JP2002037850A - Production method of maleimide derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method of a maleimide carboxylate polyol ester at a high yield by ester interchange reaction of a polyol with maleimide and a halogen substituted carboxylate ester as a starting material. SOLUTION: The production method of the maleimide derivative shown by a formula (4) (m; an integer of 1-6, R; divalent hydrocarbon group, R2; a (poly)ester bonded chain or (poly)urethane bonded chain) is provided. The maleimide derivative is obtained from the maleimide carboxylate ester obtained by reacting maleimide and a halogen substituted carboxylate ester, and then an ester interchange reaction with polyol.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to active energy ray-curable coating agents, surface treatment agents, molding materials,
The present invention relates to a method for producing an active energy ray-curable compound useful for laminates, adhesives, pressure-sensitive adhesives, binders, and the like. More specifically, a maleimide derivative which is cured by a practical irradiation amount of ultraviolet light in the absence of a photopolymerization initiator And a method for producing the same.

[0002]

2. Description of the Related Art Active energy ray-curable compositions which are polymerized by active energy rays such as ultraviolet rays and visible rays have the advantage of fast curing, and are widely used in paints, printing inks, adhesives, coating agents and the like. ing. However, conventional active energy ray-curable compounds do not initiate polymerization by themselves, and therefore require the use of a photopolymerization initiator.

As the photopolymerization initiator, a compound having an aromatic ring is generally used in order to efficiently absorb light, and the cured product is liable to yellow by a compound or heat. have. In addition, the photopolymerization initiator is usually used as a low molecular weight compound because it is necessary to dissolve it in various active energy ray-curable monomers and / or oligomers to start a polymerization reaction efficiently. Many have a high vapor pressure and generate a bad smell in a state of normal temperature to 150 ° C. From the ultraviolet lamp which is one of the light sources of the active energy rays, since infrared rays are also generated in addition to ultraviolet rays, when a large number of ultraviolet lamps are continuously arranged and irradiated with light, the active energy ray-curable composition is considerably heated,
There was a drawback that a bad smell due to the photopolymerization initiator was generated and the working environment was deteriorated. Further, when a cured product comprising an active energy ray-curable composition containing a photopolymerization initiator is left in water or the like, an unreacted photopolymerization initiator or a photopolymerization initiator decomposition product is eluted and transferred into water or the like. Therefore, its use as a food packaging material was unsuitable.

[0004] From such a background, Japanese Patent Application Laid-Open No. H11-1244 has been disclosed.
No. 03 discloses that it does not use a photopolymerization initiator which causes malodor at the time of curing, yellowing of the cured coating, and elution from the cured coating, and cures with a practical light intensity and light irradiation amount. An active energy ray-curable maleimide derivative composition which is liquid at room temperature and a method for curing the composition by active energy rays are disclosed.

As one of the maleimide derivatives disclosed in JP-A-11-124403, there is a maleimide carboxylic acid polyol ester derivative obtained by dehydration condensation of a maleimide carboxylic acid and a polyol. Generally, an ester compound is obtained by dehydrating and condensing a carboxylic acid and a polyol, but it may be difficult to obtain an ester compound in high yield depending on the type of a reaction substrate.

For example, in the synthesis example described in JP-A-11-124403, an acid-catalyzed dehydration ester of a polyol having an ether-linked chain in the molecule and a maleimide carboxylic acid such as maleimidocaproic acid and maleimideacetic acid is disclosed. In the case where the excess ratio of the carboxylic acid to the hydroxyl group is about 1.1 times, the yield of the maleimide derivative is around 50% in many cases. In this dehydration esterification reaction, it is possible to increase the excess ratio of the carboxylic acid to the hydroxyl group to improve the yield, but in such a case, if the excess carboxylic acid compound is not recovered and reused, it is industrially economical. It is not a typical method.

As a method for solving such problems, the present inventors have invented a method for producing a maleimide carboxylic acid polyol ester derivative by a transesterification reaction between a maleimide carboxylic acid ester and a polyol using a tin catalyst. Application (Japanese Patent Application No. 11-128387)
No.).

The maleimide carboxylic acid ester used in the production method of Japanese Patent Application No. 11-128387 is, for example, as shown in the examples, a maleamic acid obtained from maleic anhydride and an aminocarboxylic acid, and an acid catalyst. After reacting with alcohol in the presence of
JP-A-3-173866 and JP-A-2-2-2
No. 00670, for example, by a method of performing alcohol-free ring-closing imidization.

Further, as a method for producing maleamic acid, which is a precursor for producing the above maleimide carboxylic acid ester, the present inventors have proposed a method in which a non-polar hydrocarbon solvent is used.
A method has been devised for obtaining a high yield of maleic anhydride and aminocarboxylic acid by reacting the same, and the applicant has filed a patent application (Japanese Patent Application No. Hei 11 (1999)).
1-127008 publication).

However, Japanese Patent Application Laid-Open No. 11-124403
No industrially advantageous method for obtaining the maleimide derivative disclosed in Japanese Patent Application Laid-Open Publication No. H07-15083 in high yield from maleimide or the like as a starting material has been disclosed at all. For example, JP-A-3-173
As disclosed in Japanese Patent Publication No. 866, it is not industrially advantageous in terms of cost to isolate maleamic acid obtained from maleic anhydride and aminocarboxylic acid and then esterify it. . Further, the maleamic acid is esterified, and the esterified product is disclosed in JP-A-2-2006.
When an attempt is made to derivatize a maleimide carboxylic acid ester by a dealcoholization ring-closing imidization reaction by a method as disclosed in JP-A-70-70, the maleimide carboxylic acid ester as a product is decomposed by the action of a basic catalyst, and the yield is reduced. There is a problem that the rate decreases.

[0011]

The problem to be solved by the present invention is that, as described above, a maleimide carboxylic acid polyol ester derivative, which is one of the maleimide derivatives, is prepared by using maleimide and a halogen-substituted carboxylic acid ester as starting materials. A transesterification reaction with a polyol to produce a high yield.

[0012]

Means for Solving the Problems The present inventors have made intensive studies in order to solve the above-mentioned problems, and as a result, (i) reacting maleimide with a halogen-substituted carboxylic acid ester to form a maleimide carboxylic acid ester And (ii) found that a maleimide carboxylic acid polyol ester derivative disclosed in JP-A-11-124403 can be obtained in high yield by reacting the maleimide carboxylic acid ester with a polyol, thereby completing the present invention. .

That is, in order to solve the above-mentioned problems, the present invention provides (A) maleimide and a compound represented by the general formula (1):

Embedded image (1) (In the formula, R represents a divalent hydrocarbon group. R ₁ represents an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms. X represents a halogen atom. Is reacted with a compound represented by the general formula (2).

Embedded image (2) (In the formula, R represents a divalent hydrocarbon group. R1 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or 3 carbon atoms.
Represents 10 to 10 cycloalkyl groups. A) a maleimide carboxylic acid ester obtained in the first step for producing a maleimide carboxylic acid ester represented by the following formula: R _2- (OH) m (3) (where m is an integer of 1 to 6) R ₂ represents at least one organic group selected from the group consisting of a straight-chain alkylene group, a branched alkylene group, a cycloalkylene group, an aryl group and an aralkylene group, at least one bond selected from an ether bond or a urethane bond; (Representing a (poly) ether-linked chain or a (poly) urethane-linked chain) represented by the following general formula (4):

Embedded image (4) (In the formula, m represents an integer of 1 to 6. R represents a divalent hydrocarbon group. R ₂ represents a linear alkylene group, a branched alkylene group, a cycloalkylene group, an aryl group, and an aralkylene. At least one organic group selected from the group consisting of
A (poly) ether-linked chain or (poly) urethane-linked chain connected by at least one bond selected from an ether bond or a urethane bond. A) a method for producing a maleimide derivative, the method comprising:

(B) R in general formulas (3) and (4)
Is a alkylene chain having 1 to 7 carbon atoms, the method for producing a maleimide derivative according to the above (A),

(C) m in general formulas (3) and (4)
Wherein (A) or (B) is an integer of 2 to 4,

(D) The method for producing a maleimide derivative as described in (A) to (C) above, wherein a dialkyltin (II) oxide is used as a catalyst in the transesterification reaction.

[0017]

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a maleimide derivative represented by the general formula (4), that is, a maleimide carboxylic acid polyol ester derivative. As the maleimide used in the first step of the production method of the present invention, a commercially available product may be used as it is, or a synthetic product,
For example, a material synthesized from maleic anhydride and ammonia may be used.

The halogen-substituted carboxylic acid ester used in the first step of the production method of the present invention has the general formula (1)

Embedded image (1) (In the formula, R represents a divalent hydrocarbon group. R ₁ represents an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms. X represents a halogen atom. ).

Specifically, for example, methyl monochloroacetate, ethyl monochloroacetate, propyl monochloroacetate,
Alkyl chlorocarboxylates such as butyl monochloroacetate, octyl monochloroacetate and methyl monobutyrate; cycloalkyls such as cyclohexyl monochloroacetate; alkyl bromocarboxylates such as methyl monobromoacetate and ethyl monobromoacetate; cyclohexyl monobromoacetate And alkyl iodocarboxylates such as methyl monoiodoacetate and ethyl monoiodoacetate, and cycloalkyl iodocarboxylates such as cyclohexyl monoiodoacetate.

The polyol used in the first step of the production method of the present invention has a general formula (3) R ^2- (OH) m (3) (where m represents an integer of 1 to 6; R ² is Wherein at least one organic group selected from the group consisting of a linear alkylene group, a branched alkylene group, a cycloalkylene group, an aryl group and an arylalkylene group is connected by at least one bond selected from an ether bond or a urethane bond. (Representing a (poly) ether-linked chain or a (poly) urethane-linked chain).

In the formula, R ² is at least one selected from the group consisting of a linear alkylene group, a branched alkylene group, a cycloalkylene group, an aryl group and an arylalkylene group.
(A) (poly) ether-linked chain or (b) (poly) urethane-linked chain having a number average molecular weight of 44 to 100,000, wherein two organic groups are linked by at least one bond selected from the group consisting of an ether bond and a urethane bond. Represents a chain. R ²
May be a connecting chain composed of an oligomer or a polymer in which these connecting chains are repeated as one unit.

Specific examples of these connecting chains include (a) a linear alkylene group having 1 to 24 carbon atoms, and a linear alkylene group having 2 to 2 carbon atoms.
4, at least one hydrocarbon group selected from the group consisting of a branched alkylene group, a cycloalkylene group, and an aryl group has a number average molecular weight of 44 to 100,00 having one or a repeating unit thereof bonded by an ether bond.
A connecting chain composed of 0 (poly) ether (poly) ol residues, or (b) a linear alkylene group having 1 to 24 carbon atoms, a branched alkylene group having 2 to 24 carbon atoms,
At least one hydrocarbon group selected from the group consisting of a cycloalkylene group and an aryl group is a (poly) urethane (poly) having a number average molecular weight of 230 to 100,000 and having one or a repeating unit thereof bonded by a urethane bond. ) Consists of all residues.

Specific examples of the (poly) ether (poly) ol constituting the linking chain (a) include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polybutylene glycol and polytetramethylene glycol. Ethylene glycol, propanediol, propylene glycol, tetramethylene glycol, pentamethylene glycol, hexanediol, neopentyl glycol, glycerin,
Alkylene glycols such as trimethylolpropane, pentaerythritol, diglycerin, ditrimethylolpropane, dipentaerythritol, ethylene oxide-modified, propylene oxide-modified, butylene oxide-modified, tetrahydrofuran-modified;

Copolymers such as ethylene oxide and propylene oxide copolymers, propylene glycol and tetrahydrofuran copolymers, ethylene glycol and tetrahydrofuran copolymers, polyisoprene glycol, hydrogenated polyisoprene glycol, polybutadiene glycol, and hydrogenated polybutadiene glycol Examples include hydrogenated polyols, polyvalent hydroxyl compounds such as polytetramethylene hexaglyceryl ether (modified tetrahydrofuran of hexaglycerin), among which various modified alkylene glycols are preferable, but those are not limited thereto. is not.

Specific examples of the (poly) urethane (poly) ol constituting the linking chain (b) include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polybutylene glycol and polytetramethylene glycol. Ethylene glycol, propanediol, propylene glycol, tetramethylene glycol, pentamethylene glycol, hexanediol, neopentyl glycol, glycerin,
Trimethylolpropane, pentaerythritol, diglycerin, ditrimethylolpropane, alkylene glycols such as dipentaerythritol, ethylene oxide modified products, propylene oxide modified products, butylene oxide modified products, polyvalent hydroxyl compounds such as tetrahydrofuran modified products, and the following And those obtained by subjecting the isocyanate compound described in (1) to addition polymerization under the condition of an excess of hydroxyl groups.

As the isocyanate compound, for example,
p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4 ′
-Diphenylmethane diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate, 3,
Aromatic diisocyanates such as 3'-diethyldiphenyl-4,4'-diisocyanate and naphthalene diisocyanate;

Diisocyanates having an aliphatic or alicyclic structure such as isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate and lysine diisocyanate; one or more burettes of isocyanate compounds Or, a polyisocyanate such as an isocyanurate obtained by trimerizing the diisocyanate compound is exemplified.

The (poly) urethane (poly) ol of the connecting chain (b) thus obtained is not particularly limited to these.

In the general formula (3), m represents the number of hydroxyl groups of the polyol. The number of hydroxyl groups is preferably in the range of 1 to 6, and more preferably 2 to 4.

Next, a method for producing the maleimide derivative of the present invention will be described. The maleimide carboxylic acid ester represented by the general formula (2) obtained in the first step of the present invention is:
It can be obtained by reacting maleimide with a halogen-substituted carboxylic acid ester represented by the general formula (1) while removing generated hydrogen halide in the presence of a basic compound.

The solvent used in this reaction is not particularly limited as long as it is an organic solvent which is inert under the reaction conditions. For example, toluene, xylene, cyclohexaneethylbenzene, cumene, chlorobenzene, petroleum ether, hexane, dioxane, dichloromethane , Chloroform, diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, acetone, butanone, dimethylformamide and the like. These reaction solvents are used so that the concentration of the maleimide carboxylic acid ester represented by the general formula (2) becomes 5 to 80% by weight, preferably 10 to 70% by weight.

The basic compound used in this reaction includes:
Although not particularly limited, for example, triethylamine, pyridine, N, N-dimethylaniline, N, N-dimethylaminopyridine, diazabicyclooctane (DABC
O), diazabicyclononene (DBN), diazabicycloundecene (DBU), sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, sodium acetate, potassium acetate and the like. These basic compounds are used in an amount of 0.1 to 5 moles, preferably 1 to 5 moles, based on the maleimide carboxylic acid ester represented by the general formula (2).
Use 1.5 molar times.

In the present invention, maleimide and a halogen-substituted carboxylic acid ester represented by the general formula (1) are converted to a basic compound under normal pressure or reduced pressure in a temperature range from the ice-cooling temperature to the boiling point of the solvent to be used. In the presence of More preferably, the solution containing the halogen-substituted carboxylic acid ester represented by the general formula (1) and the solution containing the basic compound are separately dropped into a solution containing maleimide at a temperature of 0 to 50 ° C. To react. As a raw material, 0.5 to 2 moles, preferably 1 to 1.
5 mol of the halogen-substituted carboxylic acid ester represented by the general formula (1) is used.

After completion of the reaction, water is added, the product is extracted with an organic solvent, and the solvent is removed to obtain a maleimide carboxylic acid ester represented by the general formula (2).
If necessary, it can be purified by recrystallization or the like.

Next, the maleimide carboxylic acid polyol represented by the general formula (4) in the second step of the present invention is different from the maleimide carboxylic acid ester represented by the general formula (2) obtained in the first step by the general formula (2). It is obtained by subjecting a polyol represented by the formula (3) to a transesterification reaction.

As the catalyst used in the second step of the production method of the present invention, acidic catalysts and heavy metal catalysts other than generally used catalysts for transesterification, excluding alkaline catalysts such as metal alkoxides, are effective. It is. When an alkaline catalyst such as a metal alkoxide is used, a reaction or decomposition of a maleimide carboxylic acid ester occurs, and it is difficult to obtain a target maleimide derivative with high purity.

The acidic catalyst used in the second step of the production method of the present invention includes, for example, inorganic acids such as sulfuric acid and phosphoric acid;
Organic sulfonic acids such as methanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid, and the like.

The heavy metal catalyst used in the second step of the production method of the present invention includes, for example, titanium tetrabutoxide, titanium tetraisopropoxide, titanium tetraethoxide, titanium tetraphenoxide, aluminum triisopropoxide, silicon tetraisopropoxide. Isopropoxide,
Metal alkoxides such as zirconium tetraisopropoxide; aluminum halides, titanium halides,
Metal halides such as magnesium halide, manganese halide, tin halide, iron halide, lead halide, zinc halide, zirconium halide, vanadium halide; zinc, lead, tin, zirconium, copper, antimony, titanium , Magnesium, manganese, cobalt, germanium oxide, and the like.

Among these transesterification catalysts, metal alkoxides such as aluminum, titanium and zirconium; dimethyl tin oxide (II) and dibutyl tin oxide (I
Dialkyltin (II) oxides such as I), dihexyltin (II) oxide, and dioctyltin (II) oxide are preferred because of the high transesterification reaction rate. Metal alkoxides such as aluminum, titanium and zirconium use a large amount of catalyst, whereas dimethyl tin oxide (II), dibutyl tin oxide (II), dihexyl tin oxide (II), and dioctyl tin oxide (II) The dialkyltin (II) oxide is particularly preferable from the viewpoints of a high transesterification rate with a small amount of a catalyst, a low cost, and a low coloration of the product.

The amount of the catalyst used is 0.1 to 50 mol% based on the maleimide carboxylic acid ester in the case of an acidic catalyst.
Is preferable, and the range of 1 to 20 mol% is particularly preferable. When a metal alkoxide such as aluminum, titanium or zirconium is used, the amount of the catalyst to be used is preferably in the range of 1 to 15 mol%, particularly preferably in the range of 3 to 10 mol%, based on the maleimide carboxylate. Dimethyl tin oxide (II), dibutyl tin oxide (I
When a dialkyltin oxide (II) such as I), dihexyltin oxide (II) or dioctyltin oxide (II) is used, the amount of the catalyst used is in the range of 0.01 to 10 mol% based on the total charged amount. Is preferable, and the range of 0.1 to 5 mol% is particularly preferable. If the amount of the catalyst used is too small, the reaction does not proceed practically, and if it is too large, the reaction rate does not change, which is economically disadvantageous. Further, in the case of metal alkoxides such as aluminum, titanium and zirconium, if the amount of the catalyst used is large, the product may be colored, which is not advantageous.

The second step of the production method of the present invention is preferably carried out under normal pressure or reduced pressure at a temperature in the range of room temperature to 150 ° C. while removing the alcohol produced by the reaction.
Further, the reaction solvent is not particularly required, but if necessary,
For example, hexane, cyclohexane, benzene, toluene, xylene, ethylbenzene, cumene, diisopropyl ether, dibutyl ether, tetrahydrofuran,
A solvent inert to the reaction, such as dioxane, may be used. When the alcohol generated by the transesterification reaction is a high-boiling component, a method of adding a reaction solvent azeotropic with the produced alcohol and removing the alcohol by azeotropic distillation with the reaction solvent can be adopted. For example, when the generated alcohol is n-butanol, isobutanol or isoamyl alcohol, cyclohexane, toluene, or the like can be used as a reaction solvent that azeotropically evaporates.

In the second step of the production method of the present invention, for the purpose of suppressing the radical polymerization of the maleimide group,
It is desirable to use a radical polymerization inhibitor. Examples of the radical polymerization inhibitor include hydroquinone, tert-
Butylhydroquinone, methoquinone, 2,4-dimethyl-
Phenolic compounds such as 6-tert-butylphenol, catechol and tert-butylcatechol; amines such as phenothiazine, p-phenylenediamine and diphenylamine; copper complexes such as copper dimethyldithiocarbamate, copper diethyldithiocarbamate and copper dibutyldithiocarbamate; And the like. These polymerization inhibitors can be used alone or in combination of two or more. The addition amount of the polymerization inhibitor is preferably in the range of 10 to 10,000 ppm based on the whole charged amount.

[0043]

The present invention will be described in more detail with reference to the following examples. However, the invention is not limited to these examples.

<Synthesis Example 1> -Synthesis of polyether urethane polyol A capacity 1 equipped with a stirrer, thermometer, dropping funnel and cooling pipe
400 g of polyethylene glycol 200 (manufactured by Kanto Chemical Co., number average molecular weight 200) in a 000 ml four-necked flask,
After charging 100 mg of dibutyltin dilaurate, 222 g of isophorone diisocyanate (manufactured by Kanto Kagaku) was added dropwise over 40 minutes while maintaining the liquid temperature at 70 ° C. by heating. After the completion of the dropwise addition, the reaction was further continued at 70 ° C. for 5 hours.
After cooling the reaction mixture, the infrared absorption spectrum (IR
The absorption of free isocyanate was confirmed to be disappeared by spectrum), and 620 g of polyether urethanediol having a number average molecular weight of 622 was obtained.

Example 1 A 1000-ml five-necked flask equipped with a stirrer, a thermometer and two dropping funnels was prepared as follows:
After 97 g of maleimide and 300 ml of toluene were charged, 101 g of triethylamine and 50 ml of toluene were added at room temperature.
Methyl chloroacetate dissolved in ml (manufactured by Daicel Chemical Industries, Ltd.)
109 g were dropped from each dropping funnel over 1 hour. After completion of the dropwise addition, the mixture was further stirred at room temperature for 4 hours.
After washing three times with 0 ml, toluene was distilled off to obtain 158 g of maleimide acetic acid methyl ester.

Next, polytetramethylene glycol ("Terathane 650" manufactured by DuPont) 30 having a number average molecular weight of 650 was placed in a four-necked flask having a capacity of 1000 ml and equipped with a stirrer, a thermometer and a Dean-Stark type fractionator.
5 g, maleimide acetic acid methyl ester 158 g, dibutyltin (II) oxide 4.5 g and hydroquinone 450 mg
And reacted at 110 ° C. for 8 hours under a reduced pressure of 7.5 kPa. It was confirmed by gas chromatography that maleimide acetic acid methyl ester had almost disappeared. 80 g of toluene was added to the reaction solution, and the mixture was washed twice with 50 ml of a saturated aqueous solution of sodium hydrogencarbonate and once with 50 ml of saturated saline, and then the organic layer was concentrated to obtain a yield of 93 based on maleimide.
% To obtain 2-maleimidoacetic acid polytetramethylene glycol ester.

<Example 2> In Example 1, 123 g of ethyl chloroacetate (manufactured by Daicel Chemical Industries, Ltd.) was used instead of 109 g of methyl chloroacetate, and 305 g of polytetramethylene glycol having a number average molecular weight of 650 was used instead of 305 g of polytetramethylene glycol having a number average molecular weight of 650. The procedure was performed in the same manner as in Example 1 except that 119 g of polytetramethylene glycol ("Terathane 250" manufactured by DuPont) was used. 2-Maleimidoacetic acid polytetramethylene glycol ester was obtained in a yield of 94% based on maleimide.

Example 3 In Example 1, 123 g of methyl 2-chloropropionate (manufactured by Daicel Chemical Industries, Ltd.) was used instead of 109 g of methyl chloroacetate.
The procedure was performed in the same manner as in Example 1 except that 290 g of the polyether urethanediol of Synthesis Example 1 was used instead of 305 g of the polytetramethylene glycol of 50. 2-Maleimidopropionic acid polyether urethane diol ester was obtained in a yield of 90% based on maleimide.

<Comparative Example> A stirrer, thermometer, dropping funnel,
Toluene 825 was added to a 3-liter separable four-necked flask equipped with a Dean-Stark fractionator and a condenser.
g, 31.4 g of p-toluenesulfonic acid monohydrate and 16.7 g of triethylamine were sequentially charged, and 180 g of maleic anhydride was added thereto with stirring, followed by dissolving while heating to 30 ° C. After further adding 163 g of β-alanine, the mixture was reacted at 70 ° C. for 3 hours with stirring. 300 g of toluene and 370 g of triethylamine were added, and the mixture was reacted for 1 hour while heating and refluxing the solvent to remove generated water. The residue obtained by evaporating the solvent from the reaction mixture was adjusted to pH 2 by adding 0.1 mol / m ³ hydrochloric acid, and then extracted three times with 100 ml of ethyl acetate. After magnesium sulfate was added to the obtained organic layer to dry it, ethyl acetate was distilled off and a pale yellow solid of maleimidopropionic acid was obtained.
7 g were obtained.

In a 1 liter round bottom flask equipped with a stirrer, thermometer, Dean-Stark fractionator and condenser,
127 g of the obtained maleimidopropionic acid, "Tera
thane650 ”240 g, toluene 200 g, p-
14.8 g of toluenesulfonic acid monohydrate and 2,6-t
0.74 g of tert-butyl-p-cresol was sequentially charged. Under reduced pressure, toluene was refluxed at 80 ° C. with stirring, and the reaction was carried out for 4 hours while removing generated water. To the reaction mixture was added 350 g of toluene, washed twice with 80 ml of a saturated aqueous solution of sodium hydrogen carbonate, and further washed with a saturated aqueous solution of sodium chloride 8.
After washing twice with 0 ml, the organic layer was concentrated to obtain maleimidopropionic acid polytetramethylene glycol ester in a yield of 40% based on maleic anhydride.

[0051]

According to the production method of the present invention, a maleimide derivative can be produced at a high yield by performing a transesterification reaction between a maleimide and a halogen-substituted carboxylic acid ester as starting materials.

 ──────────────────────────────────────────────────続 き Continued on front page F term (reference) 4J005 AA02 BD02 BD05 4J034 BA03 DG03 DG04 DG09 HA07 HC12 HC13 HC17 HC22 HC46 HC64 HC67 HC71 HC73 LA13 LA32 RA07 RA08 RA17

Claims (4)

[Claims] 1. Maleimide and a compound represented by the general formula (1) (1) (In the formula, R represents a divalent hydrocarbon group. R ₁ represents an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms. X represents a halogen atom. Is reacted to give a compound represented by the general formula (2): (2) (wherein, R represents a divalent hydrocarbon group; R ₁ represents an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms). A first step of producing a carboxylic acid ester, the maleimide carboxylic acid ester obtained in the first step, and R ₂ — (OH) m (3) (where m represents an integer of 1 to 6; R ₂ is At least one organic group selected from the group consisting of a linear alkylene group, a branched alkylene group, a cycloalkylene group, an aryl group, and an aralkylene group is connected by at least one bond selected from an ether bond or a urethane bond (poly ) Which represents an ether-linked chain or a (poly) urethane-linked chain), by a transesterification reaction with a polyol represented by the general formula (4): (4) (wherein, m represents an integer of 1 to 6. R represents a divalent hydrocarbon group. R ₂ represents a linear alkylene group, a branched alkylene group, a cycloalkylene group, an aryl group, and an aralkylene. At least one organic group selected from the group consisting of
A (poly) ether-linked chain or (poly) urethane-linked chain connected by at least one bond selected from an ether bond or a urethane bond. A) producing a maleimide derivative represented by the following formula: 2. The method for producing a maleimide derivative according to claim 1, wherein R is an alkylene chain having 1 to 7 carbon atoms. 3. The formula (3) and the formula (4) wherein m is 2
The method for producing a maleimide derivative according to claim 1 or 2, wherein the method is an integer of 4. 4. The method for producing a maleimide derivative according to claim 1, wherein a dialkyltin (II) oxide is used as a transesterification catalyst.