DE102020205101A1 - Use of inorganic sulfites and / or thiosulfates for stabilizing thermoplastic condensation polymers, stabilized molding compounds and molding compounds and molded parts produced therefrom - Google Patents

Abstract

The present invention relates to the use of inorganic sulfites and / or thiosulfates for stabilizing thermoplastic condensation polymers, a stabilized molding compound and molded parts made therefrom, a process for stabilizing thermoplastic condensation polymers and possible uses of the molding compound.

Description

The present invention relates to the use of inorganic sulfites and / or thiosulfates for stabilizing thermoplastic condensation polymers, a stabilized molding compound and molded parts made therefrom, a method for stabilizing thermoplastic condensation polymers and possible uses of the molding compound.

Condensation polymers such as polyester such as PET and polyamides such as PA-6 are important plastics for packaging and technical applications that are often intended for long-term use. Furthermore, today, polyester-based polymers made from renewable raw materials such as PLA (polylactide) or PBS (polybutylene succinate) are viewed as possible substitutes for oil-based plastics, especially in the packaging industry and for agricultural applications. However, these applications, e.g. in the form of foils, tend to have a short-term useful life. Regardless of the useful life, however, it is necessary that condensation polymers do not experience any (pre-) damage during processing, i.e. during the manufacture of parts or during compounding, in order not to suffer premature loss of properties, e.g. in the case of mechanical properties. For this purpose, additives such as stabilizers and / or antioxidants are often added to the polymers.

The stabilization of polyesters based on renewable raw materials has so far been carried out by conventional phenolic antioxidants and / or phosphites such as in Meng, Xin; Shi, Guotao; Wu, Chushi; Chen, Weijie; Xin, Zhong; Shi, Yaoqi; Sheng, Yan (2016): Chain extension and oxidation stabilization of Triphenyl Phosphite (TPP) in PLA, Polymer Degradation and Stability 124, pp. 112-118 , in Georgousopoulou, loanna nectaria; Vouyiouka, Stamatina; Dole, Patrice; Papaspyrides, Constantine D. (2016): Thermo-mechanical degradation and stabilization of poly (butylene succinate), Polymer Degradation and Stability 128, pp. 182-192 or in WO 2010000638 (Applicant: BASF SE). However, these solutions are not based on renewable raw materials, which would be particularly desirable for polymers that already consist of renewable raw materials such as PLA and PBS.

Inorganic sulfites, for example in the form of calcium sulfite or lead sulfite, are used as stabilizers for halogen-containing polymers such as PVC (e.g. EP 0 313 113 , U.S. 3,542,725 , US 2003/0104954 ) and for polyvinylpyrrolidone ( U.S. 2,872,433 , DE 10 2005 005 974 ) proposed, but have not yet been described for the thermal stabilization of thermoplastic condensation polymers such as polyesters or polyamides in the processing or production of molded parts.

Organic esters of sulphurous acid are well known for the stabilization of polymers (e.g. DD 247 913 , U.S. 3,542,725 ). The use of sulfur-containing catalysts in the +6 oxidation state for the production of polylactic acid (PLA) via solid-phase condensation is also known ( JP 2011-201946 ) and the addition of different classes of stabilizers, which can also contain sulfur compounds in different oxidation states. One of the aims is to obtain a hydrolysis-stable polymer.

The object of the present invention was therefore to develop stabilizers, in particular for stabilizing the processing of condensation polymers, which are effective, inexpensive, environmentally friendly and based on readily available raw materials. This object could be achieved with the stabilizers according to the invention with inorganic sulfites as stabilizing agent.

This object is related to the use of at least one stabilizer selected from the group consisting of inorganic sulfites and / or thiosulfates for stabilizing thermoplastic condensation polymers with the features of claim 1, with respect to a condensation polymer composition with the features of claim 9, with respect to a molding compound or a molded part with the features of claim 13, with respect to a method for oxidative, thermal and / or actinic stabilization of a thermoplastic condensation polymer with the features of claim 14 and with respect to uses of the condensation polymer compositions with the features of claim 16. The dependent claims represent advantageous developments.

In a first aspect, the invention thus relates to the use of at least one stabilizer selected from the group consisting of inorganic sulfites and / or thiosulfates for stabilizing thermoplastic condensation polymers, in particular against oxidative, thermal and / or actinic degradation.

Surprisingly, it has been found that the inventive use of the stabilizers allows the production and applications of thermoplastic condensation polymers, in particular from renewable raw materials such as, for example, polylactic acid (PLA), without premature loss of properties during processing.

A preferred embodiment provides that the thermal stabilization takes place during the thermal processing of the condensation polymers, in particular by adding, adding or incorporating the at least one stabilizer to or into the thermoplastic condensation polymer.

An exemplary thermal processing of the condensation polymers can be, for example, processing in the thermoplastic state, the condensation polymer generally being melted, preferably by a mixer, kneader or extruder. Preferred processing machines are extruders such as single-screw extruders, twin-screw extruders, planetary roller extruders, ring extruders, co-kneaders, which are preferably equipped with vacuum degassing. Processing can take place under air or, if necessary, under inert gas conditions. Here, the addition or incorporation of the at least one stabilizer can take place during processing.

It is also possible to mix the at least one stabilizer with the thermoplastic condensation polymers, which can be present, for example, as chips, powder, beads or granules, before thermal processing, and then to process the mixture in the thermoplastic state.

Thermal processing is preferably carried out under aprotic conditions, i.e. in the substantial absence of substances that easily release protons, such as acids or water. In particular, aprotic conditions are characterized in that the thermoplastic condensation polymer has a maximum water content of up to 0.5% by weight, preferably up to 0.05% by weight.

The inorganic salts can be sulfites, disulfites or hydrogen sulfites. Preferred salts of sulphurous acid (sulphites) are salts of mono, di, trivalent or tetravalent metals, preferred are alkali metals, alkaline earth metals and zinc, such as sodium sulphite, potassium sulphite, lithium sulphite, calcium sulphite, magnesium sulphite, aluminum sulphite or zinc sulphite.

Exemplary disulfites are potassium disulfite or sodium disulfite.

An exemplary thiosulfate is, for example, sodium thiosulfate.

The forms of the salts listed which are free of water of crystallization are very particularly preferred. Salts that are free of water of crystallization are those which lose a maximum of 10% by weight of water of crystallization under the respective processing conditions. This also includes, in particular, salts that can be converted into this state by conventional drying methods.

Furthermore, the sulfites, disulfites or thiosulfates used must be selected in such a way that sufficient thermal stability is present at the processing temperatures of the respective polymers. Corresponding decomposition temperatures are known to the person skilled in the art or can be determined, for example, by thermogravimetric analysis (TGA).

Based on the condensation polymer, the at least one stabilizer is preferably used in a weight ratio of from 0.01 to 10.00% by weight, preferably from 0.05 to 5.00% by weight, particularly preferably from 0.10 to 1% by weight. % used.

An exemplary condensation polymer is selected from the group consisting of

Polyesters made from aliphatic or aromatic dicarboxylic acids and diols or from hydroxycarboxylic acids such as polylactic acid (PLA), polybutylene succinate, polybutylene succinate-co-adipate), poly (butylene adipate) (PBA), polyethylene terephthalate (PET), polybutylene terephthalate (PPTerephthalate), polypropylene terephthalate (PBTerephthalate) Polyethylene furanoate (poly (ethylene-2,5-furandicarboxylate)) (PEF), polyethylene naphthylate, poly-1,4-dimethylolcyclohexane terephthalate, polyhydroxybenzoate, polyhydroxynaphthalate, polycaprolactone (PCL), poly-3-hydroxybutyrate, poly-4-hydroxybutyrate, poly 3-hydroxyvalerate, poly (hexamethylene succinate), poly (butylene succinate) and copolymers and mixtures or blends of two or more of the aforementioned polymers;

Polyamides such as PA 6, PA 6.6, PA 6.10, PA 4.6, PA 4.10, PA 6.12, PA 10.10, PA 10.12, PA 12.12, PA 11, PA 12;
partially aromatic polyamides such as polyphthalamides, for example prepared from terephthalic acid and / or isophthalic acid and aliphatic diamines or from aliphatic dicarboxylic acids such as adipic acid or sebacic acid and aromatic diamines such as 1,4- or 1,3-diaminobenzene;
Polycarbonates or polyester carbonates;
and also mixtures, combinations or blends of two or more of the aforementioned polymers.

Preferred condensation polymers are aliphatic polyesters such as polycaprolactone, poly-3-hydroxybutyrate, poly-4-hydroxybutyrate, poly-3-hydroxyvalerate, poly (hexamethylene succinate), poly (butylene succinate), poly (butylansuccinate-co-adipate), polylactic acid, very particularly preferred is polylactic acid (PLA).

The very particularly preferred polylactic acid (PLA) can be produced from L-lactide or D-lactide or a mixture L / D, usually by ring-opening polymerization of the lactide (dimer of lactic acid). PLA can also be in the form of a copolymer. Hydroxycarboxylic acids such as glycolic acid, 4-hydroxybutyric acid, 3-hydroxybutyric acid, 3-hydroxyvaleric acid or mandelic acid are preferably used as comonomers in PLA copolymers. In principle, copolymers of PLA obtained from a diol such as ethylene glycol or butanediol and a dicarboxylic acid such as adipic acid or terephthalic acid are also possible. Copolymers can be in the form of statistical (“random”), block or “tapered” structures or as stereoblock copolymers.

In principle, the condensation polymers can contain additives of other thermoplastic polymers to a minor extent.

1. A) mindestens einen Stabilisator, ausgewählt aus der Gruppe bestehend aus anorganischen Sulfiten und/oder Thiosulfaten, sowie
2. B) mindestens ein thermoplastisches Kondensationspolymer

Bezüglich des Stabilisators sei auf die voranstehenden Ausführungen verwiesen, die vollumfänglich ebenso für die erfindungsgemäße Zusammensetzung gelten.In a further aspect, the present invention relates to a condensation polymer composition containing or consisting of

1. A) at least one stabilizer selected from the group consisting of inorganic sulfites and / or thiosulfates, as well as
2. B) at least one thermoplastic condensation polymer

With regard to the stabilizer, reference is made to the statements above, which also apply in full to the composition according to the invention.

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

enthält oder hieraus besteht.The condensation polymer composition according to the invention can additionally contain at least one additive. It is advantageous here if the composition

1. (A) 0.01 to 10.00% by weight, preferably 0.05 to 5.00% by weight, particularly preferably 0.10 to 1.00% by weight of the at least one stabilizer,
2. (B) 85.00 to 99.98% by weight, preferably 96 to 99.90% by weight of a condensation polymer, as well as
3. (C) 0.01 to 5.00% by weight, preferably 0.05 to 1.00% by weight, of at least one additive

contains or consists of it.

Exemplary additives are selected from the group consisting of primary antioxidants, secondary antioxidants with the exception of phosphites or phosphonites, UV absorbers, light stabilizers, metal deactivators, filler deactivators, antiozonants, nucleating agents, antinucleating agents, impact strength improvers, processing agents, thixotropic additives, lubricants, chain modifiers , Mold release agents, flame retardants, pigments, dyes, optical brighteners, antimicrobial agents, antistatic agents, slip agents, antiblocking agents, coupling agents, crosslinking agents, anti-crosslinking agents, hydrophilizing agents, hydrophobizing agents, hydrolysis stabilizers, anti-adhesive agents, anti-foaming agents, acid release agents, dispersants, compatibilizers , Odor traps, tracers and anti-fogging agents.

Plasticizers, fibers such as glass fibers and / or carbon fibers and fillers are not included in the additives. In the event that plasticizers, fibers and / or filler are contained in the condensation polymer composition, these substances in their total can contain up to 80 parts by weight, preferably 0.1 to 60 parts by weight, particularly preferably 1 to 50 Parts by weight based on 100 parts by weight of the condensation polymer composition described above (ie the sum of components (A) to (C)).

In a preferred embodiment, the compositions contain in particular further classes of nucleating agents, additives for increasing molecular weight (chain extenders) or fillers.

Preferred nucleating agents are talc, alkali or alkaline earth salts of mono- and polyfunctional carboxylic acids such as. B. benzoic acid, succinic acid, adipic acid, for example sodium benzoate, zinc glycerolate, aluminum hydroxybis (4-tert-butyl) benzoate, 2,2'-methylene-bis (4,6-di-tert-butylphenyl) phosphate, and trisamides and diamides such as e.g. trimesic acid tri-cyclohexylamide, trimesic acid tri (4-methylcyclohexylamide), trimesic acid tri (tert-butylamide), N, N ', N "- 1,3,5-benzenetriyltris (2,2-dimethyl-propanamide) or 2,6-naphthalenedicarboxylic acid dicyclohexylamide or Orotic acid.

Preferred additives for increasing molecular weight (chain extenders) are diepoxides, bis-oxazolines, bis-oxazolones, bis-oxazines, diisocyanates, dianhydrides, bis-acyllactams, bis-maleimides, dicyanates, carbodiimides. Further suitable chain extenders are polymeric compounds such as polystyrene-polyacrylate-polyglycidyl (meth) acrylate copolymers, polystyrene-maleic anhydride copolymers and polyethylene-maleic anhydride copolymers.

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

• Geeignete primäre Antioxidantien (A) sind phenolische Antioxidantien, Amine und Lactone.
• Geeignete phenolische Antioxidantien sind beispielsweise:
  • Alkylierte Monophenole, wie z.B. 2,6-Di-tert-butyl-4-methylphenol, 2-tert-Butyl-4,6-dimethylphenol, 2,6-Di-tert-butyl-4-ethylphenol, 2,6-Di-tert-butyl-4-n-butylphenol, 2,6-Di-tert-butyl-4-isobutylphenol, 2,6-Dicyclopentyl-4-methylphenol, 2-(α-Methylcyclohexyl)-4,6-dimethylphenol, 2,6-Dioctadecyl-4-methylphenol, 2,4,6-Tricyclohexylphenol, 2,6-Di-tert-butyl-4-methoxymethylphenol, lineare oder verzweigte Nonylphenole, wie z.B. 2,6-Dinonyl-4-methylphenol, 2,4-Dimethyl-6-(1'-methylundec-1'-yl)phenol, 2,4-Dimethyl-6-(1'-methylheptadec-1'-yl)phenol, 2,4-Dimethyl-6-(1'-methyltridec-1'-yl)phenol und Mischungen hiervon;
  • Alkylthiomethylphenole, wie z.B. 2,4-Dioctylthiomethyl-6-tert-butylphenol, 2,4-Dioctylthiomethyl-6-methylphenol, 2,4-Dioctylthiomethyl-6-ethylphenol, 2,6-Didodecylthiomethyl-4-nonylphenol;
  • Hydrochinone und alkylierte Hydrochinone, wie z.B. 2,6-Di-tert-butyl-4-methyoxyphenol, 2,5-Di-tert-butylhydrochinon, 2,5-Di-tert-amylhydrochinon, 2,6-Diphenyl-4-octadecyloxyphenol, 2,6-Di-tert-butylhydrochinon, 2,5-Di-tert-butyl-4-hydroxyanisol, 3,5-Di-tert-butyl-4-hydroxyanisol, 3,5-Di-tert-butyl-4-hydroxyphenylstearat, Bis(3,5-di-tert-butyl-4-hydroxylphenyl)adipat;
  • Tocopherole, wie z.B. α-, β-, γ-, δ-Tocopherol und Mischungen aus diesen (Vitamin E);
  • Hydroxylierte Thiodiphenylether, wie z.B. 2,2'-Thiobis(6-tert-butyl-4-methylphenol), 2,2'-Thiobis(4-octylphenol), 4,4'-Thiobis(6-tert-butyl-3-methylphenol), 4,4'-Thiobis(6-tert-butyl-2-methylphenol), 4,4'-Thiobis(3,6-di-secamylphenol), 4,4'-Bis(2,6-dimethyl-4-hydroxyphenyl)disulfid;
  • Alkylidenbisphenole, wie z.B. 2,2'Methylenbis(6-tert-butyl-4-methylphenol), 2,2'-Methylenbis(6-tert-butyl-4-ethylphenol), 2,2'-Methylenbis[4-methyl-6-(α-methylcyclohexyl)phenol], 2,2'-Methylenbis(4-methyl-6-cyclhexylphenol), 2,2'-Methylenbis(6-nonyl-4-methylphenol), 2,2'-Methylenbis(4,6-di-tert-butylphenol), 2,2'-Ethylidenbis(4,6-di-tert-butylphenol), 2,2'-Ethylidenbis(6-tert-butyl-4-isobutylphenol), 2,2'-Methylenbis[6-(α-methylbenzyl)-4-nonylphenol], 2,2'-Methylenbis[6-(α,αmethylbenzyl)-4-nonylphenol], 4,4'-Methylenbis(2,6-di-tert-butylphenol, 4,4'-Methylenbis(6-tert-butyl-2-methylphenol), 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butan, 2,6-Bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-Tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butan, 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutan, Ethylenglycol-bis[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)butyrat], Bis(3-tert-butyl-4-hydroxy-5-methylphenyl)-dicyclopentadien, Bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalat, 1,1-Bis-(3,5-dimethyl-2-hydroxyphenyl)-butan, 2,2-Bis(3,5-di-tert-butyl-4-hydroxyphenyl)propan, 2,2-Bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutan, 1,1,5,5-Tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)pentan;
  • O-, N- und S-Benzyl-Verbindungen, wie z.B. 3,5,3',5'-Tetra-tert-butyl-4,4'-dihydroxydibenzylether, Octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetat, Tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetat, Tris(3,5-di-tert-butyl-4-hydroxybenzyl)amin, , Bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalat, Bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfid, Isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetat;
  • Hydroxybenzylierte Malonate, wie z.B. Dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonat, Dioctadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonat, Didodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonat, Bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonat;
  • Aromatische Hydroxybenzylverbindungen, wie z.B. 1,3,5-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzol, 1,4-Bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzol, 2,4,6-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol;
  • Triazinverbindungen, wie z.B. 2,4-Bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazin, 2-Octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazin, 2-Octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazin, 2,4,6-Tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazin, 1,3,5-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurat, 1,3,5-Tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurat, 2,4,6-Tris(3,5-di-tert-butyl-4-hydroxphenylethyl)-1,3,5-triazin, 1,3,5-Tris(3,5-di-tert-butyl-4-hydroyphenylpropionyl)hexahydro-1,3,5-triazin, 1,3,5-Tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurat;
  • Benzylphosphonate, wie z.B. Dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonat, Dietyhl-3,5-di-i-eri--butyl-4-hydroxybenzylphosphonat, Dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonat, Dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonat, das Calciumsalz des Monoethylesters der 3,5-Di-tert-butyl-4-hydroxybenzylphosphonsäure;
  • Acylaminophenole, wie z.B. 4-Hydroxylauranilid, 4-Hydroxystearanilid, Octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamat;
  • Ester der β-(3,5-Di-tert-butyl-4-hydroxyphenyl)propionsäure mit ein- oder mehrwertigen Alkoholen, z.B. Methanol, Ethanol, n-Octanol, i-Octanol, Octadecanol, 1,6-Hexandiol, 1,9-Nonandiol, Ethylenglycol, 1,2-Propandiol, Neopentylglycol, Thiodiethylenglycol, Diethylenglycol, Triethylenglycol, Pentaerythritol, Tris(hydroxyethyl)isocyanurat, N,N'-Bis(hydroxyethyl)oxamid, 3-Thiaundecanol, 3-Thiapentadecanol, Trimethylhexandiol, Trimethylolpropan, 4-Hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octan;
  • Ester der β-(5-tert-Butyl-4-hydroxy-3-methylphenyl)propionsäure mit ein- oder mehrwertigen Alkoholen, z.B. Methanol, Ethanol, n-Octanol, i-Octanol, Octadecanol, 1,6-Hexandiol, 1,9-Nonandiol, Ethylenglycol, 1,2-Propandiol, Neopentylglycol, Thiodiethylenglycol, Diethylenglycol, Triethylenglycol, Pentaerythritol, Tris(hydroxyethyl)isocyanurat, N,N'-bis(hydroxyethyl)oxamid, 3-Thiaundecanol, 3-Thiapentadecanol, Trimethylhexandiol, Trimethylolpropan, 4-Hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octan, 3,9-Bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxyl-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecan;
  • Ester der β-(3,5-Dicyclohexyl-4-hydroxyphenyl)propionsäure mit ein- oder mehrwertigen Alkoholen, z.B. Methanol, Ethanol, Octanol, Octadecanol, 1,6-Hexandiol, 1,9-Nonandiol, Ethylenglycol, 1,2-Propandiol, Neopentylglycol, Thiodiethylenglycol, Diethylenglycol, Triethylenglycol, Pentaerythritol, Tris-(hydroxyethyl)isocyanurat, N,N'-bis(hydroxyethyl)oxamid, 3-Thiaundecanol, 3-Thiapentadecanol, Trimethylhexandiol, Trimethylolpropan, 4-Hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octan;
  • Ester der (3,5-Di-tert-butyl-4-hydroxyphenyl)essigsäure mit ein- oder mehrwertigen Alkoholen, z.B. Methanol, Ethanol, Octanol, Octadecanol, 1,6-Hexandiol, 1,9-Nonandiol, Ethylenglycol, 1,2-Propandiol, Neopentylglycol, Thiodiethylenglycol, Diethylenglycol, Triethylenglycol, Pentaerythritol, Tris(hydroxyethyl)isocyanurat, N,N'-bis(hydroxyethyl)oxamid, 3-Thiaundecanol, 3-Thiapentadecanol, Trimethylhexandiol, Trimethylolpropan, 4-Hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octan;
  • Amide der β-(3,5-Di-tert-butyl-4-hydroxyphenyl)propionsäure, wie z.B. N,N'-Bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylendiamid, N,N'-Bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylendiamid, N,N'-Bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylendiamid, N,N'-Bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazid, N,N'-Bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamid (Naugard^®XL-1, vertrieben durch Uniroyal);
  • Ascorbinsäure (Vitamin C).
• Besonders bevorzugte phenolische Antioxidantien sind die folgenden Strukturen:
  
  
  
  
  
  
  
  
  
  
• Weitere besonders bevorzugte phenolische Antioxidantien basieren auf nachwachsenden Rohstoffen wie z. B. Tocopherole (Vitamin E), Tocotrienole, Tocomonoenole, Carotenoide, Hydroxytyrosol, Flavonole wie z.B. Chrysin, Quercitin, Hesperidin, Neohesperidin, Naringin, Morin, Kaempferol, Fisetin, Anthocyane, wie z.B. Delphinidin und Malvidin, Curcumin, Carnosolsäure, Carnosol, Rosmarinsäure und Resveratrol.
• Geeignete aminische Antioxidantien sind beispielsweise: N,N'-Di-isopropyl-p-phenylendiamin, N,N'-Di-sec-butyl-p-phenylendiamin, N,N'-Bis(1,4-dimethylpentyl)-p-phenylendiamin, N,N'-Bis(1-ethyl-3-methylpentyl)-p-phenylendiamin, N,N'-Bis(1-methylheptyl)-p-phenylendiamin, N,N'-Dicyclohexyl-p-phenylendiamin, N,N'-Diphenyl-p-phenylendiamin, N,N'-Bis(2-naphthyl)-p-phenylendiamin, N-Isopropyl-N'-phenyl-p-phenylendiamin, N-(1,3-Dimethylbutyl)-N'-phenyl-p-phenylen-diamin, N-(1-Methylheptyl)-N'phenyl-p-phenylendiamin, N-Cyclohexyl-N'-phenyl-p-phenylendiamin, 4-(p-Toluolsulfamoyl)diphenylamin, N,N'-Dimethyl-N,N'-di-sec-butyl-p-phenylendiamin, Diphenylamin, N-Allyldiphenylamin, 4-Isopropoxydiphenylamin, N-Phenyl-1-naphthylamin, N-(4-tert-Octylphenyl)-1-naphthylamin, N-Phenyl-2-naphthylamin, octyliertes Diphenylamin, z.B. p,p'-Di-tert-octyldiphenylamin, 4-n-Butylaminophenol, 4-Butyrylaminophenol, 4-Nonanoylaminophenol, 4-Dodecanoylaminophenol, 4-Octadecanoylamino-phenol, Bis(4-methoxyphenyl)amin, 2,6-Di-tert-butyl-4-dimethylaminomethyl-phenol, 2,4'-Diaminodiphenylmethan, 4,4'-Diaminodiphenylmethan, N,N,N',N'-Tetra-methyl-4,4'-diaminodiphenylmethan, 1,2-Bis[(2-methyl-phenyl)amino]ethan, 1,2-Bis-(phenylamino)propan, (o-Tolyl)biguanid, Bis[4-(1',3'-dimethylbutyl)phenyl]-amin, tert-octyliertes N-Phenyl-1-naphthylamin, ein Gemisch aus mono- und dialkylierten tert-Butyl/tert-Octyldiphenylaminen, ein Gemisch aus mono- und dialkylierten Nonyldiphenylaminen, ein Gemisch aus mono- und dialkylierten Dodecyldiphenylaminen, ein Gemisch aus mono- und dialkylierten Isopropyl/- Isohexyl-diphenylaminen, ein Gemisch aus mono- und dialkylierten tert-Butyldiphenylaminen, 2,3-Dihydro-3,3-dimethyl-4H-1,4-benzothiazin, Phenothiazin, ein Gemisch aus mono- und dialkylierten tert-Butyl/tert-Octylphenothiazinen, ein Gemisch aus mono- und dialkylierten tert-Octylphenothiazinen, N-Allylphenothiazin, N,N,N',N'-Tetraphenyl-1,4-diaminobut-2-en sowie Mischungen oder Kombinationen hiervon.
• Bevorzugte aminische Antioxidantien sind: N,N'-Di-isopropyl-p-phenylendiamin, N,N'-Di-sec-butyl-p-phenylendiamin, N,N'-Bis(1,4-dimethylpentyl)-p-phenylendiamin, N,N'-Bis(1-ethyl-3-methylpentyl)-p-phenylendiamin, N,N'-Bis(1-methylheptyl)-p-phenylendiamin, N,N'-Dicyclohexyl-p-phenylendiamin, N,N'-Diphenyl-p-phenylendiamin, N,N'-Bis(2-naphthyl)-p-phenylendiamin, N-Isopropyl-N'-phenyl-p-phenylendiamin, N-(1,3-Dimethylbutyl)-N'-phenyl-p-phenylen-diamin, N-(1-Methylheptyl)-N'-phenyl-p-phenylendiamin, N-Cyclohexyl-N'-phenyl-p-phenylendiamin
• Weitere bevorzugte aminische Antioxidantien sind Hydroxylamine bzw. N-oxide (Nitrone), wie z.B. N,N-Dialkylhydroxylamine, N,N-Dibenzylhydroxylamin, N,N-Dilaurylhydroxylamin, N,N-Distearylhydroxylamin, N-Benzyl-α-phenylnitron, N-Octadecyl-a-hexadecylnitron, sowie Genox EP (SI Group Inc.) ) gemäß der Formel:
  
• Geeignete Lactone sind Benzofuranone und Indolinone wie z.B. 3-(4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butyl-benzofuran-2-on, 5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-on, 3,3'-bis[5,7-di-tert-butyl-3-(4-(2-hydroxyethoxy]phenyl )benzofuran-2-on), 5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-on, 3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-on, 3-(3,5-dimethyl-4-pivaloyloxyphenyl )-5,7-di-tert-butyl-benzofuran-2-on, 3-(3,4-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-on, 3-(2,3-di methylphenyl)-5,7-di-tert-butyl-benzofuran-2-on.
• Geeignete sekundäre Antioxidantien sind Organo-Schwefelverbindungen wie z.B. Sulfide und Disulfide z.B. Distearylthiodipropionat, Dilaurylthiodipropionat; Ditridecyldithiopropionat, Ditetradecylthiodipropionat, 3-(Dodecylthio)-,1,1'-[2,2-bis[[3-(dodecylthio)-1-oxopropoxy]methyl]-1,3-propandiyl]propansäureester.
• Geeignete Lichtstabilisatoren sind beispielsweise Verbindungen auf der Basis von 2-(2'-Hydroxyphenyl)benzotriazolen, 2-Hydroxybenzophenonen, Estern von Benzoesäuren, Acrylaten, Oxamiden und 2-(2-Hydroxyphenyl)-1,3,5-Triazinen.

Examples of further additives that the compositions according to the invention can additionally contain are primary and secondary antioxidants:

• Suitable primary antioxidants (A) are phenolic antioxidants, amines and lactones.
• Suitable phenolic antioxidants are, for example:
  • Alkylated monophenols, such as, for example, 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di -tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- (α-methylcyclohexyl) -4,6-dimethylphenol, 2 , 6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, linear or branched nonylphenols, such as 2,6-dinonyl-4-methylphenol, 2, 4-dimethyl-6- (1'-methylundec-1'-yl) phenol, 2,4-dimethyl-6- (1'-methylheptadec-1'-yl) phenol, 2,4-dimethyl-6- (1 '-methyltridec-1'-yl) phenol and mixtures thereof;
  • Alkylthiomethylphenols such as 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol;
  • Hydroquinones and alkylated hydroquinones, such as, for example, 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol , 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4 hydroxyphenyl stearate, bis (3,5-di-tert-butyl-4-hydroxylphenyl) adipate;
  • Tocopherols, such as, for example, α-, β-, γ-, δ-tocopherol and mixtures of these (vitamin E);
  • Hydroxylated thiodiphenyl ethers, such as 2,2'-thiobis (6-tert-butyl-4-methylphenol), 2,2'-thiobis (4-octylphenol), 4,4'-thiobis (6-tert-butyl-3- methylphenol), 4,4'-thiobis (6-tert-butyl-2-methylphenol), 4,4'-thiobis (3,6-di-secamylphenol), 4,4'-bis (2,6-dimethyl- 4-hydroxyphenyl disulfide;
  • Alkylidenebisphenols, such as 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 2,2'-methylenebis [4-methyl- 6- (α-methylcyclohexyl) phenol], 2,2'-methylenebis (4-methyl-6-cyclhexylphenol), 2,2'-methylenebis (6-nonyl-4-methylphenol), 2,2'-methylenebis (4 , 6-di-tert-butylphenol), 2,2'-ethylidenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (6-tert-butyl-4-isobutylphenol), 2,2 ' -Methylene bis [6- (α-methylbenzyl) -4-nonylphenol], 2,2'-methylenebis [6- (α, α-methylbenzyl) -4-nonylphenol], 4,4'-methylenebis (2,6-di-tert -butylphenol, 4,4'-methylenebis (6-tert-butyl-2-methylphenol), 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis (3 -tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1,1-bis (5- tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecyl mercaptobutane, ethylene glycol bis [3,3-bis (3'-tert-butyl-4'-hydroxyphenyl) butyrate], bis (3-tert- butyl-4-hydroxy-5-methylphenyl) -dicyclopentadiene, bis [2- (3'-tert-butyl-2'-hydroxy -5'-methylbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate, 1,1-bis (3,5-dimethyl-2-hydroxyphenyl) butane, 2,2-bis (3,5-di -tert-butyl-4-hydroxyphenyl) propane, 2,2-bis- (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecyl mercaptobutane, 1,1,5,5-tetra (5 -tert-butyl-4-hydroxy-2-methylphenyl) pentane;
  • O-, N- and S-benzyl compounds, such as, for example, 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzyl mercaptoacetate, tridecyl -4-hydroxy-3,5-di-tert-butylbenzyl mercaptoacetate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) amine,, bis (4-tert-butyl-3-hydroxy-2,6- dimethylbenzyl) dithioterephthalate, bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzyl mercaptoacetate;
  • Hydroxybenzylated malonates, such as dioctadecyl 2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, dioctadecyl 2- (3-tert-butyl-4-hydroxy-5-methylbenzyl) malonate, Didodecylmercaptoethyl-2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, bis [4- (1,1,3,3-tetramethylbutyl) phenyl] -2,2-bis (3, 5-di-tert-butyl-4-hydroxybenzyl) malonate;
  • Aromatic hydroxybenzyl compounds such as 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3,5-di-tert- butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) phenol;
  • Triazine compounds such as 2,4-bis (octylmercapto) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3 , 5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,3 , 5-triazine, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,2,3-triazine, 1,3,5-tris (3,5-di- tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris (3,5-di- tert-butyl-4-hydroxphenylethyl) -1,3,5-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroyphenylpropionyl) hexahydro-1,3,5-triazine, 1 , 3,5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate;
  • Benzyl phosphonates, such as, for example, dimethyl 2,5-di-tert-butyl-4-hydroxybenzyl phosphonate, diethl-3,5-di-i-eri-butyl-4-hydroxybenzyl phosphonate, dioctadecyl-3,5-di-tert-butyl -4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid;
  • Acylaminophenols such as 4-hydroxylauranilide, 4-hydroxystearanilide, octyl-N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate;
  • Esters of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with monohydric or polyhydric alcohols, e.g. methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1, 9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapethylentadecanol., , 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane;
  • Esters of β- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with monohydric or polyhydric alcohols, e.g. methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1, 9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapethylentadecanol., , 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxyl -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane;
  • Esters of β- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid with monohydric or polyhydric alcohols, e.g. methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2- Propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-phosphate methyl 2,6,7-trioxabicyclo [2.2.2] octane;
  • Esters of (3,5-di-tert-butyl-4-hydroxyphenyl) acetic acid with monohydric or polyhydric alcohols, e.g. methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1, 2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, 1-trimethylolpropane., 2,6,7-trioxabicyclo [2.2.2] octane;
  • Amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, such as N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylene diamide, N, N ' -Bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylene diamide, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylene diamide, N, N'-bis (3 , 5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazide, N, N'-bis [2- (3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyloxy) ethyl] oxamide (Naugard ^® XL-1, sold by Uniroyal);
  • Ascorbic acid (vitamin C).
• Particularly preferred phenolic antioxidants are the following structures:
  
  
  
  
  
  
  
  
  
  
• Other particularly preferred phenolic antioxidants are based on renewable raw materials such as. B. tocopherols (vitamin E), tocotrienols, tocomonoenols, carotenoids, hydroxytyrosol, flavonols such as chrysin, quercitin, hesperidin, neohesperidin, naringin, morin, kaempferol, fisetin, anthocyanins such as delphinidin and malvidin, curcumin, carnosolic acid and resveratrol.
• Suitable aminic antioxidants are, for example: N, N'-di-isopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-bis (1,4-dimethylpentyl) -p- phenylenediamine, N, N'-bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N'-bis (1-methylheptyl) -p-phenylenediamine, N, N'-dicyclohexyl-p-phenylenediamine, N , N'-diphenyl-p-phenylenediamine, N, N'-bis (2-naphthyl) -p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N '-phenyl-p-phenylenediamine, N- (1-methylheptyl) -N'phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4- (p-toluenesulfamoyl) diphenylamine, N, N'-dimethyl-N, N'-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N- (4-tert-octylphenyl) -1- naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, for example p, p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylamino (4-methoxyphenyl) amine, 2,6- Di-tert-butyl-4-dimethylaminomethyl-phenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N, N, N ', N'-tetra-methyl-4,4'-diaminodiphenylmethane, 1,2 -Bis [(2-methyl-phenyl) amino] ethane, 1,2-bis (phenylamino) propane, (o-tolyl) biguanide, bis [4- (1 ', 3'-dimethylbutyl) phenyl] amine, tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- and dialkylated tert-butyl / tert-octyldiphenylamines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl / isohexyl-diphenylamines, a mixture of mono- and dialkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a mixture of mono- and dialkylated tert- Butyl / tert-octylphenothiazines, a mixture of mono- and dialkylated tert-octylphenothiazines, N-allylphenothiazine, N, N, N ', N'-tetraphenyl-1,4-diaminobut-2-en and mixtures or combinations thereof.
• Preferred aminic antioxidants are: N, N'-di-isopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-bis (1,4-dimethylpentyl) -p-phenylenediamine , N, N'-bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N'-bis (1-methylheptyl) -p-phenylenediamine, N, N'-dicyclohexyl-p-phenylenediamine, N, N'-Diphenyl-p-phenylenediamine, N, N'-bis (2-naphthyl) -p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N ' -phenyl-p-phenylenediamine, N- (1-methylheptyl) -N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine
• Further preferred aminic antioxidants are hydroxylamines or N-oxides (nitrones), such as, for example, N, N-dialkylhydroxylamines, N, N-dibenzylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-distearylhydroxylamine, N-benzyl-α-phenylnitrone, N -Octadecyl-a-hexadecylnitron, as well as Genox EP (SI Group Inc.)) according to the formula:
  
• Suitable lactones are benzofuranones and indolinones such as 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-dimethylphenyl) -5,7-di-tert-butyl-benzofuran-2-one.
• Suitable secondary antioxidants are organosulfur compounds such as sulfides and disulfides, for example distearyl thiodipropionate, dilauryl thiodipropionate; Ditridecyldithiopropionate, ditetradecylthiodipropionate, 3- (dodecylthio) -, 1,1 '- [2,2-bis [[3- (dodecylthio) -1-oxopropoxy] methyl] -1,3-propanediyl] propanoic acid ester.
• Suitable light stabilizers are, for example, compounds based on 2- (2'-hydroxyphenyl) benzotriazoles, 2-hydroxybenzophenones, esters of benzoic acids, acrylates, oxamides and 2- (2-hydroxyphenyl) -1,3,5-triazines.

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

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'-dimethoxy derivatives of 2-hydroxybenzophenones.

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

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

Suitable oxamides are, for example, 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di- tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) -oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixtures with 2-ethoxy-2 '-ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and p-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.

Suitable 2- (2-hydroxyphenyl) -1,3,5-triazines are, for example, 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy- 4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1 , 3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl ) -4,6-bis (4-methylphenyl-1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5 -triazine, 2- (2-hydroxy-4-tridecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy- 3-butyloxypropoxy) phenyl] -4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxypropyloxy) phenyl] - 4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2- [4- (dodecyloxy / tridecyloxy-2-hydroxypropoxy) -2-hydroxyphenyl] -4,6-bis (2,4 -dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-dodecyloxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl-1,3, 5-triazine, 2- (2-hydroxy-4-hexyloxy) -phenyl-4,6-diphenyl-1,3,5-triazine , 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2,4,6-tris [2-hydroxy-4- (3-butoxy-2-hydroxypropoxy) -phenyl] -1,3,5-triazine, 2- (2-hydroxyphenyl) -4- (4-methoxyphenyl) -6-phenyl-1,3,5-triazine, 2- {2-hydroxy-4- [ 3- (2-ethylhexyl-1-oxy) -2-hydroxypropyloxy] -phenyl} -4,6-bis (2,4-dimethylphenyl-1,3,5-triazine.

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

Suitable hindered amines are, for example, 1,1-bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1 -octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebazate, bis (1,2,2, 6,6-pentamethyl-4-piperidyl) -n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensation product of 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl- 4-hydroxypiperidine and succinic acid, linear or cyclic condensation products of N, N'-bis (2, 2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3, 5-triazine, tris (2, 2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis (2, 2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 1 , 1 '- (1,2-ethanediyl) -bis (3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6 -tetramethylpiperidine, linear or cyclic condensation products from N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine the reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro- [4.5] decane and epichlorohydrin.

Oligomeric and polymeric hindered amines of the following structures are preferred:

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

• Polyacrylate, z.B. Copolymere mit langkettigen Seitengruppen, Polyacrylat-Blockcopolymere, Alkylamide: z.B. N,N'-1,2-Ethandiylbisoctadecanamid Sorbitanester, z.B. Monostearylsorbitanester, Titanate und Zirconate, reaktive Copolymere mit funktionellen Gruppen z.B. Polypropylen-co-Acrylsäure, Polypropylen-co-Maleinsäureanhydrid, Polyethylen-co-Glycidylmethacrylat, Polystyrol-alt-Maleinsäureanhydrid-Polysiloxane: z.B. Dimethylsilandiol-Ethylenoxid Copolymer, Polyphenylsiloxan Copolymer, Amphiphile Copolymere: z.B. Polyethylen-block-Polyethylenoxid, Dendrimere, z.B. hydroxylgruppenhaltige Dendrimere.

Suitable dispersants are, for example:

• Polyacrylates, e.g. copolymers with long-chain side groups, polyacrylate block copolymers, alkylamides: e.g. N, N'-1,2-ethanediylbisoctadecanamide sorbitan esters, e.g. monostearyl sorbitan ester, titanates and zirconates, reactive copolymers with functional groups e.g. polypropylene-co-acrylic acid, polypropylene-co- Maleic anhydride, polyethylene-co-glycidyl methacrylate, polystyrene-alt-maleic anhydride-polysiloxanes: for example dimethylsilanediol-ethylene oxide copolymer, polyphenylsiloxane copolymer, amphiphilic copolymers: for example polyethylene-block-polyethylene oxide, dendrimers, for example dendrimers containing hydroxyl groups.

Suitable anti-nucleating agents are azine dyes such as nigrosine.

Suitable flame retardants are, in particular, inorganic flame retardants such as Al (OH) ₃ , Mg (OH) ₂ , AIO (OH), MgCO ₃ , sheet silicates such as montmorillonite or sepiolite, unmodified or organically modified, double salts such as Mg-Al silicates, POSS (Polyhedral Oligomeric Silsesquioxane) compounds, huntite, hydromagnesite or halloysite

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

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

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

Suitable antistatic agents are, for example, ethoxylated alkyl amines, fatty acid esters, alkyl sulfonates and polymers such as polyether amides.

Suitable antiozonants are the above-mentioned amines such as, for example, N, N'-diisopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-bis (1,4-dimethylpentyl) -p -phenylenediamine, N, N'-dicyclohexyl-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'phenyl-p-phenylenediamine, N- ( 1-methylheptyl) -N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine. Suitable mold release agents are, for example, montan waxes.

The above-described additive composition and optionally the additional additives are incorporated into the plastic or the condensation polymer by customary processing methods, the polymer being melted and mixed with the additive composition according to the invention and any other additives, preferably using a mixer, kneader or extruder. Preferred processing machines are extruders such as single-screw extruders, twin-screw extruders, planetary roller extruders, ring extruders, co-kneaders, which are preferably equipped with vacuum degassing. Processing can take place under air or, if necessary, under inert gas conditions.

Furthermore, the additive compositions according to the invention can be produced and introduced in the form of so-called masterbatches or concentrates which contain, for example, 10-90% of the compositions according to the invention in a polymer.

The present invention also relates to a molding compound or a molded part that can be produced or produced from the condensation polymer composition according to the invention, in particular in the form of foils (films), in particular agricultural foils such as mulch, tunnel or perforated foils, tapes, hollow bodies and foams, injection molded parts, Fibers, profiles and other extrudates, parts from additive or generative manufacturing processes, such as fused layer modeling (FLM), layer laminate modeling (LLM), selective laser sintering (SLS) and other 3D printing processes, packaging for food or cosmetic products, encapsulation of active ingredients and biologically active substances, bandages, surgical sutures and / or hygiene products, in particular as a component of disposable diapers, sanitary towels and tampons.

The present invention further relates to a method for the oxidative, thermal and / or actinic stabilization of a thermoplastic condensation polymer, in particular against oxidative, thermal and / or actinic degradation by adding, adding or incorporating at least one stabilizer selected from the group consisting of inorganic sulfites and thiosulfates to or into the thermoplastic condensation polymer. With regard to the stabilizer, reference is made to the statements above, which also apply in full to the process according to the invention.

The thermal stabilization is preferably carried out during the thermal processing of the condensation polymers, the thermal processing taking place in particular under aprotic conditions.

• - für die Herstellung von Verpackungen, insbesondere Verpackungen für Lebensmittel oder Kosmetikprodukte;
• - in der Pharmaindustrie, insbesondere zur Verkapselung von Wirkstoffen und biologisch aktiven Substanzen;
• - in der Medizintechnik, insbesondere zur Herstellung von Verbandsmaterial und chirurgischem Nahtmaterial;
• - in Hygieneprodukten, insbesondere als Bestandteil von Einwegwindeln, Binden und Tampons; und/oder
• - in landwirtschaftlichen Anwendungen, z.B. für die Herstellung von landwirtschaftlichen Folien wie Mulch-, Tunnel- oder Lochfolien.

The invention also relates to the use of a condensation polymer composition according to the invention

• - for the production of packaging, in particular packaging for food or cosmetic products;
• - In the pharmaceutical industry, in particular for the encapsulation of active ingredients and biologically active substances;
• - in medical technology, in particular for the production of bandages and surgical sutures;
• - in hygiene products, in particular as a component of disposable diapers, sanitary towels and tampons; and or
• - in agricultural applications, e.g. for the production of agricultural films such as mulch, tunnel or perforated films.

The present invention is described in more detail with reference to the following exemplary embodiments, without restricting the invention to the specific parameters.

Embodiments:

As PLA Luminy L 175 (≤ 0.5% of D-lactic acid according to certificate, MVR = 4.7 cm ^3/10 min measured at 190 ° C / 2.16 kg ram weight) was used Corbion company. Before processing, the polymers were dried in a vacuum drying cabinet at 80 ° C. for at least 16 h.

The examples according to the invention and the comparative examples were produced by extrusion with a co-rotating Process 11 twin-screw extruder from Thermo Fisher Scientific, with a screw diameter of 11 mm and a length to diameter ratio (L / D) of 40.

The additives were mixed manually with the matrix polymer in a plastic bag and dosed volumetrically. Processing took place at a throughput of 1 kg / h and a screw speed of 200 rpm at 200 ° C.

The MVR was measured on an MI-2 melt index tester from Göttfert at a test temperature of 190 ° C. and a punch weight of 2.16 kg. Before the measurement, the samples were dried in a vacuum oven at 80 ° C. for at least 16 h. The preheating time was 4 minutes. Indicated the MVR is min in ^cm3 / 10 min. example additive MVR after extrusion Comparative example 1 Without addition 5.98 Example 1 according to the invention 0.5% sodium sulfite 4.58

The addition of salts of sulphurous acid (inventive example) demonstrates very good processing stability of the polymer, since the MVR value is lower than in comparative example 1 without addition, ie the degradation of the polymer during processing is reduced and the molecular weight of the polymer is retained .

QUOTES INCLUDED IN THE DESCRIPTION

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

Patent literature cited

• WO 2010000638 [0003]
• EP 0313113 [0004]
• US 3542725 [0004, 0005]
• US 2003/0104954 [0004]
• US 2872433 [0004]
• DE 102005005974 [0004]
• DD 247913 [0005]
• JP 2011201946 [0005]

Non-patent literature cited

• Meng, Xin; Shi, Guotao; Wu, Chushi; Chen, Weijie; Xin, Zhong; Shi, Yaoqi; Sheng, Yan (2016): Chain extension and oxidation stabilization of triphenyl phosphite (TPP) in PLA, Polymer Degradation and Stability 124, pp. 112-118 [0003]
• Georgousopoulou, loanna nectaria; Vouyiouka, Stamatina; Dole, Patrice; Papaspyrides, Constantine D. (2016): Thermo-mechanical degradation and stabilization of poly (butylene succinate), Polymer Degradation and Stability 128, pp. 182-192 [0003]

Claims (17)

Use of at least one stabilizer selected from the group consisting of inorganic sulfites and / or thiosulfates for stabilizing thermoplastic condensation polymers, in particular against oxidative, thermal and / or actinic degradation. Use after Claim 1 , characterized in that the thermal stabilization takes place during the thermal processing of the condensation polymers, in particular by adding, adding or incorporating the at least one stabilizer to or into the thermoplastic condensation polymer. Use according to the preceding claim, characterized in that the thermal processing takes place under aprotic conditions. Use according to one of the preceding claims, characterized in that the inorganic sulfite is a sulfite, a disulfite or a hydrogen sulfite of a mono-, di-, tri- or tetravalent metal, the metal preferably being an alkali metal, an alkaline earth metal, aluminum and / or Zinc is where the inorganic sulfite is used in particular in its anhydrous form. Use according to one of the preceding claims, characterized in that the thiosulfate is a thiosulfate of a mono-, di-, trivalent or tetravalent metal, the metal preferably being an alkali metal, an alkaline earth metal, aluminum and / or zinc, the thiosulfate in particular is used in its water-free form. Use according to one of the preceding claims, characterized in that the at least one stabilizer, based on the condensation polymer, in a weight ratio of 0.01 to 10.00% by weight, preferably 0.05 to 5.00% by weight, particularly preferably from 0.10 to 1.00 wt% is used. Use according to one of the preceding claims, characterized in that the condensation polymer is selected from the group consisting of polyesters from aliphatic or aromatic dicarboxylic acids and diols or from hydroxycarboxylic acids such as polylactic acid (PLA), polybutylene succinate, poly (butylene succinate-co-adipate), poly (butylene adipate) (PBA), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polypropylene terephthalate (PPT), polyethylene furanoate (poly (ethylene-2,5-furandicarboxylate)) (PEF), polyethylene naphthylate, poly-1,4-dimethylolcyclohexane terephthalate, Polyhydroxybenzoate, polyhydroxynaphthalate, poly (butylene adipate) (PBA), polycaprolactone (PCL), poly-3-hydroxybutyrate, poly-4-hydroxybutyrate, poly-3-hydroxyvalerate, poly (hexamethylene succinate), poly (butylene succinate) and copolymers and mixtures or blends from two or more of the aforementioned polymers; Polyamides such as PA 6, PA 6.6, PA 6.10, PA 4.6, PA 4.10, PA 6.12, PA 10.10, PA 10.12, PA 12.12, PA 11, PA 12; partially aromatic polyamides such as polyphthalamides, for example prepared from terephthalic acid and / or isophthalic acid and aliphatic diamines or from aliphatic dicarboxylic acids such as adipic acid or sebacic acid and aromatic diamines such as 1,4- or 1,3-diaminobenzene; Polycarbonates or polyester carbonates; and also mixtures, combinations or blends of two or more of the aforementioned polymers. Use according to one of the preceding claims, characterized in that the condensation polymer is selected from the group consisting of PLA, PBA and copolymers thereof, the PLA copolymers preferably selected from by ring-opening polymerization of D-lactide and / or L-lactide with comonomers Hydroxycarboxylic acids, in particular glycolic acid, 4-hydroxybutyric acid, 3-hydroxybutyric acid, 3-hydroxyvaleric acid or mandelic acid; Diols, especially ethylene glycol or butanediol; and / or carboxylic acids, in particular adipic acid or terephthalic acid; were obtained. Condensation polymer composition containing or consisting of A) at least one stabilizer selected from the group consisting of inorganic sulfites and / or thiosulfates, as well as B) at least one thermoplastic condensation polymer. Condensation polymer composition according to one of the two preceding claims, characterized in that the condensation polymer composition (A) 0.01 to 10.00% by weight, preferably 0.05 to 5.00% by weight, particularly preferably 0.10 to 1.00% by weight of the at least one stabilizer, (B) 85 , 00 to 99.98% by weight, preferably 96 to 99.90% by weight of at least one condensation polymer, and (C) 0.01 to 5.00% by weight, preferably 0.05 to 1.00% by weight .-% contains or consists of at least one additive. Condensation polymer composition according to any one of Claims 9 until 10 , characterized in that the at least one additive is selected from the group consisting of primary antioxidants, secondary antioxidants with the exception of phosphites and phosphonites, UV absorbers, light stabilizers, metal deactivators, filler deactivators, antiozonants, nucleating agents, antinucleating agents, impact strength improvers, lubricants, rheology modifiers Thixotropic agents, chain extenders, processing aids, mold release agents, flame retardants, pigments, dyes, optical brighteners, antimicrobial agents, antistatic agents, slip agents, antiblocking agents, coupling agents, crosslinking agents, anti-crosslinking agents, hydrophilizing agents, water repellants, composting agents, acid scavengers, acid scavengers, adhesion promoters, dispersing agents Additives, defoaming agents, odor traps, marking agents and anti-fogging agents and mixtures thereof. Condensation polymer composition according to one of the two preceding claims that, based on 100 parts by weight of components (A) to (C) up to 80 parts by weight, preferably 0.1 to 60 parts by weight, particularly preferably 1 contains up to 50 parts by weight of at least one plasticizer, filler and / or reinforcing material. Condensation polymer composition according to one of the two preceding claims, characterized in that the i) degradation additives are selected from the group consisting of organic transition metal compounds such as transition metal carboxylates, in particular iron (III) stearate and / or manganese (II) stearate; ii) plasticizers are selected from the group consisting of tributyl acetyl citrate, tributyl citrate, triethyl acetyl citrate, triethyl citrate, glycerol triacetate, epoxidized soybean oil and / or epoxidized linseed oil; iii) nucleating agents are selected from the group consisting of talc, alkali or alkaline earth salts of mono- and polyfunctional carboxylic acids, in particular of benzoic acid, succinic acid, adipic acid, for example sodium benzoate and aluminum hydroxy-bis (4-tert-butyl) benzoate; Zinc glycerolate, 2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphate, trisamides and diamides such as trimesic acid tricyclohexylamide, trimesic acid tri (4-methylcyclohexylamide), trimesic acid tri (tert-butylamide), N, N ', N "- 1,3,5-benzenetriyltris (2,2-dimethyl-propanamide), 2,6-naphthalenedicarboxylic acid dicyclohexylamide; and / or orotic acid; iv) chain extenders are selected from the group consisting of diepoxides, bis-oxazolines, bis-oxazolones, bis-oxazines, diisocyanates, dianhydrides, bis-acyllactams, bis-maleimides, dicyanates, carbodiimides and / or polymeric chain extenders, for example polystyrene-polyacrylate Polyglycidyl (meth) acrylate copolymers, polystyrene-maleic anhydride copolymers and polyethylene-maleic anhydride copolymers; v) Fillers and / or reinforcing materials are selected from the group consisting of calcium carbonates, silicates, talc, mica, kaolins, metal oxides, metal hydroxides, carbon black, graphite, wood flour, fibers from natural products such as cellulose, glass fibers, carbon fibers, polyaramid fibers and other synthetic fibers Polymer fibers, hydrotalcites, zeolites and / or sheet silicates such as, for example, montmorillonite, bentonite, beidelite, mica, hectorite, saponite, vermiculite, ledikite, magadite, illite, kaolinite, wollastonite, attapulgite. Molding compound or molded part can be produced from a condensation polymer composition according to one of the Claims 9 until 12th , in particular in the form of foils (films), in particular agricultural foils such as mulch, tunnel or perforated foils, tapes, hollow bodies and foams, injection molded parts, fibers, profiles and other extrudates, parts from additive or generative manufacturing processes, such as fused layer modeling ( FLM), Layer Laminate Modeling (LLM), Selective Laser Sintering (SLS) and other 3D printing processes, packaging for food or cosmetic products, encapsulation of active ingredients and biologically active substances, bandages, surgical sutures and / or hygiene products, especially as part of Disposable diapers, pads and tampons. Process for the oxidative, thermal and / or actinic stabilization of a thermoplastic condensation polymer, in particular against oxidative, thermal and / or actinic degradation by adding, adding or incorporating at least one stabilizer selected from the group consisting of inorganic sulfites and thiosulfates to or into the thermoplastic Condensation polymers. Method according to the preceding claim, characterized in that the thermal stabilization takes place during the thermal processing of the condensation polymers, the thermal processing taking place in particular under aprotic conditions. Use of the condensation polymer composition according to any one of Claims 9 until 12th - for the production of packaging, in particular packaging for food or cosmetic products; - In the pharmaceutical industry, in particular for the encapsulation of active ingredients and biologically active substances; - in medical technology, in particular for the production of bandages and surgical sutures; - in hygiene products, in particular as a component of disposable diapers, sanitary towels and tampons; and / or - in agricultural applications, for example for the production of agricultural films such as mulch, tunnel or perforated films.