Polycarbodiimide compositions as polymer stabilizers

Abstract

The present invention relates to a polycarbodiimide composition, particularly comprising a specific polycarbodiimide and a small amount of P. The polycarbodiimide composition can be used as a stabilizer for polymers, particularly as a hydrolysis stabilizer for thermoplastic polyurethane compositions. Furthermore, the present invention relates to a process for preparing the polycarbodiimide composition, and a polycarbodiimide composition obtainable or obtainable by said process.

Description

[Technical Field]

[0001] The present invention relates to a polycarbodiimide composition, a process for its preparation, a polycarbodiimide composition obtained or obtainable by said process, and uses of the polycarbodiimide composition.

[0002] Introduction Carbodiimides are compounds known as polycarbodiimides, preferably in their oligomeric or polymeric forms, and can be used in a wide range of applications, particularly as stabilizers in plastics, lubricants, or plasticizers, or as crosslinkers for carboxylic acid (-COOH) groups, such as coatings, adhesives, and printing and packaging applications, which are undesirable due to hydrolysis.In the context of the present invention, the term polycarbodiimide includes its oligomeric and polymeric forms.For example, thermoplastic polyurethanes or polyesters, in particular, are typically stabilized by polycarbodiimides.

[0003] DE 112015000659 A1 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.

[0004] EP 3875538 A1 relates to a polyester resin modifier suitable for improving the hydrolysis resistance of polyester resins, a method for producing the same, and a polyester resin composition. The disclosed polyester resin modifier is obtained by reacting an aliphatic diisocyanate, an isocyanate end-capping agent, and a carbodiimide catalyst. The obtained polyester resin modifier contains a polycarbodiimide compound with a low content of the carbodiimide catalyst used to produce the polyester resin modifier.

[0005] EP 3943550 A1 relates to a powdered polycarbodiimide compound capable of improving the hydrolysis resistance of ester resins, and an ester resin composition containing the same.

[0006] EP 4053201 A1 relates to a compatibilizer for polyester resins to improve compatibility between different types of resins, and a polyester resin composition using the same.

[0007] US Patent Application Publication No. 2020 / 017628 relates to a carboxyl group-containing aqueous resin composition, a molded article formed from the resin composition, and a method for producing a polycarbodiimide compound used in the resin composition.

[0008] 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 cured resin, and a carbodiimide crosslinking agent for treating fibers.

[0009] However, the prior art does not describe a process for the preparation of polycarbodiimides in which at least a portion of the carbodiimidization catalyst is removed from the reaction mixture.

[0010] Polycarbodiimides are generally formed by the condensation of diisocyanates. Subsequently, the polycarbodiimides are end-capped, for example, with mono-OH functionalized polyethylene oxide (PEO). It has been found that only meta-tetramethylxylylene diisocyanate (also referred to herein as m-TMXDI or TMXDI) can be used as an aliphatic isocyanate monomer to obtain good performance, particularly in terms of properties, especially in thermoplastic polyurethane (TPU) applications. However, attempts to transfer this concept to polycarbodiimides formed with alternative isocyanate monomers, such as hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), or hydrogenated MDI (also known as H12MDI or 4,4'-diisocyanatodicyclohexylmethane), have failed.

[0011] The object of the present invention was to provide novel polycarbodiimide compositions with improved performance in terms of polymer stabilization properties.

[0012] Detailed Description Surprisingly, it has been found that polycarbodiimide compositions containing small amounts of phosphorus, particularly small amounts of phospholene oxide, and in which the polycarbodiimide is end-capped with specific groups, exhibit improved performance with respect to their properties as hydrolytic stabilizers for polymers.

[0013] In particular, polycarbodiimide compositions based on 4,4'-diisocyanatodicyclohexylmethane (H12MDI), in which the polycarbodiimide is end-capped with relatively long alkyl chains, have been found to exhibit better performance in terms of hydrolytic stability when used in TPUs, especially when compared to monoalcohol PEOs.

[0014] Therefore, the present invention provides a compound represented by formula (1) [ka] and / or, preferably, a polycarbodiimide represented by the formula (2): [ka] Polycarbodiimide shown in (wherein R1 may be branched (C 11 ~C 50 ) alkoxy and optionally branched (C 11 ~C 50 ) alkenoxy; R1 contains carbon atoms calculated as the total number of carbon atoms contained in R1 and oxygen atoms calculated as the total number of oxygen atoms contained in R1, with an atomic ratio C:O of 11 or more; R2 is —C6H8-CH2-C6H8-(4,4′-diyldicyclohexylmethane); R3 is selected from the group consisting of alkylene, which may be branched and / or alkoxylated, alkylene consisting of C, H and optionally O; R4 is selected from the group consisting of optionally branched and / or alkoxylated alkane-triyl, which consists of C, H and optionally O; m is an integer ranging from 1 to 20; p is an integer ranging from 1 to 10; n is an integer ranging from 1 to 20. wherein the polycarbodiimide composition contains 110 ppm by weight or less of P, calculated as elemental P, based on the total weight of the polycarbodiimide composition, and the P content of the polycarbodiimide composition is preferably determined according to Reference Example 2.

[0015] R1 may be branched (C 12 ~C 40 ) alkoxy and optionally branched (C 12 ~C 40 ) alkenoxy, more preferably optionally branched (C 13 ~C 35 ) alkoxy and optionally branched (C 13 ~C 35) alkenoxy, more preferably optionally branched (C 14 ~C 30 ) alkoxy and optionally branched (C 14 ~C 30 ) alkenoxy, more preferably optionally branched (C 15 ~C 25 ) alkoxy and optionally branched (C 15 ~C 25 ) alkenoxy, more preferably optionally branched (C 16 ~C 22 ) alkoxy and optionally branched (C 16 ~C 22 ) alkenoxy, more preferably optionally branched (C 17 ~C 21 ) alkoxy and optionally branched (C 17 ~C 21 ) alkenoxy, more preferably optionally branched (C 18 ~C 20 ) alkoxy and optionally branched (C 18 ~C 20 ) alkenoxy, and R1 is more preferably optionally branched (C 18 ~C 20 ) alkoxy or optionally branched (C 18 ~C 20 ) alkenoxy, more preferably branched (C 18 ~C 20 ) alkoxy or (C 18 ~C 20 ) alkenoxy, more preferably branched C 20 Alkoxy or C 18 It is alkenoxy.

[0016] R1 is -(CH2)8-CH=CH-(CH2)7-CH3, preferably -(CH2)8-CH=CH-(CH2)7-CH3 in the (Z) configuration, and -CH2-CH[(CH2)7-CH3][-(CH2)9-CH3] Preferably, the compound is selected from the group consisting of: R1 is more preferably -(CH2)8-CH=CH-(CH2)7-CH3, more preferably -(CH2)8-CH=CH-(CH2)7-CH3 in the (Z) configuration, or -CH2-CH[(CH2)7-CH3][-(CH2)9-CH3].

[0017] It is preferable that R1 contains an atomic ratio C:O of carbon atoms calculated as the total of carbon atoms contained in R1 to oxygen atoms calculated as the total of oxygen atoms contained in R1 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, and more preferably in the range of 18 to 20, and R1 contains an atomic ratio C:O of carbon atoms calculated as the total of carbon atoms contained in R1 to oxygen atoms calculated as the total of oxygen atoms contained in R1 of 18 or 20.

[0018] It is preferred that 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 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.

[0019] R3 may be branched (C1 to C 25 ) alkylene, -[CR5H-CH2-O] x1 -CR5H-CH2- (wherein R5 is H or CH3, and x1 is an integer ranging from 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 ranging from 1 to 15 and x3 is an integer ranging from 1 to 15), and -[CH2-CH2-CH2-CH2-O] x4-CH2-CH2-CH2-CH2- (wherein x4 is an integer ranging from 1 to 30, preferably from 1 to 15), more preferably optionally branched (C1 to C 25 ) alkylene, more preferably optionally branched (C1 to C 20 ) alkylene, more preferably optionally branched (C2 to C 15 ) alkylene, more preferably optionally branched (C3 to C 12 ) alkylene, more preferably optionally branched (C4 to C 10 R3 is more preferably selected from the group consisting of optionally branched C5 alkylenes, and R4 is more preferably selected from the group consisting of branched C5 alkylenes.

[0020] R3 may be branched (C1 to C 25 ) alkylene, -[CR5H-CH2-O] x1 -CR5H-CH2- (wherein R5 is H or CH3, and x1 is an integer ranging from 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 ranging from 1 to 15 and x3 is an integer ranging from 1 to 15), and -[CH2-CH2-CH2-CH2-O] x4 -CH2-CH2-CH2-CH2- (wherein x4 is an integer ranging from 1 to 30, preferably from 1 to 15), more preferably optionally branched (C1 to C 25) alkylene, 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) 10 - and -(CH2) 12 - selected from the group consisting of More preferably, it is 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-, and -(CH2)6-; R3 is more preferably -CH2-C(CH3)2-CH2- or -(CH2)5-.

[0021] R4 may be alkoxylated (C3-C 50 ) alkane-triyl, [ka] [ka] and [ka] (Wherein, R6 is —[CR7H—CH2—O] x1 -CR7H-CH2- (wherein R7 is H or CH3, and x1 is an integer ranging from 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 ranging from 1 to 15 and x3 is an integer ranging from 1 to 15), and -[CH2-CH2-CH2-CH2-O] x4-CH2-CH2-CH2-CH2- (wherein x4 is an integer ranging from 1 to 30, preferably from 1 to 15) Preferably, the compound is selected from the group consisting of: R4 is more preferably an optionally alkoxylated (C3-C 50 ) alkane-triyl, and [ka] is selected from the group consisting of R4 is more preferably (C3 to C 40 ) alkane-triyl, more preferably (C3-C 30 ) alkane-triyl, more preferably (C3-C 20 ) alkane-triyl, more preferably (C3-C 10 )alkane-triyl, more preferably (C3-C5)alkane-triyl; R4 is more preferably [ka] (propane-1,2,3-triyl).

[0022] It is preferable 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, and more preferably in the range of 6 to 15.

[0023] It is preferred that 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.

[0024] n is preferably 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.

[0025] It is preferred that the polycarbodiimide contain not more than 100 ppm by weight of P, calculated as elemental P, based on the total weight of the polycarbodiimide composition, more preferably not more than 90 ppm by weight, more preferably not more than 80 ppm by weight, more preferably not more than 75 ppm by weight, more preferably not more than 70 ppm by weight, more preferably not more than 65 ppm by weight, more preferably not more than 60 ppm by weight of P, calculated as elemental P, based on the total weight of the polycarbodiimide composition.

[0026] Preferably, the polycarbodiimide comprises not more than 410 ppm by weight of phospholene oxide, calculated as the sum of the weight of phospholene oxide, based on the total weight of the polycarbodiimide composition, more preferably not more than 370 ppm by weight, more preferably not more than 335 ppm by weight, more preferably not more than 295 ppm by weight, more preferably not more than 280 ppm by weight, more preferably not more than 260 ppm by weight, more preferably not more than 240 ppm by weight, more preferably not more than 220 ppm by weight of phospholene oxide, calculated as the sum of the weight of phospholene oxide, based on the total weight of the polycarbodiimide composition.

[0027] When the polycarbodiimide contains 410 ppm by weight or less of phospholene oxide, calculated as the sum of the weights of phospholene oxides, based on the total weight of the polycarbodiimide composition, the phospholene oxide is 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 The one or more phospholene oxides are preferably 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 and mixtures of two or more thereof, and 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, and the phospholene oxide is more preferably 1-methyl-2-phospholene-1-oxide (MPO).

[0028] It is preferred that 99.0 to 100% by weight, more preferably 99.5 to 100% by weight, and even more preferably 99.9 to 100% by weight of the polycarbodiimide composition consists of polycarbodiimide and P, preferably polycarbodiimide and phospholene oxide.

[0029] The viscosity of the polycarbodiimide composition is preferably within the range of 5 to 20 Pa·s.

[0030] The polycarbodiimide composition preferably has a content of N=C=N functional groups in the range of 4.0 to 12.0%, more preferably in the range of 6.0 to 9.8%, more preferably in the range of 6.2 to 9.6%, and the content of N=C=N functional groups is more preferably determined according to Reference Example 1.

[0031] 1. A process for preparing a polycarbodiimide composition, preferably according to any one of the embodiments disclosed herein, comprising the steps of: (i) preparing a mixture comprising 4,4'-diisocyanatodicyclohexylmethane and one or more phospholene oxides; (ii) subjecting the mixture obtained in (i) to carbodiimidization conditions in a gas atmosphere, the carbodiimidization conditions comprising 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 one or more monoalcohols are, independently of one another, optionally branched monohydroxy (C 11 ~C 50 ) alkanes and optionally branched monohydroxy (C 11 ~C 50 ) alkenes, One or more optionally branched monohydroxy (C 11 ~C 50 ) alkanes and optionally branched monohydroxy (C 11 ~C 50 ) alkenes, independently of one another, optionally branched monohydroxy (C 11 ~C 50 ) alkanes and optionally branched monohydroxy (C 11 ~C 50 ) alkene and optionally branched monohydroxy (C 11 ~C 50) alkanes and optionally branched monohydroxy (C 11 ~C 50 ) The atomic ratio C:O of the oxygen atoms calculated as the sum of the oxygen atoms contained in each alkene is 11 or more, the one or more polyalcohols are, independently of one another, 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 the trihydroxyalkanes consist of C, H and O; and subjecting the resulting mixture to reaction conditions in a gas atmosphere, the reaction conditions including 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); The process includes:

[0032] The one or more phospholene oxides are preferably 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. is preferably 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 and mixtures of two or more thereof, and 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, and the one or more phospholene oxides are more preferably 1-methyl-2-phospholene-1-oxide (MPO).

[0033] The mixture obtained in (i) preferably contains a molar ratio of 4,4'-diisocyanatodicyclohexylmethane, calculated as the molar amount of 4,4'-diisocyanatodicyclohexylmethane, to one or more phospholene oxides, calculated as the sum of the molar amounts of the one or more phospholene 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, and more preferably in the range of 300:1 to 350:1.

[0034] The mixture obtained in (i) preferably contains 0 to 1 wt %, more preferably 0 to 0.1 wt %, more preferably 0 to 0.01 wt % of xylene, more preferably alkyl-substituted benzene or alkyl-substituted dibenzene (wherein alkyl includes one or more of methyl, ethyl, and propyl), more preferably a solvent; The mixture obtained in (i) is more preferably substantially free of xylene, more preferably substantially free of alkyl-substituted benzene or alkyl-substituted dibenzene, and more preferably substantially free of solvent.

[0035] The carbodiimidization conditions (ii) preferably include 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.

[0036] The gas atmosphere (ii) preferably comprises an inert gas, more preferably consists of an inert gas, and the gas atmosphere (ii) preferably comprises one or more of nitrogen and argon, more preferably consists of one or more of nitrogen and argon.

[0037] The carbodiimidization conditions in (ii) preferably include applying a pressure 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 to the mixture obtained in (i).

[0038] The carbodiimidization conditions in (ii) preferably include agitating, more preferably stirring, the mixture obtained in (i).

[0039] The mixture obtained in (i) is preferably subjected to the carbodiimidization conditions in (ii) for a duration in the range of 1 to 50 hours, more preferably in the range of 1.5 to 40 hours, more preferably in the range of 2 to 25 hours.

[0040] The one or more monoalcohols added to the mixture obtained in (ii) according to (iii) may be, independently of one another, optionally branched monohydroxy (C 12 ~C 40 ) alkane and optionally branched monohydroxy (C 12 ~C 40 ) alkenes, more preferably optionally branched monohydroxy (C 13 ~C 35 ) alkane and optionally branched monohydroxy (C 13 ~C 35 ) alkenes, more preferably optionally branched monohydroxy (C 14 ~C 30 ) alkane and optionally branched monohydroxy (C 14 ~C 30 ) alkenes, more preferably optionally branched monohydroxy (C 15 ~C 25 ) alkane and optionally branched monohydroxy (C 15 ~C 25 ) alkenes, more preferably optionally branched monohydroxy (C 16 ~C 22 ) alkane and optionally branched monohydroxy (C 16 ~C 22 ) alkenes, more preferably optionally branched monohydroxy (C 17 ~C 21 ) alkane and optionally branched monohydroxy (C 17 ~C 21 ) alkenes, more preferably optionally branched monohydroxy (C 18 ~C 20 ) alkane and optionally branched monohydroxy (C 18 ~C20 ) alkenes, and the one or more monoalcohols are preferably selected independently from one another, more preferably from the group consisting of optionally branched monohydroxy (C 18 ~C 20 ) alkane or optionally branched monohydroxy (C 18 ~C 20 ) alkenes, 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 It is an alkene.

[0041] The one or more monoalcohols added according to (iii) to the mixture obtained in (ii) are preferably selected independently from one another from the group consisting of HO-(CH2)8-CH=CH-(CH2)7-CH3, preferably HO-(CH2)8-CH=CH-(CH2)7-CH3 in the (Z) configuration, and HO-CH2-CH[(CH2)7-CH3][-(CH2)9-CH3], and 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 the (Z) configuration, or HO-CH2-CH[(CH2)7-CH3][-(CH2)9-CH3].

[0042] One or more optionally branched monohydroxy (C 11 ~C 50 ) alkane and optionally branched monohydroxy (C 11 ~C 50 ) alkenes are independently optionally branched monohydroxy (C 11 ~C 50 ) alkane and optionally branched monohydroxy (C 11 ~C 50 ) alkene and the carbon atoms calculated as the sum of the carbon atoms contained in each alkene, and optionally branched monohydroxy (C 11~C 50 ) alkane and optionally branched monohydroxy (C 11 ~C 50 The atomic ratio C:O of the oxygen atoms, calculated as the sum of the oxygen atoms contained in each alkene, is preferably 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, and more preferably in the range of 18 to 20, and the alkylene (C 11 ~C 50 ) alkane and optionally branched monohydroxy (C 11 ~C 50 ) alkene may be, independently of one another, one or more optionally branched monohydroxy (C 11 ~C 50 ) alkane and optionally branched monohydroxy (C 11 ~C 50 ) alkene and one or more optionally branched monohydroxy (C 11 ~C 50 ) alkane and optionally branched monohydroxy (C 11 ~C 50 ) The atomic ratio C:O of the oxygen atoms, calculated as the sum of the oxygen atoms contained in each alkene, is 18 or 20.

[0043] The one or more polyalcohols added according to (iii) to the mixture obtained in (ii) may be, independently of one another, propane-1,2,3-triol, a triester of glycerol and ricinoleic acid, HO-[CR5H-CH2-O] x1 -CR5H-CH2-OH (wherein R5 is H or CH3, and x1 is an integer ranging from 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 ranging from 1 to 15 and x3 is an integer ranging from 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 (C1-C 25 ) alkanes, more preferably optionally branched and / or optionally alkoxylated dihydroxy (C1-C 20 )alkane, more preferably optionally branched dihydroxy (C2-C 15 ) alkane, more preferably optionally branched dihydroxy (C3-C 12 ) alkane, more preferably optionally branched dihydroxy (C4-C 10 )alkanes, more preferably optionally branched dihydroxy(C5-C6)alkanes, The one or more polyalcohols are more preferably selected independently from one another from the group consisting of optionally branched dihydroxy C5 alkanes, and the one or more polyalcohols are more preferably selected from the group consisting of branched dihydroxy C5 alkanes.

[0044] In the context of the present invention, ricinoleic acid is (9Z,12R)-12-hydroxyoctadec-9-enoic acid.

[0045] The one or more polyalcohols added according to (iii) to the mixture obtained in (ii) may, independently of one another, be branched and / or alkoxylated (C3 to C 50 ) alkane-triols, more preferably (C3-C 40 ) alkane-triols, more preferably (C3-C 30 ) alkane-triols, more preferably (C3-C 20 ) alkane-triols, more preferably (C3-C 10) alkane-triol, more preferably (C3-C5) alkane-triol, triester of glycerol and ricinoleic acid, [ka] and [ka] (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 ranging from 1 to 15, x2 is an integer ranging from 1 to 15, x3 is an integer ranging from 1 to 15, and x4 is an integer ranging from 1 to 30, more preferably an integer ranging from 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-C H2-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) 10 -OH, and HO-(CH2) 12 -OH More preferably, propane-1,2,3-triol, [ka] a triester of glycerol and ricinoleic acid having the formula: 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 Preferably, the compound is selected from the group consisting of: The one or more polyalcohols added according to (iii) to the mixture obtained in (ii) are more preferably selected independently from one another from the group consisting of propane-1,2,3-triol, a triester of glycerol and ricinoleic acid having formula (3), and HO-(CH2)5-OH.

[0046] The mixture obtained in (iii) preferably contains 5 to 70 wt. % of one or more monoalcohols, more preferably 25 to 50 wt. %, calculated as the sum of the weights of the one or more monoalcohols, based on the total weight of the mixture obtained in (iii).

[0047] The mixture obtained in (iii) preferably contains 0.1 to 20 wt. % of one or more polyalcohols, more preferably 1 to 15 wt. %, calculated as the sum of the weights of the one or more polyalcohols, based on the total weight of the mixture obtained in (iii).

[0048] The mixture obtained in (iii) preferably contains 5.1 to 90 wt. % of one or more monoalcohols and one or more polyalcohols, more preferably 26 to 65 wt. %, calculated as the sum of the weight of the one or more monoalcohols and the weight of the one or more polyalcohols, respectively, based on the total weight of the mixture obtained in (iii).

[0049] Preferably, the reaction conditions according to (iii) include 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.

[0050] Removing at least a portion of the one or more phospholene oxides from the mixture obtained in (iii) according to (iv) comprises (iv.1) optionally adding one or more azeotropic agents to the mixture obtained in (iii); (iv.2) Distilling the mixture obtained in (iii) or (iv.1) to obtain a fraction containing the polycarbodiimide composition and a fraction containing at least a portion of the one or more phospholene oxides. It is preferred that the compound contains:

[0051] When the removal of at least a portion of one or more phospholene oxides from the mixture obtained in (iii) according to (iv) optionally comprises (iv.1) and (iv.2), the one or more azeotropic agents preferably 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 (absolute), and the one or more azeotropic agents are more preferably acetates comprising C, H and O, more preferably consisting of C, H and O (acetates containing 6 to 16, preferably 8 to 14, C and O atoms calculated as the sum of carbon and oxygen atoms), (C1 to C 10 ) Alkyl (C1-C 10 (C1-C2)alkyloxy(C3-C5)alkyl acetate, diethylene glycol mono(C2-C6)alkyl ether acetate, di(C1-C5)alkyl adipate, and a mixture 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 a mixture of two or more thereof, and the one or more azeotropic agents are more preferably selected from the group consisting of diethyl adipate.

[0052] Furthermore, when the removal of at least a portion of one or more phospholene oxides from the mixture obtained in (iii) according to (iv) optionally includes (iv.1) and (iv.2), the distillation of the mixture obtained in (iii) or (iv.1) is preferably carried out at a temperature in the range of 130 to 190°C, more preferably in the range of 140 to 180°C, more preferably in the range of 150 to 170°C.

[0053] Furthermore, if the removal of at least a portion of one or more phospholene oxides according to (iv) from the mixture obtained in (iii) optionally comprises (iv.1) and (iv.2), it is preferred that the distillation of the mixture obtained in (iii) or (iv.1) is carried out at a pressure of less than 0.150 bar (absolute), more preferably less than 0.125 bar (absolute), more preferably less than 0.100 bar (absolute).

[0054] A polycarbodiimide composition obtainable or obtained by the process according to any one of the embodiments disclosed herein.

[0055] Use of the polycarbodiimide composition according to 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 polyurethane (PU), preferably thermoplastic polyurethane (TPU), polyurea, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polylactide (PLA), polyamide, polyesteramide, polycaprolactone, and polyethersulfone (PES).

[0056] The unit bar (absolute) is 1 bar = 10 5 Refers to absolute pressure equal to Pa.

[0057] The present invention is further described by the following sets of embodiments and combinations of embodiments resulting from dependencies and backward references as indicated. In particular, in each instance where a range of embodiments is mentioned, it should be noted that in the context of terms such as "the polycarbodiimide composition according to any one of embodiments 1 to 4," all embodiments within this range are expressly disclosed to those skilled in the art, i.e., the wording of this term should be understood by those skilled in the art as being synonymous with "the polycarbodiimide composition according to any one of embodiments 1, 2, 3, and 4." Furthermore, it should be explicitly noted that the following sets of embodiments represent a properly structured portion of the description of the general and preferred aspects of the present invention, rather than a set of claims determining the degree of protection.

[0058] 1.Equation (1) [ka] and / or, preferably, a polycarbodiimide represented by the formula (2): [ka] Polycarbodiimide shown in (wherein R1 may be branched (C 11 ~C 50 ) alkoxy and optionally branched (C 11 ~C 50 ) alkenoxy; R1 contains carbon atoms calculated as the total number of carbon atoms contained in R1 and oxygen atoms calculated as the total number of oxygen atoms contained in R1, with an atomic ratio C:O of 11 or more; R2 is —C6H8-CH2-C6H8-(4,4′-diyldicyclohexylmethane); R3 is selected from the group consisting of alkylene, which may be branched and / or alkoxylated, alkylene consisting of C, H and optionally O; R4 is selected from the group consisting of optionally branched and / or alkoxylated alkane-triyl, which consists of C, H and optionally O; m is an integer ranging from 1 to 20; p is an integer ranging from 1 to 10; n is an integer ranging from 1 to 20. wherein the P content of the polycarbodiimide composition is preferably determined according to Reference Example 2.

[0059] 2. R1 may be branched (C 12 ~C 40 ) alkoxy and optionally branched (C 12 ~C 40 ) alkenoxy, preferably optionally branched (C 13 ~C 35 ) alkoxy and optionally branched (C 13 ~C 35 ) alkenoxy, more preferably optionally branched (C 14 ~C 30 ) alkoxy and optionally branched (C 14 ~C 30 ) alkenoxy, more preferably optionally branched (C 15 ~C 25 ) alkoxy and optionally branched (C 15 ~C 25 ) alkenoxy, more preferably optionally branched (C 16 ~C 22 ) alkoxy and optionally branched (C 16 ~C 22 ) alkenoxy, more preferably optionally branched (C 17 ~C 21 ) alkoxy and optionally branched (C 17 ~C 21) alkenoxy, more preferably optionally branched (C 18 ~C 20 ) alkoxy and optionally branched (C 18 ~C 20 ) alkenoxy, and R1 is more preferably optionally branched (C 18 ~C 20 ) alkoxy or optionally branched (C 18 ~C 20 ) alkenoxy, more preferably branched (C 18 ~C 20 ) alkoxy or (C 18 ~C 20 ) alkenoxy, more preferably branched C 20 Alkoxy or C 18 2. The polycarbodiimide composition of embodiment 1, wherein the polycarbodiimide composition is an alkenoxy.

[0060] 3.R1 is, -(CH2)8-CH=CH-(CH2)7-CH3, preferably -(CH2)8-CH=CH-(CH2)7-CH3 in the (Z) configuration, and -CH2-CH[(CH2)7-CH3][-(CH2)9-CH3] is selected from the group consisting of The polycarbodiimide composition of embodiment 1 or 2, wherein R1 is more preferably —(CH2)8-CH═CH—(CH2)7-CH3, more preferably —(CH2)8-CH═CH—(CH2)7-CH3 in the (Z) configuration, or —CH2-CH[(CH2)7-CH3][—(CH2)9-CH3].

[0061] 4. The polycarbodiimide composition according to any one of embodiments 1 to 3, wherein R1 has an atomic ratio C:O of carbon atoms, calculated as the sum of carbon atoms contained in R1, to oxygen atoms, calculated as the sum of oxygen atoms contained in R1, in the range of 11 to 50, more preferably 12 to 40, more preferably 13 to 35, more preferably 14 to 30, more preferably 15 to 25, more preferably 16 to 22, more preferably 17 to 21, or more preferably 18 to 20; and wherein R1 has an atomic ratio C:O of carbon atoms, calculated as the sum of carbon atoms contained in R1, to oxygen atoms, calculated as the sum of oxygen atoms contained in R1, of 18 or 20.

[0062] 5. The polycarbodiimide composition according to any one of embodiments 1 to 4, wherein R1 has a molecular weight greater than 210 g / mol, preferably in the range of greater than 210 g / mol 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.

[0063] 6. R3 may be branched (C1 to C 25 ) alkylene, -[CR5H-CH2-O] x1 -CR5H-CH2- (wherein R5 is H or CH3, and x1 is an integer ranging from 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 ranging from 1 to 15 and x3 is an integer ranging from 1 to 15), and -[CH2-CH2-CH2-CH2-O] x4 -CH2-CH2-CH2-CH2- (wherein x4 is an integer ranging from 1 to 30, preferably from 1 to 15), and is preferably an optionally branched (C1 to C 25 ) alkylene, more preferably optionally branched (C1 to C20 ) alkylene, more preferably optionally branched (C2 to C 15 ) alkylene, more preferably optionally branched (C3 to C 12 ) alkylene, more preferably optionally branched (C4 to C 10 ) alkylene, more preferably optionally branched (C5-C6) alkylene, and R 3が 6. The polycarbodiimide composition of any one of the preceding embodiments, wherein R is more preferably selected from the group consisting of optionally branched C5 alkylenes.

[0064] 7. R3 may be branched (C1 to C 25 ) alkylene, -[CR5H-CH2-O] x1 -CR5H-CH2- (wherein R5 is H or CH3, and x1 is an integer ranging from 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 ranging from 1 to 15 and x3 is an integer ranging from 1 to 15), and -[CH2-CH2-CH2-CH2-O] x4 -CH2-CH2-CH2-CH2- (wherein x4 is an integer ranging from 1 to 30, preferably from 1 to 15), and is preferably an optionally branched (C1 to C 25 ) alkylene, 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) 10 - and -(CH2) 12 - selected from the group consisting of Preferably, it is 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-, and -(CH2)6-; 7. The polycarbodiimide composition of any one of embodiments 1 to 6, wherein R3 is more preferably —CH2—C(CH3)2—CH2— or —(CH2)5—.

[0065] 8. R4 may be alkoxylated (C3 to C 50 ) alkane-triyl, [ka] [ka] and [ka] (Wherein, R6 is —[CR7H—CH2—O] x1 -CR7H-CH2- (wherein R7 is H or CH3), -[CH2-CH2-O] x2 -CH2-CH2-O-ran-{[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 ranging from 1 to 15, x2 is an integer ranging from 1 to 15, x3 is an integer ranging from 1 to 15, and x4 is an integer ranging from 1 to 30, preferably from 1 to 15) is selected from the group consisting of R4 is more preferably an optionally alkoxylated (C3 to C 50 ) alkane-triyl, and [ka] is selected from the group consisting of R4 is more preferably (C3 to C 40) alkane-triyl, more preferably (C3-C 30 ) alkane-triyl, more preferably (C3-C 20 ) alkane-triyl, more preferably (C3-C 10 )alkane-triyl, more preferably (C3-C5)alkane-triyl; R4 is more preferably [ka] (propane-1,2,3-triyl).

[0066] 9. The polycarbodiimide composition according to 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.

[0067] 10. The polycarbodiimide composition according to 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.

[0068] 11. The polycarbodiimide composition according to 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, and more preferably in the range of 6 to 15.

[0069] 12. The polycarbodiimide composition of any one of the preceding embodiments, wherein the polycarbodiimide comprises 100 ppm by weight or less of P, calculated as elemental P, based on the total weight of the polycarbodiimide composition, and preferably 90 ppm by weight or less, more preferably 80 ppm by weight or less, more preferably 75 ppm by weight or less, more preferably 70 ppm by weight or less, more preferably 65 ppm by weight or less, more preferably 60 ppm by weight or less of P, calculated as elemental P, based on the total weight of the polycarbodiimide composition.

[0070] 13. The polycarbodiimide composition of any one of embodiments 1 to 12, wherein the polycarbodiimide comprises 410 ppm by weight or less of phospholene oxide, calculated as the sum of the weight of phospholene oxide, based on the total weight of the polycarbodiimide composition, and preferably 370 ppm by weight or less, more preferably 335 ppm by weight or less, more preferably 295 ppm by weight or less, more preferably 280 ppm by weight or less, more preferably 260 ppm by weight or less, more preferably 240 ppm by weight or less, more preferably 220 ppm by weight or less of phospholene oxide, calculated as the sum of the weight of phospholene oxide, based on the total weight of the polycarbodiimide composition.

[0071] 14. 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 mixtures of two or more thereof, preferably 1- 14. The polycarbodiimide composition of embodiment 13, wherein the phospholene oxide is selected from the group consisting of 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 mixtures of two or more thereof; the phospholene oxide is more preferably 1-methyl-2-phospholene-1-oxide (MPO), 3-methyl-1-phenyl-2-phospholene-1-oxide (MPPO), and mixtures thereof; and the one or more phospholene oxides is more preferably 1-methyl-2-phospholene-1-oxide (MPO).

[0072] 15. The polycarbodiimide composition according to any one of embodiments 1 to 14, wherein 99.0 to 100 wt %, preferably 99.5 to 100 wt %, more preferably 99.9 to 100 wt % of the polycarbodiimide composition consists of polycarbodiimide and P, preferably polycarbodiimide and phospholene oxide.

[0073] 16. The polycarbodiimide composition of any one of embodiments 1 to 15, having a viscosity in the range of 16.5 to 20 Pa·s.

[0074] 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 4.0 to 12.0%, more preferably in the range of 6.0 to 9.8%, more preferably in the range of 6.2 to 9.6%, wherein the content of N=C=N functional groups is preferably determined according to Reference Example 1.

[0075] 18. A process for preparing a polycarbodiimide composition, preferably according to any one of embodiments 1 to 17, comprising the steps of: (i) preparing a mixture comprising 4,4'-diisocyanatodicyclohexylmethane and one or more phospholene oxides; (ii) subjecting the mixture obtained in (i) to carbodiimidization conditions in a gas atmosphere, the carbodiimidization conditions comprising 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 one or more monoalcohols are, independently of one another, optionally branched monohydroxy (C 11 ~C 50 ) alkane and optionally branched monohydroxy (C 11 ~C 50 ) alkenes, One or more optionally branched monohydroxy (C 11 ~C 50 ) alkane and optionally branched monohydroxy (C 11 ~C 50 ) alkenes are, independently of one another, optionally branched monohydroxy (C 11 ~C 50 ) alkane and optionally branched monohydroxy (C 11 ~C 50 ) alkene and the carbon atoms calculated as the sum of the carbon atoms contained in each alkene, and optionally branched monohydroxy (C 11 ~C 50) alkane and optionally branched monohydroxy (C 11 ~C 50 ) The atomic ratio C:O of the oxygen atoms calculated as the sum of the oxygen atoms contained in each alkene is 11 or more, the one or more polyalcohols are selected, independently from one another, 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, and the trihydroxyalkanes consist of C, H and O, and subjecting the resulting mixture to reaction conditions in a gas atmosphere, the reaction conditions including 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); The process includes:

[0076] 19. 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 mixtures of two or more thereof, preferably 1 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 and mixtures 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, and the one or more phospholene oxides are more preferably 1-methyl-2-phospholene-1-oxide (MPO).

[0077] 20. The process of embodiment 18 or 19, wherein the mixture obtained in (i) comprises a molar ratio of 4,4'-diisocyanatodicyclohexylmethane, calculated as the molar amount of 4,4'-diisocyanatodicyclohexylmethane, to the one or more phospholene oxides, calculated as the sum of the molar amounts of the one or more phospholene 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.

[0078] 21. The mixture obtained in (i) contains 0-1 wt. %, preferably 0-0.1 wt. %, more preferably 0-0.01 wt. % of xylene, preferably alkyl-substituted benzene or alkyl-substituted dibenzene (wherein alkyl comprises one or more of methyl, ethyl and propyl), more preferably a solvent; 21. The process of any one of embodiments 18 to 20, wherein the mixture obtained in (i) is more preferably substantially free of xylene, preferably substantially free of alkyl-substituted benzene or alkyl-substituted dibenzene, and more preferably substantially free of solvent.

[0079] 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.

[0080] 23. The process of any one of embodiments 18 to 22, wherein the gas atmosphere of (ii) comprises, and preferably consists of, an inert gas; the gas atmosphere of (ii) preferably comprises, and more preferably consists of, one or more of nitrogen and argon.

[0081] 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.

[0082] 25. The process of any one of embodiments 18 to 24, wherein the carbodiimidization conditions in (ii) comprise agitating, preferably by stirring, the mixture obtained in (i).

[0083] 26. The process of any one of embodiments 18 to 25, wherein the mixture obtained in (i) is subjected to the carbodiimidization conditions of (ii) for a duration in the range of 1 to 50 hours, preferably in the range of 1.5 to 40 hours, more preferably in the range of 2 to 25 hours.

[0084] 27. One or more monoalcohols added to the mixture obtained in (ii) according to (iii) may be, independently of one another, optionally branched monohydroxy (C 12 ~C 40 ) alkane and optionally branched monohydroxy (C 12 ~C 40 ) alkenes, preferably optionally branched monohydroxy (C 13 ~C 35 ) alkane and optionally branched monohydroxy (C 13 ~C 35 ) alkenes, more preferably optionally branched monohydroxy (C 14 ~C 30 ) alkane and optionally branched monohydroxy (C 14 ~C 30 ) alkenes, more preferably optionally branched monohydroxy (C 15 ~C 25 ) alkane and optionally branched monohydroxy (C 15 ~C 25 ) alkenes, more preferably optionally branched monohydroxy (C 16 ~C 22 ) alkane and optionally branched monohydroxy (C 16 ~C 22 ) alkenes, more preferably optionally branched monohydroxy (C 17 ~C 21 ) alkane and optionally branched monohydroxy (C 17 ~C 21 ) alkenes, more preferably optionally branched monohydroxy (C 18 ~C 20) alkane and optionally branched monohydroxy (C 18 ~C 20 ) alkenes, wherein one or more monoalcohols are, independently of one another, more preferably optionally branched monohydroxy (C 18 ~C 20 ) alkane or optionally branched monohydroxy (C 18 ~C 20 ) alkenes, 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 27. The process of any one of embodiments 18 to 26, wherein the alkene is an alkene.

[0085] 28. The process of any one of embodiments 18 to 27, wherein the one or more monoalcohols added to the mixture obtained in (ii) according to (iii) are, independently of one another, selected from the group consisting of HO-(CH2)8-CH=CH-(CH2)7-CH3, preferably HO-(CH2)8-CH=CH-(CH2)7-CH3 in the (Z) configuration, and HO-CH2-CH[(CH2)7-CH3][-(CH2)9-CH3], and 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 the (Z) configuration, or HO-CH2-CH[(CH2)7-CH3][-(CH2)9-CH3].

[0086] 29. One or more optionally branched monohydroxy (C 11 ~C 50 ) alkane and optionally branched monohydroxy (C 11 ~C 50 ) alkenes are, independently of one another, optionally branched monohydroxy (C 11 ~C 50 ) alkane and optionally branched monohydroxy (C11 ~C 50 ) alkene and the carbon atoms calculated as the sum of the carbon atoms contained in each alkene, and optionally branched monohydroxy (C 11 ~C 50 ) alkane and optionally branched monohydroxy (C 11 ~C 50 The atomic ratio C:O of the alkene to the oxygen atoms calculated as the sum of the oxygen atoms contained in each alkene is 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, and one or more optionally branched monohydroxy (C 11 ~C 50 ) alkane and optionally branched monohydroxy (C 11 ~C 50 ) alkenes independently of each other may be one or more branched monohydroxy (C 11 ~C 50 ) alkane and optionally branched monohydroxy (C 11 ~C 50 ) alkene and one or more optionally branched monohydroxy (C 11 ~C 50 ) alkane and optionally branched monohydroxy (C 11 ~C 50 29. The process of any one of embodiments 18 to 28, wherein the atomic ratio C:O of the oxygen atoms, calculated as the sum of the oxygen atoms contained in each alkene, is 18 or 20.

[0087] 30. The one or more polyalcohols added according to (iii) to the mixture obtained in (ii) may be, independently of one another, propane-1,2,3-triol, a triester of glycerol and ricinoleic acid, HO-[CR5H-CH2-O] x1 -CR5H-CH2-OH (wherein R5 is H or CH3, and x1 is an integer ranging from 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 ranging from 1 to 15 and x3 is an integer ranging from 1 to 15), and HO-[CH2-CH2-CH2-CH2-O] x4 -CH2-CH2-CH2-CH2-OH (wherein x4 is an integer ranging from 1 to 30, preferably from 1 to 15), and optionally branched and / or optionally alkoxylated dihydroxy (C1-C 25 ) alkanes, preferably dihydroxy (C1-C2) which may be branched and / or alkoxylated 20 )alkane, more preferably optionally branched dihydroxy (C2-C 15 ) alkane, more preferably optionally branched dihydroxy (C3-C 12 ) alkane, more preferably optionally branched dihydroxy (C4-C 10 )alkanes, more preferably optionally branched dihydroxy(C5-C6)alkanes, 30. The process according to any one of embodiments 18 to 29, wherein the one or more polyalcohols are, independently of one another, more preferably selected from the group consisting of optionally branched dihydroxy C5 alkanes, and the one or more polyalcohols are more preferably selected from the group consisting of branched dihydroxy C5 alkanes.

[0088] 31. The one or more polyalcohols added according to (iii) to the mixture obtained in (ii) may, independently of one another, be branched and / or alkoxylated (C3-C 50 ) alkane-triols, preferably (C3-C 40 ) alkane-triols, more preferably (C3-C 30 ) alkane-triols, more preferably (C3-C 20 ) alkane-triols, more preferably (C3-C 10) alkane-triol, more preferably (C3-C5) alkane-triol, triester of glycerol and ricinoleic acid, [ka] and [ka] (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 ranging from 1 to 15, x2 is an integer ranging from 1 to 15, x3 is an integer ranging from 1 to 15, and x4 is an integer ranging from 1 to 30, preferably from 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-C H2-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) 10 -OH, and HO-(CH2) 12 -OH From the group consisting of: Preferably, propane-1,2,3-triol, formula (3) [ka] a triester of glycerol and ricinoleic acid having the formula: 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 is selected from the group consisting of 31. The process according to any one of embodiments 18 to 30, wherein the one or more polyalcohols added according to (iii) to the mixture obtained in (ii) are, independently of one another, 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—(CH)—OH.

[0089] 32. The process of any one of embodiments 18 to 31, wherein the mixture obtained in (iii) comprises 5 to 70 wt. %, preferably 25 to 50 wt. %, of one or more monoalcohols, calculated as the sum of the weights of the one or more monoalcohols, based on the total weight of the mixture obtained in (iii).

[0090] 33. The process according to any one of embodiments 18 to 32, wherein the mixture obtained in (iii) comprises 0.1 to 20% by weight, preferably 1 to 15% by weight, of one or more polyalcohols, calculated as the sum of the weights of the one or more polyalcohols, based on the total weight of the mixture obtained in (iii).

[0091] 34. The process according to any one of embodiments 18 to 33, wherein the mixture obtained in (iii) comprises 5.1 to 90 wt. %, preferably 26 to 65 wt. %, of one or more monoalcohols and one or more polyalcohols, calculated as the sum of the weight of the one or more monoalcohols and the weight of the one or more polyalcohols, respectively, based on the total weight of the mixture obtained in (iii).

[0092] 35. 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.

[0093] 36. Removing at least a portion of one or more phospholene oxides from the mixture obtained in (iii) according to (iv), (iv.1) optionally adding one or more azeotropic agents to the mixture obtained in (iii); (iv.2) Distilling the mixture obtained in (iii) or (iv.1) to obtain a fraction containing the polycarbodiimide composition and a fraction containing at least a portion of the one or more phospholene oxides. 36. The process of any one of embodiments 18 to 35, comprising:

[0094] 37. One or more azeotropic agents have a boiling point in the range of 200-300°C, preferably in the range of 200-250°C, at a pressure in the range of 0.950-1.050 bar (absolute), and the one or more azeotropic agents are preferably acetates containing C, H and O, preferably consisting of C, H and O (acetates contain 6-16, preferably 8-14, C and O atoms, calculated as the sum of carbon and oxygen atoms), (C1-C 10 ) Alkyl (C1-C 1037. The process according to embodiment 36, wherein the one or more azeotroping agents are selected from the group consisting of (C1-C2)alkyloxy(C3-C5)alkyl acetates, diethylene glycol mono(C2-C6)alkyl ether acetates, di(C1-C5)alkyl adipates, and mixtures of two or more thereof, preferably from the group consisting of (C1-C2)alkyloxy(C3-C5)alkyl acetates, diethylene glycol mono(C2-C6)alkyl ether acetates, di(C1-C5)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, and the one or more azeotroping agents are more preferably diethyl adipate.

[0095] 38. The process of embodiment 36 or 37, wherein 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, preferably in the range of 140 to 180°C, more preferably in the range of 150 to 170°C.

[0096] 39. The process of any one of embodiments 36 to 38, wherein the distillation of the mixture obtained in (iii) or (iv.1) is carried out at a pressure of less than 0.150 bar (absolute), preferably less than 0.125 bar (absolute), more preferably less than 0.100 bar (absolute).

[0097] 40. A polycarbodiimide composition obtainable or obtained by the process of any one of embodiments 18 to 39.

[0098] 41. Use of the polycarbodiimide composition according to 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 polyurethane (PU), preferably thermoplastic polyurethane (TPU), polyurea, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polylactide (PLA), polyamide, polyesteramide, polycaprolactone and polyethersulfone (PES).

[0099] The present invention will be further illustrated by the following Reference Examples, Examples and Comparative Examples. [Example]

[0100] Reference Example 1: Determination of FTIR and ATR-FTIR spectra FTIR spectra, specifically to determine the characteristic bands of isocyanate groups, were recorded using a single-reflection ATR module on a Brucker Eco-ATR. The samples were loaded directly onto the ATR crystal without any modification. Typically, the isocyanate group NCO appears at approximately 2200 cm in the FTIR spectrum. -1 The carbodiimide (N=C=N) group exhibits a band at approximately 2100 cm -1 It is expected to show a band of

[0101] Reference Example 2: Determination of residual phosphorus The phosphorus content was determined by elemental analysis (ICP-OES, DIN ISO 17025).

[0102] Comparative Example 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-methylphospholene-1-oxide (MPO; 1.20 mmol) were added to a 500 ml four-neck round-bottom flask equipped with a thermometer (combined with a thermoregulated oil bath), mechanical stirring, a cold water condenser, and a nitrogen inlet. The reaction mixture was stirred and heated to 170 °C. After approximately 17 h, a second aliquot of MPO (0.13 g; 1.11 mmol) was added. After 20 h, the NCO content reached a value of 12.8%. Then, 92.8 g of oleyl alcohol and 8.1 g of neopentyl glycol were added. After several hours, the NCO content reached 0.0% (complete 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).

[0103] Comparative Example 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) having a molecular weight of approximately 500 g / mol were mixed in a 1000 ml four-neck round-bottom flask equipped with a thermometer (combined with 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 approximately 4 hours, the NCO content reached a value of 13.7% (urethane reaction). The reaction temperature was then increased to 180 °C, and 0.99 g of 1-methylphospholene-1-oxide (MPO; 8.52 mmol) was added. After 71 hours, the NCO content reached 1.1% and the remaining NCO was end-capped by adding 113 g of Pluriol A500E. After an additional 5 hours, the NCO content reached 0.0%.

[0104] 200 g of the product was then transferred together with 200 g of diethyl adipate (DEA) to a 500 ml four-neck round-bottom flask equipped with a thermometer (combined with a thermostated 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 also remove some of the remaining MPO (DEA served as an azeotrope). The corresponding product had an NCN content of 5.0% and an MPO content of 650 ppm.

[0105] Comparative Example 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 added to a 1000 ml four-neck round-bottom flask equipped with a thermometer (combined with 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 approximately 4 h, the NCO content reached a value of 18.7% (urethane reaction). The reaction temperature was then increased to 180 °C, and 0.20 g of 1-methyl-phospholene-1-oxide (MPO; 1.72 mmol) was added. After 70 h, the NCO content reached 1.2%, and the remaining NCO was end-capped by adding 20 g of oleyl alcohol. After an additional 4 h of mixing, the NCO content reached 0.0%. The reaction was cooled to room temperature, and then 250 g of diethyl adipate was added. The diethyl adipate was then distilled off using a bridge (180 °C and 1 mbar) (DEA served as an azeotrope) to also remove some of the remaining MPO. The corresponding product had an NCN content of 4.8% and an MPO content of 380 ppm.

[0106] Comparative Example 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.

[0107] Comparative Example 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-methylphospholene-1-oxide (MPO; 1.72 mmol) were added to a 1000 ml four-neck round-bottom flask equipped with a thermometer (combined with a thermoregulated oil bath), mechanical stirring, a cold water condenser, and a 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%. 200.0 g of oleyl alcohol was then added. After 5 hours, the NCO content reached 0.0% (complete urethane reaction), and the reaction mixture was cooled. The reaction was cooled to room temperature, and then 400 g of diethyl adipate was added. Next, diethyl adipate was distilled off using a bridge (180 °C and 5 mbar) (DEA served as an azeotropic agent) to remove some of the remaining MPO. This operation was carried out twice. The corresponding product had an NCN content of 11.5% and an MPO content of 124 ppm.

[0108] Example 6: Preparation of a 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-methylphospholene-1-oxide (MPO; 2.24 mmol) were added to a 500 ml four-neck round-bottom flask equipped with a thermometer (combined with a thermoregulated 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%. 60.0 g of oleyl alcohol and 10 g of neopentyl glycol were then added. After 5 hours, the NCO content reached 0.0% (complete urethane reaction), and the reaction mixture was cooled. The reaction was cooled to room temperature, and then 400 g of diethyl adipate was added. Next, to remove some of the remaining MPO, diethyl adipate was distilled off using a bridge (180 °C and 15 mbar) (DEA served as an azeotropic agent). This operation was carried out twice. The corresponding product had an NCN content of 7.4% and an MPO content of 225 ppm.

[0109] Example 7: Preparation of a 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-methylphospholene-1-oxide (MPO; 1.29 mmol) were added to a 500 ml four-neck round-bottom flask equipped with a thermometer (combined with 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 approximately 20 hours, the NCO content reached a value of 11.9%. Subsequently, 116.6 g of 2-octyl-1-dodecanol (Eutanol® G, BASF) and 2.3 g of pentane-1,5-diol were added. After 4 hours, the NCO content reached 0.0% (complete urethane reaction), and the reaction mixture was cooled to room temperature. 200 g of diethyl adipate was then added. Next, to remove some of the remaining MPO, diethyl adipate was distilled off using a bridge (160 °C and 50 mbar) (DEA served as an azeotropic agent). This operation was carried out twice. The corresponding product had an NCN content of 9.4% and an MPO content of 165 ppm.

[0110] Example 8: Preparation of a 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-methylphospholene-1-oxide (MPO; 2.58 mmol) were added to a 500 ml four-neck round-bottom flask equipped with a thermometer (combined with a thermoregulated oil bath), mechanical stirring, a cold water condenser, and a nitrogen inlet. The reaction mixture was stirred and heated to 180 °C. After 18 h, the NCO content reached a value of 10.8%. 84.3 g of oleyl alcohol and 33.7 g of a triester of glycerol and ricinoleic acid (castor oil) were then added. After 5 h, the NCO content reached 0.0% (complete urethane reaction), and the reaction mixture was cooled to room temperature. 400 g of diethyl adipate was then added. Next, to remove some of the remaining MPO, diethyl adipate was distilled off using a bridge (180 °C and 10 mbar) (DEA served as an azeotrope). This operation was carried out twice. The corresponding product had an NCN content of 6.4% and an MPO content of 150 ppm.

[0111] Example 9: Preparation of a 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 instead of 92.8 g of oleyl alcohol and 8.1 g of neopentyl glycol. Finally, 200 g of diethyl adipate was added. Next, to remove some of the remaining MPO, the diethyl adipate was distilled off using a bridge (180 °C and 10 mbar) (DEA served as an azeotropic agent). This operation was carried out twice. The corresponding product had an NCN content of 6.7% and an MPO content of 160 ppm.

[0112] Example 10: Determination of tensile strength of polycarbodiimide compositions Thermoplastic polyurethane (TPU) compositions were prepared by hand cast procedure, where the TPU was based on 4,4'-MDI (methylene diphenyl diisocyanate), 1,2-ethylene glycol / adipic acid polyester polyol (molar mass between 500 and 3000 g / mol), and 1,4-butanediol as a chain extender.

[0113] TPU compositions were prepared without additional polycarbodiimide, or by incorporating approximately 1.0 wt. % polycarbodiimide as a hydrolysis stabilizer. In the latter case, the polycarbodiimide was added to a premix of polyol and chain extender, followed by the addition of the isocyanate using a hand-casting procedure. The resulting TPU slabs for each composition were annealed at 110 °C for 3 hours and then ground into granules.

[0114] After drying, the granules were first injection molded into test specimens and then further annealed for 10 h at 100° C. The hydrolytic stability of the TPU injection-molded parts was evaluated by storing the test specimens in water at 80° C. and periodically determining the tensile strength thereafter (initial tensile strength (t=0) was set to 100%).

[0115] Therefore, the polycarbodiimide compositions according to Comparative Examples 1-5 and Examples 6-9 were tested as hydrolysis stabilizers in TPU. In this regard, tensile strength was measured and performance was determined as the number of days until the tensile strength reached 70% of its initial value. In addition, Comparative Example 11 was also tested, in which the TPU composition was tested alone, i.e., without the addition of the polycarbodiimide composition.

[0116] Table 1 below summarizes the polycarbodiimide compositions prepared, including the alcohols used in the preparation. Additionally, Table 2 below summarizes the results of tensile strength measurements.

[0117] [Table 1]

[0118] [Table 2]

[0119] As can be seen from the above results, polycarbodiimide compositions containing relatively high amounts of phospholene oxide catalyst perform poorly in the tests. In contrast, polycarbodiimide compositions according to the present invention, and thus made from combinations of monoalcohols with dialcohols or polyalcohols, perform better.

[0120] References - DE 112015000659 A1 -EP 3875538 -EP 3943550 -EP 4053201 -US Patent Application Publication No. 2020 / 017628 -EP 3835333

Claims

1. Formula (1) 【Chemistry 1】 and / or a polycarbodiimide represented by formula (2): 【Chemistry 2】 Polycarbodiimide shown in (In the formula, R １ may be branched (C １１ ~C ５０ ) alkoxy and optionally branched (C １１ ~C ５０ ) alkenoxy; R １ is R １ and carbon atoms calculated as the sum of carbon atoms contained in R １ The atomic ratio C:O calculated as the sum of the oxygen atoms contained in R ２ is -C ６ H ８ -CH ２ -C ６ H ８ -(4,4'-diyldicyclohexylmethane), R ３ is selected from the group consisting of optionally branched and / or alkoxylated alkylene, said alkylene consisting of C, H and optionally O; R ４ is selected from the group consisting of optionally branched and / or alkoxylated alkane-triyl, said alkane-triyl consisting of C, H and optionally O; m is an integer ranging from 1 to 20; p is an integer ranging from 1 to 10; n is an integer ranging from 1 to 20.

1. A polycarbodiimide composition comprising:

2. R １ may be branched (C １２ ~C ４０ ) alkoxy and optionally branched (C １２ ~C ４０ 2. The polycarbodiimide composition of claim 1, wherein the alkyl group is selected from the group consisting of aryl, aryloxy ...

3. R １ But -(CH ２ ) ８ -CH=CH-(CH ２ ) ７ -CH ３ and -CH ２ -CH[(CH ２ ) ７ -CH ３ ][-(CH ２ ) ９ -CH ３ 3. The polycarbodiimide composition according to claim 1, wherein the polycarbodiimide is selected from the group consisting of:

4. R １ But, R １ and carbon atoms calculated as the sum of carbon atoms contained in R １ 4. The polycarbodiimide composition according to claim 1, wherein the atomic ratio C:O of the polycarbodiimide composition to the oxygen atoms contained in the polycarbodiimide compound (C):O, calculated as the sum of the oxygen atoms contained in the polycarbodiimide compound (C):O, is in the range of 11 to 50.

5. R １ 5. The polycarbodiimide composition of claim 1, wherein the polycarbodiimide has a molecular weight greater than 210 g / mol.

6. R ３ may be branched (C １ ~C ２５ ) alkylene, -[CR ５ H-CH ２ -O] ｘ１ -CR ５ H-CH ２ - (wherein, R ５ is H or CH ３ and x1 is an integer ranging from 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 ranging from 1 to 15, and x3 is an integer ranging from 1 to 15), and —[CH ２ -CH ２ -CH ２ -CH ２ -O] ｘ４ -CH ２ -CH ２ -CH ２ -CH ２ 6. The polycarbodiimide composition of claim 1, wherein x4 is selected from the group consisting of:

7. R ４ may be alkoxylated (C ３ ~C ５０ ) alkane-triyl, 【Transformation 3】 【Chemistry 4】 and 【Transformation 5】 (In the formula, R ６ Ha-[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 ranging from 1 to 15, x2 is an integer ranging from 1 to 15, x3 is an integer ranging from 1 to 15, and x4 is an integer ranging from 1 to 30) 7. The polycarbodiimide composition of claim 1, selected from the group consisting of:

8. 8. The polycarbodiimide composition according to claim 1, wherein m is an integer ranging from 2 to 18.

9. 9. The polycarbodiimide composition according to claim 1, wherein p is an integer ranging from 1 to 5.

10. 10. The polycarbodiimide composition according to claim 1, wherein n is an integer ranging from 2 to 18.

11. 11. The polycarbodiimide composition of claim 1, wherein the polycarbodiimide comprises 410 ppm by weight or less of the phospholene oxide, calculated as the sum of the weights of phospholene oxide, based on the total weight of the polycarbodiimide composition.

12. 12. The polycarbodiimide composition of claim 11, wherein the phospholene oxide is 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. 1. A process for preparing a polycarbodiimide composition, comprising the steps of: (i) preparing a mixture comprising 4,4′-diisocyanatodicyclohexylmethane and one or more phospholene oxides; (ii) subjecting the mixture obtained in (i) to carbodiimidization conditions in a gas atmosphere, the carbodiimidization conditions comprising 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 of one another, optionally branched monohydroxy (C １１ ~C ５０ ) alkane and optionally branched monohydroxy (C １１ ~C ５０ ) alkenes; The one or more optionally branched monohydroxy (C １１ ~C ５０ ) alkane and optionally branched monohydroxy (C １１ ~C ５０ ) alkenes are each independently an optionally branched monohydroxy (C １１ ~C ５０ ) alkane and optionally branched monohydroxy (C １１ ~C ５０ ) carbon atoms calculated as the sum of the carbon atoms contained in each alkene, and optionally branched monohydroxy (C １１ ~C ５０ ) alkane and optionally branched monohydroxy (C １１ ~C ５０ ) the atomic ratio C:O of oxygen atoms calculated as the sum of the oxygen atoms contained in each alkene is 11 or more; the one or more polyalcohols are, independently of one another, selected from the group consisting of optionally branched and / or alkoxylated and optionally branched and / or alkoxylated trihydroxyalkanes, the dihydroxyalkanes consisting of C, H, and O, the trihydroxyalkanes consisting of C, H, and O, and subjecting the resulting mixture to reaction conditions in a gas atmosphere, the reaction conditions comprising 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); The process includes:

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

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

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