EP3870641A1

EP3870641A1 - Method of stabilizing virgin thermoplastic material and stabilized plastics compositions, moulding compounds and mouldings produced therefrom, stabilizer compositions and uses thereof

Info

Publication number: EP3870641A1
Application number: EP19802078.6A
Authority: EP
Inventors: Elke Metzsch-Zilligen; Rudolf Pfaendner
Original assignee: Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Current assignee: Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Priority date: 2018-10-23
Filing date: 2019-10-17
Publication date: 2021-09-01
Also published as: WO2020083740A1; CN113166470A; KR20210102884A; DE102018218120A1; JP2022505635A; US20210388176A1

Abstract

The present invention relates to a method of stabilizing virgin thermoplastic material against oxidative, thermal and/or actinic degradation. In the method of the invention, at least one polyphenol and at least one alditol and/or cyclitol are introduced into a virgin thermoplastic material. The method of the invention can stabilize virgin thermoplastic material with high efficacy and in a very environmentally friendly and inexpensive manner against oxidative, thermal and/or actinic degradation. The present invention additionally also relates to correspondingly stabilized virgin thermoplastic material and to moulding compounds and mouldings produced therefrom. The present invention also further relates to stabilizer compositions and to the use thereof for stabilization of virgin thermoplastic material against oxidative, thermal and/or actinic degradation.

Description

Process for the stabilization of new thermo-elastic plastic as well as stabilized plastic composition. molding compounds and molded parts made from them. Stabilizer compositions and uses thereof

The present invention relates to a method for stabilizing new thermoplastic synthetic material against oxidative, thermal and / or actinic degradation. In the method according to the invention, at least one polyphenol and at least one alditol and / or cyclitol are introduced into a new thermoplastic material. The process according to the invention can be used to stabilize new thermoplastic material with high effectiveness and in a very environmentally friendly and cost-effective manner against oxidative, thermal and / or actinic degradation. In addition, the present invention also relates to appropriately stabilized new thermoplastic synthetic material and to molding compositions and molded parts produced therefrom. Furthermore, the present invention also relates to stabilizer compositions and their use for stabilizing new thermoplastic plastic against oxidative, thermal and / or actinic degradation.

Organic materials such as plastics are subject to aging processes, which ultimately lead to a loss of the desired properties, e.g. of the mechanical parameters. This process, called autoxidation, leads to changes in the polymer chain starting from radical chain splitting by mechanochemical processes or by UV radiation in the presence of oxygen, e.g. in molecular weight or the formation of new chemical groups. Stabilizers are therefore used to prevent or at least delay this aging. Important representatives of stabilizers are antioxidants, which interfere with the radicals formed in the autoxidation and thus interrupt the degradation process. A distinction is generally made between primary antioxidants that can react directly with oxygen-containing free radicals or C radicals and secondary antioxidants that react with intermediate hydroperoxides (see C. Kröhnke et al. Antioxidants in Ullmann's Encyclopedia of Industrial Chemistry , Wiley-VCH Verlag, Weinheim 2015). Typical representatives of primary antioxidants are, for example, phenolic antioxidants, amines but also lactones. Classes of secondary antioxidants are phosphorus compounds such as Phosphites and phosphonites, but also organosulfur compounds such as Sulfides and disulfides. In practice, primary and secondary antioxidants are usually combined, which leads to a synergistic effect.

Plastics made from fossil raw materials such as petroleum or natural gas are increasingly being supplemented or replaced by plastics based on renewable raw materials, accessible through biochemical processes. However, the primary and secondary antioxidants used for this (and for plastics made from fossil raw materials) are still not entirely based on renewable raw materials.

Basically, primary antioxidants from renewable raw materials are known, which are also used occasionally in plastics. A typical example is tocopherols (vitamin E). Tocopherols have the usual tioxidants have a sterically hindered phenol structure and can be used alone or in combination with secondary antioxidants (eg S. Al-Malaika, Macromol. Symp. 2001, 176, 107). Tocopherols can e.g. be isolated from natural substances such as wheat germ oil, sunflower oil or olive oil. However, secondary antioxidants, ie phosphite or phosphonite structures, cannot be found in nature, so that synergistic combinations of primary and secondary antioxidants from renewable raw materials have so far hardly been accessible.

It was therefore an object of the present invention to provide synergistic stabilizer combinations based on renewable raw materials, especially for new plastics, which at least correspond or are superior in their effects to combinations of classic primary and secondary antioxidants. It was also an object of the present invention to provide a method for stabilizing new plastics and correspondingly stabilized new plastics.

This object is achieved with regard to a method for stabilizing new thermoplastic plastic with the features of patent claim 1, with regard to a plastic composition with the features of patent claim 10, with regard to a molding compound or a molded part which can be produced from the plastic composition with the features of Claim 15, with regard to a stabilizer composition with the features of claim 16 and with regard to the use of the stabilizer compositions with the features of claim 18. The respective dependent claims represent advantageous developments.

According to the invention, a method for stabilizing new thermoplastic plastic against oxidative, thermal and / or actinic degradation is thus specified, in which at least one polyphenol (hereinafter also referred to as “component (A)”) and at least one alditol and / or cylitol (hereinafter also referred to as "components (B)") is introduced into a new thermoplastic material.

The plastics to be stabilized can be based on fossil fuels Raw materials or made from renewable raw materials.

New thermoplastic materials are not yet used, i. H. plastic material that has not yet been used. Corresponding new plastic material is also referred to in English as "virgin resin" or "pristine resin". New plastics can also be called "new plastics" or "brand new plastics". In the sense of the present invention, the new plastic material can be present, for example, as fresh plastic granulate or plastic powder, or also as a plastic melt that occurs during the manufacturing process. New plastic goods are therefore different from recycled plastics.

In contrast to plastic recyclates, plastic new goods mostly show no or no significant pre-damage, ie there are no or only very minor new chemical groups on the polymer chain created by oxidative or (photo) oxidative processes. In the case of polyolefin recyclates, for example, these are predominantly carbonyl groups, which are not present in new goods or are only present to a very minor extent. The same applies to the concentration of acid groups, which are not or only to a minor extent found in new goods, while recyclates have a significant concentration. The concentration of the carbonyl groups is therefore also a measure of the pre-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. Here, the absorption of the carbonyl vibration is measured in the range of 1720 cm ¹ . In the case of new goods, the concentration of carbonyl groups is generally below 5 mmol / kg, the concentration of acid groups below 2 mmol / kg.

Surprisingly, it has been found that the combination of polyphenols and sugar alcohols (alditols / cyclitols) shows a very good stabilizing effect in new thermoplastic materials.

In the process according to the invention, the at least one polyphenol (component (A)) and the at least one alditol or cyclitol (component nente (B)) introduced into a new thermoplastic material. Components (A) and (B) can be introduced into the new plastic material individually or separately from one another, or components (A) and (B) can be put together in the form of a composition or composition containing components (A) and (B) are introduced into the new plastic material in the form of a composition consisting of components (A) and (B).

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

Preferably, components (A) and (B), which may be in the form of powder, compact, granules, liquid, syrup, solution or flakes, are mixed with the new polymer to be stabilized, the polymer matrix is converted into the melt and then cooled. Alternatively, it is also possible to introduce an additive which is solid at room temperature in a molten state into a polymer melt.

Furthermore, components (A) and (B) can be in the form of so-called masterbatches or concentrates, which, for example, 10-90% of a stabilizer composition consisting of components (A) and (B) in a polymer or oligomer such as a polyethylene wax, Contain polypropylene wax or a natural vegetable wax, manufactured and introduced.

Components (A) and (B) can be introduced into the new thermoplastic material by mixing components (A) and (B) with the new thermoplastic material as a solid, and the resulting mixture is melted and then cooled.

The component (A) and component (B) used according to the invention act together as a synergistic stabilizer for the new thermoplastic material, the oxidative, thermal and / or actinic degradation of the new thermoplastic material being inhibited or prevented. In other words, by introducing component (A) and additionally component (B) into the new thermoplastic material, the Plastic stabilized against oxidative, thermal and / or actinic degradation.

The present invention is particularly characterized in that a combination of polyphenols and alditols (sugar alcohols) and / or cyclitols is used to stabilize new thermoplastic materials.

A combination of polyphenols and sugar alcohols or polyols has not previously been used to stabilize new thermoplastic materials. 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 the zinc compounds which promote PVC degradation are chelated and deactivated (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 in order to achieve a reaction as an HCI scavenger in Zn-free PVC (see J. Steenwijk et al. Pol. Degr. Stab. 2006, 2233-2240).

According to the invention, it was surprisingly found that the introduction of at least one polyphenol and at least one alditol and / or at least one cyclitol alone and optionally together with at least one further primary and / or at least one secondary antioxidant is a very effective one Stabilization of new thermoplastic material against oxidative, thermal and / or actinic degradation can be achieved. In addition, both polyphenols and alditols or cyclitols are very environmentally friendly and inexpensive compounds. The process according to the invention can thus be used to stabilize new thermoplastic plastics in a very effective, environmentally friendly and cost-effective manner against oxidative, thermal and / or actinic degradation.

According to a preferred embodiment, the polyphenols (A) have at least at least one aromatic group with at least 2 phenol groups or at least two aromatic groups with one phenol group each and are preferably isolated from natural products, obtained from natural products by a bio-chemical route, chemically modified from natural products or produced in a nature-identical manner by chemical means.

Suitable polyphenols (A) are, for example, bile acids, hydroxytyrosol, flavonols such as e.g. Chrysin, quercetin, hesperidin, neohesperidin, naringin, marin, kaempferol, fisetin, anthocyanins, e.g. Delphinidine and malvidin, carnosolic acid, carnosol, rosemic acid and resveratrol, tannins, silymarin, containing silybin, isosylibine, silydianine, ellagic acid. The polyphenols are preferably isolated from natural substances and are therefore renewable raw materials; if necessary, a chemical-synthetic reaction can take place after isolation and purification. Examples of these are esters of bile acid e.g. Hexyl, heptyl, octyl, nonyl, decyl, isodecyl, lauryl, stearyl, myristyl, cetyl or oleyl gallate. Furthermore, natural products are often mixtures of different active substances and mixtures of optical isomers.

Preferred polyphenols are the following structures:

Tannins such as Gallotannin (Corilagin)

10th

15

Tannin or quercetin are particularly preferred.

According to a further preferred variant of the process 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 (ORi)] CH ₂ OH

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

The at least one alditol is preferably selected from the group consisting of 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 mannitol or erythritol is very particularly preferred. Maltitol can also be present as a so-called syrup, which is obtained industrially by hydrogenating glucose and, in addition to maltitol, sorbitol, also contains hydrogenated oligo- and polysaccharides with alditol end groups. The alditols can be present in different optical isomers, for example in the D or L form or meso form.

Examples of heptitol and octitol 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

Preferred alditols and substituted alditols have a melting point of> 100 ^° C., have low water solubility and low water absorption (hygroscopy). Other preferred compounds melt at the usual processing conditions of polyolefins in the range from 150 to -250 C, and ^e have a decomposition temperature> 250 ^e C.

The structures and fixed points of preferred alditols can be found in Table 1 below.

As an alternative or in addition to the aforementioned alditols, in the process according to the invention (or for the purposes of the plastic composition according to the invention, the molding composition or the molding or the stabilizer composition), cyclitols, ie. H. ring-shaped polyols can be used.

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

For the purposes of the present invention, the alditols or cyclitols contained as components (B) are understood in terms of their total weight as component (B), so that the entirety of the alditols and / or cyclitols contained is always to be understood here.

A further preferred embodiment provides that component (A) and component (B) in a weight ratio of 5:95 to 90:10, preferably 10:90 to 90:10, particularly preferably 20:80 to 80 : 20, into which new thermoplastic materials are introduced.

Furthermore, preferably in the method according to the invention

(A) 0.02 to 3.0 parts by weight, preferably 0.06 to 1.0 parts by weight, of at least one polyphenol,

(B) 0.02 to 3.0 parts by weight, preferably 0.03 to 0.5 parts by weight, of at least one alditol and / or at least one cyclitol, in

(C) 94.0 to 99.96 parts by weight, preferably 98.5 to 99.91 parts by weight of a thermoplastic synthetic material or mixtures thereof.

so that 100% can be obtained from (A), (B), (C).

For the purposes of the present invention, it is particularly preferred if the thermoplastic new material is selected from the group consisting of

a) polymers of olefins or diolefins, such as e.g. Polyethylene, especially 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 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, for example, polypropylene-g-maleic anhydride, polypropylene-g-acrylic acid and polyethylene-g-acrylic acid, polyethylene-polybutyl acrylate-g-maleic acid hydride, long chain branched polypropylene copolymers, which are produced with alpha-olefins as comonomers, in particular 1-butene. 1-hexene, 1-octene and / or 1-octadecene and blends of several of the aforementioned polymers, such as LLPE / LLDPE, b) 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 styrene on butadiene, maleic anhydride on SBS or SEBS, as well as graft copolymers of methyl methacrylate, styrene-butadiene and ABS (MABS) and hydrogenated polystrylro-derivatives such as polyvinyl cyclohexa

c) halogen-containing polymers, e.g. Polyvinyl chloride (PVC), polychloroprene, polyvinylidene chloride (PVDC), copolymers of vinyl chloride and vinylidene chloride, copolymers of vinyl chloride and vinyl acetate, chlorinated polyethylene, polyvinylidene fluoride, epichlorohydrin homo- and copolymers, in particular with ethylene oxide (ECO),

d) 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,

e) polymers of unsaturated alcohols and derivatives, e.g.

Polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyallyl phthalate, polylallyl melamine,

f) polyacetals, e.g. Polyoxymethylene (POM), and corresponding copolymers, e.g. Copolymers with butanal,

g) polyphenylene oxides and blends of these with polystyrene or polyamides,

h) polymers of cyclic ethers such as e.g. Polyethylene glycol,

Polypropylene glycol, polyethylene oxide, polypropylene oxide, polytet ra hyd rof u ra n, i) polyurethanes of hydroxy-terminated polyethers or polyesters and aromatic or aliphatic isocyanates, such as

2,4- or 2,6-toluene diisocanate or methylene diphenyl diisocyanate, linear polyurethanes (TPU) or polyureas,

j) polyamides such as Polyamide-6, 6.6, 6.10, 4.6, 4.10, 6.12, 10.10, 10.12, 12.12, polyamide 11, polyamide 12 and (partially) aromatic polyamides such as Polyphthalamides, e.g. made from terephthalic acid and / or isophthalic acid and aliphatic diamines such as e.g. Hexamethylene diamine or m-xylylenediamine 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, blends of different polyamides, e.g. PA-6 and PA 6.6 or blends of polyamides and polyolefins such as e.g. PA / PP,

k) polyimides, polyamide-imides, polyetherimides, polyesterimides, poly (ether) ketones, polysulfones, polyether sulfones, polyarylsulfones, polyphenylene sulfide, polybenzimidazoles, polyhydantoins,

L) 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 (PTT), polyethylene naphthylate (PEN), poly

1,4-di methylolcyclohexane terephthalate, polyhydrooxybenzoate,

Polyhydroxynaphthalate, polylactic acid (PLA), polyhydroxybutyrate (PBT), polyhydroxyvalate (PHV), polyethylene succinate,

Polybutylene succinate (PBS) and polycaprolactone,

m) polycarbonates (PC), polyester carbonates, and blends of these, such as PC / ABS, PC / PBT, PC / PET / PBT, PC / PA

n) cellulose derivatives, e.g. Cellulose nitrate, cellulose acetate, cellulose propionate, cellulose butyrate,

o) epoxy resins consisting of di- or polyfunctional epoxy compounds in combination with e.g. Hardeners based on amines, anhydrides, dicyandiamide, mercaptans, isoicyanates or catalytic hardeners,

p) phenolic resins, such as, for example, phenol-formaldehyde resins, urea-formaldehyde resins or melamine-formaldehyde resins, q) unsaturated polyester resins made from unsaturated dicarboxylic acids and diols with vinyl compounds such as styrene, alkyd resins, r) silicones, such as those based on dimethylsiloxanes, methylphenylsiloxanes or diphenylsiloxanes, the silicones mentioned also being fully or partially terminated, for example vinyl-terminated can

s) Polymers based on natural products such as Starch, alginates, chitin or chitosan,

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

All of the aforementioned polymers are used as new goods.

The new thermoplastic material is particularly preferably selected from the group consisting of polymers of olefins or diolefins, such as e.g. Polyethylene, especially 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, 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.

The thermoplastic new polyolefin is very particularly preferred. For example, the new thermoplastic material can be polypropylene, in particular thus a polypropylene or polyethylene, in particular therefore a polyethylene.

Polymers made from renewable raw materials, in particular polyesters such as polylactic acid (PLA), polyhydroxybutyrate (PBT), polyhydroxyvalerate (PHV), polyethylene succinate, polybutylene succinate (PBS) and polyamides made from renewable raw materials such as polyamide 10, 10 or polyamide 11, are also particularly preferred. In a further preferred embodiment, the polymers are halogen-free.

Furthermore, it is also possible for additional stabilizers, for example a further primary antioxidant, to be incorporated into the thermoplastic synthetic material. For the purposes of the method according to the invention, however, it is also possible to dispense with the use of a phenolic antioxidant. In the event that a primary antioxidant is used to stabilize the new thermoplastic material, this is preferred, selected from the group consisting of phenolic antioxidants, amines, lactones and mixtures thereof.

Examples of other phenolic antioxidants that can be used are:

Alkylated monophenols, such as 2,6-di-te / t-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-te / t-butyl-4-ethylphenol, 2 , 6-di-tert-butyl-4- n-butylphenol, 2,6-di-te / t-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-te / t-butyl-4-methoxymethylphenol, linear or branched nonylphenols, such as, for example 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6- (l ^, -methylundec-l ^, -yl) phenol, 2,4-dimethyl-6- (l'-methylheptadec-l'- yOphenol, 2,4-dimethyl-6- (l ^, -methyltridec-l ^, -yl) phenol and mixtures thereof;

Alkylthiomethylphenols, e.g. 2,4-dioctylthiomethyl-6-te / t-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol;

Hydroquinones and alkylated hydroquinones such as e.g. 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-te / t-butylhydroquinone, 2,5-di-te / t-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2, 6-di-te / t-butylhydroquinone, 2,5-di-ferf-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-te / t-butyl- 4-hydroxyphenyl stearate, bis (3,5-di-tert-butyl-4-hydroxylphenyl) adipate;

Tocopherols, such as, for example, α-, β-, y-, d-tocopherol and mixtures of these (vitamin E); Hydroxylated thiodiphenyl ethers, such as ^2,2, thiobis (6-tert-butyl-4-methylphenol), 2,2'-thiobis (4-octylphenol), 4,4'-thiobis (6-te / t- butyl-3-methylphenol), 4,4'-thiobis (6-te / t-butyl-2-methylphenol), 4,4 ^, -thiobis (3,6-di-sec-amylphenol), 4,4 '-Bis (2,6-dimethyl-4-hydroxyphenyl) disulfide;

Alkylidene bisphenols, such as 2,2'-methylenebis (6-te / t-butyl-4-methylphenol), ^{2,2-methylenebis} (6-fe / f-butyl-4-ethylphenol), 2,2'-methylenebis [ 4-methyl-6- (a-methylcyclohexyl) phenol], 2,2 ^, -methylene bis (4-methyl-6-cyclhexylphenol),

2,2 ^, -Methylenbis (6-nonyl-4-methylphenol), 2,2 ^, -Methylenbis (4 _i 6-di-fert-butyl-phenol), 2,2 ^, -Ethylidenbis (4,6-di-fert -butylphenol) _i 2,2'-ethylidenebis (6-te / t-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-te / t-butylphenol, 4,4'-methylenebis (6-te / t-butyl -2-methylphenol), 1,1- bis (5-te / t-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis (3-te / t-butyl-5-methyl-2- hydroxybenzyl) -4-methylphenol, l, l, 3-tris (5-te / t-butyl-4-hydroxy-2-methylphenyQbutan, l, l-bis (5-te / t-butyl-4-hydroxy-2 -methylphenyl) -3-n-do-decyl mercaptobutane, ethylene glycol bis [3,3-bis (3'-te / t-butyl-4'-hydroxyphenyl) butyrate], bis (3-te / t-butyl -4-hydroxy-5-methylphenyl) dicyclopentadiene, bis [2- (3'-te / t-butyl-2'-hydroxy-5'-methylbenzyl) -6-te / t-butyl-4-methylphenyl] terephthalate , l, l-bis- (3,5-dimethyl-2-hydroxyphenyl) butane, 2,2-bis (3,5-di-te / t-butyl-4-hydroxyphenyl) propane, 2,2-bis- (5-te / t-butyl-4-hydroxy-2-methyl-p henyl) -4-n-dodecyl mercaptobutane, 1,1,5,5-tetra (5-te / t-butyl-4-hydroxy-2-methylphenyQpentane;

0-, N- and S-benzyl compounds, e.g. 3,5,3 ', 5'-tetra / t-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy-3,5-di -te / t-butylbenzylmercaptoacetate, tris (3,5-di- / t-butyl-4-hydroxybenzyl) amine,, bis (4-te / t-butyl-3-hydroxy-2,6-dimethyl-benzylQdithioterephthalate, Bis (3,5-di-te / t-butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5-di-te / t-butyl-4-hydroxybenzylmercaptoacetate;

Hydroxybenzylated malonates, such as, for example, dioctadecyl 2,2-bis (3,5-di-tert-butvl-2-hydroxybenzyl malonate, dioctadecyl 2- (3-te / t-butyl-4-hydroxy-5-methyl-benzyl Qmalonate, Didodecylmercaptoethyl-2,2-bis (3,5-di-te / t-butyl-4-hydroxybenzylQmalonate, bis [4- (l, l, 3,3-tetramethylbutyl) phenyl] -2,2-bis ( 3,5-di-te / t-butyl-4-hydroxybenzyl) malonate; Aromatic hyd roxybenzyl compounds, such as 1,3,5-tris (3,5-di-fert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3,5-di-te / t-butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di-te / t-butyl- 4-hydroxybenzyl) phenol;

Triazine compounds, e.g. 2,4-bis (octylmercapto) -6- (3,5-di-fert-butyl-4-hydroxyanilino) -l, 3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di -te / t-butyl-4-hydroxyanilino) -l, 3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di-te / t-butyl-4-hydroxyphenoxy) -l, 3rd , 5-triazine, 2,4,6-tris (3,5-di-te / t-butyl-4-hydroxyphenoxy) - 1,2,3-triazine, 1,3,5-tris (3,5- di-te / t-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-te / t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris ( 3,5-di- / t-butyl-4-hydroxphenylethyl) -l, 3,5-triazine, 1,3,5-tris (3,5-di-te / t-butyl-4-hydroxyphenylpropionyl) hexahydro-l, 3,5-triazine, l, 3,5-tris (3,5-dicyclohexyl-4-hydroxybenzyl I) isocyanate;

Benzylphosphonates, e.g. Dimethyl-2,5-di-te / t-butyl-4-hydroxybenzylphosphonate, Dietyhl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, di-octadecyl-3,5-di-te / t- butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-fert-butyl-4-hydroxy-3-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-te / t-butyl-4-hydroxybenzylphosphonic acid;

Acylaminophenols, e.g. 4-hydroxylauranilide, 4-hydroxystearanilide, octyl-N- (3,5-di-t / t-butyl-4-hydroxyphenyl) carbamate;

Esters of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with mono- or polyhydric alcohols, e.g. Methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylol propane, 4-hydroxymethyl-l-phospha-2,6,7-trioxabicyclo [2.2.2] octane;

Esters of ß- (5-te / t-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, penta- erythritol, tris (hydroxyethyl) isocyanate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-l-phospha-2,6,7-trioxabicyclo [2.2.2] octane, 3,9-bis [2- {3- (3-te / t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -l, l-dimethylethyl] - 2,4,8 , 10-tetraoxaspiro [5.5] undecane;

Esters of ß- (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-l-phospha-2,6,7-trioxabicyclo [2.2.2] octane;

Esters of (3,5-di-fert-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, thiodethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-l-phospha-2,6,7-trioxabicyclo [2.2.2] octane;

Amides of ß- (3,5-di-te / t-butyl-4-hydroxyphenyl) propionic acid, e.g. N, N'- bis (3,5-di-te / t-butyl-4-hydroxyphenylpropionyl) hexamethylenediamide, N, N'- bis (3,5-di-te / t-butyl-4-hydroxyphenylpropionyl) hexamethylenediamide, N, N'- bis (3,5-di-te / t-butyl-4-hydroxyphenylpropionyl) hexamethylenediamide, N, N'- bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazide, N, N'-bis [2- (3- [3,5-di / t-butyl-4-hydroxyphenyl] propionyloxy) ethyl] oxamide (Naugard * XL-1, sold by additive);

Ascorbic acid (vitamin C).

The following structures are particularly preferred phenolic antioxidants:

Other preferred phenolic antioxidants are monophenolic antioxidants based on renewable raw materials such as. B. Tocopherols (Vitamin E).

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 (l-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- phenylenediamine, 4- (p-toluenesulfamoyl) diphenylamine, N, N'-dimethyl-N, N'-di-sec-butyl-p-phenylene-diamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-l -naphthylamine, N- (4-tert-octylphenyl) -l-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, e.g. r, r'-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylamino-phenol, bis (4-methoxyphenyQamine, 2,6-di-tert -butyl-4-dimethylaminomethyl-phenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N, N, N ', N'-tetra-methyl-4,4'-diaminodiphenylmethane, l, 2- Bis [(2-methylphenyl) amino] ethane, l, 2-bis (phenylamino) propane, (o-tolyl) biguanide, bis [4- (l ', 3'-dimethylbutyl) phenyl] amine, te / t-octylated N-phenyl-l-naphthylamine, a mixture of mono- and dialkylated te / t-butyl / te / t-octyldiphenylamines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture from 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 a us mono- and dialkylated tert-octylphenothiazines, N-allylphenothiazine, N, N, N ', N'-tetraphenyl-l, 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 (l-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- (l ^ -DimethylbutyQ-N'-phenyl-p-phenylene-diamine, N- (1-methylheptyl) -N'-phenyl-p-phenylene diamine, N-cyclohexyl-N'-phenyl-p-phenylene diamine.

Other preferred amine antioxidants are:

Hydroxylamines or N-oxides (nitrones), e.g. N, N-dialkylhydroxylamines, N, N-dibenzylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-distearylhydroxylamine, N-benzyl-a-phenylnitron, N-octadecyl-a-hexadecylnitron, and 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 methylphenyl) -5,7-di-tert-butyl-benzofuran-2-one, and lactones, which additionally have a phosphite group

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.

Examples of phosphites or phosphonites that can be used are: triphenyl phosphite, diphenylalkyl phosphite, phenyl dialkyl phosphite, tri (nonyl phenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris (2,4-di-te / t-butylphenyl) phosphite - erythritol diphosphite, bis (2,4-di-te / t-butylphenyl) pentaerythritol diphosphite, bis (2,4-di-cumylphenyl) pentaerythritol diphosphite, bis (2,6-di-te / t-butyl-4-methylphenyl) pentaerythritol diphosphite , Diisodecyloxypentaerythritol diphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tris (te / t-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di -te / t-butylphenyl) -4,4'-biphenylene diphosphonite, 6-isooctyloxy- 2,4,8,10-tetra-te / t-butyl-12H-dibenz [d, g] -l, 3,2-dioxaphosphocin, bis (2,4-di-te / t-butyl-6-methylphenyl ) methylphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) methylphosphite, 6-fluoro-2,4,8,10-tetra-te / t-butyl-12-methyl-dibenz- [d, g] -l, 3,2-dioxaphosphocin, 2,2'2 "-nitrilo [triethyltris (3.3", 5,5'-tetra-te / t-butvl-l, l'-biphenyl-2,2 ^, -diyl) phosphite], 2-ethylhexyl (3 _i 3 ' _i 5 _i 5'-tetra-fert-butyl-l, l'-biphenyl-2,2 ^, -diyl)) phosphite, 5-butyl-5- ethyl 2- (2,4,6-tri-te / t-butylphenoxy) -1, 3,2-dioxaphosphirane.

Particularly preferred phosphites / phosphonites are:

with n = 3-100

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

Preferred sulfur compounds are:

Distearyl thiodipropionate, dilauryl thiodipropionate; Ditridecyldithiopropionate, Ditetradecylthiodipropionat, 3- (dodecylthio) -l, l '- [2,2-bis [[3- (dodecylthio) -l-oxopropoxy] methyl] -l, 3-propanediyl] propanoic acid ester.

In a further preferred embodiment, in addition to the minimum A secondary antioxidant can also be used as another primary antioxidant.

In the event that additional components are added to the thermoplastic synthetic material, 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, nucleating agents, antinucleating agents, toughness improvers, plasticizers, anti-plasticizers, lubricants, rheology modifiers, can preferably also be introduced into the new thermoplastic plastic , Thixotropic agents, chain extenders, optical brighteners, antimicrobial agents, antistatic agents, thermally and / or electrically conductive additives, slip agents, antiblocking agents, coupling agents, crosslinking agents, anti-crosslinking agents, hydrophilizing agents, hydrophobizing agents, adhesion promoters, detergents, anti-caking agents, acidifiers, blowing agents -Additives, defoaming agents, odor scavengers, marking agents In, antifogging agents, fillers, reinforcing materials and mixtures thereof.

It is further preferred that at least one additive, which is selected from the group consisting of, is additionally introduced into the thermoplastic new plastic

a) Acid scavengers, preferably calcium stearate, magnesium stearate, zinc stearate, aluminum stearate, calcium lactate, calcium stearoyl 2-lactate, hydrotalcites, in particular synthetic hydrotalcites based on aluminum, magnesium and zinc, hydrocalumites, zeolites, alkaline earth metal oxides, in particular calcium oxide and magnesium oxide, alkaline earth metal carbonates Calcium carbonate, magnesium carbonate and dolomite, and hydroxides, in particular brucite (magnesium hydroxide), b) light stabilizers, preferably light stabilizers from the group of hindered amines,

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-te / t-butyl-2'-hydroxyphenyl) benzotriazole, 2- (5'-te / t-butyl-2'-hydroxy-phenyl) benzotriazole, 2- (2'-hydroxy-5 '- (l, l, 3,3-tetramethylbutyl) phenyl) benzotriazole, 2 - (3 ', 5'-Di-te / t-butyl-2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-te / t-butyl-2'-hydroxy-5'-methylphenyl-5- chlorobenzotriazole, 2- (3'-sec-butyl-5'-te / t-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) benzotriazole, 2- (3 ' , 5'-di / t-amyl-2'-hydroxyphenyl) benzotriazole, 2- (3 ', 5'-bis (a, a-dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole, 2- (3'- te / t-butyl-2'-hydroxy-5 '- (2-octyloxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-te / t-butyl-5' - [2- (2-ethyl - hexyloxy) carbonylethyl] -2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-methoxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3rd 't / t-butyl-2'-hydroxy-5' - (2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-but yl-2'-hydroxy-5 '- (2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-5' - [2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) benzo triazole, 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-isooctyloxycarbonylethyl) phenylbenzotriazole, 2.2 '- methylenebis [4- (l, l, 3,3-tetramethylbutyl) -6-benzotriazol-2-ylphenol]; the product of the transesterification of 2- [3'-te / t-butyl-5 '- (2-methoxycarbonylethyl) -2'-hydroxyphenyl] -2H-benzotriazole with polyethylene glycol 300; [R - CH2CH2 - COO - CH2CH2 + 2, where R = 3'-te / t-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl, 2- [2'-hydroxy-3'- (a, a-dimethylbenzyl) -5 '- (l, l, 3,3-tetramethylbutyl) phenyl] benzotriazole, 2- [2'-hydroxy-3' - (l, l, 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-β, β-diphenyl acrylate, isooctyl-a-cyano-β, β-diphenyl acrylate, methyl-a-carbomethoxycinnamate, methyl-a-cyano-β-methyl-p-methoxycinnamate, Butyl-a-cya no-ß-methyl-p-methoxycinnamate, methyl-a-carbomethoxy-p-methoxycinnamate and N- (ß-carbomethoxy-ß-cyanovinyl) -2-methylindoline.

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

3,5-di-te / t-butyl-4-hydroxybenzoate.

Suitable oxamides are, for example ^, 4,4'-dioctyloxyoxanilide, 2,2'-diethoxy-oxanilide, 2,2'-dioctyloxy-5,5'-di-te / t-butoxanilide, 2,2'-didodecyloxy-5,5 '-di-te / t-butoxanilide, 2-ethoxy-2 ^, -ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) oxamide, 2-ethoxy-5-te / t-butyl-2'-ethoxanilide and its blends with 2-

Ethoxy-2'-ethyl-5,4'-di-te / t-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) -l, 3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -l , 3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2 _i 4-dimethylphenyl) -l, 3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl ) -4,6-bis (4-methylphenyl-l, 3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -l, 3.5 -triazine, 2- (2-hydroxy-4-tridecyloxyphenyl) -4,6-bis (2 _i 4-dimethylphenyl) -l, 3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy- 3-butyloxypropoxy) phenyl] -4,6-bis (2,4-dimethyl) -l, 3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxypropyloxy) phenyl] - 4,6-bis (2,4-dimethyl) -l, 3,5-triazine, 2- [4- (dodecyl- oxy / tridecyloxy-2-hydroxypropoxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -l, 3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy -3-dodecyloxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl-l, 3,5-triazine, 2- (2-hydroxy-4-hexyloxy) phenyl-4,6-diphenyl-l , 3,5-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-l, 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- {2nd -Hydroxy-4- [3- (2-ethylhexyl-l-oxy) -2-hydroxypropyloxy] phenyl} -4 _/ 6-bis (2,4-dimethylphenyl-l, 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-l, 2,4-triazole,

Bis (benzylidene) oxalyldihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoylbisphenylhydrazide, N, N'-diacetyladipoyldihydrazide, N, N'-bis (salicyloyl) oxylyldihydrazide, N, N'-bis (salicylyloyl) thioprop.

Suitable hindered amines are, for example, l, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (1,2,6,6-pentamethyl-4-piperidyl) sebazate, bis (l octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebazate, l-cyclohexyloxy-2, 2,6,6-tetramethyl-4-octadecylaminopiperidine, bis (l-acyl-2,2,6,6 tetramethyl piperidin-4-yl) sebazate 1- (2-hydroxy-2-methylpropoxy) -4-hydroxy-2, 2,6,6-tetramethylpiperidine, 1- (2-hydroxy-2-methylpropoxy) -4-oxo -2,2,6,6-tetra-methylpiperidine, bis (l-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate, N, N'-bis-formyl-N, N'-bis (2.2 , 6,6-tetramethyl-4-pi peridyl) hexamethylenediamine, (33a) bis (l-undecanyloxy-2, 2,6, 6-tetramethylpiperidin-4-yl) carbonate, 1,2, 2,6,6-pentamethyl -4-aminopiperidine, 2-undecyl-7, 7,9,9-tetramethyl-l-oxa-3,8-diaza-4-oxo-spiro [4,5] decane-tris (2,2,6,6 -tetramethyl-4-pi pe ridy I) nit ri lot ri- acetatl, l '- (l, 2-ethanediyl) -bis (3,3,5,5-tetramethylpiperazinone), 3-n-octyl-7,

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

7.7.9.9-tetramethyl-l, 3,8-triazaspiro [4.5] decane-2,4-dione, 3-dodecyl-l- (2,2,6,6-tetramethyl-4-piperidyl) pyrrolidine-2,5 -dione, 3-dodecyl-l- (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 l- (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-l, 3,5-triazine, tris (2, 2,6,6-tetramethyl-4-piperidyQnitrilotriacetat, tetrakis (2, 2,6,6-tetramethyl-4-piperidyl) -l , 2,3,4-butanetetracarboxylate, l, l '- (l, 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 of N, N'- bis (2,2,6,6- tetramethyl-4-piperidyl) hexamethylenediamine and 4-morpholino-2,6-dichloro-l, 3,5-triazine the reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-l-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 aforementioned compounds, 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 each with long chain substituents, reactive copolymers with functional groups e.g. Polypropylene-co-acrylic acid, polypropylene-co-maleic anhydride, polyethylene n-co-glycidyl methacrylate, polystyrene-old maleic anhydride, poly

Siloxanes: 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, e.g. Sodium benzoate, zinc glycerolate, aluminum hydroxy-bis (4-te / t-butyl) benzoate, benzylidene sorbitols such as e.g. 1,3: 2,4-bis (benzylidene) sorbitol or 1,3: 2,4-bis (4-methylbenzylidene) sorbitol, 2,2'-methylene-bis- (4,6-di-te / t- butylphenyl) phosphate, as well as trisamides and diamides such as Trimesic acid tricyclohexylamide, trimesic acid tri (4-methylcyclohexylamide), trimesic acid tri (tert.butylamide), N, N ', N "-l, 3,5-benzenetriyltris- (2,2-dimethyl-propanamide) or 2,6-naphthalenedicarboxylic acid di -cyclohexyl amide.

Suitable anti-nucleating agents are, for example, azine dyes such as e.g. Nigrosine, ionic liquids and / or lithium salts.

Suitable flame retardants include:

a) Inorganic flame retardants such as Al (OH) ₃ , Mg (OH) ₂ , AIO (OH), MgC0 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 0 ₃ (ATO), Sb ₂ 0 ₅ , MO0 ₃ , ammonium molybdate (AOM), zinc stannate, zinc hydroxystate, b) Nitrogen-containing flame retardants such as melamine, Meier, melam, melon, melamine derivatives, melamine condensation products or melamine salts, benzoguanamine, polyisocyanurates, allantoin, phosphacenes, in particular melamine cyanurate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, melamine polyphosphate, melamine polyphosphate such as, for example, melamine aluminum phosphate, melamine zinc phosphate, melamine magnesium phosphate, and the corresponding pyrophosphates and polyphosphates, poly- [2,4- (piperazin-l, 4-yl) -6- (morpholin-4-yl) -l, 3, 5-triazine], ammonium polyphosphate, melamine borate, melamine hydrobromide,

c) radical formers, e.g. Alkoxyamines, hydroxylamine esters, azo compounds, sulfenamides, sulfenimides, dicumyl or polycumyl, hydroxyimides and their derivatives such as e.g. Hydroxyimide ester or hydroxyimide ether

d) phosphorus-containing flame retardants such as red phosphorus, phosphates such as e.g. Resorcinol diphosphate, bisphenol A diphosphate and their oligomers, triphenyl phosphate, ethylenediamine diphosphate, phosphinates such as e.g. Salts of hypophosphorous acid and its derivatives such as alkylphosphinate salts e.g. Diethylphosphinate aluminum or diethylphosphinate zinc or aluminum phosphinate, aluminum phosphite, aluminum phosphonate, phosphonate ester, 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, brominated polycarbonates, optionally in combination with Sb ₂ 0 ₃ and / or Sb ₂ 0 ₅ , f) Borates such as zinc borate or calcium borate, possibly on a carrier material such as silica

g) Sulfur-containing compounds such as elemental sulfur, disulfides and polysulfides, thiuram sulfide, dithiocarbamates, mercaptobenzothiazole and sulfenamides,

h) antidrip agents such as Polytetrafluoroethylene,

i) Silicon-containing compounds such as Polyphenylsiloxanes, j) carbon modifications such as e.g. Carbon nanotubes (CNT), expanded graphite or graphene

k) and combinations or mixtures thereof.

Suitable fillers and reinforcing materials are, for example, synthetic or natural materials such as e.g. Calcium carbonate, silicates, glass fibers, glass balls (solid or hollow), talc, mica, kaolin, barium sulfate, metal oxides and metal hydroxides, carbon black, graphite, carbon nanotubes, graphene, wood flour or fibers from natural products such as e.g. Cellulose or synthetic fibers such as polyester or polyamide 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, and organic pigments are, for example

Anthraquinones, anthanthrones, benzimidazolones, quinacridones,

Diketopyrrolopyrroles, dioxazines, indanthrones, isoindolinones, 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-acyl lactams, bis-maleimides, dicyanates, carbodiimides or polycarbodiimides. Other suitable chain extenders are polymeric compounds such as polystyrene-polyacrylate-polyglycidyl (meth) acrylate Copolymers, polystyrene-maleic anhydride copolymers and polyethylene-maleic anhydride copolymers.

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

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

25th

30th

5

10th

Suitable antistatic agents include ethoxylated alkylamines, fatty acid esters, alkyl sulfonates and polymers such as e.g. Polyether amides.

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- (l-methylheptyl) -N'-phenyl-p-phenylene diamine, N-cyclohexyl-N'-phenyl-p-phenylene diamine.

Suitable electrically conductive additives are the antistatic agents already mentioned and, furthermore, electrically conductive fillers such as carbon black, graphene, carbon nanotubes (CNTs), metal powder such as copper or silver, but also conductive polymers such as polyanilines, polypyrrole or polythiophenes.

Suitable thermally conductive additives are, for example, aluminosilicates, aluminum nitride or boron nitride. Suitable odor traps are, for example, inorganic absorbents such as zeolites, hydrotalcites, silicates or organic complexing or reactive compounds such as zinc riceneolate or epoxides.

Suitable marking agents are, for example, fluorescent dyes, rare earths or antistokes crystals such as yttrium oxysulfides, gadolinium oxysulfides or cerium tantalum oxides, which are associated with rare earths such as e.g. ERbium or ytterbium are doped and show luminescence under IR irradiation. These markers can be used in small ppm amounts to identify the polymer or the additive for identification e.g. of the manufacturer are added.

Suitable mold release agents are, for example, 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.

The present invention further relates to a plastic composition containing or consisting of

(A) at least one polyphenol,

(B) at least one alditol and / or a cyclitol,

(C) at least one new thermoplastic material or mixtures thereof.

In a preferred embodiment, the plastic composition is characterized in that the plastic composition

(A) 0.02 to 3.0 parts by weight, preferably 0.06 to 1.0 parts by weight, of at least one polyphenol, (B) 0.02 to 3.0 parts by weight, preferably 0.03 to 0.5 parts by weight, of at least one alditol and / or at least one cyclitol, and

(C) 94.0 to 99.96 parts by weight, preferably 98.5 to 99.91 parts by weight, of a thermoplastic synthetic material or mixtures thereof,

so that from (A) (B) (C) together 100% are obtained, contains or consists of.

The composition according to the invention preferably contains at least one primary antioxidant and at least one secondary antioxidant, but it is also possible for the composition according to the invention to be free from the further primary and / or secondary antioxidants.

With regard to the polyphenols, alditols or cyclitols which can be used and their mixing ratios, reference is made to the above explanations in connection with the method according to the invention, which also apply in full to the plastic composition according to the invention. This applies accordingly to the plastics which can be used in plastics. new goods.

According to a further preferred embodiment, the plastic composition according to the invention 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, adhesion promoters, diperging agents, compatibilizers, oxygen scavengers, additive agents, de-scavenger agents, de-scavenger agents, de-scavenger agents Odor traps, markers, anti-fogging agents, fillers, reinforcement substances and mixtures thereof. It is further preferred 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, zinc oxide Alkaline earth carbonates, in particular calcium carbonate, magnesium carbonate and dolomite, and hydroxides, in particular brucite,

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

c) dispersants,

d) filler deactivators, and

Mixtures of these.

The plastic composition according to the invention can preferably be produced using a method according to the invention for stabilizing new thermoplastic material against oxidative, thermal and / or actinic degradation, or was produced therewith.

Another preferred embodiment of the plastic composition 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 phosphite tris (2,4-diet / t-butylphenyl) phosphite is particularly preferably contained as a secondary antioxidant in the plastic composition according to the invention.

The present invention also relates to a molding compound or a molded part which can be produced from the plastic composition according to the invention, in particular in the form of injection molded parts, foils, films, lacquers, coatings, Foams, fibers, cables, pipes, profiles, hollow bodies, tapes, membranes, eg geomembranes and / or adhesives, which are manufactured by extrusion, injection molding, blow molding, calendering, pressing processes, spinning processes, brushing, dipping and / or rotomoulding eg for the electrical industry, for the construction industry, for the transport industry, for medical applications, for household and electrical appliances, for vehicle parts, for mechanical engineering, for agricultural applications, for medical technology, for consumer goods, for sporting goods, for Packaging, for furniture, and / or for textiles.

Furthermore, the present invention also relates to a stabilizer composition for stabilizing new thermoplastic material against oxidative, thermal and / or actinic degradation, consisting of

(A) at least one polyphenol, and

(B) at least one alditol and / or at least one cyclitol. It is preferred here that component (A) and component (B) are present in a weight ratio of 5:95 to 90:10, preferably 10:90 to 90:10, particularly preferably 20:80 to 80:20.

All of the preferred variants, exemplary embodiments and comments already described with regard to the method according to the invention and with regard to the plastic composition according to the invention (e.g. with regard to possible components and additives to be used) also apply accordingly to the stabilizer composition according to the invention.

The present invention also relates to the use of a stabilizer composition containing or consisting of

(A) at least one polyphenol, and

(B) at least one alditol and / or at least one cyclitol for stabilizing new thermoplastic plastics (thermoplastic virgin resins, thermoplastic pristine resins) against oxidative, thermal and / or actinic degradation.

All already with regard to the method according to the invention and with regard to the plastic composition according to the invention and with regard to the The preferred variants, exemplary embodiments and comments described according to the stabilizer composition according to the invention (for example with regard to possible components and additives to be used) also apply correspondingly to the stabilizer composition according to the invention or to its use.

The present invention is explained in more detail on the basis of the following exemplary embodiments without restricting the invention to the specifically illustrated parameters.

3.4. Examples:

Example 1

To test the effect of the stabilizers according to the invention, a commercially available polypropylene (Moplen HP 500N, Lyondell Basell Industries) was homogenized in a powder-powder mixture with the stabilizers specified in Table 2 and in a twin-screw microextruder (MC 5, manufacturer DSM) circulated for 30 minutes at 200 ^° C and 200 revolutions per minute and the decrease in force recorded. The force is a direct measure of the molecular weight of polypropylene, the lower the decrease, the higher the stability.

Table 2: Stabilization of polypropylene

A0-1: 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 A0-1 and PI (comparative example 2), since there is less degradation of the polymer over the test period. The individual components, on the other hand, have little or no effect, since the degradation of the polymer takes place close to the polymer without addition. Example 2

To further test the effect of the stabilizers according to the invention, a commercially available base-stabilized polypropylene (Moplen HP 500N, Lyondell Basell Industries) in the form of a granulate was homogenized with the powdery stabilizers specified in Table 3 and in a 16 mm twin screw extruder (PTW 16, manufacturer: Haake, L / D ratio: 20) at 210 ° C maximum temperature and 140 revolutions / min extruded and granulated. After extrusion, the MVR (230 ° C / 2.16 kg) was measured in accordance with DIN / ISO 1133.

Table 3: Stabilization of polypropylene: extrusion

Sabostab UV40 is a 1,6-hexanediamine,

NX-bis & ZAe-tetramethyM-piperidinyl) - polymer with

2,4,6-trichloro-l, 3,5-triazine, and the reaction product with N-butyl-1-butanamine and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine of the following formula:

Araldit GT 6071 is a commercial product from Huntsman.

Compared to the comparative examples, the examples according to the invention have a lower MVR during processing, i.e. less degradation and thus improved processing stability.

Example 3

To further test the effect of the stabilizers according to the invention, a commercially available polypropylene (Moplen HP 500N, Lyondell Basell Industries, Basis stabilized) in the form of a powder / powder mixture was homogenized with the stabilizers specified in Table 4 and mixed in a 11 mm twin screw extruder (Process 11, manufactured by Thermo Fisher, L / D ratio: 40) extruded min at 230 ^e C ma- ximaltemperatur and 200 revolutions / and granulated. After extrusion, the MVR (230 ^e C / 2.16 kg) was measured in accordance with ISO DIN / ISO 1133. Table 4: Stabilization of polypropylene: extrusion

Example 4

To test the effect of the stabilizers according to the invention Further, a commercially available polylactic acid (PLA, luminyl L130, manufacturer, Corbion-Purac) after pre-drying (90 ^e C, 70 hours) in a powder-powder mixture homogenized with the conditions shown in Table 5, stabilizers, and in a twin Micro extruder (MC 5 , Manufacturer DSM) in a circuit for 30 minutes at 210 ^e C and 200 revolutions per minute and the decrease in force is recorded. The force is a direct measure of the molecular weight of PLA, the smaller the decrease, the higher the stabilizing effect.

Table 5: Stabilization of polylactic acid

The synergistic combination according to the invention shows a clear stabilizing effect, since less degradation, i.e. a higher residual force is proven.

In an analogous manner to the stabilization of polylactic acid, tests were carried out with polybutylene succinate, polybutylene terephthalate, crystal polystyrene, HD polyethylene, polyamide 6 and ABS. In all cases there is a corresponding stabilizing effect compared to the starting polymer.

Example 5

The granules of Comparative Examples 6, 7 and 8, as well as the erfindungsgemä- SEN Examples 10, 11 and 12 were STORED ^e at 150 C for 5 days in a convection oven and the MVR according to DIN / ISO 1133 measured. It can be seen that the compositions according to the invention have a smaller MVR increase, ie improved molecular weight maintenance and thus improved long-term heat stability, compared to the comparative examples. The results are shown in Table 6. Table 6: Long-term heat aging

Furthermore, the inventive example 7 for 504 hours at 150 ^e C in a convection oven was stored, it is shown an unchanged after storage MVR value of 15.0 [cm ^3/10 min].

Claims

1. A method for stabilizing new thermoplastic plastics (thermoplastic virgin resins, thermoplastic pristine resins) against oxidative, thermal and / or actinic degradation, in which

(A) at least one polyphenol, and

(B) at least one alditol and / or a cyclitol,

be introduced into a new thermoplastic material or mixtures thereof.

2. The method according to claim 1, characterized in that the at least one polyphenol has at least one aromatic radical with at least two hydroxyl substituents, preferably at least two aromatic radicals with at least two hydroxyl substituents.

3. The method according to any one of the preceding claims, characterized in that the at least one polyphenol is selected from the group consisting of bile acids; Hydroxytyrosol; Flavonols, e.g. Chrysin, Quercetin, Hesperdin, Neohesperidin, Naringin, Marin, Kaempferol and Fisetin; Anthocyanins, e.g.

Delphinidin and malvidin; Carnosolic acid; Carnosol; Rosemic acid; Resveratrol; Tannins, silymarin and combinations thereof.

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

with n = 2-5, where Ri is an optionally substituted sugar residue.

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

6. 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, quebrachitol, quinic acid, shikimic acid and valienol.

7. The method according to any one of the preceding claims, characterized in that component (A) and component (B) in a weight ratio of 5:95 to 90:10, preferably from 10:90 to 90:10, particularly preferably from 20:80 to 80:20, in which new thermoplastic materials are introduced.

8. The method according to any one of the preceding claims, characterized in that the components (A) and (B) are introduced into the thermoplastic new material in that the components (A) and (B) with the thermoplastic present as a solid New plastic goods are mixed and the resulting mixture is melted and then cooled.

9. The method according to any one of the preceding claims, characterized in that the thermoplastic new material is selected from the group consisting of

a) polymers of 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-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, polyethylene-polybutyl acrylate-g-maleic anhydride, long-chain branched polypropylene copolymers which are prepared with alpha-olefins as comonomers, in particular 1-butene. 1-hexene, 1-octene and / or 1-octadecene and blends of several of the aforementioned polymers, such as e.g. LLPE / LLDPE, b) polystyrene, polymethylstyrene, polyvinylnaphthalene, styrene-butadiene (SB), styrene-butadiene-styrene (SBS), styrene-ethylene-butylene-styrene (SEBS), styrene-ethylene-propylene-styrene, styrenoprene, styrene -Isoprene-styrene (SIS), styrene-butadiene-acrylonitrile (ABS), styrene-acrylonitrile-acrylate (ASA), styrene-ethylene, styrene-maleic anhydride polymers including corresponding graft copolymers such as, for example Styrene on butadiene, maleic anhydride on SBS or SEBS, as well as graft copolymers of methyl methacrylate, styrene-butadiene and ABS (MABS) as well as hydrogenated polystrylro derivatives such as

Polyvinyl cyclohexane,

c) halogen-containing polymers, e.g. Polyvinyl chloride (PVC), polychloroprene, polyvinylidene chloride (PVDC), copolymers of vinyl chloride and vinylidene chloride, copolymers of vinyl chloride and vinyl acetate, chlorinated polyethylene, polyvinylidene fluoride,

Epichlorohydrin homo- and copolymers, especially with

Ethylene oxide (ECO),

d) polymers of unsaturated esters such as 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, e) polymers of unsaturated alcohols and derivatives, such as, for example, polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyallyl phthalate, polylallyl melamine,

g) polyphenylene oxides and blends of these with polystyrene or polyamides,

h) polymers of cyclic ethers such as e.g. Polyethylene glycol,

Polypropylene glycol, polyethylene oxide, polypropylene oxide,

Po lytet ra hyd rof u ra n,

I) polyurethanes from hydroxy-terminated polyethers or polyesters and aromatic or aliphatic isocyanates, such as e.g. 2,4- or 2,6-toluene diisocanate or methylene diphenyl diisocyanate, linear polyurethanes (TPU) or polyureas,

j) polyamides such as Polyamide-6, 6.6, 6.10, 4.6, 4.10, 6.12, 10.10, 10.12, 12.12, polyamide 11, polyamide 12 and (partially) aromatic polyamides such as Polyphthalamides, e.g. made of

Terephthalic acid and / or isophthalic acid and aliphatic diamines, e.g. Hexamethylene diamine or m-xylylenediamine 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, blends of different polyamides, e.g. PA-6 and PA 6.6 or blends of polyamides and polyolefins such as e.g. PA / PP,

L) 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 (PTT), polyethylene naphthylate (PEN), poly 1,4-di methylolcyclohexane phthalate, polyhydrooxybenzoate, polyhydroxy naphthalate, polylactic acid (PLA), polyhydroxybutyrate (PBT), polyhydroxyvalerate (PHV), polyethylene succinate, polybutylene succinate (PBS) and polycaprolactone,

n) cellulose derivatives, e.g. Cellulose nitrate, cellulose acetate,

Cellulose propionate, cellulose butyrate,

p) phenolic resins, e.g. Phenol-formaldehyde resins, urea-formaldehyde resins or melamine-formaldehyde resins, q) unsaturated polyesters resins from unsaturated dicarboxylic acids and diols with vinyl compounds such as e.g. Styrene, alkyd resins, r) silicones, e.g. based on dimethylsiloxanes, methyl-phenylsiloxanes or diphenylsiloxanes, the silicones mentioned also being terminated in whole or in part, e.g. may be vinyl group terminated,

10. Plastic composition containing or consisting of

(A) at least one polyphenol,

(B) at least one alditol and / or a cyclitol,

(C) at least one new thermoplastic material or mixtures thereof.

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

(B) 0.02 to 3.0 parts by weight, preferably 0.03 to 0.5 parts by weight, of at least one alditol and / or at least one cyclitol, and

(C) 94.0 to 99.96 parts by weight, preferably 98.5 to 99.91 parts by weight of a new thermoplastic material or mixtures thereof

contains or consists of.

12. Plastic composition according to one of the two preceding claims, characterized in that the plastic composition contains, in addition to components (A) to (C), at least one additive which is selected from the group consisting of primary antioxidants , secondary antioxidants, UV absorbers, light stabilizers, metal deactivators, filler deactivators, antiozonants, nucleating agents,

Antinucleating agents, impact strength improvers, plasticizers, lubricants, rheology modifiers, thixotropy agents, chain extenders, processing aids, mold release agents, flame retardants, pigments, dyes, optical brighteners, antimicrobial agents, antistatic agents, thermally and / or electroconductive additive agents, slip additives, antiblocking agents, slip inhibitors, slip additives Crosslinking agents, anti-crosslinking agents, hydrophilizing agents, hydrophobizing agents, adhesion promoters, dipergizing agents, compatibilizers, oxygen scavengers, acid scavengers, blowing agents, degradation additives, defoaming agents, odor scavengers, marking agents, antifogging agents, fillers, reinforcing materials and mixtures thereof.

13. Plastic composition according to one of claims 10 to 12, characterized in that the plastic composition additionally lent 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 lactate, calcium stearoyl 2-lactate, hydrotalcites, in particular synthetic hydrotalcites based on aluminum, magnesium and zinc, hydrocalumites, zeolites, alkaline earth metal oxides, in particular calcium oxide and magnesium oxide, alkaline earth metal carbonates Calcium carbonate, magnesium carbonate and dolomite, and hydroxides, in particular brucite, b) light stabilizers, preferably light stabilizers from the group of the hindered amines,

c) dispersants,

d) filler deactivators, and

e) mixtures thereof.

14. Plastic composition according to one of claims 10 to 13, characterized in that the plastic composition can be produced by a method according to one of claims 1 to 9.

15. Molding compound or molded part producible from a plastic composition according to one of claims 10 to 14, 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 and / or adhesives, which are produced by extrusion, injection molding, blow molding, calendering, pressing processes, spinning processes, painting, dipping 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 mechanical engineering, for agricultural applications, for medical technology, for consumer goods, for sporting goods, for packaging, for Furniture, and / or for textiles.

16. Stabilizer composition for stabilizing thermoplastic virgin resins, thermoplastic pristine resins) against oxidative, thermal and / or actinic degradation, consisting of

(A) at least one polyphenol, and

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

17. Stabilizer composition according to the preceding claim, characterized in that component (A) and component (B) in a weight ratio of 5:95 to 90:10, preferably 10:90 to 90:10, particularly preferred from 20:80 to 80:20.

18. Use of a stabilizer composition containing or consisting of

(A) at least one polyphenol, and

(B) at least one alditol and / or at least one cyclitol for stabilizing the thermoplastic virgin resins (thermoplastic virgin resins, thermoplastic pristine resins) against oxidative, thermal and / or actinic degradation.