Aromatic carbodiimides, process for their production and use

Abstract

The present invention relates to novel carbodiimides, to a process for their production, and to the use of the novel carbodiimides in ester-based polyols, in polyethylene terephthalate (PET), in polybutylene terephthalate (PBT), in polytrimethylene terephthalate (PTT), in copolyesters, in thermoplastic polyester elastomers (TPE E), in ethylene vinyl acetate (EVA), in polylactic acid (PLA) and / or in PLA derivatives, in polybutylene adipate terephthalate (PBAT), in polybutylene succinate (PBS), in polyhydroxyalkanoates (PHA), in blends, in triglycerides, in thermoplastic polyurethanes, in polyurethane elastomers, in PU adhesives, in PU casting resins, for PU coatings or in PU foams as stabilizers.

Description

Background Technology

[0001] Carbodiimide has proven to be advantageous in many applications, such as as a hydrolysis inhibitor in thermoplastics, polyols, polyurethanes, triglycerides, and lubricants.

[0002] For this purpose, highly sterically hindered polycarbodiimides are preferred, although these polycarbodiimides are produced from very specialized raw materials and are therefore very expensive to procure. Furthermore, highly sterically hindered carbodiimides, such as those based on triisopropylphenyl isocyanate, have very high melting points, are insoluble, and, if possible, require considerable time and equipment investment to introduce into the starting materials of polyurethanes. Aromatic carbodiimides based on cheaper raw materials, such as those described in EP 2997010 B1, can achieve very good hydrolysis inhibition in some ester polymers such as PET or PLA, but in other applications, such as in polyurethanes, these aromatic carbodiimides have the disadvantage of insufficient hydrolysis inhibition and are therefore not widely used. Prior art carbodiimides are generally in difficult-to-measure forms, particularly in the form of viscous compositions.

[0003] Therefore, there is a need for novel carbodiimides that do not exhibit the disadvantages of existing technologies, are easy to produce, exhibit high thermal stability, achieve excellent hydrolysis inhibition in polyurethane applications, and are additionally easier to quantify. Summary of the Invention

[0004] This goal was surprisingly achieved using carbodiimide of formula (I).

[0005]

[0006] in

[0007] R can be the same or different and is selected from -NCN-R I and -NHCOOR III ,in

[0008] R I Indicates C1-C 22 -alkyl, C6-C 12 -Cycloalkyl, C6-C 18 -Aryl or C6-C 18 -Aryl group, preferably triisopropylphenyl, and

[0009] R III This indicates an alkylated polyoxyalkylene group.

[0010] R 1 R 2 and R3 Each can independently represent methyl, isopropyl, or n-propyl, wherein on each benzene ring, the group R 1 R 2 and R 3 One of them is methyl, and

[0011] n ranges from 0 to 500, preferably from 1 to 50.

[0012] The molar mass of the alkylated polyoxyethylene group is preferably at least 200 g / mol, particularly preferably from 200 g / mol to 600 g / mol, and most preferably from 350 g / mol to 550 g / mol.

[0013] The carbodiimide content (NCN content, measured by titration with oxalic acid) of the carbodiimide according to the invention is typically 2%-17% by weight. To determine the NCN content, the NCN groups are reacted with an excess of oxalic acid, and then the unreacted oxalic acid is potentiometrically titrated with sodium methoxide, taking into account the blank value of the system.

[0014] The preferred form is carbodiimide, wherein R 1 R 2 and R 3 Each can be represented independently as methyl- or isopropyl-.

[0015] The preferred form is a carbodiimide of formula (I), where R represents NCN-R I Wherein n is from 0 to 500, preferably from 1 to 100 and most preferably from 1 to 50, and the carbodiimide content is preferably 10%-17% by weight, particularly preferably 11%-15% by weight and most preferably 13%-14% by weight.

[0016] Further preferred embodiments involve carbodiimides of formula (I), wherein R represents NHCOOR III Where n is from 0 to 20, preferably from 1 to 10, particularly preferably from 3 to 8, and the carbodiimide content is preferably from 4% to 13% by weight, particularly preferably from 10% to 13% by weight.

[0017] Carbodiimide of formula (I) (where R = -NCN-R) I , where R I As defined above, and R 1 R 2 and R 3 Each independently represents methyl- or isopropyl-, wherein on each benzene ring, the group R 1 R 2 and R 3One of them (methyl) is a solid and has a softening point >40°C. Therefore, they are very suitable for stabilizing ester-based polymers, preferably polymers selected from the following: polyester polyols, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polypropylene terephthalate (PTT), copolyesters such as cyclohexanediol and modified polyesters of terephthalic acid (PCTA), thermoplastic polyester elastomers (TPE E), ethylene vinyl acetate (EVA), polylactic acid (PLA) and / or PLA derivatives, polybutylene adipate terephthalate (PBAT), polybutylene succinate (PBS), polyhydroxyalkanoate (PHA), polyurethane elastomers (preferably thermoplastic polyurethane (TPU)) and blends (preferably PA / PET or PHA / PLA blends).

[0018] The present invention further relates to a method for stabilizing ester polymers by adding the aforementioned carbodiimide. Preferably, the carbodiimide is added to the ester polymer using a solid metering unit.

[0019] In the context of this invention, the solid metering unit is preferably a single-screw extruder, a twin-screw extruder, or a multi-screw extruder; a continuous co-kneader (Buss type) or an intermittent kneader (e.g., a Banbury type).

[0020] In yet another embodiment of the invention, the preferred material is a carbodiimide of formula (I), wherein R represents -NHCOOR. III And R III Represents alkylated polyoxyethylene, and R 1 R 2 and R 3 Each of the components independently represents methyl- or isopropyl-, n is from 0 to 20, preferably from 1 to 10, particularly preferably from 1 to 4 and most preferably from 2 to 3, and the carbodiimide content is preferably from 2% to 10% by weight, particularly preferably from 4% to 8% by weight and most preferably from 5% to 7% by weight.

[0021] Preferred alkylated polyoxyethylene groups are monoalkylated polyethylene glycol ethers, particularly preferred polyethylene glycol monomethyl ethers, especially those monoalkylated polyethylene glycol ethers having a molar mass of 200 g / mol-600 g / mol, preferably 350 g / mol-550 g / mol.

[0022] The carbodiimide of formula (I) above (where R = -NHCOOR) III , where R III(The alkylated polyoxyethylene group) is usually liquid at room temperature, and therefore, in contrast to most solid carbodiimides, it is also permissible to incorporate into liquid polyester polyols used in the production of TPU and PU foams.

[0023] Therefore, the present invention also relates to a method for stabilizing TPU and PU foam, wherein the above-mentioned carbodiimide is added to a liquid polyester polyol from which TPU and PU foam are produced.

[0024] The present invention further relates to a method for stabilizing ester-based oils and / or lubricants or greases, wherein the above-mentioned carbodiimide is added to the ester-based polymer.

[0025] The concentration of the carbodiimide of formula (I) according to the invention in the ester polymer / in the ester oil, lubricant or grease is preferably from 0.1% to 5% by weight, preferably from 0.5% to 3% by weight, and particularly preferably from 1% to 2% by weight.

[0026] The carbodiimide according to the invention preferably has an average molar mass (Mw) of 1000 g / mol to 20000 g / mol, more preferably 1500 g / mol to 5000 g / mol, and particularly preferably 2000 g / mol to 4000 g / mol.

[0027] Carbodiimide with a polydispersity of D = Mw / Mn of 1.2 to 2, particularly preferably 1.4 to 1.8, is also preferred.

[0028] The scope of this invention covers all the general definitions, indices, parameters, and interpretations of the groups listed above and below, or given in the preferred scope, that is, including any desired combination between the respective scope and the preferred scope.

[0029] The present invention further provides a method for producing carbodiimide according to the invention by means of: [Formula (II)]

[0030]

[0031] Aromatic diisocyanates are carbodiiminated at temperatures from 80°C to 200°C in the presence of a catalyst and optionally a solvent to remove carbon dioxide, and subsequently treated with NOR... III The alcohol functionalizes the free NCO group, wherein R 1 To R 3 and R I To R III As defined for compounds of formula (I).

[0032] In this method, the aromatic diisocyanate of formula (II) used is preferably an aromatic diisocyanate of formula (III) and / or (IV):

[0033]

[0034] Particularly preferred is the use of a mixture of diisocyanates of formula (III) and (IV), preferably in a ratio of 60:40 to 95:5, particularly preferably 70:30 to 90:10.

[0035] The aromatic diamines required to produce these diisocyanates can be generated (as is known to those skilled in the art) by Friedel-Crafts alkylation of the corresponding toluene diamine with the corresponding olefin or haloalkane. These diamines are then reacted with phosgene to provide the corresponding diisocyanate.

[0036] To produce the carbodiimide according to the invention, for example, diisocyanates of formula (III) and / or (IV) can advantageously be used in conjunction with a catalyst and optionally have an R group. I The carbon dioxide is eliminated by condensation at elevated temperatures, preferably between 80°C and 200°C, particularly preferably between 100°C and 180°C, and very particularly preferably between 120°C and 140°C, in the presence of additional monoisocyanates. Methods suitable for this are described, for example, in DE-A 1130594 and DE-A 11564021.

[0037] In one embodiment of the invention, a phosphorus compound is preferably used as a catalyst for producing the compound of formula (I). The phosphorus compound used is preferably a cyclophosphine oxide, phospholidene, or phospholine oxide and the corresponding cyclophosphine sulfide. Other catalysts that can be used include: tertiary amines; basic metal compounds; alkali metal and alkaline earth metal oxides, hydroxides, alcohols, or phenolates; metal carboxylates; and non-basic organometallic compounds.

[0038] Carbodiimide oxidation can be carried out in a substance or in a solvent. Preferred solvents are alkylbenzenes, paraffin oils, polyethylene glycol dimethyl ethers, ketones, or lactones.

[0039] In one embodiment of the invention, for this purpose, the temperature of the reaction mixture is reduced to 50°C-120°C, preferably 60°C-100°C, particularly preferably 80°C-90°C, and the catalyst is distilled off under reduced pressure. In a preferred variant of the production method of the carbodiimide according to the invention, excess diisocyanate is then distilled off at a temperature of 150°C-200°C, preferably 160°C-180°C. Subsequently, optionally in the presence of a PU catalyst known to those skilled in the art, preferably a tertiary amine or organotin compound, particularly preferably DBTL (dibutyltin dilaurate) or DOTL (dioctyltin dilaurate), preferably with a slight excess of -OH groups, the free terminal isocyanate groups of the carbodiimide are reacted with an alcohol. The molar ratio of alcohol to carbodiimide is preferably 1.005-1.05:1, particularly preferably 1.01-1.03:1, based on the presence of N=C=O groups.

[0040] In another embodiment of the invention, to interrupt carbodiimide reaction, the temperature of the reaction mixture is lowered to a value in the range of 50°C to 120°C, preferably from 60°C to 100°C, and particularly preferably from 80°C to 90°C. Optionally, after the addition of a solvent (preferably selected from the group consisting of alkylbenzenes, particularly preferably toluene), the free terminal isocyanate group of the carbodiimide is reacted with the alcohol, preferably in the presence of a PU catalyst known to those skilled in the art, preferably a tertiary amine or organotin compound, particularly preferably DBTL (dibutyltin dilaurate) or DOTL (dioctyltin dilaurate), preferably in a slight excess of -OH groups. The molar ratio of alcohol to carbodiimide is preferably 1.005-1.05:1, particularly preferably 1.01 to 1.03:1, based on the presence of N=C=O groups.

[0041] After the reaction is complete, the catalyst and optionally the solvent are distilled off under reduced pressure at a temperature of 80°C to 200°C.

[0042] The present invention additionally provides a further method for producing the carbodiimide according to the invention by means of: removing the free NCO group of an aromatic diisocyanate of formula (II).

[0043]

[0044] HOR III The alcohol undergoes partial, preferably <50% functionalization, and subsequently carbodiimide oxidase at a temperature of 80°C to 200°C in the presence of a catalyst and optionally a solvent to eliminate carbon dioxide, wherein R 1 To R 3 and R III As defined for compounds of formula (I).

[0045] Similarly, in this method, the aromatic diisocyanate of formula (II) used is preferably of formula (III):

[0046]

[0047] And / or form (IV)

[0048]

[0049] Aromatic diisocyanates.

[0050] The carbodiimide according to the invention is preferably purified after its production. The crude product can be purified by distillation and / or by solvent extraction. Suitable solvents that can be preferably used for purification are polyethylene glycol dimethyl ether, alkylbenzene, paraffin oil, alcohol, ketone or ester. These are commercially available solvents.

[0051] The present invention further provides a method for producing carbodiimide according to the invention by: using formula (II)

[0052]

[0053] Aromatic diisocyanates are carbodiiminated at temperatures from 80°C to 200°C in the presence of a catalyst and optionally a solvent to eliminate carbon dioxide, wherein, before, during, or after this carbodiimination of the diisocyanates, an additive OCN-R is used. I The monoisocyanate, wherein R 1 To R 3 and R I As defined for compounds of formula (I). In the case of addition following the carbodiimide addition of a diisocyanate, carbodiimide addition is continued with a monoisocyanate to convert the remaining isocyanate (terminal) group of the carbodiimide into the formula -NCN-R. I The functionalization of the terminal groups occurs spontaneously during carbodiimide oxidation when monoisocyanate is added before or during the carbodiimide oxidation of diisocyanate.

[0054] Similarly, in this method, the aromatic diisocyanate of formula (II) used is preferably of formula (III):

[0055]

[0056] And / or form (IV)

[0057]

[0058] Aromatic diisocyanates.

[0059] The monoisocyanate used is preferably triisopropylphenyl isocyanate.

[0060] The present invention further provides a composition comprising:

[0061] - at least one ester polymer and

[0062] - At least one carbodiimide of formula (I) of the present invention.

[0063] The ester-based polymer is preferably a polymer selected from the following: polyester polyols, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polypropylene terephthalate (PTT), copolyesters such as cyclohexanediol and modified polyesters of terephthalic acid (PCTA), thermoplastic polyester elastomers (TPE E), ethylene vinyl acetate (EVA), polylactic acid (PLA) and / or PLA derivatives, polybutylene adipate terephthalate (PBAT), polybutylene succinate (PBS), polyhydroxyalkanoates (PHA), polyurethane elastomers (preferably thermoplastic polyurethane (TPU)), and blends (preferably PA / PET or PHA / PLA blends).

[0064] In a particularly preferred embodiment of the present invention, the polymer containing ester groups is thermoplastic polyurethane (TPU).

[0065] In the composition according to the invention, the concentration of the carbodiimide of formula (I) of the invention is preferably 0.1%-5% by weight, preferably 0.5%-3% by weight, and particularly preferably 1%-2% by weight.

[0066] The polyester polyols that are ester polymers are preferably long-chain compounds, and these long-chain compounds preferably have a molecular weight (in g / mol) of up to 2000, preferably between 500 and 2000, and particularly preferably between 500 and 1000.

[0067] In the context of this invention, the term "polyester polyol" encompasses both long-chain diols and triols, and also includes compounds having more than three hydroxyl groups per molecule.

[0068] It is advantageous when the polyester polyol has an OH content of up to 200, preferably between 20 and 150, and particularly preferably between 50 and 115. Polyester polyols that are reaction products of different polyols with aromatic or aliphatic dicarboxylic acids and / or lactone polymers are particularly suitable.

[0069] In the context of this invention, the polyester polyols used are those from Covestro (Deutschland AG) under the trade name... and Commercially available compounds.

[0070] The present invention further provides a method for producing carbodiimide of formula (I) of the present invention, wherein R = -NCN-R I Following carbodiimide formation, the melt is granulated, either in its unpurified form or, preferably after purification, on a granulation line. Both conventional granulation and conventional pelletizing systems can be used. These systems are available, for example, from Sandvik Holding GmbH or GMF Gouda.

[0071] The carbodiimide of formula (I) of the present invention (where R = -NCN-R) I And R I =Triisopropylphenyl) is particularly suitable.

[0072] The present invention additionally relates to the use of the carbodiimide according to the invention as an inhibitor of hydrolytic decomposition against: ester polymers, preferably polymers selected from: polyester polyols, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polypropylene terephthalate (PTT), copolyesters such as cyclohexanediol and terephthalic acid-modified polyesters (PCTA), thermoplastic polyester elastomers (TPE) E), ethylene vinyl acetate (EVA), polylactic acid (PLA) and / or PLA derivatives, polybutylene adipate terephthalate (PBAT), polybutylene succinate (PBS), polyhydroxyalkanoates (PHA), polyurethane elastomers (preferably thermoplastic polyurethane (TPU)) and blends (such as preferably PA / PET or PHA / PLA blends); or in triglycerides, preferably trimethylolpropane trioleate (TMP oleate); in oil formulations for use in the lubricant industry; in PU adhesives; in PU molding resins. Uses in polyurethanes particularly include PU foams and PU coatings for wood, leather, synthetic leather and textiles. Uses in thermoplastic polyurethanes (TPU) are especially preferred. Detailed Implementation

[0073] The following examples are used to explain the present invention and are not intended to be limiting.

[0074] Work examples

[0075] Test the following items:

[0076] 1) CDI A: A solid carbodiimide with terminal functionalization of cyclohexanol, based on about 80% by weight of diethyltoluene-2,4-diisocyanate and 20% by weight of diethyltoluene-2,6-diisocyanate, having an NCN content of about 12% by weight (a comparative example similar to EP 2997010 B1).

[0077] 2) CDI(B): Based on 80% by weight of diethyltoluene-2,4-diisocyanate and 20% by weight of diethyltoluene-2,6-diisocyanate, having an NCN content of approximately 14% by weight, and using -NCN-R I Terminal functionalization was performed (where R I High viscosity carbodiimide (comparative example) = triisopropylphenyl and n>40.

[0078] 3) CDI(C): Based on diisopropyltoluene diisocyanate (formulas III and IV, in a weight ratio of about 1:4), having an NCN content of about 14% by weight, and using -NCN-R I Terminal functionalization was performed (where R I Solid polymeric carbodiimide (=triisopropylphenyl and n>40) (Example of the present invention).

[0079] 4) CDI(D): A solid polymeric carbodiimide based on diisopropyltoluene diisocyanate and terminally functionalized with ethylamine (a comparative example similar to CN 105778026).

[0080] 5) CDI(E): A solid polymeric carbodiimide based on diisopropyltoluene diisocyanate (formulas III and IV, in a weight ratio of about 1:4), having an NCN content of about 6%-7% by weight, and terminally functionalized with methyl polyethylene glycol (Mw of about 550 g / mol) (where n = 4-5) (example of the present invention).

[0081] Ester polymers:

[0082] 6) Unstable thermoplastic polyurethane (TPU) is available from Covestro AG under the name Desmopan.

[0083] Production of carbodiimide CDI(A)

[0084] First, a preheated 250ml four-necked flask filled with nitrogen was filled with 150g diisocyanate and 37.5g cyclohexanol under a nitrogen atmosphere. 50mg of 1-methylcyclophosphine oxide was added, and the mixture was then slowly heated to 180°C. Carbodiimide was then carried out at 180°C until an NCO content of <1% by weight was achieved.

[0085] Carbodiimide Production of CDI(B) and CDI(C):

[0086] First, a preheated 250ml four-necked flask filled with nitrogen was filled with 150g of diisocyanate and 37.5g of triisopropylphenyl isocyanate under a nitrogen atmosphere. 50mg of 1-methylcyclophosphine oxide was added, and the mixture was then slowly heated to 180°C. Carbodiimide was then carried out at 180°C until an NCO content of <1% by weight was achieved.

[0087] Carbodiimide CDI(D) production

[0088] First, a preheated 250ml four-necked flask filled with nitrogen was filled with 150g diisocyanate and 7.0g ethylamine under a nitrogen atmosphere. 50mg of 1-methylcyclophosphide oxide was added, and the mixture was then slowly heated to 180°C. Carbodiimide was then carried out at 180°C until an NCO content of <0.1% by weight was achieved.

[0089] Carbodiimide CDI(E) production

[0090] First, a baked 250ml four-necked flask filled with nitrogen was filled with 150g of diisocyanate and 100g of MPEG (methyl polyethylene glycol, Mw approximately 550g / mol). 50mg of 1-methylcyclophosphide oxide was added, and the mixture was then slowly heated to 180°C. Carbodiimide was then carried out at 180°C until an NCO content of <0.1% by weight was achieved.

[0091] Hydrolysis inhibition in thermoplastic polyurethane (TPU)

[0092] To evaluate hydrolysis inhibition in TPU, the studied carbodiimide, at a weight of 1.5%, was dispersed into the TPU using a ZSK 25 laboratory twin-screw extruder from Werner & Pfleiderer prior to the measurements described below. Standard test samples for measuring tensile strength were then produced from the resulting granules on an Arburg Allrounder 320S150-500 injection molding machine.

[0093] For the hydrolysis test, these standard test samples were stored in water at a temperature of 80°C, and the breaking strength (in MPa) of these samples was measured.

[0094] The results are shown in Table 1:

[0095] Table 1

[0096]

[0097]

[0098] vgl. = Comparative example, erf. = Invention

[0099] The results from Table 1 show that the carbodiimide of the present invention achieves significantly better hydrolysis inhibition compared to the prior art.

[0100] Solubility in polyester polyols

[0101] The stabilization of ester-based TPU elastomers against hydrolysis is, in principle, carried out directly during the production process. For this purpose, carbodiimide is typically added to the polyester polyol or polyester plasticizer before reacting with the isocyanate to provide the polyurethane. Therefore, the solubility of the carbodiimide is important. Table 2 shows the different carbodiimides in a standard polyester polyol (Desmophen 2000MM from Covestro AG) with Mw=2000 based on adipic acid and ethylene glycol at 80°C.

[0102] Table 2

[0103]

[0104] Hydrolysis inhibition in polyethylene terephthalate (PET)

[0105] To evaluate the hydrolysis inhibition in PET, the studied carbodiimide, at a weight of 1.5%, was dispersed into PET using a ZSK 25 laboratory twin-screw extruder from Werner & Pfleiderer prior to the measurements described below. F3 standard test samples for measuring breaking strength were then produced from the resulting pellets on an Arburg Allrounder 320S150-500 injection molding machine.

[0106] For the hydrolysis test, these F3 standard test samples were stored in water at 90°C, and their tensile strength (in MPa) was measured. Table 2 shows the relative tensile strength = (tensile strength after x days of storage / tensile strength after 0 days) × 100. The lower limit of the relative tensile strength is typically 70%-75%.

[0107] The results are shown in Table 3:

[0108] Table 3

[0109]

[0110] vgl. = Comparative example, erf. = Invention

[0111] Testing of the granulability and quantifiability of solid carbodiimide

[0112] To clarify the processability, handling, and measurability of different solid carbodiimides, these solid carbodiimides were compared in terms of appearance, granulability, and softening point. A Koffler stage was used to determine the softening point.

[0113] The results are shown in Table 4:

[0114]

[0115] vgl. = Comparative example, erf. = Invention

[0116] The results in Table 4 show that, compared with polymerizable carbodiimides based on diethyltoluene diisocyanate, which is also capped with monoisocyanate, and compared with carbodiimide D, the carbodiimide based on diisopropyltoluene capped with monoisocyanate of the present invention exhibits superior granulability and a high softening point, thus providing advantages in the stabilization of ester polymers during solid processing and metering. The carbodiimide E according to the present invention is a liquid and can be added as is.

Claims

1. A carbodiimide of formula (I) in R can be the same or different and is selected from -NCN-R I -and-NHCOOR III ,in R I Indicates C1-C 22 -alkyl, C6-C 12 -Cycloalkyl, C6-C 18 -Aryl or C6-C 18 -Aryl groups, and R III This indicates an alkylated polyoxyethylene group. R 1 R 2 and R 3 Each can independently represent methyl, isopropyl, or n-propyl, wherein on each benzene ring, the group R 1 R 2 and R 3 One of them is methyl, and n ranges from 0 to 500.

2. The carbodiimide according to claim 1, wherein R I It represents triisopropylphenyl.

3. The carbodiimide according to claim 1, wherein n is from 1 to 50.

4. The carbodiimide according to claim 1, wherein R 1 R 2 and R 3 Each can be represented independently as methyl- or isopropyl-.

5. The carbodiimide according to any one of claims 1-4, wherein the carbodiimide content is 2%-17% by weight.

6. The carbodiimide according to any one of claims 1 to 4, wherein in formula (I), R represents NCN-R I n is from 0 to 500.

7. The carbodiimide according to claim 6, wherein n is from 1 to 100.

8. The carbodiimide according to claim 6, wherein n is from 1 to 50.

9. The carbodiimide according to claim 6, wherein the carbodiimide content is 10%-17% by weight.

10. The carbodiimide according to claim 6, wherein the carbodiimide content is 11%-15% by weight.

11. The carbodiimide according to claim 6, wherein the carbodiimide content is 13%-14% by weight.

12. The carbodiimide according to any one of claims 1 to 4, wherein in formula (I), R represents -NHCOOR III n is from 0 to 20.

13. The carbodiimide according to claim 12, wherein n is from 1 to 10.

14. The carbodiimide according to claim 12, wherein n is from 3 to 8.

15. The carbodiimide according to claim 12, wherein the carbodiimide content is from 4% to 13% by weight.

16. The carbodiimide according to claim 12, wherein the carbodiimide content is from 10% to 13% by weight.

17. The carbodiimide according to any one of claims 1 to 4, wherein in formula (I), R represents -NHCOOR III And R III The alkylation polyoxyethylene group represents the alkylated polyoxyethylene group, where n ranges from 0 to 20.

18. The carbodiimide according to claim 17, wherein n is from 1 to 10.

19. The carbodiimide according to claim 17, wherein n is from 1 to 4.

20. The carbodiimide according to claim 17, wherein n is from 2 to 3.

21. The carbodiimide according to claim 17, wherein the carbodiimide content is 2%-10% by weight.

22. The carbodiimide according to claim 17, wherein the carbodiimide content is 4%-8% by weight.

23. The carbodiimide according to claim 17, wherein the carbodiimide content is 5%-7% by weight.

24. The carbodiimide according to claim 17, wherein R III This indicates monoalkylated polyethylene glycol ether.

25. The carbodiimide according to claim 24, wherein the monoalkylated polyethylene glycol ether is polyethylene glycol monomethyl ether.

26. The carbodiimide according to claim 25, wherein the polyethylene glycol monomethyl ether has a molar mass of 200 g / mol to 600 g / mol.

27. The carbodiimide according to claim 25, wherein the polyethylene glycol monomethyl ether has a molar mass of 350 g / mol to 550 g / mol.

28. A method for producing carbodiimide according to any one of claims 1 to 27, the method comprising the following steps: a) Equation (II) Aromatic diisocyanates are carbodiiminated at temperatures from 80°C to 200°C in the presence of a catalyst and optionally a solvent to eliminate carbon dioxide, and b) Using the formula HOR III The free NCO group of the carbodiimide obtained in step a) is functionalized by an alcohol, wherein R 1 To R 3 and R III Same as that defined for compounds of formula (I).

29. A method for producing carbodiimide according to any one of claims 1 to 27, the method comprising the following steps: a) The free NCO group of the aromatic diisocyanate of formula (II) HOR III The alcohol undergoes partial functionalization, and b) Subsequently, the partially functionalized aromatic diisocyanate of formula (II) obtained in step a) is carbodiiminated at a temperature of 80°C to 200°C in the presence of a catalyst and optionally a solvent to remove carbon dioxide. Where R 1 To R 3 and R III Same as that defined for compounds of formula (I).

30. The method according to claim 29, wherein the free NCO group of the aromatic diisocyanate of formula (II) is represented by the formula HOR III The alcohol undergoes <50% functionalization.

31. A method for producing carbodiimide according to any one of claims 1 to 27, the method comprising: Aromatic diisocyanates are carbodiiminated at temperatures from 80°C to 200°C in the presence of a catalyst and optionally a solvent to eliminate carbon dioxide, wherein, before, during, or after the carbodiimination of the diisocyanate, an additive of OCN-R is used. I The monoisocyanate, wherein R 1 To R 3 and R I Same as that defined for compounds of formula (I).

32. The method according to any one of claims 28 to 31, wherein the aromatic diisocyanate of formula (II) used is of formula (III). And / or form (IV) Compounds.

33. The method according to any one of claims 28 to 31, wherein R = -NCN - R I , where R I The same as that defined for compounds of formula (I), and the melt of the carbodiimide obtained in this carbodiimide is granulated in unpurified form or after purification.

34. Use of the carbodiimide according to any one of claims 1 to 27 as an inhibitor of hydrolytic decomposition in ester polymers.

35. The use according to claim 34, wherein the ester-based polymer is a polymer selected from the group consisting of: polyester polyols; polyethylene terephthalate (PET); polybutylene terephthalate (PBT); polypropylene terephthalate (PTT); copolyesters; thermoplastic polyester elastomers (TPE E); ethylene vinyl acetate (EVA); polylactic acid (PLA) and / or PLA derivatives; polybutylene adipate (PBAT); polybutylene succinate (PBS); polyhydroxyalkanoates (PHA); polyurethane elastomers; and blends.

36. The use according to claim 35, wherein the copolyester is a modified polyester PCTA of cyclohexanediol and terephthalic acid.

37. The use according to claim 35, wherein the polyurethane elastomer is thermoplastic polyurethane (TPU).

38. The use according to claim 35, wherein the blend is a PA / PET or PHA / PLA blend.

39. Use of the carbodiimide according to any one of claims 1 to 27 as protection against hydrolytic degradation in thermoplastic polyurethane (TPU).

40. A composition comprising: at least one carbodiimide according to any one of claims 1 to 27; and at least one ester polymer.

41. The composition according to claim 40, wherein the ester polymer is an ester polymer selected from the following: polyester polyols; polyethylene terephthalate (PET); polybutylene terephthalate (PBT); polypropylene terephthalate (PTT); copolyesters; thermoplastic polyester elastomers (TPE E); ethylene vinyl acetate (EVA); polylactic acid (PLA) and / or PLA derivatives; polybutylene adipate terephthalate (PBAT); polybutylene succinate (PBS); Polyhydroxyalkanoate (PHA); polyurethane elastomers; and blends.

42. The composition according to claim 41, wherein the copolyester is a modified polyester PCTA of cyclohexanediol and terephthalic acid.

43. The composition of claim 41, wherein the polyurethane elastomer is thermoplastic polyurethane (TPU).

44. The composition according to claim 41, wherein the blend is a PA / PET or PHA / PLA blend.

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