TW202440703A - A polycarbodiimide composition as stabilizer for polymers - Google Patents

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

Polycarbodiimide compositions as polymer stabilizers

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

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

DE 11 2015 000659 T5 relates to a polyester resin composition containing a polyester resin and a carbodiimide compound, a method for preparing the polyester resin composition, and a molded product using the polyester resin composition.

EP 3875538 A1 relates to a polyester resin modifier suitable for improving the hydrolysis resistance of polyester resins, a preparation method thereof and a polyester resin composition. The disclosed polyester resin modifier is obtained by reacting aliphatic diisocyanate, isocyanate end-capping agent and carbodiimidization catalyst. The obtained polyester resin modifier includes a small amount of polycarbodiimide compound used as carbodiimidization catalyst for preparing the polyester resin modifier.

EP 3943550 A1 relates to a powdered polycarbodiimide compound capable of improving the hydrolysis resistance of an ester resin, and an ester resin composition comprising the compound.

EP 4053201 A1 relates to a compatibilizer for polyester resin to improve the compatibility between different types of resins, and a polyester resin composition using the compatibilizer.

US 2020/017628 A1 relates to a carboxyl-containing aqueous resin composition, a molded product formed from the resin composition, and a method for producing a polycarbodiimide compound used in the resin composition.

EP 3835333 A1 relates to a polycarbodiimide composition, a method for producing the polycarbodiimide composition, an aqueous dispersion composition, a solution composition, a resin composition, a resin cured product and a carbodiimide crosslinking agent for fiber processing.

However, the prior art does not mention a method for preparing polycarbodiimide in which at least a portion of the carbodiimidization catalyst is removed from the reaction mixture.

Polycarbodiimides are usually formed via condensation of diisocyanates. Subsequently, the polycarbodiimides are end-capped, for example with mono-OH-functionalized polyethylene oxide (PEO). Especially for thermoplastic polyurethane (TPU) applications, only meta-tetramethylxylylene diisocyanate (also abbreviated herein as m-TMXDI or TMXDI) has been shown to be useful as aliphatic isocyanate monomers to achieve good properties, especially with regard to its properties. However, attempts to transfer this concept to polycarbodiimides formed from alternative isocyanate monomers such as hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), or hydrogenated MDI (also known as H12MDI or 4,4'-diisocyanatodicyclohexylmethane) have failed.

One object of the present invention is to provide a novel polycarbodiimide composition having improved properties in terms of polymer stability.

Surprisingly, it has been found that polycarbodiimide compositions comprising a reduced amount of phosphorus, particularly reduced amounts of phospholene oxide, wherein the polycarbodiimide is end-capped with specific groups, exhibit improved performance in their properties as hydrolysis stabilizers for polymers.

In particular, it was found that a polycarbodiimide composition, wherein the polycarbodiimide is based on 4,4'-diisocyanatodicyclohexylmethane (H12MDI) end-capped with a relatively long alkyl chain, exhibits better performance in terms of hydrolytic stability when used in TPU, especially when compared to monool PEO.

Therefore, the present invention relates to a polycarbodiimide composition comprising a polycarbodiimide having formula (1): (1), and/or, preferably, a polycarbodiimide having formula (2) (2), wherein R ₁ is selected from the group consisting of optionally branched (C ₁₁ -C ₅₀ ) alkoxy groups and optionally branched (C ₁₁ -C ₅₀ ) alkenyloxy groups, wherein R ₁ comprises an atomic ratio of carbon atoms calculated based on the total carbon atoms contained in R ₁ to oxygen atoms calculated based on the total oxygen atoms contained in R ₁ , C:O, which is equal to or greater than 11, wherein R ₂ is -C ₆ H ₈ -CH ₂ -C ₆ H ₈ -(4,4'-diyldicyclohexylmethane), wherein R ₃ is selected from the group consisting of optionally branched and/or optionally alkoxylated alkylene groups, wherein the alkylene groups consist of C, H and optionally selected O, wherein R ₄ is selected from the group consisting of optionally branched and/or optionally alkoxylated alkanetriyl groups, wherein the alkanetriyl groups consist of C, H and optionally selected 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 contains equal to or less than 110 ppm by weight 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.

Preferably, _R1 is selected from the group consisting of an optionally branched ( _C12 - _C40 )alkoxy group and an optionally branched ( _C12 - _C40 )alkenyloxy group, more preferably selected from the group consisting of an optionally branched ( _C13 - _C35 )alkoxy group and an optionally branched ( _C13 - _C35 )alkenyloxy group, more preferably selected from the group consisting of an optionally branched ( _C14 - _C30 )alkoxy group and an optionally branched ( _C14 - _C30 )alkenyloxy group, more preferably selected from the group consisting of an optionally branched ( _C15 - _C25 )alkoxy group and an optionally branched ( _C15 - _C25 )alkenyloxy group, more preferably selected from the group consisting of an optionally branched ( _C16 - _C22) R1 is preferably an optionally branched ( _C18 - _C20 )alkoxy group or an optionally branched ( _C18 - _C20 )alkenyloxy group, more preferably a branched ( _C18 - _C20 )alkoxy group or a ( _C18 - _C20 )alkenyloxy group, more _preferably a branched _{(C18-C20)alkoxy group or a (C18-C20 ) alkenyloxy group , and} more preferably _a branched _C20alkoxy group or _{a C18alkenyloxy group .}

Preferably, R ₁ is selected from the group consisting of -(CH ₂ ) ₈ -CH=CH-(CH ₂ ) ₇ -CH ₃ , preferably -(CH ₂ ) ₈ -CH=CH-(CH ₂ ) ₇ -CH ₃ in (Z) configuration, and -CH ₂ -CH[(CH ₂ ) ₇ -CH ₃ ][-(CH ₂ ) ₉ -CH ₃ ], wherein R ₁ is more preferably -(CH ₂ ) ₈ -CH=CH-(CH ₂ ) ₇ -CH ₃ , more preferably -(CH ₂ ) ₈ -CH=CH-(CH ₂ ) ₇ -CH ₃ in (Z) configuration, or -CH ₂ -CH[(CH ₂ ) ₇ -CH ₃ ][-(CH ₂ ) ₉ -CH ₃ ].

Preferably, _R1 comprises an atomic ratio of carbon atoms calculated based on the total carbon atoms contained in R1 to oxygen atoms calculated based on the total oxygen atoms contained in _{R1, 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 _R1 comprises an atomic ratio of carbon atoms calculated based on the total carbon atoms contained in _R1 to oxygen atoms calculated based on the total oxygen atoms contained in R1, C:O, of 18 or 20.

Preferably, _R1 has a molecular weight greater than 210 g/mol, more preferably in the range of greater than 210 g/mol to 700 g/mol, more preferably in the range of 220 g/mol 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.

Preferably, _R3 is selected from the group consisting of an optionally branched ( _C1 - _C25 ) alkylene group, -[ _CR5H - _CH2 -O] _x1 - _CR5H - _CH2- , wherein _R5 is H or _CH3 , wherein x1 is an integer in the range of 1 to 15, -[ _CH2 - _CH2 -O] _x2 - _CH2 - _CH2 -O- ran -{[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 1 to 15, more preferably selected from the group consisting of optionally branched (C ₁ -C ₂₅ ) alkylene groups, more preferably selected from the group consisting of optionally branched (C ₁ -C ₂₀ ) alkylene groups, more preferably selected from the group consisting of optionally branched (C ₂ -C ₁₅ ) alkylene groups, more preferably selected from the group consisting of optionally branched (C ₃ -C ₁₂ ) alkylene groups, more preferably selected from the group consisting of optionally branched (C ₄ -C _{10 )} alkylene groups, more preferably selected from the group consisting of optionally branched (C ₅ -C ₆ ) alkylene groups, wherein R ₃ is more preferably selected from the group consisting of optionally branched C ₅ alkylene groups, wherein R ₃ is more preferably selected from the group consisting of optionally branched C A group consisting of ₅ -alkylene groups.

Preferably, _R3 is selected from the group consisting of an optionally branched ( _C1 - _C25 ) alkylene group, -[ _CR5H - _CH2 -O] _x1 - _CR5H - _CH2- , wherein _R5 is H or _CH3 , wherein x1 is an integer in the range of 1 to 15, -[ _CH2 - _CH2 -O] _x2 - _CH2 - _CH2 -O- ran -{[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, and is more preferably selected from the group consisting of optionally branched (C ₁ -C ₂₅ ) alkylene groups, and more preferably selected from the group consisting of -(CH ₂ ) ₂ -, -(CH ₂ ) ₃ -, -(CH ₂ ) ₄ -, -CH ₂ -CH ₂ -CH(CH ₃ )-, -(CH ₂ ) ₅ -, -CH ₂ -C(CH ₃ ) ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -CH(CH ₃ )-, -CH ₂ -CH ₂ -CH(CH ₃ )-CH ₂ -, -(CH ₂ ) ₆ -, -(CH ₂ ) ₇ -, -(CH ₂ ) ₈ -, -(CH ₂ ) ₉ -, -(CH ₂ ) _{R 10} - and -(CH ₂ ) ₁₂ - are more preferably selected from the group consisting of -CH ₂ -CH ₂ -CH(CH ₃ ) -, -(CH ₂ ) ₅ -, -CH ₂ -C(CH ₃ ) ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -CH(CH _{3 ) -, -CH 2 -CH 2 -CH(CH 3} ) -, -CH ₂ -CH ₂ -CH(CH ₃ ) -CH ₂ - and -(CH ₂ ) ₆ -, wherein R ₃ is more preferably -CH ₂ -C(CH ₃ ) ₂ -CH ₂ - or -(CH ₂ ) ₅ -.

Preferably, R ₄ is selected from the group consisting of: optionally alkoxylated (C ₃ -C ₅₀ ) alkanetriyl, , and wherein R ₆ is -[CR ₇ H-CH ₂ -O] _x1 -CR ₇ H-CH ₂ -, wherein R ₇ is H or CH ₃ , wherein x1 is an integer in the range of 1 to 15, -[CH ₂ -CH ₂ -O] _x2 -CH ₂ -CH ₂ -O- ran -{[C(CH ₃ )H-CH ₂ -O] _x3 -C(CH ₃ )H-CH ₂ }-, 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 -[CH ₂ -CH ₂ -CH ₂ -CH ₂ -O] _x4 -CH ₂ -CH ₂ -CH ₂ -CH ₂ -, wherein x4 is in the range of 1 to 30, preferably an integer in the range of 1 to 15, wherein R ₄ is more preferably selected from the group consisting of: optionally alkoxylated (C ₃ -C ₅₀ )alkanetriyl, and , wherein R ₄ is more preferably selected from the group consisting of (C ₃ -C ₄₀ )alkanetriyl, more preferably (C ₃ -C ₃₀ )alkanetriyl, more preferably (C ₃ -C ₂₀ )alkanetriyl, more preferably (C ₃ -C ₁₀ )alkanetriyl, more preferably (C ₃ -C ₅ )alkanetriyl, wherein R ₄ is more preferably (Propane-1,2,3-triyl).

Preferably, 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, and more preferably in the range of 6 to 15.

Preferably, p is an integer in the range of 1 to 5, more preferably in the range of 1 to 4, and even more preferably in the range of 1 to 3.

Preferably, 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, and more preferably in the range of 6 to 15.

Preferably, the polycarbodiimide contains P equal to or less than 100 wt ppm, calculated as elemental P and based on the total weight of the polycarbodiimide composition, more preferably equal to or less than 90 wt ppm, more preferably equal to or less than 80 wt ppm, more preferably equal to or less than 75 wt ppm, more preferably equal to or less than 70 wt ppm, more preferably equal to or less than 65 wt ppm, more preferably equal to or less than 60 wt ppm of P, calculated as elemental P and based on the total weight of the polycarbodiimide composition.

Preferably, the polycarbodiimide contains 410 wt ppm or less of phosphane oxide, calculated as the total weight of the phosphane oxides and based on the total weight of the polycarbodiimide composition, more preferably 370 wt ppm or less, more preferably 335 wt ppm or less, more preferably 295 wt ppm or less, more preferably 280 wt ppm or less, more preferably 260 wt ppm or less, more preferably 240 wt ppm or less, more preferably 220 wt ppm of phosphane oxide, calculated as the total weight of the phosphane oxides and based on the total weight of the polycarbodiimide composition.

In the case where the polycarbodiimide comprises 410 ppm by weight or less of phosphane oxide, calculated as the total weight of the phosphane oxide and based on the total weight of the polycarbodiimide composition, the phosphane oxide is preferably selected from the group consisting of 1-methyl-2-phosphane-1-oxide (MPO), 3-methyl-1-phenyl-2-phosphane-1-oxide (MPPO), 3-methyl-1-ethyl-2-phosphane-1-oxide (MPO), Phosphene-1-oxide, 1,3-dimethyl-2-cyclophosphene-1-oxide, 1-phenyl-2-cyclophosphene-1-oxide, 1-ethyl-2-cyclophosphene-1-oxide, 1-methyl-3-cyclophosphene-1-oxide, 3-methyl-1-phenyl-3-cyclophosphene-1-oxide, 3-methyl-1-ethyl-3-cyclophosphene-1-oxide, 1,3-dimethyl-3-cyclophosphene-1-oxide, 1- Phenyl-3-cyclophosphene-1-oxide, 1-ethyl-3-cyclophosphene-1-oxide, and a mixture of two or more thereof, more preferably selected from the group consisting of 1-methyl-2-cyclophosphene-1-oxide (MPO), 3-methyl-1-phenyl-2-cyclophosphene-1-oxide (MPPO), 3-methyl-1-ethyl-2-cyclophosphene-1-oxide, 1,3-dimethyl-2-cyclophosphene-1-oxide, 1-phenyl-2-cyclophosphene-1-oxide, 1-ethyl-2-cyclophosphene-1-oxide, and a mixture of two or more thereof, wherein one or more of the cyclophosphene oxides are more preferably 1-methyl-2-cyclophosphene-1-oxide (MPO), 3-methyl-1-phenyl-2-cyclophosphene-1-oxide (MPPO), and a mixture thereof, wherein the cyclophosphene oxide is more preferably 1-methyl-2-cyclophosphene-1-oxide (MPO).

Preferably, 99.0 to 100% by weight, more preferably 99.5 to 100% by weight, and more preferably 99.9 to 100% by weight of the polycarbodiimide composition consists of polycarbodiimide and P, and more preferably consists of polycarbodiimide and phosphine oxide.

Preferably, the polycarbodiimide composition has a viscosity in the range of 5 to 20 Pa·s.

Preferably, the polycarbodiimide composition has an N=C=N-functional group content in the range of 4.0 to 12.0%, more preferably in the range of 6.0 to 9.8%, and more preferably in the range of 6.2 to 9.6%, wherein the content of the N=C=N-functional group is more preferably determined according to Reference Example 1.

A method for preparing a polycarbodiimide composition, preferably a polycarbodiimide composition of any one of the embodiments disclosed herein, comprising: (i) preparing a mixture comprising 4,4'-diisocyanatodicyclohexylmethane and one or more phosphine 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 monohydric alcohols and one or more polyhydric alcohols to the mixture obtained in (ii), wherein the one or more monohydric alcohols are independently selected from the group consisting of optionally branched monohydroxy (C 11 -C 50 ) alkanes and optionally branched _monohydroxy (C ₁₁ -C ₅₀ ) alkanes. wherein one or more optionally branched monohydroxy (C ₁₁ -C ₅₀ )alkane and optionally branched monohydroxy (C ₁₁ -C ₅₀ )alkene independently contain an atomic ratio of carbon atoms calculated based on the total carbon atoms contained in each of the optionally branched monohydroxy (C ₁₁ -C ₅₀ )alkane and the optionally branched monohydroxy (C ₁₁ -C ₅₀ )alkene to oxygen atoms calculated based on the total oxygen atoms contained in each of the optionally branched monohydroxy (C ₁₁ -C ₅₀ )alkane and the optionally branched monohydroxy (C ₁₁ -C ₅₀ )alkene, C:O, which is equal to or greater than 11 _. wherein the one or more polyols are independently selected from the group consisting of optionally branched and/or optionally alkoxylated dihydroxyalkanes and optionally branched and/or optionally alkoxylated trihydroxyalkanes, wherein the dihydroxyalkanes consist of C, H and O, and wherein the trihydroxyalkanes consist of C, H and O, and subjecting the resulting mixture to reaction conditions under 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 phosphine oxides from the mixture obtained in (iii); to obtain a polycarbodiimide composition.

Preferably, the one or more phosphane oxides are selected from the group consisting of: 1-methyl-2-phosphane-1-oxide (MPO), 3-methyl-1-phenyl-2-phosphane-1-oxide (MPPO), 3-methyl-1-ethyl-2-phosphane-1-oxide, 1,3-dimethyl-2-phosphane-1-oxide, 1-phenyl-2-phosphane-1-oxide, 1-ethyl-2-phosphane-1-oxide, 1-methyl-3-phosphane-1-oxide, 3-methyl-1-phenyl-3-phosphane-1-oxide, 3-methyl-1-ethyl-3-phosphane-1-oxide, 1,3-dimethyl-3-phosphane-1-oxide, 1-phenyl-3-phosphane-1-oxide, 1-ethyl-3-phosphane-1-oxide The phosphine oxide is preferably selected from the group consisting of 1-methyl-2-cyclophosphine-1-oxide (MPO), 3-methyl-1-phenyl-2-cyclophosphine-1-oxide (MPPO), 3-methyl-1-ethyl-2-cyclophosphine-1-oxide, 1,3-dimethyl-2-cyclophosphine-1-oxide, 1-phenyl-2-cyclophosphine-1-oxide, 1-ethyl-2-cyclophosphine-1-oxide and a mixture of two or more thereof, wherein one or more phosphine oxides are more preferably 1-methyl-2-cyclophosphine-1-oxide (MPO), 3-methyl-1-phenyl-2-cyclophosphine-1-oxide (MPPO) and a mixture thereof, wherein the phosphine oxide is more preferably 1-methyl-2-cyclophosphine-1-oxide (MPO).

Preferably, the mixture obtained in (i) has a molar ratio of 4,4'-diisocyanatodicyclohexylmethane calculated on the molar amount of 4,4'-diisocyanatodicyclohexylmethane to one or more phosphene oxides calculated on the molar amount of the one or more phosphene oxides in the range of 10:1 to 1,000:1, more preferably in the range of 50:1 to 750:1, more preferably in the range of 80:1 to 510:1, more preferably in the range of 150:1 to 450:1, more preferably in the range of 200:1 to 400:1, more preferably in the range of 300:1 to 350:1.

Preferably, the mixture obtained in (i) contains 0 to 1% by weight, more preferably 0 to 0.1% by weight, more preferably 0 to 0.01% by weight of xylene, more preferably alkyl-substituted benzene or alkyl-substituted diphenyl, wherein the alkyl group comprises one or more of methyl, ethyl and propyl, and more preferably a solvent, wherein the mixture obtained in (i) preferably contains substantially no xylene, more preferably contains substantially no alkyl-substituted benzene or alkyl-substituted diphenyl, and more preferably contains substantially no solvent.

Preferably, 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.

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

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

Preferably, the carbodiimidization conditions in (ii) comprise agitating the mixture obtained in (i), preferably by stirring.

Preferably, the mixture obtained in (i) is subjected to the carbodiimidization conditions in (ii) for a period of time ranging from 1 to 50 hours, more preferably from 1.5 to 40 hours, and more preferably from 2 to 25 hours.

Preferably, the one or more monohydric alcohols added to the mixture obtained in (ii) according to (iii) are independently selected from the group consisting of optionally branched monohydroxy (C ₁₂ -C ₄₀ ) alkanes and optionally branched monohydroxy (C ₁₂ -C ₄₀ ) alkenes, more preferably selected from the group consisting of optionally branched monohydroxy (C ₁₃ -C ₃₅ ) alkanes and optionally branched monohydroxy (C ₁₃ -C ₃₅ ) alkenes, more preferably selected from the group consisting of optionally branched monohydroxy (C ₁₄ -C ₃₀ ) alkanes and optionally branched monohydroxy (C ₁₄ -C _{30 )} alkenes. The group consisting of optionally branched monohydroxy (C ₁₅ -C ₂₅ )alkane and optionally branched monohydroxy (C ₁₅ -C ₂₅ )alkene is more preferably selected from the group consisting of optionally branched monohydroxy (C ₁₆ -C ₂₂ )alkane and optionally branched monohydroxy (C ₁₆ -C ₂₂ )alkene, more preferably selected from the group consisting of optionally branched monohydroxy (C ₁₇ -C ₂₁ )alkane and optionally branched monohydroxy (C ₁₇ -C ₂₁ )alkene, more preferably selected from the group consisting of optionally branched monohydroxy (C ₁₈ -C ₂₀ )alkane and optionally branched monohydroxy (C ₁₈ -C ₂₀ )alkene, wherein the one or more monohydric alcohols are more preferably independently optionally branched monohydroxy (C ₁₈ -C ₂₀ )alkane or optionally branched monohydroxy (C ₁₈ -C ₂₀ )alkene, more preferably branched monohydroxy (C ₁₈ -C ₂₀ )alkane or monohydroxy (C ₁₈ -C ₂₀ )alkene, more preferably branched monohydroxy C ₂₀ alkane or monohydroxy C ₁₈ alkene.

Preferably, the one or more monohydric alcohols added to the mixture obtained in (ii) according to (iii) are independently selected from the group consisting of HO-(CH ₂ ) ₈ -CH=CH-(CH ₂ ) ₇ -CH ₃ , preferably HO-(CH ₂ ) ₈ -CH=CH-(CH ₂ ) ₇ -CH ₃ in (Z) configuration, and HO-CH ₂ -CH[(CH ₂ ) ₇ -CH ₃ ][-(CH ₂ ) ₉ -CH ₃ ], wherein the one or more monohydric alcohols are more preferably HO-(CH ₂ ) ₈ -CH=CH-(CH ₂ ) ₇ -CH ₃ , more preferably HO-(CH 2 ) ₈ -CH=CH-(CH ₂ ) ₇ -CH ₃ in (Z) configuration, or HO-CH ₂ -CH[(CH ₂ ) ₇ -CH 3][-(CH ₂ ) 9 -CH 3 ] ₃ ][-(CH ₂ ) ₉ -CH ₃ ].

Preferably, the number of one or more optionally branched monohydroxy (C ₁₁ -C ₅₀ ) alkane and optionally branched monohydroxy (C ₁₁ -C ₅₀ ) alkene is independently within the range of 11 to 50, more preferably within the range of 12 to 40, more preferably within the range of 13 to 35, more preferably within the range of 14 to 30, more preferably within the range of 15 to 25, more preferably within the range of 16 to 22, more preferably within the range of 17 to ₂₁ , and more preferably within the range of ₁₈ to _{20 .} The atomic ratio of carbon atoms calculated as the total carbon atoms of the optionally branched monohydroxy (C ₁₁ -C ₅₀ )alkane and the optionally branched monohydroxy (C 11 -C ₅₀ )alkene to oxygen atoms calculated as the total oxygen atoms contained in each of the optionally branched monohydroxy (C ₁₁ -C 50 )alkane and the optionally branched monohydroxy (C _{11 -C 50 )alkene, C:O, wherein the one or more optionally branched monohydroxy (C 11} -C ₅₀ )alkane and the optionally branched monohydroxy (C ₁₁ -C ₅₀ )alkene each independently contains 18 or 20 carbon atoms, and the atomic ratio of oxygen atoms calculated as the total oxygen atoms contained in each of the one or more optionally branched monohydroxy (C ₁₁ -C ₅₀ )alkane and the optionally branched monohydroxy (C ₁₁ -C _{50 )} alkene each independently contains 18 or 20 carbon atoms. )olefins to the total of oxygen atoms contained in one or more optionally branched monohydroxy (C ₁₁ -C ₅₀ )alkane and optionally branched monohydroxy (C ₁₁ -C ₅₀ )alkene, respectively, C:O.

Preferably, the one or more polyols added to the mixture obtained in (ii) according to (iii) are independently selected from the group consisting of propane-1,2,3-triol, triesters of glycerol and ricinoleic acid, HO-[ _CR5H - _CH2 -O] _x1 - _CR5H - _CH2- OH, wherein _R5 is H or _CH3 , wherein x1 is an integer in the range of 1 to 15, HO-[ _CH2 - _CH2 -O] _x2 - _CH2 - _CH2 -O- ran -{[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 -CH ₂ - _CH2 - _CH2 -OH, wherein x4 is an integer in the range of 1 to 30, preferably 1 to 15, and is optionally branched and/or optionally alkoxylated dihydroxy ( _C1 - _C25 ) alkane, more preferably optionally branched and/or optionally alkoxylated dihydroxy ( _C1 - _C20 ) alkane, more preferably optionally branched dihydroxy ( _C2 - _C15 ) alkane, more preferably optionally branched dihydroxy ( _C3 - _C12 ) alkane, more preferably optionally branched dihydroxy ( _C4 - _C10 ) alkane, more preferably optionally branched dihydroxy ( _C5 - _C6) alkane. )alkanes, wherein the one or more polyols are independently more preferably selected from the group consisting of optionally branched dihydroxy _C5 alkanes, wherein the one or more polyols are more preferably selected from the group consisting of branched dihydroxy _C5 alkanes.

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

Preferably, the one or more polyols added to the mixture obtained in (ii) according to (iii) are independently selected from the group consisting of: optionally branched and/or optionally alkoxylated (C ₃ -C ₅₀ )alkane-triols, more preferably (C ₃ -C ₄₀ )alkane-triols, more preferably (C ₃ -C ₃₀ )alkane-triols, more preferably (C ₃ -C ₂₀ )alkane-triols, more preferably (C ₃ -C ₁₀ )alkane-triols, more preferably (C ₃ -C ₅ )alkane-triols, triesters of glycerol and ricinoleic acid, ,and wherein _R6 is -[ _CR7H - _CH2 -O] _x1 - _CR7H -CH2 _- OH, wherein _R7 is H or _CH3 , -[ _CH2 - _CH2 -O] _x2 - _CH2-CH2 - _O - ran -{[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 an integer in the range of 1 to 15, HO-( _CH2 ) ₂ -OH, HO-( _CH2 ) ₃ -OH, HO-(CH ₂ ) ₄ -OH, HO-CH ₂ -CH ₂ -CH(CH ₃ )-OH, HO-(CH ₂ ) ₅ -OH, HO-CH ₂ -C(CH ₃ ) ₂ -CH ₂ -OH, HO-CH ₂ -CH ₂ -CH ₂ -CH(CH ₃ )-OH, HO-CH ₂ -CH ₂ -CH(CH ₃ )-OH, HO-CH 2 -CH ₂ -CH(CH 3 )-CH 2 -OH, HO-(CH ₂ ) ₆ -OH, HO-(CH ₂ ) ₇ -OH, HO-(CH ₂ ) ₈ -OH, HO-(CH ₂ ) ₉ -OH, HO-(CH ₂ ) ₁₀ -OH and HO-(CH ₂ ) ₁₂ -OH, more preferably selected from the group consisting of propane-1,2,3-triol, glycerol and triesters of ricinoleic acid, the triesters of glycerol and ricinoleic acid having the 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)-OH, HO- _CH2 - _CH2 -CH( _CH3 )-CH2 _- OH and HO-( _CH2 ) ₆ -OH, wherein the one or more polyols added to the mixture obtained in (ii) according to (iii) are independently preferably selected from the group consisting of propane-1,2,3-triol, triesters of glycerol and ricinoleic acid having formula (3) and HO-( _CH2 ) ₅ -OH.

Preferably, the mixture obtained in (iii) comprises 5 to 70 wt %, more preferably 25 to 50 wt %, of the one or more monohydric alcohols, calculated as the sum of the weights of the one or more monohydric alcohols, based on the total weight of the mixture obtained in (iii).

Preferably, the mixture obtained in (iii) comprises 0.1 to 20 wt %, more preferably 1 to 15 wt %, of one or more polyols, calculated as the sum of the weights of the one or more polyols, based on the total weight of the mixture obtained in (iii).

Preferably, the mixture obtained in (iii) comprises 5.1 to 90 wt. %, more preferably 26 to 65 wt. %, of one or more monohydric alcohols and 5.1 to 90 wt. %, more preferably 26 to 65 wt. %, of one or more polyhydric alcohols, calculated as the total weight of the one or more monohydric alcohols and the total weight of the one or more polyhydric alcohols, respectively, based on the total weight of the mixture obtained in (iii).

Preferably, 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.

Preferably, removing at least a portion of one or more phosphine oxides according to (iv) from the mixture obtained in (iii) comprises: (iv.1) adding one or more entrainers to the mixture obtained in (iii) as needed, (iv.2) distilling the mixture obtained in (iii) or (iv.1) to obtain a distillate containing a polycarbodiimide composition and a distillate containing at least a portion of one or more phosphine oxides.

In case that at least a portion of the one or more phosphine oxides according to (iv) are removed from the mixture obtained in (iii) comprises (iv.1) and (iv.2) as appropriate, preferably, the one or more azeotropes 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 (absolute) bar, wherein the one or more azeotropes are more preferably selected from the group consisting of acetates containing C, H and O, more preferably from the group consisting of C, H and O, wherein the acetate contains 6 to 16, preferably 8 to 14 C and O atoms, calculated as the sum of carbon atoms and oxygen atoms, (C ₁ -C ₁₀ )alkyl (C _{1 -C 10 )alkyl ethers, di(C 1} -C ₁₀ ) _adipic acid, The azeotropic agent is preferably selected from the group consisting of ( _C1 - _C2 )alkoxy ( _C3 - _C5 )alkyl acetate, diethylene glycol mono( _C2 - _C6 )alkyl ether acetate, adipate di( _C1 - _C5 )alkyl ester and a mixture of two or more thereof, more preferably selected from the group consisting of methoxybutyl acetate, diethylene glycol monobutyl ether acetate, diethyl adipate, diisopropyl adipate, dimethyl adipate and a mixture of two or more thereof, wherein _the one or more azeotropic agents are more preferably diethyl adipate.

Furthermore, when removing at least a portion of one or more phosphine oxides according to (iv) from the mixture obtained in (iii) comprises (iv.1) and (iv.2) as required, preferably, the distillation of the mixture obtained in (iii) or (iv.1) is carried out at a temperature in the range of 130 to 190°C, more preferably in the range of 140 to 180°C, and more preferably in the range of 150 to 170°C.

Furthermore, when removing at least a portion of the one or more phosphine oxides according to (iv) from the mixture obtained in (iii) comprises (iv.1) and (iv.2) as required, preferably, the distillation of the mixture obtained in (iii) or (iv.1) is carried out at a pressure of less than 0.150 (absolute) bar, more preferably less than 0.125 (absolute) bar, and more preferably less than 0.100 (absolute) bar.

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

A use of a polycarbodiimide composition according to any of the embodiments disclosed herein as a stabilizer, preferably as a hydrolysis stabilizer, for a polymer, preferably a thermoplastic polymer, preferably a thermoplastic polyester, more preferably a polyurethane (PU), preferably a thermoplastic polyurethane (TPU), polyurea, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polylactic acid (PLA), polyamide, polyesteramide, polycaprolactone and polyethersulfone (PES) One or more.

The unit bar (abs) refers to absolute pressure, where 1 bar is equal to 10 ⁵ Pa.

The present invention is further illustrated by the following specific example group and the combination of specific examples generated by the indicated dependencies and back references. In particular, it is worth noting that in each case of referring to a series of specific examples, for example, in the context of the term "polycarbodiimide composition of any one of specific examples 1 to 4", it means that each specific example within the scope is clearly disclosed to a person skilled in the art, that is, the wording of the term should be understood by a person skilled in the art as being synonymous with "polycarbodiimide composition of any one of specific examples 1, 2, 3 and 4". In addition, it is explicitly pointed out that the following specific example group is not a claim group for determining the scope of protection, but represents a suitable structural part of the description of the general and preferred aspects of the present invention.

1. A polycarbodiimide composition comprising a polycarbodiimide having formula (1) (1), and/or, preferably, a polycarbodiimide having formula (2) (2), wherein R ₁ is selected from the group consisting of optionally branched (C ₁₁ -C ₅₀ ) alkoxy groups and optionally branched (C ₁₁ -C ₅₀ ) alkenyloxy groups, wherein R ₁ comprises an atomic ratio of carbon atoms calculated based on the total carbon atoms contained in R ₁ to oxygen atoms calculated based on the total oxygen atoms contained in R ₁ , C:O, which is equal to or greater than 11, wherein R ₂ is -C ₆ H ₈ -CH ₂ -C ₆ H ₈ -(4,4'-diyldicyclohexylmethane), wherein R ₃ is selected from the group consisting of optionally branched and/or optionally alkoxylated alkylene groups, wherein the alkylene groups consist of C, H and optionally selected O, wherein R ₄ is selected from the group consisting of optionally branched and/or optionally alkoxylated alkanetriyl groups, wherein the alkanetriyl groups consist of C, H and optionally selected 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 contains equal to or less than 110 ppm by weight 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.

2. The polycarbodiimide composition of embodiment 1, wherein _R1 is selected from the group consisting of an optionally branched ( _C12 - _C40 ) alkoxy group and an optionally branched ( _C12 - _C40 ) alkenyloxy group, preferably selected from the group consisting of an optionally branched ( _C13 - _C35 ) alkoxy group and an optionally branched ( _C13 - _C35 ) alkenyloxy group, more preferably selected from the group consisting of an optionally branched ( _C14 - _C30 ) alkoxy group and an optionally branched ( _C14 - _C30 ) alkenyloxy group, more preferably selected from the group consisting of an optionally branched ( _C15 - _{C25) alkoxy group and an optionally branched (C15-C25} ) alkenyloxy group, more preferably selected from the group consisting of an optionally branched ( _C15 - _{C25) alkoxy group and an optionally branched (C15-C25} ) alkenyloxy group, Preferably, R 1 is an optionally branched (C ₁₆ -C ₂₂ )alkoxy group and an optionally branched (C ₁₆ -C ₂₂ )alkenyloxy group, more preferably an optionally branched (C ₁₇ -C ₂₁ )alkoxy group and an optionally branched (C ₁₇ -C ₂₁ )alkenyloxy group, more preferably an optionally branched (C ₁₈ -C ₂₀ )alkoxy group and an optionally branched (C ₁₈ -C ₂₀ )alkenyloxy group, wherein R ₁ is more preferably an optionally branched (C ₁₈ -C ₂₀ )alkoxy group or an optionally branched (C ₁₈ -C ₂₀ )alkenyloxy group, more preferably a branched (C ₁₈ -C ₂₀ )alkoxy group or a (C ₁₈ -C ₂₀ )alkenyloxy group, more preferably a branched C ₂₀ alkoxy group or a C 20 alkoxy group. ₁₈ -Alkenyloxy.

3. The polycarbodiimide composition of embodiment 1 or 2, wherein R ₁ is selected from the group consisting of: -(CH ₂ ) ₈ -CH=CH-(CH ₂ ) ₇ -CH ₃ , preferably -(CH ₂ ) ₈ -CH=CH-(CH ₂ ) ₇ -CH ₃ in (Z) configuration, and -CH ₂ -CH[(CH ₂ ) ₇ -CH ₃ ][-(CH ₂ ) ₉ -CH ₃ ], wherein R ₁ is more preferably -(CH ₂ ) ₈ -CH=CH-(CH ₂ ) ₇ -CH ₃ , more preferably -(CH ₂ ) ₈ -CH=CH-(CH ₂ ) ₇ -CH ₃ in (Z) configuration, or -CH ₂ -CH[(CH ₂ ) ₇ -CH ₃ ][-(CH ₂ ) ₉ -CH ₃ ].

4. The polycarbodiimide composition of any one of embodiments 1 to 3, wherein _R1 comprises an atomic ratio of carbon atoms calculated based on the total carbon atoms contained in R1 to oxygen atoms calculated based on the total oxygen atoms contained in R1, C:O, in the range of 11 to 50, 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 _R1 comprises an atomic ratio of carbon atoms calculated based on the total carbon atoms contained in _R1 to oxygen atoms calculated based on the total oxygen atoms contained in _R1 , C:O, of 18 or 20.

5. The polycarbodiimide composition of any one of embodiments 1 to 4, wherein _R1 has a molecular weight greater than 210 g/mol, more preferably in the range of greater than 210 g/mol to 700 g/mol, more preferably in the range of 220 g/mol 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.

6. The polycarbodiimide composition of any one of embodiments 1 to 5, wherein _R3 is selected from the group consisting of an optionally branched ( _C1 - _C25 ) alkylene group, -[ _CR5H - _CH2 -O] _x1 - _CR5H - _CH2- , wherein _R5 is H or _CH3 , wherein x1 is an integer in the range of 1 to 15, -[ _CH2 - _CH2 -O] _x2 - _CH2 - _CH2 -O- ran -{[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 1 to 15, preferably selected from the group consisting of optionally branched (C ₁ -C ₂₅ ) alkylene groups, more preferably selected from the group consisting of optionally branched (C ₁ -C ₂₀ ) alkylene groups, more preferably selected from the group consisting of optionally branched (C ₂ -C ₁₅ ) alkylene groups, more preferably selected from the group consisting of optionally branched (C ₃ -C ₁₂ ) alkylene groups, more preferably selected from the group consisting of optionally branched (C ₄ -C _{10 )} alkylene groups, more preferably selected from the group consisting of optionally branched (C ₅ -C ₆ ) alkylene groups, wherein R ₃ is more preferably selected from the group consisting of optionally branched C ₅ alkylene groups, wherein R ₃ is more preferably selected from the group consisting of optionally branched C A group consisting of ₅ -alkylene groups.

7. The polycarbodiimide composition of any one of embodiments 1 to 6, wherein _R3 is selected from the group consisting of an optionally branched ( _C1 - _C25 ) alkylene group, -[ _CR5H - _CH2 -O] _x1 - _CR5H - _CH2- , wherein _R5 is H or _CH3 , wherein x1 is an integer in the range of 1 to 15, -[ _CH2 - _CH2 -O] _x2 - _CH2 - _CH2 -O- ran -{[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, and is more preferably selected from the group consisting of optionally branched (C ₁ -C ₂₅ ) alkylene groups, and more preferably selected from the group consisting of -(CH ₂ ) ₂ -, -(CH ₂ ) ₃ -, -(CH ₂ ) ₄ -, -CH ₂ -CH ₂ -CH(CH ₃ )-, -(CH ₂ ) ₅ -, -CH ₂ -C(CH ₃ ) ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -CH(CH ₃ )-, -CH ₂ -CH ₂ -CH(CH ₃ )-CH ₂ -, -(CH ₂ ) ₆ -, -(CH ₂ ) ₇ -, -(CH ₂ ) ₈ -, -(CH ₂ ) ₉ -, -(CH ₂ ) _R10- and -( _CH2 ) _12- are more preferably selected from the group consisting of _-CH2 - _CH2 -CH( _CH3 )-, -( _CH2 ) _5- , _-CH2 -C( _CH3 )2-CH2-, -CH2- _CH2 - _CH2 - _{CH ( CH3} )-, -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- .

8. The polycarbodiimide composition of any one of embodiments 1 to 7, wherein R ₄ is selected from the group consisting of: optionally alkoxylated (C ₃ -C ₅₀ )alkanetriyl, , and wherein R ₆ is -[CR ₇ H-CH ₂ -O] _x1 -CR ₇ H-CH ₂ -, wherein R ₇ is H or CH ₃ , -[CH ₂ -CH ₂ -O] _x2 -CH ₂ -CH ₂ -O- ran -{[C(CH ₃ )H-CH ₂ -O] _x3 -C(CH ₃ )H-CH ₂ }- and -[CH ₂ -CH ₂ -CH ₂ -CH ₂ -O] _x4 -CH ₂ -CH ₂ -CH ₂ -CH ₂ -, 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 an integer in the range of 1 to 15, wherein R ₄ is more preferably selected from the group consisting of optionally alkoxylated (C ₃ -C ₅₀ ) alkanetriyl, and , wherein R ₄ is more preferably selected from the group consisting of (C ₃ -C ₄₀ )alkanetriyl, more preferably (C ₃ -C ₃₀ )alkanetriyl, more preferably (C ₃ -C ₂₀ )alkanetriyl, more preferably (C ₃ -C ₁₀ )alkanetriyl, more preferably (C ₃ -C ₅ )alkanetriyl, wherein R ₄ is more preferably (Propane-1,2,3-triyl).

9. 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, and more preferably in the range of 6 to 15.

10. The polycarbodiimide composition of any one of Examples 1 to 9, wherein p is an integer in the range of 1 to 5, preferably in the range of 1 to 4, and more preferably in the range of 1 to 3.

11. The polycarbodiimide composition of any one of Examples 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, and more preferably in the range of 6 to 15.

12. A polycarbodiimide composition as in any one of Examples 1 to 11, wherein the polycarbodiimide contains equal to or less than 100 wt ppm of P, calculated as elemental P and based on the total weight of the polycarbodiimide composition, preferably equal to or less than 90 wt ppm, more preferably equal to or less than 80 wt ppm, more preferably equal to or less than 75 wt ppm, more preferably equal to or less than 70 wt ppm, more preferably equal to or less than 65 wt ppm, more preferably equal to or less than 60 wt ppm of P, calculated as elemental P and based on the total weight of the polycarbodiimide composition.

13. A polycarbodiimide composition as in any one of specific examples 1 to 12, wherein the polycarbodiimide contains 410 wt ppm or less of phosphine oxide, calculated as the total weight of the phosphine oxides and based on the total weight of the polycarbodiimide composition, preferably 370 wt ppm or less, more preferably 335 wt ppm or less, more preferably 295 wt ppm or less, more preferably 280 wt ppm or less, more preferably 260 wt ppm or less, more preferably 240 wt ppm or less, more preferably 220 wt ppm of phosphine oxide, calculated as the total weight of the phosphine oxides and based on the total weight of the polycarbodiimide composition.

14. The polycarbodiimide composition of embodiment 13, wherein the phosphotene oxide is selected from the group consisting of: 1-methyl-2-phosphotene-1-oxide (MPO), 3-methyl-1-phenyl-2-phosphotene-1-oxide (MPPO), 3-methyl-1-ethyl-2-phosphotene-1-oxide, 1,3-dimethyl-2-phosphotene-1-oxide, 1-phenyl-2- Phosphene-1-oxide, 1-ethyl-2-phosphene-1-oxide, 1-methyl-3-phosphene-1-oxide, 3-methyl-1-phenyl-3-phosphene-1-oxide, 3-methyl-1-ethyl-3-phosphene-1-oxide, 1,3-dimethyl-3-phosphene-1-oxide, 1-phenyl-3-phosphene-1-oxide, 1-ethyl-3-phosphene The phosphene-1-oxide and a mixture of two or more thereof are preferably selected from the group consisting of 1-methyl-2-phosphene-1-oxide (MPO), 3-methyl-1-phenyl-2-phosphene-1-oxide (MPPO), 3-methyl-1-ethyl-2-phosphene-1-oxide, 1,3-dimethyl-2-phosphene-1-oxide, 1-phenyl-2-phosphene-1-oxide, 1-ethyl-2-phosphene-1-oxide and a mixture of two or more thereof, wherein one or more of the phosphene oxides are more preferably 1-methyl-2-phosphene-1-oxide (MPO), 3-methyl-1-phenyl-2-phosphene-1-oxide (MPPO) and a mixture thereof, wherein the phosphene oxide is more preferably 1-methyl-2-phosphene-1-oxide (MPO).

15. A polycarbodiimide composition as described in any one of Examples 1 to 14, wherein 99.0 to 100% by weight, preferably 99.5 to 100% by weight, and more preferably 99.9 to 100% by weight of the polycarbodiimide composition consists of polycarbodiimide and P, and more preferably consists of polycarbodiimide and phosphotene oxide.

16. A polycarbodiimide composition as in any one of Examples 1 to 15, having a viscosity in the range of 5 to 20 Pa·s.

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

18. A method for preparing a polycarbodiimide composition, preferably a polycarbodiimide composition as in any one of embodiments 1 to 17, the method comprising: (i) preparing a mixture comprising 4,4'-diisocyanatodicyclohexylmethane and one or more phosphane 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 monohydric alcohols and one or more polyhydric alcohols to the mixture obtained in (ii), wherein the one or more monohydric alcohols are independently selected from optionally branched monohydroxyl (C ₁₁ -C ₅₀ )alkane and optionally branched monohydroxy (C ₁₁ -C ₅₀ )alkene, wherein one or more optionally branched monohydroxy (C ₁₁ -C ₅₀ )alkane and optionally branched monohydroxy (C 11 -C ₅₀ )alkene independently contain equal to or more than 11 carbon atoms, calculated as the total carbon atoms contained in each of the optionally branched monohydroxy (C ₁₁ -C ₅₀ )alkane and optionally branched monohydroxy (C ₁₁ -C ₅₀ )alkene, and the number of carbon atoms contained in each of the optionally branched monohydroxy (C ₁₁ -C ₅₀ )alkane and optionally branched monohydroxy (C ₁₁ -C _{50 ) alkene} . (iv) removing at least a portion of the one or more phosphine oxides from the mixture obtained in (iii) to obtain a polycarbodiimide composition.

19. In the method of specific example 18, one or more phosphane oxides are selected from the group consisting of: 1-methyl-2-phosphane-1-oxide (MPO), 3-methyl-1-phenyl-2-phosphane-1-oxide (MPPO), 3-methyl-1-ethyl-2-phosphane-1-oxide, 1,3-dimethyl-2-phosphane-1-oxide, 1-phenyl-2-phosphane-1-oxide, 1-Oxyphene-1-oxide, 1-ethyl-2-cyclophosphene-1-oxide, 1-methyl-3-cyclophosphene-1-oxide, 3-methyl-1-phenyl-3-cyclophosphene-1-oxide, 3-methyl-1-ethyl-3-cyclophosphene-1-oxide, 1,3-dimethyl-3-cyclophosphene-1-oxide, 1-phenyl-3-cyclophosphene-1-oxide, 1-ethyl-3-cyclophosphene-1 -oxides and mixtures of two or more thereof, preferably selected from the group consisting of 1-methyl-2-cyclophosphane-1-oxide (MPO), 3-methyl-1-phenyl-2-cyclophosphane-1-oxide (MPPO), 3-methyl-1-ethyl-2-cyclophosphane-1-oxide, 1,3-dimethyl-2-cyclophosphane-1-oxide, 1-phenyl-2-cyclophosphane-1-oxide, 1-ethyl-2-cyclophosphane-1-oxide and mixtures of two or more thereof, wherein one or more cyclophosphane oxides are more preferably 1-methyl-2-cyclophosphane-1-oxide (MPO), 3-methyl-1-phenyl-2-cyclophosphane-1-oxide (MPPO) and mixtures thereof, wherein one or more cyclophosphane oxides are more preferably 1-methyl-2-cyclophosphane-1-oxide (MPO).

20.  A method as in specific example 18 or 19, wherein the mixture obtained in (i) has a molar ratio of 4,4'-diisocyanatodicyclohexylmethane calculated as the molar amount of 4,4'-diisocyanatodicyclohexylmethane to one or more phosphine oxides calculated as the sum of the molar amounts of the one or more phosphine oxides in the range of 10:1 to 1,000:1, preferably in the range of 50:1 to 750:1, more preferably in the range of 80:1 to 510:1, more preferably in the range of 150:1 to 450:1, more preferably in the range of 200:1 to 400:1, more preferably in the range of 300:1 to 350:1.

21.  A method as in any one of specific examples 18 to 20, wherein the mixture obtained in (i) contains 0 to 1% by weight, preferably 0 to 0.1% by weight, more preferably 0 to 0.01% by weight of xylene, preferably alkyl-substituted benzene or alkyl-substituted diphenyl, wherein the alkyl group comprises one or more of methyl, ethyl and propyl, and more preferably a solvent, wherein the mixture obtained in (i) is more preferably substantially free of xylene, more preferably substantially free of alkyl-substituted benzene or alkyl-substituted diphenyl, and more preferably substantially free of solvent.

22. A method as in any one of specific examples 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, 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, and more preferably in the range of 160 to 180°C.

23. A method as in any one of specific examples 18 to 22, wherein the gas atmosphere in (ii) comprises an inert gas, preferably consists of an inert gas, wherein the gas atmosphere in (ii) preferably comprises one or more of nitrogen and argon, more preferably consists of one or more of nitrogen and argon.

24. A method as described in any one of specific examples 18 to 23, wherein the carbodiimidization conditions in (ii) comprise applying a pressure in the range of 1 to 1000 hPa, preferably in the range of 2 to 1000 hPa, and more preferably in the range of 2.5 to 1000 hPa to the mixture obtained in (i).

25. A method as in any one of specific examples 18 to 24, wherein the carbodiimidization conditions in (ii) comprise agitating the mixture obtained in (i), preferably by stirring.

26. A method as in any one of specific examples 18 to 25, wherein the mixture obtained in (i) is subjected to the carbodiimidization conditions in (ii) for a period of time in the range of 1 to 50 hours, preferably in the range of 1.5 to 40 hours, and more preferably in the range of 2 to 25 hours.

27. The method of any one of embodiments 18 to 26, wherein the one or more monohydric alcohols added to the mixture obtained in (ii) according to (iii) are independently selected from the group consisting of optionally branched monohydroxy (C ₁₂ -C ₄₀ )alkanes and optionally branched monohydroxy (C ₁₂ -C ₄₀ )alkenes, preferably selected from the group consisting of optionally branched monohydroxy (C ₁₃ -C ₃₅ )alkanes and optionally branched monohydroxy (C ₁₃ -C ₃₅ )alkenes, more preferably selected from the group consisting of optionally branched monohydroxy (C ₁₄ -C ₃₀ )alkanes and optionally branched monohydroxy (C ₁₄ -C _{30 )} alkenes. The group consisting of optionally branched monohydroxy (C ₁₅ -C ₂₅ )alkane and optionally branched monohydroxy (C ₁₅ -C ₂₅ )alkene is more preferably selected from the group consisting of optionally branched monohydroxy (C ₁₆ -C ₂₂ )alkane and optionally branched monohydroxy (C ₁₆ -C ₂₂ )alkene, more preferably selected from the group consisting of optionally branched monohydroxy (C ₁₇ -C ₂₁ )alkane and optionally branched monohydroxy (C ₁₇ -C ₂₁ )alkene, more preferably selected from the group consisting of optionally branched monohydroxy (C ₁₈ -C ₂₀ )alkane and optionally branched monohydroxy (C ₁₈ -C ₂₀ )alkene, wherein the one or more monohydric alcohols are more preferably independently optionally branched monohydroxy (C ₁₈ -C ₂₀ )alkane or optionally branched monohydroxy (C ₁₈ -C ₂₀ )alkene, more preferably branched monohydroxy (C ₁₈ -C ₂₀ )alkane or monohydroxy (C ₁₈ -C ₂₀ )alkene, more preferably branched monohydroxy C ₂₀ alkane or monohydroxy C ₁₈ alkene.

28. The method of any one of embodiments 18 to 27, wherein the one or more monohydric alcohols added to the mixture obtained in (ii) according to (iii) are independently selected from the group consisting of HO-(CH ₂ ) ₈ -CH=CH-(CH ₂ ) ₇ -CH ₃ , preferably HO-(CH _{2 ) 8 -CH=CH-(CH 2 ) 7 -CH 3 in (Z) configuration, and HO-CH 2 -CH[(CH 2 ) 7 -CH 3][-(CH 2 ) 9 -CH 3 ], wherein the one or more monohydric alcohols are more preferably HO-(CH 2 ) 8 -CH = CH- ( CH 2 ) 7 -CH 3 , more} preferably HO-(CH ₂ ) ₈ -CH=CH-(CH ₂ ) ₇ -CH 3 in (Z) configuration, or HO-CH 2 -CH[(CH 2 ) ₇ -CH ₃ ][-(CH ₂ ) 9 -CH ₃ -CH[(CH ₂ ) ₇ -CH ₃ ][-(CH ₂ ) ₉ -CH ₃ ].

29. The method of any one of embodiments 18 to 28, wherein the one or more optionally branched monohydroxy (C ₁₁ -C ₅₀ ) alkane and optionally branched monohydroxy (C ₁₁ -C ₅₀ ) alkene are independently contained in the range of 11 to 50, 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, and the number of each of the optionally branched monohydroxy (C ₁₁ -C 50 ) alkane and optionally branched monohydroxy (C 11 -C 50 ) alkene is independently contained 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. The atomic ratio of carbon atoms calculated as the total carbon atoms of the optionally branched monohydroxy (C ₁₁ -C ₅₀ )alkane and the optionally branched monohydroxy (C 11 -C ₅₀ )alkene to oxygen atoms calculated as the total oxygen atoms contained in each of the optionally branched monohydroxy (C ₁₁ -C 50 )alkane and the optionally branched monohydroxy (C _{11 -C 50 )alkene, C:O, wherein the one or more optionally branched monohydroxy (C 11} -C ₅₀ )alkane and the optionally branched monohydroxy (C ₁₁ -C ₅₀ )alkene each independently contains 18 or 20 carbon atoms, and the atomic ratio of oxygen atoms calculated as the total oxygen atoms contained in each of the one or more optionally branched monohydroxy (C ₁₁ -C ₅₀ )alkane and the optionally branched monohydroxy (C ₁₁ -C _{50 )} alkene each independently contains 18 or 20 carbon atoms. )olefins to the total of oxygen atoms contained in one or more optionally branched monohydroxy (C ₁₁ -C ₅₀ )alkane and optionally branched monohydroxy (C ₁₁ -C ₅₀ )alkene, respectively, C:O.

30. The method of any one of embodiments 18 to 29, wherein the one or more polyols added to the mixture obtained in (ii) according to (iii) are independently selected from the group consisting of propane-1,2,3-triol, triesters of glycerol and ricinoleic acid, HO-[ _CR5H -CH2 _- O] _x1 - _CR5H -CH2 _- OH, wherein _R5 is H or _CH3 , wherein x1 is an integer in the range of 1 to 15, HO-[ _CH2 - _CH2 -O] _x2 - _CH2 - _CH2 -O- ran -{[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 -CH ₂ -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 is optionally branched and/or optionally alkoxylated dihydroxy ( _C1 - _C25 ) alkane, preferably optionally branched and/or optionally alkoxylated dihydroxy ( _C1 - _C20 ) alkane, more preferably optionally branched dihydroxy ( _C2 - _C15 ) alkane, more preferably optionally branched dihydroxy ( _C3 - _C12 ) alkane, more preferably optionally branched dihydroxy ( _C4 - _C10 ) alkane, more preferably optionally branched dihydroxy ( _C5 - _C6) alkane. )alkanes, wherein the one or more polyols are independently selected from the group consisting of optionally branched dihydroxy _C5 alkanes, wherein the one or more polyols are more preferably selected from the group consisting of branched dihydroxy _C5 alkanes.

31. The method of any one of embodiments 18 to 30, wherein the one or more polyols added to the mixture obtained in (ii) according to (iii) are independently selected from the group consisting of optionally branched and/or optionally alkoxylated (C ₃ -C ₅₀ )alkane-triols, preferably (C ₃ -C ₄₀ )alkane-triols, more preferably (C ₃ -C ₃₀ )alkane-triols, more preferably (C ₃ -C ₂₀ )alkane-triols, more preferably (C ₃ -C ₁₀ )alkane-triols, more preferably (C ₃ -C ₅ )alkane-triols, triesters of glycerol and ricinoleic acid, ,and wherein R ₆ is -[CR ₇ H-CH ₂ -O] _x1 -CR ₇ H-CH ₂ -OH, wherein R ₇ is H or CH ₃ , -[CH ₂ -CH ₂ -O] _x2 -CH ₂ -CH ₂ -O- ran -{[C(CH ₃ )H-CH ₂ -O] _x3 -C(CH ₃ )H-CH ₂ }-OH, and -[CH ₂ -CH ₂ -CH ₂ -CH ₂ -O] _x4 -CH ₂ -CH ₂ -CH ₂ -CH ₂ -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 an integer in the range of 1 to 15, HO-(CH ₂ ) ₂ -OH, HO-(CH ₂ ) ₃ -OH,HO-(CH ₂ ) ₄ -OH,HO-CH ₂ -CH ₂ -CH(CH ₃ )-OH,HO-(CH ₂ ) ₅ -OH,HO-CH ₂ -C(CH ₃ ) ₂ -CH ₂ -OH,HO-CH ₂ -CH ₂ -CH ₂ -CH(CH ₃ )-OH,HO-CH ₂ -CH ₂ -CH(CH ₃ )-CH ₂ -OH,HO-(CH ₂ ) ₆ -OH, HO-(CH ₂ ) ₇ -OH, HO-(CH ₂ ) ₈ -OH, HO-(CH ₂ ) ₉ -OH, HO-(CH ₂ ) ₁₀ -OH and HO-(CH ₂ ) ₁₂ -OH, Preferably, the compound is selected from the group consisting of propane-1,2,3-triol, glycerol and triester of ricinoleic acid, wherein the triester of glycerol and ricinoleic acid has the 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)-OH, HO- _CH2 - _CH2 -CH( _CH3 )-CH2 _- OH and HO-( _CH2 ) ₆ -OH, wherein the one or more polyols added to the mixture obtained in (ii) according to (iii) are independently preferably selected from the group consisting of propane-1,2,3-triol, triesters of glycerol and ricinoleic acid having formula (3) and HO-( _CH2 ) ₅ -OH.

32. A method as in any one of specific examples 18 to 31, wherein the mixture obtained in (iii) contains 5 to 70% by weight, preferably 25 to 50% by weight, of one or more monohydric alcohols, calculated as the total weight of the one or more monohydric alcohols, based on the total weight of the mixture obtained in (iii).

33. A method as in any one of specific examples 18 to 32, wherein the mixture obtained in (iii) contains 0.1 to 20% by weight, preferably 1 to 15% by weight, of one or more polyols, calculated as the total weight of the one or more polyols, based on the total weight of the mixture obtained in (iii).

34. A method as in any one of specific examples 18 to 33, wherein the mixture obtained in (iii) comprises 5.1 to 90% by weight, preferably 26 to 65% by weight, of one or more monohydric alcohols and 5.1 to 90% by weight, more preferably 26 to 65% by weight, of one or more polyhydric alcohols, calculated as the total weight of the one or more monohydric alcohols and the total weight of the one or more polyhydric alcohols, respectively, based on the total weight of the mixture obtained in (iii).

35. A method as in any one of specific examples 18 to 34, wherein the reaction conditions according to (iii) include 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, and more preferably in the range of 150 to 170°C.

36.  The method of any one of the specific examples 18 to 35, wherein removing at least a portion of one or more phosphane oxides according to (iv) from the mixture obtained in (iii) comprises: (iv.1) adding one or more azeotropes to the mixture obtained in (iii) as needed, (iv.2) distilling the mixture obtained in (iii) or (iv.1) to obtain a distillate containing a polycarbodiimide composition and a distillate containing at least a portion of one or more phosphane oxides.

37. The method of embodiment 36, wherein the boiling point of the one or more azeotropes at a pressure in the range of 0.950 to 1.050 (absolute) bar is in the range of 200 to 300°C, preferably in the range of 200 to 250°C, wherein the one or more azeotropes are preferably selected from the group consisting of acetates, the acetates comprising C, H and O, preferably the group consisting of C, H and O, wherein the acetates comprise 6 to 16, preferably 8 to 14 C and O atoms, calculated as the sum of carbon atoms and oxygen atoms, (C ₁ -C ₁₀ )alkyl (C ₁ -C ₁₀ )alkyl ethers, di(C ₁ -C ₅ )alkyl adipates and mixtures of two or more thereof, preferably selected from the group consisting of (C ₁ -C ₂ )alkoxy (C ₃ -C The azeotropic _agent is preferably selected from the group consisting of methoxybutyl acetate _, diethylene _glycol monobutyl ether acetate, diethyl adipate, diisopropyl adipate, dimethyl adipate and a mixture of two or more thereof, wherein the one _{or more} azeotropes are more preferably diethyl adipate.

38. The method of embodiment 36 or 37, wherein the mixture obtained in distillation (iii) or (iv.1) is carried out at a temperature in the range of 130 to 190°C, preferably in the range of 140 to 180°C, and more preferably in the range of 150 to 170°C.

39. A method according to any one of embodiments 36 to 38, wherein the mixture obtained in distillation (iii) or (iv.1) is carried out at a pressure of less than 0.150 (absolute) bar, preferably less than 0.125 (absolute) bar, more preferably less than 0.100 (absolute) bar.

40. A polycarbodiimide composition obtainable or obtained by a method as described in any one of Examples 18 to 39.

41. Use of a polycarbodiimide composition as in any one of specific examples 1 to 17 and 40 as a stabilizer for a polymer, preferably a thermoplastic polymer, preferably a thermoplastic polyester, more preferably a polyurethane (PU), preferably thermoplastic polyurethane (TPU), polyurea, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polylactic acid (PLA), polyamide, polyesteramide, polycaprolactone and polyether sulfone (PES), preferably a hydrolysis stabilizer.

The present invention is further described with reference to the following examples, embodiments and comparative examples.

Embodiment

Reference Examples 1 : FTIR Spectrum and ATR-FTIR Spectrum measurement

FTIR spectra, in particular for the determination of characteristic bands of isocyanate groups, are recorded via a single reflection ATR module on a Brücker Eco-ATR. The sample is added directly to the ATR crystal without any modification. Typically, isocyanate groups NCO are expected to show a band at about 2200 cm ^-1 in the FTIR spectrum and carbodiimide (N=C=N) groups at about 2100 cm ^-1 .

Reference Examples 2 ：Determination of phosphorus residue

Phosphorus content was determined by elemental analysis (ICP-OES, DIN ISO 17025).

Comparative Examples 1 ：Preparation of polycarbodiimide composition

143.0 g of 1,1'-methylenebis(4-isocyanatocyclohexane) (H12MDI; Evonik; 0.55 mol) and 0.14 g of 1-methyl-1-phosphotene-1-oxide (MPO; 1.20 mmol) were charged into a 500 ml 4-neck round-bottom flask equipped with a thermometer (coupled to a temperature-controlled oil bath), mechanical stirring, a cold water condenser and a nitrogen inlet. The reaction mixture was stirred and heated to 170 °C. After about 17 h, a second aliquot of MPO (0.13 g; 1.11 mmol) was added. After 20 h, an NCO content of 12.8% was reached. Subsequently, 92.8 g of oleyl alcohol and 8.1 g of neopentyl glycol were added. After a few hours, the NCO content reached 0.0% (full urethane reaction) and the reaction mixture was cooled. The corresponding product had an NCN content of 6.2% and an MPO content of 1000 ppm.

Comparative Examples 2 ：Preparation of polycarbodiimide composition

492.50 g of 1,1'-methylenebis(4-isocyanatocyclohexane) (H12MDI; Evonik; 1.88 mol) and 375.00 g of methoxypoly(ethylene glycol) (MPEG) (Pluriol A500E; BASF; 0.75 mol) with a molecular weight of about 500 g/mol were mixed and charged into a 1000 ml 4-neck round-bottom flask equipped with a thermometer (coupled to a temperature-controlled oil bath), mechanical stirring, a cold water condenser and a nitrogen inlet. The reaction mixture was stirred and heated to 90°C. After about 4 hours, the NCO content reached 13.7% (urethane reaction). The reaction temperature was then raised to 180°C and 0.99 g of 1-methyl-cyclophosphene-1-oxide (MPO; 8.52 mmol) was added. After 71 hours, the NCO content reached 1.1%, and the remaining NCO was capped by adding 113 g of Pluriol A500E. After another 5 hours, the NCO content reached 0.0%.

200 g of the product was then transferred together with 200 g of diethyl adipate (DEA) into a 500 ml 4-neck round-bottom flask equipped with a thermometer (coupled to a temperature-controlled oil bath), mechanical stirring, a cold water condenser and a nitrogen inlet. The diethyl adipate was then distilled off using a bridge (160°C and 34 mbar) to remove some residual MPO (DEA acts as an azeotrope). The corresponding product had an NCN content of 5.0% and an MPO content of 650 ppm.

Comparative Examples 3 ：Preparation of polycarbodiimide composition

200.00 g of 1,1'-methylenebis(4-isocyanatocyclohexane) (H12MDI; Evonik; 0.76 mol) and 80.00 g of oleyl alcohol (BASF, 0.30 mol) were charged into a 1000 ml 4-neck round-bottom flask equipped with a thermometer (coupled to a temperature-controlled oil bath), mechanical stirring, a cold water condenser and a nitrogen inlet. The reaction mixture was stirred and heated to 90°C. After about 4 hours, the NCO content reached 18.7% (urethane reaction). The reaction temperature was then raised to 180°C and 0.20 g of 1-methyl-cyclophosphene-1-oxide (MPO; 1.72 mmol) was added. After 70 hours, the NCO content reached 1.2%, and the remaining NCO was capped by adding 20 g of oleyl alcohol. After a further 4 hours of mixing, the NCO content reached 0.0%. The reaction was cooled to room temperature and 250 g of diethyl adipate were then added. The diethyl adipate was then distilled off using a condenser (180°C and 1 mbar) to remove some of the remaining MPO (DEA acts as an azeotrope). The corresponding product had an NCN content of 4.8% and an MPO content of 380 ppm.

Comparative Examples 4 ：Preparation of polycarbodiimide composition

The reaction was carried out according to the reaction conditions of Comparative Example 2, except that 200 g of dimethyl adipate was used as the azeotropic agent instead of diethyl adipate. After distillation at 180° C. and 50 mbar, the corresponding product had an NCN content of 5.0% and an MPO content of 300 ppm.

Comparative Examples 5 ：Preparation of polycarbodiimide composition

200.0 g of 1,1'-methylenebis(4-isocyanatocyclohexane) (H12MDI; Evonik; 0.76 mol) and 0.2 g of 1-methyl-1-phosphotene-1-oxide (MPO; 1.72 mmol) were charged into a 1000 ml 4-neck round-bottom flask equipped with a thermometer (coupled to a temperature-controlled oil bath), mechanical stirring, a cold water condenser and a nitrogen inlet. The reaction mixture was stirred and heated to 180° C. After about 17 hours, the NCO content reached a value of 15.1%. 200.0 g of oleyl alcohol were subsequently added. After 5 hours, the NCO content reached 0.0% (complete urethane reaction) and the reaction mixture was cooled. The reaction mixture was cooled at room temperature and then 400 g of diethyl adipate were added. The diethyl adipate was then distilled off using a condenser (180°C and 5 mbar) to remove some residual MPO (DEA acts as an azeotrope). This operation was performed twice. The corresponding product had an NCN content of 11.5% and an MPO content of 124 ppm.

Embodiment 6 : Preparation of the polycarbodiimide composition according to the present invention

130.0 g of 1,1'-methylenebis(4-isocyanatocyclohexane) (H12MDI; Evonik; 0.50 mol) and 0.26 g of 1-methyl-1-phosphotene-1-oxide (MPO; 2.24 mmol) were charged into a 500 ml 4-neck round-bottom flask equipped with a thermometer (coupled to a temperature-controlled oil bath), mechanical stirring, a cold water condenser and a 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 of oleyl alcohol and 10 g of neopentyl glycol were added. After 5 hours, the NCO content reached 0.0% (complete urethane reaction) and the reaction mixture was cooled. The reaction mixture was cooled at room temperature and then 400 g of diethyl adipate were added. The diethyl adipate was then distilled off using a condenser (180°C and 15 mbar) to remove some residual MPO (DEA acts as an azeotrope). This operation was performed twice. The corresponding product had an NCN content of 7.4% and an MPO content of 225 ppm.

Embodiment 7 : Preparation of the polycarbodiimide composition according to the present invention

150.0 g of 1,1'-methylenebis(4-isocyanatocyclohexane) (H12MDI; Evonik; 0.57 mol) and 0.15 g of 1-methyl-1-phosphotene-1-oxide (MPO; 1.29 mmol) were charged into a 500 ml 4-neck round-bottom flask equipped with a thermometer (coupled to a temperature-controlled oil bath), mechanical stirring, a cold water condenser and a nitrogen inlet. The reaction mixture was stirred and heated to 180°C. After about 20 hours, the NCO content reached a value of 11.9%. 116.6 g of 2-octyl-1-dodecanol (Eutanol® G, BASF) and 2.3 g of pentane-1,5-diol were subsequently added. After 4 hours, the NCO content reached 0.0% (complete urethane reaction) and the reaction mixture was cooled to room temperature. Then, 200 g of diethyl adipate were added. The diethyl adipate was then distilled off using a condenser (160° C. and 50 mbar) to remove some residual MPO (DEA acts as an azeotrope). This operation was performed twice. The corresponding product had an NCN content of 9.4% and an MPO content of 165 ppm.

Embodiment 8 : Preparation of the polycarbodiimide composition according to the present invention

150.0 g of 1,1'-methylenebis(4-isocyanatocyclohexane) (H12MDI; Evonik; 0.57 mol) and 0.3 g of 1-methyl-1-phosphotene-1-oxide (MPO; 2.58 mmol) were charged into a 500 ml 4-neck round-bottom flask equipped with a thermometer (coupled to a temperature-controlled oil bath), mechanical stirring, a cold water condenser and a 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 of 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% (complete urethane reaction) and the reaction mixture was cooled to room temperature. Then, 400 g of diethyl adipate were added. The diethyl adipate was then distilled off using a condenser (180°C and 10 mbar) to remove some residual MPO (DEA acts as an azeotrope). This operation was performed twice. The corresponding product had an NCN content of 6.4% and an MPO content of 150 ppm.

Embodiment 9 : Preparation of the polycarbodiimide composition according to the present invention

The reaction was carried out according to the reaction conditions of Comparative Example 1, except that 115 g of oleyl alcohol and 8.1 g of glycerol were added to replace 92.8 g of oleyl alcohol and 8.1 g of neopentyl glycol. Finally, 200 g of diethyl adipate was added. The diethyl adipate was then distilled off using a condenser (180°C and 10 mbar) to remove some residual MPO (DEA acts as an azeotropic agent). The operation was performed twice. The corresponding product had an NCN content of 6.7% and an MPO content of 160 ppm.

Embodiment 10 ：Determination of tensile strength of polycarbodiimide compositions

Thermoplastic polyurethane (TPU) compositions were prepared by hand casting process, where TPU was based on 4,4'-MDI (ethylene diphenyl diisocyanate), 1,2-ethylene glycol/adipic acid polyester polyol (molar mass 500 to 3000 g/mol) and 1,4-butanediol as chain extender.

The TPU compositions were prepared once without additional polycarbodiimide and in the other case by mixing about 1.0 wt. % polycarbodiimide as a hydrolysis stabilizer. In the latter case, the polycarbodiimide was added to the premix of polyol and chain extender before adding the isocyanate in the hand casting process. The TPU sheets obtained for each composition were annealed at 110°C for 3 hours and then ground into pellets.

After drying, the pellets were first injection molded into test specimens and then further annealed at 100°C for 10 hours. The hydrolytic stability of TPU injection molded parts can be evaluated by storing the test specimens in water at 80°C and subsequently determining the tensile strength at regular intervals (tensile strength at the beginning, where t=0, is set to 100%).

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

Table 1 below gives an overview of the prepared polycarbodiimide composition, including the alcohol used in its preparation. In addition, the tensile strength measurement results are shown in Table 2 below.

surface 1 : Overview of the prepared polycarbodiimide compositions. # Monoalcohol Diols/polyols N=C=N content [%] Residual MPO [ppm] Residual P [ppm] Comparative Example 1 Oleyl alcohol [(Z)-octadec-9-en-1-ol)] Neopentyl glycol 6.2 1000 267 Comparative Example 2 Methoxypolyethylene glycol (mPEG) without 5.0 650 173 Comparative Example 3 Oleyl alcohol without 4.8 394 105 Comparative Example 4 Methoxypolyethylene glycol without 5.0 281 75 Comparative Example 5 Oleyl alcohol without 11.5 124 33 Example 6 Oleyl alcohol Neopentyl glycol 7.4 225 60 Example 7 2-Octyl-1-dodecanol (Eutanol® G) Pentane-1,5-diol 9.4 165 44 Example 8 Oleyl alcohol Triglycerides of glycerol and ricinoleic acid (castor oil) 6.4 150 40 Example 9 Oleyl alcohol Propane-1,2,3-triyl (Glycerol) 6.7 150 40

surface 2 : With or without polycarbodiimide composition TPU Tensile strength measurement results of the composition. # Monoalcohol Diols/polyols Efficiency [d] Comparative Example 1 Oleyl alcohol [(Z)-octadec-9-en-1-ol)] Neopentyl glycol 9 Comparative Example 2 Methoxypolyethylene glycol (mPEG) without 8 Comparative Example 3 Oleyl alcohol without 12 Comparative Example 4 Methoxypolyethylene glycol without 12 Comparative Example 5 Oleyl alcohol without 14 Example 6 Oleyl alcohol Neopentyl glycol 18 Example 7 2-Octyl-1-dodecanol (Eutanol® G) Pentane-1,5-diol 18 Example 8 Oleyl alcohol Triglycerides of glycerol and ricinoleic acid (castor oil) 18 Example 9 Oleyl alcohol Propane-1,2,3-triyl (Glycerol) 18 Comparative Example 11 Polycarbodiimide-free Polycarbodiimide-free 8

From the results, it can be seen that the polycarbodiimide composition containing a relatively high content of phosphine oxide catalyst shows poor performance in the test. In contrast, the polycarbodiimide composition prepared from a combination of monohydric alcohol and dihydric alcohol or polyhydric alcohol according to the present invention shows better performance.

References - DE 11 2015 000659 T5 - EP 3875538 A1 - EP 3943550 A1 - EP 4053201 A1 - US 2020/017628 A1 - EP 3835333 A1

without

without

Claims (15)

A polycarbodiimide composition comprising a polycarbodiimide having formula (1) (1), and/or, preferably, a polycarbodiimide having formula (2) (2), wherein R ₁ is selected from the group consisting of optionally branched (C ₁₁ -C ₅₀ ) alkoxy groups and optionally branched (C ₁₁ -C ₅₀ ) alkenyloxy groups, wherein R ₁ comprises an atomic ratio of carbon atoms calculated based on the total carbon atoms contained in R ₁ to oxygen atoms calculated based on the total oxygen atoms contained in R ₁ , C:O, which is equal to or greater than 11, wherein R ₂ is -C ₆ H ₈ -CH ₂ -C ₆ H ₈ -(4,4'-diyldicyclohexylmethane), wherein R ₃ is selected from the group consisting of optionally branched and/or optionally alkoxylated alkylene groups, wherein the alkylene groups consist of C, H and optionally selected O, wherein R ₄ is selected from the group consisting of optionally branched and/or optionally alkoxylated alkanetriyl groups, wherein the alkanetriyl groups consist of C, H and optionally selected 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 ppm by weight of P, calculated as elemental P and based on the total weight of the polycarbodiimide composition. The polycarbodiimide composition of claim 1, wherein R ₁ is selected from the group consisting of optionally branched (C ₁₂ -C ₄₀ ) alkoxy groups and optionally branched (C ₁₂ -C ₄₀ ) alkenyloxy groups. The polycarbodiimide composition of claim 1 or 2, wherein R ₁ is selected from the group consisting of -(CH ₂ ) ₈ -CH=CH-(CH ₂ ) ₇ -CH ₃ and -CH ₂ -CH[(CH ₂ ) ₇ -CH ₃ ][-(CH ₂ ) ₉ -CH ₃ ]. A polycarbodiimide composition as claimed in any one of claims 1 to 3, wherein _R1 comprises an atomic ratio of carbon atoms calculated based on the total carbon atoms contained in _R1 to oxygen atoms calculated based on the total oxygen atoms contained in _R1 , C:O, in the range of 11 to 50. The polycarbodiimide composition of any one of claims 1 to 4, wherein R ₁ has a molecular weight greater than 210 g/mol. The polycarbodiimide composition of any one of claims 1 to 5, wherein _R3 is selected from the group consisting of an optionally branched ( _C1 - _C25 ) alkylene group, -[ _CR5H - _CH2 -O] _x1 - _CR5H - _CH2- , wherein _R5 is H or _CH3 , wherein x1 is an integer in the range of 1 to 15, -[ _CH2 - _CH2 -O] _x2 - _CH2 - _CH2 -O- ran -{[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 -, where x4 is an integer in the range of 1 to 30. The polycarbodiimide composition of any one of claims 1 to 6, wherein R ₄ is selected from the group consisting of: optionally alkoxylated (C ₃ -C ₅₀ ) alkanetriyl, , and , wherein R ₆ is -[CR ₇ H-CH ₂ -O] _x1 -CR ₇ H-CH ₂ -, wherein R ₇ is H or CH ₃ , -[CH ₂ -CH ₂ -O] _x2 -CH ₂ -CH ₂ -O- ran -{[C(CH ₃ )H-CH ₂ -O] _x3 -C(CH ₃ )H-CH ₂ }-, and -[CH ₂ -CH ₂ -CH ₂ -CH ₂ -O] _x4 -CH ₂ -CH ₂ -CH ₂ -CH ₂ -, 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. The polycarbodiimide composition of any one of claims 1 to 7, wherein m is an integer in the range of 2 to 18. The polycarbodiimide composition of any one of claims 1 to 8, wherein p is an integer in the range of 1 to 5. The polycarbodiimide composition of any one of claims 1 to 9, wherein n is an integer in the range of 2 to 18. A polycarbodiimide composition as claimed in any one of claims 1 to 10, wherein the polycarbodiimide comprises equal to or less than 410 ppm by weight of phosphane oxide, calculated as the total weight of phosphane oxide and based on the total weight of the polycarbodiimide composition. The polycarbodiimide composition of claim 11, wherein the phosphotene oxide is selected from the group consisting of: 1-methyl-2-phosphotene-1-oxide (MPO), 3-methyl-1-phenyl-2-phosphotene-1-oxide (MPPO), 3-methyl-1-ethyl-2-phosphotene-1-oxide, 1,3-dimethyl-2-phosphotene-1-oxide, 1-phenyl-2-phosphotene-1-oxide , 1-ethyl-2-cyclophosphene-1-oxide, 1-methyl-3-cyclophosphene-1-oxide, 3-methyl-1-phenyl-3-cyclophosphene-1-oxide, 3-methyl-1-ethyl-3-cyclophosphene-1-oxide, 1,3-dimethyl-3-cyclophosphene-1-oxide, 1-phenyl-3-cyclophosphene-1-oxide, 1-ethyl-3-cyclophosphene-1-oxide, and a mixture of two or more thereof. A method for preparing a polycarbodiimide composition, the method comprising: (i) preparing a mixture comprising 4,4'-diisocyanatodicyclohexylmethane and one or more cyclophosphene 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 monohydric alcohols and one or more polyhydric alcohols to the mixture obtained in (ii), wherein the one or more monohydric alcohols are independently selected from the group consisting of optionally branched monohydroxy (C ₁₁ -C ₅₀ ) alkanes and optionally branched monohydroxy (C ₁₁ -C ₅₀ ) alkenes, wherein the one or more optionally branched monohydroxy (C ₁₁ -C ₅₀ ) alkane and optionally branched monohydroxy (C ₁₁ -C ₅₀ ) alkene independently contain an atomic ratio of carbon atoms calculated based on the total carbon atoms contained in each of the optionally branched monohydroxy (C ₁₁ -C ₅₀ ) alkane and the optionally branched monohydroxy (C ₁₁ -C ₅₀ ) alkene to oxygen atoms calculated based on the total oxygen atoms contained in each of the optionally branched monohydroxy (C ₁₁ -C ₅₀ ) alkane and the optionally branched monohydroxy (C ₁₁ -C ₅₀ ) alkene, which is equal to or greater than 11, C:O, wherein the one or more polyols are independently 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 under 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 phosphane oxides from the mixture obtained in (iii); to obtain the polycarbodiimide composition. A polycarbodiimide composition is obtainable or obtained by the method of claim 13. A use of the polycarbodiimide composition of any one of claims 1 to 12 and 14 as a stabilizer.