DE102021202508A1 - Use of a stabilizer composition for stabilizing polyolefin recyclates, stabilizer composition, masterbatch concentrate, plastic composition, molding material or molding, method for stabilizing a polyolefin recyclate and use of a plastic composition - Google Patents

Abstract

The present invention relates to the use of a stabilizer composition for stabilizing polyolefin recyclates, in particular against oxidative, thermal and/or actinic degradation. In addition, the present invention relates to a corresponding plastic molding compound, a stabilizer composition, a method for stabilizing polyolefin recyclates, a molding compound or moldings produced from a plastic composition according to the invention, and possible uses thereof.

Description

The present invention relates to the use of a stabilizer composition for stabilizing polyolefin recyclates, in particular against oxidative, thermal and/or actinic degradation. In addition, the present invention relates to a corresponding plastic molding compound, a stabilizer composition, a method for stabilizing polyolefin recyclates, a molding compound or moldings produced from a plastic composition according to the invention, and possible uses thereof.

Plastic recyclates are a growing market and an important element in the circular economy of raw materials, with recyclates ideally replacing new plastics with an identical or at least comparable property profile. However, recyclates from the production of plastic parts (so-called "post-industrial" recyclates) and from collections of old plastics (so-called "post-consumer" recyclates) differ chemically from new plastics. During the first processing steps (e.g. by compounding, extrusion or injection molding) and the application, often over many years and in demanding areas of application (e.g. high temperatures and/or UV light), irreversible changes in the polymer chains result from mechano-chemical, chemical or light-induced changes Processes (see e.g. R. Pfaendner et al., Angew. Makromol. Chemie 1995, 232, 193-227, R. Pfaendner, Kunststoffe International 12/2015, 41-44, J. Pospisil et al., Pol. Degr. Stab. 1995, 48, 351-358, FP La Mantia, Macromol Symp 1998, 135, 157-165).

Radical reactions in the presence of oxygen, commonly referred to as autoxidation, create new chemical groups in the polymer chain and/or change the composition of the polymer at the molecular level. The chemical changes that occur as a result of the damage process and the aging process are primarily hydroperoxide groups, aliphatic carbonyl groups, alpha-beta unsaturated carbonyl groups, alcohol groups, acid groups, ester groups and peracid groups, i.e. structures that are not usually present in new polyolefin goods and are not present primarily as a result of oxidation processes (J. Pospisil et al. Macromol. Symp. 1998, 135, 247-263). Furthermore, recyclates, in particular polyolefins, often contain unsaturated structures, i.e. vinylidene, vinylene and vinyl groups, where vinylene groups can even be conjugated. Unsaturated structures result from chain cleavage and disproportionation reactions (H. Hinsken et al., Pol. Degr. Stab. 1991, 34, 279-293). The concentration of these newly formed groups increases with the processing intensity (process control, shearing, temperature), the application area (UV light, high temperatures, contact media) and the application time. In addition, the formation of these structures in oxidation processes and subsequent reactions can be catalyzed by (transition) metals and pigments. The structural inhomogeneities of a recyclate consequently influence the plastic properties, such as the mechanical properties or the morphology. Due to the newly formed chemical structures, recyclates or previously damaged plastics are more sensitive to oxidation than new material, since these act as initiator sites for further oxidation or as prodegradants (A. S. Maxwell, Pol. Eng. Sci. 2008, 48, 381-385, I. H. Craig, J. R. White, J Mater Sci 2006, 41, 993-1006, S Luzuriaga et al Pol Degr Stab 2006, 91, 1226-1232). Furthermore, it has been proven that the degradation rate depends on the concentration of the chromophoric "impurities" (M. S. Rabello, J. R. White, Polym. Degrad Stab. 1997, 56, 55-73). The concentrations of the "aging" structures described in the recyclates can increase by several orders of magnitude compared to the new material.

In order to improve the quality of plastic recyclates, post-stabilization with selected stabilizers such as antioxidants is an essential method. The stabilizers used protect the recyclate from further oxidative (or photo-oxidative) damage or at least delay it. Since new plastic and recyclates differ significantly chemically as described and recyclates are more sensitive to oxidation due to this pre-damage and initiator sites, it is a challenging task to develop high-performance stabilizers for the efficient stabilization of recyclates of plastic, which are due to the described structural deviations of the will distinguish recyclate from new material. The latter applies above all to polyolefins such as polypropylene or polyethylene, which make up the majority of post-consumer recyclates.

• WO 2019063550 : Stabilisierungszusammensetzung enthaltend Alditole oder Cyclitole
• WO 2020152337 : Stabiliserungszusammensetzung enthaltend Verbindungen, die mit Carbonylgruppen reagieren können und primären und/oder sekundären Antioxidantien
• WO2020193563 : Stabilisierungszusammensetzung enthaltend substituierte Zuckermoleküle

Due to the differences between new plastics and recycled plastics that are recognized today, special recycled stabilizer compositions are known and are also available as commercial products (e.g. Recyclobyk products from BYK-Chemie GmbH, Wesel). Known technical stabilization solutions that meet the requirements of recyclates are described, for example, in the following patents/patent applications:
Stabilizing composition consisting of a phenolic antioxidant, a phosphite and a fatty acid salt ( EP 0662101 ).
Stabilizing composition consisting of a phenolic antioxidant, a phosphite and a metal oxide such as calcium oxide ( U.S.6525158 , US6251972 ).
Stabilizing composition consisting of a phenolic antioxidant and a polyfunctional epoxide ( EP 0702704 ).
Stabilization by a macrocyclic piperidine ( U.S.5789470 ).
Stabilizing composition consisting of a secondary aromatic amine and a polyfunctional epoxide ( WO 97/30112 ).
Decolorization of damaged polyolefins by a hydroxylamine ( EP 0470048 )
Mixture of antioxidants, lubricants, antiblocking agents, UV stabilizers and antistatic agents for recycled films ( DD288161 )
Stabilizing composition for mixed plastics consisting of a phenolic antioxidant and a phosphite/phosphonite ( EP0506614 ) Furthermore, the following own registrations for the stabilization of recyclates are available:

• WO2019063550 : Stabilizing composition containing alditols or cyclitols
• WO2020152337 : Stabilizing composition containing compounds which can react with carbonyl groups and primary and/or secondary antioxidants
• WO2020193563 : Stabilizing composition containing substituted sugar molecules

Inorganic phosphites are described as additives in plastics, e.g. aluminum phosphite is used as a flame retardant (see e.g WO2015103006 , WO2016165964 , WO 2020 201811 ), sodium phosphite for color improvement/stabilization of polyamides (see eg JP 4446747 , CN 109082115 , CN 104804412 ) or potassium phosphite as a processing aid for wood plastic composites (see eg WO2008008186 ) suggested. Organic phosphites such as esters of phosphorous acid are common secondary antioxidants and are also known to be found in recyclates (see e.g EP 0662101 ).
However, the use of inorganic phosphites in polyolefin recyclates has not been described to date.

Despite the known solutions for post-stabilization of recyclates, there is still a need for particularly effective, environmentally friendly and cost-effective stabilizer compositions for recyclates, which are obtained with the compositions of inorganic phophites according to the invention.

This object is achieved with the features of the independent patent claims.

The invention thus relates to the use of at least one stabilizer composition containing or consisting of at least one inorganic phosphite in combination with at least one primary antioxidant for stabilizing polyolefin recyclates, in particular against oxidative, thermal and/or actinic degradation.

New stabilizer compositions and a new method for stabilizing plastic recyclates in particular are proposed, which are highly effective, environmentally friendly and have a favorable cost structure.

In the case of recyclates (in contrast to the known organic phosphites), the present inorganic phosphites act both as hydroperoxide decomposers and as acid scavengers in order to compensate for the increased acid content of the recyclates from the aging process. The latter function is retained even after reaction with hydroperoxides and oxidation of the phosphites to the corresponding phosphate.

According to a preferred embodiment, the at least one inorganic phosphite is selected from the group consisting of metal phosphites of a monovalent, bivalent, trivalent or tetravalent metal, the metal preferably being an alkali metal, an alkaline earth metal, aluminum and/or zinc, sodium phosphite, potassium phosphite , lithium phosphite, calcium phosphite, magnesium phosphite, aluminum phosphite, zinc phosphite, and mixtures and combinations thereof. Also included according to the invention are the corresponding diphosphites and polyphosphites, as well as mixtures of monophosphites and diphosphites and mixed salts such as, for example, calcium-magnesium phosphite.

Due to the structure of the inorganic phosphites and the presence of tautomeric forms, these are also referred to as phosphonates, with the tautomeric equilibrium also being preferably based on the phos phonate structure. These are then salts of phosphorous acid or phosphonic acid. The two terms are considered synonymous here, for example the preferred phosphites can therefore also be referred to as sodium phosphonate, potassium phosphonate, lithium phosphonate, calcium phosphonate, magnesium phosphonate, aluminum phosphonate, zinc phosphonate. Diphosphites and polyphosphites are then referred to as diphosphonates or polyphosphonates.

The inorganic phosphites or phosphonates are commercially available or can be synthesized from phosphorous acid by reaction with, for example, metal oxides, metal hydroxides or metal carbonates using known methods. Sodium phosphite is available, for example, from L. Brüggemann GmbH & Co. KG (Heilbronn, Germany) under the name Brüggolen H 10. Potassium phosphite can, for example, according to US7887616 , Aluminum phosphite according to WO2013083247 or US20200277191 , Calcium phosphite according to WO2015024487 and zinc phosphite according to US4328152 be obtained. A mixed phosphite is, for example, from dolomite according to WO2019238675 accessible. A diphosphite can, for example, according to M. Ebert et al. Collection of Czechoslovak Chemical Communications (1978), 43(12), 3317-24.

The at least one primary antioxidant is preferably selected from the group consisting of H donors, radical scavengers, phenolic antioxidants, (partly) aromatic amines, hydroxylamines or N-oxides (nitrones) and lactones.

It is particularly preferred here if the phenolic antioxidants are selected from the group consisting of 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-(α-methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, linear or branched nonylphenols such as 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6-(1'-methylundec-1'-yl)phenol, 2,4-dimethyl-6-(1'- methylheptadec-1'-yl)phenol, 2,4-dimethyl-6-(1'-methyltridec-1'yl)phenol and mixtures thereof; alkylthiomethyl phenols such as 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol; Hydroquinones and alkylated hydroquinones, such as 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, 2,5-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-,6-tocopherol and mixtures of these (vitamin E); Tocotrienols, tocomomonoenols, ubiquinol, hydroxytyrosol, flavonoids and flavonols such as chrysin, quercitin, hesperidin, neohesperidin, naringin, morin, kaempferol, fisetin, datiscetin, luteolin, apigenin, taxifolin, isoflavones such as genistein, genistin, daidzein, daidzin, formononetin, Anthocyanins, such as delphinidin and malvidin, curcumin, carnosic acid, carnosol, rosmarinic acid, tannin and resveratrol, and carotenoids with alcoholic groups, such as beta-cryptoxanthin, lutein, zeaxanthin or astaxanthin; 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, alkylidene bisphenols, such as 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'-methylenebis(6-tert-butyl-4-ethylphenol), 2 ,2'-methylenebis[4-methyl-6-(a-methylcyclohexyl)phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-nonyl-4-methylphenol ), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(6-tert-butyl -4-isobutyl phenol), 2,2'-methylenebis[6-(α-methylbenzyl)-4-nonylphenol], 2,2'-methylenebis[6-(α,α-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-methylphe nol, 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n -dodecylmercaptobutane, ethylene glycol bis[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl) butyrate], bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene, bis[2- ((3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate, 1,1-bis(3,5-dimethyl-2-hydroxyphenyl)butane , 2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane , 1,1,5,5-tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane; O-, N- and S-benzyl compounds 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-butylbenzylmercaptoacetate, Tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, Bis((4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate, hydroxybenzylated malonates such as dioctadecyl-2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl)malonate, dioctadecyl 2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, didodecylmercaptoethyl 2,2-bis(3,5- di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl) malonate;
aromatic hydroxybenzyl compounds such as 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert- butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol; Triazine compounds such as 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3 ,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3 ,5-triazine, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3;5-tris(3,5- di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 2,4,6-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, 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate; Benzyl phosphonates such as dimethyl 2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate, dioctadecyl-3,5-di-tert-butyl-4- hydroxybenzylphosphonate, dioctadecyl 5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate; the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid; acylaminophenols such as 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate; Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with monohydric or polyhydric alcohols, e.g. methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1, 9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane , 4-Hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane; Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with monohydric or polyhydric alcohols, e.g. methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1, 9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, 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)propiony -loxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with monohydric or polyhydric alcohols, for example methanol , ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N' -bis( hydroxyethyl)oxamide, 3-thiaundecanol , 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane; Esters of (3,5-di-tert-butyl-4-hydroxyphenyl)acetic acid with monohydric or polyhydric alcohols, e.g. methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1, 2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1 -phospha-2,6,7-trioxabicyclo[2.2.2]octane; 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 sold by SI group); Ascorbic Acid (Vitamin C)

The (semi-)aromatic amines are preferably selected from the group consisting of 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-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N-(4 -tert-octylphenyl)-1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, e.g., p,p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol , 4-octadecanoylaminophenol, Bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 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 di-alkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono- and di-alkylated nonyldiphenylamines, a mixture of mono- and di-alkylated Dodecyldiphenylamines, a mixture of mono- and di-alkylated isopropyl/isohexyldiphenylamines, a mixture of mono- and di-alkylated 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 di-alkylated tert-octylphenothiazines, N-allylphenothiazine, N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene, and mixtures or combinations thereof

Preferred hydroxylamines or N-oxides (nitrones) are selected from the group consisting of N,N-dialkylhydroxylamines, N,N-dibenzylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-distearylhydroxylamine, N-benzyl-α- phenylnitron, N-octadecyl-α-hexadecylnitron, and Genox EP (SI Group) according to the formula:

Preferred lactones here are selected from the group consisting of benzofurones and indolinones, in particular are selected from the group consisting of 3-(4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butyl-benzofuran -2-one, 5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one, 3,3'-bis[5,7-di-tert-butyl -3-(4-(2-hydroxyethoxy]phenyl)benzofuran-2-one), 5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one, 3-(4-acetoxy- 3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one, 3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran -2-one, 3-(3,4-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(2,3-dimethylphenyl)-5,7-di-tert-butyl-benzof -uran-2-one, and lactones, which also contain phosphite groups such as

It is also possible to use mixtures or combinations of the aforementioned compounds.

Particularly preferred phenolic antioxidants are from the group consisting of the following compounds

Particularly preferred phenolic antioxidants are here

wobei n von 2 bis 100 beträgt.Preferred arminic antioxidants are formed from the group consisting of the following compounds:

where n is from 2 to 100.

In the further preferred embodiment, the stabilizer composition, based on the polyolefin recyclates, is used in a weight ratio of 0.01 to 10.00% by weight, preferably 0.02 to 5.00% by weight, particularly preferably 0.05 up to 2.00% by weight.

A further preferred embodiment provides that all of the at least one inorganic phosphite and all of the at least one primary antioxidant in a weight ratio of 1:99 to 99:1, preferably 20:80 to 80:20, more preferably 30:70 to 70:30, more preferably from 40:60 to 60:40 can be used.

The polyolefin recyclate preferably contains or consists of polymers selected from the group consisting of polymers made from olefins or diolefins such as polyethylene (LDPE, LLDPE, VLDPE, ULDPE, MDPE, HDPE, UHMWPE), metallocene PE (m-PE ), polypropylene, polyisobutylene, poly-4-methyl-pentene-1, polybutadiene, polyisoprene such as natural rubber (NR), polycyclooctene, polyalkylene-carbon monoxide copolymers, and copolymers in the form of random or block structures such as polypropylene-polyethylene (EP), EPM or EPDM with e.g. 5-ethylidene-2-norbornene as a comonomer, ethylene vinyl acetate (EVA}, ethylene acrylic esters such as ethylene butyl acrylate, ethylene acrylic acid and its salts (ionomers), and terpolymers such as ethylene -Acrylic acid glycidyl (meth)acrylate, graft polymers such as polypropylene graft maleic anhydride, polypropylene graft acrylic acid, polyethylene graft acrylic acid, polyethylene polybutyl acrylate graft maleic anhydride and blends such as LDPE/LLDPE or l contains or consists of chain-branched polypropylene copolymers which are produced with alpha-olefins as comonomers, such as with 1-butene, 1-hexene, 1-octene or 1-octadecene, and also mixtures, combinations or blends of two or more of the aforementioned polymers.

Since processing and separating systems, especially in the case of post-consumer recyclates, often do not deliver material flows of one type, i.e. consisting of 100% polyolefins, the polyolefin recyclate can be used to a lesser extent, i.e. up to 20% by weight, preferably less than 10% by weight, particularly preferably less than 5% by weight % contain other non-polyolefinic fractions. Polyesters such as polyethylene terephthalate or polylactide, polyamides such as polyamide 6 or polyamide 6.6, PVC in the form of hard PVC or soft PVC, styrene polymers such as GPPS, IPS, HIPS, TIPS or ABS can be non-polyolefinic components.

It is also possible for the stabilizer composition to be used in combination with at least one additive, the at least one additive being used, the at least one additive preferably being selected from the group consisting of secondary antioxidants such as phosphites or phosphonites, UV absorbers, Light stabilizers, metal deactivators, filler deactivators, antiozonants, nucleating agents, antinucleating agents, impact modifiers, 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, hydrophobicizing agents, adhesion promoters, dispersing agents, compatibilizers, oxygen scavengers, acid scavengers, blowing agents, Fig au additives, defoamers, odor scavengers, marking agents and antifogging agents, fillers, reinforcing materials and mixtures thereof.

In a preferred embodiment, the compositions contain, in particular, light stabilizers, fillers, acid scavengers, polyol co-stabilizers or compatibilizers.

Preferred fillers are calcium carbonate, silicates, talc, mica, kaolin, metal oxides and metal hydroxides, carbon black, graphite, wood flour or fibers from natural products such as cellulose. Other suitable fillers are hydrotalcites or zeolites or sheet silicates such as montmorillonite, bentonite, beidelite, mica, hectorite, saponite, vermiculite, ledikite, magadite, illite, kaolinite, wollastonite, attapulgite.

Suitable secondary antioxidants are in particular phosphites or phosphonites such as triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tri(nonylphenyl) phosphite, trilauryl phosphites, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris-(2,4-di-tert-butylphenyl) phosphite, diisodecylpentaerythritol diphosphite, bis(2,4 -di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-di-cumylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis(2,4-di -tert-butyl-6-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylenediphos -phonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-di-xaphosphocin, 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-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin, 2,2'2"-nitrilo[triethyl-tris(3,3",5,5'-tetra-tert-butyl- 1,1'-biphenyl-2,2'-diyl)phosphite], 2-ethylhexyl(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl ))phosphite, 5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxaphosphiran.

wobei n= 3-100 bedeutet.Particularly preferred phosphites/phosphonites are:

where n= 3-100.

The phosphite tris-(2,4-di-tert-butylphenyl)phosphite is very particularly preferably used as the secondary antioxidant.
where n = 3-100.

The phosphite tris-(2,4-di-tert-butylphenyl)phosphite is very particularly preferably used as the secondary antioxidant.

A preferred phosphonite is:

Suitable secondary antioxidants are also organo-sulphur compounds such as, for example, sulfides and disulfides, for example distearyl thiodipropionate, dilauryl thiodipropionate; Ditridecyldithiopropionate, Ditetradecylthiodipropionate, 3-(dodecylthio)-,1,1'-[2,2-bis[[3-(dodecylthio)-1-oxopropoxy]methyl]-1,3-propanediyl]propanoic acid ester. The following structures are preferred:

Suitable acid scavengers (“antacids”) are salts of mono, di, tri or tetravalent metals, preferably alkali metals, alkaline earth metals, aluminum or zinc, formed in particular with fatty acids such as calcium stearate, magnesium stearate, zinc stearate, aluminum stearate, calcium laurate, calcium behenate, calcium lactate, Calcium stearoyl-2-lactate. Other classes of suitable acid scavengers are hydrotalcites, in particular synthetic hydrotalcites based on aluminium, magnesium and zinc, hydrocalumites, zeolites, alkaline earth metal oxides, in particular calcium oxide and magnesium oxide and zinc oxide, alkaline earth metal carbonates, in particular calcium carbonate, magnesium carbonate and dolomite and hydroxides, in particular brucite (magnesium hydroxide).

Suitable co-stabilizers are also polyols, in particular alditols or cyclitols. Examples of polyols are pentaerythritol, dipentaerythritol, tripentaerythritol, short-chain polyether polyols or short-chain polyester polyols, and hyperbranched polymers/oligomers or dendrimers with alcohol groups, e.g. e.g.:

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. The at least one preferred alditol is particularly preferably selected from the group consisting of erythritol, mannitol, isomalt, maltitol and mixtures thereof.

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

In particular, the at least one cyclitol can be selected from the group consisting of inositol (myo, scyllo-, D-chiro-, L-chiro-, muco-, neo-, allo-, epi- and cis-inositol), 1,2 ,3,4-tetrahydroxycyclohexane, 1,2,3,4,5-pentahydroxycyclohexane, quercitol, viscumitol, bornesitol, conduritol, ononitol, pinitol, pinpollitol, quebrachitol, ciceritol, quinic acid, shikimic acid and valienol, myo-inositol ( myo-inositol).

Examples of suitable light stabilizers are compounds based on 2-(2'-hydroxyphenyl)benzotriazoles, 2-hydroxybenzophenones, esters of benzoic acids, acrylates, oxamides and 2-(2-hydroxyphenyl)-1,3,5-triazines.

Examples of suitable 2-(2'-hydroxyphenyl)benzotriazoles are 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'-hydroxy-5'-( 2-octyloxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-( 3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl) phenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy- 5'-(2-octyloxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)benzotriazole, 2-(3'-dodecyl -2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2'-methylenebis[4-(1, 1,3,3-tetramethylbutyl)-6-benzotriazol-2-ylphenol]; the transesterification product of 2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazole with polyethylene glycol 300; [R-CH ₂ CH ₂ -COO-CH ₂ CH ₂ -] ₂ where R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl, 2-[2'- Hydroxy-3'-(a,a-dimethylbenzyl)-5'-(1,1,3,3-tetramethylbutyl)phenyl]benzotriazole, 2-[2'-hydroxy-3'-(1,1,3,3 -tetramethylbutyl)-5'-(α,α-dimethylbenzyl)phenyl]benzotriazole.

Examples of suitable 2-hydroxybenzophenones are 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4 ,4'-dimethyloxy derivatives of 2-hydroxybenzophenones.

Examples of suitable acrylates are ethyl α-cyano-β,β-diphenyl acrylate, isooctyl α-cyano-β,β-diphenyl acrylate, methyl α-carbomethoxycinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate, butyl α-cyano-β-methyl-p-methoxycinnamate, methyl α-carbomethoxy-p-methoxycinnamate and N-(β-carbo-methoxy-β-cyanovinyl)-2-methylindoline.

Examples of suitable esters of benzoic acids are 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.

Examples of suitable oxamides are 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.

Examples of suitable 2-(2-hydroxyphenyl)-1,3,5-triazines are 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy- 4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1 ,3,5-triazine, 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl). )-4,6-bis(4-methylphenyl-1,3,5-triazine, 2-(2-Hydroxy-4-dodecyloxyphenyl)-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-4-(2-hydroxy- 3-butyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl ]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[4-(dodecyloxy/tridecyl-oxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis (2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-Hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl-1 ,3,5-triazine, 2-(2-Hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine , 2-(2-Hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2,4,6-Tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy) phenyl]-1,3,5-triazine, 2-(2-Hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine, 2-{2-Hydroxy-4-[3 -(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis(2,4-dimethylphenyl-1,3,5-triazine.

Examples of suitable metal deactivators are N,N'-diphenyloxamide, N-salicylal-N'-salicyloylhydrazine, N,N'-bis(salicyloyl)hydrazine, N,N'-bis(3,5-di-tert-butyl-4- hydroxyphenylpropionyl)hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyldihydrazide, oxanilide, isophthaloyldihydrazide, sebacoylbisphenylhydrazide, N,N'-diacetyladipoyldihydrazide, N,N'-bis(salicyloyl)oxylyldi-hydrazide, N ,N'-Bis(salicyloyl)thiopropionyldihydrazide.

Particularly preferred as metal deactivators are:

Examples of suitable low molecular weight hindered amines are 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-hydroxy-benzylmalonate, 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-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, linear or cyclic condensation products from N,N'-bis(2 ,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine the Re Action product of 7,7,9,9-Tetramethyl-2-cyclo-loundecyl-l-oxa-3,8-diaza-4-oxospiro-[4,5]decane and epichlorohydrin.

Included in the structures given above are the sterically hindered N-H, N-alkyl such as N-methyl or N-octyl, the N-alkoxy derivatives such as N-methoxy or N-octyloxy, the cycloalkyl derivatives such as N-cyclohexyloxy and the N-(2-hydroxy-2-methylpropoxy) analogs.

Preferred hindered amines also have the following structures:

Preferred oligomeric and polymeric hindered amines have the following structures:

In the compounds mentioned above, n is in each case from 3 to 100.

wobei R-O-C(O)-C₁₅H₃₁ oder -O-C(O)-C₁₇H₃₅ bedeutet.Another suitable light stabilizer is Hostanox NOW (manufacturer: Clariant SE) with the following general structure:

where ROC(O)-C ₁₅ H ₃₁ or -OC(O)-C ₁₇ H ₃₅ means.

Compatibilizers or compatibilizers are used, for example, in thermodynamically immiscible blends or in recyclate mixtures and contain structural elements of the respective blend components that are mixed. Suitable compatibilizers for polyolefin blends are, for example, olefin block copolymers consisting of ethylene, propylene and alpha-olefins such as: e.g. 1-octene. Examples of other compatibilizers, in particular for compatibilizing polar polymers such as PET or polyamides, and non-polar polymers such as PP or PE, are polypropylene-g-maleic anhydride, polyethylene-g-maleic anhydride, polypropylene-g-acrylic acid, polyethylene-g-acrylic acid, poly(ethylene- co-maleic anhydride), SBS-g-maleic anhydride or SEBS-g-maleic anhydride.

Examples of suitable dispersing agents are:

Polyacrylates, e.g., copolymers with long chain pendant 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 antinucleating agents are azine dyes such as nigrosine.

Suitable flame retardants are in particular
Inorganic flame retardants such as Al(OH) ₃ , Mg(OH) ₂ , AlO(OH), MgCO ₃ , sheet silicates such as montmorillonite or sepiolite, unmodified or organically modified, double salts such as Mg-Al silicates, POSS (Polyhedral Oligomeric Silsesquioxane) compounds, huntite, hydromagnesite or halloysite as well as Sb ₂ O ₃ , Sb ₂ O ₅ , MoO ₃ , zinc stannate, zinc hydroxystannate,
Nitrogen-containing flame retardants such as melamine, melem, melam, melon, melamine derivatives, melamine condensation products or melamine salts, benzoguanamine, polyisocyanurates, allantoin, phosphacene, in particular melamine cyanurate, melamine phosphate, dimelamin phosphate, melamine pyrophosphate, melamine polyphosphate, melamine metal phosphates such as melamine aluminum phosphate, melamine zinc phosphate, melamine magnesium 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 borate, melamine hydrobromide,
Radical formers, such as alkoxyamines, hydroxylamine esters, azo compounds, triazene compounds, disulfides, polysulfides, thiols, thiuram sulfides, dithiocarbamates, mercaptobenzothiazoles, 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, ethylene diamine diphosphate, phosphinates such as salts of hypophosphorous acid and their derivatives such as alkyl phosphinate salts such as diethyl phosphinate aluminum or diethyl phosphinate zinc or aluminum phosphinate, aluminum phosphite, aluminum phosphonate, Phosphonate esters, oligomeric and polymeric derivatives of methanephosphonic acid, 9,10-dihydro-9-oxa-10-phosphorylphenanthrene-10-oxide (DOPO) and their substituted compounds,
Halogen-containing flame retardants based on chlorine and bromine, such as polybrominated diphenyl oxides, such as decabromodiphenyl oxide, tris(3-bromo-2,2-bis(bromomethyl)propyl phosphate, tris(tribromoneopentyl) phosphate, tetrabromophthalic acid, 1,2-bis(tribromophenoxy )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, polypentabromobenzyl acrylate, possibly in combination with Sb ₂ O ₃ and/or Sb ₂ O ₅ ,
Borates such as zinc borate or calcium borate, optionally on a carrier material such as silica
Sulfur-containing compounds such as elemental sulphur, disulfides and polysulfides, thiuram sulfide, dithiocarbamates, mercaptobenzothiazole and sulfenamides,
anti-drip agents such as polytetrafluoroethylene,
Silicon-containing compounds such as polyphenylsiloxanes,
Carbon modifications such as carbon nanotubes (CNT), expandable graphite or graphene
and combinations or mixtures thereof.

Examples of suitable plasticizers are phthalic acid esters, adipic acid esters, citric acid esters, 1,2-cyclohexanedicarboxylic acid esters, trimellitic acid esters, isosorbide esters, phosphate esters, epoxides such as epoxidized soybean oil or aliphatic polyesters.

Suitable lubricants and processing aids are, for example, polyethylene waxes, polypropylene waxes, salts of fatty acids such as calcium stearate, zinc stearate or salts of montan waxes, amide waxes such as erucic acid amide or oleic acid amides, fluoropolymers, silicones or neoalkoxy titanate and zirconates.

Suitable pigments can be inorganic or organic in nature. Inorganic pigments are, for example, titanium dioxide, zinc oxide, zinc sulfide, iron oxide, ultramarine, carbon black, organic pigments are, for example, anthraquinones, anthanthrones, benzimidazolones, quinacridones, diketopyrrolopyrroles, dioxazines, indanthrones, isoindolinones, azo compounds, perylenes, phthalocyanines or pyranthrones. Other suitable pigments are metal-based effect pigments or metal-oxide-based pearlescent pigments.

Suitable optical brighteners are, for example, bisbenzoxazoles, phenylcoumarins or bis(styryl)biphenyls and in particular optical brighteners of the formulas:

Suitable filler deactivators are, for example, polysiloxanes, polyacrylates, in particular block copolymers such as polymethacrylic acid-polyalkylene oxide or polyglycidyl (meth)acrylates and their copolymers, for example with styrene, and epoxides, for example of the following structures:

Examples of suitable antistatic agents are ethoxylated alkylamines, fatty acid esters, alkylsulfonates and polymers such as polyetheramides.

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

Suitable nucleating agents are talc, alkali metal or alkaline earth metal salts of mono- and polyfunctional carboxylic acids such as. B. 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, and trisamides 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-dimethylpropanamide) or 2,6- naphthalene dicarboxylic acid dicyclohexylamide.

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

Suitable additives for increasing the electrical conductivity are, for example, the antistatic agents mentioned, soot and carbon compounds such as carbon nanotubes and graphene, metal powder such as copper powder and conductive polymers such as polypyrroles, polyanilines and polythiophenes. Examples of suitable additives for increasing the thermal conductivity are aluminum nitrides and boron nitrides.

Examples of suitable infrared-active additives are aluminum silicates, hydrotalcites or dyes such as phthalocyanines or anthraquinones.

Suitable mold release agents are, for example, silicones, soaps and waxes such as montan waxes.

The additive composition described above and any additional additives are incorporated into the plastic using conventional processing methods, with the polymer being melted and mixed with the additive composition according to the invention and any other additives, preferably using mixers, kneaders or extruders. Extruders such as single-screw extruders, twin-screw extruders, planetary roller extruders, ring extruders, co-kneaders, which are preferably equipped with vacuum degassing, are preferred as processing machines. The processing can take place under air or optionally under inert gas conditions.

The present invention also relates to a stabilizer composition according to the invention for stabilizing polyolefin recyclates, in particular against oxidative, thermal and/or actinic degradation, consisting of at least one inorganic phosphite in combination with at least one primary antioxidant.

A preferred embodiment of the stabilizer composition provides that all of the at least one inorganic phosphite in combination with all of the at least one primary antioxidant in a weight ratio of 1: 99 to 99: 1, preferably 20: 80 to 80: 20, more preferably from from 30:70 to 70:30, more preferably from 40:60 to 60:40.

In addition, the present invention relates to a masterbatch or concentrate containing 10 to 90% by weight of a stabilizer composition according to one of the two preceding claims and 90 to 10% by weight of a polyolefin or polyolefin recyclate.

1. A) einer erfindungsgemäßen Stabilisatorzusammensetzung sowie
2. B) einem Polyolefin-Recyclat.

Furthermore, the present invention relates to a plastic composition containing or consisting of

1. A) a stabilizer composition according to the invention and
2. B) a polyolefin recyclate.

1. (A) 0,01 bis 10,00 Gew.-%, bevorzugt 0,02 bis 5,00 Gew.-%, besonders bevorzugt 0,05 bis 2,00 Gew.-% des Stabilisatorzusammensetzung,
2. (B) 85,00 bis 99,98 Gew.-%, bevorzugt 96 bis 99,90 Gew.-% eines Polyolefin-Recyclats, sowie
3. (C) 0,01 bis 5,00 Gew.-%, bevorzugt 0,05 bis 1,00 Gew.-% mindestens eines Zusatzstoffs

enthält oder hieraus besteht.A preferred embodiment provides that the composition

1. (A) 0.01 to 10.00% by weight, preferably 0.02 to 5.00% by weight, particularly preferably 0.05 to 2.00% by weight of the stabilizer composition,
2. (B) 85.00 to 99.98% by weight, preferably 96 to 99.90% by weight, of a polyolefin recyclate, and
3. (C) 0.01 to 5.00% by weight, preferably 0.05 to 1.00% by weight, of at least one additive

contains or consists of.

The plastic composition according to the present invention can also contain at least one additive selected from the group consisting of secondary antioxidants with the exception of phosphites and phosphonites, UV absorbers, light stabilizers, metal deactivators, filler deactivators, antiozonants, nucleating agents, antinucleating agents, impact modifiers, 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, hydrophobicizing agents, adhesion promoters, dispersants, compatibilizers, oxygen scavengers, acid scavengers, blowing agents, degradation additives, defoamers, odor scavengers, marking and antifogging agents, fillers, reinforcing materials, and mixtures thereof.

A preferred embodiment of the plastic composition provides that, based on 100 parts by weight of components (A) to (C), up to 80 parts by weight, preferably 0.1 to 60 parts by weight, particularly preferably 1 to 50 Parts by weight of at least one filler and/or reinforcing material is included.

Furthermore, the present invention relates to a molding compound or a molded part that can be produced from a plastic composition according to the invention described above, in particular in the form of foils (films), in particular agricultural foils such as mulch, tunnel or perforated foils, tapes, hollow bodies and foams, injection molded parts, Fibers, profiles, membranes such as geomembranes and other extrudates, parts from additive or generative manufacturing processes such as fused layer modeling (FLM), layer laminate modeling (LLM), selective laser sintering (SLS) and other 3D printing processes, packaging for food or cosmetic products.

The present invention also relates to a method for the oxidative, thermal and/or actinic stabilization of a recycled polyolefin, in particular against oxidative, thermal and/or actinic degradation, by addition, additization or incorporation of at least one stabilizer composition according to the invention to or in the recycled polyolefin.

• - Verpackungen, insbesondere Verpackungen für Lebensmittel oder Kosmetikprodukte wie Getränkeflaschen, Flaschen für Kosmetik, Reinigungsmitte, Klebstoffe;
• - Bauprodukte wie Baufolien, Rohre wie z.B. Kabelschutzrohre, Drainagerohre, Entwässerungsrinnen, Profile wie Fenster- und Türprofile, Profilbretter
• - Straßenbauprodukte wie Bakenfüße, Pfosten, Absperrungen, Leitzylinder
• - Transportbehälter wie Fässer, Eimer, Tragetaschen, Säcke und Paletten
• - Automobilteile und Teile für die Elektro- und Elektronikindustrie wie Gehäuseteile, Möbel, Haushaltswaren, Sport- und Freizeitgeräte
• - in landwirtschaftlichen Anwendungen, z.B. für die Herstellung von landwirtschaftlichen Folien wie Mulch-, Tunnel oder Lochfolien.

Furthermore, the present invention relates to the use of a plastic composition according to the invention for the production of use of the plastic composition according to the invention for the production of

• - Packaging, in particular packaging for food or cosmetic products such as beverage bottles, cosmetic bottles, cleaning agents, adhesives;
• - Construction products such as construction foils, pipes such as cable protection pipes, drainage pipes, drainage channels, profiles such as window and door profiles, profile boards
• - Road construction products such as beacon bases, posts, barriers, guide cylinders
• - Transport containers such as barrels, buckets, carrier bags, sacks and pallets
• - Automotive parts and parts for the electrical and electronics industry such as housing parts, furniture, household goods, sports and leisure equipment
• - in agricultural applications, eg for the production of agricultural films such as mulch, tunnel or perforated films.

The present invention is explained in more detail using the following examples, without restricting the invention to the specific exemplary embodiments.

Examples:

To test the effect of the stabilizer composition according to the invention, a post-consumer polypropylene recyclate from ground battery boxes (supplier: BSB Braubach) at 210 ° C in a twin-screw microextruder (Micro 5cc, manufacturer DSM) in continuous mode at 200 revolutions per minute during 30 minutes promoted in the melt in a circle. The force absorption is measured after 30 minutes. The force is a measure of the viscosity of the melt and thus of the molecular weight of the polymer. The higher the remaining force, the less degradation of the polymer.

The addition of 0.2% sodium phosphite results in a higher residual stability than the recyclate without the addition, by adding 0.1% sodium phosphite and 0.1% pentaerythritol-tetrakis [3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate, the residual stability can be further increased.

QUOTES INCLUDED IN DESCRIPTION

This list of documents cited by the applicant was generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

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Claims (21)

Use of at least one stabilizer composition containing or consisting of at least one inorganic phosphite in combination with at least one primary antioxidant for stabilizing polyolefin recyclates, in particular against oxidative, thermal and/or actinic degradation. use after claim 1 , characterized in that the at least one inorganic phosphite is selected from the group consisting of metal phosphites of a mono-, di-, tri- or tetravalent metal, the metal preferably being an alkali metal, an alkaline earth metal, aluminum and/or zinc, sodium phosphite , potassium phosphite, lithium phosphite, calcium phosphite, magnesium phosphite, aluminum phosphite, zinc phosphite, and mixtures and combinations thereof. Use according to one of the preceding claims, characterized in that the at least one primary antioxidant is selected from the group consisting of H donors, radical scavengers, phenolic antioxidants, (partly) aromatic amines, hydroxylamines or N-oxides (nitrones) and lactones . Use according to the preceding claim, characterized in that a) the phenolic antioxidants are selected from the group consisting of alkylated monophenols, such as 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6- dimethylphenol, 2,6-di-tert-butyl-4-ethyl-phenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2, 6-dicyclopentyl-4-methylphenol, 2-(α-methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl- 4-methoxymethyl-phenol, linear or branched nonylphenols such as 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6-(1'-methylundec-1'-yl)phenol, 2,4-dimethyl- 6-(1'-methylheptadec-1'-yl)phenol, 2,4-dimethyl-6-(1'-methyltridec-1'yl)phenol and mixtures thereof; alkylthiomethyl phenols such as 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol; Hydroquinones and alkylated hydroquinones, such as 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, 2,5-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-, 6-tocopherol and mixtures of these (vitamin E); Tocotrienols, tocomomonoenols, ubiquinol, hydroxytyrosol, flavonoids and flavonols such as chrysin, quercitin, hesperidin, neohesperidin, naringin, morin, kaempferol, fisetin, datiscetin, luteolin, apigenin, taxifolin, isoflavones such as genistein, genistin, daidzein, daidzin, formononetin, Anthocyanins, such as delphinidin and malvidin, curcumin, carnosic acid, carnosol, rosmarinic acid, tannin and resveratrol, and carotenoids with alcoholic groups, such as beta-cryptoxanthin, lutein, zeaxanthin or astaxanthin; Hydroxylated thiodiphenyl ethers such as 2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'-thiobis((4-octyl phenol), 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, alkylidene bisphenols, such as 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'-methylenebis(6-tert-butyl-4-ethylphenol), 2, 2'-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol], 2,2'-methylenebis(4-methyl-6-cyclhexylphenol), 2,2'-methylenebis(6-nonyl- 4-methylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(6- tert-butyl-4-isobutyl phenol), 2,2'-methylenebis[6-(α-methylbenzyl)-4-nonyl phenol], 2,2'-methylenebis[6-(α,α-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-methyl phenol, 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3- n-dodecyl mercaptobutane, ethylene glycol bis[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl) butyrate], bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene, bis [2-((3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate, 1,1-bis(3,5-dimethyl-2- hydroxyphenyl)butane, 2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-4 -n-dodecylmercaptobutane, 1,1,5,5-tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane; O-, N- and S-benzyl compounds 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-butyl-benzylmercaptoacetate, Tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, Bis((4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate, hydroxybenzylated malonates such as dioctadecyl-2 ,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate, Dioctadecyl 2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, Didodecylmercaptoethyl 2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, Bis[4-( 1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate; aromatic hydroxybenzyl compounds such as 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert- butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol; Triazine compounds such as 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3 ,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3 ,5-triazine, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3;5-tris-(3,5-di -tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 2,4,6-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, 1,3,5-tris-(3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate; Benzyl phosphonates such as dimethyl 2,5-di-tert-butyl-4-hydroxy-benzylphosphonate, diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di-tert-butyl- 4-hydroxybenzylphosphonate, dioctadecyl 5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate; the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxy-benzylphosphonic acid; 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 monohydric or polyhydric alcohols, e.g. methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1, 9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane; Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with monohydric or polyhydric alcohols, e.g. methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1, 9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, 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-tetraoxaspiro[5.5]undecane, esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with monohydric or polyhydric alcohols, for example methanol, ethanol , octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane; Esters of (3,5-di-tert-butyl-4-hydroxyphenyl)acetic acid with monohydric or polyhydric alcohols, e.g. methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1, 2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha -2,6,7-trioxabicyclo[2.2.2]octane; 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 sold by Uniroyal); ascorbic acid (vitamin C); b) the aminic antioxidants are selected from the group consisting of 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-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1 -naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, e.g. p,p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis( 4-metho xyphenyl)amine, 2,6-di-tert-butyl-4-dimethylaminomethyl-phenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N,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, 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 di-alkylated isopropyl/isohexyldiphenylamines, Mixture of mono- and di-alkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, mixture of mono- and di-alkylated tert-butyl/tert-octylphenothiazines, a mixture of mono- and di-alkylated tert-octylphenothiazines, N-allylphenothiazine, N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene and mixtures or combinations thereof, c) the hydroxylamines or N-oxides (nitrones) are selected from the group consisting of N,N-dialkylhydroxylamines, N,N-dibenzylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-distearylhydroxylamine, N-benzyl-α -phenylnitron, N-octadecyl-α-hexadecylnitron, as well as Genox EP (SI Group) according to the formula:

d) the lactones are selected from the group consisting of benzofurones and indolinones, in particular are selected from the group consisting of 3-(4-(2-acetoxyethoxy)-phenyl]-5,7-di-tert-butyl-benzofuran-2 -one, 5,7-di-tert-butyl-3-[4-(2-stearoyloxy-ethoxy)phenyl]benzofuran-2-one, 3,3'-bis[5,7-di-tert-butyl -3-(4-(2-hydroxyethoxy]phenyl)benzofuran-2-one), 5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one, 3-(4-acetoxy- 3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one, 3-(3,5-dimethyl-4-pivaloyloxy-phenyl)-5,7-di-tert-butyl-benzofuran -2-one, 3-(3,4-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(2,3-dimethylphenyl)-5,7-di-tert-butyl-benzofuran -2-one, and lactones, which also contain phosphite groups such as

e) and mixtures and combinations thereof. Use according to one of the two preceding claims, characterized in that the phenolic antioxidants are selected from the group consisting of the following compounds

Use according to one of the two preceding claims, characterized in that the phenolic antioxidants are selected from the group consisting of the following compounds

Use according to one of the preceding claims, characterized in that the aminic antioxidants are selected from the group consisting of the following compounds:

where n is from 2 to 100. Use according to one of the preceding claims, characterized in that the stabilizer composition, based on the polyolefin recyclates in a weight ratio of 0.01 to 10.00% by weight, preferably 0.02 to 5.00% by weight, particularly preferably from 0.05 to 2.00% by weight. Use according to any one of the preceding claims, characterized in that all of the at least one inorganic phosphite and all of the at least one primary antioxidant in a weight ratio of 1: 99 to 99: 1, preferably 20: 80 to 80: 20, more preferably from 30:70 to 70:30, more preferably from 40:60 to 60:40 can be used. Use according to one of the preceding claims for stabilizing plastics, the polyolefin recyclate being polymers selected from the group consisting of polymers made from olefins or diolefins such as polyethylene (LDPE, LLDPE, VLDPE, ULDPE, MDPE, HDPE, UHMWPE), metallocene -PE (m-PE), polypropylene, polyisobutylene, poly-4-methyl-pentene-1, polybutadiene, polyisoprene such as natural rubber (NR), polycyclooctene, polyalkylene-carbon monoxide copolymers, and copolymers in the form of random or block structures such as e.g. polypropylene-polyethylene (EP), EPM or EPDM with e.g. 5-ethylidene-2-norbornene as a comonomer, ethylene vinyl acetate (EVA}, ethylene acrylic esters such as e.g. ethylene butyl acrylate, ethylene acrylic acid and its salts (ionomers), as well as Terpolymers such as ethylene acrylic acid glycidyl (meth)acrylate, graft polymers such as polypropylene graft maleic anhydride, polypropylene graft acrylic acid, polyethylene graft acrylic acid, polyethylene polybutyl acrylate graft maleic anhydride rid and blends such as LDPE/LLDPE or long-chain branched polypropylene copolymers which are produced with alpha-olefins as comonomers such as 1-butene, 1-hexene, 1-octene or 1-octadecene, and mixtures, combinations or blends of two or more contains or consists of the aforementioned polymers. Use according to one of the preceding claims, characterized in that the stabilizer composition in combination with at least one additive, in particular at least one additive selected from the group consisting of secondary antioxidants with the exception of phosphites and phosphonites, UV absorbers, light stabilizers, metal deactivators, filler deactivators, antiozonants , nucleating agents, antinucleating agents, impact modifiers, lubricants, rheology modifiers, thixotropy 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, hydrophilicizing agents, hydrophobicizing agents, adhesion promoters, dispersing agents , compatibilizers, oxygen scavengers, acid scavengers, blowing agents, degradation additives, Ent foaming agents, odor scavengers, marking agents and anti-fogging agents, fillers, reinforcing materials and mixtures thereof. Stabilizer composition for stabilizing polyolefin recyclates, in particular against oxidative, thermal and/or actinic degradation, consisting of at least one inorganic phosphite in combination with at least one primary antioxidant. Stabilizer composition according to the preceding claim, characterized in that all of the at least one inorganic phosphite in combination with all of the at least one primary antioxidant in a weight ratio of 1: 99 to 99: 1, preferably 20: 80 to 80: 20, more preferably from from 30:70 to 70:30, more preferably from 40:60 to 60:40. Masterbatch or concentrate containing 10 to 90% by weight of a stabilizer composition according to one of the two preceding claims, and 90 to 10% by weight of a polyolefin or polyolefin recyclate. Plastic composition containing or consisting of A) a stabilizer composition according to one of Claims 12 until 13 and B) a polyolefin recyclate. Composition according to the preceding claim, characterized in that the composition (A) 0.01 to 10.00% by weight, preferably 0.02 to 5.00% by weight, more preferably 0.05 to 2.00% by weight of the stabilizer composition, (B) 85.00 to 99.98% by weight, preferably 96 to 99.90% by weight, of a polyolefin recyclate, and (C) 0.01 to 5.00% by weight, preferably 0.05 to 1.00% by weight. -% contains or consists of at least one additive. Plastic composition according to the preceding claim, characterized in that the at least one additive is selected from the group consisting of secondary antioxidants with the exception of phosphites and phosphonites, UV absorbers, light stabilizers, metal deactivators, filler deactivators, antiozonants, nucleating agents, antinucleating agents, impact modifiers, 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, hydrophilicizing agents, hydrophobicizing agents, adhesion promoters, dispersing agents, compatibilizers, oxygen scavengers, acid scavengers, blowing agents, degradation -Additives, defoamers, odor scavengers, marking agents and antifogging agents, fillers substances, reinforcing substances and mixtures thereof. Plastic composition according to one of the two preceding claims, that, based on 100 parts by weight of components (A) to (C), up to 80 parts by weight, preferably 0.1 to 60 parts by weight, particularly preferably 1 to 50 Parts by weight of at least one filler and/or reinforcing material is included. i) Plastic composition according to one of the two preceding claims, characterized in that the nucleating agents are selected from the group consisting of talc, alkali metal or alkaline earth metal salts of mono- and polyfunctional carboxylic acids, in particular of benzoic acid, succinic acid, adipic acid, for example sodium benzoate and aluminum hydroxy- bis(4-tert-butyl)benzoate; Zinc glycerolate, 2,2'-methylene-bis-(4,6-di-tert-butylphenyl) phosphate, trisamides 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), 2,6-naphthalenedicarboxylic acid dicyclohexylamide; and/or orotic acid; ii) Fillers and/or reinforcing materials are selected from the group consisting of calcium carbonates, silicates, talc, mica, kaolins, metal oxides, metal hydroxides, carbon black, graphite, wood flour, fibers from natural products such as cellulose, glass fibers, carbon fibers, polyaramid fibers and other synthetic fibers Polymer fibers, hydrotalcites, zeolites and/or phyllosilicates such as montmorillonite, bentonite, beidelite, mica, hectorite, saponite, vermiculite, ledikite, magadite, illite, kaolinite, wollastonite, attapulgite. iii) acid scavenger salts of mono, di, tri or tetravalent metals, preferably alkali metals, alkaline earth metals, aluminum or zinc, formed in particular with fatty acids such as calcium stearate, magnesium stearate, zinc stearate, aluminum stearate, calcium laurate, calcium behenate, calcium lactate, calcium stearoyl-2-lactate . Other classes of suitable acid scavengers are hydrotalcites, in particular synthetic hydrotalcites based on aluminium, magnesium and zinc, hydrocalumites, zeolites, alkaline earth metal oxides, in particular calcium oxide and magnesium oxide and zinc oxide, alkaline earth metal carbonates, in particular calcium carbonate, magnesium carbonate and dolomite, and hydroxides, in particular brucite (magnesium hydroxide) iv ) Light stabilizers are selected from the group consisting of hindered amines. Molding compound or molding producible from a plastic composition according to one of Claims 15 until 18 , in particular in the form of foils (films), in particular agricultural foils such as mulch, tunnel or perforated foils, tapes, hollow bodies and foams, injection molded parts, fibers, profiles, membranes, such as geomembranes and other extrudates, parts from additive or generative manufacturing processes, such as Fused Layer Modeling (FLM), Layer Laminate Modeling (LLM), Selective Laser Sintering (SLS) and other 3D printing processes, packaging for food or cosmetic products. Process for the oxidative, thermal and/or actinic stabilization of a polyolefin recyclate, in particular against oxidative, thermal and/or actinic degradation, by addition, additization or incorporation of at least one stabilizer composition according to the invention to or in the polyolefin recyclate. Use of the plastic composition according to one of Claims 15 until 18 , for the manufacture of - packaging, in particular packaging for foodstuffs or cosmetic products, such as beverage bottles, cosmetic bottles, cleaning agents, adhesives; - Construction products such as construction foils, pipes such as cable protection pipes, drainage pipes, drainage channels, profiles such as window and door profiles, profile boards - Road construction products such as beacon bases, posts, barriers, guide cylinders - Transport containers such as barrels, buckets, carrier bags, sacks and pallets - Automotive parts and parts for the electrical and electronics industry such as housing parts, furniture, household goods, sports and leisure equipment - in agricultural applications, e.g the production of agricultural foils such as mulch, tunnel or perforated foils.