Aromatic carbodiimides, processes for producing them, and uses thereof - Patent Application 20070122997

Abstract

The present invention relates to novel carbodiimides, a process for their preparation and their use as stabilizers in: ester-based polyols, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene 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), polyhydroxyalkanoates (PHAs), blends, triglycerides, thermoplastic polyurethanes, polyurethane elastomers, PU adhesives, PU casting resins, PU coatings or PU foams.

Description

[Technical Field]

[0001] Carbodiimides have found utility as hydrolysis inhibitors for many applications, such as thermoplastics, polyols, polyurethanes, triglycerides, and lubricating oils. [Background technology]

[0002] For this purpose, highly sterically hindered polycarbodiimides are preferred, but they are produced from highly specialized raw materials and are therefore very expensive to procure. In addition, highly sterically hindered carbodiimides, such as those based on triisopropylphenylisocyanate, have extremely high melting points and are insoluble, requiring significant time and capital investments even if they can be incorporated into polyurethane starting materials. Aromatic carbodiimides based on cheaper raw materials, such as those described in U.S. Pat. No. 5,629,499, can achieve very good hydrolysis inhibition in some ester-based polymers, such as PET or PLA, but have the disadvantage of not being able to sufficiently inhibit hydrolysis in other applications, such as polyurethanes, and therefore not being universally applicable. Prior art carbodiimides often have a form that makes metering difficult, especially when they are in the form of sticky compositions. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] European Patent No. 2997010B1 Summary of the Invention [Problem to be solved by the invention]

[0004] Therefore, there is a need for new carbodiimides that are easy to prepare, exhibit high thermal stability, achieve excellent hydrolysis inhibition in polyurethane applications, and, in addition, can be more easily metered without exhibiting the drawbacks of the prior art. [Means for solving the problem]

[0005] This object has surprisingly been achieved by carbodiimides of formula (I) below: [ka] [In the formula, R may be the same or different and is -NCN-R I and -NHCOOR III is selected from, where: R I is C1~C 22 -Alkyl, C6-C 12 -Cycloalkyl, C6-C 18 -aryl or C6-C 18 -aralkyl, preferably triisopropylphenyl, R III represents an alkylated polyoxyalkylene group, R 1 , R 2 , and R 3 each independently represent methyl, i-propyl, or n-propyl, where on each benzene ring, the group R 1 , R 2 , and R 3 one of which is methyl, and n is 0 to 500, preferably 1 to 50. DETAILED DESCRIPTION OF THE INVENTION

[0006] The molar mass of the alkylated polyoxyalkylene group is preferably at least 200 g / mol, particularly preferably 200 to 600 g / mol, most preferably 350 to 550 g / mol.

[0007] The carbodiimide content (NCN content, measured by titration with oxalic acid) of the carbodiimides of the present invention is typically 2 to 17% by weight. To measure the NCN content, the NCN groups are reacted with an excess of oxalic acid, and the unreacted oxalic acid is then back-titrated potentiometrically with sodium methoxide, taking into account the blank value of the system.

[0008] Preferred is R 1 , R 2 , and R 3 are each independently methyl- or i-propyl-carbodiimides.

[0009] Preferably, R is NCN-R I wherein n is 0 to 500, preferably 1 to 100, and most preferably 1 to 50, and the carbodiimide content is preferably 10 to 17% by weight, particularly preferably 11 to 15% by weight, and most preferably 13 to 14% by weight.

[0010] A further preferred embodiment is where R is NHCOOR III wherein n is 0 to 20, preferably 1 to 10, particularly preferably 3 to 8, and the carbodiimide content is preferably 4% by weight to 13% by weight, particularly preferably 10% by weight to 13% by weight.

[0011] R is -NCN-R I (where R I is as defined above), R 1 , R 2 , and R 3 each independently represents methyl- or i-propyl-, and wherein on each benzene ring, the group R 1 , R 2 , and R 3Carbodiimides of formula (I), in which one of the groups is methyl, are solid and have a softening point above 40° C. They are therefore particularly suitable for stabilizing ester-based polymers, preferably polymers selected from the following: polyester polyols, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), copolyesters such as modified polyesters of cyclohexanediol and terephthalic acid (PCTA), thermoplastic polyester elastomers (TPE E), ethylene vinyl acetate (EVA), polylactic acid (PLA) and / or derivatives of PLA, polybutylene adipate terephthalate (PBAT), polybutylene succinate (PBS), polyhydroxyalkanoates (PHAs), polyurethane elastomers, preferably thermoplastic polyurethanes (TPUs), and blends, preferably PA / PET or PHA / PLA blends.

[0012] The present invention also relates to a method for stabilizing ester-based polymers by adding the above-mentioned carbodiimides, preferably by using a solids metering unit into the ester-based polymers.

[0013] In the context of the present invention, solids metering units are preferably: single-screw, twin-screw and multi-screw extruders, continuous co-kneaders (Buss type) and discontinuous kneaders, for example Banbury type.

[0014] In a further embodiment of the invention, preferred are carbodiimides of formula (I) where R is -NHCOOR III represents R III represents an alkylated polyoxyalkylene, and R 1 , R 2 , and R 3are each independently methyl or i-propyl, n is 0 to 20, preferably 1 to 10, particularly preferably 1 to 4, and most preferably 2 to 3, and the carbodiimide content is preferably 2 to 10% by weight, particularly preferably 4 to 8% by weight, and most preferably 5 to 7% by weight.

[0015] Preferred alkylated polyoxyalkylene groups are monoalkylated polyethylene glycol ethers, particularly preferably polyethylene glycol monomethyl ethers, especially those with a molar mass of 200 to 600 g / mol, preferably 350 to 550 g / mol.

[0016] R is -NHCOOR III (where R III (wherein R is an alkylated polyoxyalkylene group) The carbodiimides of formula (I) above are typically liquid at room temperature and therefore, in contrast to most solid carbodiimides, can be incorporated into the liquid polyester polyols used for the production of TPU and PU foams.

[0017] The present invention therefore also relates to a method for stabilizing TPU and PU foams, in which the above-mentioned carbodiimides are added to the liquid polyester polyols from which the TPU and PU foams are produced.

[0018] The present invention further relates to a method for stabilizing an ester-based oil and / or lubricant or grease, in which the carbodiimide described above is added to an ester-based polymer.

[0019] The concentration of the carbodiimides of formula (I) according to the invention in the ester-based polymer or in the ester-based oil, lubricant or grease is preferably 0.1% to 5% by weight, preferably 0.5% to 3% by weight, particularly preferably 1% to 2% by weight.

[0020] The carbodiimides according to the invention preferably have an average molar mass (Mw) of 1000 to 20000 g / mol, preferably 1500 to 5000 g / mol, particularly preferably 2000 to 4000 g / mol.

[0021] Preference is further given to carbodiimides having a polydispersity (D=Mw / Mn) of 1.2 to 2, particularly preferably 1.4 to 1.8.

[0022] The scope of the present invention encompasses all of the general definitions of radicals set out above and hereinafter, and the definitions set out in the preferred ranges, indices, parameters and combinations thereof with one another, i.e. it includes each range and everything between the preferred ranges in any desired combination.

[0023] The present invention further relates to a compound represented by the following formula (II): [ka] The present invention also provides for the preparation of carbodiimides according to the invention by carbodiimidizing aromatic diisocyanates of the formula NOR, by elimination of carbon dioxide at a temperature of between 80° C. and 200° C. in the presence of a catalyst and, optionally, a solvent, followed by the formation of a carbodiimide of the formula NOR III and functionalizing their free NCO groups with an alcohol of the formula: 1 ~R 3 and R I ~R III is as defined for compounds of formula (I).

[0024] In this method, the aromatic diisocyanate of formula (II) used is preferably an aromatic diisocyanate of formula (III) and / or (IV): [ka]

[0025] It is particularly preferred to use mixtures of diisocyanates of the formulae (III) and (IV), preferably in the range from 60:40 to 95:5, particularly preferably from 70:30 to 90:10.

[0026] The aromatic diamines required to prepare these diisocyanates can be prepared by Friedel-Crafts alkylation of the corresponding tolylenediamines with the corresponding alkenes or haloalkanes, as known to those skilled in the art. These diamines are then reacted with phosgene to give the corresponding diisocyanates.

[0027] To prepare the carbodiimides according to the invention, for example, diisocyanates of formula (III) and / or (IV) are reacted with a catalyst and optionally with a group R I It can be advantageous to carry out the condensation in the presence of a further monoisocyanate of the formula (I), with elimination of carbon dioxide, at elevated temperatures, preferably at temperatures from 80 to 200° C., particularly preferably from 100 to 180° C., very particularly preferably from 120 to 140° C. Suitable processes for this are described, for example, in DE-A 1 130 594 and DE-A 11 564 021.

[0028] In one embodiment of the present invention, phosphorus compounds are preferred as catalysts for producing the compound of formula (I).The phosphorus compounds used are preferably phospholene oxides, phosphoridenes, or phospholine oxides, and their corresponding phospholene sulfides.Additional catalysts that can be used include tertiary amines, basic metal compounds, oxides, hydroxides, alkoxides, or phenoxides of alkali metals and alkaline earth metals, metal carboxylate salts, and non-basic organometallic compounds.

[0029] The carbodiimidization can be carried out neat or in a solvent, preferably alkylbenzene, paraffin oil, polyethylene glycol dimethyl ether, ketones, or lactones.

[0030] In one embodiment of the present invention, the temperature of the reaction mixture is reduced to 50-120°C, preferably 60-100°C, particularly preferably 80-90°C, and the catalyst is distilled off under reduced pressure. In a preferred variant of the preparation of carbodiimides according to the present invention, the excess diisocyanate is then distilled off at temperatures of 150-200°C, preferably 160-180°C. The free terminal isocyanate groups of the carbodiimide are then reacted with an alcohol, preferably with a slight excess of -OH groups, optionally in the presence of a PU catalyst known to those skilled in the art, preferably a tertiary amine or an organotin compound, particularly preferably DBTL (dibutyltin dilaurate) or DOTL (dioctyltin dilaurate). The molar ratio of alcohol to carbodiimide, based on the N=C=O groups present, is preferably 1.005-1.05:1, particularly preferably 1.01-1.03:1.

[0031] In a further embodiment of the present invention, to prevent carbodiimidization, the temperature of the reaction mixture is reduced to a value in the range of 50 to 120°C, preferably 60 to 100°C, particularly preferably 80 to 90°C, and, optionally after adding a solvent, preferably a solvent selected from the group of alkylbenzenes, particularly preferably toluene, the free terminal isocyanate groups of the carbodiimide are reacted with an alcohol, preferably with a slight excess of -OH groups, optionally in the presence of a PU catalyst known to those skilled in the art, preferably a tertiary amine or an organotin compound, particularly preferably DBTL (dibutyltin dilaurate) or DOTL (dioctyltin dilaurate). The molar ratio of alcohol to carbodiimide, based on the N=C=O groups present, is preferably 1.005 to 1.05:1, particularly preferably 1.01 to 1.03:1.

[0032] After the reaction is complete, the catalyst, and optionally the solvent, are preferably distilled off under reduced pressure at a temperature of 80-200°C.

[0033] The present invention further relates to a compound represented by the following formula (II): [ka] The free NCO groups of the aromatic diisocyanate of the formula HOR III and then carbodiimidization with elimination of carbon dioxide at a temperature between 80° C. and 200° C. in the presence of a catalyst and optionally a solvent, to partially functionalize, preferably less than 50%, the carbodiimide, wherein R 1 ~R 3 and R III is as defined for compounds of formula (I).

[0034] Also in this process, the aromatic diisocyanate of formula (II) used is preferably an aromatic diisocyanate of formula (III): [ka] and / or the following formula (IV): [ka] It is an aromatic diisocyanate.

[0035] The carbodiimides according to the present invention are preferably purified after their preparation. The crude reaction product can be purified by distillation and / or solvent extraction. Suitable solvents for purification that can be preferably used are polyethylene glycol dimethyl ether, alkyl benzene, paraffin oil, alcohols, ketones, or esters. These solvents are commercially available.

[0036] The present invention further relates to a compound represented by the following formula (II): [ka] The present invention also provides for the preparation of carbodiimides according to the invention by carbodiimidizing an aromatic diisocyanate of the formula OCN-R, by eliminating carbon dioxide at a temperature of between 80°C and 200°C in the presence of a catalyst and, optionally, a solvent, wherein, before, during or after carbodiimidization of the diisocyanate, a compound of the formula OCN-R is added. I of monoisocyanate is added, where R 1 ~R 3 and R I is as defined for compounds of formula (I). If the diisocyanate is added after carbodiimidization, the carbodiimidization reaction is continued to convert the remaining isocyanate (terminal) groups of the carbodiimide to compounds of the formula -NCN-R with the monoisocyanate. I When a monoisocyanate is added before or during the carbodiimidization reaction of a diisocyanate, functionalization of the end groups occurs automatically during the carbodiimidization process.

[0037] In this method as well, the aromatic diisocyanate of formula (II) used is preferably a diisocyanate of the following formula (III): [ka] and / or the following formula (IV): [ka] It is an aromatic diisocyanate.

[0038] The monoisocyanate used is preferably triisopropylphenyl isocyanate.

[0039] The present invention further provides a composition comprising: at least one ester-based polymer, and at least one carbodiimide of formula (I) according to the invention;

[0040] The ester-based polymer is preferably a polymer chosen from polyester polyols, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), copolyesters such as modified polyesters of cyclohexanediol and terephthalic acid (PCTA), thermoplastic polyester elastomers (TPE E), ethylene vinyl acetate (EVA), polylactic acid (PLA) and / or derivatives of PLA, polybutylene adipate-terephthalate (PBAT), polybutylene succinate (PBS), polyhydroxyalkanoates (PHAs), polyurethane elastomers, preferably thermoplastic polyurethanes (TPUs), and blends, preferably PA / PET or PHA / PLA blends.

[0041] In a particularly preferred embodiment of the present invention, the ester group-containing polymer is a thermoplastic polyurethane (TPU).

[0042] The concentration of the carbodiimide of formula (I) of the present invention in the composition according to the present invention is preferably 0.1 to 5% by weight, preferably 0.5 to 3% by weight, particularly preferably 1 to 2% by weight.

[0043] The polyester polyols as ester-based polymers are preferably long-chain compounds having a molecular weight (unit: g / mol) of up to 2000, preferably between 500 and 2000, particularly preferably between 500 and 1000.

[0044] In the context of the present invention, the term "polyester polyol" includes both long chain diols and triols as well as compounds with more than three hydroxyl groups per molecule.

[0045] Advantageously, the polyester polyols have an OH number of up to 200, preferably between 20 and 150, particularly preferably between 50 and 115. Polyester polyols which are reaction products of various polyols with aromatic or aliphatic dicarboxylic acids and / or polymers of lactones are particularly suitable.

[0046] The polyester polyols used in connection with the present invention are commercially available compounds available from Covestro Deutschland AG under the trade names Baycoll® and Desmophen®.

[0047] The present invention further provides a method for treating a gastric cancer, wherein R is -NCN-R I The present invention provides a process for producing carbodiimides of formula (I), wherein after carbodiimidization, the melt is pelletized, preferably in a pelletizing line, either in crude form or after purification. Both conventional pelletizing and granulating systems can be used, such as those available from Sandvik Holding GmbH or GMF Gouda.

[0048] R is -NCN-R I and R I Carbodiimides of formula (I) according to the invention, in which is triisopropylphenyl, are very particularly preferred.

[0049] The present invention further relates to the use of the carbodiimides according to the invention as inhibitors of hydrolysis in ester-based polymers, preferably polymers selected from the following: polyester polyols, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), copolyesters such as modified polyesters of cyclohexanediol and terephthalic acid (PCTA), thermoplastic polyester elastomers (TPE E), ethylene vinyl acetate (EVA), polylactic acid (PLA) and / or derivatives of PLA, polybutylene adipate terephthalate (PBAT), polybutylene succinate (PBS), polyhydroxyalkanoates (PHAs), polyurethane elastomers, preferably thermoplastic polyurethanes (TPUs), and blends, such as preferably PA / PET or PHA / PLA blends, or in triglycerides, preferably trimethylolpropane trioleate (oleic acid ester of TMP), in oil formulations for the lubricant industry, in PU adhesives, in PU casting resins. Uses in urethanes include, inter alia, PU foams, PU coatings for wood, leather, synthetic leather, and textiles. Use in thermoplastic polyurethanes (TPUs) is particularly preferred.

[0050] The following examples are intended to illustrate the invention but do not have any limiting effect on it. [Example]

[0051] Tests were conducted on the following: 1) CDI(A): A solid carbodiimide based on approximately 80% by weight of diethyl tolylene-2,4-diisocyanate and 20% by weight of diethyl tolylene-2,6-diisocyanate, end-functionalized with cyclohexanol, with an NCN content of approximately 12% by weight (comparative example, similar to EP 2997010 B1). 2) CDI(B): -NCN-R having an NCN content of about 14% by weight IA high viscosity carbodiimide based on 80 wt. % diethyl tolylene-2,4-diisocyanate and 20 wt. % diethyl tolylene-2,6-diisocyanate, end-functionalized with I is triisopropylphenyl and n is greater than 40) (Comparative Example). 3) CDI(C): having an NCN content of about 14% by weight, -NCN-R I

[0033] A solid, high molecular weight carbodiimide (wherein R I is triisopropylphenyl and n is greater than 40) (Example of the present invention). 4) CDI(D): A solid, high molecular weight carbodiimide based on diisopropyl tolylene diisocyanate end-functionalized with ethylamine (comparison example, similar to China Patent No. 105778026). 5) CDI(E): A solid, high molecular weight carbodiimide (where n is 4-5) based on diisopropyl tolylene diisocyanate (formulas II and IV, weight ratio of about 1:4) having an NCN content of about 6-7 wt. % and end-functionalized with methyl polyethylene glycol (MW about 550 g / mol) (inventive example).

[0052] Ester-based polymers: 6) Unstabilized thermoplastic polyurethane (TPU) (available from Covestro AG under the name Desmopan).

[0053] Preparation of carbodiimide CDI(A) A baked-out, nitrogen-filled 250 mL four-neck flask was initially charged with 150 g of diisocyanate and 37.5 g of cyclohexanol under a nitrogen stream. 50 mg of 1-methylphospholene oxide was added, and the mixture was then slowly heated to 180° C. Carbodiimidization was then carried out at 180° C. until the NCO content reached less than 1 wt %.

[0054] Preparation of carbodiimides CDI(B) and CDI(C) : A 250 mL four-neck flask, heated and filled with nitrogen, was initially charged with 150 g of diisocyanate and 37.5 g of triisopropylphenyl isocyanate under a nitrogen stream. 50 mg of 1-methylphospholene oxide was added, and the mixture was then slowly heated to 180° C. Carbodiimidization was then carried out at 180° C. until the NCO content reached less than 1 wt %.

[0055] Preparation of carbodiimide CDI(D) A 250 mL four-neck flask, heated and filled with nitrogen, was first charged with 150 g of diisocyanate and 7.0 g of ethylamine under a nitrogen stream. 50 mg of 1-methylphospholene oxide was added, and the mixture was then slowly heated to 180° C. Carbodiimidization was then carried out at 180° C. until the NCO content reached less than 0.1 wt %.

[0056] Preparation of carbodiimide CDI(E) A 250 mL four-neck flask, heated and filled with nitrogen, was initially charged with 150 g of diisocyanate and 100 g of MPEG (methyl polyethylene glycol, Mw ∼550 g / mol). 50 mg of 1-methylphospholene oxide was added, and the mixture was then slowly heated to 180°C. Carbodiimidization was then carried out at 180°C until the NCO content reached less than 0.1 wt%.

[0057] Hydrolysis inhibition in thermoplastic polyurethanes (TPUs) To evaluate the hydrolysis inhibition in TPU, each of the carbodiimides investigated was dispersed in TPU in an amount of 1.5 wt % using a Werner & Pfleiderer ZSK25 twin-screw extruder, after which the following measurements were carried out: The pellets thus obtained were then used to prepare standard test specimens used to measure the breaking strength using an Arburg Allrounder 320 S 150-500 injection molding machine.

[0058] For the hydrolysis test, the standard specimens were stored in water at a temperature of 80° C. and their breaking strength (unit: MPa) was measured.

[0059] The results are shown in Table 1.

[0060] [Table 1]

[0061] The results from Table 1 show that the carbodiimides of the present invention achieve significantly better hydrolysis inhibition compared to the prior art.

[0062] Solubility in polyester polyol Stabilization of ester-based TPU elastomers against hydrolysis is typically carried out directly during production. For this purpose, carbodiimides are usually added to polyester polyols or polyester plasticizers prior to their reaction with isocyanates to obtain polyurethanes. Therefore, the solubility of the carbodiimides is important. Table 2 shows the solubility of various carbodiimides in a standard polyester polyol (Desmophen 2000MM, manufactured by Covestro AG) with Mw=2000, based on adipic acid and ethanediol, at 80°C.

[0063] [Table 2]

[0064] Inhibition of hydrolysis in polyethylene terephthalate (PET). To evaluate the hydrolysis inhibition in PET, each of the carbodiimides to be investigated was dispersed in PET in an amount of 1.5 wt. % using a Werner & Pfleiderer ZSK25 twin-screw extruder, after which the following measurements were carried out: From the pellets thus obtained, F3 standard specimens for measuring the breaking strength were then prepared using an Arburg Allrounder 320 S 150-500 injection molding machine.

[0065] For the hydrolysis test, the F3 standard specimens were stored in water at 90°C, and their breaking strength (unit: MPa) was measured. Table 2 shows the relative breaking strength = (breaking strength after x days of storage / breaking strength after 0 days) x 100. The lower limit of the relative breaking strength is usually 70-75%.

[0066] The results are shown in Table 3.

[0067] [Table 3]

[0068] Testing the pelletizability and metering properties of solid carbodiimides. To determine the processability, handling, and metering properties of various solid carbodiimides, they were compared for appearance, pelletizability, and softening point, which was measured using a Koffler bench.

[0069] The results are shown in Table 4.

[0070] [Table 4]

[0071] The results in Table 4 show that the carbodiimides of the invention based on diisopropyl tolylene end-capped with monoisocyanates have exceptional pelletizability and high softening points compared to high molecular weight carbodiimides based on diethyl tolylene diisocyanate end-capped with monoisocyanates, and compared to Carbodiimide D, thus offering advantages in processability and metering of the solids in the stabilization of ester-based polymers. Carbodiimide E according to the invention is liquid and can be added as is.

Claims

1. A carbodiimide of formula (I): 【Chemistry 1】 [In the formula, R may be the same or different and is -NCN-R Ｉ and -NHCOOR ＩＩＩ is selected from, where: R Ｉ is C ６ ~C １８ -aryl, or C ６ ~C １８ - represents aralkyl, R ＩＩＩ represents a monoalkylated polyethylene glycol ether having a molar mass between 200 and 600 g / mol, R １ , R ２ , and R ３ each independently represent methyl, i-propyl, or n-propyl, where on each benzene ring, a group R １ , R ２ , and R ３ is methyl, and n is 0 to 500.

2. R １ , R ２ , and R ３ 2. The carbodiimide of claim 1, wherein each independently of the other represents methyl or i-propyl.

3. 3. The carbodiimide according to claim 1, wherein the content of the carbodiimide is 2 to 17% by weight.

4. In formula (I), R is NCN-R Ｉ 3. The carbodiimide according to claim 1, wherein n is 0 to 500.

5. In formula (I), R is —NHCOOR ＩＩＩ 3. The carbodiimide according to claim 1, wherein n is 0 to 20.

6. In formula (I), R is —NHCOOR ＩＩＩ 3. The carbodiimide according to claim 1, wherein n is 0 to 20.

7. R ＩＩＩ 7. The carbodiimide of claim 6, wherein represents polyethylene glycol monomethyl ether.

8. 3. A method for producing the carbodiimide of claim 1 or 2, comprising the steps of: a) a compound represented by the following formula (II): 【Chemistry 2】 Carbodiimidization of the aromatic diisocyanate of formula (I) at a temperature of 80°C to 200°C in the presence of a catalyst and, optionally, a solvent, with elimination of carbon dioxide; and b) converting the free NCO group of the carbodiimide obtained in step a) into a compound of formula HOR ＩＩＩ functionalizing with an alcohol of (where R １ ~R ３ and R ＩＩＩ is as defined above for compounds of formula (I). A method comprising:

9. 3. A method for producing the carbodiimide of claim 1 or 2, comprising the steps of: a) partially comprising a compound represented by the following formula (II): 【Transformation 3】 The free NCO groups of the aromatic diisocyanate of the formula HOR ＩＩＩ functionalizing with an alcohol of b) subsequently, the partially functionalized aromatic diisocyanate of formula (II) obtained in step a) is subjected to carbodiimidization at a temperature between 80° C. and 200° C. in the presence of a catalyst and, optionally, a solvent, with elimination of carbon dioxide, where R １ ~R ３ and R ＩＩＩ is as defined above for compounds of formula (I).

10. A method for producing the carbodiimide according to claim 1 or 2, comprising the steps of: The following formula (II) 【Chemistry 4】 at a temperature of 80°C to 200°C in the presence of a catalyst and optionally a solvent, with elimination of carbon dioxide; wherein, before, during, or after the carbodiimidization of the diisocyanate, a compound of the formula OCN-R Ｉ A method of adding a monoisocyanate of R １ ~R ３ and R Ｉ is as defined above for compounds of formula (I).

11. The aromatic diisocyanate of the formula (II) used is a diisocyanate of the following formula (III): 【Transformation 5】 and / or a compound of the following formula (IV): 【Transformation 6】 The method of claim 8, wherein the compound is

12. R is -NCN-R Ｉ where R Ｉ is as defined for the compound of formula (I), and the melt of carbodiimide obtained in the carbodiimidization is pelletized in crude or purified form.

13. 3. Use of a carbodiimide according to claim 1 or 2 as an inhibitor against hydrolysis in ester-based polymers.

14. 3. Use of the carbodiimide according to claim 1 or 2 as a protective agent against hydrolysis in thermoplastic polyurethanes (TPU).

15. A composition comprising at least one carbodiimide of the present invention according to claim 1 or 2, and at least one ester-based polymer.

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