Use of linear or branched aliphatic secondary and / or tertiary amines, for stabilizing halogen-free thermoplastic plastics materials, preferably recycled plastics materials, against oxidative, thermal or actinic degradation, thermoplastic plastics composition, stabilzation method

Abstract

The present invention relates to the use of linear or branched aliphatic secondary and / or tertiary amines for stabilizing thermoplastic plastics materials, preferably recycled plastics materials, against oxidative, thermal or actinic degradation.

Description

[0001] Use of linear or branched aliphatic secondary and / or tertiary amines for stabilizing halogen-free thermoplastics, preferably plastic recyclates against oxidative, thermal or actinic degradation, thermoplastic composition, process for stabilization and molded part

[0002] Plastic recyclates are a growing market and an important element in the circular economy of raw materials. Ideally, recyclates should replace virgin plastics with an identical or at least comparable property profile. However, recyclates from the production of plastic parts (so-called "post-industrial" recyclates) and from collections of used plastics (so-called "post-consumer" recyclates) differ chemically from virgin plastics. During the initial processing steps (e.g. compounding, extrusion or injection molding) and the application, often over many years and in demanding areas of application (e.g. high temperatures and / or UV light), irreversible changes in the polymer chains occur due to mechanochemical, chemical or light-induced processes (see e.g. R. Pfaendner et al., Angew. Makromol. Chemie 1995, 232, 193-227, R. Pfaendner, Polymer Degradation and Stability 2022, 203, 110082, J. Pospisil et al., Pol. Degr.Stab. 1995, 48, 351-358, La Mantia, Macromol. Symp. 1998, 135, 157-165). Radical reactions in the presence of oxygen, generally referred to as autoxidation, generate new chemical groups in the polymer chain and / or alter the composition of the polymer at the molecular level. The chemical modifications resulting from the damage and aging processes primarily involve the formation of hydroperoxide groups, aliphatic carbonyl groups, alcohol groups, acid groups, ester groups, and peracid groups, i.e., structures that are not usually present in virgin polyolefins, for example, and only arise as a result of oxidation processes (J. Pospisil et al. Macromol. Symp. 1998, 135, 247-263). Furthermore, recyclates often contain unsaturated structures, ie vinylene, vinylidene and vinyl groups, the former of which can even be conjugated.Unsaturated structures are formed by chain scission and disproportionation reactions (H. Hinsken et al., Pol. Degr. Stab. 1991, 34, 279-293). The concentration of these newly formed groups increases with the processing intensity (process control, shear, temperature), the application area (UV light, high temperatures, contact media), and the application time. Furthermore, the formation of these structures in oxidation processes and subsequent reactions can be catalyzed by metals and certain pigments.

[0003] The structural inhomogeneities of a recyclate influence the plastic properties, such as the mechanical properties, the processing behavior or the morphology. Due to the newly formed chemical structures, recyclates or pre-damaged plastics are more sensitive to oxidation than virgin material, as these act as initiator sites for further oxidation or as prodegradants (AS Maxwell, Pol. Eng. Sci. 2008, 381-385, 1. H. Craig, JR White, J. Mater.. Sci. 2006, 41, 993-1006, S. Luzuriaga et al. Pol. Degr. Stab. 2006, 91, 1226-1232, C. Signoret et al., Journal of Polymers and the Environment 2020, 28, 2055-2077, FP La Mantia et al., Polymers 2023, 15, 2173). Furthermore, it has been proven that the degradation rate of a polymer depends on the concentration of chromophore impurities (MS Rabello, JR White, Polym. Degr. Stab. 1997, 56, 55).The concentration of the described chemical structures in the recyclates can increase by several orders of magnitude compared to the virgin material (e.g. X. Tao et al. J. Polym. Environ. 2020, 28, 2616-2630).

[0004] To improve the quality of plastic recyclates, post-stabilization with selected stabilizers such as antioxidants is an essential method. The stabilizers used protect the recyclate from further oxidative (or photooxidative) damage or at least delay it. Since virgin plastics and plastic recyclates differ significantly chemically, as described above, and recyclates are more sensitive to oxidation due to these pre-damages and initiator sites, it is a challenging task to develop effective stabilizers for the efficient stabilization of plastic recyclates. Due to the described structural differences between the recyclate and the virgin material, the optimized stabilizer composition for a recyclate also differs from the stabilization composition of the virgin material (see, for example, R. Pfaendner, Kunststoffe International 12 / 2015, 41-44).

[0005] Due to the now recognized differences between virgin plastics and plastic recyclates, special recycled stabilizer compositions are known and also available as commercial products (see, for example, R. Pfaendner, Kunststoffe International 2023, (3), 56-61).

[0006] However, current stabilizers for recycled materials still exhibit certain weaknesses. For example, the frequently used phenolic antioxidants and phosphites, such as those claimed in EP 0662101 (stabilization composition consisting of a phenolic antioxidant, a phosphite, and a fatty acid salt) or EP 0556614 (stabilization composition for mixed plastics consisting of a phenolic antioxidant and a phosphite / phosphonite), are potentially volatile, migrating, and extractable components. Improved stabilization compositions have been obtained, for example, through inorganic additives, as claimed in US 6525158, US 6251972 (stabilization composition consisting of a phenolic antioxidant, a phosphite, and a metal oxide such as calcium oxide) or in EP1849822 (method for suppressing hydrochloric acid in recycling of waste plastics).However, these inorganic additives are present in the recyclates as particles and can therefore negatively impact surface properties and complicate production processes through water absorption. For these reasons, stabilizing compositions for recyclates have already been proposed in WO 97 / 30112 that are phenol- and phosphite-free and do not require inorganic additives. These consist of a secondary aromatic amine and a polyfunctional epoxy resin. However, these secondary aromatic amines are now considered to be of concern due to toxicity and environmental reasons (e.g., R. Jin et al. Chemosphere 2023, 317, 137913).

[0007] Furthermore, WO 2020 / 152337 describes stabilizers for recyclates that can react with carbonyl groups, thus leading to improved stabilization of recyclates. Primary amines are used, among others. Secondary and tertiary amines are not mentioned there, as they cannot react with carbonyl groups.

[0008] The object of the present invention was therefore to propose stabilizers for plastics, especially for recyclates, that are both highly effective and, due to their oligomeric / polymeric structure, exhibit low volatility and are free of aromatic structures. This challenging task was solved by using aliphatic secondary and / or tertiary amine structures, and in particular polyethyleneimines, to stabilize plastics, especially recyclates.

[0009] This object is achieved with regard to a use having the features of patent claim 1, with regard to a thermoplastic composition having the features of patent claim 10, with regard to a method for stabilizing halogen-free thermoplastics having the features of patent claim 14, and with regard to a molded part having the features of patent claim 15. The respective dependent patent claims represent advantageous developments.

[0010] The present invention thus relates to the use of linear or branched aliphatic secondary and / or tertiary amines for stabilizing halogen-free thermoplastics, preferably halogen-free thermoplastic recyclates, against oxidative, thermal or actinic degradation.

[0011] According to a preferred embodiment, the linear or branched secondary or tertiary amines are liquid or solid and have a boiling point of > 200 °C or a molecular weight of > 1000 g / mol. Particularly preferably, the linear or branched aliphatic secondary and / or tertiary amine is selected from the group consisting of polyethyleneimines, alkanolamines, and N-methyl-D-glucamine.

[0012] Suitable alkanolamines are in particular tris(hydroxyalkylamines) and dihydroxyalkylamines with N-substituted long-chain alkyl groups, as well as heterocyclic hydroxyethyl compounds such as triethanolamine, tris(2-hydroxy-1-propyl)amine, n-butyl-N,N-bis(2-hydroxyethyl)amine, N,N-bis(2-hydroxyethyl)_N-oleylamine, N,N-bis(2-hydroxyethyl)-N-palmitylamine, N,N-bis(2-hydroxyethyl)-N-stearylamine, N-(2-hydroxy-3-octyloxypropyl)diethanolamine, N-2-hydroxyethyl)-morpholine.

[0013] Preferred polyethyleneimines are selected from the group consisting of molecules of the following formulas where n and m are each integers between 3 and 100.

[0014] It has been shown that compounds according to the invention are particularly effective when they contain tertiary nitrogen compounds. Therefore, branched polyethyleneimines are particularly preferred.

[0015] Excluded from the invention are heterocyclic hindered secondary and tertiary amines, so-called HALS compounds, which are known to be used as light stabilizers as piperidine and piperazine derivatives.

[0016] Amino acids are also excluded from the invention, since primary amines are generally present in the form of zwitterions, which are accordingly inactive for the present stabilizing effect.

[0017] A further preferred embodiment provides that the totality of all linear or branched aliphatic secondary and / or tertiary amines is contained in the halogen-free thermoplastic in a weight proportion of 0.01 to 10.00 wt.%, preferably 0.02 to 5.00 wt.%, particularly preferably 0.05 to 3.00 wt.%, in particular 0.10 to 2.00 wt.%.

[0018] The halogen-free thermoplastic is particularly preferably selected from the group consisting of a) polymers made of olefins or diolefins such as polyethylene (LDPE, LLDPE, VLDPE, ULDPE, MDPE, HDPE, UHMWPE), metallocene-PE (m-PE), polypropylene, polyisobutylene, poly-4-methylpentene-1, polybutadiene, polyisoprene, such as natural rubber (NR), polycyclooctene, polyalkylene-carbon monoxide copolymers, as well as copolymers in the form of statistical or block structures such as polypropylene-polyethylene (EP), EPM or EPDM with e.g. 5-ethylidene-2-norbornene as comonomer, ethylene-vinyl acetate (EVA), ethylene-acrylic esters, such as ethylene butyl acrylate, ethylene-acrylic acid and its salts (ionomers), as well as terpolymers such as e.g. ethylene-acrylic acid-glycol- cidyl (meth)acrylate, graft polymers such as polypropylene-graft-maleic anhydride, polypropylene-graft-acrylic acid, polyethylene-graft-acrylic acid, polyethylenepolybutylacrylate-graft-maleic anhydride and blends such asLDPE / LLDPE or long-chain branched polypropylene copolymers produced with alpha-olefins as comonomers such as 1-butene, 1-hexene, 1-octene or 1-octadecene, b) polystyrene, polymethylstyrene, poly-alpha-methylstyrene, polyvinylnaphthalene, polyvinylbiphenyl, polyvinyltoluene, styrene-butadiene (SB), styrene-butadiene-styrene (SBS), styrene-ethylene-butylene-styrene (SEBS), styrene-ethylene-propylene-styrene, styrene-isoprene, styrene-isoprene-styrene (SIS), styrene-lutadiene-acrylonitrile (ABS), styrene-acrylonitrile (SAN), styrene-acrylonitrile acrylate (ASA), styrene-ethylene, styrene-maleic anhydride polymers including corresponding graft copolymers such as styrene on butadiene, maleic anhydride on SBS or SEBS, as well as graft copolymers of methyl methacrylate, styrene-butadiene and ABS (MABS), as well as hydrogenated polystyrene derivatives such as polyvinylcyclohexane, c) polymers of unsaturated esters such asPolyacrylates and polymethacrylates such as polymethyl methacrylate (PMMA), polybutyl acrylate, polylauryl acrylate, polystearyl acrylate, polyglycidyl acrylate, polyglycidyl methacrylate, polyacrylonitrile, polyacrylamides, copolymers such as polyacrylonitrile-polyalkyl acrylate, d) polymers of unsaturated alcohols and derivatives, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyallyl phthalate, polyallyl melamine, e) polyacetals, such as polyoxymethylene (POM) or copolymers with e.g. butanal, f) polyphenylene oxides and blends with polystyrene or polyamides, g) polymers of cyclic ethers such as polyethylene glycol, polypropylene glycol, polyethylene oxide, polypropylene oxide, polytetrahydrofuran, h) polyurethanes, made from hydroxy-terminated polyethers or polyesters and aromatic or aliphatic isocyanates such as e.g. 2,4- or 2,6-toluene diisocyanate or methylenediphenyl diisocyanate, in particular linear polyurethanes (TPU), polyureas, i) polyamides such asPolyamide 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 hexamethylenediamine or m-xylylenediamine or from aliphatic dicarboxylic acids such as adipic acid or sebacic acid and aromatic diamines such as 1,4- or 1,3-diaminobenzene, blends of different polyamides such as PA 6 and PA 6.6 or blends of polyamides and polyolefins such as PA / PP, j) polyimides, polyamideimides, polyetherimides, polyesterimides, poly(ether)ketones, polysulfones, polyethersulfones, polyarylsulfones, Polyphenylene sulfides, polybenzimidazoles, polyhydantoins, k) polyesters made from aliphatic or aromatic dicarboxylic acids and diols or from hydroxycarboxylic acids such asPolyethylene terephthalate (PET), polybutylene terephthalate (PBT), polypropylene terephthalate (PTI), polyethylene naphthylate (PEN), poly-l,4-dimethylolcyclohexane terephthalate, polyhydroxybenzoate, polyhydroxynaphthalate, polylactic acid (PLA), polyhydroxybutyrate (PHB), polyhydroxyvalerate (PHV), polyethylene succinate, polytetramethylene succinate, polycaprolactone, l) polycarbonates, polyester carbonates, and blends such as PC / ABS, PC / PBT, PC / PET / PBT, PC / PA, m) cellulose derivatives such as cellulose nitrate, cellulose acetate, cellulose propionate, cellulose butyrate, n) and mixtures, combinations or blends of two or more of the aforementioned polymers.

[0019] The polymers or polymer mixtures or recyclates are essentially halogen-free, i.e. free from chlorine- or fluorine-containing polymers such as PVC or PVDC and contain less than 0.5%, preferably less than 0.2%, of halogen-containing polymers.

[0020] A preferred embodiment is the use for stabilizing polyolefins or polystyrenes according to a) and b) of the above list.

[0021] A particularly preferred embodiment provides for the use of the linear or branched aliphatic secondary and / or tertiary amines for stabilizing polyolefin recyclates, very particularly preferably polyethylene and / or polypropylene recyclates, or relates to the thermoplastic compositions formed therefrom. Polyethylene recyclates are, in particular, HDPE, LDPE, LLDPE, and MDPE. Polypropylene recyclates are, in particular, polypropylene homopolymers and copolymers with polyethylene, or mixtures thereof. Very particularly preferred recyclates are post-consumer recyclates.

[0022] According to a further preferred embodiment, at least one further additive is selected from the group consisting of primary antioxidants, secondary antioxidants, UV absorbers, light stabilizers, in particular hindered amines as light (HALS) and long-term heat stabilizers (HAS), metal deactivators, filler deactivators, antiozonants, nucleating agents, antinucleating agents, transparency improvers (clarifiers), impact strength improvers, plasticizers, lubricants, rheology or viscosity modifiers, thixotropic agents, chain extenders, processing aids, mold release agents, flame retardants, pigments, dyes, optical brighteners, antimicrobial agents, antistatic agents, slip agents, antiblocking agents, coupling agents, crosslinking agents, anticrosslinking agents, hydrophilizing agents, hydrophobizing agents, surface modifiers, hydrolysis stabilizers, adhesion promoters, dispersants, comp- patibilizers,Oxygen scavengers, acid scavengers, acetaldehyde and formaldehyde scavengers, blowing agents, degradation additives (prodegradants), defoaming agents, odor scavengers and odor-improving substances, marking agents, antifogging agents, gloss improvers, matting agents, additives to increase electrical and / or thermal conductivity, repellants, fillers and reinforcing materials and mixtures thereof, which are added to the halogen-free thermoplastic during use or are contained in the halogen-free thermoplastic.

[0023] In the aforementioned embodiment, it is particularly preferred if the at least one additive is selected from the group consisting of phenolic antioxidants, phosphites, phosphonites, sulfites, polyols, acid scavengers, hindered amines and mixtures and combinations thereof.

[0024] The at least one additive is further preferably present in an amount of 0.01 to 50 wt.%, preferably from 0.01 to 9.99 wt.%, further preferably from 0.01 to 4.98 wt.%, particularly preferably from 0.02 to 2.00 wt.%, based on the total of all linear or branched aliphatic secondary and / or tertiary amines, the halogen-free thermoplastic and the at least one additive, or is added in a corresponding amount.

[0025] The present invention also relates to a thermoplastic composition containing or consisting of at least one halogen-free thermoplastic, in particular a halogen-free thermoplastic recyclate and at least one linear or branched aliphatic secondary or tertiary amine, in particular at least one polyethyleneimine.

[0026] According to a preferred embodiment, the thermoplastic composition contains

[0027] 99.95 to 49.99% of at least one halogen-free thermoplastic,

[0028] 0.01 - 10.00% of at least one linear or branched aliphatic or tertiary amine, particularly preferably 0.1 - 2.0%,

[0029] 0 - 50.00 parts of at least one additive, or consists of these.

[0030] A particularly preferred embodiment provides that the thermoplastic composition

[0031] 99.95 to 49.95% of at least one halogen-free thermoplastic,

[0032] 0.01 to 10.00 wt.%, preferably from 0.02 to 5.00 wt.%, particularly preferably from 0.05 to 3.00 wt.%, in particular 0.10 to 2.00 wt.% of at least one linear or branched aliphatic or tertiary amine,

[0033] Contains or consists of 0.01 to 50.00 wt.%, preferably 0.01 to 9.99 wt.%, more preferably 0.01 to 4.98 wt.%, particularly preferably 0.02 to 2.00 wt.% of at least one additive.

[0034] In particular, it is preferred that at least one primary and / or secondary antioxidant is included as at least one additive, preferably in a weight amount of 0.01 to 3.00 wt.%, particularly preferably 0.05 - 2.0 wt.%.

[0035] In addition, the present invention relates to a process for stabilizing halogen-free thermoplastics, in particular plastic recyclates, against oxidative, thermal or actinic degradation by adding at least one linear or branched aliphatic secondary and / or tertiary amine, in particular at least one polyethyleneimine, to the plastic.

[0036] Furthermore, the present invention relates to a molded part which contains or consists of a thermoplastic composition as described above. In particular, the molded part is selected from the group consisting of

[0037] - Packaging e.g. for food, detergents, cosmetics, adhesives in the form of films, bottles, bags, screw jars

[0038] - Storage and transport containers such as boxes, crates, barrels, buckets, pallets

[0039] - Automotive, railway, aircraft, ship and machine parts such as bumpers, trim parts, fittings and functional parts, upholstery

[0040] - Construction applications such as profiles, construction foils, cable ducts, house cladding, noise barriers, drainage channels, professional boards, floor coverings

[0041] - Road and landscaping applications such as beacon bases, posts, barriers, geotextiles,

[0042] - Electrical and electronic applications such as housing parts and accessories for televisions, computers, mobile phones, washing machines, dishwashers, coffee machines, drills, connectors, storage media

[0043] - Cable insulation

[0044] - Pipes for e.g. water, gas, sewage, irrigation, drainage pipes - Hygiene products such as diapers

[0045] - Furniture and textile applications, such as curtains and upholstery, worktops

[0046] - Household, leisure and sporting goods such as balls, tennis rackets, skis, flower pots, rain barrels, coat hangers

[0047] - Mulch, tunnel or perforated films, plant pots

[0048] - Encapsulation of active ingredients and biologically active substances

[0049] - Sutures, dressings, orthoses and prostheses.

[0050] The preferred embodiments described above for the use of the linear or branched aliphatic secondary and / or tertiary amine naturally also apply for the purposes of the present invention, as long as a thermoplastic composition, a process for stabilizing halogen-free thermoplastics or a molded part is concerned.

[0051] The present invention is explained in more detail with reference to the following examples, without limiting the present invention to the preferred embodiments shown.

[0052] To test the effectiveness of the stabilizers according to the invention, a post-consumer polypropylene recyclate from battery boxes (manufacturer: BSB Braubach) was homogenized in a polymer powder / additive mixture containing the stabilizers according to the invention and extruded in a twin-screw microextruder (MC15HT, manufacturer: Xplore Instruments BV) at 210 °C and a speed of 200 rpm for 30 minutes in a circular motion. The torque retention was measured. The torque curve is a measure of the formulation's stability during processing; the higher the torque retention over time, the better the processing stability.

[0053] PEI-2: Polyethylenimine (branched), Supplier: ThermoScientific Molecular weight: 10,000 g / mol

[0054] Triethanolamine, supplier: Scharlau

[0055] N-Methyl-D-Glucamine, Supplier: Sigma Aldrich

[0056] AO-1 = Pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate)

[0057] Pl = Tris-(di-tert. butyl phenyl) phosphite

[0058] To test the effectiveness of the stabilizers according to the invention, a post-consumer polypropylene recyclate from battery boxes (manufacturer: BSB Braubach) was homogenized in a polymer powder / additive mixture containing the stabilizers according to the invention and extruded in a twin-screw microextruder (MC15HT, manufacturer: Xplore Instruments BV) at 210 °C and a speed of 200 rpm for 30 minutes in a circular motion. The torque retention was measured. The torque curve is a measure of the formulation's stability during processing; the higher the torque retention over time, the better the processing stability. PEI-1: Polyethylenimine (branched), Supplier: ThermoScientific Molecular weight: 25,000 g / mol

[0059] PEI-2: Polyethylenimine (branched), Supplier: ThermoScientific Molecular weight: 10,000 g / mol

[0060] PEI-3: Polyethylenimine (branched), Supplier: ThermoScientific Molecular weight: 1,200 g / mol PEI-4: Polyethylenimine (linear), Supplier: ThermoScientific Molecular weight: 10,000 g / mol ERY: Erythritol

[0061] AO-1 = Pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate)

[0062] The combination of polyethyleneimine and antioxidant results in very good processing stability for the polypropylene recyclate; the effect can be further increased by the addition of an alditol (erythritol).

[0063] To test the effectiveness of the stabilizers according to the invention, a post-consumer polyethylene recyclate from injection molding waste (manufacturer: Kunststoff Recycling Grünstadt GmbH) was homogenized in a polymer powder / additive mixture with the stabilizers according to the invention. Processing was carried out in a twin-screw extruder (HAAKE PolyLab OS, manufacturer: ThermoScientific, 16 mm, L / D 25) with a temperature profile ranging from 180 °C (feed) to 255 °C (die), a speed of 200 rpm, and a target throughput of 2.0 kg / h. The resulting granules were then processed four more times at a target throughput of 2.0 kg / h. The melt volume flow rate is a measure of the stability of the formulation during processing; the more constant and higher the melt volume flow rate is across multiple extrusions, the better the processing stabilization.

[0064] PEI-1: Polyethylenimine (branched), Supplier: ThermoScientific Molecular weight: 25,000 g / mol

[0065] ERY: Erythritol CS: Calcium stearate, supplier: Baerlocher

[0066] AO-1 = Pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate)

[0067] The combination of polyethyleneimine and antioxidant results in very good processing stability for the polyethylene recyclate; the effect can be further enhanced by the addition of an alditol (erythritol).

Claims

Patent claims 1. Use of linear or branched aliphatic secondary and / or tertiary amines for stabilizing halogen-free thermoplastics, preferably plastic recyclates, against oxidative, thermal or actinic degradation.

2. Use according to claim 1, characterized in that the linear or branched secondary or tertiary amines are liquid or solid and have a boiling point of > 200 °C and / or a molecular weight of > 1000 g / mol.

3. Use according to one of the preceding claims, characterized in that the linear or branched aliphatic secondary and / or tertiary amine is selected from the group consisting of polyethyleneimines, alkanolamines and N-methyl-D-glucamine.

4. Use according to the preceding claim, characterized in that the polyethyleneimines are selected from the group consisting of molecules of the following formulas where n and m are each an integer between 3 and 100.

5. Use according to one of the preceding claims, characterized in that the totality of all linear or branched aliphatic secondary and / or tertiary amines is contained in the halogen-free thermoplastic in a weight proportion of 0.01 to 10.00 wt.%, preferably 0.02 to 5.00 wt.%, particularly preferably 0.05 to 3.00 wt.%, in particular 0.10 to 2.00 wt.%.

6. Use according to one of the preceding claims, characterized in that the halogen-free thermoplastic is selected from the group consisting of a) polymers of olefins or diolefins such as polyethylene (LDPE, LLDPE, VLDPE, ULDPE, MDPE, HDPE, UHMWPE), metallocene-PE (m-PE), polypropylene, polyisobutylene, poly-4-methylpentene-1, polybutadiene, polyisoprene, such as natural rubber (NR), polycyclooctene, polyalkylene-carbon monoxide copolymers, and copolymers in the form of statistical or block structures such as polypropylene-polyethylene (EP), EPM or EPDM with e.g. 5-ethylidene-2-norbornene as comonomer, ethylene-vinyl acetate (EVA), ethylene-acrylic esters, such as ethylene-butyl acrylate, ethylene-acrylic acid and their salts (ionomers), and terpolymers such as Ethylene-acrylic acid-glycidyl(meth)acrylate, graft polymers such asPolypropylene graft-maleic anhydride, polypropylene graft-acrylic acid, polyethylene graft-acrylic acid, polyethylene-polybutyl acrylate graft-maleic anhydride as well as blends such as LDPE / LLDPE or long-chain branched polypropylene copolymers produced with alpha-olefins as comonomers such as 1-butene, 1-hexene, 1-octene or 1-octadecene, b) polystyrene, polymethylstyrene, poly-alpha-methylstyrene, polyvinylnaphthalene, polyvinylbiphenyl, polyvinyltoluene, styrene-butadiene (SB), styrene-butadiene-styrene (SBS), styrene-ethylene-butylene-styrene (SEBS). Styrene-ethylene-propylene-styrene, styrene-isoprene, styrene-isoprene-styrene (SIS), styrene-lutadiene-acrylonitrile (ABS), styrene-acrylonitrile (SAN), styrene-acrylonitrile acrylate (ASA), styrene-ethylene, styrene-maleic anhydride polymers including corresponding graft copolymers such as styrene on butadiene, maleic anhydride on SBS or SEBS, as well as graft copolymers of methyl methacrylate, styrene-butadiene and ABS (MABS), as well as hydrogenated polystyrene derivatives such as polyvinylcyclohexane, c) polymers of unsaturated esters such as polyacrylates and polymethacrylates such as polymethyl methacrylate (PMMA), polybutyl acrylate, polylauryl acrylate, polystearyl acrylate, polyglycidyl acrylate, Polyglycidyl methacrylate, polyacrylonitrile, polyacrylamides, copolymers such as polyacrylonitrile-polyalkyl acrylate, d) polymers of unsaturated alcohols and derivatives, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyallyl phthalate, polyallyl melamine, e) polyacetals, such asPolyoxymethylene (POM) or copolymers with e.g. butanal, f) polyphenylene oxides and blends with polystyrene or polyamides, g) polymers of cyclic ethers such as polyethylene glycol, polypropylene glycol, polyethylene oxide, polypropylene oxide, polytetrahydrofuran, h) polyurethanes, from hydroxy-terminated polyethers or polyesters and aromatic or aliphatic isocyanates such as e.g. 2,4- or 2,6-toluene diisocyanate or methylene diphenyl diisocyanate, in particular also linear polyurethanes (TPU), polyureas, i) polyamides such as e.g. 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 e.g. polyphthalamides, e.g. produced from terephthalic acid and / or Isophthalic acid and aliphatic diamines such as hexamethylenediamine or m-xylylenediamine or from aliphatic. Dicarboxylic acids such as adipic acid or sebacic acid and aromatic diamines such as 1,4- or 1,3-diaminobenzene, blends of different polyamides such as PA-6 and PA 6.6 or blends of polyamides and polyolefins such as PA / PP, j) polyimides, polyamideimides, polyetherimides, polyesterimides, poly(ether)ketones, polysulfones, polyethersulfones, polyarylsulfones, polyphenylene sulfides, polybenzimidazoles, polyhydantoins, k) polyesters made from aliphatic or aromatic dicarboxylic acids and diols or from hydroxycarboxylic acids such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polypropylene terephthalate (PTI), polyethylene naphthylate (PEN), poly-1,4-dimethylcyclohexane terephthalate, polyhydroxybenzoate, polyhydroxynaph- thalate, polylactic acid (PLA), polyhydroxybutyrate (PHB), polyhydroxyvalerate (PHV), polyethylene succinate, polytetramethylene succinate, polycaprolactone, l) polycarbonates, polyester carbonates, as well as blends such asPC / ABS, PC / PBT, PC / PET / PBT, PC / PA, m) cellulose derivatives such as cellulose nitrate, cellulose acetate, cellulose propionate, cellulose butyrate, n) as well as mixtures, combinations or blends of two or more of the aforementioned polymers.

7. Use according to one of the preceding claims, characterized in that at least one further additive selected from the group consisting of primary antioxidants, secondary antioxidants, UV absorbers, light stabilizers, in particular hindered amines as light (HALS) and long-term heat stabilizers (HAS), metal deactivators, filler deactivators, antiozonants, nucleating agents, antinucleating agents, transparency improvers (clarifiers), impact strength improvers, plasticizers, lubricants, rheology or viscosity modifiers, thixotropy modifiers tel, chain extenders, processing aids, mold release agents, flame retardants, pigments, dyes, optical brighteners, antimicrobial agents, antistatic agents, slip agents, antiblocking agents, coupling agents, crosslinking agents, anticrosslinking agents, hydrophilizing agents, hydrophobizing agents, surface modifiers, hydrolysis stabilizers, adhesion promoters, dispersants, compatibilizers, oxygen scavengers, acid scavengers, acetaldehyde and formaldehyde scavengers, blowing agents, degradation additives (prodegradants), defoaming aids, odor scavengers and odor-improving substances, [Ki] marking agents, antifogging agents, gloss improvers, matting agents, additives to increase electrical and / or thermal conductivity, repellants, fillers and reinforcing materials and mixtures thereof, which are added to the halogen-free thermoplastic during use or are contained in the halogen-free thermoplastic.

8. Use according to the preceding claim, characterized in that the at least one additive is selected from the group consisting of phenolic antioxidants, phosphites, phosphonites, sulfites, polyols, acid scavengers, hindered amines and mixtures and combinations thereof.

9. Use according to one of the two preceding claims, characterized in that the at least one additive is present or added in an amount of 0.01 to 50 wt.%, preferably from 0.01 to 9.99 wt.%, more preferably from 0.01 to 4.98 wt.%, particularly preferably from 0.02 to 2.00 wt.%, based on the totality of all linear or branched aliphatic secondary and / or tertiary amines, the halogen-free thermoplastic and the at least one additive.

10. Thermoplastic composition containing or consisting of at least one halogen-free thermoplastic, in particular a halogen-free recycled plastic and at least one linear or branched aliphatic secondary or tertiary amine, in particular at least one polyethyleneimine.

11. Thermoplastic composition according to the preceding claim, containing or consisting of 99.95 to 49.99% of at least one halogen-free thermoplastic, 0.01 - 10.00% of at least one linear or branched aliphatic or tertiary amine, particularly preferably 0.1 - 2.0% 0 - 50.00 parts of at least one additive.

12. Thermoplastic composition according to one of the two preceding claims, containing or consisting of 99.95 to 49.95% of at least one halogen-free thermoplastic, 0.01 to 10.00 wt.%, preferably from 0.02 to 5.00 wt.%, particularly preferably from 0.05 to 3.00 wt.%, in particular 0.10 to 2.00 wt.% of at least one linear or branched aliphatic or tertiary amine, 0.01 to 50.00 wt.%, preferably from 0.01 to 9.99 wt.%, more preferably from 0.01 to 4.98 wt.%, particularly preferably from 0.02 to 2.00 wt.% of at least one additive.

13. Thermoplastic composition according to one of the two preceding claims, characterized in that at least one primary and / or secondary antioxidant is included as at least one additive, preferably in a weight amount of 0.01 to 3.00 wt.%, particularly preferably 0.05 - 2.0 wt.%.

14. A process for stabilising halogen-free thermoplastics, in particular plastic recyclates, against oxidative, thermal or actinic degradation by adding to the plastic at least one linear or branched aliphatic secondary and / or tertiary amine, in particular at least one polyethyleneimine becomes.

15. A molded part containing or consisting of a thermoplastic composition according to any one of claims 10 to 13, in particular selected from the group consisting of - Packaging e.g. for food, detergents, cosmetics, adhesives in the form of films, bottles, bags, screw jars - Storage and transport containers such as boxes, crates, barrels, buckets, pallets - Automotive, railway, aircraft, ship and machine parts such as bumpers, trim parts, fittings and functional parts, upholstery - Construction applications such as profiles, construction foils, cable ducts, house cladding, noise barriers, drainage channels, professional boards, floor coverings - Road and landscaping applications such as beacon bases, posts, barriers, geotextiles, - Electrical and electronic applications such as housing parts and accessories for televisions, computers, mobile phones, washing machines, dishwashers, coffee machines, drills, connectors, storage media - Cable insulation - Pipes for e.g. water, gas, sewage, irrigation, drainage pipes - Hygiene items such as diapers - Furniture and textile applications, such as curtains and upholstery, worktops - Household, leisure and sporting goods such as balls, tennis rackets, skis, flower pots, rain barrels, coat hangers - Mulch, tunnel or perforated films, plant pots - Encapsulation of active ingredients and biologically active substances - Sutures, dressings, orthoses and prostheses.

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