DE102022206467A1 - Stabilizer composition, use of the stabilizer composition, process for stabilizing condensation polymers against hydrolytic degradation as well as hydrolysis-stabilized composition and shaped body or molded part thereof - Google Patents

Abstract

The present invention relates to a novel stabilizer composition based on an aziridine and at least one oxide, carbonate and/or hydroxide of calcium, magnesium, aluminum or zinc or mixtures of several of the aforementioned compounds, with the exception of hydrotalcites, zeolites and dawsonites. The stabilizer composition is suitable for stabilizing condensation polymers, in particular aliphatic polyesters, against hydrolytic degradation. The invention also relates to the use of the stabilizer composition according to the invention and to a process for stabilizing condensation polymers against hydrolytic degradation. The present invention further relates to moldings and moldings that can be produced from the composition according to the invention.

Description

The present invention relates to a novel stabilizer composition based on an aziridine and at least one oxide, carbonate and/or hydroxide of calcium, magnesium, aluminum or zinc or mixtures of several of the aforementioned compounds, with the exception of hydrotalcites, zeolites and dawsonites. The stabilizer composition is suitable for stabilizing condensation polymers, in particular aliphatic polyesters, against hydrolytic degradation. The invention also relates to the use of the stabilizer composition according to the invention and to a process for stabilizing condensation polymers against hydrolytic degradation. The present invention further relates to moldings and moldings that can be produced from the composition according to the invention.

Polycondensation polymers such as polyesters, polyamides and polycarbonates are generally classified as hydrolysis-sensitive polymers because the chemical bonds of these polymers can be broken by water. This can be advantageous for the degradation of these polymers, for example in the environment, but is also often a disadvantage, particularly in technical applications and when extended service lives are desired. Polymers made from fossil raw materials are increasingly being replaced by polymers made from renewable raw materials. These “bio” polymers are, for example, based on aliphatic polyesters such as polylactic acid, also known as polylactide or PLA. However, aliphatic ester groups are significantly more sensitive to hydrolysis than (partially) aromatic ester groups (see e.g M. Dröscher et al, Applied Macromolecular Chemistry 1984, 128, 203-213 ).

Improving the hydrolysis stability of polycondensation polymers and PLA is a well-known issue. For example, in WO 2012 072 489 Carbodiimides, polycarbodiimides, epoxides, alkyl ketene dimers and oxazolidinones are mentioned as hydrolysis stabilizers. In CN 101 759 969 Hydrolysis-resistant PLA-based compositions are described that contain carbodiimides, epoxy, oxoazolines, oxazines or aziridines. There are also, for example, WO 94/24201 Compositions are known which, in addition to the hydrolysis stabilizer in the form of epoxides, contain other additives such as calcium oxide or calcium silicates. The use of aziridines in polyesters and PLA continues to be used, for example US 3,959,228 , in TW 1472575 or in US 2014/0100318 mentioned. However, certain additives such as fillers can also negatively influence the hydrolysis resistance; for example, it is known that layered silicates such as montmorillonite accelerate the hydrolysis of PLA ( A. Rapacz-Kmita et al. Materials Letters 2015, 146, 73-76, Q. Zhao et al. Polymer Degradation and Stability 2008, 93, 1450-1459 ).

Drilling fluids are also known that can contain aziridines, hydrotalcites and degradable polymers ( WO2015/065575 ).

Polycondensates that contain aziridines are therefore considered to be the next state of the art. For example, the use of aziridines in polyesters and PLA in US 3959228 , in TW 1472575 , in US 2014/0100318 or US 2016/024297 mentioned.

However, there is still a need to increase the hydrolysis stability of polycondensation polymers, in particular of polyesters and especially of aliphatic polyesters such as PLA, in order to expand the possible uses of these polymers.

This object is achieved with regard to a stabilizer composition with the features of patent claim 1. Claim 7 specifies possible uses of the stabilizer composition, while claim 10 relates to a method for stabilizing condensation polymers against hydrolytic degradation. Claim 11 relates to a hydrolysis-stabilized composition, claim 16 relates to a molded part or a shaped body that can be produced from the hydrolysis-stabilized composition.

The dependent patent claims each relate to advantageous developments.

According to a first aspect, the present invention therefore relates to a stabilizer composition consisting of at least one aziridine and at least one oxide, carbonate and/or hydroxide of calcium, magnesium, aluminum or zinc or mixtures of several of the aforementioned compounds. However, the oxides, carbonates and hydroxides mentioned do not include hydrotalcites, zeolites and dawsonites; these are therefore excluded.

It is surprising that polyesters with combinations of aziridines with at least one oxide, carbonate and/or hydroxide of calcium, magnesium, aluminum or zinc or mixtures of several of the aforementioned compounds have particularly good hydrolysis stability. These combinations have not yet been described in the literature.

New hydrolysis-stabilized plastic compositions made from polycondensation polymers such as polyesters or polyamides, as well as new stabilizer compositions to improve hydrolysis stability with high effectiveness, especially in the case of biopolymers such as PLA, are made available.

1. A) Monofunktionellen Aziridinen
   • 1-Aziridincarboxamid, N-octadecyl-;
   • 1-Aziridincarboxamid, N-phenyl-;
   • 1-Aziridincarboxamid, N-cyclohexyl-;
   • 1-Aziridincarboxamid, N-1-naphthalenyl-;
   • 1-Aziridincarboxamid, N-decyl-;
   • N-Benzyloxycarbonylaziridine;
   • (4-Methoxyphenyl)(2-methyl-1-aziridinyl)methanone;
   • N-(4-Cyclohexylphenyl)-1-aziridincarboxamid;
   • 2-[2-(1-Aziridinyl)ethoxy]-4-pyridinpyridincarbonsäure;
   • 6-[2-(1-Aziridinyl)ethoxy]-3-pyridinmethanamine;
   • 6-[2-(1-Aziridinyl)ethoxy]-2-pyridinpyridincarbonsäure;
   • 2-[2-(1-Aziridinyl)ethoxy]pyridin;
   • 2-[2-(1-Aziridinyl)ethoxy]-4-pyridinmethanamine;
   • 2-methyl-aziridine;
   • 2-[1-(1-Aziridinylmethyl)propoxy]-pyridin;
2. B) difunktionellen Aziridinen
   • N,N'-Hexamethylen-1,6-bis(1-aziridincarboxamid);
   • N,N'-(Methylendi-p-phenylen)bis(aziridin-1-carboxamid);
   • N,N'-(Methylenedi-4,1-phenylen)bis[2-methyl-1-aziridincarboxamid];
   • 1-Aziridincarboxamid, N,N'-(3,3'-dimethyl[1,1'-biphenyl]-4,4'-diyl)bis-;
   • 1-Aziridincarboxamid, N,N'-[1,1'-biphenyl]-4,4'-diylbis-;
   • 1-Aziridincarboxamid, N,N'-(methylenedi-4,1-phenylen)bis-;
   • 1-Aziridincarboxamid, N,N'-(4-methyl-1,3-phenylen)bis-;
   • 1-Aziridincarboxamid, N,N'-(1,4-phenylendi-2,1-ethanediyl)bis-;
   • 1-Aziridincarboxamid, N,N'-1,4-phenylenbis-;
   • N,N'-(hexane-1,6-diyl)bis(2-methylaziridine-1-carboxamide);
   • N,N'-1,2-Ethanediylbis[1-aziridincarboxamid];
   • N,N'-1,3-Propandiylbis[1-aziridincarboxamid];
   • N,N'-1,4-Butandiylbis[1-aziridincarboxamid];
   • N,N'-1,5-Pentandiylbis[1-aziridincarboxamid];
   • N,N'-1,6-Hexanediylbis[1-aziridincarboxamid];
   • N,N'-1,7-Heptanediylbis[1-aziridincarboxamid];
   • N,N'-1,8-Octanediylbis[1-aziridincarboxamid];
   • N,N'-1,9-Nonanediylbis[1-aziridincarboxamid];
   • N,N'-1,10-Decanediylbis[1-aziridincarboxamid];
   • 1-Aziridincarboxamid, N,N'-(3-hydroxy-1,5-pentandiyl)bis-
   • 1-Aziridincarboxamid, N,N'-1,5-naphthalenediylbis-;
   • 1-Aziridincarboxamid, N,N'-(3,3'-dimethoxy[1,1'-biphenyl]-4,4'-diyl)bis;pentan
   • 1-Aziridincarboxamid, N,N'-(methyl-1,3-phenylen)bis-;
   • 1-Aziridincarboxamid, N,N'-[1,1'-biphenyl]-4,4'-diylbis-; Poly(oxy-1,4-butanediyl),α-[[[3-[(1-aziridinylcarbonyl)amino]-4-methylphenyl]amino]carbonyl]-ω-[[[[3-[(1-aziridinylcarbonyl)amino]-4-methylphenyl]amino]carbonyl]oxy]-;
   • N,N''-(methylenedi-4,1-phenylen)bis[N'-1-aziridinyl-harnstoff;
3. C) Trifunktionellen Aziridinen
   • Pentaerythritol tris[3-(1-aziridinyl)propionat]; Trimethylolpropan tris[3-(2-methylaziridin-1-yl)propionat]; Trimethylolpropan Tris[3-(aziridin-1-yl)propionat];
   • 1-Aziridinpropionsäure, 2-[[3-(1-aziridinyl)-1-oxopropoxy]methyl]-1,3-propandiylester;
   • 1-Aziridinpropionsäure, α-methyl-, 1,1'-[2-[[3-(1-aziridinyl)-2-methyl-1-oxopropoxy]methyl]-2-ethyl-1,3-propandiyl]ester;
   • 1-Aziridinpropionsäure, 2-[[(1-aziridinylacetyl)oxy]methyl]-2-ethyl-1,3-propandiylester;
   • 1-Aziridinpropionsäure, 2-methyl-, 1,1',1''-(2-ethyl-1,2,3-propantriyl)ester;
   • 1-Aziridincarboxamid, N,N',N"-(methylidynetri-4,1-phenylen)tris;
   • 1-Aziridincarboxamid, N,N'-[[[6-[(1-aziridinylcarbonyl)amino]hexyl]-imino]bis(carbonylimino-6,1-hexanediyl)]bis-;
   • 1-Aziridinpropionsäure, 2-methyl-, 1,1'-[2-ethyl-2-[[3-(2-methyl-1-aziridinyl)-1-oxopropoxy]methyl]-1,3-propandiyl]ester; 1-Aziridinpropionsäure, 1,1'-[2-[[3-(1-aziridinyl)-1-oxopropoxy]methyl]-2-ethyl-1,3-propandiyl]ester;
   • 1-Aziridinpropionsäure, 1,1'-[2-[[3-(1-aziridinyl)-1-oxopropoxy]methyl]-2-(hydroxymethyl)-1,3-propandiyl]ester; Poly(oxy-1,2-ethanediyl), α,α',α''-1,2,3-propantriyltris[ω-[[[[3-[(1-aziridinylcarbonyl)amino]-4-methylphenyl]amino]carbonyl]oxy]-; Aziridine, 1,1',1''-(s-phenenyltricarbonyl)tris[2-methyl-;
4. D) Tetrafunktionellen Aziridinen
   • Pentaerythritol tetrakis(β-aziridino)propionat; 1-Aziridinpropionsäure, 1,1'-[2,2-bis[[3-(1-aziridinyl)-1-oxopropoxy]-methyl]-1,3-propandiyl]ester;
   • 1-Aziridinpropionsäure, 2-methyl-, 1,1'-[2,2-bis[[3-(2-methyl-1-aziridinyl)-1-oxopropoxy] methyl]-1,3-propandiyl]ester;
   • 1-Aziridinethanol, α,α'-[[2,2-bis[2-hydroxy-3-(2-methyl-1-aziridinyl)-propoxy]methyl]-1,3-propandiyl]bis(oxymethylene)]bis[2-methyl-; Ethanon, 2,2',2'',2'''-[[2,2'-bipyridin]-6,6'-diylbis(methylenenitrilo)]-tetrakis[1-(2-methyl-1-aziridinyl)-;
   • 1,5-Pentandion, 2-[bis[2-(2-methyl-1-aziridinyl)-2-oxoethyl]amino]-1,5-bis(2-methyl-1-aziridinyl)-;
   • Ethanon, 2,2',2'',2'''-(1,2-ethanediyldinitrilo)tetrakis[1-(2-methyl-1-aziridinyl)-;
   • Methanon, 1,1',1'',1'''-(1,4,5,8-naphthalenetetrayl)tetrakis[1-(2-methyl-1-aziridinyl)-;
   • 1-Aziridinethanol, α,α'-[[2,2-bis[2-hydroxy-3-(2-methyl-1-aziridinyl)propoxy]methyl]-1,3-propandiyl]bis(oxymethylen)]bis[2-methyl-;
5. E) Multifunktionellen Aziridinen
   • 1-Aziridinpropionsäure, 1,1'-[2-[[3-[3-(1-aziridinyl)-1-oxopropoxy]-2,2-bis[[3-(1-aziridinyl)-1-oxopropoxy]methyl]propoxy]methyl]-2-[[3-(1-aziridinyl)-1-oxopropoxy]methyl]-1,3-propandiyl]ester; 1-Aziridinpropionsäure, 2-methyl-, 1,1'-[2-[[3-[3-(1-aziridinyl)-1-oxopropoxy]-2-(hydroxymethyl)-2-[[3-(2-methyl-1-aziridinyl)-1-oxopropoxy] methyl] propoxy] methyl]-2-[[3-(2-methyl-1-aziridinyl)-1-oxopropoxy]methyl]-1,3-propandiyl]ester;
   • 1-Aziridinpropionsäure, β,2-dimethyl-, benzylhexaylhexamethylenester;
   • 1-Aziridinpropionsäure, 2-ethyl-β-methyl-, benzylhexaylhexakis(methylen)ester;
   sowie Mischungen und Kombinationen aus den zuvor genannten Aziridinen.

According to a preferred embodiment, the at least one aziridine is selected from the group consisting of monofunctional, difunctional, trifunctional, tetrafunctional and/or multifunctional aziridines with, for example, the following structures:

1. A) Monofunctional aziridines
   • 1-aziridinecarboxamide, N-octadecyl-;
   • 1-aziridinecarboxamide, N-phenyl-;
   • 1-aziridinecarboxamide, N-cyclohexyl-;
   • 1-aziridinecarboxamide, N-1-naphthalenyl-;
   • 1-aziridinecarboxamide, N-decyl-;
   • N-Benzyloxycarbonylaziridines;
   • (4-Methoxyphenyl)(2-methyl-1-aziridinyl)methanone;
   • N-(4-Cyclohexylphenyl)-1-aziridinecarboxamide;
   • 2-[2-(1-aziridinyl)ethoxy]-4-pyridinepyridinecarboxylic acid;
   • 6-[2-(1-aziridinyl)ethoxy]-3-pyridinemethanamine;
   • 6-[2-(1-aziridinyl)ethoxy]-2-pyridinepyridinecarboxylic acid;
   • 2-[2-(1-aziridinyl)ethoxy]pyridine;
   • 2-[2-(1-aziridinyl)ethoxy]-4-pyridinemethanamine;
   • 2-methylaziridine;
   • 2-[1-(1-aziridinylmethyl)propoxy]-pyridine;
2. B) difunctional aziridines
   • N,N'-hexamethylene-1,6-bis(1-aziridinecarboxamide);
   • N,N'-(methylenedi-p-phenylene)bis(aziridine-1-carboxamide);
   • N,N'-(Methylenedi-4,1-phenylene)bis[2-methyl-1-aziridinecarboxamide];
   • 1-aziridinecarboxamide, N,N'-(3,3'-dimethyl[1,1'-biphenyl]-4,4'-diyl)bis-;
   • 1-aziridinecarboxamide, N,N'-[1,1'-biphenyl]-4,4'-diylbis-;
   • 1-aziridinecarboxamide, N,N'-(methylenedi-4,1-phenylene)bis-;
   • 1-aziridinecarboxamide, N,N'-(4-methyl-1,3-phenylene)bis-;
   • 1-aziridinecarboxamide, N,N'-(1,4-phenylenedi-2,1-ethanediyl)bis-;
   • 1-aziridinecarboxamide, N,N'-1,4-phenylenebis-;
   • N,N'-(hexane-1,6-diyl)bis(2-methylaziridine-1-carboxamide);
   • N,N'-1,2-Ethanediylbis[1-aziridinecarboxamide];
   • N,N'-1,3-propanediylbis[1-aziridinecarboxamide];
   • N,N'-1,4-butanediylbis[1-aziridinecarboxamide];
   • N,N'-1,5-pentanediylbis[1-aziridinecarboxamide];
   • N,N'-1,6-hexanediylbis[1-aziridinecarboxamide];
   • N,N'-1,7-heptanediylbis[1-aziridinecarboxamide];
   • N,N'-1,8-Octanediylbis[1-aziridinecarboxamide];
   • N,N'-1,9-nonanediylbis[1-aziridinecarboxamide];
   • N,N'-1,10-decanediylbis[1-aziridinecarboxamide];
   • 1-aziridinecarboxamide, N,N'-(3-hydroxy-1,5-pentanediyl)bis-
   • 1-aziridinecarboxamide, N,N'-1,5-naphthalenediylbis-;
   • 1-aziridinecarboxamide, N,N'-(3,3'-dimethoxy[1,1'-biphenyl]-4,4'-diyl)bis;pentane
   • 1-aziridinecarboxamide, N,N'-(methyl-1,3-phenylene)bis-;
   • 1-aziridinecarboxamide, N,N'-[1,1'-biphenyl]-4,4'-diylbis-; Poly(oxy-1,4-butanediyl),α-[[[3-[(1-aziridinylcarbonyl)amino]-4-methylphenyl]amino]carbonyl]-ω-[[[[3-[(1-aziridinylcarbonyl) amino]-4-methylphenyl]amino]carbonyl]oxy]-;
   • N,N''-(methylenedi-4,1-phenylene)bis[N'-1-aziridinylurea;
3. C) Trifunctional aziridines
   • Pentaerythritol tris[3-(1-aziridinyl)propionate]; trimethylolpropane tris[3-(2-methylaziridin-1-yl)propionate]; trimethylolpropane tris[3-(aziridin-1-yl)propionate];
   • 1-aziridinepropionic acid, 2-[[3-(1-aziridinyl)-1-oxopropoxy]methyl]-1,3-propanediyl ester;
   • 1-aziridinepropionic acid, α-methyl, 1,1'-[2-[[3-(1-aziridinyl)-2-methyl-1-oxopropoxy]methyl]-2-ethyl-1,3-propanediyl]ester;
   • 1-aziridinepropionic acid, 2-[[(1-aziridinylacetyl)oxy]methyl]-2-ethyl-1,3-propanediyl ester;
   • 1-aziridinepropionic acid, 2-methyl, 1,1',1''-(2-ethyl-1,2,3-propanetriyl)ester;
   • 1-aziridinecarboxamide, N,N',N"-(methylidynetri-4,1-phenylene)tris;
   • 1-aziridinecarboxamide, N,N'-[[[6-[(1-aziridinylcarbonyl)amino]hexyl]-imino]bis(carbonylimino-6,1-hexanediyl)]bis-;
   • 1-aziridinepropionic acid, 2-methyl, 1,1'-[2-ethyl-2-[[3-(2-methyl-1-aziridinyl)-1-oxopropoxy]methyl]-1,3-propanediyl] ester; 1-aziridinepropionic acid, 1,1'-[2-[[3-(1-aziridinyl)-1-oxopropoxy]methyl]-2-ethyl-1,3-propanediyl]ester;
   • 1-aziridinepropionic acid, 1,1'-[2-[[3-(1-aziridinyl)-1-oxopropoxy]methyl]-2-(hydroxymethyl)-1,3-propanediyl]ester; Poly(oxy-1,2-ethanediyl), α,α',α''-1,2,3-propanetriyltris[ω-[[[[3-[(1-aziridinylcarbonyl)amino]-4-methylphenyl]amino ]carbonyl]oxy]-; Aziridine, 1,1',1''-(s-phenenyltricarbonyl)tris[2-methyl-;
4. D) Tetrafunctional aziridines
   • Pentaerythritol tetrakis(β-aziridino)propionate; 1-aziridinepropionic acid, 1,1'-[2,2-bis[[3-(1-aziridinyl)-1-oxopropoxy]methyl]-1,3-propanediyl]ester;
   • 1-aziridinepropionic acid, 2-methyl, 1,1'-[2,2-bis[[3-(2-methyl-1-aziridinyl)-1-oxopropoxy]methyl]-1,3-propanediyl] ester;
   • 1-aziridineethanol, α,α'-[[2,2-bis[2-hydroxy-3-(2-methyl-1-aziridinyl)-propoxy]methyl]-1,3-propanediyl]bis(oxymethylene)]bis [2-methyl-; Ethanone, 2,2',2'',2'''-[[2,2'-bipyridine]-6,6'-diylbis(methyleneenitrilo)]-tetrakis[1-(2-methyl-1-aziridinyl) -;
   • 1,5-pentanedione, 2-[bis[2-(2-methyl-1-aziridinyl)-2-oxoethyl]amino]-1,5-bis(2-methyl-1-aziridinyl)-;
   • Ethanone, 2,2',2'',2'''-(1,2-ethanediyldinitrilo)tetrakis[1-(2-methyl-1-aziridinyl)-;
   • Methanone, 1,1',1'',1'''-(1,4,5,8-naphthalenetetrayl)tetrakis[1-(2-methyl-1-aziridinyl)-;
   • 1-aziridineethanol, α,α'-[[2,2-bis[2-hydroxy-3-(2-methyl-1-aziridinyl)propoxy]methyl]-1,3-propanediyl]bis(oxymethylene)]bis[ 2-methyl-;
5. E) Multifunctional aziridines
   • 1-aziridinepropionic acid, 1,1'-[2-[[3-[3-(1-aziridinyl)-1-oxopropoxy]-2,2-bis[[3-(1-aziridinyl)-1-oxopropoxy]methyl ]propoxy]methyl]-2-[[3-(1-aziridinyl)-1-oxopropoxy]methyl]-1,3-propanediyl]ester; 1-aziridinepropion acid, 2-methyl-, 1,1'-[2-[[3-[3-(1-aziridinyl)-1-oxopropoxy]-2-(hydroxymethyl)-2-[[3-(2-methyl- 1-aziridinyl)-1-oxopropoxy]methyl]propoxy]methyl]-2-[[3-(2-methyl-1-aziridinyl)-1-oxopropoxy]methyl]-1,3-propanediyl]ester;
   • 1-aziridinepropionic acid, β,2-dimethyl, benzylhexaylhexamethylene ester;
   • 1-aziridinepropionic acid, 2-ethyl-β-methyl, benzylhexaylhexakis(methylene) ester;
   as well as mixtures and combinations of the aforementioned aziridines.

N,N'-(Methylendi-p-phenylen)bis(aziridin-1-carboxamid),

Pentaerythritol tris[3-(1-aziridinyl)propionat]

N,N'-(hexan-1,6-diyl)bis(2-methylaziridine-1-carboxamid)

Trimethylolpropan tris[3-(2-methylaziridin-1-yl)propionat]

Trimethylolpropan tris[3-(aziridin-1-yl)propionat]Particularly suitable aziridines are:

N,N'-(methylenedi-p-phenylene)bis(aziridine-1-carboxamide),

Pentaerythritol tris[3-(1-aziridinyl)propionate]

N,N'-(hexane-1,6-diyl)bis(2-methylaziridine-1-carboxamide)

Trimethylolpropane tris[3-(2-methylaziridin-1-yl)propionate]

Trimethylolpropane tris[3-(aziridin-1-yl)propionate]

Other preferred aziridines are in WO 2020/020714 and in WO 2021/148570 described. The disclosure content of these patent applications regarding the aziridines mentioned is included in the disclosure content of the present invention.

Particularly preferred aziridines are the following compounds:

Some of the aziridines mentioned are commercially available, for example from Menadiona (Barcelona, Spain), Polyaziridine LLC (Palm Beach, USA) or Covestro (Leverkusen, Germany).

According to an advantageous embodiment, the oxide, carbonate and/or hydroxide of calcium, magnesium, aluminum or zinc has a pK _s value of at least 10.

For example and particularly preferably, the oxide, carbonate and/or hydroxide of calcium, magnesium, aluminum or zinc is selected from the group consisting of CaO, CaCO ₃ , Ca(OH) ₂ , MgO, MgCO ₃ , Mg(OH) ₂ , CaMg (CO ₃ ) ₂ (dolomite), Al ₂ O ₃ , Al ₂ (CO ₃ ) ₃ , Al(OH) ₃ , ZnO, ZnCO ₃ , and Zn(OH) ₂ as well as mixtures and combinations thereof.

In the stabilizer composition according to the present invention, it is further advantageous if the weight ratio of the total of the aziridines to the total of the at least one oxide, carbonate or hydroxide of calcium, magnesium, aluminum or zinc is 20:1 to 1:20, preferably from 10 :1 to 1:10, particularly preferably from 5:1 to 1:5, in particular 1:1 to 1:4.

In addition, the present invention relates to the use of a previously described stabilizer composition according to the invention for stabilizing condensation polymers against hydrolytic degradation.

In a further aspect, the present invention relates to a method for stabilizing condensation polymers against hydrolytic degradation, in which a stabilizer composition according to the invention, described above, is mixed into the condensation polymer or blended with it.

Both the use according to the invention and the method according to the invention are advantageously characterized in that the stabilizer composition is in a weight ratio of 0.01 to 10% by weight, preferably from 0.05 to 5% by weight, particularly preferably from 0 .1 to 3% by weight based on the polycondensation polymer is used or mixed in.

1. a) Polyamiden, wie z.B. Polyamid-6, 6.6, 6.9, 6.10, 4.6, 4.10, 6.12, 10.10, 10.12, 12.12, Polyamid 4, Polyamid, 7, Polyamid 8, Polyamid 9, Polyamid 11, Polyamid 12 sowie (teil-)aromatische Polyamide wie z.B. Polyphthalamide, z.B. hergestellt aus Terephthalsäure und/oder Isophthalsäure und aliphatischen Diaminen wie z.B. Hexamethylendiamin oder m-Xylylendiamin oder aus aliphatischen Dicarbonsäuren wie z.B. Adipinsäure oder Sebazinsäure und aromatischen Diaminen wie z.B. 1,4- oder 1,3-Diaminobenzol, bezeichnet z.B. als Polyamid 6T, Polyamid 9T, Polyamid 6I, Polyamid-6-3-T, Blends von unterschiedlichen Polyamiden wie z.B. PA-6 und PA 6.6, PA6T und PA6I, PA-6.6 und PA6T bzw. Blends von Polyamiden und Polyolefinen wie z.B. PA/PP oder PA/PE.
2. b) Polyestern aus aliphatischen oder aromatischen Dicarbonsäuren und Diolen oder aus Hydroxy-Carbonsäuren, insbesondere aliphatischen Polyestern, wie z.B. Polyethylenterephthalat (PET), Polybutylenterephthalat (PBT), Polytrimethylenterephthalat (PTT), , Polyethylennaphthylat (PEN), Poly-1,4-dimethylol-cyclohexanterephthalat, Polyhydroxybenzoat, Polyhydroxynaphthalat, Polymilchsäure (PLA), Polyhydroxybutyrat (PHB), Polyhydroxyvalerat (PHV), Polybutylensuccinat (PBS), Polybutylensuccinatadipat (PBSA), Polyethylensuccinat, Polycaprolacton, Polyethylenfuranoat (PEF)
3. c) Polycarbonaten, Polyestercarbonaten, sowie Blends wie z.B. PC/ABS, PC/PBT, PC/PET/PBT, PC/PA,
4. d) sowie Mischungen, Kombinationen oder Blends aus zwei oder mehr der zuvor genannten Polymeren.

In a preferred embodiment of the use, the process or the composition it is provided that the condensation polymer is selected from the group consisting of

1. a) polyamides, such as polyamide-6, 6.6, 6.9, 6.10, 4.6, 4.10, 6.12, 10.10, 10.12, 12.12, polyamide 4, polyamide 7, polyamide 8, polyamide 9, polyamide 11, polyamide 12 and (partially )aromatic polyamides such as polyphthalamides, for example prepared 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, denotes, for example, polyamide 6T, polyamide 9T, polyamide 6I, polyamide-6-3-T, blends of different polyamides such as PA-6 and PA 6.6, PA6T and PA6I, PA-6.6 and PA6T or blends of polyamides and polyolefins such as e.g. PA/PP or PA/PE.
2. b) Polyesters made from aliphatic or aromatic dicarboxylic acids and diols or from hydroxycarboxylic acids, in particular aliphatic polyesters, such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene naphthylate (PEN), poly-1,4-dimethylol -cyclohexane terephthalate, polyhydroxybenzoate, polyhydroxynaphthalate, polylactic acid (PLA), polyhydroxybutyrate (PHB), polyhydroxyvalerate (PHV), polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), polyethylene succinate, polycaprolactone, polyethylene furanoate (PEF)
3. c) polycarbonates, polyester carbonates, as well as blends such as PC/ABS, PC/PBT, PC/PET/PBT, PC/PA,
4. d) as well as mixtures, combinations or blends of two or more of the aforementioned polymers.

Furthermore, the polymers specified under a) to c) can have both amorphous and (partially) crystalline morphologies.

Particularly preferred polyesters are aliphatic polyesters, i.e. H. Polyesters that can be produced from aliphatic dicarboxylic acids and aliphatic diols or from aliphatic lactones.

Suitable diols for aliphatic polyesters are, for example, ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 2,5-hexanediol, 3-methyl -2,4pentanediol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, -1, 6,2-Ethylhexanediol-1,3, 2,2-Diethylpropanediol-1,3, 2,2-Bis-(4-hydroxycyclohexyl)-propane, 2,2-Bis-(4-hydroxypropoxyphenyl)-propane, 1, 4-Cyclohexanediol, 1,3-Cyclohexanediol, 1,4-Cyclohexanedimethanol, 1,3-Cyclohexanedimethanol.

Suitable dicarboxylic acids for aliphatic polyesters are, for example, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, hexadecanedioic acid, cyclohexane-1,3-dicarboxylic acid or cyclohexane-1,4-dicarboxylic acid.

In addition to aliphatic structures, aromatic structures can also be present to a minor extent up to 20 mol%, preferably less than 10 mol%, very particularly preferably less than 1 mol%. Suitable aro matic structures for diols are hydroquinone, resorcinol, 2,6-naphthalenediol, 1,8-naphthalenediol, bisphenol-A, for dicarboxylic acids terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, an example of a heterocyclic aromatic dicarboxylic acid is 2,5- Furandicarboxylic acid.

Suitable hydroxycarboxylic acids are, for example, lactic acid, glycolic acid, 4-hydroxybutyric acid, 3-hydroxybutyric acid or 3-hydroxyvaleric acid; a hydroxycarboxylic acid with aromatic components is mandelic acid.

Further preferred polyesters are, in particular, polybutylene terephthalate (PBT) and copolymers of 1,4-butanediol with terephthalic acid, adipic acid or sebacic acid, as well as polyethylene furanoate (PEF), obtainable from ethylene glycol and 1,4-furandicarboxylic acid.

Preferred polyamides are in particular polyamide-6, polyamide-6.6, blends of polyamide 6 with polyamide 6.6, polyamide-10.10, polyamide-10.12, polyamide-12.12, polyamide-11 and polyamide-12.

Particularly preferably, the at least one condensation polymer is selected from the group consisting of aliphatic polyesters, in particular polylactic acid (PLA), polybutylene succinate (PBS), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene furanoate (PEF), polyamide-6 or polyamide-6.6.

In addition, the present invention relates to a hydrolysis-stabilized composition containing or consisting of at least one condensation polymer and a stabilizer composition according to the invention described above. The preferred embodiments described above for the stabilizer composition and their use also apply without restriction to the hydrolysis-stabilized composition.

The hydrolysis stability is particularly evident in the small increase in the melt volume flow rate (MVR) of the hydrolysis-stabilized composition when it is exposed to hydrolyzing conditions, which indicates a reduction in the molecular weight of the polymers used and thus a degradation caused by hydrolysis. For example, the hydrolysis-stabilized composition is characterized by a melt volume flow rate (MVR), determined according to DIN EN ISO 1133-1:2012 after storage of an extruded polymer granulate with a granule diameter between 1 and 3 mm (for example 2 mm) in deionized water for a period of time of 336 hours at a temperature of 60 ° C (aliphatic polyesters) or 936 hours at a temperature of 85 ° C ((partially) aromatic polyesters), which is increased by a maximum of 100%, preferably a maximum of 90%, compared to that Melt Volume Flow Rate (MVR) of the same sample before storage.

In addition, the compositions may contain further additives selected from the group consisting of primary antioxidants, secondary antioxidants, UV absorbers, light stabilizers, metal deactivators, filler deactivators, antiozonants, nucleating agents, antinucleating agents, impact modifiers, plasticizers, lubricants, rheology modifiers, thixotropic agents, Chain extenders, processing aids, mold release aids, flame retardants, pigments, dyes, optical brighteners, antimicrobial active ingredients, antistatic agents, slip agents, antiblocking agents, coupling agents, crosslinking agents, anticrosslinking agents, hydrophilizing agents, hydrophobicizing agents, hydrolysis stabilizers, adhesion promoters, dispersants, compatibilizers, oxygen scavengers, acid scavengers, blowing agents, degradants. Additives, defoaming aids, odor traps, marking agents, antifogging agents, fillers and reinforcing agents.

In a preferred embodiment, the compositions contain in particular phenolic antioxidants, phosphites or phosphonites, fillers or reinforcing fibers such as glass fibers.

• 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-(αmethylcyclohexyl)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,α-dimethylbenzyl)-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)dicyclo-pentadien, 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-butyl-benzyl-mercaptoacetat, 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-tert-butyl-4-hydroxybenzylphosphonat, Dioctadecyl-3,5-di-i-eri--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)propionyloxy}-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-hydroxy-phenyl]propionyloxy)ethyl]oxamid (Naugard^®XL-1, vertrieben durch Uniroyal);

Examples of suitable phenolic antioxidants are:

• Alkylated monophenols such as 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 2,6-di-tert-butyl-4-methyoxyphenol, 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 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-methylphenol 6-(αmethylcyclohexyl)phenol], 2,2'-methylenebis(4-methyl-6-cyclhexylphenol), 2,2'-methylenebis(6-nonyl-4-methylphenol), 2,2'-methylenebis(4,6 -di-tert-butylphenol), 2,2'-ethylidenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis [6-(α-methylbenzyl)-4-nonylphenol], 2,2'-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol], 4,4'-methylenebis(2,6-di-tert -butylphenol, 4,4'-methylenebis(6-tert-butyl-2-methylphenol), 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3 -tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-bis(5- tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane, 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-dodecylmercaptobutane, 1,1,5,5-tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)-pentane;
• O-, N- and S-benzyl compounds, such as 3,5,3',5'-tetra-tert-butyl-4,4'dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzyl mercaptoacetate, tridecyl 4-hydroxy-3,5-di-tert-butyl-benzyl-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-hydrophenylpropionyl)hexahydro-1,3,5-triazine, 1 ,3,5-Tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate;
• Benzylphosphonates, such as dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, dietyhl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di-i-eri--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 mono- or polyhydric alcohols, e.g. methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1, 9-Nonanediol, Ethylene Glycol, 1,2-Propanediol, Neopentyl Glycol, Thiodiethylene Glycol, Diethylene Glycol, Triethylene Glycol, Pentaerythritol, Tris(hydroxyethyl)isocyanurate, N,N'-Bis(hydroxyethyl)oxamide, 3-Thiaundecanol, 3-Thiapentadecanol, Trimethylhexanediol, Trimethylolpropane , 4-Hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane;
• Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or polyhydric alcohols, e.g. methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1, 9-Nonanediol, Ethylene Glycol, 1,2-Propanediol, Neopentyl Glycol, Thiodiethylene Glycol, Diethylene Glycol, Triethylene Glycol, Pentaerythritol, Tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-Thiaundecanol, 3-Thiapentadecanol, Trimethylhexanediol, Trimethylolpropane , 4-Hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane, 3,9-Bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy }-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane;
• Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, e.g. methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2- Propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris-(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha- 2,6,7-trioxabicyclo[2.2.2]octane;
• Esters of (3,5-di-tert-butyl-4-hydroxyphenyl)acetic acid with mono- or polyhydric alcohols, e.g. methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1, 2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha -2,6,7-trioxabicyclo[2.2.2]octane;
• Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, such as N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N' -Bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamide, N,N'-Bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N'-Bis(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, distributed by Uniroyal);

Ascorbic acid (vitamin C).

wobei in den zuvor genannten Verbindungen n eine ganze Zahl ist und bei zwischen 2 und 10 liegt.Particularly preferred phenolic antioxidants are the following structures:

where in the aforementioned compounds n is an integer and is between 2 and 10.

Further preferred phenolic antioxidants are phenolic antioxidants based on renewable raw materials such as: B. α-, β-, γ-, δ-tocopherol and mixtures of these (vitamin E), tocotrienols, tocomonoenols, ubiquinol, hydroxytyrosol, flavonoids and flavonols such as chrysin, quercitin, hesperidin, neohesperidin, naringin, morin, kaempferol, Fisetin, datiscetin, luteolin, apigenin, taxifolin, isoflavones such as genistein, genistin, daidzein, daidzin, formononetin, anthocyanins such as delphinidin and malvidin, curcumin, carnosic acid, carnosol, rosmarinic acid, tannin and resveratrol as well as carotenoids with alcoholic groups such as beta -Cryptoxanthin, lutein, zeaxanthin or astaxanthin.

• 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.

Examples of suitable amine antioxidants are:

• N,N'-Di-isopropyl-p-phenylenediamine, N,N'-Di-sec-butyl-p-phenylenediamine, N,N'-Bis(1,4-dimethylpentyl)-p-phenylenediamine, N,N' -Bis(1-ethyl-3-methylpentyl)-p-phenylenediamine, N,N'-bis(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, e.g. p,p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylamino-phenol, bis(4-methoxyphenyl)amine , 2,6-Di-tert-butyl-4-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)pro pan, (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-ene 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

Particularly preferred aminic antioxidants are the structures:

Preferred hydroxylamines or N-oxides (nitrones) are, for example, N,N-dialkylhydroxylamines, N,N-dibenzylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-distearylhydroxylamine, N-benzyl-α-phenylnitrone, N-octadecyl-α- hexadecylnitron, as well as Genox EP (SI Group) 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)benzofu ran-2-one, 3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one, 3-(3,5-dimethyl-4-pivaloyloxyphenyl)- 5,7-di-tert-butyl-benzofuran-2-one, 3-(3,4-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one, 3-(2,3-di - methylphenyl)-5,7-di-tert-butyl-benzofuran-2-one, as well as lactones that additionally contain phosphite groups such as

Preferred fillers are calcium carbonate, silicates, talc, mica, kaolin, metal oxides and metal hydroxides, soot, graphite, wood flour or fibers from natural products such as cellulose. Other suitable fillers are hydrotalcites or zeolites or layered silicates such as montmorillonite, bentonite, beidelite, mica, hectorite, saponite, vermiculite, ledikite, magadite, illite, kaolinite, wollastonite, attapulgite.

Suitable secondary antioxidants are in particular phosphites or phosphonites such as e.g.

Triphenyl phosphite, diphenyl alkyl phosphites, phenyldialkyl phosphites, tri(nonylphenyl) phosphite, trilauryl phosphites, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris-(2,4-di-tert-butylphenyl) phosphite, diisodecylpentaerythritol diphosphite, bis(2,4-di-tert- butylphenyl)pentaerythritol diphosphite, Bis (2,4-di-cumylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite, bis (2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylenediphosphonite, 6-isooctyloxy-2,4,8,10-tetra -tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin, bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite, bis(2,4-di-tert- butyl-6-methylphenyl)ethyl phosphite, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin, 2,2'2 ''-Nitrilo[triethyltris(3,3'',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl)phosphite], 2-ethylhexyl(3,3', 5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl))phosphite, 5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy )-1,3,2-dioxaphosphiran.

mit n= 3-100Particularly preferred phosphites are:

with n= 3-100

A preferred phosphonite is:

Suitable secondary antioxidants are also organosulfur compounds such as sulfides and disulfides, for example distearylthiodipropionate, dilaurylthiodipropionate, ditridecyldithiopropionate, ditetradecylthiodipropionate, 3-(dodecylthio)-, 1,1'-[2,2-bis[[3-(dodecylthio)-1- oxopropoxy]methyl]-1,3-propanediyl]propanoic acid ester. The following structures are preferred:

Suitable acid scavengers (“antiacids”) are salts of monovalent, bivalent, trivalent or tetravalent metals, preferably alkali, alkaline earth metals, aluminum or zinc, in particular formed with fatty acids, such as calcium stearate, magnesium stearate, zinc stearate, aluminum stearate, calcium laurate, calcium behenate, calcium lactate, Calcium stearoyl-2-lactate. Other classes of suitable acid scavengers are hydrotalcites, in particular synthetic hydrotalcites based on aluminum, magnesium and zinc, hydrocalumites, zeolites, alkaline earth metal oxides, in particular calcium oxide and magnesium oxide as well as zinc oxide, alkaline earth metal carbonates, in particular calcium carbonate, magnesium carbonate and dolomite, and hydroxides, in particular brucite (magnesium hydroxide),

Suitable co-stabilizers are also polyols, in particular alditols or cyclitols. Polyols are, for example, pentaerythritol, dipentaerythritol, tripentaerythritol, short-chain polyether polyols or polyester polyols, as well as hyperbranched polymers/oligomers or dendrimers with alcohol groups, for example

Preferably, the at least one alditol is selected from the group consisting of threitol, erythritol, galactitol, mannitol, ribitol, sorbitol, xylitol, arabitol, isomalt, lactitol, maltitol, altritol, iditol, maltotritol and hydrogenated oligo- and polysaccharides with polyol end groups and Mixtures thereof. Particularly preferably, the at least one preferred alditol is selected from the group consisting of erythritol, mannitol, isomalt, maltitol and mixtures thereof.

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

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

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

Suitable 2-(2'-hydroxyphenyl)benzotriazoles are, for example, 2-(2'-hydroxy-5'methylphenyl)benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2 -(5'-tert-butyl-2'-hydroxy-phenyl)benzotriazole, 2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3', 5'-Di-tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl-5-chlorobenzotriazole, 2-(3'-sec -Butyl-5'-tert-butyl-2'-hydroxy-phenyl)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-methoxycarbonyl-ethyl)phenyl)-5-chlorobenzotriazole,2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbony- lethyl)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)-phenyl-benzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-ylphenol]; the transesterification product 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'-(α,α-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'-dimethyoxy derivatives of 2-hydroxybenzophenones. Suitable acrylates are, for example, ethyl-α-cyano-β,β-diphenyl acrylate, isooctyl-α-cyano-β,β-diphenyl acrylate, methyl-α-carbomethoxycinnamate, methyl-α-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, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl- 4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert- butylphenyl-3,5-di-i-eri--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- hydroxy-phenyl-propionyl)hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyldihydrazide, oxanilide, isophthaloyldihydrazide, sebacoylbisphenyl hydrazide, N,N'-diacetyladipoyl dihydrazide, N,N'-bis(salicyloyl)oxylyl dihydrazide, N,N'-bis(salicyloyl)thiopropionyl dihydrazide. Particularly preferred metal deactivators are:

Examples of suitable low molecular weight hindered amines are:

1,1-Bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, Bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebazate, Bis(1-octyloxy-2, 2,6,6-tetramethyl-4-piperidyl) sebazate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-n-butyl-3,5-di-tert-butyl-4-hydroxybenzyl malonate , 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-di-chloro-1,3,5-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate, tetrakis(2, 2,6,6-tetra-methyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate, 1,1'-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone) , 4-benzoyl-2,2,6,6-tetramethylpiperidine or 4-stearyloxy-2,2,6,6-tetramethylpiperidine.

Included in the above structures are the sterically hindered NH, N-alkyl such as N-methyl or N-octyl, the N-alkoxy derivatives such as N-methoxy or N-octyloxy, the cycloalkyl derivatives such as N-cyclohexyloxy and the N-(2-hydroxy-2-methylpropoxy) analogues. Preferred low molecular weight hindered amines also have the following structures:

Preferred oligomeric or polymeric hindered amines are:

For the previously mentioned compounds, n means 3 to 100.

wobei R -O-C(O)-C₁₅H₃₁ oder-O-C(O)-C₁₇H₃₅ bedeutet.Another suitable light stabilizer is Hostanox NOW (manufacturer: Clariant SE) with the following general structure:

where R means -OC(O)-C ₁₅ H ₃₁ or -OC(O)-C ₁₇ H ₃₅ .

Included in the above structures are the sterically hindered N-H, N-alkyl such as N-methyl or N-octyl, the N-alkoxy derivatives such as N-methoxy or N-octyloxy, the cycloalkyl derivatives such as N-cyclohexyloxy and the N-(2-hydroxy-2-methylpropoxy) analogues.

• 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.

Examples of suitable dispersants are:

• 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 esters, 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 rid polysiloxanes: e.g. dimethylsilanediol-ethylene oxide copolymer, polyphenylsiloxane copolymer, amphiphilic copolymers: e.g. polyethylene-block-polyethylene oxide, dendrimers, e.g. dendrimers containing hydroxyl groups.

Suitable antinucleating agents are azine dyes such as nigrosine.

1. a) Anorganische Flammschutzmittel wie z.B. Al(OH)₃, Mg(OH)₂, AlO(OH), MgCO₃, Schichtsilikate wie z.B. Montmorillonit oder Sepiolit, nicht oder organisch modifiziert, Doppelsalze, wie z.B. Mg-Al-Silikate, POSS-(Polyhedral Oligomeric Silsesquioxane) Verbindungen, Huntit, Hydromagnesit oder Halloysit sowie Sb₂O₃, Sb₂O₅, MoO₃, Zinkstannat, Zinkhydroxystannat,
2. b) Stickstoffhaltige Flammschutzmittel wie z.B. Melamin, Melem, Melam, Melon, Melaminderivate, Melaminkondensationsprodukte oder Melaminsalze, Benzoguanamin, Polyisocyanurate, Allantoin, Phosphacene, insbesondere Melamincyanurat, Melaminphosphat, Dimelaminphosphat, Melaminpyrophosphat, Melaminpolyphosphat, Melamin-Metall-Phosphate wie z.B. Melaminaluminiumphosphat, Melaminzinkphosphat, Melaminmagnesiumphosphat, sowie die entsprechenden Pyrophosphate und Polyphosphate, Poly-[2,4-(piperazin-1,4-yl)-6-(morpholin-4-yl)-1,3,5-triazin], Ammonium-polyphosphat, Melaminborat, Melaminhydrobromid,
3. c) Radikalbildner, wie z.B. Alkoxyamine, Hydroxylaminester, Azoverbindungen, Sulfenamide, Sulfenimide, Dicumyl oder Polycumyl, Hydroxyimide und deren Derivate wie z.B. Hydroxyimidester oder Hydroxyimidether
4. d) Phosphorhaltige Flammschutzmitteln wie z.B. roter Phosphor, Phosphate wie z.B. Resorcindiphosphat, Bisphenol-A-diphosphat und ihre Oligomere, Triphenylphosphat, Ethylendiamindiphosphat, Phosphinate wie z.B. Salze der hypophosphorigen Säure und Ihrer Derivate wie Alkylphosphinatsalzen z.B. Diethylphosphinataluminium oder Diethylphosphinat-Zink oder Aluminiumphosphinat, Aluminiumphosphit, Aluminiumphosphonat, Phosphonatester, oligomere und polymere Derivate der Methanphosphonsäure, 9,10-Dihydro-9-oxa-10-phosphorylphenanthren-10-oxid (DOPO) und deren substituierte Verbindungen,
5. e) Halogenhaltige Flammschutzmittel auf Chlor- und Brombasis wie z.B. polybrominierte Diphenyloxide, wie z.B. Decabromdiphenyloxid,Tris(3-bromo-2,2-bis(bromomethyl)propyl-phosphat, Tris(tribromneopentyl)phosphat, Tetrabromphthalsäure, 1,2-Bis(tribromphenoxy)ethan, Hexabromcyclododecan, bromiertes Diphenylethan, Tris-(2,3-dibrompropyl)isocyanurat, Ethylen-bis(tetrabromophthalimid), Tetrabromo-bisphenol A, bromiertes Polystyrol, bromiertes Polybutadien bzw, Polystyrol-bromiertes Polybutadien-Copolymere, bromierter Polyphenylenther, bromiertes Epoxidharz, Polypentabrombenzylacrylat, ggf. in Kombination mit Sb₂O₃ und/oder Sb₂O₅,
6. f) Borate wie z.B. Zinkborat oder Calciumborat, ggf. auf Trägermaterial wie z.B. Silica
7. g) Schwefelhaltige Verbindungen wie z.B. elementarer Schwefel, Disulfide und Polysulfide, Thiuramsulfid, Dithiocarbamate, Mercaptobenzthiazol und Sulfenamide,
8. h) Antidrip-Mitteln wie z.B. Polytetrafluorethylen,
9. i) Siliciumhaltige Verbindungen wie z.B. Polyphenylsiloxane,
10. j) Kohlenstoffmodifikationen wie z.B. Carbon-Nanoröhren (CNT), Blähgraphit oder Graphen
11. k) sowie Kombinationen oder Mischungen hieraus.

Suitable flame retardants are in particular

1. a) Inorganic flame retardants such as Al(OH) ₃ , Mg(OH) ₂ , AlO(OH), MgCO ₃ , layered silicates such as montmorillonite or sepiolite, not or organically modified, double salts such as Mg-Al silicates, POSS- (Polyhedral Oligomeric Silsesquioxane) compounds, huntite, hydromagnesite or halloysite as well as Sb ₂ O ₃ , Sb ₂ O ₅ , MoO ₃ , zinc stannate, zinc hydroxystannate,
2. b) Nitrogen-containing flame retardants such as melamine, melem, melam, melon, melamine derivatives, melamine condensation products or melamine salts, benzoguanamine, polyisocyanurates, allantoin, phosphacenes, in particular melamine cyanurate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, melamine polyphosphate, melamine-metal phosphates such as melamine aluminum phosphate, melamine zinc phosphate, Melamine magnesium phosphate, as well as the corresponding pyrophosphates and polyphosphates, poly-[2,4-(piperazin-1,4-yl)-6-(morpholin-4-yl)-1,3,5-triazine], ammonium polyphosphate, melamine borate , melamine hydrobromide,
3. c) Radical formers, such as alkoxyamines, hydroxylamine esters, azo compounds, sulfenamides, sulfenimides, dicumyl or polycumyl, hydroxyimides and their derivatives such as hydroxyimide esters or hydroxyimide ethers
4. d) Phosphorus-containing flame retardants such as red phosphorus, phosphates such as resorcinol diphosphate, bisphenol A diphosphate and their oligomers, triphenyl phosphate, ethylenediamine diphosphate, phosphinates such as salts of hypophosphorous acid and its derivatives such as alkylphosphinate salts such as diethylphosphinataluminum or diethylphosphinate-zinc or aluminum phosphinate, aluminum phosphite, Aluminum phosphonate, phosphonate esters, oligomeric and polymeric derivatives of methanephosphonic acid, 9,10-dihydro-9-oxa-10-phosphorylphenanthrene-10-oxide (DOPO) and their substituted compounds,
5. e) Halogen-containing flame retardants based on chlorine and bromine such as polybrominated diphenyl oxides, such as decabromodiphenyl oxide, tris(3-bromo-2,2-bis(bromomethyl)propyl phosphate, tris(tribromoneopentyl) phosphate, tetrabromophthalic acid, 1,2-bis( tribromphenoxy)ethane, hexabromocyclododecane, brominated diphenylethane, tris-(2,3-dibromopropyl)isocyanurate, ethylene bis(tetrabromophthalimide), tetrabromo-bisphenol A, brominated polystyrene, brominated polybutadiene or, polystyrene-brominated polybutadiene copolymers, brominated polyphenylene ether, brominated Epoxy resin, polypentabromobenzyl acrylate, possibly in combination with Sb ₂ O ₃ and/or Sb ₂ O ₅ ,
6. f) Borates such as zinc borate or calcium borate, possibly on a carrier material such as silica
7. g) Sulfur-containing compounds such as elemental sulfur, disulfides and polysulfides, thiuram sulfide, dithiocarbamates, mercaptobenzothiazole and sulfenamides,
8. h) anti-drip agents such as polytetrafluoroethylene,
9. i) silicon-containing compounds such as polyphenylsiloxanes,
10. j) Carbon modifications such as carbon nanotubes (CNT), expanded graphite or graphene
11. k) as well as combinations or mixtures thereof.

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

Suitable lubricants and processing aids are, for example, polyethylene waxes, polypropylene waxes, salts of fatty acids such as calcium stearate, zinc stearate or salts of montan waxes, amide waxes such as erucic acid amide or oleic acid amides, fluoropolymers, silicones or neoalkoxytitanates and zirconates.

Suitable pigments can be inorganic or organic in nature. Examples of inorganic pigments are titanium dioxide, zinc oxide, zinc sulfide, iron oxide, ultramarine, carbon black, and organic pigments are for example anthraquinones, anthanthrones, benzimidazolones, quinacridones, diketopyrrolopyrroles, dioxazines, indanthrones, isoindolinones, azo compounds, perylenes, phthalocyanines or pyranthrones. Other suitable pigments are metal-based effect pigments or metal oxide-based pearlescent pigments.

Suitable optical brighteners are, for example, bisbenzoxazoles, phenylcoumarins or bis(styryl)biphenyls and in particular optical brighteners with 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 include, for example, ethoxylated alkyl amines, fatty acid esters, alkyl sulfonates and polymers such as polyetheramides.

Suitable antiozonants are the above-mentioned amines such as 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 nucleating agents are talc, alkali or alkaline earth metal salts of mono- and polyfunctional carboxylic acids such as. B. benzoic acid, succinic acid, adipic acid, e.g. sodium benzoate, zinc glycerolate, aluminum hydroxy-bis (4-tert-butyl) benzoate, 2,2'-methylene-bis- (4,6-di-tert-butylphenyl) phosphate, as well as trisamides and Diamides such as trimesic acid tricyclohexylamide, trimesic acid tri(4-methylcyclohexylamide), trimesic acid tri(tert-butylamide), N,N',N''-1,3,5-benzenetriyltris(2,2-dimethyl-propanamide) or 2,6- Naphthalene dicarboxylic acid dicyclohexylamide.

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

Suitable additives for increasing electrical conductivity are, for example, the antistatic agents mentioned, soot and carbon compounds such as carbon nanotubes and graphene, metal powders such as copper powder and conductive polymers such as polypyrroles, polyanilines and polythiophenes. Suitable additives for increasing thermal conductivity are, for example, aluminum nitrides and boron nitrides.

Suitable infrared-active additives are, for example, aluminum silicates, hydrotalcites or dyes such as phthalocyanines or anthraquinones.

Suitable mold release aids include, for example, silicones, soaps and waxes such as montan waxes.

The additive composition described above and, if applicable, the additional additives are incorporated into the plastic using conventional processing methods, the polymer being melted and mixed with the additive composition according to the invention and any additional additives, preferably by mixers, kneaders or extruders. Extruders such as single-screw extruders, twin-screw extruders, planetary roller extruders, ring extruders, co-kneaders, which are preferably equipped with vacuum degassing, are preferred as processing machines. 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.

Furthermore, the present invention relates to a molded part or a molded body that can be produced from a hydrolysis-stabilized composition according to the present invention. In particular, the molded part or the molded body is selected from the group consisting of foils, films, foams, fibers, cables and pipes, profiles, hollow bodies, tapes, membranes, such as geomembranes, or adhesives, which are produced via extrusion, injection molding, blow molding, calendering , pressing processes, spinning processes, rotomoulding are produced for example for the electrical and electronics industry, construction industry, transport industry (cars, planes, ships, trains), for medical applications, for household and electrical appliances, vehicle parts, consumer goods, packaging, furniture, textiles.

The present invention is explained in more detail using the following examples, without the examples being understood as limiting the subject matter of the present invention.

Examples:

To test the effect of the stabilizer composition according to the invention, a polylactide (PLA) (Luminy L130, supplier: Total Corbion) was used together with the additives listed in Table 1 at 200 ° C max. in a twin-screw extruder (Process 11, manufacturer ThermoScientific ) compounded at a throughput of 800 g/h. Polymer and additives were dried overnight in a vacuum dryer before processing. After compounding, the compounds were aged in deionized water at 60 °C in an oven for 14 days (336 hours). After aging, the samples were dried overnight and the MVR was determined (190 °C / 2.16 kg). The results are shown in Table 1. Table 1: Hydrolysis stability of PLA additions MVR after compounding [cm ³ /10 min] MVR change after water storage (14 days) [%] Comparative example 1 Without addition 9.26 + 10,000 Comparative example 2 Aziridine (2.0%) 10.88 + 140 Comparative example 3 CaO (2.0%) 18.49 + 192 Comparative example 4 CaCO3 (2.0%) 7.77 + 518 Comparative example 5 MgO (2.0%) 7.03 + 429 Comparative example 6 MgCO3 (2.0%) 6.24 + 450 Inventive example 1 Aziridine (0.5%) + CaO (1.5%) 9.77 +64 Example 2 according to the invention Aziridine (0.5%) + CaCO3 (1.5%) 7.78 +48 Inventive example 3 Aziridine (0.5%) + MgO (1.5%) 8.54 +79 Inventive example 4 Aziridine (0.5%) + MgCO3 (1.5%) 7.65 + 86 Inventive example 5 Aziridine (0.5%) + CaMg (CO3)2 (1.5%) 9.88 +40

To test the effect of the stabilizer composition according to the invention, a polybutylene terephthalate (PBT) (Pocan B1204, supplier: Lanxess AG) was used together with the additives listed in Table 2 at 250 ° C max. in a twin-screw extruder (Process 11, manufacturer ThermoScientific ) compounded at a throughput of 800 g/h. Polymer and additives were dried overnight in a vacuum dryer before processing. After compounding, the compounds were aged in deionized water at 85 °C in an oven for 39 days (936 hours). After aging, the samples were dried overnight and the MVR was determined (250 °C / 2.16 kg). The results are shown in Table 2. Table 2: Hydrolysis stability of PBT additions MVR after compounding [cm ³ /10 min] MVR change after water storage (39 days) [%] Comparative example 1 Without addition 53.65 +313 Comparative example 2 Aziridine (2.0%) 13.22 + 196 Comparative example 3 CaCO3 (2.0%) 45.58 + 301 Inventive example 1 Aziridine (0.5%) + CaO (1.5%) 30.05 +48 Example 2 according to the invention Aziridine (0.25%) + CaCO3 (0.75%) 36.67 + 131 Inventive example 3 Aziridine (0.5%) + CaCO3 (1.5%) 33.64 +40

The examples according to the invention show a much higher hydrolysis stability than the comparative examples, which is evidenced by a smaller increase in the MVR value after storage in water.

The MVR is a measure of the flowability of the melt and therefore also of the molecular weight of the polymer. The lower the molecular weight, the higher the MVR and thus also the degradation of the polymer through hydrolysis. The smaller the increase in MVR, the higher the hydrolysis stability. The combinations according to the invention therefore show excellent hydrolysis stability.

QUOTES INCLUDED IN THE DESCRIPTION

This list of 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.

Cited patent literature

• WO 2012072489 [0003]
• CN 101759969 [0003]
• WO 9424201 [0003]
• US 3959228 [0003, 0005]
• TW 1472575 [0003, 0005]
• US 20140100318 [0003, 0005]
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• WO 2020/020714 [0014]
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Non-patent literature cited

• M. Dröscher et al, Applied Macromolecular Chemistry 1984, 128, 203-213 [0002]
• A. Rapacz-Kmita et al. Materials Letters 2015, 146, 73-76, Q. Zhao et al. Polymer Degradation and Stability 2008, 93, 1450-1459 [0003]

Claims (16)

Stabilizer composition consisting of at least one aziridine and at least one oxide, carbonate and/or hydroxide of calcium, magnesium, aluminum or zinc or mixtures of several of the aforementioned compounds, where hydrotalcites, zeolites and dawsonites are excluded from the oxides, carbonates and hydroxides mentioned. Stabilizer composition according to Claim 1 , characterized in that the at least one aziridine is selected from the group consisting of monofunctional, difunctional, trifunctional, tetrafunctional and / or multifunctional aziridines with, for example, the following structures: A) monofunctional aziridines 1-aziridinecarboxamide, N-octadecyl; 1-aziridinecarboxamide, N-phenyl-; 1-aziridinecarboxamide, N-cyclohexyl-; 1-aziridinecarboxamide, N-1-naphthalenyl-; 1-aziridinecarboxamide, N-decyl-; N-Benzyloxycarbonylaziridines; (4-Methoxyphenyl)(2-methyl-1-aziridinyl)methanone; N-(4-Cyclohexylphenyl)-1-aziridinecarboxamide; 2-[2-(1-aziridinyl)ethoxy]-4-pyridinecarboxylic acid; 6-[2-(1-aziridinyl)ethoxy]-3-pyridinemethanamine; 6-[2-(1-aziridinyl)ethoxy]-2-pyridinecarboxylic acid; 2-[2-(1-aziridinyl)ethoxy]pyridine; 2-methylaziridine; 2-[1-(1-aziridinylmethyl)propoxy]-pyridine; 2-[2-(1-aziridinyl)ethoxy]-4-pyridinemethanamine; B) difunctional aziridines N,N'-hexamethylene-1,6-bis(1-aziridinecarboxamide);N,N'-(methylenedi-p-phenylene)bis(aziridine-1-carboxamide);N,N'-(Methylenedi-4,1-phenylene)bis[2-methyl-1-aziridinecarboxamide]; 1-aziridinecarboxamide, N,N'-(3,3'-dimethyl[1,1'-biphenyl]-4,4'-diyl)bis-; 1-aziridinecarboxamide, N,N'-[1,1'-biphenyl]-4,4'-diylbis-; 1-aziridinecarboxamide, N,N'-(methylenedi-4,1-phenylene)bis-; 1-aziridinecarboxamide, N,N'-(4-methyl-1,3-phenylene)bis-; 1-aziridinecarboxamide, N,N'-(1,4-phenylenedi-2,1-ethanediyl)bis-; 1-aziridinecarboxamide, N,N'-1,4-phenylenebis-;N,N'-(hexane-1,6-diyl)bis(2-methylaziridine-1-carboxamide);N,N'-1,2-ethanediylbis[1-aziridinecarboxamide];N,N'-1,3-propanediylbis[1-aziridinecarboxamide];N,N'-1,4-butanediylbis[1-aziridinecarboxamide];N,N'-1,5-pentanediylbis[1-aziridinecarboxamide];N,N'-1,6-hexanediylbis[1-aziridinecarboxamide];N,N'-1,7-heptanediylbis[1-aziridinecarboxamide];N,N'-1,8-Octanediylbis[1-ziridinecarboxamide];N,N'-1,9-nonandiylbis[1-aziridinecarboxamide];N,N'-1,10-decanediylbis[1-aziridinecarboxamide]; 1-aziridinecarboxamide, N,N'-(3-hydroxy-1,5-pentanediyl)bis-1-aziridinecarboxamide, N,N'-1,5-naphthalenediylbis-; 1-aziridinecarboxamide, N,N'-(3,3'-dimethoxy[1,1'-biphenyl]-4,4'-diyl)bis: 1-aziridinecarboxamide, N,N'-(methyl-1,3- phenylene)bis-; 1-aziridinecarboxamide, N,N'-[1,1'-biphenyl]-4,4'-diylbis-; Poly(oxy-1,4-butanediyl), α-[[[3-[(1-aziridinylcarbonyl)amino]-4-methylphenyl]amino]carbonyl]-ω-[[[[3-[(1-aziridinylcarbonyl) amino]-4-methylphenyl]amino]carbonyl]oxy]-; N,N"-(methylenedi-4,1-phenylene)bis[N'-1-aziridinyl-urea; C) Trifunctional aziridines pentaerythritol tris[3-(1-aziridinyl)propionate]; trimethylolpropane tris[3-( 2-methylaziridin-1-yl)propionate], trimethylolpropane tris[3-(aziridin-1-yl)propionate]; 1-aziridinepropionic acid 2-[[3-(1-aziridinyl)-1-oxopropoxy]methyl]-1,3-propanediyl ester; 1-aziridinepropionic acid α-methyl, 1,1'-[2-[[3-(1-aziridinyl)-2-methyl-1-oxopropoxy]methyl]-2-ethyl-1,3-propanediyl] ester; 1-aziridinepropionic acid 2-[[(1-aziridinylacetyl)oxy]methyl]-2-ethyl-1,3-propanediyl ester; 1-aziridinepropionic acid 2-methyl-1,1',1"-(2-ethyl-1,2,3-propanetriyl)ester;1-aziridinecarboxamide-N,N',N"-(methylidynetri-4,1-phenylene)tris;1-aziridinecarboxamide,N,N'-[[[6-[(1-aziridinylcarbonyl)amino]hexyl]-imino]bis(carbonylimino-6,1-hexanediyl)]bis-; 1-aziridinepropionic acid 2-methyl, 1,1'-[2-ethyl-2-[[3-(2-methyl-1-aziridinyl)-1-oxopropoxy]methyl]-1,3-propanediyl] ester; 1-aziridinepropionic acid 1,1'-[2-[[3-(1-aziridinyl)-1-oxopropoxy]methyl]-2-ethyl-1,3-propanediyl]ester; 1-aziridinepropionic acid 1,1'-[2-[[3-(1-aziridinyl)-1-oxopropoxy]methyl]-2-(hydroxymethyl)-1,3-propanediyl]ester;Poly(oxy-1,2-ethanediyl)-α,α',α''-1,2,3-propanetriyltris[ω-[[[[3-[(1-aziridinylcarbonyl)amino]-4-methylphenyl]amino]carbonyl]oxy]-;Aziri-din-1,1',1"-(S-phenenyltricarbonyl)tris[2-methyl-]; D) Tetrafunctional aziridines pentaerythritol tetrakis(β-aziridino)propionate; 1-aziridinepropionic acid-1,1'-[2,2 -bis[[3-(1-aziridinyl)-1-oxopropoxy]-methyl]-1,3-propanediyl]ester; 1-aziridinepropionic acid-2-methyl-, 1,1'-[2,2-bis[[ 3-(2-methyl-1-aziridinyl)-1-oxopropoxy]methyl]-1,3-propanediyl]ester; 1-aziridineethanol-α,α'-[[2,2-bis[2-hydroxy-3- (2-methyl-1-aziridinyl)-propoxy]methyl]-1,3-propanediyl]bis(oxymethylene)]bis[2-methyl-; ethanone-2,2',2'',2'''-[ [2,2'-bipyridine]-6,6'-diylbis(methyleneenitrilo)]tetrakis[1-(2-methyl-1-aziridinyl)-; 1,5-pentanedione-2-[bis[2-(2- methyl-1-aziridinyl)-2-oxoethyl]amino]-1,5-bis(2-methyl-1-aziridinyl)-; ethanone-2,2',2'',2'''-(1,2 -ethanediyldinitrilo)tetrakis[1-(2-methyl-1-aziridinyl)-; methanone-1,1',1'',1'''-(1,4,5,8-naphthalenetetrayl)tetrakis[1-( 2-methyl-1-aziridinyl)-; 1-aziridineethanol-α,α'-[[2,2-bis[2-hydroxy-3-(2-methyl-1-aziridinyl)propoxy]methyl]-1,3 -propanediyl]bis(oxymethylene)]bis[2-methyl-; E) Multifunctional aziridines 1-aziridineproprioic acid-1,1'-[2-[[3-[3-(1-aziridinyl)-1-oxopropoxy]-2,2-bis[[3-(1-aziridinyl)-1 -oxopropoxy]methyl]propoxy]methyl]-2-[[3-(1-aziridinyl)-1-oxopropoxy]methyl]-1,3-propanediyl]ester; 1-aziridinepropionic acid-2-methyl-, 1,1'-[2-[[3-[3-(1-aziridinyl)-1-oxopropoxy]-2-(hydroxymethyl)-2-[[3-(2- methyl-1-aziridinyl)-1-oxopropoxy]methyl]propoxy]methyl]-2-[[3-(2-methyl-1-aziridinyl)-1-oxopropoxy]methyl]-1,3-propanediyl]ester; 1-aziridinepropionic acid-β,2-dimethyl, benzylhexaylhexamethylene ester; 1-Aziridineproprioic acid 2-ethyl-β-methyl, benzylhexaylhexakis(methylene) ester; as well as mixtures and combinations of the aforementioned aziridines. Stabilizer composition according to one of the preceding claims, characterized in that at least one aziridine is selected from the group consisting of the following compounds

Stabilizer composition according to one of the preceding claims, characterized in that the oxide, carbonate and/or hydroxide of calcium, magnesium, aluminum or zinc has a pK _s value of at least 10. Stabilizer composition according to one of the preceding claims, characterized in that the oxide, carbonate and/or hydroxide is composed of calcium, magnesium, aluminum or zinc is selected from the group consisting of CaO, CaCO ₃ , Ca(OH) ₂ , MgO, MgCO ₃ , Mg(OH) ₂ , CaMg(CO ₃ ) ₂ , Al ₂ O ₃ , Al ₂ (CO ₃ ) ₃ , Al (OH) ₃ , ZnO, ZnCO ₃ , and Zn(OH) ₂ as well as mixtures and combinations thereof. Stabilizer composition according to one of the preceding claims, characterized in that the weight ratio of the total of the aziridines to the total of the at least one oxide, carbonate or hydroxide of calcium, magnesium, aluminum or zinc is 20:1 to 1:20, preferably from 10:1 to 1:10, particularly preferably from 5:1 to 1:5, in particular 1:1 to 1:4. Use of a stabilizer composition according to one of the Claims 1 until 6 for stabilizing condensation polymers against hydrolytic degradation. Process for stabilizing condensation polymers against hydrolytic degradation, in which the condensation polymer is given a stabilizer composition according to one of Claims 1 until 6 is mixed in or blended with it. Use or process according to one of the Claims 7 or 8th , characterized in that the stabilizer composition is based on a weight ratio of 0.01 to 10% by weight, preferably from 0.05 to 5% by weight, particularly preferably from 0.1 to 3% by weight the polycondensation polymer is used or mixed in. Use or process according to one of the Claims 7 until 9 , characterized in that the polycondensation polymer is selected from the group consisting of a) polyamides, such as polyamide-6, 6.6, 6.9, 6.10, 4.6, 4.10, 6.12, 10.10, 10.12, 12.12, polyamide 4, polyamide, 7, polyamide 8, polyamide 9, polyamide 11, polyamide 12 and (partially) aromatic polyamides such as polyphthalamides, for example 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, referred to for example as polyamide 6T, polyamide 9T, polyamide 6I, polyamide-6-3-T, blends of different polyamides such as PA-6 and PA 6.6, PA6T and PA6I, PA-6.6 and PA6T or blends of polyamides and polyolefins such as PA/PP or PA/PE, b) polyesters made from aliphatic or aromatic dicarboxylic acids and diols or from hydroxycarboxylic acids, in particular aliphatic polyesters, such as polyethylene terephthalate (PET ), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polypropylene terephthalate (PPT), polyethylene naphthalate (PEN), poly-1,4-dimethylol-cyclohexane terephthalate, polyhydroxybenzoate, polyhydroxynaphthalate, polylactic acid (PLA), polyhydroxybutyrate (PHB), polyhydroxyvalerate ( PHV), polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), polyethylene succinate, polycaprolactone, polyethylene furanoate (PEF), c) polycarbonates, polyester carbonates, as well as blends such as PC/ABS, PC/PBT, PC/PET/PBT, PC/ PA, d) as well as mixtures, combinations or blends of two or more of the aforementioned polymers. Hydrolysis-stabilized composition, containing or consisting of at least one condensation polymer and a stabilizer composition according to one of Claims 1 until 8th . Hydrolysis-stabilized composition according to the preceding claim, characterized in that the stabilizer composition is in a weight ratio of 0.01 to 10% by weight, preferably from 0.05 to 5% by weight, particularly preferably from 0.1 to 3% by weight .-% based on the polycondensation polymer is contained. Hydrolysis-stabilized composition according to one of the two preceding claims, characterized in that at least one additive selected from the group consisting of primary or secondary antioxidants, UV absorbers, light stabilizers, metal deactivators, filler deactivators, antiozonants, nucleating agents, antinucleating agents, impact modifiers, Plasticizers, lubricants, rheology modifiers, thixotropy agents, chain extenders, processing aids, mold release aids, flame retardants, pigments, dyes, optical brighteners, antimicrobial agents, antistatic agents, slip agents, antiblocking agents, coupling agents, crosslinking agents, anticrosslinking agents, hydrophilizing agents, hydrophobicizing agents, hydrolysis stabilizers, adhesion promoters, dispersants, compatibilizers, Oxygen scavengers, acid scavengers, blowing agents, degradation additives, defoaming aids, odor traps, marking agents, antifogging agents, fillers and reinforcing agents are included. Hydrolysis-stabilized composition according to one of the Claims 11 until 13 , characterized in that the at least one condensation polymer is selected from the group consisting of aliphatic polyesters, in particular polylactic acid (PLA), polybutylene succinate (PBS), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene furanoate (PEF), polyamide-6 or polyamide-6.6. Hydrolysis-stabilized composition according to one of the Claims 11 until 14 , characterized by a melt volume flow rate (MVR), determined according to DIN EN ISO 1133-1:2012 after storage of an extruded polymer granulate with a granule diameter between 1 and 3 mm in deionized water for a period of 336 hours at a temperature of 60 ° C (aliphatic polyesters) or 936 hours at a temperature of 85 ° C ((partially) aromatic polyesters), which is increased by a maximum of 100%, preferably a maximum of 90%, compared to the melt volume flow rate (MVR) of the same sample of storage. Molded part or shaped body, producible from a hydrolysis-stabilized composition according to one of Claims 11 until 15 , in particular foils or films, foams, fibers, cables and pipes, profiles, hollow bodies, tapes, membranes, such as geomembranes, or adhesives that are produced via extrusion, injection molding, blow molding, calendering, pressing processes, spinning processes, rotomoulding, for example for electrical purposes - and electronics industry, construction industry, transport industry (cars, planes, ships, trains), for medical applications, for household and electrical appliances, vehicle parts, consumer goods, packaging, furniture, textiles.