JP2002003473A - Method of manufacturing derivative of maleimide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a maleimide carboxylic acid polyol ester derivative in high yield without carrying out an isolation and purification of its intermediate by using a polyol, maleic anhydride and an aminocarboxylic acid as a starting material. SOLUTION: This method of manufacturing a maleimide derivative expressed by general formula (4) comprises carrying out an esterification or an transesterification of a polyol and an aminocarboxylic acid, an aminocarboxylate or their salt to obtain a polyamine compound, and then reacting the polyamine compound with maleic anhydride. ((m) is an integer of 1-6; R is a divalent hydrocarbon group; and R2 is a (poly)ether bonding chain or a (poly)urethane bonding chain).

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 process for obtaining the compound with high yield.

[Prior art]

An active energy ray-curable composition which is polymerized by an active energy ray such as an ultraviolet ray or a visible light ray has an advantage of fast curing, and is widely used in paints, printing inks, adhesives, coating agents and the like. . However,
Conventionally used active energy ray-curable compounds are:
Since polymerization does not start by itself, a photopolymerization initiator must be used in combination.

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 compounds to efficiently start the polymerization reaction. , Room temperature ~ 15
In the state of 0 ° C., many of them produce a bad smell. 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.

[0004] Further, in a cured product comprising an active energy ray-curable composition containing a photopolymerization initiator, an unreacted photopolymerization initiator or a decomposition product of the photopolymerization initiator remains. When left undissolved in water or the like, unreacted photopolymerization initiators or decomposed products of the photopolymerization initiator are eluted and transferred to water or the like, so that they are not suitable for use as food packaging materials.

From such a background, Japanese Patent Application Laid-Open No. 11-1244
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 maleimide caproic acid or maleimide acetic 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 target 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 maleimide carboxylic acid is not recovered and reused, it is industrially economical. It is not a typical method.

As a method for solving such a problem, 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 has already been filed (Japanese Patent Application No. 11-128387)
No.).

The maleimide carboxylic acid ester used in the production method of the Japanese Patent Application No. 11-128387 is, for example, a maleamic acid obtained from maleic anhydride and an aminocarboxylic acid, as shown in the examples. After diesterification by reacting with alcohol in the presence of a catalyst, JP-A-3-173866 and
-200670, for example, a method for performing alcohol-free ring-closing imidization.

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 for preparing maleic anhydride and aminocarboxylic acid in a non-polar hydrocarbon solvent. And react with
The inventors have invented a method for obtaining this in a high yield, and have already filed an application (Japanese Patent Application No. 11-127008).

However, Japanese Patent Application Laid-Open No. 11-124403
No industrially advantageous method for obtaining the maleimide carboxylic acid polyol ester derivative disclosed in Japanese Patent Application Laid-Open Publication No. H08-27139 in high yield using inexpensive maleic anhydride or the like as a starting material has not been disclosed at all.

For example, as disclosed in JP-A-3-173866, it is costly to isolate maleamic acid obtained from maleic anhydride and aminocarboxylic acid and then esterify it. It is not an industrially advantageous method. In addition, when the maleamic acid is esterified and is converted to a maleimide carboxylic acid ester by a dealcoholization ring-closing imidization reaction by a method as disclosed in JP-A-2-200670, it is a product. There is a problem that the maleimide carboxylic acid ester is decomposed by the action of a basic catalyst, and the yield is reduced.

[0013]

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 maleimide derivatives, is obtained by starting from a polyol, maleic anhydride and aminocarboxylic acid. It is an object of the present invention to provide a method for producing a high-yield intermediate without isolating and purifying an intermediate.

[0014]

Means for Solving the Problems The present inventors have made intensive studies to solve the above problems, and as a result, starting from polyol, maleic anhydride and aminocarboxylic acid as starting materials.
(I) After reacting an aminocarboxylic acid or an aminocarboxylic acid ester with a polyol to form a polyamine, and (ii) reacting the polyamine with maleic anhydride, a maleimide disclosed in JP-A-11-124403 is disclosed. The present inventors have found that a carboxylic acid polyol ester derivative can be obtained in a high yield without isolating and purifying an intermediate, thereby completing the present invention.

That is, the present invention provides (A) general formula (1)

R ^2- (OH) _m (1) (In the formula, m represents an integer of 1 to 6. 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 polyol represented by a (poly) ether-linked chain or a (poly) urethane-linked chain in which an organic group is linked by at least one bond selected from an ether bond or a urethane bond), and a general formula (2)

H ₂ N—R—COOR ¹ (2) (wherein, R represents a divalent hydrocarbon group; R ¹ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms). The aminocarboxylic acid, aminocarboxylic acid ester or salt thereof is reacted by an esterification reaction or a transesterification reaction to obtain a compound represented by the general formula (3):

(H ₂ N—R—COO) _m R ² (3) (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 aryl. At least one organic group selected from the group consisting of an alkylene group represents a (poly) ether-linked chain or a (poly) urethane-linked chain connected by at least one bond selected from an ether bond or a urethane bond.) A first step of producing a polyamine compound to be

The polyamine compound represented by the general formula (3) obtained in the first step is reacted with maleic anhydride to obtain a compound of the general formula (4)

[0020]

Embedded image (4)

(Wherein, m represents an integer of 1 to 6; R is 2
Represents a monovalent hydrocarbon group. R ² is a group in which 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 at least one bond selected from an ether bond or a urethane bond. Represents a linked (poly) ether or (poly) urethane linkage. )
A method for producing a maleimide derivative comprising a second step of producing a maleimide derivative represented by

(B) R in general formulas (2) and (3)
Is a alkylene chain having 1 to 7 carbon atoms, the method for producing a maleimide derivative according to the above (A),

(C) The method for producing a maleimide derivative according to the above (A) or (B), wherein m in the general formulas (1), (3) and (4) 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.

[0025]

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.

The polyol used in the first step of the production method of the present invention is specifically represented by the general formula (1)

R ^2- (OH) m (1) (wherein m represents an integer of 1 to 6. R ² represents a linear alkylene group, a branched alkylene group, a cycloalkylene group, an aryl group and an arylalkylene. At least one organic group selected from the group consisting of groups represented by a (poly) ether-linked chain or a (poly) urethane-linked chain connected by at least one bond selected from an ether bond or a urethane bond. Compound.

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 copolymers of ethylene oxide and propylene oxide, copolymers of propylene glycol and tetrahydrofuran, copolymers of ethylene glycol and tetrahydrofuran, 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; such as isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate and lysine diisocyanate Diisocyanates having an aliphatic or alicyclic structure; polyisocyanates such as one or more types of burettes of isocyanate compounds or isocyanurates obtained by trimerizing the above diisocyanate compounds. The (poly) urethane (poly) ol of the connecting chain (b) thus obtained is not particularly limited to these.

In the general formula (1), 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.

The aminocarboxylic acid used in the first step of the production method of the present invention is represented by the general formula (2)

H ₂ N—R—COOR ¹ (2) (wherein, R represents a divalent hydrocarbon group, and R ¹ represents a hydrogen atom). In particular,
For example, asparagine, alanine, β-alanine, arginine, isoleucine, glycine, glutamine, tryptophan, threonine, valine, phenylalanine, homophenylalanine, α-methyl-phenylalanine,
Lysine, leucine, cycloleucine, 3-aminopropionic acid, α-aminobutyric acid, 4-aminobutyric acid, aminovaleric acid, 6-aminocaproic acid, 7-aminoheptanoic acid, 2
-Aminocaprylic acid, 3-aminocaprylic acid, 6-aminocaprylic acid, 8-aminocaprylic acid, 2-aminononanoic acid, 4-aminononanoic acid, 9-aminononanoic acid, 2-
Aminocapric acid, 9-aminocapric acid, 10-aminocapric acid, 2-aminoundecanoic acid, 10-aminoundecanoic acid, 11-aminoundecanoic acid, 2-aminolauric acid, 11-aminolauric acid, 12-aminolauric acid Acid, 2-aminotridecanoic acid, 13-aminotridecanoic acid,

2-aminomistinic acid, 14-aminomistinic acid, 2-aminopentadecanoic acid, 15-aminopentadecanoic acid, 2-aminopalmitic acid, 16-aminopalmitic acid, 2-aminoheptadecanoic acid, 17-aminoheptadecanoic acid 2-aminostearic acid, 18-aminostearic acid, 2-aminoeicosanonic acid, 20-aminoeicosanonic acid, aminocyclohexanecarboxylic acid, aminomethylcyclohexanecarboxylic acid, 2-amino-3-propionic acid, 3 -Amino-3-phenylpropionic acid, and the like.

Among them, an aminocarboxylic acid in which R is an alkylene chain having 1 to 7 carbon atoms is preferable because the maleimide derivative produced has good curability.

These aminocarboxylic acids may be in the form of a salt such as hydrochloride, sulfate, paratoluenesulfonate or the like, or may be derivatized to the salt form before the reaction in this step.

Further, the aminocarboxylic acid ester used in the first step of the present invention comprises the aminocarboxylic acid and an alkyl group having 1 to 10 carbon atoms or 3 to 10 carbon atoms.
With an alcohol having a cycloalkyl group of the general formula (2)

H ₂ N—R—COOR ¹ (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. is there.

Specifically, the above aminocarboxylic acid and, for example, alcohols such as methanol, ethanol, n
-Propanol, n-butanol, isobutanol, n
-Pentanol, 2-methyl-1-butanol, isoamyl alcohol, neopentyl alcohol, 2-ethyl-1-butanol, n-hexanol, n-heptanol, n-nonanol, n-octanol, 2-ethyl-
Primary alcohols such as 1-hexanol and benzyl alcohol, secondary alcohols such as isopropanol, sec-butanol, cyclopentanol and cyclohexanol;
Esters with tertiary alcohols such as tert-butanol, unsaturated alcohols such as allyl alcohol, and the like.

Among them, aminocarboxylic acid esters in which R is an alkylene chain having 1 to 7 carbon atoms are preferred because the produced maleimide derivative has good curability.

These aminocarboxylic acid esters are generally available in the form of salts such as hydrochloride, sulfate, paratoluenesulfonate, and the like. It is also possible to generate in-system by an esterification reaction. Further, in the case of esterification of a secondary or tertiary alcohol, which is difficult to produce under general esterification reaction conditions, it can be produced by an addition reaction of a carboxylic acid to a corresponding olefin. Aminocarboxylic acid esters, particularly esters of tertiary alcohols, produced by such a reaction can be obtained in a form in which the amino group is free since aminolysis hardly occurs.

Regarding the first step of the present invention, the reaction of a polyol with an aminocarboxylic acid or an aminocarboxylic acid ester or a salt thereof, various methods are possible depending on the combination thereof.

In the reaction between a polyol and an aminocarboxylic acid or an aminocarboxylic acid salt, when a free aminocarboxylic acid is used, the aminocarboxylic acid salt is used after the aminocarboxylic acid is previously derivatized in the system. In that case, the general esterification conditions, ie,
Dehydration esterification in the presence of an acid can produce the desired polyamine salt.

The derivatization of an aminocarboxylic acid into a salt can be carried out by directly introducing hydrogen chloride gas or using hydrogen chloride generated by a chemical reaction in a reaction system. Further, hydrochloric acid which is easy to handle can be used.
However, when hydrochloric acid is used, it is desirable to remove a large amount of water present in the system before the reaction with the polyol. The reaction with the polyol is also a dehydration reaction, and dehydration at the same time appears to be more efficient in operation, but some polyols cause undesirable changes such as decomposition and polymerization due to prolonged heating under acidic conditions etc. Lots of things, so
It is industrially advantageous to shorten the heating time in the presence of the polyol as much as possible.

For the dehydration in the dehydration esterification reaction between the polyol and the aminocarboxylate, various known methods such as heating or a method using an appropriate dehydrating agent or a permselective membrane can be used. In the case of dehydration by heating, an azeotropic agent such as toluene may be used for the purpose of increasing efficiency. There is no problem in using an appropriate solvent that does not hinder the reaction.

The aminocarboxylate used in this reaction is
It is preferable to use 0.5 to 1.5 equivalents to the hydroxyl group amount of the polyol. It is more preferably 0.8 to 1.2 equivalents.

When the aminocarboxylic acid salt is used in an amount of more than 1.5 equivalents to the polyol, the reaction can proceed completely, but the remaining aminocarboxylic acid causes a side reaction such as an addition reaction after the next step. Nor is it economically advantageous. Conversely, if the amount of the amino carboxylate is less than 0.5 equivalent, the remaining hydroxyl group reacts with maleic anhydride in the next step or causes an addition reaction to the double bond of maleimide to increase the molecular weight. On the other hand, when the concentration of the polymerizable functional group in the final product is lowered, the curing properties are deteriorated, which is not preferable.

The acid used as a catalyst in this reaction may be an inorganic acid or an organic acid. For example, hydrochloric acid, sulfuric acid,
Inorganic acids such as orthophosphoric acid, pyrophosphoric acid, phosphorous acid and nitric acid; organic sulfonic acids such as methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid and naphthalenesulfonic acid; organic phosphonic acids such as methylphosphonic acid and benzenephosphonic acid Halogenocarboxylic acids such as trichloroacetic acid, trifluoroacetic acid, and chloropropionic acid; It is necessary to select an appropriate acid according to the dehydration esterification reaction conditions.

The reaction temperature of this reaction varies greatly depending on the type of aminocarboxylate, the type and combination of polyols, and the dehydration technique, but is approximately 2 to room temperature.
A range of 00 ° C is desirable. If the reaction temperature exceeds 200 ° C., the polyol or aminocarboxylate may be decomposed or cause a side reaction depending on the reaction time.

In the reaction of the polyol with the aminocarboxylic acid ester salt or free aminocarboxylic acid ester in the first step of the present invention, the salt or the free polyamine compound of interest is subjected to a transesterification reaction in the presence of a suitable catalyst. A polyamine can be obtained.

Examples of the catalyst used in this reaction include various catalysts generally used in a transesterification reaction. Among them, an acidic transesterification catalyst and a heavy metal transesterification catalyst are preferable.

For example, when a salt of an aminocarboxylic acid ester is combined with an alkaline catalyst such as a metal alkoxide, the addition of the metal alkoxide converts the aminocarboxylic acid ester into a free amine. Must use the above amount,
In this case, it is not preferable because aminolysis of the ester occurs depending on the form of the alcohol residue of the aminocarboxylic acid ester. Conversely, when an aminocarboxylic acid ester having a stable free form, such as a tertiary butyl ester, is used, an alkaline catalyst such as a metal alkoxide can be used.

Examples of the acidic transesterification catalyst used in this reaction include inorganic acids such as sulfuric acid and phosphoric acid; and organic sulfonic acids such as methanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid.

The heavy metal transesterification catalyst used in this reaction includes, for example, titanium tetrabutoxide, titanium tetraisopropoxide, titanium tetraethoxide, titanium tetraphenoxide, aluminum triisopropoxide, silicon tetraisopropoxide, zirconium tetraoxide. Metal alkoxides such as isopropoxide; metals such as aluminum halide, titanium halide, magnesium halide, manganese halide, tin halide, iron halide, lead halide, zinc halide, zirconium halide, and vanadium halide Halides: oxides of zinc, lead, tin, zirconium, copper, antimony, titanium, magnesium, manganese, cobalt, germanium, and the like.

Among these transesterification catalysts, metal alkoxides such as aluminum, titanium and zirconium and metal alkoxides such as dimethyltin (II) oxide, dibutyltin (II) oxide, dihexyltin (II) oxide and dioctyltin (II) oxide Dialkyltin (II) oxide is preferred because of its high transesterification reaction rate. Among them, dialkyltin (II) such as dimethyltin (II) oxide, dibutyltin (II) oxide, dihexyltin (II) oxide and dioctyltin (II) oxide are preferred. Tin (II) oxide is particularly preferred in view of the high transesterification rate with a small amount of catalyst used, the cost reduction, and the low coloration of products, as compared with metal alkoxides such as aluminum, titanium and zirconium. .

In the case of an acidic transesterification catalyst, the amount of the catalyst used is based on the aminocarboxylic acid ester or a salt thereof.
The range of 0.1-50 mol% is preferable, and 1-20 mol%
Is particularly preferred. Also, aluminum, titanium,
The amount of the metal alkoxide transesterification catalyst such as zirconium to be used is preferably in the range of 1 to 15 mol%, particularly preferably 3 to 10 mol%, based on the aminocarboxylic acid ester or a salt thereof. Dialkyl tin oxide (I) such as dimethyl tin oxide (II), dibutyl tin oxide (II), dihexyl tin oxide (II), dioctyl tin oxide (II)
I) The amount of transesterification catalyst used is
The range is preferably from 0.01 to 10 mol%, particularly preferably from 0.1 to 5 mol%.

If the amount of the catalyst is too small, the reaction does not proceed practically. If the amount is too large, the reaction rate does not change, which is economically disadvantageous. Further, in the case of a metal alkoxide such as aluminum, titanium and zirconium, if the amount of the catalyst used is too large, the product may be undesirably colored.

In this reaction, since it is reacted with maleic anhydride in the next step, it is necessary to keep the alcohol liberated in the transesterification as little as possible in the system. Therefore, it is preferable to carry out the reaction under a normal pressure or reduced pressure in a temperature range of room temperature to 150 ° C. while removing generated alcohol. When the alcohol produced by the transesterification reaction is a high boiling component, a reaction solvent that azeotropes with the produced alcohol may be added, and the alcohol may be removed by azeotropy with the reaction solvent. 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 addition, a reaction solvent is not particularly required,
If necessary, a solvent inert to the reaction such as hexane, cyclohexane, benzene, toluene, xylene, ethylbenzene, cumene, diisopropyl ether, dibutyl ether, tetrahydrofuran or dioxane may be used.

In the second step of the present invention, the polyamine compound or its salt obtained in the first step is reacted with maleic anhydride by a known method to form a polyamic acid.
Further, the desired maleimide derivative is obtained by a ring closure reaction.

The polyamic acid is produced by the following method. When a salt of a polyamine compound is used, the reaction is performed while adding an appropriate base to release an amino group. However, when the system becomes basic, the carboxyl group of the polyamic acid becomes undesirable due to the high molecular weight caused by side reactions such as addition to the double bond of the maleic acid residue.
The amount of the base to be added for this purpose depends on the type of the acid forming the salt of the polyamine compound and the type of the base to be added, but is the minimum amount necessary to release the amino group of the polyamine compound. Desirably. Various bases can be used as long as they can release the amino group of the polyamine compound, such as organic bases and inorganic bases.

The amount of maleic anhydride used in the second step of the present invention can be used in an arbitrary equivalent to the amino group of the polyamine, but is preferably 5 equivalent or less. If the amount is more than 5 equivalents, there is no improvement in the reaction time, and conversely, there are many economic disadvantages such as an increase in the load of the wastewater in the washing step.

In this reaction, various known catalysts may be used as long as the reaction is not hindered, and an appropriate solvent may be used.

In the ring closing reaction of the polyamic acid in the second step of the present invention, a method of dehydrating and ring closing in the presence of a suitable catalyst,
Various known methods can be used, such as a method of forming an ester by reaction with an alcohol and de-alcoholization-ring closure.

As a method of dehydrating and cyclizing in the presence of a suitable catalyst, a method of performing thermal dehydration using a protonic acid or a Lewis acid as a catalyst (JP-A-53-9320), an acid anhydride and other dehydrating agents A method of performing dehydration by using (Japanese Patent Laid-Open No. 58-96066) is mentioned as an example.

Further, a method of forming an ester by reacting with an alcohol and subjecting it to dealcoholization and ring closure is described in JP-A-3-173866 and JP-A-53-84964.
For example, the method described in Japanese Patent Application Laid-Open No. H10-26095 is cited.

In the ring closure reaction of the second step 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, and 2,4-dimethyl-6.
Phenolic compounds such as tert-butylphenol, catechol and tert-butylcatechol; amines such as phenothiazine, p-phenylenediamine and diphenylamine;

Copper complexes such as copper dimethyldithiocarbamate, copper diethyldithiocarbamate, copper dibutyldithiocarbamate, and the like can be mentioned. 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.

[0072]

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 Capacity 1 equipped with stirrer, thermometer, dropping funnel and cooling pipe
Polyethylene glycol 200 (manufactured by Kanto Chemical Co., number average molecular weight 200) 400 in a 000 ml four-necked flask
g and dibutyltin dilaurate (100 mg), 222 g of isophorone diisocyanate (manufactured by Kanto Chemical Co., Ltd.) was added dropwise over 40 minutes while heating to keep the liquid temperature at 70 ° C. After the completion of the dropwise addition, the reaction was further continued at 70 ° C. for 5 hours. After cooling the reaction mixture, disappearance of absorption of free isocyanate was confirmed by an infrared absorption spectrum (IR spectrum), and 620 g of polyether urethanediol having a number average molecular weight of 622 was obtained.

<Example 1> Capacity 3 equipped with a stirrer, thermometer, dropping funnel, Dean-Stark fractionator and cooling pipe
A liter separable four-necked flask was charged with 230 g of β-alanine hydrochloride, 400 g of toluene, 571 g of the polyether urethane diol having a number average molecular weight of 622 synthesized in Synthesis Example 1, and 5 g of p-toluenesulfonic acid monohydrate, and the pressure was reduced. Under reflux, the mixture was dehydrated and esterified by heating under reflux.
When the amount of water generated by the reaction and separated from the system reached 34 g, the reaction was terminated and cooled. 97 g of sodium carbonate and 182 g of maleic anhydride were added to the reaction mixture, and the mixture was heated to 80 ° C. Gas chromatography confirmed that the amount of maleic anhydride remaining in the reaction system was 2 g or less, and the reaction was completed.

0.8 g of hydroquinone was added to the reaction mixture.
And 5 g of p-toluenesulfonic acid monohydrate were further added as a catalyst, and the mixture was heated under reflux. The reaction was completed when the amount of water generated by the reaction and separated from the system reached 32 g. 200 g of toluene was added to this reaction solution, and the mixture was washed twice with 200 ml of a saturated aqueous solution of sodium hydrogencarbonate and twice with 200 ml of saturated saline, and then the organic layer was concentrated to give a yield of 95% based on polyetherurethanediol. Thus, maleimide propionic acid polyether urethane diol ester was obtained.

Example 2 The procedure of Example 1 was repeated, except that 282 g of valine hydrochloride was used instead of 230 g of β-alanine hydrochloride. As a result, a maleimide isovaleric acid polyether urethane diol ester was obtained at a yield of 90%.

<Example 3> The procedure of Example 1 was repeated, except that 308 g of 6-aminocaproic acid hydrochloride was used instead of 230 g of β-alanine hydrochloride. As a result, a maleimide caproic acid polyether urethane diol ester was obtained at a yield of 90%.

<Example 4> In Example 1, 205 g of glycine hydrochloride was used instead of 230 g of β-alanine hydrochloride.
Was carried out in accordance with Example 1 except that was used. As a result, maleimide acetic acid polyether urethane diol ester was obtained at a yield of 95%.

<Example 5> Capacity 3 equipped with a stirrer, thermometer, dropping funnel, Dean-Stark fractionator and cooling pipe
A liter separable four-necked flask was charged with 163 g of β-alanine and 180 g of 37% hydrochloric acid, and stirred at room temperature for 1 hour. 400 g of toluene was added thereto, and under reduced pressure,
Heat to dehydrate. After cooling to room temperature, 571 g of polyether urethane diol having a number average molecular weight of 622 synthesized in Synthesis Example 1 and 5 g of p-toluenesulfonic acid monohydrate
And heated under reflux under reduced pressure for dehydration-esterification. When the amount of water generated by the reaction and separated from the system reached 34 g, the reaction was terminated and cooled. 97 g of sodium carbonate and 182 g of maleic anhydride were added to the reaction mixture.
And heated to 80 ° C. Gas chromatography confirmed that the amount of maleic anhydride remaining in the reaction system was 2 g or less, and the reaction was completed.

0.8 g of hydroquinone was added to the reaction mixture.
And 5 g of p-toluenesulfonic acid monohydrate were further added as a catalyst, and the mixture was heated under reflux. The reaction was completed when the amount of water generated by the reaction and separated from the system reached 32 g. 200 g of toluene was added to the reaction solution, and the mixture was washed twice with 200 ml of a saturated sodium hydrogen carbonate aqueous solution and twice with 200 ml of a saturated saline solution. Then, the organic layer was concentrated, and the yield based on polyetherurethanediol was 92%. Thus, maleimide propionic acid polyether urethane diol ester was obtained.

<Example 6> Capacity 3 equipped with a stirrer, thermometer, dropping funnel, Dean-Stark fractionator and cooling pipe
In a liter separable four-necked flask, 230 g of glycine methyl ester hydrochloride, polytetramethylene glycol having a number average molecular weight of 650 (“Terat manufactured by DuPont”)
650 g) and 6 g of dibutyltin (II) oxide were heated and subjected to transesterification by heating under reduced pressure. When the amount of methanol generated by the reaction and separated from the system reached 60 g, the reaction was terminated and cooled. 300 g of toluene, 151 g of sodium acetate and 182 g of maleic anhydride were added to the reaction mixture,
Heated at 0 ° C. After confirming that the amount of maleic anhydride remaining in the reaction system was 2 g or less by gas chromatography, the reaction system was heated under reduced pressure to remove acetic acid generated in the system together with toluene.

To this reaction mixture, 300 g of butanol, 0.8 g of hydroquinone and 19 g of 97% sulfuric acid were added, and the mixture was refluxed and heated under reduced pressure to perform dehydration esterification. When the amount of water generated by the reaction and separated from the system reached 32 g, the fractionator was replaced with a distillator, butanol was distilled off, and the temperature was further raised to effect ring closure imidization at 90 ° C. 600 g of toluene was added to the reaction solution, and the mixture was washed twice with 200 ml of a saturated aqueous solution of sodium hydrogencarbonate.
After washing twice with 1, the organic layer was concentrated to obtain maleimide acetic acid polytetramethylene glycol ester in a yield of 95% based on polytetramethylene glycol.

<Example 7> The procedure of Example 5 was repeated, except that 6.0 g of dioctyl tin (II) oxide was used instead of 6.0 g of dibutyl tin (II) oxide. As a result, maleimide acetic acid polytetramethylene glycol ester was obtained at a yield of 95%.

<Embodiment 8> In the fifth embodiment, "Term"
The procedure was performed in the same manner as in Example 1 except for using 918 g of polytetramethylene glycol having a number average molecular weight of 1000 (“Terathane 1000” manufactured by DuPont) instead of 597 g of “athane650”. As a result, the yield is 88.
% Of maleimide acetic acid polytetramethylene glycol ester was obtained.

Example 9 Capacity 3 equipped with a stirrer, thermometer, dropping funnel, Dean-Stark fractionator and cooling pipe
A liter separable four-necked flask was charged with 482 g of glycine tert-butyl ester and a number average molecular weight of 250.
Polytetramethylene Glycol (“Te” manufactured by DuPont
Ratane 250 ") and 460 g of dibutyltin (II) oxide were charged and subjected to transesterification by heating under reduced pressure. When the amount of tertiary butyl alcohol generated by the reaction and separated from the system reached 265 g, the reaction was terminated and cooled. 400 g of toluene and 362 g of maleic anhydride were added to the reaction mixture,
Heated. The reaction was terminated after confirming that the amount of maleic anhydride remaining in the reaction system was 2 g or less by gas chromatography.

To this reaction mixture were added 600 g of butanol, 0.8 g of hydroquinone and 38 g of 97% sulfuric acid, and the mixture was heated to 60 ° C. under reduced pressure to perform dehydration esterification. When the amount of water generated by the reaction and separated from the system reached 32 g, the fractionator was replaced with a distillator, butanol was distilled off, and the temperature was further raised to effect ring closure imidization at 90 ° C. 600 g of toluene was added to the reaction solution, and the mixture was washed twice with 200 ml of a saturated aqueous solution of sodium hydrogencarbonate.
After washing twice with 0 ml, the organic layer was concentrated to obtain maleimide acetic acid polytetramethylene glycol ester in a yield of 92% based on polytetramethylene glycol.

<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.

[0089]

According to the production method of the present invention, a maleimide carboxylic acid polyol ester derivative can be produced in high yield from a polyol, maleic anhydride and aminocarboxylic acid as starting materials without isolation and purification of intermediates. can do.

Continued on the front page F term (reference) 4C069 AD08 BB02 BB49 CC02 4J100 AM47P AM54P BA07P BA08P BA39P BC01P BC41P JA01 JA03 JA05

Claims (4)

[Claims] 1. Formula (1): R ² — (OH) _m (1) (In the formula, m represents an integer of 1 to 6. 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. An organic group representing a (poly) ether-linked chain or (poly) urethane-linked chain linked by at least one bond selected from an ether bond or a urethane bond); ₂ NR-COOR ¹ (2) (wherein, R represents a divalent hydrocarbon group; R ¹ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms). The aminocarboxylic acid, aminocarboxylic acid ester or a salt thereof is reacted by an esterification reaction or a transesterification reaction to obtain a compound represented by the following general formula (3): (H ₂ N—R—COO) _m R ² (3) (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 aryl. At least one organic group selected from the group consisting of an alkylene group represents a (poly) ether-linked chain or a (poly) urethane-linked chain connected by at least one bond selected from an ether bond or a urethane bond.) A first step of producing the polyamine compound represented by the general formula (4) by reacting the polyamine compound represented by the general formula (3) obtained in the first step with maleic anhydride; (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 aryl group. At least one organic group selected from the group consisting of an alkylene group represents a (poly) ether-linked chain or a (poly) urethane-linked chain connected by at least one bond selected from an ether bond or a urethane bond.) A method for producing a maleimide derivative, comprising: a second step of producing a maleimide derivative to be produced. 2. The method for producing a maleimide derivative according to claim 1, wherein R in the general formulas (2) and (3) is an alkylene chain having 1 to 7 carbon atoms. 3. The method for producing a maleimide derivative according to claim 1, wherein m in the general formulas (1), (3) and (4) is an integer of 2 to 4. 4. A transesterification reaction comprising using a dialkyltin (II) oxide as a catalyst.
4. The method for producing a maleimide derivative according to item 3.