JP5114864B2 - Method for producing polyfunctional maleimide compound - Google Patents

Description

  The present invention relates to a novel polyfunctional maleimide compound, a process for producing the same, and a shape memory resin containing them. Furthermore, this invention relates to the manufacturing method of a polyfunctional maleimide compound.

  Polyfunctional maleimide compounds are useful for a variety of materials. The inventor's patent discloses an example in which a polyfunctional maleimide compound is used as a cross-linking agent for a shape memory resin (Patent Document 1). By using a thermoreversible reaction between a maleimide group and a furan group, and cross-linking the resin with a maleimide group and a furan group, a re-moldable shape memory resin is obtained. A thermoreversible reaction refers to a reaction in which a bond is cleaved at a predetermined temperature and recombined upon cooling. Since this shape memory resin is covalently crosslinked in a practical temperature range, it has an excellent shape recovery force, and during molding and remolding, the bond is cleaved by heating, and is excellent in moldability and recyclability. Further, since the covalent bond cross-linking is again performed at the time of cooling, a shape memory resin equivalent to that before molding is obtained, and the shape recovery rate is not reduced by repeated deformation.

  On the other hand, polyfunctional maleimide compounds include, for example, coating agents, lining agents, surface treatment agents, molding materials, paints, printing inks, adhesives, adhesives, sealants, binders, laminated materials for electronic products, electrical insulating materials, It is known that it can be used for conductive pastes, medicines, agricultural chemicals, and the like.

  Generally, a polyfunctional maleimide compound is obtained by maleimidizing a polyfunctional amine compound, or a method of synthesizing a maleimide compound having a carboxyl group as a precursor and subjecting the compound having a hydroxyl group to a dehydration condensation reaction is disclosed ( Patent Document 2). However, a polyfunctional maleimide compound synthesized from a biodegradable polyester resin and maleimide carboxylic acid is not known.

  In recent years, biodegradable resins have attracted attention because of increasing interest in environmental problems. However, since biodegradable resins do not have properties that are superior to petroleum-derived resins in addition to environmental compatibility, it is important to increase the added value by introducing highly functional functional groups into biodegradable resins. is there.

  Maleimide carboxylic acid can be produced by various known methods. After maleamide carboxylic acid is obtained by reacting aminocarboxylic acid and maleic anhydride, maleimide carboxylic acid can be synthesized by dehydration reaction. For example, according to the method described in Non-Patent Document 1, maleimide carboxylic acid can be synthesized by heating maleamide carboxylic acid with sodium acetate in acetic anhydride. However, this reaction is not efficient because of low yield and complicated purification.

In another example, a method is known in which an acid catalyst is added to a maleamide compound and an inert organic solvent that is hardly soluble in water, such as benzene, toluene, xylene, and the like, and a dehydration cyclization reaction is performed (for example, non-patent literature). 2). However, detailed reaction conditions for the synthesis method of maleimide carboxylic acid have not been studied.
WO2005 / 056642 Patent No. 3599160 Macromolecules vol. 23, 2636 (1990) Journal of Medicinal Chemistry, Vol. 18, no. 10, 1004 (1975)

  The present invention provides a novel polyfunctional maleimide compound, a production method thereof, and a shape memory resin containing them. Furthermore, this invention provides the manufacturing method of maleimide carboxylic acid which is a precursor for polyfunctional maleimide compound manufacture.

  In order to achieve the above object, in the present invention, first, efficient reaction conditions for maleimide carboxylic acid were found. Next, it was shown that maleimide groups can be introduced into the biodegradable polyester resin in a short time and in a high yield by converting maleimide carboxylic acid into an acid chloride and then reacting with the biodegradable polyester resin at room temperature. Finally, it was clarified that a crosslinked product containing a polyfunctional maleimide compound having a maleimide group introduced into a biodegradable polyester resin has both excellent shape memory and remoldability.

That is, the present invention
The present invention relates to a polyfunctional maleimide compound represented by the following general formula (1).

（式中、Ｘは炭素数１〜２０の直鎖又は分岐のアルキレン基を示し、Ｙは生分解性ポリエステル樹脂残基を示す。ｎは２以上の整数を示す。）

(In the formula, X represents a linear or branched alkylene group having 1 to 20 carbon atoms, Y represents a biodegradable polyester resin residue, and n represents an integer of 2 or more.)

  The present invention also relates to a biodegradable shape memory resin containing the polyfunctional maleimide compound.

  Furthermore, this invention relates to the manufacturing method of the said polyfunctional maleimide compound, The biodegradable polyester resin represented by following formula (3) after converting maleimide carboxylic acid represented by following General formula (2) into an acid chloride. And transesterification.

（式中、Ｘは炭素数１〜２０の直鎖又は分岐のアルキレン基を示し、Ｙは生分解性ポリエステル樹脂残基を示す。ｍは２以上の整数を示す。）

(In the formula, X represents a linear or branched alkylene group having 1 to 20 carbon atoms, Y represents a biodegradable polyester resin residue, and m represents an integer of 2 or more.)

  In particular, in the present invention, the maleimide carboxylic acid represented by the following formula (4) obtained by reacting the maleimide carboxylic acid represented by the above general formula (2) with maleic anhydride and aminocarboxylic acid is inactivated. It has the process obtained by carrying out dehydration ring closure reaction at 110 degreeC or more and 145 degrees C or less using a catalyst in the mixed solvent of an organic solvent and an aprotic polar solvent.

（式中、Ｘは式（２）中のＸと同義である。）

(In the formula, X has the same meaning as X in formula (2).)

  The method for producing a polyfunctional maleimide compound of the present invention is effective in the synthesis of various polyfunctional maleimide compounds because a large number of maleimide groups can be introduced by a reaction at room temperature in a short time. Since maleimide acid chloride is highly reactive, it is an effective method especially for polyester resins having a high molecular weight and a small amount of hydroxyl groups. By introducing a high-functional functional group, the added value of the biodegradable resin can be increased. Moreover, the obtained polyfunctional maleimide compound can be used as a precursor of a re-moldable shape memory resin.

  Next, embodiments of the present invention will be described in detail.

  The polyfunctional maleimide compound represented by the general formula (1) of the present invention reacts with the biodegradable polyester resin represented by the formula (3) after converting the maleimide carboxylic acid of the general formula (2) to an acid chloride. Can be obtained.

  Maleimide carboxylic acid (2) is obtained by a dehydration ring-closing reaction of maleamide carboxylic acid represented by the above formula (4). Maleamide carboxylic acid (4) can be easily synthesized by stirring aminocarboxylic acid and maleic anhydride in a solution at room temperature.

  Examples of the aminocarboxylic acid include 2-aminopropionic acid (alanine), 3-aminopropionic acid (β-alanine), 2-methyl-3-methylvaleric acid (isoleucine), aminoacetic acid (glycine), 2-amino -3-methylbutyric acid (valine), 2-amino-4-methylvaleric acid (leucine), α-aminobutyric acid, γ-aminobutyric acid, aminovaleric acid, 6-aminohexanoic acid (ε-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 Amino lauric acid, 11-amino lauric acid, 12-amino lauric acid, 2-amino tridecanoic acid, 13-amino tridecanoic acid, 2-amino myristic acid, 14-amino myristic acid, 2-amino pentadecanoic acid, 15-amino pentadecane Acid, 2-amino palmitic acid, 16-amino palmitic acid, 2-aminoheptadecanoic acid, 17-aminoheptadecanoic acid, 2-aminostearic acid, 18-aminostearic acid, 2-aminoeicosanoic acid, 20- Examples thereof include aminoeicosanonic acid and 2-amino-3-propionic acid, but are not limited thereto, and any primary aminocarboxylic acid can be used. In addition, lactams such as pyrrolidone, δ-valerolactam, and ε-caprolactam can be used, and ring reaction is caused by reaction with maleic anhydride to produce maleamide carboxylic acid represented by the formula (4). In the present invention, these lactams are also included in the category of aminocarboxylic acids. These aminocarboxylic acids may be used alone or in combination of two or more.

  The maleamide carboxylic acid dehydration cyclization reaction is preferably carried out in an inert organic solvent that is hardly soluble in water such as benzene, toluene, xylene, etc. with the addition of a catalyst. The amount of the inert organic solvent used is 1 to 100 times (weight ratio), preferably 4 to 50 times the amount of maleamide carboxylic acid. If the amount is less than 1 time, the dehydration efficiency is lowered, and if it is 100 times or more, the amount is excessive, which is not efficient. Further, since maleimide carboxylic acid is hardly soluble in the above-mentioned solvent, it is preferable to use an aprotic polar solvent such as dimethylamide, dimethyl sulfoxide, dimethylacetamide, dioxane or the like together. The aprotic polar solvent is used in an amount of 0.001 to 10 times, preferably 0.01 to 2 times the amount of maleamide carboxylic acid. If the amount is 0.001 or less, maleimide carboxylic acid is not dissolved, and the reaction efficiency is lowered. When the amount is 10 times or more, the water produced by the dehydration reaction is dissolved in the aprotic polar solvent, so that the dehydration efficiency is lowered.

  In the present invention, it is important to strictly control the temperature of the dehydration ring closure reaction of maleamide carboxylic acid. A solvent is used alone or in combination so that the reaction temperature is 110 ° C. or higher and 145 ° C. or lower, preferably 115 ° C. or higher and 135 ° C. or lower. If it is less than 110 degreeC, the efficiency of a dehydration reaction will fall. At temperatures exceeding 145 ° C., the polymerization of maleimide groups proceeds and the yield decreases.

  As the catalyst, sulfuric acid, phosphoric acid, phosphoric anhydride, p-toluenesulfonic acid and the like are used, and the amount used is 1 wt% to 200 wt%, preferably 10 wt% to 100 wt% of maleamide carboxylic acid.

  The reaction of the hydroxyl group in the biodegradable polyester resin represented by the formula (3) with maleimide carboxylic acid is carried out by converting the carboxyl group of maleimide into an acid chloride using thionyl chloride or oxalyl chloride, and then at room temperature. It can be easily esterified by adding to the above. Conditions for converting maleimide carboxylic acid to acid chloride with thionyl chloride or the like are known (see Non-Patent Document 1). Carboxylic acid and hydroxyl group can be esterified using carbodiimides, but are not efficient because by-products are formed.

  The polyester resin used in the present invention is a biodegradable polyester resin. For example, polylactic acid (polylactic acid obtained by polymerizing L-lactic acid or D-lactic acid, or a mixture thereof, polylactic acid in which the monomer unit is composed solely of L-lactic acid, and polylactic acid composed of only D-lactic acid) Mixture), polyhydroxyalkanoate, polyhydroxybutyrate, polyethylene succinate, polyethylene succinate adipate, polyethylene succinate carbonate, polyethylene succinate terephthalate, polyethylene adipate terephthalate, polyethylene succinate adipate terephthalate, polybutylene succinate, poly Butylene succinate adipate, polybutylene succinate carbonate, polybutylene succinate terephthalate, polybutylene adipate terephthalate, polybutylene Adipate terephthalate, polytetramethylene adipate terephthalate, polycaprolactone polybutylene succinate, polycaprolactone, polyglycolic acid and the like.

  For polyester resins synthesized using dicarboxylic acid and diol as raw materials, by increasing the diol / dicarboxylic acid molar ratio of the raw material used to more than 1, it is possible to make all end groups of the molecular chain hydroxyl groups. is there. In addition, a resin composed of a hydroxycarboxylic acid such as polylactic acid can have a terminal hydroxyl group by a transesterification reaction. That is, the polyester resin having a terminal hydroxyl group can be obtained by transesterifying the polyester resin with a compound having two or more hydroxyl groups.

  Examples of the compound having a hydroxyl group include dihydric alcohols such as ethylene glycol, propylene glycol, dipropylene glycol, 1,3- and 1,4-butanediol, and 1,6-hexanediol, glycerin, and trimethylolpropane. , Trihydric alcohols such as trimethylolethane and hexanetriol, tetrahydric alcohols such as pentaerythritol, methylglycoside and diglycerin, polyglycerins such as triglycerin and tetraglycerin, polypentaerythritol such as dipentaerythritol and tripentaerythritol, And cycloalkane polyols such as tetrakis (hydroxymethyl) cyclohexanol. Sugar alcohols such as adonitol, arabitol, xylitol, sorbitol, mannitol, iditol, tallitol, maltitol, dulcitol, and sugars such as glucose, mannose glucose, mannose, fructose, sorbose, sucrose, lactose, raffinose, and cellulose can also be used. The use of a compound having three or more hydroxyl groups is particularly desirable because a crosslinking point having a three-dimensional crosslinked structure can be formed. For example, by transesterifying the ester bond of polylactic acid with D-sorbitol, a polyester resin having a total of six hydroxyl groups at the end of the molecular chain can be obtained.

  Incidentally, a resin having a carboxylic acid at a terminal part or a compound having an unreacted hydroxyl group can be easily purified and removed.

  The polyfunctional maleimide compound as described above can be used as a precursor of a remoldable shape memory resin. In addition, coating agents, lining agents, surface treatment agents, molding materials, paints, printing inks, adhesives, adhesives, sealants, binders, laminated materials for electronic products, electrical insulating materials, conductive pastes, pharmaceuticals, agricultural chemicals, etc. It is also possible to use it.

  Hereinafter, a method of using the polyfunctional maleimide compound of the present invention as a precursor of a remoldable shape memory resin will be described.

  Shape memory property obtained by cross-linking by thermoreversible reaction with a compound in which two or more conjugated dienes are introduced as functional groups using Diels-Alder [4 + 2] cyclization reaction using the polyfunctional maleimide compound of the present invention as a dienophile Obtain a resin. Examples of the conjugated diene include a furan ring, a thiophene ring, a pyrrole ring, a cyclopentadiene ring, 1,3-butadiene, a thiophene-1-oxide ring, a thiophene-1,1-dioxide ring, and a cyclopenta-2,4-dienone. Ring, 2H pyran ring, cyclohexa-1,3-diene ring, 2H pyran 1-oxide ring, 1,2-dihydropyridine ring, 2H thiopyran-1,1-dioxide ring, cyclohexa-2,4-dienone ring, pyran A 2-one ring and a substituted product thereof are used as a functional group. In particular, a three-dimensionally crosslinked molded product can be obtained by crosslinking a compound having three or more of these functional groups with the polyfunctional maleimide compound of the present invention. For example, the following thermoreversible crosslinking is formed with a compound into which a furan ring is introduced.

  The dissociation temperature (Td) of the above-mentioned furanyl-maleimide bond is about 150 ° C., and is sufficiently high, for example, with respect to the glass transition temperature (Tg = about 60 ° C.) of the polylactic acid resin. For this reason, as described in the above-mentioned Patent Document 1, what is molded into a desired first shape (original shape) at a temperature equal to or higher than Td can be transformed into another second shape at a temperature equal to or higher than Tg and lower than Td. The second shape can be fixed by cooling to less than Tg. Furthermore, it becomes shape memory resin which is excellent in the resilience to the 1st shape provided by heating this 2nd shape thing again at the temperature below Tg or more and Td. In addition, it can be reshaped at temperatures above Td.

  The present invention will be described in more detail with reference to the following examples, but these examples do not limit the present invention. Unless otherwise specified, commercially available high-purity products were used as reagents. The number average molecular weight was measured by gel permeation chromatogram method and converted using standard polystyrene. The maleimide modification rate indicates the number of moles of maleimide groups per mole of resin.

1. Method for producing maleimide carboxylic acid [Example 1]
Maleamide propionic acid [R1] (yield 96%) was obtained by stirring 25.0 g of β-alanine, 28.9 g of maleic anhydride, and 100 mL of THF at room temperature under nitrogen for 24 hours and then filtering the solid. Next, 22.1 g of [R1], 6.11 g of orthophosphoric acid, 0.0937 g of BHT (dibutylhydroxytoluene), 100 mL of xylene, 300 mL of toluene, and 20 mL of dioxane were weighed into a three-necked flask and refluxed for 3 hours. The reaction temperature was 116 ° C. After cooling to room temperature, the solution was filtered and the solvent was distilled off under reduced pressure and dissolved in chloroform. This solution was filtered, the solvent was distilled off under reduced pressure, and then recrystallized with diethyl ether to obtain maleimide carboxylic acid [R2] (yield 42%).

[Comparative Example 1]
[R1] Synthesized by the method of Example 1 using 22.1 g, 6.11 g of orthophosphoric acid, 0.0937 g of BHT, 350 mL of xylene, and 70 mL of dioxane. The reaction temperature was 149 ° C. The yield of [R2] was 29%.

[Comparative Example 2]
[R1] Synthesized by the method of Example 1 using 22.1 g, orthophosphoric acid 6.11 g, BHT 0.0937 g, toluene 350 mL, and dioxane 70 mL. The reaction temperature was 105 ° C. The yield of [R2] was 8.2%.

  The production method of [R2] is shown in Example 1, Comparative Example 1 and Comparative Example 2. The yields of Comparative Examples 1 and 2 are lower than those of Example 1. In Example 1, the reaction rate could be increased by controlling the reaction temperature with a mixed solvent of toluene and xylene. On the other hand, in Comparative Example 1, since the reaction temperature was high and the polymerization of the maleimide group proceeded, in Comparative Example 2, the reaction temperature was low and the dehydration reaction efficiency was lowered, so the yield was lowered.

2. Synthesis of polyfunctional maleimide compound [Example 2]
2000 g of commercially available polylactic acid (“Teramac” (trade name), manufactured by Unitika) and 69.5 g of sorbitol were melt-mixed at 230 ° C. for 10 hours to conduct a transesterification reaction. This was dissolved in 2 L of chloroform, poured into excess methanol, and reprecipitated to obtain terminal hydroxypolylactic acid [R3].

  [R2] 62.5 g was dissolved in chloroform 900 mL and cooled to 0 ° C., and then 122 g of oxalyl dichloride was added dropwise. After stirring at room temperature for 5 hours under nitrogen, maleimide carboxylic acid chloride [R4] was synthesized by distilling off the solvent and excess oxalyl dichloride under reduced pressure. [R4] was diluted in a small amount of chloroform, and then added dropwise to a solution of [R3] 91.4 g, pyridine 65.9 mL, and chloroform 300 mL. After stirring at room temperature for 30 minutes under nitrogen, the reaction solution was poured into a mixed solvent of methanol and water (methanol 3.5 L, water 500 mL), and the precipitated solid was filtered to obtain maleimide-modified polylactic acid [R5] (yield 92 %). (Molecular weight 7550, maleimide modification rate f = 6).

[Example 3]
1000 g of commercially available polylactic acid (“Teramac” (trade name), manufactured by Unitika) and 75.6 g of pentaerythritol were transesterified by melt mixing at 200 ° C. for 3 hours. This was dissolved in 1 L of chloroform, poured into excess methanol, and reprecipitated to obtain terminal hydroxypolylactic acid [R6].

  [R2] 84.6 g was dissolved in 1 L of chloroform and cooled to 0 ° C., and 165 g of oxalyl dichloride was added dropwise. After stirring at room temperature for 5 hours under nitrogen, maleimide carboxylic acid chloride [R4] was synthesized by distilling off the solvent and excess oxalyl dichloride under reduced pressure. [R4] was diluted in a small amount of chloroform, and then added dropwise to a solution of 100 g of [R6], 72.1 mL of pyridine, and 400 mL of chloroform. After stirring at room temperature for 30 minutes under nitrogen, the reaction solution was poured into a mixed solvent of methanol and water (methanol 1750 mL, water 250 mL), and the precipitated solid was filtered to obtain maleimide-modified polylactic acid [R7] (yield 90%) Got. (Molecular weight 3810, maleimide modification rate f = 4).

[Example 4]
A polybutylene succinate [R8] having hydroxyl groups at both ends was obtained by performing polycondensation under reduced pressure at 220 ° C. for 7 hours using 310 g of 1,4-butanediol and 338 g of succinic acid.

  [R2] 13.7 g was dissolved in 200 mL of chloroform and cooled to 0 ° C., and then 26.7 g of oxalyl dichloride was added dropwise. After stirring at room temperature for 5 hours under nitrogen, maleimide carboxylic acid chloride [R4] was synthesized by distilling off the solvent and excess oxalyl dichloride under reduced pressure. [R4] was diluted in a small amount of chloroform, and then added dropwise to a solution of 50 g of [R8], 11.6 mL of pyridine, and 200 mL of chloroform. After stirring at room temperature for 30 minutes under nitrogen, the reaction solution was poured into a mixed solvent of methanol and water (1.75 L of methanol, 250 mL of water), and the precipitated solid was filtered to obtain maleimide-modified polybutylene succinate [R9] (recovery). Rate 89%). (Molecular weight 4950, maleimide modification rate f = 2).

[Comparative Example 3]
To 100 mL of chloroform, 6.49 g of 1-ethyl-3- (3′-dimethylaminopropyl) carbodiimide hydrochloride (WSC), 2.68 mL of pyridine, 5.0 g of [R2] and 11.7 g of [R3] were added, Refluxed for 50 hours. This was washed with water, dried over magnesium sulfate, dissolved in 30 mL of chloroform, poured into excess methanol, and reprecipitated. Further, purification by silica gel chromatography (developing solvent: chloroform / ethyl acetate) gave maleimide-modified polylactic acid [R5] (yield 68%) (molecular weight 7410, maleimide modification rate f = 5.8).

  About the manufacturing method of a polyfunctional maleimide compound, it shows in Examples 2-4 and Comparative Example 3. FIG. Examples 2 to 4 using acid chlorides are production methods in which a polyfunctional maleimide compound is obtained in a high yield by a simple purification method with a short reaction time, compared to Comparative Example 3 using carbodiimide. It was revealed.

3. Evaluation of Shape Memory Property / Remoldability As an application example of the polyfunctional maleimide compound, an example in which the polyfunctional maleimide compound is used as a precursor of the shape memory resin is shown. By using a thermoreversible reaction between a maleimide group and a furan group, and cross-linking the resin with a maleimide group and a furan group, a re-moldable shape memory resin is obtained. Therefore, a furan linker was synthesized, a crosslinked product with maleimide-modified polylactic acid ([R5] and [R7]) was prepared, and shape memory property and remoldability were verified.

Synthesis of furan linker After dissolving 40.0 g of furfuryl alcohol and 0.2 mL of dilaurate dibutyltin in 150 mL of dioxane, 24.2 g of lysine triisocyanate was added dropwise. After reacting at 60 ° C. for 6 hours, the solvent was distilled off under reduced pressure and dissolved in 200 mL of chloroform. After washing with 200 mL of water three times and drying with magnesium sulfate, the solvent was distilled off under reduced pressure. The obtained crude product was recrystallized from ethyl acetate to obtain furan linker [R10].

Preparation of a test piece: 10.0 g of maleimide-modified polylactic acid [R5] and furan linker [R10] 1.49 were melt-mixed at 160 ° C., compression-molded, and heated at 100 ° C. for 1 hour and 75 ° C. for 20 hours. A film of 5 cm × 1.8 mm was created [R11].

  10.0 g of maleimide-modified polylactic acid [R7] and 1.97 g of furan linker [R10] are melt-mixed at 160 ° C., compression-molded, and heated at 100 ° C. for 1 hour and 75 ° C. for 20 hours to obtain 2 cm × 5 cm × 1. An 8 mm film was created [R12].

Shape memory evaluation test The films of [R11] and [R12] were heated at 80 ° C., the center of the film was bent at 90 °, deformed for 10 seconds, and then cooled to room temperature. When the deformability of the film at this time was evaluated by angle, both [R11] and [R12] were 90 °, and excellent shape memory was obtained. Further, the deformed film was heated again at 80 ° C. for 10 seconds, and the recoverability was evaluated by angle. As a result, both [R11] and [R12] were 0 °, and the shape was completely recovered.

Remoldability evaluation test The films of [R11] and [R12] were melted at 160 ° C. and reshaped into a circle having a radius of 1.8 cm. The film that could be reshaped was evaluated for deformability and recoverability in the same manner as described above. Then, the same results as above were obtained, and it was found that both [R11] and [R12] showed excellent shape memory properties even after re-molding. From the above, the cross-linked product of polyfunctional maleimide compounds ([R5] and [R7]) and furan linker [R10] becomes a remoldable shape memory resin, and the polyfunctional maleimide compound is used as a precursor of the shape memory resin. It became clear that it was possible.

  The polyfunctional maleimide compound of the present invention can be used as an environment-adaptive high-functional resin. For example, it can be used as a precursor of a remoldable shape memory resin. Applications of this resin include, for example, exterior materials for electronic devices (such as personal computers and mobile phones), screws, fastening pins, switches, sensors, information recording devices, rollers such as OA equipment, parts such as belts, sockets, pallets, etc. It can be used for packing materials, on-off valves for air conditioning units, heat-shrinkable tubes, etc. In addition, it can be applied in various fields as automobile members such as bumpers, handles, rearview mirrors, household members such as casts, toys, glasses frames, orthodontic wires, bed slip prevention bedding, and the like. In addition, coating agents, lining agents, surface treatment agents, molding materials, paints, printing inks, adhesives, adhesives, sealants, binders, laminated materials for electronic products, electrical insulating materials, conductive pastes, pharmaceuticals It can be used for agricultural chemicals.

Claims (6)

A method for producing maleimide carboxylic acid represented by the following general formula (2),
  Maleimide carboxylic acid represented by the following formula (4) is subjected to a dehydration ring-closing reaction at 110 ° C. or higher and 145 ° C. or lower using a catalyst in a mixed solvent of an inert organic solvent and an aprotic polar solvent. A method for producing carboxylic acid.

(In the formula, X represents a linear or branched alkylene group having 1 to 20 carbon atoms.) The method for producing maleimide carboxylic acid according to claim 1, wherein the aprotic polar solvent is used in an amount of 0.001 to 10 times the maleamide carboxylic acid represented by the formula (4). A method for producing a polyfunctional maleimide compound represented by the following general formula (1) :
The maleamide carboxylic acid represented by the following formula (4) is subjected to a dehydration ring-closing reaction at 110 ° C. or higher and 145 ° C. or lower using a catalyst in a mixed solvent of an inert organic solvent and an aprotic polar solvent, A step of obtaining maleimide carboxylic acid represented by 2);
And a step of transesterifying the biodegradable polyester resin represented by the following formula (3) after converting the maleimide carboxylic acid represented by the general formula (2) into an acid chloride. A method for producing a maleimide compound.

(In the formula, X represents a linear or branched alkylene group having 1 to 20 carbon atoms, Y represents a biodegradable polyester resin residue, and m and n represent an integer of 2 or more.) The method for producing a polyfunctional maleimide compound according to claim 3, wherein the acid chloride of maleimide carboxylic acid is maleimide propionic acid chloride obtained by reacting maleimide propionic acid and oxalyl chloride.   A method for producing a polyfunctional maleimide compound represented by the following general formula (1):
  A polyfunctional maleimide comprising a step of transesterifying the biodegradable polyester resin represented by the following formula (3) after converting the maleimide carboxylic acid represented by the following general formula (2) into an acid chloride Compound production method.

(In the formula, X represents a linear or branched alkylene group having 1 to 20 carbon atoms, Y represents a biodegradable polyester resin residue, and m and n represent an integer of 2 or more.) The method for producing a polyfunctional maleimide compound according to claim 5, wherein the acid chloride of maleimide carboxylic acid is maleimide propionic acid chloride obtained by reacting maleimide propionic acid and oxalyl chloride.