EP3914641A1

EP3914641A1 - Method of stabilizing halogen-free thermoplastic recyclates, plastics composition, stabilizer composition and use of the stabilizer composition

Info

Publication number: EP3914641A1
Application number: EP20702106.4A
Authority: EP
Inventors: Rudolf Pfaendner; Elke METZSCH-ZILLINGEN
Original assignee: Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Current assignee: Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Priority date: 2019-01-24
Filing date: 2020-01-24
Publication date: 2021-12-01
Also published as: JP7464611B2; CN113348205A; BR112021013753A2; CN113348205B; MX2021008425A; US20220119624A1; DE102019200905A1; KR20210122267A; JP2022518047A; WO2020152337A1

Abstract

The invention relates to a method of stabilizing halogen-free thermoplastic recyclates against oxidative, thermal and/or actinic degradation. The invention also relates to a correspondingly stabilized plastics composition, a stabilizer composition for stabilizing halogen-free thermoplastic recyclates and uses thereof.

Description

Process for stabilizing halogen-free thermoplastic recycled plastics, plastic composition. Stabilizer composition and use of the stabilizer composition The present invention relates to a method for stabilizing halogen-free thermoplastic recycled plastics against oxidative, thermal and / or actinic degradation. The present invention also relates to a correspondingly stabilized plastic composition, a stabilizer composition for stabilizing halogen-free thermoplastic recycled plastics, and uses thereof.

Plastic recyclates are a growing market and an important element in the circular economy of raw materials. Ideally, recyclates should replace new plastics with an identical or at least a comparable property profile. However, with recyclates it comes from the

Production of plastic parts (so-called "post industrial" recyclates) and above all for waste plastics (so-called "post-consumer" recyclates) during the first processing steps (e.g. compounding, injection molding) and the application often over many years to irreversible changes in the polymer chain due to mechano-chemical, chemical or light-induced processes (see e.g. R. Pfaendner et al., Angew. Makromol. Chemie 1995, 232, 193-227, J. Pospisil et al., Pol. Degr. Stab. 1995, 48, 351-358). Radical reactions in the presence of oxygen, generally 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 groups formed in the aging process are often carbonyl, aldehyde or acid groups, in particular polyolefins such as polyethylene or polypropylene. The concentration of these newly formed groups increases with the time of use and the area of use (UV light, high temperatures, contact media). The structural inhomogeneities of a recyclate influence the plastic properties, such as the mechanical properties. Furthermore, recyclates or previously damaged plastics are more sensitive to oxidation than new material, since degradation products act as initiators for further oxidation or as product degradants (AS Maxwell, Pol. Eng. Sei. 2008, 381-385, IH Craig, JR White, J. Mater .. Be. 2006, 41, 993-1006). Post-stabilization with selected stabilizers, such as antioxidants, is an essential method to improve the quality of plastic recyclates. The stabilizers used protect the recyclate from further oxidative (or photooxidative) damage or at least delay it. Due to the structural deviations of the recyclate and the new goods described, the optimized stabilizer composition for a recyclate also differs from the stabilizing composition of the new goods (see, for example, R. Pfaendner, Kunststoffe International 12/2015, 41-44).

Due to the currently recognized differences between new plastics and recycled plastics, special recyclate stabilizer compositions are known and are also available as commercial products (for example Recyclostab products from BYK-Chemie GmbH, Wesel). Known technical stabilization solutions that take the requirements of recyclates into account 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 (US 6525158, US 6251972).

Stabilizing composition consisting of a phenolic antioxidant and a polyfunctional epoxide (EP 0702704).

Stabilization using a macrocyclic piperidine (US 5789470).

Stabilizing composition consisting of a secondary aromatic amine and a polyfunctional epoxide (WO 97/30112).

Decolorization of damaged pololefins by a hydroxylamine (EP 0470048)

Mixture of antioxidants, lubricants, antiblocking agents, UV stabilizers and antistatic agents for recycled films (DD 288161)

Stabilizing composition for mixed plastics consisting of a phenolic antioxidant and a phosphite / phosphonite (EP 0506614)

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

Previous recyclate stabilizers (see above) are modifications of stabilizers for new plastics, none of the combinations mentioned enables an interaction or reaction with the carbonyl groups that frequently occur during aging / oxidation. The present invention thus represents a new approach in the stabilization of recycled plastics. WO 97/30112 describes stabilizing compositions consisting of a secondary aromatic amine and a polyfunctional epoxide. However, these are (partially) aromatic amines and not aliphatic amines. EP 0470048 (see Appendix, decolorization of damaged pololefins by a hydroxylamine. The hydroxylamines mentioned there have a free OH group and thus differ structurally from the hydroxylamine ethers or hydroxylamine esters mentioned which contain a free amino group.

The object of the present invention is therefore to specify means and ways of stabilizing halogen-free thermoplastic recycled plastics.

This object is achieved with regard to a stabilization method with the features of patent claim 1, with regard to a stabilized plastic recyclate composition with the features of patent claim 11, with regard to a stabilizer composition with the features of patent claim 20 and with the purposes of using the stabilizer composition solved the features of claim 24. The respective dependent patent claims represent advantageous developments.

The subject matter of the present invention therefore flows in a first aspect: a method for stabilizing halogen-free thermoplastic recycled plastics against oxidative, thermal and / or actinic degradation, in which

(A) at least one compound capable of reacting with carbonyl groups, in combination with

(B) at least one primary antioxidant and / or

(C) at least one secondary antioxidant, be introduced into a halogen-free thermoplastic recycled plastic, whereby no alditols and cyclitols are used.

Surprisingly, it was found that compounds which can react with the carbonyl groups present in their plastic recyclates have a high potential to effectively protect the corresponding plastic recyclates against oxidative, thermal and / or actinic degradation.

According to a preferred embodiment, the at least one compound capable of reacting with carbonyl groups is selected from the group consisting of primary aliphatic amines, secondary aliphatic amines, thiols, hydroxylamine ethers, hydroxylamine esters, hydrazines, oligomers or polymers with alcohol groups such as polyvinyl alcohols and bonded to aliphatic carbons their copolymers with vinyl acetate or polyhydroxy (meth) acrylates and hydantoins or thiohydantoins.

Exemplary oligomers / polymers with alcohol groups bound to aliphatic carbons are, for example, the compounds having the structures shown below:

In connection with the aforementioned connections, the index n preferably denotes 1 to 10.

The at least one compound capable of reacting with carbonyl groups is particularly advantageously selected from the group consisting of laurylamine, stearylamine, hexamethylenediamine, decanediamine, dodecanediamine, dilaurylamine, distearylamine, 1-dodecanethiol, 1-hexadecanethiol, polycaprolactone tetra-3-mercaptopropionate, Polvinyl alcohol with a weight-average molecular weight of 1,000 to 50,000 g / mol, polyhydroxy (meth) acrylates with a weight-average molecular weight of 1,000 to 50,000 g / mol, imidazolidine-2,4-dione, and compounds with the following structures:

According to the present invention, a plastic recyclate is understood to mean a plastic recyclate according to the conceptual definition according to standard DIN EN 15347: 2007. There are also relevant international standards for many types of recycled plastic. For example, DIN EN 15353: 2007 applies to recycled PET plastics. PS recyclates are described in more detail in DIN EN 15342: 2008. PE recyclates are dealt with in DIN EN 15344: 2008. PP recyclates are characterized in DIN EN 15345: 2008. For the purpose of the corresponding special plastic recyclates, the present patent application adopts the definitions of these international standards.

Recycled plastics, in contrast to new plastics, mostly show previous damage, ie new chemical groups are generated on the polymer chain by oxidative or (photo) oxidative processes. In the case of polyolefins, for example, these are predominantly carbonyl groups, which are not present or are only present to a very minor extent in new goods. The concentration of the carbonyl groups is therefore also a measure of the pre-damage to the Polymers. The concentration of carbonyl groups can be determined by known analytical methods such as infrared spectroscopy, as described, for example, in E. Richaud et al. Pole. Degr. Rod. 2009, 94, 410-420. The absorption of the carbonyl vibration is measured in the range of 1720 cm ^-1 .

According to the invention, “halogen-free” means that the thermoplastic contains less than 1% of halogen-containing polymers, such as PVC or PVDC. The halogen-free thermoplastic preferably contains less than 0.5%, particularly preferably less than 0, 1%, of halogen-containing polymers, very particularly preferably the halogen-free thermoplastic contains no halogen-containing polymers at all.

In the process according to the invention, at least one compound (component (A)) capable of reacting with carbonyl groups is thus combined with at least one primary antioxidant (component (B)) and / or at least one secondary antioxidant (component (C)) a halogen-free thermoplastic recycled material was introduced. Components (A) to (C) can be introduced individually or separately into the recycled plastic. Alternatively, it is possible that components (A) to (C) together in the form of a composition comprising components (A) to (C) or in the form of a composition consisting of components (A) to (C) in the recycled plastic can be introduced.

If at least one primary antioxidant and at least one secondary antioxidant are used, these can also be introduced into the plastic recyclate individually or separately or together in the form of a mixture.

The component (A) used according to the invention in combination with the component (B) and / or component (C) used in addition to component (A) together act as a stabilizer for the halogen-free thermoplastic recycled plastic, the oxidative, thermal and / or actinic degradation of the halogen-free thermoplastic recycled plastic is inhibited or prevented. In other words, by introducing the Component (A) and, if necessary, additionally component (B) in the halogen-free thermoplastic recycled plastic, the plastic stabilized against oxidative, thermal and / or actinic degradation.

The halogen-free thermoplastic recycled plastics used in the process according to the invention is preferably a polyolefin recycled material, e.g. a polypropylene recyclate or a polyethylene recyclate.

The composition according to the invention is also particularly suitable for stabilizing previously damaged recyclates, in particular polyolefin recyclates whose carbonyl group content, determined by absorption in the infrared spectrum, is at least 0.01 mol / kg, preferably greater than 0.02 mol / kg and particularly preferably greater than 0.05 mol / kg is.

In a preferred embodiment, the at least one primary antioxidant (B) is selected from the group consisting of phenolic antioxidants, hydroxylamines, lactones and mixtures thereof.

Examples of phenolic antioxidants that can be used are:

Alkylated monophenols, e.g. 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, linear or branched nonylphenols, such as, for example 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;

Alkylthiomethylphenols, e.g. 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, e.g. a-, b-, y-, d-tocopherol and mixtures of these (vitamin E);

Hydroxylated thiodiphenyl ethers, e.g. 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, e.g. 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-cyclhexylphenol), 2,2'-methylenebis (6-nonyl-4-methylphenol), 2,2'-methylenebis (4,6-di -tert-butylphenol), 2,2'-ethylidenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis [6- (a-methylbenzyl) -4-nonylphenol], 2,2'-methylenebis [6- (a, a-dimethylbenzyl) -4-nonylphenol], 4,4'-methylenebis- (2,6-di- tert-butylphenol, 4,4'-methylenebis (6-tert-butyl-2-methylphenol), 1,1- bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis ( 3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1,1-bis (5th -tert-butyl-4-hydroxy-2-methylphenyl) -3-n-do-decyl 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'-methylbene zyl) -6-tert-butyl-4-methylphenyl] terephthalate, 1,1-bis (3,5-dimethyl-2-hydroxyphenyl) butane, 2,2-bis (3,5-di-tert-butyl) -4-hydroxyphenyl) propane, 2,2-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecyl mercaptobutane, 1,1,5,5-tetra (5-tert -butyl-4-hydroxy-2-methylphenyl) pentane;

O-, N- and S-benzyl compounds, such as 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate , 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 -dimethyl-benzyl) dithioterephthalate, bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, iso- octyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate;

Hydroxybenzylated malonates, e.g. Dioctadecyl-2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, dioctadecyl-2- (3-tert-butyl-4-hydroxy-5-methyl-benzyl) 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, e.g. 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3,5-di-tert-butyl-4-hydroxy) - benzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) phenol;

Triazine compounds, e.g. 2,4-bis (octylmercapto) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,3,5-triazine , 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,2,3-triazine, 1,3,5-tris (3,5-di-tert-butyl- 4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris (3,5-di-tert-butyl -4-hydroxphenylethyl) -1,3,5-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexahydro-1,3,5-triazine, 1,3, 5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate;

Benzylphosphonates, e.g. Dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, Dietyhl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, di-octadecyl-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, e.g. 4-hydroxylauranilide, 4-hydroxystearanilide, octyl-N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate;

Esters of b- (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, trimethylol propane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane;

Esters of b- (5-tert-butyl-4-hydroxy-3-methylphenyl) 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-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 b- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid with mono- 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;

Esters of (3,5-di-tert-butyl-4-hydroxyphenyl) acetic acid with mono- 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 b- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, such as, for example, 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 (3rd , 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, var driven by additive);

Ascorbic acid (vitamin C).

The following structures are particularly preferred phenolic antioxidants:

Particularly preferred phenolic antioxidants are octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate and pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate)

Other preferred phenolic antioxidants are phenolic antioxidants based on renewable raw materials such as. B. tocopherols (vitamin E), tocotrienols, tocomonoenols, carotenoids, hydroxytyrosol, flavonols such as e.g. Chrysin, Quercitin, Hesperidin, Neohesperidin, Naringin, Morin, Kaempferol, Fisetin, Anthocyanins, e.g. Delphinidin and Malvidin, Curcumin, Carnosolic acid, Carnosol, Rosmarinsäure, Tannin and Resveratrol. The phenolic antioxidant pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate or octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate is very particularly preferred as primary antioxidant used.

The following can be used as aminic antioxidants:

N, N'-di-isopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-bis (1,4-dimethylpentyl) -p-phenylenediamine, N, N ' -Bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N'-bis (1-methylheptyl) -p-phenylenediamine, N, N'-dicyclohexyl-p-phenylenediamine, N, N'- Diphenyl-p-phenylenediamine, N, N'- bis (2-naphthyl) -p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl- p-phenylene diamine, N- (1-methylheptyl) -N'- phenyl-p-phenylene diamine, N-cyclohexyl-N'-phenyl-p-phenylene diamine, 4- (p-toluenesulfamoyl) diphenylamine, N, N'- Dimethyl-N, N'-di-sec-butyl-p-phenylene-diamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N- (4-tert-octylphenyl) -l-naphthylamine , N-phenyl-2-naphthylamine, octylated diphenylamine, for example p, p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylamino-phenol, bis (4-methoxyphenyl) amine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N, N, N ', N'-tetramethyl-4,4'-diaminodiphenylmethane, 1,2-bis [(2-methylphenyl) amino] ethane, 1,2-bis (phenylamino) propane, (o-tolyl) biguanide, bis [4- (1 ', 3'-dimethylbutyl) phenyl] amine, tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- and dialkylated tert-butyl / tert-octyldiphenylamines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl / isohexyl-diphenylamines, a mixture of mono - and dialkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a mixture of mono- and dialkylated tert-butyl / tert-octylphenothiazines, a mixture of mono- and dialkylated ter t-octylphenothiazines, N-allylphenothiazine, N, N, N ', N'-tetraphenyl-1,4-diaminobut-2-ene and mixtures or combinations thereof.

Preferred amine antioxidants are:

N, N'-di-isopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-bis (1,4-dimethylpentyl) -p-phenylenediamine, N, N ' -Bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N'-bis (l-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-phenylene diamine, N- (1-methylheptyl) -N'-phenyl-p-phenylene diamine, N-cyclohexyl-N'-phenyl-p-phenylene diamine.

Further preferred antioxidants are hydroxylamines or their N-oxides (nitrones) such as e.g. N, N-dialkylhydroxylamine, N, N-dibenzylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-distearylhydroxylamine, N-benzyl-a-phenylnitron, N-octadecyl-a-hexadecylnitron, as well as Genox EP (sold by Addivant) according to the Formula:

Preferred lactones are:

Benzofuranones and indolinones such as e.g. 3- (4- (2-acetoxyethoxy) phenyl] -5,7-di-tert-butyl-benzofuran-2-one, 5,7-di-tert-butyl-3- [4- (2-stearoyloxyethoxy) - phenyl] benzofuran-2-one, 3,3'-bis [5,7-di-tert-butyl-3- (4- (2-hydroxyethoxy] phenyl) benzofuran-2-one), 5,7-di tert-butyl-3- (4-ethoxyphenyl) benzofuran-2-one, 3- (4-acetoxy-3,5-dimethylphenyl) -5,7-di-tert-butyl-benzofuran-2-one, 3- (3,5-dimethyl-4-pivaloyloxyphenyl) -5,7-di-tert-butyl-benzofuran-2-one, 3- (3,4-dimethylphenyl) -5,7-di-tert-butyl-benzofuran 2-one, 3- (2,3-di-methyl-phenyl) -5,7-di-tert-butyl-benzofuran-2-one, and lactones which additionally have a phosphite group, such as, for example

Another suitable group of antioxidants are isoindolo [2,1-A] quinazolines such as, for example

Another preferred variant of the method according to the invention is characterized in that the at least one secondary antioxidant is selected from the group consisting of phosphorus compounds, in particular phosphites and phosphonites, organosulfur compounds, in particular sulfides and disulfides, and Mixtures of these.

The following can be used as phosphites or phosphonites:

Triphenylphosphite, diphenylalkylphosphite, phenyldialkylphosphite, tri (nonylphenyl) phosphite, trilaurylphosphite, trioctadecylphosphite, distearylpenta- erythritol diphosphite, tris- (2,4-di-tert-butylphenyl) phosphite, diisodecylpenta- di-tert-bisthritol -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, tristearitylsorbitol trisphosphorus tritearitol, di-tert-butylphenyl) -4,4'-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz [d, g] -1,3,2-dioxaphosphocin, 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 [triethyltris (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-dioxaphosphirane.

Particularly preferred phosphites / phosphonites are:

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

Preferred sulfur compounds are:

Distearyl thiodipropionate, dilauryl thiodipropionate; Ditridecyldithiopropionate, Ditetradecylthiodipropionat, 3- (dodecylthio) -1,1 '- [2,2-bis [[3- (dodecylthio) -1-oxopropoxy] methyl] -1,3-propanediyl] propanoic acid ester. Sulfur compounds with the following structures are particularly preferably used:

In the event that both a primary and a secondary antioxidant are used in the process, it is preferred if component (B) (primary antioxidant) is a phenolic antioxidant and component (C) (secondary antioxidant) is a phosphite or Is phosphonite.

In a further preferred embodiment, components (B) and (C) consist of a renewable raw material.

According to a further preferred variant of the process according to the invention, component (A) is in a weight ratio to component (B) and / or component (C) from 90:10 to 10:90, preferably from 80:20 to 20:80, particularly preferably from 60:40 to 40:60, introduced into the halogen-free thermoplastic recycled plastic.

It is also advantageous that, based on the total weight of the plastic recyclate and component (A) to (C), 0.02 to 3.00% by weight, preferably 0.03 to 1.00% by weight. %, particularly preferably 0.02 to 0.50% by weight, in particular 0.10 to 0.30% by weight, of the at least one compound (A) capable of reacting with carbonyl groups, and 0.02 to 3 .00% by weight, preferably 0.03 to 1.00% by weight, particularly preferably 0.02 to 0.50% by weight, in particular 0.05 to 0.20% by weight of the at least one primary antioxidant (B) and / or 0.02 to 3.00% by weight, preferably 0.03 to 1.00% by weight, particularly more preferably 0.02 to 0.50% by weight, in particular 0.05 to 0.20% by weight, of the at least one secondary antioxidant (C) are introduced into the halogen-free thermoplastic recycled plastic.

The components (A) and (B) and / or (C) can be introduced into the halogen-free thermoplastic recycled plastic by the components (A) and (B) and / or (C) present as a solid with the Halogen-free thermoplastic recycled plastics present as a solid are mixed and the resulting mixture is melted and then cooled, or the components (A) and (B) and / or (C) present as a solid are melted and the resulting melt is melted Melt of the halogen-free thermoplastic recycled plastic is introduced.

Components (A), (B), and / or (C), which may be in the form of powder, compacted, granules, solution or flakes, are preferably mixed with the polymer to be stabilized, the polymer matrix is converted into the melt and then cooled . As an alternative to this, it is also possible to introduce the additive into a polymer melt in a molten state.

The halogen-free thermoplastic recycled plastic is preferably from the group consisting of a) recycled polymers from olefins or diolefins, such as polyethylene, in particular LDPE, LLDPE, VLDPE, ULDPE, MDPE, HDPE and UHMWPE, metallocene-PE (m-PE ), Polypropylene, polyisobutylene, poly-4-methyl-pentene-1, polybutadiene, polyisoprene, polycyclooctene, polyalkylene-carbon monoxide copolymers, and corresponding copolymers in the form of statistical or block structures such as polypropylene-polyethylene (EP), EPM or EPDM, Ethylene vinyl acetate (EVA), ethylene acrylic esters, such as ethylene butyl acrylate, ethylene acrylic acid glycidyl acrylate, and corresponding graft polymers such as polypropylene g maleic anhydride, polypropylene g acrylic acid and polyethylene g acrylic acid, b) recycled polystyrene, polymethylstyrene, polyvinylnaphthalene, styrene-butadiene (SB), styrene-butadiene-styrene (SBS), styrene-ethylene-butylene-styrene (SEBS), styrene-ethylene-propylene-styrene,

Styrene soprene, styrene-isoprene-styrene (SIS), styrene-butadiene-acrylonitrile (ABS), styrene-acrylonitrile-acrylate (ASA), styrene-ethylene, styrene-maleic anhydride polymers including corresponding graft copolymers such as e.g. Styrene on butadiene, maleic anhydride on SBS or SEBS, as well as graft copolymers of methyl methacrylate, styrene-butadiene and ABS (MABS), c) recycled polymers of unsaturated esters such as e.g.

Polyacrylates and polymethacrylates such as polymethyl methacrylate (PMMA), polybutyl acrylate, polylauryl acrylate, polystearyl acrylate, polyacrylonitrile, polyacrylamides, and corresponding copolymers such as e.g. Polyacrylonitrile-polyalkyl acrylate, d) recycled polymers from unsaturated alcohols and derivatives, such as e.g. Polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, e) recycled polyacetals, e.g. Polyoxymethylene (POM), and corresponding copolymers, e.g. Copolymers with butanal, f) recycled polyphenylene oxides and blends of these with polystyrene or polyamides, g) recycled polymers of cyclic ethers such as e.g.

Polyethylene glycol, polypropylene glycol, polyethylene oxide, polypropylene oxide, h) recycled polyurethanes from hydroxy-terminated polyethers or polyesters and aromatic or aliphatic isocyanates, in particular linear polyurethanes, polyureas, i) recycled polyamides such as polyamide-6, 6.6, 6.10, 4.6, 4.10, 6.12, 12.12 , Polyamide 11, polyamide 12 and (partially) aromatic poly lyamides such as polyphthalamides, for example made from terephthalic acid and / or isophthalic acid and aliphatic diamines or from aliphatic dicarboxylic acids such as adipic acid or sebacic acid and aromatic diamines such as 1,4- or 1,3-diaminobenzene, j) recycled polyimides, polyamide- imides, polyetherimides,

Polyesterimides, poly (ether) ketones, polysulfones,

Polyether sulfones, polyarylsulfones, polyphenylene sulfide, polybenzimidazoles, polyhydantoins, k) recycled polyesters from aliphatic or aromatic

Dicarboxylic acids and diols or from hydroxy carboxylic acids such as e.g. Polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polypropylene terephthalate, polyethylene naphthylate, poly-1,4-dimethylocyclohexane phthalate, polyhydroxybenzoate,

Polyhydroxynaphthalate, polylactic acid,

L) recycled polycarbonates, polyester carbonates, and blends of these such as PC / ABS, PC / PBT, PC / PET / PBT, m) recycled cellulose derivatives, e.g. Cellulose nitrate, cellulose acetate, cellulose propionate, cellulose butyrate, n) and mixtures, combinations or blends of two or more of the aforementioned polymers.

In the event that further constituents are added to the halogen-free thermoplastic recycled plastic, these can be added to the polymers separately, in the form of liquids, powders, granules or compacted products or together with the additive composition according to the invention, as previously described.

At least one additive, which is selected from the group consisting of UV absorbers, light stabilizers, can preferably also be introduced into the halogen-free thermoplastic recycled plastic. Metal deactivators, filler deactivators, antiozonants,

Nucleating agents, anti-nucleating agents, impact strength improvers, plasticizers, lubricants, rheology modifiers, thixotropy agents, chain extenders, optical brighteners, antimicrobial active ingredients (e.g. biocides), antistatic agents, slip agents, antiblocking agents, coupling agents, crosslinking agents, branching agents, hydrophobic agents, anti-microscopic agents

Dispersing agents, compatibilizers, oxygen scavengers, acid scavengers, blowing agents, degradation additives, defoaming agents, odor scavengers, marking agents, antifogging agents, additives for increasing the electrical conductivity and / or thermal conductivity, infrared absorbers or infrared reflectors, gloss improvers, matting agents, repellents, fillers , Reinforcing materials and mixtures thereof.

Furthermore, it is preferred that at least one additive, which is selected from the group consisting of a) acid scavengers, preferably calcium stearate, magnesium stearate, zinc stearate, aluminum stearate, calcium stearate, calcium lactate, calcium stearoyl, is additionally introduced into the halogen-free thermoplastic recycled plastic -2-lactate, hydrotalcites, especially synthetic hydrotalcites based on aluminum, magnesium and zinc, hydrocalumites, zeolites, alkaline earth oxides, especially calcium oxide and magnesium oxide, alkaline earth carbonates, especially calcium carbonate, magnesium carbonate and dolomite, and hydroxides, especially brucite, b) light stabilizers , preferably light stabilizers from the group of hindered amines, which can simultaneously act as long-term heat stabilizers c) dispersants, d) filler deactivators, and

Mixtures of these. Suitable light stabilizers are, for example, compounds based on 2- (2'-hydroxyphenyl) benzotriazoles, 2-hydroxybenzophenones, esters of benzoic acids, acrylates, oxamides and 2- (2-hydroxyphenyl) -1,3,5-triazines.

Suitable 2- (2'-hydroxyphenyl) benzotriazoles are, for example, 2- (2'-hydroxy-5'methylphenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (5'-tert-Butyl-2'-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'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) benzotriazole, 2- (3 ', 5'-di-tert-amyl- 2'-hydroxyphenyl) benzotriazole, 2- (3 ', 5'-bis (a, a-dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'- (2-octyloxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-5 '- [2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) -5-chlorobenzotriazole, 2 - (3'-tert-Butyl-2'-hydroxy-5 '- (2-methoxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5' - ( 2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-Bu tyl-2'-hydroxy-5 '- (2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-5' - [2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) benzotriazole, 2- (3'-Dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-isooctyloxycarbonylethyl) phenylbenzotriazole, 2.2 '-Methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-ylphenol]; the product of the transesterification of 2- [3'-tert-butyl-5 '- (2-methoxycarbonylethyl) -2'-hydroxyphenyl] -2H-benzotriazole with polyethylene glycol 300; [R - CH ₂ CH ₂ - COO - CH ₂ CH] 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 '- (a, a-dimethylbenzyl) phenyl] benzotriazole.

Suitable 2-hydroxybenzophenones are, for example, 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy-4-dodecyloxy, 4-benzyloxy, 4,2 ', 4'-trihydroxy- and 2'-hydroxy-4 , 4'-dimethyoxy derivatives of 2-hydroxybenzophenones.

Suitable acrylates are, for example, ethyl a-cyano-b, b-diphenyl acrylate, isooctyl-a-cyano-b, b-diphenyl acrylate, methyl-a-carbomethoxycinnamate, methyl-a-cyano-b-methyl-p-methoxycinnamate, butyl-a-cyano-b-methyl-p-methoxycinnamate, methyl a-carbomethoxy-p-methoxycinnamate and N- (b-carbomethoxy-b-cyanovinyl) -2-methylindoline.

Suitable esters of benzoic acids are, for example, 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis (4-tert-butylbenzoyl) resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl-3,5-di-tert- butyl-4-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, octa-decyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di- tert-butylphenyl 3,5-di-tert-butyl 4-hydroxybenzoate.

Suitable oxamides are, for example, 4,4'-dioctyloxyoxanilide, 2,2'-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.

Suitable 2- (2-hydroxyphenyl) -1,3,5-triazines are, for example, 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy- 4-octyloxyphenyl) -4,6- bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1 , 3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl ) -4,6-bis (4-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 / tridecyloxy-2-hydroxypropoxy) -2-hydroxyphenyl] -4,6-bis (2nd , 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-dipheny l-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.

Suitable metal deactivators are, for example, N, N'-diphenyloxamide, N-salicylal-N'-salicyloylhydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3,5-di-tert-butyl-4-) hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis (benzylidene) oxalyldihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoylbisphenyl hydrazide, N, N'-diacetyladipoyldihydrazide, N, N'-bis (salicylic) N, N'-bis (salicyloyl) thiopropionyl dihydrazide.

Suitable hindered amines which can simultaneously act as long-term heat stabilizers are, 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, 1-cyclohexyloxy-2, 2,6,6-tetramethyl-4-octadecylaminopiperidine, bis (1-acyl -2,2,6,6-tetramethylpiperidin-4-yl) sebazate 1- (2-hydroxy-2-methylpropoxy) -4-hydroxy-2,2,6,6-tetra-methylpiperidine, 1- ( 2-hydroxy-2-methylpropoxy) -4-oxo-2,2,6,6-tetramethylpiperidine, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate, N, N'-bis- formyl-N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylene diamine, (33a) bis (1-undecanyloxy-2, 2,6, 6-tetramethylpiperidin-4-yl) carbonate , 1,2,2,6,6-pentamethyl-4-aminopiperidine, 2-undecyl-7, 7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro [4,5 ] decane-tris (2,2,6,6-tetramethyl-4-pi peridyl) nitrilotriacetate 1,1 '- (1,2-ethanediyl) -bis (3,3,5,5-tetramethylpiperazinone), 3- n-octyl-7,

7.9.9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, 8-acetyl-3-dodecyl-

7.7.9.9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, 3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidyl) pyrrolidine-2,5 -dione, 3-dodecyl-1- (1,2,2,6,6-pentamethyl-4-piperidyl) pyrrolidine-2,5-dione, 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-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetra- methylpiperidine, linear or cyclic condensation products from N, N'-bis (2,2,6,6- tetramethyl-4-piperidyl) hexamethylene diamine and 4-morpholino-2,6-dichloro-1,3,5-triazine the reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8- diaza-4-oxospiro- [4,5] decane and epichlorohydrin.

The structures specified above also include the sterically hindered NH, N-alkyl such as N-methyl or N-octyl, the N-alkoxy derivatives such as N-methoxy or N-octyloxy, the cycloalkyl derivatives such as N-cyclohexyloxy and the N- (2-hydroxy-2-methylpropoxy) analogs.

Preferred hindered amines also have the following structures:

Preferred oligomeric and polymeric hindered amines have the following structures:

In the case of the compounds mentioned above, n is in each case 3 to 100. Suitable dispersants are, for example:

Polyacrylates, e.g. Copolymers with long chain side groups, polyacrylate block copolymers, alkyl amides: 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, poly-propylene-co-maleic anhydride, polyethylene-co-glycidyl methacrylate, polystyrene-old maleic anhydride polysiloxanes: e.g. Dimethylsilanediol-ethylene oxide copolymer, polyphenylsiloxane copolymer, amphiphilic copolymers: e.g. Polyethylene block polyethylene oxide, dendrimers, e.g. hydroxyl group-containing dendrimers.

Suitable nucleating agents are, for example, talc, alkali or alkaline earth metal salts of mono- and polyfunctional carboxylic acids such as, for. B. benzoic acid, succinic acid, adipic acid, for example sodium benzoate, zinc glycerolate, aluminum-hydroxy-bis (4-tert-butyl) benzoate, benzylidene sorbitols such as 1.3: 2, 4-bis (benzylidene) sorbitol or 1.3: 2, 4-bis (4-methylbenzylidene) sorbitol, 2,2'-methylene-bis- (4,6-di-tert-butylphenyl) phosphate, as well as trisamides and diamides such as trimesic acid tricyclohexylami, trimesic acid tri (4-methylcyclohexylamide), trimesic acid tri (tert.butylamide), N, N ', N "-1,3,5-benzenetriyltris (2,2-dimethyl-propanamide) or 2,6-naphthalenedicarboxylic acid di cyclohexylamide.

Suitable anti-nucleating agents are for example azine dyes such as e.g.

Nigrosine, ionic liquids and / or lithium salts.

Suitable flame retardants are, for example: a) inorganic flame retardants such as Al (OH) ₃ , Mg (OH) ₂ , AIO (OH), MgCO ₃ , layered silicates such as montmorillonite or sepiolite, not or organically modified, double salts such as Mg-Al -Silicates, POSS- (polyhedral oligomeric silsesquioxane) compounds, huntite, hydromagnesite or halloysite as well as Sb ₂ O ₃ , Sb ₂ O ₅ , MoO ₃ , zinc stannate, zinc hydroxystannate, b) Nitrogen-containing flame retardants such as melamine, melem, melam, melon , Melamine derivatives, melamine condensation products or melamine salts, benzoguanamine, polyisocyanurates, allantin, phosphacenes, in particular melamine cyanurate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, melamine polyphosphate, melamine metal phosphates such as melamine aluminum phosphate, melate phosphate, melate the corresponding pyrophosphates and polyphosphates, poly- [2,4- (piperazin-1,4-yl) -6- (morpholin-4-yl) -1,3,5-triazine], ammonium polyphosphate, melamine borate, M elamine hydrobromide, c) radical formers, such as, for example, alkoxyamines, hydroxylamine esters, azo compounds, sulfenamides, sulfenimides, dicumyl or polycumyl, hydroxyimides and their derivatives, such as, for example, hydroxyimide esters or hydroxyimide ethers, d) phosphorus-containing flame retardants, such as, for example, red phosphorus, phosphates, such as resorphenol, for example resorphenol diphosphate and its oligomers, triphenyl phosphate, ethylenediamine diphosphate, phosphinates such as, for example, salts of hypophosphorous acid and their derivatives such as alkyl phosphinate salts, for example diethyl phosphinate. 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, for example, polybrominated diphenyl oxides, such as, for example, 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, polystyrene-brominated Copolymers, brominated polyphenylene ether, brominated epoxy resin, polypentabromobenzyl acrylate, possibly in combination with Sb ₂ O ₃ and / or Sb ₂ O ₅ , f) borates such as zinc borate or calcium borate, optionally on a carrier material wi e eg silica g) sulfur-containing compounds such as elemental sulfur, disulfides and polysulfides, thiuram sulfide, dithiocarbamates, mercaptobenzthiazole and sulfenamides, h) antidrip agents such as polytetrafluoroethylene, i) silicon-containing compounds such as polyphenylsiloxanes, j) carbon modifications such as carbon CNT), expanded graphite or graphene k) and combinations or mixtures thereof.

Suitable plasticizers are, for example, phthalic acid esters, adipic acid esters, esters of citric acid, esters of 1,2- Cyclohexanedicarboxylic acid, trimellitic acid ester, isosorbide ester, phosphate ester, epoxides such as epoxidized soybean oil or aliphatic polyester.

Suitable fillers and reinforcing materials are, for example, synthetic or natural materials such as e.g. Calcium carbonate, silicates, glass fibers, glass spheres (solid or hollow), talc, dolomite, mica, feldspar, kaolin, quartz, wollastonite, calcium sulfate, barium sulfate, silicon carbide, metal oxides and metal hydroxides, aluminum silicate, calcium silicate, zirconium silicate, carbon black, graphite, carbon nanotube , Graphene, wood flour or fibers from natural products such as Cellulose or synthetic fibers. Other suitable fillers are hydrotalcites or zeolites or layered silicates such as e.g. Montmorillonite, bentonite, beidelite, mica, hectorite, saponite, vermiculite, ledikite, magadite, lllite, kaolinite, wollastonite, attapulgite.

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, quinophthalones, diketopyrrolopyrroles, dioxazines, indanthrones, isoindolines, isoindolinones, azo compounds, azo compounds Perylenes, phthalocyanines or pyranthrones. Other suitable pigments are effect pigments based on metal or pearlescent pigments based on metal oxide.

Suitable chain extenders for the linear molecular weight build-up of polycondensation polymers such as polyesters or polyamides are, for example, diepoxides, bis-oxazolines, bis-oxazolones, bis-oxazines, diisocyanates, dianhydrides, bis-acyllactams, 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 optical brighteners are, for example, bisbenzoxazoles, phenylcoumarins or bis (styryl) biphenyls and in particular optical brighteners of the formulas:

10th Suitable filler deactivators are, for example, polysiloxanes, polyacrylates, in particular block copolymers such as polymethacrylic acid-polyalkylene oxide or polyglycidyl (meth) acrylates and their copolymers, for example with styrene and epoxides, for example of the following structures:

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

Suitable antiozonants are the amines mentioned above, e.g. N, N'-di-isopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'- bis (1,4-dimethylpentyl) -p-phenylenediamine, N, N ' -Dicyclohexyl-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylene-diamine, N- (1-methylheptyl) -N '-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine.

Suitable additives for increasing the electrical conductivity are, for example, the aforementioned antistatic agents, carbon black and carbon compounds such as carbon nanotubes and graphene, metal powder such as e.g. Copper powder and conductive polymers such as Polypyrroles, polyanilines and polythiophenes. Suitable additives for increasing the thermal conductivity are, for example, aluminum nitrides and boron nitrides.

Suitable mold release agents are, for example, silicones, soaps and waxes such as e.g. Montan waxes.

Components (A) and (B) and, if appropriate, the additional additives can be incorporated into the plastic recyclate by customary processing methods, the polymer being melted and mixed with the additive composition according to the invention and any further additives, preferably by mixer, kneader and extruder. Preferred processing machines are extruders such as e.g. Single-screw extruders, twin-screw extruders, planetary roller extruders, ring extruders, co-kneaders, which are preferably equipped with vacuum degassing. Processing can be carried out under air or possibly under inert gas conditions such as done under nitrogen.

Furthermore, components (A), (B), and / or (C) can be in the form of so-called masterbatches or concentrates, which for example contain 10-90% of a stabilizer composition consisting of components (A), (B), and / or (C) contained in a polymer, produced and introduced the.

In a second aspect, the present invention relates to a plastic composition containing or consisting of

(B) at least one primary antioxidant and / or

(C) at least one secondary antioxidant, in a halogen-free thermoplastic recycled plastic, the plastic composition being free of alditols and cyclitols.

All of the previously made preferred embodiments and aspects mentioned in connection with the method according to the invention also apply without restriction to the previously described plastic composition.

A preferred embodiment provides that component (A) in a weight ratio to component (B) and / or component (C) from 90:10 to 10:90, preferably from 80:20 to 20:80, particularly preferably from 60:40 to 40:60, is contained in the plastic composition.

It is also advantageous that, based on the total weight of the plastic recyclate and component (A) to (C), 0.02 to 3.00% by weight, preferably 0.03 to 1.00% by weight. %, particularly preferably 0.02 to 0.50% by weight, in particular 0.10 to 0.30% by weight, of the at least one compound (A) capable of reacting with carbonyl groups, and 0.02 to 3 .00% by weight, preferably 0.03 to 1.00% by weight, particularly preferably 0.02 to 0.50% by weight, in particular 0.05 to 0.20% by weight of the at least one primary antioxidant (B) and / or 0.02 to 3.00% by weight, preferably 0.03 to 1.00% by weight, particularly which preferably contains 0.02 to 0.50% by weight, in particular 0.05 to 0.20% by weight, of the at least one secondary antioxidant (C).

It is also advantageous if at least one compound (A) capable of reacting with carbonyl groups, at least one primary antioxidant (B) and at least one secondary antioxidant (C) are present.

In particular, at least one halogen-free thermoplastic plastic recyclate is a halogen-free thermoplastic plastic recyclate, a polyolefin recyclate, in particular a polypropylene or polyethylene recyclate.

The plastic composition presented above can be produced in particular using a method according to the invention described at the beginning.

The invention also relates to a molding composition or a molded part that can be produced from the previously described plastic composition. Preferred embodiments of the molding composition or the molded part see injection molded parts, foils, films, lacquers, coatings, foams, fibers, cables, pipes, profiles, hollow bodies, tapes, membranes, e.g. Geomembranes, lubricants, colorants and / or adhesives that are manufactured by extrusion, injection molding, blow molding, calendering, pressing processes, spinning processes and / or rotomoulding, e.g. for the electrical industry, for the construction industry, for the transport industry, for medical applications, for household and electrical appliances, for vehicle parts, for consumer articles, for packaging, for furniture, and / or for textiles.

Furthermore, the present invention relates to a stabilizer composition for stabilizing halogen-free thermoplastic recycled plastics against oxidative, thermal and / or actinic degradation, consisting of

(A) at least one compound capable of reacting with carbonyl groups, in combination with (B) at least one primary antioxidant and / or

(C) at least one secondary antioxidant, the stabilizer composition being free of alditols and cyclitols.

A preferred embodiment relating to the stabilizer composition provides that component (A) in a weight ratio to component (B) and / or component (C) from 90:10 to 10:90, preferably from 80:20 to 20:80, particularly preferably from 60:40 to 40:60, is contained in the plastic composition.

In particular, the stabilizer composition consists of at least one compound (A) capable of reacting with carbonyl groups, at least one primary antioxidant (B) and at least one secondary antioxidant (C).

It is also advantageous that the stabilizer composition consists of

(A) 90.00 to 10.00% by weight or 80.00 to 20.00% by weight, preferably 60.00 to 40.00% by weight of at least one compound capable of reacting with carbonyl groups, with the exception of alditols and cyclitols, in combination with

(B) 10.00 to 90.00% by weight, preferably 20.00 to 30.00% by weight of at least one primary antioxidant and / or

(C) 10.00 to 90.00% by weight, preferably 20.00 to 30.00% by weight of at least one secondary antioxidant. In addition, the present invention relates to the use of the stabilizer composition described above for stabilizing halogen-free thermoplastic recycled plastics against oxidative, thermal and / or actinic degradation.

Suitable compounds (C) are preferably selected so that they are not or only slightly volatile at the usual processing temperatures of polymers. Usual processing temperatures of the preferred polyolefin recyclates are, for example, between 180 ° C and 250 ° C.

The present invention is illustrated with the aid of the following examples, without restricting the invention to the specific parameters shown.

To test the effect of the stabilizer composition according to the invention, a post-consumer polypropylene recyclate from battery case ground material (supplier: BSB Braubach) together with the additives specified in the table at 210 ° C. in a twin-screw microextruder (MC 5, Manufacturer DSM) in continuous mode at 90 revolutions per minute for 30 minutes in the melt in a circle. The force absorption is measured after 10, 20 and 30 minutes. The force is a measure of the toughness of the melt and thus of the molecular weight. The higher the remaining force (after a melting time of 2 minutes = 100%), the lower the degradation of the polymer.

Table 1: Stabilization of polypropylene recyclate

AO-1: pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate P-1: tris (2,4-di-tert-butylphenyl) phosphite

In the present test, the synergistic combination according to the invention proves to be superior to the synthetic commercial synergistic combinations of AO-1 and P-1 (comparative example 1), since there is less degradation of the polymer over the test period.

Table 2: Stabilization of polypropylene recyclate

The poly (vinyl alcohol-co-vinyl acetate) used consists of 80% polyvinyl nyl alcohol and has a molecular weight between 9000 and 10000.

The compositions according to the invention show less degradation of the polymer (higher residual force) and thus improved stabilization of the polymer.

Claims

1. Process for stabilizing halogen-free thermoplastic

Recycled plastics against oxidative, thermal and / or actinic degradation, in which

(A) at least one compound capable of reacting with carbonyl groups,

in combination with

(B) at least one primary antioxidant and / or

(C) at least one secondary antioxidant,

be introduced into a halogen-free thermoplastic recycled plastic, whereby no alditols and cyclitols are used.

2. The method according to claim 1, characterized in that the at least one compound capable of reacting with carbonyl groups is selected from the group consisting of primary aliphatic amines, secondary aliphatic amines, thiols, hydroxylamine ethers, hydroxylamine esters, hydrazines, oligomers or polymers with alcohol groups bound to aliphatic carbons such as polyvinyl alcohols and their copolymers with vinyl acetate,

Polyhydroxy (meth) acrylates, hydantoins and thiohydantoins.

3. The method according to any one of the preceding claims, characterized in that the at least one compound capable of reacting with carbonyl groups is selected from the group consisting of laurylamine, stearylamine, hexamethylene diamine, decanediamine, dodecanediamine, dilaurylamine, distearylamine, 1 -Dodecanethiol, 1-hexadecanethiol, polycaprolactone tetra-3-mercaptopropionate, polyvinyl alcohol with a weight-average molecular weight of 1,000 to 50,000 g / mol, polyhydroxy (meth) acrylates with a weight average molecular weight of 1,000 to 50,000 g / mol, imidazolidine-2,4-dione, and compounds with the following structures:

4. The method according to any one of the preceding claims, characterized in that the at least one primary antioxidant (B) is selected from the group consisting of phenolic antioxidants, lactones, hydroxylamines and mixtures thereof.

5. The method according to any one of the preceding claims, characterized in that the at least one secondary antioxidant (C) is selected from the group consisting of phosphorus compounds, in particular phosphites and phosphonites, organosulfur compounds, in particular sulfides and disulfides, and mixtures of this.

6. The method according to any one of the preceding claims, characterized in that at least one compound capable of reacting with carbonyl groups (A), at least one primary antioxidant (B) and at least one secondary antioxidant (C) are introduced into the halogen-free thermoplastic recycled plastic become.

7. The method according to any one of the preceding claims, characterized in that component (A) in a weight ratio to component (B) and / or component (C) from 90:10 to 10:90, preferably from 80:20 to 20:80, particularly preferably from 60:40 to 40:60, into which halogen-free thermoplastic recycled plastic is introduced.

8. The method according to any one of the preceding claims, characterized in that in each case based on the total weight of the plastic recyclate and the component (A) to (C)

0.02 to 3.00% by weight, preferably 0.03 to 1.00% by weight, particularly preferably 0.02 to 0.50% by weight, in particular 0.10 to 0.30% by weight % of the at least one compound (A) capable of reacting with carbonyl groups, and

0.02 to 3.00% by weight, preferably 0.03 to 1.00% by weight, particularly preferably 0.02 to 0.50% by weight, in particular 0.05 to 0.20% by weight .-% of the at least one primary antioxidant (B) and / or

0.02 to 3.00% by weight, preferably 0.03 to 1.00% by weight, particularly preferably 0.02 to 0.50% by weight, in particular 0.05 to 0.20% by weight % of the at least one secondary antioxidant (C)

into the halogen-free thermoplastic recycled plastic.

9. The method according to any one of the preceding claims, characterized in that the components (A) and (B) and / or (C) are introduced into the halogen-free thermoplastic recycled plastic in that

the components (A) and (B) and / or (C) in solid form are mixed with the halogen-free thermoplastic recycled material in solid form and the resulting mixture is melted and then cooled, or the components in solid form ( A) and (B) and / or (C) melted and the resulting melt is introduced into a melt of the halogen-free thermoplastic recycled plastic.

10. The method according to any one of the preceding claims, characterized in that the halogen-free thermoplastic plastic

Recycled material is selected from the group consisting of

a) recycled polymers from olefins or diolefins, such as e.g. Polyethylene, in particular LDPE, LLDPE, VLDPE, ULDPE, MDPE, HDPE and UHMWPE, metallocene-PE (m-PE), polypropylene,

Polyisobutylene, poly-4-methyl-penten-l, polybutadiene,

Polyisoprene, polycyclooctene, polyalkylene-carbon monoxide copolymers, as well as corresponding copolymers in the form of statistical or block structures such as e.g. Polypropylene-polyethylene (EP), EPM or EPDM, ethylene-vinyl acetate (EVA), ethylene-acrylic esters, e.g. Ethylene butyl acrylate, ethylene acrylic acid glycidyl acrylate, and corresponding graft polymers such as e.g. Polypropylene-g-maleic anhydride, polypropylene-g-acrylic acid and polyethylene-g-acrylic acid,

b) recycled polystyrene, polymethylstyrene, polyvinylnaphthalene, styrene-butadiene (SB), styrene-butadiene-styrene (SBS), styrene-ethylene-butylene-styrene (SEBS), styrene-ethylene-propylene-styrene,

Styrene soprene, styrene-isoprene-styrene (SIS), styrene-butadiene-acrylonitrile (ABS), styrene-acrylonitrile-acrylate (ASA), styrene-ethylene, styrene-maleic anhydride polymers including corresponding graft copolymers such as e.g. Styrene on butadiene,

Maleic anhydride on SBS or SEBS, as well as graft copolymers of methyl methacrylate, styrene-butadiene and ABS (MABS), c) recycled polymers of unsaturated esters such as e.g.

Polyacrylates and polymethacrylates such as polymethyl methacrylate (PMMA), polybutyl acrylate, polylauryl acrylate, polystearyl acrylate, polyacrylonitrile, polyacrylamides, and corresponding copolymers such as e.g. Polyacrylonitrile-polyalkyl acrylate,

d) recycled polymers from unsaturated alcohols and derivatives, such as, for example, polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, e) recycled polyacetals, such as, for example, polyoxymethylene (POM), and corresponding copolymers, such as, for example, copolymers with butanal, f) recycled polyphenylene oxides and blends of these with polystyrene or polyamides,

g) recycled polymers of cyclic ethers such as e.g.

Polyethylene glycol, polypropylene glycol, polyethylene oxide,

Polypropylene oxide,

h) recycled polyurethanes from hydroxy-terminated polyethers or polyesters and aromatic or aliphatic isocyanates, in particular linear polyurethanes, polyureas,

i) recycled polyamides such as Polyamide-6, 6.6, 6.10, 4.6, 4.10, 6.12, 12.12, polyamide 11, polyamide 12 and (partially) aromatic polyamides such as Polyphthalamides, e.g. made of

Terephthalic acid and / or isophthalic acid and aliphatic diamines or from aliphatic dicarboxylic acids such as e.g. Adipic acid or sebacic acid and aromatic diamines such as e.g. 1,4- or 1,3-diaminobenzene,

j) recycled polyimides, polyamide-imides, polyetherimides,

Polyesterimides, poly (ether) ketones, polysulfones,

Polyether sulfones, polyarylsulfones, polyphenylene sulfide,

Polybenzimidazoles, polyhydantoins,

k) recycled polyesters from aliphatic or aromatic

Polyhydroxynaphthalate, polylactic acid,

L) recycled polycarbonates, polyester carbonates, and blends of these such as PC / ABS, PC / PBT, PC / PET / PBT,

m) recycled cellulose derivatives, e.g. Cellulose nitrate,

Cellulose acetate, cellulose propionate, cellulose butyrate,

n) and mixtures, combinations or blends of two or more of the aforementioned polymers.

11. Plastic composition containing or consisting of

(A) at least one compound capable of reacting with carbonyl groups,

in combination with

(B) at least one primary antioxidant and / or

(C) at least one secondary antioxidant,

in a halogen-free thermoplastic recycled plastic, the plastic composition being free of alditols and cyclitols.

12. Plastic composition according to the preceding claim, characterized in that component (A) in a weight ratio to component (B) and / or component (C) from 90:10 to 10:90, preferably from 80:20 to 20:80, particularly preferably from 60:40 to 40:60, is contained in the plastic composition.

13. Plastic composition according to one of claims 11 to 12, characterized in that in each case based on the total weight of the plastic recyclate and the component (A) to (C)

are included.

14. Plastic composition according to one of claims 11 to 13, characterized in that at least one compound capable of reacting with carbonyl groups (A), at least one primary Antioxidant (B) and at least one secondary antioxidant (C) are contained.

15. Plastic composition according to one of claims 11 to 14, characterized in that the plastic composition additionally contains at least one additive which is selected from the group consisting of UV absorbers, light stabilizers, metal deactivators, filler deactivators, antiozonants,

Nucleating agents, antinucleating agents,

Impact improvers, plasticizers, lubricants,

Rheology modifiers, thixotropy agents, chain extenders, optical brighteners, antimicrobial agents (e.g. biocides),

Antistatic agents, slip agents, antiblocking agents, coupling agents, crosslinking agents, branching agents, anti-crosslinking agents,

Hydrophilizing agents, hydrophobizing agents, adhesion promoters, dipergizing agents, compatibilizers, oxygen scavengers, acid scavengers, blowing agents, degradation additives, defoaming agents, odor traps, marking agents, antifogging agents, additives for increasing the electrical conductivity and / or thermal conductivity, infrared absorber or infrared -Reflectors, gloss improvers, matting agents, repellents, fillers, reinforcing materials and mixtures thereof.

16. Plastic composition according to one of claims 11 to 15, characterized in that the plastic composition additionally contains at least one additive which is selected from the group consisting of

a) Acid scavengers, preferably calcium stearate, magnesium stearate, zinc stearate, aluminum stearate, calcium stearate, calcium lactate, calcium stearoyl-2-lactate, hydrotalcites, in particular synthetic hydrotalcites based on aluminum, magnesium and zinc, hydrocalumites, zeolites, alkaline earth oxides, in particular calcium oxide and magnesium oxide, Alkaline earth carbonates, in particular

Calcium carbonate, magnesium carbonate and dolomite, and hydroxides, especially brucite, b) light stabilizers, preferably light stabilizers from the group of the hindered amines,

c) dispersants,

d) filler deactivators, and

e) mixtures thereof.

17. Plastic composition according to one of claims 11 to 16, characterized in that the at least one halogen-free thermoplastic recycled plastic is a polyolefin recyclate, in particular a polypropylene or polyethylene recyclate.

18. Plastic composition according to one of claims 11 to 17, characterized in that the plastic composition can be produced by a method according to one of claims 1 to 10.

19. Molding compound or molded part producible from a plastic composition according to one of claims 11 to 18, in particular in the form of injection molded parts, foils, films, lacquers, coatings, foams, fibers, cables, pipes, profiles, hollow bodies, tapes, membranes , e.g. Geomembranes, lubricants, colorants and / or adhesives that are manufactured via extrusion, injection molding, blow molding, calendering, pressing processes, spinning processes and / or rotomoulding e.g. for the electrical industry, for the construction industry, for the transport industry, for medical applications, for household and electrical appliances, for vehicle parts, for consumer goods, for packaging, for furniture, for textiles.

20. Stabilizer composition for stabilizing halogen-free thermoplastic recycled plastics against oxidative, thermal and / or actinic degradation, consisting of

(A) at least one compound capable of reacting with carbonyl groups,

in combination with

(B) at least one primary antioxidant and / or (C) at least one secondary antioxidant, the stabilizer composition being free of alditols and cyclitols.

21. Stabilizer composition according to the preceding claim, characterized in that component (A) in a weight ratio to component (B) and / or component (C) from 90:10 to 10:90, preferably from 80: 20 to 20:80, particularly preferably from 60:40 to 40:60, is contained in the plastic composition.

22. Stabilizer composition according to one of the two preceding claims, characterized in that it consists of at least one compound (A) capable of reacting with carbonyl groups, at least one primary antioxidant (B) and at least one secondary antioxidant (C ) consists.

23. Stabilizer composition according to one of claims 21 to 23, characterized in that it consists of

(A) 90.00 to 10.00% by weight or 80.00 to 20.00% by weight, preferably 60.00 to 40.00% by weight of at least one compound capable of reacting with carbonyl groups, with the exception of alditols and cyclitols,

in combination with

(C) 10.00 to 90.00% by weight, preferably 20.00 to 30.00% by weight of at least one secondary antioxidant

consists.

24. Use of a stabilizer composition according to one of claims 21 to 23 for stabilizing halogen-free thermoplastic recycled plastics against oxidative, thermal and / or actinic degradation.