EP4662261A1

EP4662261A1 - A polycarbodiimide composition as stabilizer for polymers

Info

Publication number: EP4662261A1
Application number: EP24703573.6A
Authority: EP
Inventors: Frederic Lucas; Tobias Gienau; Stephan DOHMEN; Volker VOGELSANG; Frank Schaefer
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2023-02-07
Filing date: 2024-02-07
Publication date: 2025-12-17
Also published as: JP2026503164A; CN120693356A; WO2024165625A1; TW202440703A; KR20250142422A

Abstract

The present invention relates to a polycarbodiimide composition particularly comprising a specific polycarbodiimide and a reduced amount of P. The polycarbodiimide composition can be used as stabilizer for a polymer, especially as hydrolysis stabilizer for thermoplastic polyurethane compositions. Further, the present invention relates to a process for the preparation of a polycarbodiimide composition, a polycarbodiimide composition obtainable or obtained by said process.

Description

A polycarbodiimide composition as stabilizer for polymers

TECHNICAL FIELD

The present invention relates to a polycarbodiimide composition, a process for preparation thereof, a polycarbodiimide composition obtained or obtainable by said process, and to the use of a polycarbodiimide composition.

INTRODUCTION

Carbodiimides, preferably in their oligomeric or polymeric form as polycarbodiimides, are known compounds, which can be used in a broad range of applications, e.g. as stabilizers in plastics, lubricants or plasticizers, in particular with respect to undesired degradation due to hydrolysis, or as crosslinkers for carboxylic acid (-COOH) groups, e.g. for coatings, adhesives and printing and packaging applications. In the context of the present invention the term polycarbodiimides includes oligomeric as well as polymeric forms thereof. For example, in particular thermoplastic polyurethanes or polyesters are typically stabilized with polycarbodiimides.

DE 11 2015 000659 T5 relates to a polyester resin composition containing a polyester resin and a carbodiimide compound, a process for producing the polyester resin composition, and a molded article using the polyester resin composition.

EP 3875538 A1 relates to a polyester resin modifying agent suitable for improving hydrolysis resistance of a polyester resin, to a method for producing the same, and to a polyester resin composition. The disclosed polyester resin modifying agent was obtained by reacting an aliphatic diisocyanate, an isocyanate-terminal capping agent, and a carbodiimidizing catalyst. The resulting polyester resin modifying agent included a polycarbodiimide compound having a small content of a carbodiimidizing catalyst for producing the polyester resin modifying agent.

EP 3943550 A1 relates to powdered polycarbodiimide compound which can improve hydrolytic resistance of ester resins, and an ester resin composition comprising the same.

EP 4053201 A1 relates to a compatibilizer for polyester resin to improve compatibility among different kinds of resin, and a polyester resin composition using the same.

US 2020/017628 A1 relates to a carboxy group-containing aqueous resin composition, a molded article formed of the resin composition, and a method of producing a polycarbodiimide compound to be used for the resin composition. EP 3835333 A1 relates to a polycarbodiimide composition, a method for producing a polycarbodiimide composition, an aqueous dispersion composition, a solution composition, a resin composition, a resin cured product, and a carbodiimide cross-linking agent for fiber treatment.

However, the prior art is silent with respect to a process for the preparation of a polycarbodiimide wherein at least a portion of the carbodiimidization catalyst is removed from the reaction mixture.

Polycarbodiimides are generally formed via condensation of diisocyanates. Subsequently, polycarbodiimides are subjected to endcapping, for example with a mono-OH functionalized polyethylene oxide (PEO). Especially for thermoplastic polyurethane (TPU) applications, only metatetramethylxylylene diisocyanate (also abbreviated herein as m-TMXDI or TMXDI) proved to be usable as an aliphatic isocyanate monomer in order to get good performances, in particular with respect to its properties. However, attempts to transfer this concept on poylcarbodiimides formed by alternative isocyanate monomers such as hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), or hydrogenated MDI (also known as H12MDI or 4,4'-diisocyanato dicyclohexylmethane) failed.

It was an object of the present invention to provide a novel polycarbodiimide composition having an improved performance with respect to its stabilizing properties of polymers.

DETAILED DESCRIPTION

Surprisingly, it was found that a polycarbodiimide composition comprising a reduced amount of phosphorous, in particular a reduced amount of phospholene oxides, wherein the polycarbodiimide is end-capped with a specific group, shows an improved performance with respect to its properties as hydrolysis stabilizer for a polymer.

In particular, it was found that a polycarbodiimide composition, wherein the polycarbodiimide is based on 4,4'-diisocyanato dicyclohexylmethane (H12MDI) endcapped with comparatively long alkyl chains, shows better performance in terms of hydrolysis stability when used in TPU, especially when compared with monoalcoholic PEO.

Therefore, the present invention relates to a polycarbodiimide composition comprising a polycarbodiimide having formula (1 ) and/or, preferably or, a polycarbodiimide having formula (2) wherein Ri is selected from the group consisting of optionally branched (Cn-C5o)alkoxy and optionally branched (Cn-C5o)alkenoxy, wherein Ri comprises an atomic ratio of carbon atoms, calculated as sum of carbon atoms comprised in Ri, to oxygen atoms, calculated as sum of oxygen atoms comprised in Ri, C:O, of equal to or greater than 11 , wherein R2 is -CeHs-CF^-CeHs- (4,4’-diyldicyclohexylmethane), wherein R3 is selected from the group consisting of optionally branched and/or optionally alkox- ylated alkylenes, wherein the alkylenes consist of C, H, and optionally O, , wherein R4 is selected from the group consisting of optionally branched and/or optionally alkox- ylated alkane-triyls, wherein the alkane-triyls consist of C, H, and optionally O, wherein m is an integer in the range of 1 to 20, wherein p is an integer in the range of 1 to 10, wherein n is an integer in the range of 1 to 20, and wherein the polycarbodiimide composition comprises equal to or less than 110 weight-ppm of P, calculated as elemental P, and based on the total weight of the polycarbodiimide composition, wherein the P content of the polycarbodiimide composition is preferably determined according to Reference Example 2.

It is preferred that Ri is selected from the group consisting of optionally branched (C12- C4o)alkoxy and optionally branched (Ci2-C4o)alkenoxy, more preferably from the group consisting of optionally branched (Ci3-C3s)alkoxy and optionally branched (Ci3-C3s)alkenoxy, more preferably from the group consisting of optionally branched (Ci4-C3o)alkoxy and optionally branched (Ci4-C3o)alkenoxy, more preferably from the group consisting of optionally branched (Ci5-C2s)alkoxy and optionally branched (Cis-C25)alkenoxy, more preferably from the group consisting of optionally branched (Ci6-C22)alkoxy and optionally branched (Ci6-C22)alkenoxy, more preferably from the group consisting of optionally branched (Ci?-C2i)alkoxy and optionally branched (Ci?-C2i)alkenoxy, more preferably from the group consisting of optionally branched (Ci8-C2o)alkoxy and optionally branched (Cis-C2o)alkenoxy, wherein Ri more preferably is optionally branched (Cis-C2o)alkoxy or optionally branched (Cis-C2o)alkenoxy, more preferably branched (Cis-C2o)alkoxy or (Cis-C2o)alkenoxy, more preferably branched C2oalkoxy or Cisalkenoxy.

It is preferred that Ri is selected from the group consisting of -(CH₂)8-CH=CH-(CH₂)7-CH₃, preferably -(CH₂)8-CH=CH-(CH₂)7-CH3 in (Z)-configuration, and -CH₂-CH[(CH₂)₇-CH₃][-(CH₂)₉-CH₃], wherein Ri is more preferably -(CH₂)8-CH=CH-(CH₂)7-CH₃, more preferably -(CH₂)s-CH=CH- (CH₂)₇-CH₃ in (Z)-configuration, or -CH₂-CH[(CH₂)₇-CH₃][-(CH₂)₉-CH₃].

It is preferred that Ri comprises an atomic ratio of carbon atoms, calculated as sum of carbon atoms comprised in Ri, to oxygen atoms, calculated as sum of oxygen atoms comprised in Ri, C:O, in the range of 11 to 50, more preferably in the range of 12 to 40, more preferably in the range of 13 to 35, more preferably in the range of 14 to 30, more preferably in the range of 15 to 25, more preferably in the range of 16 to 22, more preferably in the range of 17 to 21 , more preferably in the range of 18 to 20, wherein Ri comprises an atomic ratio of carbon atoms, calculated as sum of carbon atoms comprised in Ri, to oxygen atoms, calculated as sum of oxygen atoms comprised in Ri, C:O, of 18 or 20.

It is preferred that Ri has a molecular weight greater than 210 g/mol, more preferably in the range of from greater than 210 to 700 g/mol, more preferably in the range of 220 to 600 g/mol, more preferably in the range of 230 to 500 g/mol, more preferably in the range of 240 to 400 g/mol, more preferably in the range of 250 to 350 g/mol, more preferably in the range of 260 to 310 g/mol.

It is preferred that R₃ is selected from the group consisting of optionally branched (Ci- C₂s)alkylenes, -[CR5H-CH₂-O]_XI-CR5H-CH₂-, wherein Rs is H or CH₃, wherein x1 is an integer in the range of from 1 to 15, -[CH₂-CH₂-O]_x2-CH₂-CH₂-O-/^/7 [C(CH₃)H-CH₂-O]_x3-C(CH₃)H- CH₂}-, wherein x2 is an integer in the range of 1 to 15, wherein x3 is an integer in the range of 1 to 15, and -[CH₂-CH₂-CH₂-CH₂-O]_X4-CH₂-CH₂-CH₂-CH₂-, wherein x4 is an integer in the range of 1 to 30, preferably in the range of 1 to 15, more preferably selected from the group consisting of optionally branched (Ci-C₂s)alkylenes, more preferably selected from the group consisting of optionally branched (Ci-C₂o)alkylenes, more preferably selected from the group consisting of optionally branched (C₂-Cis)alkylenes, more preferably selected from the group consisting of optionally branched (C₃-Ci₂)alkylenes, more preferably selected from the group consisting of optionally branched (C4-Cio)alkylenes, more preferably selected from the group consisting of optionally branched (Cs-Cs)alkylenes, wherein R₃ is more preferably selected from the group consisting of optionally branched Csalkylenes, wherein R₃ is more preferably selected from the group consisting of branched Csalkylenes.

It is preferred that R₃ is selected from the group consisting of optionally branched (Ci- C₂s)alkylenes, -[CRSH-CH₂-O]_XI-CRSH-CH₂-, wherein Rs is H or CH₃, wherein x1 is an integer in the range of from 1 to 15, -[CH₂-CH₂-O]_x2-CH₂-CH₂-O-ra/7-([C(CH₃)H-CH₂-O]_x3-C(CH₃)H- CH₂}-, wherein x2 is an integer in the range of 1 to 15, wherein x3 is an integer in the range of 1 to 15, and -[CH₂-CH₂-CH₂-CH₂-O]_X4-CH₂-CH₂-CH₂-CH₂-, wherein x4 is an integer in the range of 1 to 30, preferably in the range of 1 to 15, more preferably selected from the group consisting of optionally branched (Ci-C₂s)alkylenes, more preferably selected from the group consisting of -(CH₂)₂-, -(CH₂)₃-, -(CH₂)₄-, -CH₂-CH₂-CH(CH₃)-, -(CH₂)₅-, -CH₂-C(CH₃)₂- CH₂- -CH₂-CH2-CH2-CH(CH₃)- -CH₂-CH2-CH(CH₃)-CH2- -(CH₂)₆- -(CH₂)₇- -(CH₂)₈- - (CH₂)9- -(CH₂)IO- and -(CH₂)I₂- more preferably selected from the group consisting of -CH2-CH2-CH(CH₃)-, -(CH2)s-, -CH2- C(CH₃)₂-CH₂- -CH₂-CH₂-CH₂-CH(CH₃)-, -CH₂-CH₂-CH(CH₃)-CH₂-, and -(CH₂)₆- wherein R₃ is more preferably -CH2-C(CH₃)2-CH2- or -(CH₂)5-

It is preferred that R4 is selected from the group consisting of optionally alkoxylated (C₃- C5o)alkane-triyls,

CH₂-O-R₆-

C(CH₂-CH₃)-CH₂-O-R₆-

CH2-O-R6-, and

CH₂-O-R₆-

CH-O-R₆-

CH2-O-R6-, wherein Re is -[CR7H-CH2-O]_XI-CR7H-CH2-, wherein R₇ is H or CH₃, wherein x1 is an integer in the range of 1 to 15, -[CH₂-CH2-O]x2-CH2-CH2-O-/-a/7 [C(CH₃)H-CH2-O]x₃-C(CH₃)H-CH₂}-, wherein x2 is an integer in the range of 1 to 15, wherein x3 is an integer in the range of 1 to 15, and -[CH2-CH2-CH2-CH2-O]X4-CH2-CH2-CH2-CH₂-, wherein x4 is an integer in the range of 1 to 30, preferably in the range of 1 to 15, wherein R4 is more preferably selected from the group consisting of optionally alkoxylated (C₃- C5o)alkane-triyls, and wherein F is more preferably selected from the group consisting of (C3-C4o)alkane-triyls, more preferably (C3-C3o)alkane-triyls, more preferably (C3-C2o)alkane-triyls, more preferably (C3- Cio)alkane-triyls, more preferably (C3-C5)alkane-triyls,

I I I wherein R4 is more preferably CH2-CH-CH2 (propane-1 ,2, 3-triyl).

It is preferred that m is an integer in the range of 2 to 18, more preferably in the range of 3 to 17, more preferably in the range of 4 to 16, more preferably in the range of 5 to 15, more preferably in the range of 6 to 15.

It is preferred that p is an integer in the range of 1 to 5, more preferably in the range of 1 to 4, more preferably in the range of 1 to 3.

It is preferred that n is an integer in the range of 2 to 18, more preferably in the range of 3 to 17, more preferably in the range of 4 to 16, more preferably in the range of 5 to 15, more preferably in the range of 6 to 15.

It is preferred that the polycarbodiimide comprises equal to or less than 100 weight-ppm of P, calculated as elemental P, and based on the total weight of the polycarbodiimide composition, more preferably equal to or less than 90 weight-ppm, more preferably equal to or less than 80 weight-ppm, more preferably equal to or less than 75 weight-ppm, more preferably equal to or less than 70 weight-ppm, more preferably equal to or less than 65 weight-ppm, more preferably equal to or less than 60 weight-ppm, of P, calculated as elemental P, and based on the total weight of the polycarbodiimide composition.

It is preferred that the polycarbodiimide comprises equal to or less than 410 weight-ppm of phospholene oxides, calculated as sum of the weights of the phospholene oxides, and based on the total weight of the polycarbodiimide composition, more preferably equal to or less than 370 weight-ppm, more preferably equal to or less than 335 weight-ppm, more preferably equal to or less than 295 weight-ppm, more preferably equal to or less than 280 weight-ppm, more preferably equal to or less than 260 weight-ppm, more preferably equal to or less than 240 weight-ppm, more preferably equal to or less than 220 weight-ppm, of phospholene oxides, calculated as sum of the weights of the phospholene oxides, and based on the total weight of the polycarbodiimide composition.

In the case where the polycarbodiimide comprises equal to or less than 410 weight-ppm of phospholene oxides, calculated as sum of the weights of the phospholene oxides, and based on the total weight of the polycarbodiimide composition, it is preferred that the phospholene oxides are selected from the group consisting of 1-methyl-2-phospholene-1 -oxide (MPO), 3-methyl-1- phenyl-2-phospholene-1 -oxide (MPPO), 3-Methyl-1-ethyl-2-phospholene-1 -oxide, 1 ,3-dimethyl- 2-phospholene-1 -oxide, 1 -phenyl-2-phospholene-1 -oxide, 1 -ethyl-2-phospholene-1 -oxide, 1 -methyl-3-phospholene-1 -oxide, 3-methyl-1 -phenyl-3-phospholene-1 -oxide, 3-methyl-1 -ethyl-3- phospholene-1 -oxide, 1 ,3-dimethyl-3-phospholene-1 -oxide, 1-phenyl-3-phospholene-1 -oxide, 1- ethyl-3-phospholene-1 -oxide, and mixtures of two or more thereof, more preferably from the group consisting of 1-methyl-2-phospholene-1 -oxide (MPO), 3-methyl-1-phenyl-2-phospholene- 1 -oxide (MPPO), 3-methyl-1-ethyl-2-phospholene-1 -oxide, 1 ,3-dimethyl-2-phospholene-1 -oxide, 1-phenyl-2-phospholene-1 -oxide, 1-ethyl-2-phospholene-1 -oxide, and mixture of two or more thereof, wherein the one or more phospholene oxides are more preferably 1-methyl-2- phospholene-1 -oxide (MPO), 3-methyl-1-phenyl-2-phospholene-1 -oxide (MPPO), and mixtures thereof, wherein the phospholene oxides more preferably are 1-methyl-2-phospholene-1 -oxide (MPO).

It is preferred that from 99.0 to 100 weight-%, more preferably from 99.5 to 100 weight-%, more preferably from 99.9 to 100 weight-%, of the polycarbodiimide composition consist of the polycarbodiimide and P, preferably of the polycarbodiimide and the phospholene oxides.

It is preferred that the polycarbodiimide composition has a viscosity in the range of from 5 to 20 Pa s.

It is preferred that the polycarbodiimide composition has a content of N=C=N-functional groups in the range of from 4.0 to 12.0 %, more preferably in the range of from 6.0 to 9.8 %, more preferably in the range of from 6.2 to 9.6 %, wherein the content of N=C=N-functional groups is more preferably determined according to Reference Example 1 .

A process for the preparation of a polycarbodiimide composition, preferably for the preparation of a polycarbodiimide composition of any one of the embodiments disclosed herein, the process comprising

(i) preparing a mixture comprising 4,4'-diisocyanato dicyclohexylmethane and one or more phospholene oxides;

(ii) subjecting the mixture obtained in (i) to carbodiimidization conditions in a gas atmosphere, wherein the carbodiimidization conditions comprise heating the reaction mixture to a temperature in the range of 80 to 220 °C;

(iii) adding one or more monoalcohols and one or more polyalcohols to the mixture obtained in (ii), wherein the one or more monoalcohols are independently from each other selected from the group consisting of optionally branched monohydroxy(Cn-C5o)alkanes and optionally branched monohydroxy(Cn-C5o)alkenes, wherein the one or more optionally branched monohydroxy(Cn-C5o)alkanes and optionally branched monohydroxy(Cn-C5o)alkenes independently from each other comprise an atomic ratio of carbon atoms, calculated as sum of carbon atoms comprised in the optionally branched monohydroxy(Cn-C5o)alkanes and optionally branched monohydroxy(Cn- Cso)alkenes, respectively, to oxygen atoms, calculated as sum of oxygen atoms comprised in the optionally branched monohydroxy(Cn-C5o)alkanes and optionally branched monohydroxy(Cn-C5o)alkenes, respectively, C:O, of equal to or greater than 11 , wherein the one or more polyalcohols independently from each other are selected from the group consisting of optionally branched and/or optionally alkoxylated dihydroxyal- kanes, and optionally branched and/or optionally alkoxylated trihydroxyalkanes, wherein the dihydroxyalkanes consist of C, H, and O, wherein the trihydroxyalkanes consist of C, H, and O, and subjecting the resulting mixture to reaction conditions in a gas atmosphere, wherein the reaction conditions comprise heating the reaction mixture to a temperature in the range of 80 to 220 °C;

(iv) removing at least a portion of the one or more phospholene oxides from the mixture obtained in (iii); for obtaining the polycarbodiimide composition.

It is preferred that the one or more phospholene oxides are selected from the group consisting of 1-methyl-2-phospholene-1 -oxide (MPO), 3-methyl-1-phenyl-2-phospholene-1 -oxide (MPPO), 3-methyl-1 -ethyl-2-phospholene-1 -oxide, 1 ,3-dimethyl-2-phospholene-1 -oxide, 1 -phenyl-2- phospholene-1 -oxide, 1-ethyl-2-phospholene-1 -oxide, 1-methyl-3-phospholene-1 -oxide, 3- methyl-1 -phenyl-3-phospholene-1 -oxide, 3-methyl-1 -ethyl-3-phospholene-1 -oxide, 1 ,3-dimethyl- 3-phospholene-1 -oxide, 1-phenyl-3-phospholene-1 -oxide, 1-ethyl-3-phospholene-1 -oxide, and mixture of two or more thereof, more preferably from the group consisting of 1-methyl-2- phospholene-1 -oxide (MPO), 3-methyl-1-phenyl-2-phospholene-1 -oxide (MPPO), 3-methyl-1- ethyl-2-phospholene-1 -oxide, 1 ,3-dimethyl-2-phospholene-1 -oxide, 1 -phenyl-2-phospholene-1 - oxide, 1-ethyl-2-phospholene-1 -oxide, and mixture of two or more thereof, wherein the one or more phospholene oxides are more preferably 1-methyl-2-phospholene-1 -oxide (MPO), 3- methyl-1-phenyl-2-phospholene-1 -oxide (MPPO), and mixtures thereof, wherein the one or more phospholene oxides are more preferably 1-methyl-2-phospholene-1 -oxide (MPO).

It is preferred that the mixture obtained in (i) has a molar ratio of 4,4'-diisocyanato dicyclohexylmethane, calculated as molar amount of 4,4'-diisocyanato dicyclohexylmethane, to the one or more phospholene oxides, calculated as sum of the molar amounts of the one or more phospholene oxides, in the range of from 10:1 to 1 ,000:1 , more preferably in the range of from 50:1 to 750:1 , more preferably in the range of from 80:1 to 510:1 , more preferably in the range of from 150:1 to 450:1 , more preferably in the range of from 200:1 to 400:1 , more preferably in the range of from 300:1 to 350:1 .

It is preferred that the mixture obtained in (i) comprises from 0 to 1 weight-%, more preferably from 0 to 0.1 weight-%, more preferably from 0 to 0.01 weight-%, of xylene, more preferably of an alkyl substituted benzene or an alkyl substituted dibenzene, wherein the alkyl comprises one or more of methyl, ethyl, and propyl, more preferably of a solvent, wherein the mixture obtained in (i) is more preferably substantially free of xylene, more preferably substantially free of an alkyl substituted benzene or an alkyl substituted dibenzene, more preferably substantially free of a solvent.

It is preferred that the carbodiimidization conditions in (ii) comprise heating the reaction mixture to a temperature in the range of 90 to 215 °C, more preferably in the range of 100 to 210 °C, more preferably in the range of 120 to 205 °C, more preferably in the range of 140 to 200 °C, more preferably in the range of 150 to 195 °C, more preferably in the range of 160 to 180 °C.

It is preferred that the gas atmosphere in (ii) comprises, more preferably consists of, an inert gas, wherein the gas atmosphere in (ii) more preferably comprises, more preferably consists of, one or more of nitrogen and argon.

It is preferred that the carbodiimidization conditions in (ii) comprise applying a pressure to the mixture obtained in (i) in the range of 1 to 1000 hPa, more preferably in the range of 2 to 1000 hPa, more preferably in the range of 2.5 to 1000 hPa.

It is preferred that the carbodiimidization conditions in (ii) comprise agitating the mixture obtained in (i), more preferably by stirring.

It is preferred that the mixture obtained in (i) is subjected to carbodiimidization conditions in (ii) for a duration in the range of from 1 to 50 h, more preferably in the range of from 1 .5 to 40 h, more preferably in the range of from to 2 to 25 h.

It is preferred that the one or more monoalcohols added according to (iii) to the mixture obtained in (ii) are independently from each other selected from the group consisting of optionally branched monohydroxy(Ci2-C4o)alkanes and optionally branched monohydroxy(Ci2-C4o)alkenes, more preferably from the group consisting of optionally branched monohydroxy(Ci3-C35)alkanes and optionally branched monohydroxy(Ci3-C35)alkenes, more preferably from the group consisting of optionally branched monohydroxy(Ci4-C3o)alkanes and optionally branched monohy- droxy(Ci4-C3o)alkenes, more preferably from the group consisting of optionally branched mono- hydroxy(Ci5-C25)alkanes and optionally branched monohydroxy(Ci5-C25)alkenes, more preferably from the group consisting of optionally branched monohydroxy(Ci6-C22)alkanes and optionally branched monohydroxy(Ci6-C22)alkenes, more preferably from the group consisting of optionally branched monohydroxy(Ci7-C2i)alkanes and optionally branched monohydroxy(Ci7- C2i)alkenes, more preferably from the group consisting of optionally branched monohy- droxy(Ci8-C2o)alkanes and optionally branched monohydroxy(Cis-C2o)alkenes, wherein the one or more monoalcohols are independently from each other more preferably optionally branched monohydroxy(Ci8-C2o)alkanes or optionally branched monohydroxy(Ci8-C2o)alkenes, more preferably branched monohydroxy(Ci8-C2o)alkanes or monohydroxy(Ci8-C2o)alkenes, more preferably branched monohydroxyC2oalkanes or monohydroxyCisalkenes.

It is preferred that the one or more monoalcohols added according to (iii) to the mixture obtained in (ii) are independently from each other selected from the group consisting of HO-(CH2)s- CH=CH-(CH2)7-CH3, preferably HO-(CH2)s-CH=CH-(CH2)7-CH3 in (Z)-configuration, and HOCH 2-CH [(CH 2)i-C H 3] [-(CH 2)9-6 H 3], wherein the one or more monoalcohols are more preferably HO-(CH₂)8-CH=CH-(CH₂)7-CH₃, more preferably HO-(CH₂)8-CH=CH-(CH₂)7-CH₃ in (Z)- configuration, or HO-CH2-CH[(CH2)7-CH₃][-(CH2)9-CH₃]. It is preferred that the one or more optionally branched monohydroxy(Cn-C5o)alkanes and optionally branched monohydroxy(Cn-C5o)alkenes independently from each other comprise an atomic ratio of carbon atoms, calculated as sum of carbon atoms comprised in the optionally branched monohydroxy(Cn-C5o)alkanes and optionally branched monohydroxy(Cn-C5o)alkenes, respectively, to oxygen atoms, calculated as sum of oxygen atoms comprised in the optionally branched monohydroxy(Cn-C5o)alkanes and optionally branched monohydroxy(Cn-C5o)alkenes, respectively, C:O, in the range of 11 to 50, more preferably in the range of 12 to 40, more preferably in the range of 13 to 35, more preferably in the range of 14 to 30, more preferably in the range of 15 to 25, more preferably in the range of 16 to 22, more preferably in the range of 17 to 21 , more preferably in the range of 18 to 20, wherein the one or more optionally branched mon- ohydroxy(Cn-C5o)alkanes and optionally branched monohydroxy(Cn-C5o)alkenes independently from each other comprise an atomic ratio of carbon atoms, calculated as sum of carbon atoms comprised in the one or more optionally branched monohydroxy(Cn-C5o)alkanes and optionally branched monohydroxy(Cn-C5o)alkenes, respectively, to oxygen atoms, calculated as sum of oxygen atoms comprised in the one or more optionally branched monohydroxy(Cn-C5o)alkanes and optionally branched monohydroxy(Cn-C5o)alkenes, respectively, C:O, of 18 or 20.

It is preferred that the one or more polyalcohols added according to (iii) to the mixture obtained in (ii) independently from each other are selected from the group consisting of propane-1 ,2,3- triol, a triester of glycerol and ricinoleic acid, HO-[CR5H-CH2-O]_XI-CR5H-CH2-OH, wherein Rs is H or CH3, wherein x1 is an integer in the range of from 1 to 15, HO-[CH2-CH2-O]_X2-CH2- CH2-O-ra/7-{[C(CH3)H-CH2-O]_X3-C(CH3)H-CH2}-OH, wherein x2 is an integer in the range of 1 to 15, wherein x3 is an integer in the range of 1 to 15, and HO-[CH2-CH2-CH2-CH2-O]_X4-CH2- CH2-CH2-CH2-OH, wherein x4 is an integer in the range of 1 to 30, more preferably in the range of 1 to 15, and optionally branched and/or optionally alkoxylated dihydroxy(Ci- C2s)alkanes, more preferably optionally branched and/or optionally alkoxylated dihydroxy(Ci- C2o)alkanes, more preferably optionally branched dihydroxy(C2-Cis)alkanes, more preferably optionally branched dihydroxy(C3-Ci2)alkanes, more preferably optionally branched dihy- droxy(C4-Cio)alkanes, more preferably optionally branched dihydroxy(Cs-Cs)alkanes, wherein the one or more polyalcohols independently from each other are more preferably selected from the group consisting of optionally branched dihydroxyCsalkanes, wherein the one or more polyalcohols are more preferably selected from the group consisting of branched dihydroxyCsalkanes.

In the context of the present invention, ricinoleic acid is (9Z,12R)-12-hydroxyoctadec-9-enoic acid.

It is preferred that the one or more polyalcohols added according to (iii) to the mixture obtained in (ii) independently from each other are selected from the group consisting of optionally branched and/or optionally alkoxylated (C3-Cso)alkane-triols, more preferably (C3-C4o)alkane- triols, more preferably (C3-C3o)alkane-triols, more preferably (C3-C2o)alkane-triols, more preferably (C3-Cio)alkane-triols, more preferably (C3-Cs)alkane-triols, a triester of glycerol and ricinoleic acid, CH₂-O-R₆-

C(CH₂-CH₃)-CH₂-O-R₆-

CH₂- O- Re- , and

CH₂-O-R₆-

CH-O-R₆-

CH₂-O-R₆-, wherein Re is -[CR7H-CH₂-O]_XI-CR7H-CH₂-OH , wherein R? is H or CH₃, -[CH₂-CH₂-O]_x2-CH₂- CH₂-O-ra/7-{[C(CH₃)H-CH₂-O]_x3-C(CH₃)H-CH₂}-OH, and -[CH₂-CH₂-CH₂-CH₂-O]_x4-CH₂- CH₂-CH₂-CH₂-OH, wherein x1 is an integer in the range of 1 to 15, x2 is an integer in the range of 1 to 15, x3 is an integer in the range of 1 to 15, and x4 is an integer in the range of 1 to 30, more preferably in the range of 1 to 15,

HO-(CH₂)₂-OH, HO-(CH₂)₃-OH, HO-(CH₂)₄-OH, HO-CH₂-CH₂-CH(CH₃)-OH, HO-(CH₂)₅-OH, HO-CH₂-C(CH₃)₂-CH₂-OH, HO-CH₂-CH₂-CH₂-CH(CH₃)-OH, HO-CH₂-CH₂-CH(CH₃)-CH₂- OH, HO-(CH₂)₆-OH, HO-(CH₂)₇-OH, HO-(CH₂)₈-OH, HO-(CH₂)₉-OH, HO-(CH₂) -OH , and HO-(CH₂)I₂-OH , more preferably from the group consisting of propane-1 ,2,3-triol , the triester of glycerol and ric- inoleic acid having formula (3)

(3),

HO-CH₂-CH₂-CH(CH₃)-OH, HO-(CH₂)₅-OH, HO-CH₂-C(CH₃)₂-CH₂-OH, HO-CH₂-CH₂-CH₂- CH(CH₃)-OH, HO-CH₂-CH₂-CH(CH₃)-CH₂-OH, and HO-(CH₂)₆-OH, wherein the one or more polyalcohols added according to (iii) to the mixture obtained in (ii) independently from each other are more preferably selected from the group consisting of pro- pane-1 ,2,3-triol, the triester of glycerol and ricinoleic acid having formula (3), and HO-(CH₂)5- OH.

It is preferred that the mixture obtained in (iii) comprises from 5 to 70 weight-%, more preferably from 25 to 50 weight-%, of the one or more monoalcohols, calculated as sum of the weights of the one or more monoalcohols, based on the total weight of the mixture obtained in (iii). It is preferred that the mixture obtained in (iii) comprises from 0.1 to 20 weight-%, more preferably from 1 to 15 weight-%, of the one or more polyalcohols, calculated as sum of the weights of the one or more polyalcohols, based on the total weight of the mixture obtained in (iii).

It is preferred that the mixture obtained in (iii) comprises from 5.1 to 90 weight-%, more preferably from 26 to 65 weight-%, of the one or more monoalcohols and of the one or more polyalcohols, calculated as sum of the weights of the one or more monoalcohols and of the weights of the one or more polyalcohols, respectively, based on the total weight of the mixture obtained in (iii).

It is preferred that the reaction conditions according to (iii) comprise heating the reaction mixture to a temperature in the range of 90 to 200 °C, more preferably in the range of 100 to 195 °C, more preferably in the range of 110 to 190 °C, more preferably in the range of 120 to 185 °C, more preferably in the range of 130 to 180 °C, more preferably in the range of 140 to 175 °C, more preferably in the range of 150 to 170 °C.

It is preferred that removing at least a portion of the one or more phospholene oxides according to (iv) from the mixture obtained in (iii) comprises

(iv.1 ) optionally adding one or more entrainers to the mixture obtained in (iii),

(iv.2) distilling the mixture obtained in (iii) or (iv.1 ) for obtaining a fraction comprising the polycarbodiimide composition and a fraction comprising at least a portion of the one or more phospholene oxides.

In the case where removing at least a portion of the one or more phospholene oxides according to (iv) from the mixture obtained in (iii) comprises optionally (iv.1 ) and (iv.2), it is preferred that the one or more entrainers have a boiling point in the range of 200 to 300 °C, more preferably in the range of 200 to 250 °C, at a pressure in the range of 0.950 to 1 .050 bar(abs), wherein the one or more entrainers are more preferably selected from the group consisting of acetates comprising, more preferably consisting of, C, H, and O, wherein the acetates comprise from 6 to 16, preferably from 8 to 14, C and O atoms, calculated as sum of carbon atoms and oxygen atoms, (Ci-Cio)alkyl(Ci-Cio)alkylether, di(Ci-Cs)alkyl adipates, and mixtures of two or more thereof, more preferably from the group consisting of (Ci-C2)alkyloxy(C3-C5)alkyl acetates, diethylene glycol mono(C2-Ce)alkyl ether acetates, di(Ci-Cs)alkyl adipates, and mixtures of two or more thereof, more preferably from the group consisting of methoxybutyl acetate, diethylene glycol monobutyl ether acetate, diethyl adipate, diisopropyl adipate, dimethyl adipate, and mixtures of two or more thereof, wherein the one or more entrainers are more preferably diethyl adipate.

Further in the case where removing at least a portion of the one or more phospholene oxides according to (iv) from the mixture obtained in (iii) comprises optionally (iv.1 ) and (iv.2), it is preferred that distilling the mixture obtained in (iii) or (iv.1) is performed at a temperature in the range of from 130 to 190 °C, more preferably in the range of from 140 to 180 °C, more preferably in the range of from 150 to 170 °C. Further in the case where removing at least a portion of the one or more phospholene oxides according to (iv) from the mixture obtained in (iii) comprises optionally (iv.1 ) and (iv.2), it is preferred that distilling the mixture obtained in (iii) or (iv.1 ) is performed at a pressure of less than 0.150 bar(abs), more preferably less than 0.125 bar(abs), more preferably less than 0.100 bar(abs).

A polycarbodiimide composition obtainable or obtained by the process of any one of the embodiments disclosed herein.

Use of a polycarbodiimide composition of any one of the embodiments disclosed herein, as a stabilizer, more preferably as a hydrolysis stabilizer, for a polymer, more preferably for a thermoplastic polymer, more preferably for a thermoplastic polyester, more preferably for one or more of a polyurethane (PU), preferably a thermoplastic polyurethane (TPU), a polyurea, a polyethylene terephthalate (PET), a polybutylene terephthalate (PBT), a polyactide (PLA), a polyamide, a polyesteramide, a polycaprolactone, and a polyethersulfone (PES).

The unit bar(abs) refers to an absolute pressure wherein 1 bar equals 10⁵ Pa.

The present invention is further illustrated by the following set of embodiments and combinations of embodiments resulting from the dependencies and back-references as indicated. In particular, it is noted that in each instance where a range of embodiments is mentioned, for example in the context of a term such as "The polycarbodiimide composition of any one of embodiments 1 to 4", every embodiment in this range is meant to be explicitly disclosed for the skilled person, i.e. the wording of this term is to be understood by the skilled person as being synonymous to "The polycarbodiimide composition of any one of embodiments 1 , 2, 3, and 4". Further, it is explicitly noted that the following set of embodiments is not the set of claims determining the extent of protection, but represents a suitably structured part of the description directed to general and preferred aspects of the present invention.

1 . A polycarbodiimide composition comprising a polycarbodiimide having formula (1 )

(1 ), and/or, preferably or, a polycarbodiimide having formula (2)

(2), wherein Ri is selected from the group consisting of optionally branched (Cn-C5o)alkoxy and optionally branched (Cn-C5o)alkenoxy, wherein Ri comprises an atomic ratio of carbon atoms, calculated as sum of carbon atoms comprised in Ri, to oxygen atoms, calculated as sum of oxygen atoms comprised in Ri , C:O, of equal to or greater than 11 , wherein R2 is -CeHs-CI-h-CeHs- (4,4’-diyldicyclohexylmethane), wherein R3 is selected from the group consisting of optionally branched and/or optionally alkoxylated alkylenes, wherein the alkylenes consist of C, H, and optionally O, , wherein R4 is selected from the group consisting of optionally branched and/or optionally alkoxylated alkane-triyls, wherein the alkane-triyls consist of C, H, and optionally O, wherein m is an integer in the range of 1 to 20, wherein p is an integer in the range of 1 to 10, wherein n is an integer in the range of 1 to 20, and wherein the polycarbodiimide composition comprises equal to or less than 110 weight- ppm of P, calculated as elemental P, and based on the total weight of the polycarbodiimide composition, wherein the P content of the polycarbodiimide composition is preferably determined according to Reference Example 2. The polycarbodiimide composition of embodiment 1 , wherein Ri is selected from the group consisting of optionally branched (Ci2-C4o)alkoxy and optionally branched (C12- C4o)alkenoxy, preferably from the group consisting of optionally branched (Ci3-C3s)alkoxy and optionally branched (Ci3-C3s)alkenoxy, more preferably from the group consisting of optionally branched (Ci4-C3o)alkoxy and optionally branched (Ci4-C3o)alkenoxy, more preferably from the group consisting of optionally branched (Ci5-C2s)alkoxy and optionally branched (Cis-C25)alkenoxy, more preferably from the group consisting of optionally branched (Ci6-C22)alkoxy and optionally branched (Ci6-C22)alkenoxy, more preferably from the group consisting of optionally branched (Ci?-C2i)alkoxy and optionally branched (Ci7-C2i)alkenoxy, more preferably from the group consisting of optionally branched (C18- C2o)alkoxy and optionally branched (Cis-C2o)alkenoxy, wherein Ri more preferably is optionally branched (Cis-C2o)alkoxy or optionally branched (Cis-C2o)alkenoxy, more preferably branched (Cis-C2o)alkoxy or (Cis-C2o)alkenoxy, more preferably branched C2oalkoxy or Cisalkenoxy. The polycarbodiimide composition of embodiment 1 or 2, wherein Ri is selected from the group consisting of -(CH₂)8-CH=CH-(CH₂)7-CH₃, preferably -(CH₂)₈-CH=CH-(CH₂)₇-CH₃ in (Z)- configuration, and -CH₂-CH[(CH₂)₇-CH₃][-(CH₂)₉-CH₃], wherein Ri is more preferably -(CH₂)8-CH=CH-(CH₂)₇-CH₃, more preferably -(CH₂)s- CH=CH-(CH₂)₇-CH₃ in (Z)-configuration, or -CH₂-CH[(CH₂)₇-CH₃][-(CH₂)₉-CH₃], The polycarbodiimide composition of any one of embodiments 1 to 3, wherein Ri comprises an atomic ratio of carbon atoms, calculated as sum of carbon atoms comprised in Ri, to oxygen atoms, calculated as sum of oxygen atoms comprised in Ri, C:O, in the range of 11 to 50, more preferably in the range of 12 to 40, more preferably in the range of 13 to 35, more preferably in the range of 14 to 30, more preferably in the range of 15 to 25, more preferably in the range of 16 to 22, more preferably in the range of 17 to 21 , more preferably in the range of 18 to 20, wherein Ri comprises an atomic ratio of carbon atoms, calculated as sum of carbon atoms comprised in Ri, to oxygen atoms, calculated as sum of oxygen atoms comprised in Ri, C:O, of 18 or 20. The polycarbodiimide composition of any one of embodiments 1 to 4, wherein Ri has a molecular weight greater than 210 g/mol, preferably in the range of from greater than 210 to 700 g/mol, more preferably in the range of 220 to 600 g/mol, more preferably in the range of 230 to 500 g/mol, more preferably in the range of 240 to 400 g/mol, more preferably in the range of 250 to 350 g/mol, more preferably in the range of 260 to 310 g/mol. The polycarbodiimide composition of any one of embodiments 1 to 5, wherein R₃ is selected from the group consisting of optionally branched (Ci-C₂5)alkylenes, -[CRsH-CH₂- O]xi-CR5H-CH₂-, wherein Rs is H or CH₃, wherein x1 is an integer in the range of from 1 to 15, -[CH₂-CH₂-O]_x2-CH₂-CH₂-O-ra/7-{[C(CH₃)H-CH₂-O]x₃-C(CH₃)H-CH₂}-, wherein x2 is an integer in the range of 1 to 15, wherein x3 is an integer in the range of 1 to 15, and -[CH₂-CH₂-CH₂-CH₂-O]X4-CH₂-CH₂-CH₂-CH₂-, wherein x4 is an integer in the range of 1 to 30, preferably in the range of 1 to 15, preferably selected from the group consisting of optionally branched (Ci-C₂s)alkylenes, more preferably selected from the group consisting of optionally branched (Ci-C₂o)alkylenes, more preferably selected from the group consisting of optionally branched (C₂-Cis)alkylenes, more preferably selected from the group consisting of optionally branched (C₃-Ci₂)alkylenes, more preferably selected from the group consisting of optionally branched (C4-Cio)alkylenes, more preferably selected from the group consisting of optionally branched (Cs-Cs)alkylenes, wherein R₃ is more preferably selected from the group consisting of optionally branched Csalkylenes, wherein R₃ is more preferably selected from the group consisting of branched Csalkylenes. The polycarbodiimide composition of any one of embodiments 1 to 6, wherein R₃ is selected from the group consisting of optionally branched (Ci-C₂s)alkylenes, -[CRsH-CH₂- O]xi-CRsH-CH₂-, wherein Rs is H or CH₃, wherein x1 is an integer in the range of from 1 to 15, -[CH₂-CH₂-O]_x2-CH₂-CH₂-O-ra/7-{[C(CH₃)H-CH₂-O]x₃-C(CH₃)H-CH₂}-, wherein x2 is an integer in the range of 1 to 15, wherein x3 is an integer in the range of 1 to 15, and -[CH₂-CH₂-CH₂-CH₂-O]_x4-CH₂-CH₂-CH₂-CH₂-, wherein x4 is an integer in the range of 1 to 30, preferably in the range of 1 to 15, preferably selected from the group consisting of optionally branched (Ci-C25)alkylenes, more preferably selected from the group consisting of -(CH₂)₂-, -(CH₂)₃-, -(CH₂)₄-, -CH₂-CH₂-CH(CH₃)-, -(CH₂)₅-, -CH₂- C(CH₃)₂-CH₂-, -CH₂-CH₂-CH₂-CH(CH₃)-, -CH₂-CH₂-CH(CH₃)-CH₂-, -(CH₂)₆-, -(CH₂)₇- , -(CH₂)₈- -(CH₂)₉- -(CH₂)IO- and -(CH₂)i₂- preferably selected from the group consisting of -CH₂-CH₂-CH(CH₃)-, -(CH₂)s-, -CH₂- C(CH₃)₂-CH₂-, -CH₂-CH₂-CH₂-CH(CH₃)-, -CH₂-CH₂-CH(CH₃)-CH₂-, and -(CH₂)₆-, wherein R₃ is more preferably -CH₂-C(CH₃)₂-CH₂- or -(CH₂)5-. The polycarbodiimide composition of any one of embodiments 1 to 7, wherein F is selected from the group consisting of optionally alkoxylated (C₃-C5o)alkane-triyls, wherein Re is -[CR₇H-CH₂-O]_XI-CR₇H-CH₂-, wherein R₇ is H or CH₃, -[CH₂-CH₂-O]_x2- CH₂-CH₂-O-ra/7-{[C(CH₃)H-CH₂-O]_x3-C(CH₃)H-CH₂}-, and -[CH₂-CH₂-CH₂-CH₂-O]_x4- CH₂-CH₂-CH₂-CH₂-, wherein x1 is an integer in the range of 1 to 15, x2 is an integer in the range of 1 to 15, x3 is an integer in the range of 1 to 15, and x4 is an integer in the range of 1 to 30, preferably in the range of 1 to 15, wherein R4 is more preferably selected from the group consisting of optionally alkoxylated (C₃-C5o)alkane-triyls, and wherein F is more preferably selected from the group consisting of (C₃-C4o)alkane-triyls, more preferably (C₃-C₃o)alkane-triyls, more preferably (C₃-C₂o)alkane-triyls, more preferably (C₃-Cio)alkane-triyls, more preferably (C₃-C5)alkane-triyls,

I I I wherein F is more preferably CH₂-CH-CH₂ (propane-1 ,2, 3-triyl). The polycarbodiimide composition of any one of embodiments 1 to 8, wherein m is an integer in the range of 2 to 18, preferably in the range of 3 to 17, more preferably in the range of 4 to 16, more preferably in the range of 5 to 15, more preferably in the range of 6 to 15. The polycarbodiimide composition of any one of embodiments 1 to 9, wherein p is an integer in the range of 1 to 5, preferably in the range of 1 to 4, more preferably in the range of 1 to 3. The polycarbodiimide composition of any one of embodiments 1 to 10, wherein n is an integer in the range of 2 to 18, preferably in the range of 3 to 17, more preferably in the range of 4 to 16, more preferably in the range of 5 to 15, more preferably in the range of 6 to 15. The polycarbodiimide composition of any one of embodiments 1 to 11 , wherein the polycarbodiimide comprises equal to or less than 100 weight-ppm of P, calculated as elemental P, and based on the total weight of the polycarbodiimide composition, preferably equal to or less than 90 weight-ppm, more preferably equal to or less than 80 weight-ppm, more preferably equal to or less than 75 weight-ppm, more preferably equal to or less than 70 weight-ppm, more preferably equal to or less than 65 weight-ppm, more preferably equal to or less than 60 weight-ppm, of P, calculated as elemental P, and based on the total weight of the polycarbodiimide composition. The polycarbodiimide composition of any one of embodiments 1 to 12, wherein the polycarbodiimide comprises equal to or less than 410 weight-ppm of phospholene oxides, calculated as sum of the weights of the phospholene oxides, and based on the total weight of the polycarbodiimide composition, preferably equal to or less than 370 weight-ppm, more preferably equal to or less than 335 weight-ppm, more preferably equal to or less than 295 weight-ppm, more preferably equal to or less than 280 weight-ppm, more preferably equal to or less than 260 weight-ppm, more preferably equal to or less than 240 weight-ppm, more preferably equal to or less than 220 weight-ppm, of phospholene oxides, calculated as sum of the weights of the phospholene oxides, and based on the total weight of the polycarbodiimide composition.

14. The polycarbodiimide composition of embodiment 13, wherein the phospholene oxides are selected from the group consisting of 1-methyl-2-phospholene-1 -oxide (MPO), 3- methyl-1 -phenyl-2-phospholene-1 -oxide (M PPO), 3-Methyl-1 -ethyl-2-phospholene-1 - oxide, 1 ,3-dimethyl-2-phospholene-1 -oxide, 1-phenyl-2-phospholene-1 -oxide, 1-ethyl-2- phospholene-1 -oxide, 1 -methyl-3-phospholene-1 -oxide, 3-methyl-1 -phenyl-3- phospholene-1 -oxide, 3-methyl-1-ethyl-3-phospholene-1 -oxide, 1 ,3-dimethyl-3- phospholene-1 -oxide, 1 -phenyl-3-phospholene-1 -oxide, 1 -ethyl-3-phospholene-1 -oxide, and mixtures of two or more thereof, preferably from the group consisting of 1 -methyl-2- phospholene-1 -oxide (MPO), 3-methyl-1-phenyl-2-phospholene-1 -oxide (MPPO), 3- methyl-1 -ethyl-2-phospholene-1 -oxide, 1 ,3-dimethyl-2-phospholene-1 -oxide, 1 -phenyl-2- phospholene-1 -oxide, 1-ethyl-2-phospholene-1 -oxide, and mixture of two or more thereof, wherein the one or more phospholene oxides are more preferably 1-methyl-2- phospholene-1 -oxide (MPO), 3-methyl-1-phenyl-2-phospholene-1 -oxide (MPPO), and mixtures thereof, wherein the phospholene oxides more preferably are 1-methyl-2- phospholene-1 -oxide (MPO).

15. The polycarbodiimide composition of any one of embodiments 1 to 14, wherein from 99.0 to 100 weight-%, preferably from 99.5 to 100 weight-%, more preferably from 99.9 to 100 weight-%, of the polycarbodiimide composition consist of the polycarbodiimide and P, preferably of the polycarbodiimide and the phospholene oxides.

16. The polycarbodiimide composition of any one of embodiments 1 to 15, having a viscosity in the range of from 5 to 20 Pa-s.

17. The polycarbodiimide composition of any one of embodiments 1 to 16, having a content of N=C=N-functional groups in the range of from 4.0 to 12.0 %, preferably in the range of from 6.0 to 9.8 %, more preferably in the range of from 6.2 to 9.6 %, wherein the content of N=C=N-functional groups is preferably determined according to Reference Example 1.

18. A process for the preparation of a polycarbodiimide composition, preferably for the preparation of a polycarbodiimide composition of any one of embodiments 1 to 17, the process comprising

(iii) adding one or more monoalcohols and one or more polyalcohols to the mixture obtained in (ii), wherein the one or more monoalcohols are independently from each other selected from the group consisting of optionally branched monohydroxy(Cn-C5o)alkanes and optionally branched monohydroxy(Cn-C5o)alkenes, wherein the one or more optionally branched monohydroxy(Cn-C5o)alkanes and optionally branched monohydroxy(Cn-C5o)alkenes independently from each other comprise an atomic ratio of carbon atoms, calculated as sum of carbon atoms comprised in the optionally branched monohydroxy(Cn-C5o)alkanes and optionally branched monohydroxy(Cn-C5o)alkenes, respectively, to oxygen atoms, calculated as sum of oxygen atoms comprised in the optionally branched monohydroxy(Cn- Cso)alkanes and optionally branched monohydroxy(Cn-C5o)alkenes, respectively, C:O, of equal to or greater than 11 , wherein the one or more polyalcohols independently from each other are selected from the group consisting of optionally branched and/or optionally alkoxylated, and optionally branched and/or optionally alkoxylated trihydroxyalkanes, wherein the dihydroxyalkanes consist of C, H, and O, wherein the trihydroxyalkanes consist of C, H, and O, and subjecting the resulting mixture to reaction conditions in a gas atmosphere, wherein the reaction conditions comprise heating the reaction mixture to a temperature in the range of 80 to 220 °C;

19. The process of embodiment 18, wherein the one or more phospholene oxides are selected from the group consisting of 1-methyl-2-phospholene-1 -oxide (MPO), 3-methyl-1- phenyl-2-phospholene-1 -oxide (MPPO), 3-methyl-1-ethyl-2-phospholene-1 -oxide, 1 ,3- dimethyl-2-phospholene-1 -oxide, 1 -phenyl-2-phospholene-1 -oxide, 1 -ethyl-2- phospholene-1 -oxide, 1 -methyl-3-phospholene-1 -oxide, 3-methyl-1 -phenyl-3- phospholene-1 -oxide, 3-methyl-1 -ethyl-3-phospholene-1 -oxide, 1 ,3-dimethyl-3- phospholene-1 -oxide, 1 -phenyl-3-phospholene-1 -oxide, 1 -ethyl-3-phospholene-1 -oxide, and mixture of two or more thereof, preferably from the group consisting of 1 -methyl-2- phospholene-1 -oxide (MPO), 3-methyl-1-phenyl-2-phospholene-1 -oxide (MPPO), 3- methyl-1 -ethyl-2-phospholene-1 -oxide, 1 ,3-dimethyl-2-phospholene-1 -oxide, 1 -phenyl-2- phospholene-1 -oxide, 1-ethyl-2-phospholene-1 -oxide, and mixture of two or more thereof, wherein the one or more phospholene oxides are more preferably 1-methyl-2- phospholene-1 -oxide (MPO), 3-methyl-1-phenyl-2-phospholene-1 -oxide (MPPO), and mixtures thereof, wherein the one or more phospholene oxides are more preferably 1- methyl-2-phospholene-1 -oxide (M PO).

20. The process of embodiment 18 or 19, wherein the mixture obtained in (i) has a molar ratio of 4,4'-diisocyanato dicyclohexylmethane, calculated as molar amount of 4,4'-diisocyanato dicyclohexylmethane, to the one or more phospholene oxides, calculated as sum of the molar amounts of the one or more phospholene oxides, in the range of from 10:1 to 1 ,000:1 , preferably in the range of from 50:1 to 750:1 , more preferably in the range of from 80:1 to 510:1 , more preferably in the range of from 150:1 to 450:1 , more preferably in the range of from 200:1 to 400:1 , more preferably in the range of from 300:1 to 350:1 .

21 . The process of any one of embodiments 18 to 20, wherein the mixture obtained in (i) comprises from 0 to 1 weight-%, preferably from 0 to 0.1 weight-%, more preferably from

0 to 0.01 weight-%, of xylene, preferably of an alkyl substituted benzene or an alkyl substituted dibenzene, wherein the alkyl comprises one or more of methyl, ethyl, and propyl, more preferably of a solvent, wherein the mixture obtained in (i) is more preferably substantially free of xylene, preferably substantially free of an alkyl substituted benzene or an alkyl substituted dibenzene, more preferably substantially free of a solvent.

22. The process of any one of embodiments 18 to 21 , wherein the carbodiimidization conditions in (ii) comprise heating the reaction mixture to a temperature in the range of 90 to 215 °C, more preferably in the range of 100 to 210 °C, more preferably in the range of 120 to 205 °C, more preferably in the range of 140 to 200 °C, more preferably in the range of 150 to 195 °C, more preferably in the range of 160 to 180 °C.

23. The process of any one of embodiments 18 to 22, wherein the gas atmosphere in (ii) comprises, preferably consists of, an inert gas, wherein the gas atmosphere in (ii) preferably comprises, more preferably consists of, one or more of nitrogen and argon.

24. The process of any one of embodiments 18 to 23, wherein the carbodiimidization conditions in (ii) comprise applying a pressure to the mixture obtained in (i) in the range of 1 to 1000 hPa, preferably in the range of 2 to 1000 hPa, more preferably in the range of 2.5 to 1000 hPa.

25. The process of any one of embodiments 18 to 24, wherein the carbodiimidization conditions in (ii) comprise agitating the mixture obtained in (i), preferably by stirring.

26. The process of any one of embodiments 18 to 25, wherein the mixture obtained in (i) is subjected to carbodiimidization conditions in (ii) for a duration in the range of from 1 to 50 h, preferably in the range of from 1 .5 to 40 h, more preferably in the range of from to 2 to 25 h.

27. The process of any one of embodiments 18 to 26, wherein the one or more monoalcohols added according to (iii) to the mixture obtained in (ii) are independently from each other selected from the group consisting of optionally branched monohydroxy(Ci2-C4o)alkanes and optionally branched monohydroxy(Ci2-C4o)alkenes, preferably from the group consisting of optionally branched monohydroxy(Ci3-C35)alkanes and optionally branched mono- hydroxy(Ci3-C35)alkenes, more preferably from the group consisting of optionally branched monohydroxy(Ci4-C3o)alkanes and optionally branched monohydroxy(Ci4-C3o)alkenes, more preferably from the group consisting of optionally branched monohydroxy(Ci5- C2s)alkanes and optionally branched monohydroxy(Ci5-C25)alkenes, more preferably from the group consisting of optionally branched monohydroxy(Ci6-C22)alkanes and optionally branched monohydroxy(Ci6-C22)alkenes, more preferably from the group consisting of optionally branched monohydroxy(Ci7-C2i)alkanes and optionally branched monohy- droxy(Ci7-C2i)alkenes, more preferably from the group consisting of optionally branched monohydroxy(Ci8-C2o)alkanes and optionally branched monohydroxy(Ci8-C2o)alkenes, wherein the one or more monoalcohols are independently from each other more preferably optionally branched monohydroxy(Ci8-C2o)alkanes or optionally branched monohy- droxy(Ci8-C2o)alkenes, more preferably branched monohydroxy(Ci8-C2o)alkanes or mono- hydroxy(Ci8-C2o)alkenes, more preferably branched monohydroxyC2oalkanes or monohy- droxyCisalkenes. The process of any one of embodiments 18 to 27, wherein the one or more monoalcohols added according to (iii) to the mixture obtained in (ii) are independently from each other selected from the group consisting of HO-(CH2)8-CH=CH-(CH2)7-CH₃, preferably HO- (CH₂)8-CH=CH-(CH₂)7-CH₃ in (Z)-configuration, and HO-CH₂-CH[(CH₂)7-CH₃][-(CH₂)9- CH₃], wherein the one or more monoalcohols are more preferably HO-(CH2)s-CH=CH- (CH₂)₇-CH₃, more preferably HO-(CH2)s-CH=CH-(CH2)7-CH₃ in (Z)-configuration, or HOCH 2-C H [(C H ₂)₇-C H ₃] [-(C H ₂)₉-C H ₃] . The process of any one of embodiments 18 to 28, wherein the one or more optionally branched monohydroxy(Cn-C5o)alkanes and optionally branched monohydroxy(Cn- Cso)alkenes independently from each other comprise an atomic ratio of carbon atoms, calculated as sum of carbon atoms comprised in the optionally branched monohy- droxy(Cn-C5o)alkanes and optionally branched monohydroxy(Cn-C5o)alkenes, respectively, to oxygen atoms, calculated as sum of oxygen atoms comprised in the optionally branched monohydroxy(Cn-C5o)alkanes and optionally branched monohydroxy(Cn- Cso)alkenes, respectively, C:O, in the range of 11 to 50, more preferably in the range of 12 to 40, more preferably in the range of 13 to 35, more preferably in the range of 14 to 30, more preferably in the range of 15 to 25, more preferably in the range of 16 to 22, more preferably in the range of 17 to 21 , more preferably in the range of 18 to 20, wherein the one or more optionally branched monohydroxy(Cn-C5o)alkanes and optionally branched monohydroxy(Cn-C5o)alkenes independently from each other comprise an atomic ratio of carbon atoms, calculated as sum of carbon atoms comprised in the one or more optionally branched monohydroxy(Cn-C5o)alkanes and optionally branched monohydroxy(Cn- Cso)alkenes, respectively, to oxygen atoms, calculated as sum of oxygen atoms comprised in the one or more optionally branched monohydroxy(Cn-C5o)alkanes and optionally branched monohydroxy(Cn-C5o)alkenes, respectively, C:O, of 18 or 20. The process of any one of embodiments 18 to 29, wherein the one or more polyalcohols added according to (iii) to the mixture obtained in (ii) independently from each other are selected from the group consisting of propane-1 ,2,3-triol , a triester of glycerol and ricinole- ic acid, HO-[CR5H-CH2-O]_XI-CR5H-CH2-OH, wherein Rs is H or CH3, wherein x1 is an integer in the range of from 1 to 15, HO-[CH2-CH2-O]_X2-CH2-CH2-O-ra/7-{[C(CH3)H-CH2- O]_X3-C(CH3)H-CH2}-OH, wherein x2 is an integer in the range of 1 to 15, wherein x3 is an integer in the range of 1 to 15, and HO-[CH2-CH2-CH2-CH2-O]_X4-CH2-CH2-CH2-CH2- OH, wherein x4 is an integer in the range of 1 to 30, preferably in the range of 1 to 15, and optionally branched and/or optionally alkoxylated dihydroxy(Ci-C2s)alkanes, preferably optionally branched and/or optionally alkoxylated dihydroxy(Ci-C2o)alkanes, more preferably optionally branched dihydroxy(C2-Cis)alkanes, more preferably optionally branched dihy- droxy(C3-Ci2)alkanes, more preferably optionally branched dihydroxy(C4-Cio)alkanes, more preferably optionally branched dihydroxy(Cs-Cs)alkanes, wherein the one or more polyalcohols independently from each other are more preferably selected from the group consisting of optionally branched dihydroxyCsalkanes, wherein the one or more polyalcohols are more preferably selected from the group consisting of branched dihydroxyCsalkanes. The process of any one of embodiments 18 to 30, wherein the one or more polyalcohols added according to (iii) to the mixture obtained in (ii) independently from each other are selected from the group consisting of optionally branched and/or optionally alkoxylated (C3-Cso)alkane-triols, preferably (C3-C4o)alkane-triols, more preferably (C3-C3o)alkane- triols, more preferably (C3-C2o)alkane-triols, more preferably (C3-Cio)alkane-triols, more preferably (C3-Cs)alkane-triols, a triester of glycerol and ricinoleic acid, wherein Rs is -[CR7H-CH2-O]_XI-CR7H-CH2-OH, wherein R7 is H or CH3, -[CH2-CH2- O]_X2-CH₂-CH₂-O-/-a/7-{[C(CH3)H-CH2-O]_X3-C(CH3)H-CH2}-OH, and -[CH₂-CH₂-CH₂- CH₂-O]_X4-CH2-CH2-CH2-CH₂-OH, wherein x1 is an integer in the range of 1 to 15, x2 is an integer in the range of 1 to 15, x3 is an integer in the range of 1 to 15, and x4 is an integer in the range of 1 to 30, preferably in the range of 1 to 15,

HO-(CH₂)₂-OH, HO-(CH₂)₃-OH, HO-(CH₂)₄-OH, HO-CH₂-CH₂-CH(CH₃)-OH, HO- (CH₂)5-OH, HO-CH₂-C(CH₃)2-CH₂-OH, HO-CH2-CH₂-CH2-CH(CH₃)-OH, HO-CH2- CH₂-CH(CH₃)-CH₂-OH, HO-(CH₂)₆-OH, HO-(CH₂)₇-OH, HO-(CH₂)₈-OH, HO-(CH₂)₉- OH, HO-(CH₂) -OH, and HO-(CH₂)I₂-OH, preferably from the group consisting of propane-1 ,2,3-triol , the triester of glycerol and ric- inoleic acid having formula (3)

(3), HO-CH₂-CH₂-CH(CH₃)-OH, HO-(CH₂)₅-OH, HO-CH₂-C(CH₃)₂-CH₂-OH, HO-CH₂-CH₂- CH₂-CH(CH₃)-OH, HO-CH₂-CH₂-CH(CH₃)-CH₂-OH, and HO-(CH₂)₆-OH, wherein the one or more polyalcohols added according to (iii) to the mixture obtained in (ii) independently from each other are more preferably selected from the group consisting of propane-1 ,2,3-triol, the triester of glycerol and ricinoleic acid having formula (3), and HO- (CH₂)₅-OH.

The process of any one of embodiments 18 to 31 , wherein the mixture obtained in (iii) comprises from 5 to 70 weight-%, preferably from 25 to 50 weight-%, of the one or more monoalcohols, calculated as sum of the weights of the one or more monoalcohols, based on the total weight of the mixture obtained in (iii).

The process of any one of embodiments 18 to 32, wherein the mixture obtained in (iii) comprises from 0.1 to 20 weight-%, preferably from 1 to 15 weight-%, of the one or more polyalcohols, calculated as sum of the weights of the one or more polyalcohols, based on the total weight of the mixture obtained in (iii).

The process of any one of embodiments 18 to 33, wherein the mixture obtained in (iii) comprises from 5.1 to 90 weight-%, preferably from 26 to 65 weight-%, of the one or more monoalcohols and of the one or more polyalcohols, calculated as sum of the weights of the one or more monoalcohols and of the weights of the one or more polyalcohols, respectively, based on the total weight of the mixture obtained in (iii).

The process of any one of embodiments 18 to 34, wherein the reaction conditions according to (iii) comprise heating the reaction mixture to a temperature in the range of 90 to 200 °C, preferably in the range of 100 to 195 °C, more preferably in the range of 110 to 190 °C, more preferably in the range of 120 to 185 °C, more preferably in the range of 130 to 180 °C, more preferably in the range of 140 to 175 °C, more preferably in the range of 150 to 170 °C. 36. The process of any one of embodiments 18 to 35, wherein removing at least a portion of the one or more phospholene oxides according to (iv) from the mixture obtained in (iii) comprises

(iv.1) optionally adding one or more entrainers to the mixture obtained in (iii), (iv.2) distilling the mixture obtained in (iii) or (iv.1 ) for obtaining a fraction comprising the polycarbodiimide composition and a fraction comprising at least a portion of the one or more phospholene oxides.

37. The process of embodiment 36, wherein the one or more entrainers have a boiling point in the range of 200 to 300 °C, preferably in the range of 200 to 250 °C, at a pressure in the range of 0.950 to 1.050 bar(abs), wherein the one or more entrainers are preferably selected from the group consisting of acetates comprising, preferably consisting of, C, H, and O, wherein the acetates comprise from 6 to 16, preferably from 8 to 14, C and O atoms, calculated as sum of carbon atoms and oxygen atoms, (Ci-C )alkyl(Ci- Cio)alkylether, di(Ci-Cs)alkyl adipates, and mixtures of two or more thereof, preferably from the group consisting of (Ci-C2)alkyloxy(C3-C5)alkyl acetates, diethylene glycol mono(C2-Ce)alkyl ether acetates, di(Ci-Cs)alkyl adipates, and mixtures of two or more thereof, more preferably from the group consisting of methoxybutyl acetate, diethylene glycol monobutyl ether acetate, diethyl adipate, diisopropyl adipate, dimethyl adipate, and mixtures of two or more thereof, wherein the one or more entrainers are more preferably diethyl adipate.

38. The process of embodiment 36 or 37, wherein distilling the mixture obtained in (iii) or (i v.1 ) is performed at a temperature in the range of from 130 to 190 °C, preferably in the range of from 140 to 180 °C, more preferably in the range of from 150 to 170 °C.

39. The process of any one of embodiments 36 to 38, wherein distilling the mixture obtained in (iii) or (iv.1) is performed at a pressure of less than 0.150 bar(abs), preferably less than 0.125 bar(abs), more preferably less than 0.100 bar(abs).

40. A polycarbodiimide composition obtainable or obtained by the process of any one of embodiments 18 to 39.

41 . Use of a polycarbodiimide composition of any one of embodiments 1 to 17 and 40, as a stabilizer, preferably as a hydrolysis stabilizer, for a polymer, more preferably for a thermoplastic polymer, more preferably for a thermoplastic polyester, more preferably for one or more of a polyurethane (PU), preferably a thermoplastic polyurethane (TPU), a polyurea, a polyethylene terephthalate (PET), a polybutylene terephthalate (PBT), a polyactide (PLA), a polyamide, a polyesteramide, a polycaprolactone, and a polyethersulfone (PES).

The present invention is further illustrated by the following reference examples, examples, and comparative examples. EXAMPLES

Reference Example 1 : Determination of FTIR spectra and ATR-FTI spectra

FTIR spectra, in particular for determination of characteristic bands for isocyanate groups, were recorded via single reflection ATR module on an Eco-ATR from Brucker. A sample was added directly onto the ATR crystal without any modification. Typically, it is expected that an isocyanate group NCO shows a band at about 2200 cm-¹ in the FTIR spectrum and that a carbodiimide (N=C=N) group shows a band at about 2100 cm-¹.

Reference Example 2: Determination of residual amounts of phosphorous

The phosphorous content was determined via elemental analysis (ICP-OES, DIN ISO 17025).

Comparative Example 1 : Preparation of a polycarbodiimide composition

143.0 g 1 ,1 '-methylenebis(4-isocyanatocyclohexane) (H12MDI; Evonik; 0.55 mol) and 0.14 g 1- methyl-phospholene-1 -oxide (MPO; 1.20 mmol) were charged into a 500 ml, 4-neck round bottom flask equipped with a thermometer (coupled with a temperature regulated oil-bath), mechanical stirring, a cold-water condenser and nitrogen inlet. The reaction mixture was stirred and heated to 170 °C. After approximately 17 hours, a second aliquot of MPO is added, (0.13 g; 1.11 mmol). After 20 hours the NCO content reached a value of 12.8 %. Subsequently 92.8 g oleyl alcohol and 8,1g neopentyl glycol were added. After a few hours, the NCO content reached 0.0 % (full urethane reaction) and the reaction mixture was cooled down. The corresponding product had a NCN content of 6.2 % and a MPO content of 1000 ppm).

Comparative Example 2: Preparation of a polycarbodiimide composition

492.50 g 1 ,1 '-methylenebis(4-isocyanatocyclohexane) (H12MDI; Evonik; 1.88 mol) and

375.00 g methoxy poly(ethylene glycol) (MPEG) with a molecular weight around 500 g/mol (Plu- riol A500E; BASF; 0.75 mol) were mixed charged into a 1000 ml, 4-neck round bottom flask equipped with a thermometer (coupled with a temperature regulated oil-bath), mechanical stirring, a cold-water condenser and nitrogen inlet. The reaction mixture was stirred and heated to 90 °C. After approximately 4 hours, the NCO content reached a value of 13,7 % (urethane reaction). The reaction temperature was then raised to 180 °C and 0,99 g 1-methyl-phospholene-1- oxide (MPO; 8.52 mmol) were added. After 71 hours, the NCO content reached 1 .1 % and the remaining NCO is endcapped by adding 113 g Pluriol A500E. After additional 5 hours the NCO content reached 0.0 %.

200 g of the product were then transferred into a 500 ml, 4-neck round bottom flask equipped with a thermometer (coupled with a temperature regulated oil-bath), mechanical stirring, a cold- water condenser and nitrogen inlet together with 200 g diethyl adipate (DEA). Diethyl adipate is then distillated off using a bridge (160°C and 34 mbar) in order to also remove some of the MPO remaining (DEA played the role of an entrainer). The corresponding product had a NCN content of 5.0 % and a MPO content of 650 ppm).

Comparative Example 3: Preparation of a polycarbodiimide composition

200.00 g 1 ,1 '-methylenebis(4-isocyanatocyclohexane) (H12MDI; Evonik; 0.76 mol) and 80.00 g oleyl alcohol (BASF, 0.30 mol) were charged into a 1000 ml, 4-neck round bottom flask equipped with a thermometer (coupled with a temperature regulated oil-bath), mechanical stirring, a cold-water condenser and nitrogen inlet. The reaction mixture was stirred and heated to 90 °C. After approximately 4 hours, the NCO content reached a value of 18.7 % (urethane reaction). The reaction temperature was then raised to 180 °C and 0.20 g 1-methyl-phospholene-1- oxide (MPO; 1 .72 mmol) were added. After 70 hours, the NCO content reached 1 .2 % and the remaining NCO was endcapped by adding 20 g oleyl alcohol. After additional 4 hours mixing, the NCO content reached 0.0 %. The reaction was cooled down to room temperature and 250 g diethyl adipate were then added. Diethyl adipate is then distillated off using a bridge (180 °C and 1 mbar) in order to also remove some of the MPO remaining (DEA played the role of an entrainer). The corresponding product had a NCN content of 4.8 % and a MPO content of 380 ppm).

Comparative Example 4: Preparation of a polycarbodiimide composition

The reaction was performed according to the reaction conditions of Comparative Example 2 with the difference that the 200 g dimethyl adipate instead of diethyl adipate was used as entrainer. After distillation at 180 °C and 50 mbar, the corresponding product had a NCN content of 5.0 % and a MPO content of 300 ppm.

Comparative Example 5: Preparation of a polycarbodiimide composition

200.0 g 1 ,1 '-methylenebis(4-isocyanatocyclohexane) (H12MDI; Evonik; 0.76 mol) and 0.2 g 1- methyl-phospholene-1 -oxide (MPO; 1.72 mmol) were charged into a 1000 ml, 4-neck round bottom flask equipped with a thermometer (coupled with a temperature regulated oil-bath), mechanical stirring, a cold-water condenser and nitrogen inlet. The reaction mixture was stirred and heated to 180 °C. After approximately 17 hours, the NCO content reached a value of 15.1 %. Subsequently 200.0 g oleyl alcohol were added. After 5 hours, the NCO content reached 0.0 % (full urethane reaction) and the reaction mixture was cool down. The reaction was cool down at room temperature and 400 g diethyl adipate were then added. Diethyl adipate is then distillated off using a bridge (180 °C and 5 mbar) in order to also remove some of the MPO remaining (DEA played the role of an entrainer). The operation is performed twice. The corresponding product had a NCN content of 11 .5 % and a MPO content of 124 ppm.

Example 6: Preparation of a polycarbodiimide composition in accordance with the present invention 130.0 g 1 ,1 '-methylenebis(4-isocyanatocyclohexane) (H12MDI; Evonik; 0.50 mol) and 0.26 g 1- methyl-phospholene-1 -oxide (MPO; 2.24 mmol) were charged into a 500 ml, 4-neck round bottom flask equipped with a thermometer (coupled with a temperature regulated oil-bath), mechanical stirring, a cold-water condenser and nitrogen inlet. The reaction mixture was stirred and heated to 180 °C. After 22 hours, the NCO content reached a value of 8.5 %. Subsequently 60.0 g oleyl alcohol and 10 g neopentyl glycol were added. After 5 hours, the NCO content reached 0.0 % (full urethane reaction) and the reaction mixture was cool down. The reaction was cool down at room temperature and 400 g diethyl adipate were then added. Diethyl adipate is then distillated off using a bridge (180 °C and 15 mbar) in order to remove some of the MPO remaining (DEA played the role of an entrainer). The operation is performed twice. The corresponding product had a NON content of 7.4 % and a MPO content of 225 ppm.

Example 7: Preparation of a polycarbodiimide composition in accordance with the present invention

150.0 g 1 ,1 '-methylenebis(4-isocyanatocyclohexane) (H12MDI; Evonik; 0.57 mol) and 0.15 g 1- methyl-phospholene-1 -oxide (MPO; 1 .29 mmol) were charged into a 500 ml, 4-neck round bottom flask equipped with a thermometer (coupled with a temperature regulated oil-bath), mechanical stirring, a cold-water condenser and nitrogen inlet. The reaction mixture was stirred and heated to 180 °C. After approximately 20 hours, the NCO content reached a value of 11.9 %. Subsequently 116.6 g 2-octyl-1 -dodecanol (Eutanol® G, BASF) and 2.3 g pentane-1 ,5- diol were added. After 4 hours, the NCO content reached 0.0 % (full urethane reaction) and the reaction mixture was cooled down to room temperature. Then, 200 g diethyl adipate were added. Diethyl adipate is then distillated off using a bridge (160 °C and 50 mbar) in order to remove some of the MPO remaining (DEA played the role of an entrainer). The operation is performed twice. The corresponding product had a NCN content of 9.4 % and a MPO content of 165 ppm.

Example 8: Preparation of a polycarbodiimide composition in accordance with the present invention

150.0 g 1 ,1 '-methylenebis(4-isocyanatocyclohexane) (H12MDI; Evonik; 0.57 mol) and 0.3 g 1- methyl-phospholene-1 -oxide (MPO; 2,58 mmol) were charged into a 500 ml, 4-neck round bottom flask equipped with a thermometer (coupled with a temperature regulated oil-bath), mechanical stirring, a cold-water condenser and nitrogen inlet. The reaction mixture was stirred and heated to 180 °C. After 18 hours, the NCO content reached a value of 10.8 %. Subsequently 84.3 g oleyl alcohol and 33.7 g of triester of glycerol and ricinoleic acid (Castor Oil) were added. After 5 hours, the NCO content reached 0.0 % (full urethane reaction) and the reaction mixture was cool down to room temperature. Then, 400 g diethyl adipate were added. Diethyl adipate is then distillated off using a bridge (180 °C and 10 mbar) in order to remove some of the MPO remaining (DEA played the role of an entrainer). The operation is performed twice. The corresponding product had a NCN content of 6.4 % and a MPO content of 150 ppm). Example 9: Preparation of a polycarbodiimide composition in accordance with the present invention

The reaction was performed according to the reaction conditions of the Comparative Example 1 with the difference that 115 g oleyl alcohol and 8.1 g glycerol were added instead of 92.8 g oleyl alcohol and 8.1 g neopentyl glycol. Finally, 200 g diethyl adipate were added. Diethyl adipate is then distillated off using a bridge (180 °C and 10 mbar) in order to remove some of the M PO remaining (DEA played the role of an entrainer). The operation is performed twice. The corresponding product had a NCN content of 6.7 % and a MPO content of 160 ppm).

Example 10: Determination of tensile strength of polycarbodiimide compositions

Thermoplastic polyurethane (TPU) compositions were prepared by hand cast procedure, wherein the TPU was based on 4,4’-MDI (methylene diphenyl diisocyanate), 1 ,2-ethylene glycol/adipic acid polyester polyol (molar mass of 500 to 3000 g/mol), and 1 ,4-butanediol as chain extender.

TPU compositions were prepared once without additional polycarbodiimide, and in the other cases by admixing approximately 1 .0 weight-% of a polycarbodiimide as hydrolysis stabilizer. In the latter cases, the polycarbodiimide was added to the pre-mixture of polyol and chain extender before the addition of the isocyanate in the hand cast procedure. The resulting TPU slaps for each composition were annealed at 110 °C for 3 h and then milled to granules.

After drying, the granules were first injection molded to test specimens and then further annealed at 100 °C for 10 h. The hydrolysis stability of the TPU injection molding parts was evaluated by storage of test specimen in water at 80 °C and subsequent periodical determination of the tensile strength (the tensile strength at the beginning, where t = 0, was set to 100 %).

The polycarbodiimide compositions according to Comparative Examples 1-5 and Examples 6-9 were thus tested as hydrolysis stabilizer in TPU. In this respect, the tensile strength was measured, wherein the performance was determined as number of days until the tensile strength reached 70 % of the initial value. In addition thereto, a Comparative Example 11 was tested similarly, wherein the TPU composition was tested alone, thus, without addition of any polycarbodiimide composition.

Table 1 below gives an overview of the polycarbodiimide compositions prepared including the alcohols used for their preparation. Further, the results of the tensile strength measurements are shown in table 2 below.

Table 1 :

Overview on polycarbodiimide compositions prepared.

Table 2:

Results of tensile strength measurements of TPU compositions with or without polycarbodiimide composition. As can be seen from the results, a polycarbodiimide composition comprising a comparatively high content of phospholene oxide catalyst shows an inferior performance in the testing. In contrast thereto, the polycarbodiimide compositions in accordance with the present invention, thus, being made from a combination of a monoalcohol and a dialcohol or polyalcohol, show a better performance.

Cited literature

- DE 11 2015 000659 T5

- EP 3875538 A1 - EP 3943550 A1

- EP 4053201 A1

- US 2020/017628 A1

- EP 3835333 A1

Claims

(1 ), and/or a polycarbodiimide having formula (2)

(2), wherein Ri is selected from the group consisting of optionally branched (Cn-C5o)alkoxy and optionally branched (Cn-C5o)alkenoxy, wherein Ri comprises an atomic ratio of carbon atoms, calculated as sum of carbon atoms comprised in Ri, to oxygen atoms, calculated as sum of oxygen atoms comprised in Ri , C:O, of equal to or greater than 11 , wherein R2 is -CeHs-CI-h-CeHs- (4,4’-diyldicyclohexylmethane), wherein R3 is selected from the group consisting of optionally branched and/or optionally alkoxylated alkylenes, wherein the alkylenes consist of C, H, and optionally O, , wherein R4 is selected from the group consisting of optionally branched and/or optionally alkoxylated alkane-triyls, wherein the alkane-triyls consist of C, H, and optionally O, wherein m is an integer in the range of 1 to 20, wherein p is an integer in the range of 1 to 10, wherein n is an integer in the range of 1 to 20, and wherein the polycarbodiimide composition comprises equal to or less than 110 weight- ppm of P, calculated as elemental P, and based on the total weight of the polycarbodiimide composition.

2. The polycarbodiimide composition of claim 1 , wherein Ri is selected from the group consisting of optionally branched (Ci2-C4o)alkoxy and optionally branched (Ci2-C4o)alkenoxy.

3. The polycarbodiimide composition of claim 1 or 2, wherein Ri is selected from the group consisting of -(CH₂)8-CH=CH-(CH₂)7-CH₃ and -CH2-CH[(CH₂)7-CH₃][-(CH₂)9-CH₃].

4. The polycarbodiimide composition of any one of claims 1 to 3, wherein Ri comprises an atomic ratio of carbon atoms, calculated as sum of carbon atoms comprised in Ri, to oxygen atoms, calculated as sum of oxygen atoms comprised in Ri, C:O, in the range of 11 to 50.

5. The polycarbodiimide composition of any one of claims 1 to 4, wherein Ri has a molecular weight greater than 210 g/mol.

6. The polycarbodiimide composition of any one of claims 1 to 5, wherein R3 is selected from the group consisting of optionally branched (Ci-C25)alkylenes, -[CRsH-CI-h-OJxi-CRsH- CH2-, wherein R5 is H or CH3, wherein x1 is an integer in the range of from 1 to 15, - [CH₂-CH2-O]x2-CH2-CH₂-O-/-a/7-{[C(CH3)H-CH2-O]x3-C(CH3)H-CH2}-, wherein x2 is an integer in the range of 1 to 15, wherein x3 is an integer in the range of 1 to 15, and -[CH2- CH₂-CH2-CH2-O]X4-CH2-CH2-CH2-CH₂-, wherein x4 is an integer in the range of 1 to 30.

7. The polycarbodiimide composition of any one of claims 1 to 6, wherein R4 is selected from the group consisting of optionally alkoxylated (C3-C5o)alkane-triyls, wherein Re is -[CR7H-CH2-O]_XI-CR7H-CH2-, wherein R7 is H or CH3, -[CH2-CH2-O]_X2- CH₂-CH2-O-^/7 [C(CH3)H-CH2-O]X3-C(CH3)H-CH₂}-, and -[CH₂-CH2-CH2-CH₂-O]x4- CH2-CH2-CH2-CH2-, wherein x1 is an integer in the range of 1 to 15, x2 is an integer in the range of 1 to 15, x3 is an integer in the range of 1 to 15, and x4 is an integer in the range of 1 to 30.

8. The polycarbodiimide composition of any one of claims 1 to 7, wherein m is an integer in the range of 2 to 18.

9. The polycarbodiimide composition of any one of claims 1 to 8, wherein p is an integer in the range of 1 to 5.

10. The polycarbodiimide composition of any one of claims 1 to 9, wherein n is an integer in the range of 2 to 18.

11 . The polycarbodiimide composition of any one of claims 1 to 10, wherein the polycarbodiimide comprises equal to or less than 410 weight-ppm of phospholene oxides, calculated as sum of the weights of the phospholene oxides, and based on the total weight of the polycarbodiimide composition.

12. The polycarbodiimide composition of claim 11 , wherein the phospholene oxides are selected from the group consisting of 1-methyl-2-phospholene-1 -oxide (MPO), 3-methyl-1- phenyl-2-phospholene-1 -oxide (MPPO), 3-Methyl-1-ethyl-2-phospholene-1 -oxide, 1 ,3- dimethyl-2-phospholene-1 -oxide, 1 -phenyl-2-phospholene-1 -oxide, 1 -ethyl-2- phospholene-1 -oxide, 1 -methyl-3-phospholene-1 -oxide, 3-methyl-1 -phenyl-3- phospholene-1 -oxide, 3-methyl-1-ethyl-3-phospholene-1 -oxide, 1 ,3-dimethyl-3- phospholene-1 -oxide, 1 -phenyl-3-phospholene-1 -oxide, 1 -ethyl-3-phospholene-1 -oxide, and mixtures of two or more thereof.

13. A process for the preparation of a polycarbodiimide composition, the process comprising

14. A polycarbodiimide composition obtainable or obtained by the process of claim 13.

15. Use of a polycarbodiimide composition of any one of claims 1 to 12 and 14, as a stabilizer.