Process for the stabilization of halogen-free thermoplastic plastic recyclates as well as stabilized plastic compositions and molding compounds and molded parts made from them

The present invention relates to a method for stabilizing halogen-free thermoplastic plastic recyclates or previously damaged plastics against oxidative, thermal and / or actinic degradation. In the method according to the invention, at least one alditol or cyclitol is introduced as a component into a halogen-free thermoplastic recycled plastic and, if necessary, at least one primary antioxidant and / or at least one secondary antioxidant is added to a halogen-free thermoplastic recycled. With the method according to the invention, plastic recyclates can be stabilized against oxidative, thermal and / or actinic degradation with high effectiveness and in a very environmentally friendly and cost-effective manner.compositions as well as molding compounds and molded parts produced therefrom. The present invention also relates to stabilizer compositions and their use for stabilizing halogen-free thermoplastic plastic recyclates against oxidative, thermal and / or actinic degradation.

Recycled plastics are a growing market and an important element in the circular economy of raw materials, with recyclates ideally then replacing new plastics with an identical or at least comparable property profile. However, with recyclates from production or from old plastics, irreversible changes in the polymer chain occur during the first processing steps (e.g. compounding, injection molding) and use due to mechano-chemical, chemical or light-induced processes (see e.g. R. Pfaendner et al., Angew. Makromol. Chemie 1995, 232, 193-2 27; J. Pospisil et al., Pol. Degr. Stab. 1995). By

Free radical reactions in the presence of oxygen create new chemical groups in the polymer chain and / or change the composition of the polymer. 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

Recyclates influence the properties of plastics, such as the mechanical properties.

Furthermore, recyclates or previously damaged plastics are more sensitive to oxidation than new material, since degradation products act as initiator sites for further oxidation or as prodegradants (AS Maxwell, Pol. Eng. Sci. 2008, 381-385; IH Craig, JR White, J . Mater. Sci. 2006, 41, 993-1006). In order to improve the quality of plastic recyclates, post-stabilization with selected stabilizers is an essential method. The stabilizers used protect the recyclate from further oxidative (or photooxidative) damage. The optimized stabilizer composition for a recyclate differs from the stabilization composition of the new material due to the structural deviations described (see e.g. R. Pfaendner, Kunststoffe International 12/2015, 41-44).

Due to the now recognized differences between new plastic and recycled plastic, special recycled stabilizer compositions are known and are also available as commercial products (e.g. Recyclostab series from PolyAd Services GmbH, Bensheim). Well-known technical stabilization solutions that meet the requirements of recyclates

Take into account, for example:

- 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 by a macrocyclic piperidine (US 5789470).

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

- Discoloration of damaged pololefins by a hydroxylamine (EP 470048)

- 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, there is still a need for particularly high-performance or effective, environmentally friendly and inexpensive options for stabilizing recycled plastics or stabilizer compositions that can be used for this purpose.

Recycled materials have already passed through a life cycle and were already compounded to form plastic molded parts and as such, for example, mechanical, chemical, actinic and / or oxidative loads

exposed. This results in certain flaws in the polymer chain which, if the recyclates are reprocessed, cause further, disproportionate damage to the underlying plastic material. The existing damage sites in the polymer serve as initiator sites for accelerated and extended degradation of the polymer. In particular, a lowering of the molecular weight, a broadening of the molecular weight distribution, a lowering of the mechanical properties and an increase of the photosensitivity are typical phenomena that come to light with recycled plastics, especially when they are reprocessed. The overall deteriorated property profile is therefore rather detrimental to further processing.

Based on this, it was the object of the present invention to provide a method for stabilizing halogen-free thermoplastic plastic recyclates with which the plastic recyclates are stabilized against oxidative, thermal and / or actinic degradation in a very effective, environmentally friendly and inexpensive manner can.

This object is achieved with regard to a method for stabilizing halogen-free thermoplastic plastic recyclates with the features of claim 1, with regard to a plastic composition with the features of claim 11, with regard to a molding compound or a molded part which can be produced from the plastic composition with the features of claim 18, with regard to a stabilizer composition with the features of claim 19 and with regard to the use of the stabilizer compositions with the features of claim 20 solved. The respective dependent claims represent advantageous developments.

According to the invention, a method for stabilizing halogen-free thermoplastic plastic recyclates against oxidative, thermal and / or actinic degradation is thus specified, in which at least one alditol or cylitol (hereinafter also referred to as "component (A)") is the component ) is introduced into a halogen-free thermoplastic recyclate.

Since the thermoplastic plastics on which the plastic recyclates are based, primary and / or secondary antioxidants have usually already been added during their production, when reprocessing used or already used plastics, i.e. recyclates, it is not absolutely necessary to reprocess these recyclates again primary and / or secondary antioxidants. Surprisingly, it has been found that it is sufficient to incorporate at least one alditol or cylitol into the plastic recyclate in order to achieve a stabilizing effect which is particularly high in the presence of primary and / or secondary oxidants in a synergistic manner.

According to the present invention, a plastic recyclate is understood to be a plastic recyclate according to the conceptual definition according to the standard DIN EN 15347: 2007. Furthermore, there are relevant international standards for many types of plastic recyclates. For PET plastic recyclates, for example, DIN EN 15353: 2007 is relevant. 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.

In contrast to new plastics, recycled plastics mostly show previous damage, ie new chemical groups are created on the polymer chain through oxidative or (photo) oxidative processes. In the case of polyolefins, for example, these are mainly carbonyl groups, which are not present in new goods or are only present to a very minor extent. The concentration of the carbonyl groups is therefore also a measure of the previous damage to the polymer. 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 is described. The absorption of the carbonyl vibration is measured in the range of 1720 cm -1 .

According to the invention, “halogen-free” is to be understood as meaning that the thermoplastic has less than 1% of halogen-containing polymers, such as

PVC or PVDC. The halogen-free thermoplastic material preferably contains less than 0.5%, particularly preferably less than 0.1%, of halogen-containing polymers. The halogen-free thermoplastic material very particularly preferably contains no halogen-containing polymers at all.

A preferred embodiment of the method provides that in addition to the at least one alditol and / or at least one cyclitol, at least one primary antioxidant and / or at least one secondary antioxidant is introduced into a halogen-free thermoplastic recycled material.

In the process according to the invention, the alditol or cyclitol (component (A)) and optionally the at least one primary antioxidant and / or the at least one secondary antioxidant (component (B)) are introduced into a halogen-free thermoplastic recycled material. Components (A) and (B) can be introduced into the recycled plastic material individually or separately, or components (A) and (B) can be used together in the form of components (A) and (B) Composition or in the form of a composition consisting of components (A) and (B) are introduced into the plastic recyclate.

As component (B) is

- at least one primary antioxidant, or

- at least one secondary antioxidant, or

- at least one primary antioxidant and at least one secondary antioxidant are used.

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

The component (A) used according to the invention and, if applicable, the component (B) used in addition to component (A) acts or act together as a stabilizer for the halogen-free thermoplastic recycled plastic, with the oxidative, thermal and / or actinic degradation of the Ha- logen-free thermoplastic plastic recyclate is inhibited or prevented. In other words, by introducing component (A) and possibly also component (B) into the halogen-free thermoplastic plastic recyclate, the plastic is stabilized against oxidative, thermal and / or actinic degradation.

The present invention is particularly characterized in that alditols (sugar alcohols) and / or cyclitols are used alone or together with primary and / or secondary antioxidants to stabilize halogen-free thermoplastic recycled plastics.

Sugar alcohols or polyols have so far not been used to stabilize halogen-free thermoplastic recycled plastics. According to the prior art, sugar alcohols and polyols are merely components in formulations for the heat stabilization of polyvinyl chloride (PVC) and other halogen-containing polymers such as polyvinylidene chloride (PVDC) in compositions which contain metal soaps as heat stabilizers. This stabilizing effect of polyols in halogen-containing polymers is explained by the fact that chelation and deactivation of the zinc compounds promoting PVC degradation takes place (see HO Wirth, H. Andreas, Pure Appl. Chem. 1977, 49, 627-648 ; T. lida, K. Goto, J. Appl. Pol. Sci. 1980, 25, 887-900) or so that a reaction is achieved as an HCl scavenger in Zn-free PVC (see J. Steenwijk et al. Pol. Degr. Rod. 2006, 2233-2240).

However, from the known mechanisms of the effect of polyols in the heat stabilization of halogen-containing polymers such as PVC, no conclusion can be drawn for the effect as a stabilizer in non-halogen-containing plastics or even recyclates. Rather, these known mechanisms are only applicable to halogen-containing polymers and cannot be transferred to halogen-free polymers. In this respect it was not foreseeable but rather it is very surprising that with the present invention it was found that alditols (sugar alcohols) and / or cyclitols can also stabilize halogen-free polymer recyclates, alone or when they are used together with primary and / or secondary antioxidants are used.

According to the invention, it was surprisingly found that by introducing at least one alditol and / or at least one cyclitol alone and together with at least one primary and / or at least one secondary antioxidant, a very effective stabilization of halogen-free thermoplastic plastic recyclates against oxidative , thermal and / or actinic degradation can be achieved. In addition, alditols and cyclitols are very environmentally friendly and inexpensive compounds. Thus, with the method according to the invention, halogen-free thermoplastic plastic recyclates can be stabilized against oxidative, thermal and / or actinic degradation in a very effective, environmentally friendly and cost-effective manner.

The inventors assume that the alditols and / or cyclitols incorporated into the recycled plastic material, with the damage sites already present (usually carbonyl groups), contribute to half or full acetals

Processing of the recompounding can react. The damage points in the plastic are thus effectively masked and are no longer available as initiator points for further degradation. With the method according to the invention or with the additive compositions according to the invention, damage points can thus be found in

Fix plastic recyclates.

For this reason, the addition of an alditol or cyclitol to a plastic recyclate alone is an effective stabilizer, since it can often be assumed that the primary and secondary antioxidants present in the recyclate from the first application were not completely consumed during use .

The halogen-free thermoplastic plastics recyclate used in the process according to the invention is preferably a polyolefin recyclate, for example a

Polypropylene recyclate or a polyethylene recyclate.

The composition according to the invention is also particularly suitable for stabilizing previously damaged recycled materials, in particular pololefin recycled materials 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 more preferably greater than 0.05 mol / kg.

In a preferred variant of the method according to the invention, the at least one primary antioxidant is selected from the group consisting of phenolic antioxidants, amines, lactones and mixtures thereof.

The following can be used as phenolic antioxidants, for example:

Alkylated monophenols, such as, for example, 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di -tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methyl-phenol, 2- (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- methyl-phenol, 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 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, for example, 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, for example, α-, β-, γ-, δ-tocopherol and mixtures of these (vitamin E);

Hydroxylated thiodiphenyl ethers, such as 2,2'-thiobis (6-tert-butyl-4-methyl-phenol), 2,2'-thiobis (4-octylphenol), 4,4'-thiobis (6-tert-butyl- 3-methyl-phenol), 4,4'-thiobis (6-tert-butyl-2-methylphenol), 4,4'-thiobis (3,6-di-sec-amylphenol), 4,4'-bis ( 2,6-dimethyl-4-hydroxyphenyl disulfide;

Alkylidenebisphenols, such as 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 2,2'-methylenebis [4-methyl- 6- (α-methylcyclohexyl) phenol], 2,2'-methylenebis (4-methyl-6-cyclhexylphenol), 2,2'-methylenebis (6-nonyl-4-methylphenol), 2,2'-methylenebis (4 , 6-di-tert-butyl-phenol), 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- (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-methylphenol, 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-methyl-phenyl) -4-n-dodecylmercaptobutane, 1,1,5,5-tetra (5-tert-butyl-4-hydroxy-2-methylphenyl) pentane;

O-, N- and S-benzyl compounds, such as, for example, 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzyl mercapto acetate , Tridecyl-4-hydroxy-3,5-di-tert-butylbenzyl mercaptoacetate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) amine,, bis (4-tert-butyl-3-hydroxy-2, 6-dimethyl-benzyl) dithioterephthalate, bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, iso-octyl-3,5-di-tert-butyl-4-hydroxybenzyl mercaptoacetate;

Hydroxybenzylated malonates, such as dioctadecyl-2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, dioctadecyl-2- (3-tert-butyl-4-hydroxy-5-methyl-benzyl) malonate, didodecylmercaptoethyl-2,2-bis (3,5-di-tert-butyl-4-hydroxy-benzyl) 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, for example, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3,5-di-tert- butyl-4-hydroxy-benzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxy-benzyl) phenol;

Triazine compounds, such as, for example, 2,4-bis (octylmercapto) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3 , 5-di-tert-butyl-4-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-hydroyphenylpropionyl) 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-hydroxybenzyl-phosphonate, Dietyhl-3,5-di-tert-butyl-4-hydroxybenzyl phosphonate, di-octadecyl-3,5-di-tert- butyl 4-hydroxybenzyl phosphonate, dioctadecyl 5-tert-butyl-4-hydroxy-3-methylbenzyl phosphonate, the calcium salt of the mono-ethyl 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, trimethylol propane, 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, , 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, 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, 3-thiapentadecanol, 1-trimethylhexanediol, trimethylolpropane, 4-trimethylolpropane, 2,6,7-trioxabicyclo [2.2.2] octane;

Esters of (3,5-di-tert-butyl-4-hydroxyphenyl) acetic acid with one or more hydric 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 (hydroxy- ethyl) 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 Ν, Ν'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylene diamide, Ν, Ν ' - Bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylene diamide, Ν, Ν'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylene diamide, Ν, Ν'-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 Addivant);

Ascorbic acid (vitamin C).

Particularly preferred phenolic antioxidants are the following structures:

Further preferred phenolic antioxidants are phenolic antioxidants based on renewable raw materials such as. B. tocopherols (vitamin E), tocotrienols, tocomonoenols, carotenoids, hydroxytyrosol, flavonols such as chrysin, quercitin, hesperidin, neohesperidin, naringin, morin, kaempferol, fisetin, anthocyanins, such as delphinidin and malvidin, curlycumin, such as delphinidin and malvidin , Rosmarinic acid, 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 are very particularly preferred primary antioxidant used.

The following amine antioxidants can be used, for example:

N, N'-di-isopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-bis (1,4-dimethylpentyl) -p-phenylenediamine, N, N ' -Bis (1-ethyl-3-methyl-pentyl) -p-phenylenediamine, N, N'-bis (1-methylheptyl) -p-phenylenediamine, N, N'-dicyclohexyl-p-phenylenediamine, N, N'- Diphenyl-p-phenylenediamine, Ν, Ν'- 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-methoxy-

phenyl) amine, 2,6-di-tert-butyl-4-dimethylaminomethyl-phenol, 2,4'-di-aminodiphenyl methane, 4,4'-diaminodiphenyl methane, Ν, Ν, Ν ', Ν'-tetra-methyl- 4,4'-diaminodiphenylmethane, 1,2-bis [(2-methyl-phenyl) amino] ethane, 1,2-bisiphenylamino) 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 tert-octylphenothiazines, N-allylphenothiazine, Ν, Ν, Ν ', Ν'-tetraphenyl-1,4-diaminobut-2-en and mixtures or combinations thereof.

Preferred amine antioxidants are:

Ν, Ν'-di-isopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-bis (1,4-dimethylpentyl) -p-phenylenediamine, N, N ' -Bis (1-ethyl-3-methyl-pentyl) -p-phenylenediamine, N, N'-bis (1-methylheptyl) -p-phenylenediamine, Ν, Ν'- 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.

Other preferred amine antioxidants are:

Hydroxylamines or N-oxides (nitrones), such as N, N-dialkylhydroxylamines, N, N-dibenzylhydroxylamine, Ν, Ν-dilaurylhydroxylamine, N, N-distearylhydroxylamine, N-benzyl-α-phenylnitrone, N-octadecyl- α-hexadecylnitrone, as well as Genox EP (sold by Addivant) according to the formula:

phenyl) amine, 2,6-di-tert-butyl-4-dimethylaminomethyl-phenol, 2,4'-di-aminodiphenylmethane, 4,4'-diaminodiphenylmethane, Ν, Ν, Ν ', Ν'-tetra-methyl- 4,4'-diaminodiphenylmethane, 1,2-bis [(2-methyl-phenyl) amino] ethane, 1,2-bis (phenylamino) propane, (o-tolyl) biguanide, bis [4- (1 ', 3 '-dimethylbutyl) -phenyl] amine, tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- and dialkylated tert-butyl / tert-octyldiphenylamines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl / isohexyl-diphenylamines, a mixture of mono- and dialkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine Mixture of mono- and dialkylated tert-butyl / tert-octylphenothiazines,a mixture of mono- and dialkylated tert-octylphenothiazines, N-allylphenothiazine, Ν, Ν, Ν ', Ν'-tetraphenyl-1,4-diaminobut-2-en 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-methyl-pentyl) -p-phenylenediamine, N, N'-bis (1-methylheptyl) -p-phenylenediamine, Ν, Ν'-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.

Other preferred amine antioxidants are:

Hydroxylamines or N-oxides (nitrones), such as N, N-dialkylhydroxylamines, N, N-dibenzylhydroxylamine, Ν, Ν-dilaurylhydroxylamine, N, N-distearyl-hydroxylamine, N-benzyl-α-phenylnitrone, N-octadecyl- α-hexadecylnitrone, as well as Genox EP (sold by Addivant) according to the formula:

Preferred lactones are:

Benzofuranones and indolinones such as 3- (4- (2-acetoxyethoxy) phenyl] -5,7-di-tert-butyl-benzofuran-2-on, 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-dimethyl-phenyl) -5,7-di-tert-butyl-benzofuran-2-one.

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 thereof.

The following can be used as phosphites or phosphonites, for example:

Triphenyl phosphite, diphenylalkyl phosphites, phenyl dialkyl phosphites, tri (nonyl-phenyl) phosphite, trilauryl phosphites, trioctadecyl phosphite, distearylpenta-erythritol diphosphite, tris- (2,4-di-tert-butylphenyl) phosphite, bisisodecylpenta-erythritol, diisodecylpenta-erythritol, diisodecylpenta-erythritol, diisodecylpenta-erythritol -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'-biphenylenediphosphonite, 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) methylphosphite, bis ( 2,4-di-tert-butyl-6-methyl-phenyl) 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-butyl-phenoxy) -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, ditetradecylthiodipropionate, 3- (dodecylthio) -1,1 '- [2,2-bis [[3- (dodecylthio) -1-oxopropoxy] methyl] -1,3-propanediyl] propanoic acid ester.

In a further preferred embodiment, component (B) consists of both a primary antioxidant and a secondary anti-oxidant. In this case it is particularly preferred that component (B) consists of a phenolic antioxidant and a phosphite or phosphonite.

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

According to a further preferred variant of the method according to the invention, the at least one alditol has the empirical formula

HIGH 2 [CH (OH)] n CH 2 OH,

R 1 -OCH 2 [CH (OH)] n CH 2 OH, or

HIGH 2 [CH (OH)] n [CH (OR 1 )] CH 2 OH

with n = 2-6, preferably n = 3-5, where R 1 is an optionally substituted sugar residue.

The at least one alditol is preferably selected from the group consisting of threitol, erythritol, galactitol, mannitol, ribitol, sorbitol, xylitol, arabitol, isomalt, lactitol, maltitol, altritol, iditol, maltotritol and hydrogenated oligo- and polysaccharides with polyol End groups and mixtures thereof. The at least one preferred alditol is particularly preferably selected from the group consisting of erythritol, mannitol, isomalt, maltitol and mixtures thereof. The at least one alditol is very particularly preferably mannitol or erythritol. Maltitol can also be present as a so-called syrup, which is obtained industrially by hydrogenation of glucose and, in addition to maltitol and sorbitol, also contains hydrogenated oligo- and polysaccharides with alditol end groups. The alditols can be in different optical isomers, for example

Examples of heptitols and octitols are: meso-glycero-allo-heptitol, D-glycero-D-altro-heptitol, D-glycero-D-manno-heptitol, meso-glycero-gulo-heptitol, D-glycero-D-galacto -Heptitol (Perseitol), D-glycero-D-gluco-heptitol, L-glycero-D-gluco heptitol, D-erythro-L-galacto-octitol, D-threo-L-galacto-octitol

The structures and anchor points of the preferred alditols are as follows

Table 1 can be found.

Table 1

Alternatively or in addition to the aforementioned alditols, cyclitols, ie ring-shaped polyols, can also be used in the process according to the invention (or for the purposes of the plastic composition according to the invention, the molding compound or the molded part or the stabilizer composition).

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, preferred is myo-inositol ( myo-inositol).

For the purposes of the present invention, the alditols or cyclitols present as components (B) are taken to be overall as component (B) in terms of their weight fraction, so that this always means the totality of the alditols and / or cyclitols present.

A particularly preferred variant of the method according to the invention is

characterized in that at least one primary antioxidant and at least one secondary antioxidant are introduced into the halogen-free thermoplastic material. This means that at least one primary antioxidant and at least one secondary antioxidant are used as component (A). In this way an even more effective stabilization of the halogen-free thermoplastic material against oxidative, thermal and / or actinic degradation can be achieved.

In a further preferred variant of the process according to the invention, component (A) and component (B) are used in a weight ratio of 5:95 to 95: 5, preferably 10:90 to 90:10, particularly preferably 20:80 up to 80:20, incorporated into the halogen-free thermoplastic plastic recyclate.

If component (A) consists of both a primary antioxidant and a secondary antioxidant, the ratio between primary and secondary antioxidant is preferably 90:10 to 10:90, particularly preferably 80:20 to 20:80 and very particularly preferably 70: 30 to 30:70.

Another preferred variant of the method according to the invention is characterized in that components (A) and (B) are introduced into the halogen-free thermoplastic recycled plastic material by using components (A) and (B) present as solids be mixed with the halogen-free thermoplastic plastic recyclate present as a solid and the resulting mixture is melted and then cooled, or

the components (A) and (B) present as solids are melted and the resulting melt is introduced into a melt of the halogen-free thermoplastic recycled plastic.

Components (A) and (B), which can be in the form of powder, compacted, granulate, solution or flakes, are preferably mixed with the polymer to be stabilized, the polymer matrix is ​​converted into the melt and then cooled. Alternatively, it is also possible to incorporate the additive in a molten state into a polymer melt.bring.

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 described above.

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

Nucleating agents, anti-nucleating agents, impact strength improvers, plasticizers, lubricants, rheology modifiers, thixotropic agents, chain extenders, optical brighteners, antimicrobial agents, antistatic agents, slip agents, antiblocking agents, coupling agents, crosslinking agents, hydrophobizing agents, hydrophilicizing agents, acidifying agents, acidifying agents, hydrophilizing agents, acidifying agents, anti-crosslinking agents, hydrophilizing agents, acidifying agents, thixotropy agents, Propellants, breakdown additives, defoaming agents, odor traps, marking agents, anti-fogging agents, fillers, reinforcing agents and mixtures thereof.

Furthermore, it is preferred that at least one additive is additionally introduced into the halogen-free thermoplastic recycled material, 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, especially calcium carbonate, magnesium carbonate and dolomite, and hydroxides, especially brucite,

b) light stabilizers, preferably light stabilizers from the group of hindered amines,

c) dispersants,

d) filler deactivators, and

Mixtures thereof.

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

Suitable 2- (2'-hydroxyphenyl) benzotriazoles are, for example, 2- (2'-hydroxy-5'methylphenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5 '- (1,1,3,3-tetramethylbutyl) phenyl) benzotriazole, 2- (3' , 5'-di-tert-butyl-2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl-5-chlorobenzotriazole, 2- (3'- sec-butyl-5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) benzotriazole, 2- (3 ', 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-octyloxy-carbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3 '-tert-Butyl-5 '- [2- (2-ethyl-hexyloxy) 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 product of the transesterification of 2- [3'-tert-butyl-5 '- (2-methoxycarbonylethyl) -2 '-hydroxyphenyl] -2H-benzotriazole with polyethylene glycol 300;[R-CH2 CH 2 - COO - CH 2 CH 2 -] - 2 , where R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl, 2- [2'-hydroxy-3 '- (α, α-dimethylbenzyl) -5' - (1,1,3,3-tetramethylbutyl) -phenyl] benzotriazole, 2- [2'-hydroxy-3 '- (1,1,3,3-tetramethylbutyl ) -5 '- (α, α-dimethylbenzyl) phenClaims

1. Process for stabilizing halogen-free thermoplastic plastic recyclates against oxidative, thermal and / or actinic degradation, in which at least one alditol and / or at least one cyclitol (component (A)) is converted into a halogen-free thermoplastic plastic Recyclate can be introduced.

2. The method according to claim 1, characterized in that in addition to at least one alditol and / or at least one cyclitol, at least one primary antioxidant and / or at least one secondary antioxidant (component (B)) is introduced into a halogen-free thermoplastic plastic recyclate become.

3. The method according to claim 2, characterized in that the at least one primary antioxidant is selected from the group consisting of phenolic antioxidants, amines, lactones and mixtures thereof.

4. The method according to any one of the two preceding claims, 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 this.

5. The method according to any one of the preceding claims, characterized in that the at least one alditol has the empirical formula

HIGH 2 [CH (OH)] n CH 2 OH,

R 1 -OCH 2 [CH (OH)] n CH 2 OH, or

HIGH 2 [CH (OH)] n [CH (OR 1 )] CH 2 OH

with n = 2-6, preferably n = 3-5, where R 1 is an optionally substituted sugar radical.

6. The method according to any one of the preceding claims, characterized in that the at least one alditol is selected from the group consisting of threitol, erythritol, galactitol, mannitol, ribitol, sorbitol, xylitol, arabitol, isomalt, lactitol, maltitol, and maltotritol hydrogenated oligo- and polysaccharides with polyol end groups and mixtures thereof, the at least one alditol preferably being selected from the group consisting of erythritol, mannitol, isomalt, maltitol and mixtures thereof.

7. The method according to any one of the preceding claims, characterized in that the at least one cyclitol is selected from the group consisting of inositol, quercitol, viscumitol, bornesitol, conduritol, ononitol, pinitol, pinpollitol, ciceritol, quebrachitol, quinic acid, Shikimic acid and valienol, the at least one cyclitol preferably being myo-inositol.

8. The method according to any one of claims 2 to 7, characterized in that at least one primary antioxidant and at least one secondary antioxidant are introduced into the halogen-free thermoplastic recycled material.

9. The method according to any one of claims 2 to 8, characterized in that component (A) and component (B) in a weight ratio of 95: 5 to 5:95, preferably from 90:10 to 10:90 , particularly preferably from 80:20 to 20:80, are introduced into the halogen-free thermoplastic recycled plastic.

10. The method according to any one of claims 2 to 9, characterized in that components (A) and (B) are introduced into the halogen-free thermoplastic recycled plastics material in that the components (A) and (B) present as solids with the solid halogen-free thermoplastic plastic

Recyclate are mixed and the resulting mixture is melted and then cooled, or

the components (A) and (B) present as solids are melted and the resulting melt is introduced into a melt of the halogen-free thermoplastic recycled plastic.

11. The method according to any one of the preceding claims, characterized in that, based on 95.0 to 99.99 parts by weight, preferably 99.0 to 99.98 parts by weight of the halogen-free thermoplastic recycled material 0, 01 to 5.0 parts by weight, preferably 0.02 to 1.0 parts by weight of the at least one alditol and / or cyclitol (component (A)) are introduced.

12. The method according to any one of 2 to 11, characterized in that based on 91 to 99.94 parts by weight, preferably 98.5 to 99.91 parts by weight of the halogen-free thermoplastic recycled material

(A) 0.02 to 3 parts by weight, preferably 0.03 to 0.5 part by weight, of the at least one alditol and / or at least one cyclitol, and

(B) 0.04 to 6 parts by weight, preferably 0.06 to 1 part by weight, of the at least one primary antioxidant and / or of the at least one secondary antioxidant

be introduced.

13. The method according to any one of the preceding claims, characterized in that the halogen-free thermoplastic plastic recyclate is selected from the group consisting of

a) Recycled polymers made from olefins or diolefins, such as, for example, 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 random 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 isoprene, styrene Isoprene-styrene (SIS), styrene-butadiene-acrylonitrile (ABS), styrene-acrylonitrile-acrylate (ASA), styrene-ethylene, styrene-maleic anhydride polymers including the corresponding

Graft copolymers such as styrene on butadiene, maleic anhydride on SBS or SEBS, and graft copolymers made of methyl methacrylate, styrene-butadiene and ABS (MABS), c) recycled polymers of unsaturated esters such as

Polyacrylates and polymethacrylates such as polymethyl methacrylate

(PMMA), polybutyl acrylate, polylauryl acrylate, polystearyl acrylate, polyacrylonitrile, polyacrylamides, and corresponding copolymers such as polyacrylonitrile-polyalkyl acrylate,

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

g) recycled polymers of cyclic ethers such as

Polyethylene glycol, polypropylene glycol, polyethylene oxide, polypropylene oxide,

h) recycled polyurethanes made 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, e.g. produced 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 hydroxycarboxylic acids such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polypropylene terephthalate, polyethylene naphthylate, poly-1,4-dimethylocyclohexane phthalate, polyhydroxybenzoate, polyhydroxybenzoate,

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

m) recycled cellulose derivatives, such as cellulose nitrate, cellulose acetate, cellulose propionate, cellulose butyrate, n) and also mixtures, combinations or blends of two or more of the aforementioned polymers.

14. Plastic composition containing or consisting of

(A) at least one alditol and / or at least one cyclitol (component (A)), and

(B) at least one halogen-free thermoplastic plastic recyclate.

15. Plastic composition according to the preceding claim, characterized in that the plastic composition,

(A) 0.01 to 5.0 parts by weight, preferably 0.02 to 1.0 part by weight, of the at least one alditol and / or cyclitol (component (A)) and

(B) 95.0 to 99.99, preferably 99.0 to 99.98 parts of the halogen-free thermoplastic recycled plastic

contains or consists of it.

16. Plastic composition according to one of the two preceding claims, containing or consisting of

(A) at least one alditol and / or at least one cyclitol (component (A)),

(B) at least one primary antioxidant and / or at least one secondary antioxidant (component (B)), and

(C) at least one halogen-free thermoplastic recyclate.

17. Plastic composition according to the preceding claim, characterized in that the plastic composition

(A) 0.02 to 3 parts by weight, preferably 0.03 to 0.5 part by weight, of at least one alditol and / or at least one cyclitol,

(B) 0.04 to 6 parts by weight, preferably 0.06 to 1 part by weight, of at least one primary antioxidant and / or at least one secondary antioxidant, and

(C) 91 to 99.94 parts by weight, preferably 98.5 to 99.91 parts by weight, of at least one halogen-free thermoplastic recyclate

contains or consists of it.

18. Plastic composition according to one of the two preceding claims, characterized in that the plastic composition

(A) 0.02 to 3 parts by weight, preferably 0.03 to 0.5 part by weight, of at least one alditol and / or at least one cyclitol,

(B1) 0.02 to 3 parts by weight, preferably 0.03 to 0.5 part by weight, of at least one primary antioxidant,

(B2) 0.02 to 3 parts by weight, preferably 0.03 to 0.5 parts by weight, of at least one secondary antioxidant, and

(C) 91 to 99.94 parts by weight, preferably 98.5 to 99.91 parts by weight, of at least one halogen-free thermoplastic recycled material

contains or consists of it.

19. Plastic composition according to one of claims 14 to 18, 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 strength improvers, plasticizers, lubricants, rheology modifiers, thixotropic agents, chain extenders, optical brighteners, antimicrobial agents, antistatic agents, slip agents, antiblocking agents, coupling agents, crosslinking agents, anti-crosslinking agents, hydrophilizing agents, hydrophobizing agents, acidifying agents, oxygenating agents, disinfectants capture, blowing agents, degradation additives, defoaming agents,Odor traps, markers, anti-fogging agents, fillers, reinforcing agents and mixtures thereof.

20. Plastic composition according to one of claims 14 to 19, 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, especially synthetic hydrotalcites based on aluminum, magnesium and zinc, hydrocalumites, zeolites, alkaline earth oxides, especially 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 hindered amines,

c) dispersants,

d) filler deactivators, and

e) mixtures thereof.

21. Plastic composition according to one of claims 14 to 20, characterized in that the at least one halogen-free thermoplastic plastic recyclate is preferably a polyolefin recyclate.

22. Plastic composition according to one of claims 14 to 21, characterized in that the plastic composition can be produced with a method according to one of claims 1 to 13.

23. Molding compound or molded part producible from a plastic composition according to one of claims 14 to 22, 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 articles, for packaging, for furniture and / or for textiles.

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

(A) at least one primary antioxidant and / or at least one secondary antioxidant, and

(B) at least one alditol and / or at least one cyclitol.

25. Use of at least one alditol and / or at least one cyclitol to stabilize halogen-free thermoplastic recycled plastics against oxidative, thermal and / or actinic degradation.

26. Use of a stabilizer composition containing or consisting of

(A) at least one alditol and / or at least one cyclitol and

(B) at least one primary antioxidant and / or at least one secondary antioxidant

to stabilize halogen-free thermoplastic plastic recyclates against oxidative, thermal and / or actinic degradation.yl] benzotriazole.