according to claim 1, characterized by that the at least one tannin has a molecular weight of 500 to 10000 g / mol, preferably 1000 to 5000. [3] Stabiliser composition according to any of the preceding claims, characterized by that the at least one tannin is thermally pretreated, wherein the thermal pretreatment preferably takes place at temperatures between 50 and 200 °C, preferably between 80 and 150 °C and / or over a period of 10 minutes to 10 hours, preferably 1 to 3 hours. [4] Stabilizer composition according to the preceding claim, characterized by that the thermal pretreatment is carried out under reduced pressure compared to normal pressure, preferably at pressures between 0.01 and 100 mbar, particularly preferably between 0.1 and 10 mbar. [5] Stabiliser composition according to any of the preceding claims, characterized by , that at least one hydrotalcite is selected from the group consisting of compounds of the general formula (M 2+ )1-x · (M 3+ )x · (OH)2 · (A n- ) x / n · m H2O where M 2+ one or more of the metals from the group Mg, Ca, Zn or Sr, M 3+ Al or B A is an anion with valence n, preferably OH - , ClO4 - , HCO3 - , CH3COO - , C6H5COO - , CO3 2- , SO4 1- , HSO4 - " n 1 or 2 is, 0 < x < 0.5 is, and m is a number from 0 to 20, in particular the hydrotalcites are selected from the group consisting of Al2O3 · 6 MgO · CO2 · 12 H2O, Mg4,sAl2(OH) 13· CO3 · 3.5 H2O, 4 MgO · Al2O3 · CO2 · 9 H2O, 4 MgO · Al2O3 · CO2 · 6 H2O, ZnO · 3 MgO · Al2O3 · CO2 · 8-9 H2O, ZnO · 3 MgO · Al2O3 · CO2 · 5-6 H2O, Ca4Al2(OH) 12 CO3 · 5 H2O and Mg6Al2(OH) 16 · CO3 · 4 H2O. [6] Stabiliser composition according to any of the preceding claims, characterized by , that at least one hydrotalcite is anhydrous. [7] Stabiliser composition according to any of the preceding claims, characterized by , that the weight ratio of the totality of the at least one tannin to the totality of the at least one hydrotalcite is 10:1 to 1:10, preferably 5:1 to 1:5, particularly preferably 3:1 to 1:

3. [8] Use of a stabilizer composition according to any one of claims 1 to 7 for stabilizing polymers, in particular against oxidative, thermal or actinic degradation. [9] Method for stabilizing polymers, in particular against oxidative, thermal or actinic degradation, in which a stabilizer composition according to one of claims 1 to 7 is added to or blended with a polymer. [10] Use or method according to one of claims 8 or 9, characterized by that the stabilizer composition is used or added in a weight ratio of 0.01 to 10 wt.%, preferably 0.05 to 5 wt.%, particularly preferably 0.1 to 3 wt.% based on the polymer. [11] Use or method according to any one of claims 8 to 10, characterized by that the polymer is selected from the group consisting of a) Polymers made from olefins or diolefins such as polyethylene (LDPE, LLDPE, VLDPE, ULDPE, MDPE, HDPE, UHMWPE), metallocene-PE (m-PE), polypropylene, polyisobutylene, poly-4-methylpentene-1, polybutadiene, polyisoprene, such as natural rubber (NR), polycyclooctene, polyalkylene-carbon monoxide copolymers, as well as copolymers in the form of statistical or block structures such as polypropylene-polyethylene (EP), EPM or EPDM with, for example, 5-ethylidene-2-norbornene as a comonomer, ethylene vinyl acetate (EVA), ethylene acrylates such as 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-polybutylacrylate graft-maleic anhydride, and blends such as LDPE / LLDPE or long-chain branched polypropylene copolymers produced with alpha-olefins as comonomers, such as...with 1-butene, 1-hexene, 1-octene or 1-octadecene. b) Polystyrene, polymethylstyrene, poly-alpha-methylstyrene, polyvinylnaphthalene, polyvinylbiphenyl, polyvinyltoluene, styrene-butadiene (SB), styrene-butadiene-styrene (SBS), styrene-ethylene-butylene-styrene (SEBS), styrene-ethylene-propylene-styrene, styrene-isoprene, styrene-isoprene-styrene (SIS), styrolutadiene acrylonitrile (ABS), styrene-acrylonitrile (SAN), styrene-acrylonitrile acrylate (ASA), styrene-ethylene, styrene-maleic anhydride polymers including corresponding graft copolymers such as styrene on butadiene, maleic anhydride on SBS or SEBS, as well as graft copolymers of methyl methacrylate, styrene-butadiene and ABS (MABS), and hydrogenated Polystyrene derivatives such as polyvinylcyclohexane, c) Polymers of unsaturated esters such as polyacrylates and polymethacrylates like polymethyl methacrylate (PMMA), polybutyl acrylate, polylauryl acrylate, polystearyl acrylate, polyglycidyl acrylate, polyglycidyl methacrylate, polyacrylonitrile, polyacrylamides, copolymers such as polyacrylonitrile-polyalkyl acrylate, d) Polymers made from unsaturated alcohols and derivatives, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyallyl phthalate, polyallyl melamine, e) Polyacetals, such as polyoxymethylene (POM) or copolymers with, for example, butanal, f) Polyphenylene oxides and blends with polystyrene or polyamides, g) Polymers of cyclic ethers such as polyethylene glycol, polypropylene glycol, polyethylene oxide, polypropylene oxide, polytetrahydrofuran, h) Polyurethanes, made from hydroxy-terminated polyethers or polyesters and aromatic or aliphatic isocyanates such as 2,4- or 2,6-toluene diisocyanate or methylene diphenyl diisocyanate, in particular also linear polyurethanes (TPU), polyureas, i) Polyamides such as polyamide-6, 6.6, 6.10, 4.6, 4.10, 6.12, 10.10, 10.12, 12.12, polyamide 11, polyamide 12, and (partially) aromatic polyamides such as polyphthalamides, e.g., produced from terephthalic acid and / or isophthalic acid and aliphatic diamines such as hexamethylenediamine or m-xylylenediamine, or from aliphatic dicarboxylic acids such as adipic acid or sebacic acid and aromatic diamines such as 1,4- or 1,3-diaminobenzene, blends of different polyamides such as PA-6 and PA 6.6, or blends of polyamides and polyolefins such as PA / PP. j) polyimides, polyamidimides, polyetherimides, polyesterimides, poly(ether) ketones, polysulfones, polyethersulfones, polyarylsulfones, polyphenylene sulfides, polybenzimidazoles, polyhydantoins, k) Polyesters made from aliphatic or aromatic dicarboxylic acids and diols or from hydroxycarboxylic acids such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polypropylene terephthalate (PTI), polyethylene naphthylate (PEN), poly-1,4-dimethylolcyclohexane terephthalate, polyhydroxybenzoate, polyhydroxynaphthalate, polylactic acid (PLA), polyhydroxybutyrate (PHB), polyhydroxyvalerate (PHV), polyethylene succinate, polytetramethylene succinate, polycaprolactone, I) Polycarbonates, polyester carbonates, and blends such as PC / ABS, PC / PBT, PC / PET / PBT, PC / PA, m) Cellulose derivatives such as cellulose nitrate, cellulose acetate, cellulose propionate, cellulose butyrate, n) Epoxy resins consisting of di- or polyfunctional epoxy compounds in combination with, for example, hardeners based on amines, anhydrides, dicyandiamide, mercaptans, isocyanates or catalytically acting hardeners, o) Phenolic resins such as phenol-formaldehyde resins, urea-formaldehyde resins, melamine-formaldehyde resins, p) unsaturated polyester resins made from unsaturated dicarboxylic acids and diols with vinyl compounds, e.g., styrene, alkyd resins, q) Silicones, e.g. based on dimethylsiloxanes, methylphenylsiloxanes or diphenylsiloxanes, e.g. vinyl groups terminated, r) as well as mixtures, combinations or blends of two or more of the aforementioned polymers. [12] Composition comprising or consisting of at least one polymer and a stabilizer composition according to any one of claims 1 to 8. [13] Composition according to the preceding claim, characterized bythat the stabilizer composition is contained in a weight ratio of 0.01 to 10 wt.%, preferably 0.05 to 5 wt.%, particularly preferably 0.1 to 3 wt.% based on the at least one polymer. [14] Composition according to one of the two preceding claims, characterized bythat at least one additive selected from the group consisting of secondary antioxidants, UV absorbers, light stabilizers, metal deactivators, filler deactivators, antiozonants, nucleating agents, antinucleating agents, impact enhancers, plasticizers, lubricants, rheology modifiers, thixotropic agents, chain extenders, processing aids, demolding aids, flame retardants, pigments, dyes, optical brighteners, antimicrobial agents, antistatic agents, slip agents, antiblocking agents, coupling agents, crosslinking agents, anticrosslinking agents, hydrophilizing agents, hydrophobizing agents, hydrolysis stabilizers, adhesion promoters, dispersing agents, compatibilizers, oxygen scavengers, acid scavengers, blowing agents, degradation additives, defoaming agents, odor neutralizers, marking agents, antifogging agents, fillers and reinforcing agents is included. [15] Compositions according to any one of claims 12 to 14, consisting of (A) 99.9 to 50 wt.% of a plastic (B) 0.005 - 3.0 wt.%, preferably 0.01 - 1.0 wt.%, particularly preferred 0.02 - 0.50 wt.% of at least one tannin (C) 0.005 - 3.0 wt.%, preferably 0.01 to 1.0 wt.%, particularly preferably 0.02 - 0.5 wt.% of at least one hydrotalcite, (D) 0 - 3.0 wt.%, preferably 0.02 - 2.0%, particularly preferably 0.05 - 1.0 wt.% of a primary and / or secondary antioxidant, (E) 0 - 50 wt.% of at least one additive, wherein components (A) to (E) add up to 100 wt.%. [16] Composition according to any one of claims 12 to 15, characterized by that at least one polymer is selected from the group consisting of d polyolefins, in particular polyethylenes or polypropylenes. [17] Molded part or molded body, producible from a composition according to any one of claims 12 to 16, in particular foils or films, foams, fibers, cables and tubes, profiles, hollow bodies, tapes, membranes, such as geomembranes, or adhesives, which are produced by extrusion, injection molding, blow molding, calendering, pressing processes, spinning processes, rotomoulding, e.g. for the electrical and electronics industry, construction industry, transport industry (car, aircraft, ship, railway), for medical applications, for household and electrical appliances, vehicle parts, consumer goods, packaging, furniture, textiles.