JP2000256436A - Carbodiimide, production and use thereof, and mixture containing carbodiimide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a solid carbodiimide which has an urethane structures and/or an urea sructures, has a carbodiimide structures bonded to nonaromatic carbon atoms, and is useful as a stabilizer for polyester plastics. SOLUTION: This carbodiimide is solid at 25 deg.C and is produced by separating carbon dioxide in the presence of a catalyst from a diisocyanate having no isocyanate group bonded to an aromatic carbon atom, thus converting the diisocyanate into a carbodiimide, and reacting this isocyanate-group-containing carbodiimide with a compound having at least two isocyanate-reactive groups to form urethane structures and/or urea structures. Preferably, the diisocyanate is 1,3-bis(1-methyl-1-isocyanatoethyl)benzene. Preferable examples of the compound having at least two isocyanate-reactive groups are an organic compound having at least two hydroxyl groups, an organic compound having at least two amino groups, and an organic compound having at least one hydroxyl group and at least one amino group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a carbodiimide structure having a carbodiimide structure and further a urethane structure and / or a urea structure, which are solid at 25 ° C., wherein the carbodiimide structure is bonded to a non-aromatic carbon atom. It relates to carbodiimide. Furthermore, the present invention relates to a method for producing these carbodiimides, a mixture containing such a carbodiimide and a compound having an ester structure, preferably a polyurethane containing an ester structure.

[0002]

BACKGROUND OF THE INVENTION Organic carbodiimides are known and include, for example, compounds containing ester groups, such as polyaddition compounds or polycondensation products, in particular the hydrolytic cleavage of polyurethanes.
Used as a stabilizer against yticdegradation). The carbodiimide is produced by a known method, for example, by allowing a catalyst to act on monoisocyanate or polyisocyanate to remove carbon dioxide. Examples of suitable catalysts are, for example, heterocyclic compounds containing bound phosphorus, metal carbonyls, phosphorines, phosphorenes and phosphoridines, and their oxides and sulfides.

[0003] Such carbodiimides, their preparation and their use as stabilizers against hydrolytic cleavage of polyester-based plastics are described in German Offenlegungsschrift 43.
Nos. 18979, 4444224 and EP-A-460481.

[0004]

DE-A 43 18 979 discloses that the terminal isocyanate group
The use of 1,3-bis (1-methyl-1-isocyanatoethyl) benzene to produce carbodiimides and / or oligomeric polycarbodiimides having urea and / or urethane groups is described. The terminal isocyanate groups of the carbodiimides described in this document usually react with monoalcohols or monoamines. Such carbodiimides are viscous liquids and have the disadvantage of being difficult to process in metering and feeding equipment designed for processing powdery or granular solids commonly used in the plastics processing industry. .

EP-A-460 481 discloses that substituted monocarbodiimides or oligomeric substituted polycarbodiimides having up to four carbodiimide groups are obtained from substituted diisocyanates and which may be subjected to elevated temperatures or There is a description that a substantially non-toxic volatile substance derived from carbodiimide used at room temperature is released. The carbodiimide in this case has the considerable disadvantage that the carbodiimide group is directly attached to the aromatic carbon atom. That is, the carbodiimide group is cleaved under severe hydrolysis conditions or the like, whereby an aromatic amine having a toxicity problem is obtained.

Further, the carbodiimides described in DE-A-460 481 have a relatively strong tendency to yellow and are therefore not preferred in various applications.

However, the present invention is to improve carbodiimide as a stabilizer against the cleavage of polyester-based plastics by hydrolysis, to enable the carbodiimide to be easily mixed with plastics in a solid state, and to obtain excellent properties as a stabilizer. Is the subject.

[0008]

Means for Solving the Problems The present inventors have found that the object of the present invention is to provide a carbodiimide structure and a urethane structure, a urea structure or both of these structures at 25 ° C.
And a carbodiimide structure is achieved with a carbodiimide bonded to a non-aromatic carbon atom.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The method for producing a carbodiimide of the present invention mainly comprises two reaction steps. First, (1) a known reaction between the isocyanate groups, carbon dioxide is eliminated in the presence of the above-mentioned catalyst commonly used in this reaction to obtain a carbodiimide structure, and second, (2) the isocyanate group is The isocyanate is reacted with a reactive compound to form a urethane structure or a urea structure, or both. The two main processing steps may be performed in any order as long as a free isocyanate group is present in each of the above reactions.

For example, the carbodiimide of the present invention converts a diisocyanate having an isocyanate group not bonded to an aromatic carbon atom into a carbodiimide by removing carbon dioxide in the presence of a catalyst, and then converting the diisocyanate to a carbodiimide. It is obtained by reacting a carbodiimide containing a group with a compound containing two or more groups reactive to isocyanate to obtain a substituted carbodiimide, for example, a carbodiimide containing a urethane structure or a urea structure or both. NC of carbodiimide containing isocyanate group
The molar ratio of O groups to isocyanate-reactive groups is usually from 10: 1 to 0.2: 1, preferably 5: 1.
０．５0.5: 1.

In other cases, the carbodiimides of the present invention include a diisocyanate in which the isocyanate group is not bonded to an aromatic carbon atom, a compound comprising two or more groups reactive with isocyanate, The ratio of the isocyanate groups used to the isocyanate-reactive groups is from 100: 1 to 2: 1, preferably from 50: 1 to 2: 1.
And then converting the resulting reaction product containing isocyanate groups into a carbodiimide containing a urethane structure or a urea structure or both by removing carbon dioxide in the presence of a catalyst. Is also obtained. In this treatment mode, 50% by weight or less, preferably 23% by weight or less of the isocyanate group contained in the diisocyanate is reacted with a compound reactive with the isocyanate group in the first step, and then the free isocyanate is reacted. A carbodiimide or an oligomeric polycarbodiimide or both are obtained by completely or partially condensing a nato group by removing carbon dioxide in the presence of a catalyst.

It is preferable to first carry out a carbodiimide forming reaction, and then to react the carbodiimide containing this isocyanate with a compound reactive with isocyanate.

The carbodiimide production process (1) of the present invention by the reaction of diisocyanate is carried out at a high temperature, for example, at 50 to 200 ° C., preferably 150 to 185 ° C., preferably in the presence of a catalyst. Is desorbed.
Suitable methods are described in GB-A 1083410, DE-B1
130594 (GB-A851936) and DE
-A11564401 (US-A3502772). Examples of catalysts which have proven to be very effective are phosphorus compounds, preferably using phosphorene, phosphorene oxide, phosphoridine or phosphorine oxide. NC where reaction mixture is desired
In the case of having an O group content, that is, preferably having four or more corresponding to the degree of condensation, the production of polycarbodiimide usually stops. For this reason, it is possible to distill off the catalyst under reduced pressure or to deactivate the catalyst with a deactivating agent such as phosphorus trichloride. The preparation of the polycarbodiimide is carried out in the presence or absence of a solvent which is inert under the reaction conditions.

A person skilled in the art can set the degree of condensation in a conventional manner by appropriately selecting the course of the reaction, for example, the reaction temperature, the type of catalyst, the amount of catalyst used, and the reaction time. The course of the reaction is most simply adjusted by determining the NCO content. Increase in viscosity, other parameters such as evaporation thickening or CO ₂ of colors, and for monitoring the progress of the reaction, are utilized to control the reaction.

The diisocyanate used in the production of the dicarbodiimide of the present invention is a commonly used diisocyanate having no isocyanate group bonded to an aromatic carbon atom, for example, hexamethylene diisocyanate,
-Isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate), di (cyclohexyl) methane diisocyanate, trimethylhexamethylene diisocyanate, dodecane diisocyanate, octane diisocyanate and Cyclohexane 1,4-diisocyanate. In particular, it is preferable to use 1,3-bis (1-methyl-1-isocyanatoethyl) benzene (hereinafter also referred to as TMXDI) as a diisocyanate. It is also possible to use the above-mentioned diisocyanate as a mixture of two or more kinds, and it is preferably used as a mixture with 1,3-bis (1-methyl-1-isocyanatoethyl) benzene. In this case, 30 mol% or more of 1,3-bis (1-methyl-1-isocyanatoethyl) benzene is preferably used. The carbodiimide of the present invention particularly preferably contains one or more types of structural units shown below, which show a carbodiimide structure corresponding to a diisocyanate that is particularly preferably used.

[0016]

Embedded image For example, the carbodiimide of the present invention can have the following structure.

[0017]

Embedded image In the above formula, may be different and are R is respectively identical, for example mean -NHCONHR ¹ or -NHCOOR ¹ radical (the R ¹ and R ² are reactive toward isocyanates, the following examples Which can be linked to other carbodiimide structures).

N is, for example, 0, 1, 2, 3, 4, 5,
6, 7, 8, 9, 10 (n may be an integer of these, or may be a fractional value as a statistical average).

The carbodiimide according to the invention, which is solid at 25 ° C., is preferably derived from 1,3-bis (1-methyl-1-isocyanatoethyl) benzene (TMXDI).

The isocyanate-reactive compound containing two or more groups reactive to isocyanate and used for producing the carbodiimide of the present invention is a urethane group or a urea group or a urea group or a urea group thereof by a reaction with isocyanate. It is a conventional substance that forms both. For example, aromatic, aliphatic and / or arylaliphatic compounds having 2-20 carbon atoms, hydroxyl or amine groups or both as reactive groups for isocyanates can be used. An organic compound containing two or more hydroxyl groups, two or more amine groups, and / or one or more hydroxyl groups and one or more amines, as a compound containing two or more groups reactive to isocyanate Organic compounds containing a group can be suitably used. For example, aromatic, arylaliphatic and / or aliphatic polyols having 2 to 20 carbon atoms, particularly those containing a primary hydroxyl group are preferably used.
Preferred examples are 1,2-ethanediol, 1,3
-Propanediol, 1,2-propanediol, 1,
4-, 2,4- and / or 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,10- Decanediol, neopentyl glycol, 2, -methylpropane-1,3-diol, 2
-And 3-methylpentane-1,5-diol, isomers of bis (hydroxy-methyl or ethyl) benzene, hydroxyalkyl ethers of dihydroxybenzene, trimethylpropane, glycerol, pentaerythritol and / or for example 4, 5 or 6 And a saccharide having a hydroxyl group.

Other compounds which can be used as the compound containing two or more hydroxyl groups are polyester alcohol and polyether alcohol which are preferably used for producing polyurethane and the like. For such macro-ols, see "Plastic Handbook (Kunststoffha
ndbuch), Volume 7: Polyurethane ".

Particularly preferred macrools are those which have also been used to produce polymers to be protected from hydrolysis.

Macrools which are particularly useful for protecting polyesters from hydrolysis correspond to the structural parts of the polyester. Of these, oligomeric polyethylene terephthalate and polybutylene terephthalate are particularly noteworthy.

These oligomers can be prepared by the known condensation reaction of ethanediol or butanediol with terephthalic acid or lower esters of terephthalic acid, or by the conventional glycolytic cleavage of high molecular weight terephthalic esters.
degration).

The molecular weight Mn of the oligomer is 260-10
000 g / mol, preferably 260-5000 g / mol, particularly preferably 350-2000 g / mol.

The amine used is one which contains two or more primary and / or secondary amine groups. Examples of these include two or more primary, molecular weights of 32-500 g / mol, preferably 60-300 g / mol.
Amines containing one or more secondary or one primary and one secondary amino group. Specific examples include diamines such as diaminoethane, diaminopropane, diaminobutane, diaminopentane, diaminohexane, piperazine, 2,5-dimethylpiperazine, 1-amino-
3,3,5-trimethyl-5-aminomethylcyclohexane (isophoronediamine, IPDA), 4,4′-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, aminoethylethanolamine, hydrazine, hydrazine hydrate, and / or Or a triamine, such as diethylenetriamine, and / or 1,8-diamino-4-aminomethyloctane.

In addition, it is possible to use amines derived from the above-mentioned amines in which one or more primary amine groups are further substituted by substituents such as alkyl groups to form secondary amines. Furthermore, the use of compounds having both one or more hydroxyl groups and one or more amine groups, for example ethanolamine, propanolamine, isopropanolamine, aminoethylethanolamine or N-alkylamines derived therefrom Can be.

It is preferable to use linear alcohols, amines or amino alcohols, of which those having an even number of carbon atoms are particularly preferably used. Further, an alcohol amine or an amino alcohol having a cyclic structure portion is also preferably used.

Particularly when the diisocyanate is converted to carbodiimide in the first step and then the reaction of the carbodiimide containing isocyanate groups with a compound reactive to the isocyanate groups is carried out, In addition to the above compounds that have and have two or more functional groups, monofunctional compounds are also effectively used to adjust the molecular weight of the carbodiimide of the present invention. As monofunctional compounds reactive with isocyanates, for example, amines and preferably alcohols can be used. Preferred amines are, for example, primary or preferably secondary amines, preferably having 1 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms. Examples of this include methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, 2-ethylhexylamine, octylamine, decylamine, diethylamine, dipropylamine, dibutylamine, methylbutylamine, ethylbutylamine, ethylhexylamine,
Cyclohexylamine and benzylamine. However, to block the isocyanate group, alcohols such as primary or secondary alcohols having 1-18, preferably 2-8, carbon atoms are preferably used. Examples of primary and secondary alcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, n-pentanol, industrially used pentanol mixtures, n-hexanol Hexanol mixtures, 2-ethylhexanol, octanol, 2-ethyloctanol, decanol, dodecanol, cyclohexanol and benzyl alcohol used industrially.

The carbodiimides according to the invention are solid at room temperature, ie at 25 ° C., preferably at 30 ° C., more preferably at 40 ° C., in particular at 50 ° C., and under a pressure of 1013 mbar. As a result, the carbodiimide is granulated or pulverized by known methods and is handled as a solid by the equipment commonly used in the plastics processing industry for plastics processing or production. When used as a solid in conventional equipment, it is much easier to handle than when used as a liquid.

The carbodiimide of the present invention preferably has
It has at least two carbodiimide structures, more preferably more than four, and the average value (number average) of the degree of condensation, that is, the average number of carbodiimide structures in the carbodiimide of the present invention is particularly preferably 4.
It is 1-20, more preferably 5-15. Further, the compounds of the present invention are obtained by reacting the isocyanate group of the diisocyanate used in the above-mentioned production method with a group reactive with the isocyanate, for example, a hydroxyl-containing compound or an amine or both, It contains a urethane group or a urea group or both.

The carbodiimide structure of the compound of the present invention has
Attaches to non-aromatic carbon atoms. Thereby, the aromatic amine is not released upon cleavage of the carbodiimide. That is, the carbodiimide of the present invention only poses a significantly reduced toxicity problem as compared with the carbodiimide described in EP-A-460481.

In the reaction with a compound containing a carboxylic acid and / or a carboxyl group, the carbodiimide and the oligomeric polycarbodiimide of the present invention are used to prepare TMXD.
In the case of carbodiimides based on I, arylaliphatic isocyanates are produced which are less reactive than aromatic isocyanates. Therefore, the obtained aryl aliphatic isocyanate does not substantially affect the index of the addition reaction for producing urethane and the like. As a result, the molecular weight of the obtained polyurethane and its mechanical properties are constant and well reproduced.

The carbodiimide of the present invention preferably has a sterically hindered isocyanate group, a urea group and / or a urethane group, which binds to a non-aromatic carbon, and has a high resistance to hydrolysis. It has light stability equal to or higher than aromatic carbodiimide and aromatic polycarbodiimide used industrially, and is introduced into ester group-containing polycondensation products and polyaddition products while complying with business hygiene regulations. It is possible. Furthermore, it has the advantage of having many effective carbodiimide groups based on the molecular weight of the carbodiimide. Carbodiimides have good compatibility with polyaddition products and polycondensation products containing ester groups, especially polyester urethane rubbers, and are easily and homogeneously mixed with such materials in the molten state.

The monocarbodiimides and / or oligomeric polycarbodiimides of the present invention are particularly preferred as acceptors for carboxyl compounds, and therefore include compounds containing ester groups, such as polymers containing ester groups, such as thermoplastic polyesters, such as polyethylene terephthalate, polybutylene. Terephthalate, polyetherester, polyesterester, polyamide, polyesteramide, polycaprolactone, and also unsaturated polyester resins, and block copolymers of, for example, polyethylene terephthalate or polybutylene terephthalate, polycaprolactone, and polyaddition products, such as Examples include polyurethane, polyurea and polyurethane-polyurea elastomers, each containing an ester group. These compounds containing an ester group are known. These starting materials,
Manufacturing methods, structures, and properties are described in ordinary literature. Due to the good solubility in the constituents of the polyurethane production and the good compatibility with the resulting polyurethane, the (poly) carbodiimides of the present invention can be made of polyurethanes, preferably of dense or cellular nature. It is particularly suitable as a stabilizer against hydrolytic cleavage of polyurethane elastomers, especially thermoplastic polyurethanes.

When the carbodiimide of the present invention has a terminal isocyanate group, for example, when a carbodiimide having an isocyanate group and a group reactive with the isocyanate are used in an insufficient amount, the carbodiimide is converted to an isocyanate and an isocyanate. Can be used to produce polyaddition products by the reaction of compounds that are reactive towards

The concentration of the carbodiimides according to the invention in the polycondensation or polyaddition products containing ester groups to be stabilized is generally from 0.05 to 10% by weight, based on the total weight of the mixture, Preferably, it is 0.1 to 5% by weight. In special cases, this concentration may be increased, depending on the hydrolytic stress applied to the plastic.

The carbodiimides used according to the invention can be introduced in various ways into products containing ester groups to be stabilized. For example, one of the components for producing the polyaddition product of the carbodiimide of the present invention.
For example, it can be mixed with a polyisocyanate and / or a polyhydroxyl compound for producing polyurethane, and can be added to a reaction mixture for producing polyurethane for producing carbodiimide of the present invention. is there. In another embodiment of the production method, the carbodiimide of the present invention may be introduced into the melt of the polyaddition product or polycondensation product after complete reaction. Further, the carbodiimide of the present invention may be applied to the granular polyaddition product or polycondensation product, or they may be mixed with the carbodiimide of the present invention in the form of powder, pellets or granules, It is also possible to introduce it into the plastic melt during the subsequent production of the shaped body by melt extrusion. In order to produce polyurethane casting elastomers and polyester-based TPUs, the carboxyl-containing polyester polyol is firstly treated with the carbodiimide of the present invention to reduce the acid content and then further added or added to the carbodiimide in a preferred embodiment. Instead of reacting with the polyisocyanate, if necessary, in the presence of further auxiliaries and additives. Furthermore, the carbodiimides of the present invention can be introduced into polyurethane via a polyisocyanate component. However,
It is particularly preferred that the carbodiimides of the present invention are incorporated into polymers containing ester groups during general manufacturing.

Apart from its effect as stabilizer on the hydrolytic cleavage of polyaddition products or polycondensation products containing ester groups, or on the deacidification of polyesterols used in the production of polyester-containing plastics, especially polyurethane rubbers, The carbodiimide of the present invention is suitably used, for example, for stopping an esterification reaction when a desired degree of polycondensation is obtained in the production of polyester.

The present invention is not limited to the configuration of the above embodiment, and various modifications can be made within the scope of the invention.

[0041]

EXAMPLES 1,3-Bis (1-methyl-1-isocyanatoethyl) benzene 75 having an NCO content of 34.4% by weight.
0 parts by weight (3.1 mol) are heated to 180 ° C. without solvent in the presence of 1.5 parts by weight of 1-methyl-2-phospholene 1-oxide, based on isocyanate, at this temperature The condensation was carried out while gently evaporating carbon dioxide. After the NCO content of the reaction mixture reached 11.2% by weight, the added catalyst and unreacted 1,3-bis (1-
Methyl-1-isocyanatoethyl) benzene is converted to 180
C. and distilled off at 1 mbar.

This gives an NCO content of 7.79% by weight, a -N = C = N-group content of 15.2% by weight (theoretical value), a melting point of <30 ° C., and an iodine color number of 5 to 5 measured according to DIN 6162. 7 carbodiimide mixture 57
0 parts by weight were obtained.

The structure of a mixture of a monocarbodiimide containing an isocyanate group and an oligomeric polycarbodiimide is represented by the following formula:
Confirmed by IR spectrum and gel chromatography analysis.

Hereinafter, this carbodiimide mixture is referred to as carbodiimide 1.

[Example 1-12] The above carbodiimide 1
500 g of the mixture was reacted with the alcohols listed in Table 1 at 140 ° C. in a flask equipped with a stir bar until the following NCO content was obtained. The molar ratios listed in Table 1 indicate the molar ratio of isocyanate groups: diol: monool in the initial reaction mixture.

[0046]

[Table 1]

Example 13-20 500 g of the carbodiimide 1 mixture was placed in a flask equipped with an amine shown in Table 2, optionally an alcohol, and a stirrer.
Each reaction was carried out at 40 ° C. until the following NCO content was obtained. The molar ratios listed in Table 2 indicate the molar ratio of isocyanate groups: diamine: alcohol in the initial reaction mixture.

[0048]

[Table 2] Isophorone diamine: 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane

All of the carbodiimides obtained in Examples 1-20 have an iodine color number of less than 8, most of which are 5
Was less than. These carbodiimides could be easily processed by grinding in a crossbeater mill, resulting in a fine, free flowing powder without caking tendency.

The crushed carbodiimide is placed in an oven,
Stored at 35 ° C. for 14 days. After this, the carbodiimide powder retained its free-flowing property and could be easily crushed even if small lumps were formed.

[Examples 21-41] 400 g (1.76)
Mol) of diphenylmethane 4,4'-diisocyanate, 1000 g (0.5 mol) of 1,4-butanediol-1,6-hexanediol polyadipate,
In a thermoplastic polyurethane (TPU) obtained by reaction with 3 g (1.26 mol) of 1,4-butanediol, at a concentration of 0.65% by weight, based on the TPU, Example 1 of the invention was used. To the carbodiimide obtained by
It was introduced into a twin screw extruder with a solids feed.

The carbodiimide-containing granules were subjected to injection molding to obtain a specimen.

The tensile strength and elongation at break of each test object were determined by DIN.
According to 53504, it was measured both immediately after production and after storage in water at 80 ° C. for 21 days.

Table 3 shows the carbodiimides used and the measured values of their mechanical properties.

[0055]

[Table 3]

Example 42 616 g of PET oligomer having an OH value of 172 obtained by transesterification reaction of dimethyl terephthalate and 1,2-ethanediol
(0.947 mol) and 500 of polycarbodiimide 1
g (0.464 mol) were reacted at 200 ° C. in a stirred flask until the NCO content reached 0.3% by weight.

The glass transition temperature of the obtained product is 45 ° C.
Met.

Example 43 454 g of oligo-PET
Example 1 was repeated using

The glass transition temperature of the obtained reaction product is 5
7 ° C.

Example 44 404 g of oligo-PET
Example 1 was repeated using

The glass transition temperature of the obtained reaction product is 5
7 ° C.

Example 45 495 g of a PBT oligomer having an OH number of 211 and obtained by transesterification from dimethyl terephthalate and 1,4-butanediol
(0.932 mol) and German Patent Application No. 4318
500 g (0.464 mol) of polycarbodiimide having an NCO content of 7.79% by weight manufactured according to JP-A-979.
Was reacted at 200 ° C. in a stirred flask until the NCO content reached 0.3% by weight.

Example 46 273 g of oligo-PBT
Example 4 was repeated using

Example 47 330 g of oligo-PBT
Example 4 was repeated using

 ────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Karl, Heberle Germany, 67346, Speyer, Allahi Ligenstrasse, 15 (72) Inventor Rupert, Claus Germany, 67165, Waldsee, Berliner, Strasse, 6F Term ( 4H006 AA01 AA02 AA03 AB51 AC59 BA53 4J002 CF001 CF061 CF071 CF091 CF191 CF211 CK022 CL001 CL081 FD202 4J034 AA05 BA01 CA04 CA05 CA15 CA16 CB02 CC03 CC12 CC26 CC33 CC61 CC62 DA01 DB04 DC02 DC50 JA01 HA12

Claims (13)

[Claims] A carbodiimide structure and a urethane structure, a urea structure or a structure of both of them at 25 ° C.
And a carbodiimide having a carbodiimide structure bonded to a non-aromatic carbon atom. 2. The carbodiimide according to claim 1, which has four or more carbodiimide structures. 3. The carbodiimide according to claim 1, which is derived from 1,3-bis (1-methyl-1-isocyanatoethyl) benzene. 4. A method for producing a carbodiimide which has a carbodiimide structure and further has a urethane structure, a urea structure or both of them and is solid at room temperature, wherein an isocyanate group is bonded to an aromatic carbon atom. Diisocyanate is converted to carbodiimide by elimination of carbon dioxide in the presence of a catalyst, and then the carbodiimide having an isocyanate group is compounded with a compound having two or more groups reactive with isocyanate. How to react. 5. A method for producing a carbodiimide which has a carbodiimide structure and further has a urethane structure, a urea structure or both of them and is solid at room temperature, wherein an isocyanate group is bonded to an aromatic carbon atom. Diisocyanate is reacted with a compound having two or more groups reactive to isocyanate with a ratio of isocyanate groups to groups reactive to isocyanate of at least 2: 1; A method comprising converting a reaction product containing a group, obtained by the above reaction, to carbodiimide by removing carbon dioxide in the presence of a catalyst. 6. The compound having two or more groups reactive with isocyanate is an organic compound containing two or more hydroxyl groups, an organic compound containing two or more amine groups, or one or more hydroxyl groups. Organic compounds comprising a group and one or more amine groups, or a mixture thereof,
The method according to claim 4. 7. The method of claim 4 or claim 5, wherein the carbodiimide comprises four or more carbodiimide structures. 8. The process according to claim 4, wherein 1,3-bis (1-methyl-1-isocyanatoethyl) benzene is used as diisocyanate. 9. A carbodiimide which is solid at room temperature and is obtainable by the method according to claim 4 or 5. 10. A mixture comprising a compound having an ester structure and the carbodiimide according to claim 1 or 9. 11. A carbodiimide according to claim 1 or 9 and at least one compound selected from a polyurethane having an ester structure and a polycondensation product, wherein the polycondensation product is a thermoplastic polyester or a polycondensation product. A mixture comprising an ether ester, a polyester ester, a polyester amide, a polycaprolactone, an unsaturated polyester resin or a polyamide, wherein the thermoplastic polyester is polyethylene terephthalate or polybutylene terephthalate. 12. The carbodiimide according to claim 1 or 9 is used in an amount of 0.05 to 10% by weight based on the total weight of the mixture.
The mixture according to claim 10, comprising: 13. Use of the carbodiimide according to claim 1 or 9 as a stabilizer against hydrolytic degradation of a compound containing an ester group.