CN110590798A - Process for producing cyclobutanetetracarboxylic acid derivative - Google Patents

Process for producing cyclobutanetetracarboxylic acid derivative Download PDF

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CN110590798A
CN110590798A CN201910863538.8A CN201910863538A CN110590798A CN 110590798 A CN110590798 A CN 110590798A CN 201910863538 A CN201910863538 A CN 201910863538A CN 110590798 A CN110590798 A CN 110590798A
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group
reaction
maleic anhydride
anhydride
electron
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岛田淳平
近藤光正
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Nissan Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents
    • C08G73/1014—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents in the form of (mono)anhydrid
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers

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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present application relates to a method for producing a cyclobutanetetracarboxylic acid derivative. Specifically disclosed is a method for producing a cyclobutanetetracarboxylic acid-1, 2:3, 4-dianhydride derivative which is useful as a raw material for polyimides and the like, with high yield. A method for producing 1,2,3, 4-cyclobutanetetracarboxylic acid-1, 2:3, 4-dianhydride represented by the formula (2) by causing a maleic anhydride compound represented by the following formula (1) to undergo a photodimerization reaction in a reaction solvent in an amount of 100 times or more by mass relative to the maleic anhydride compound. (wherein R represents an alkyl group having 1 to 20 carbon atoms.)

Description

Process for producing cyclobutanetetracarboxylic acid derivative
This application is a divisional application of a chinese patent application having an application date of 2015, month 1, and day 16, application number of 201580004875.1, entitled "method for producing cyclobutanetetracarboxylic acid derivatives".
Technical Field
The present invention relates to a method for producing an alicyclic tetracarboxylic dianhydride which can be used as a raw material monomer for polyimide for optical materials and the like.
Background
In general, polyimide resins are widely used as electronic materials such as liquid crystal display elements, protective materials for semiconductors, and insulating materials due to their characteristics, i.e., high mechanical strength, heat resistance, insulation properties, and solvent resistance. In addition, recently, the use thereof as a material for optical communication such as a material for optical waveguide is expected.
In recent years, developments in this field have surprisingly led to the requirement for higher properties also for the materials used therein. That is, it is expected that the composition not only has excellent heat resistance and solvent resistance, but also has various properties suitable for the intended use.
However, a wholly aromatic polyimide resin using an aromatic tetracarboxylic dianhydride and an aromatic diamine as raw materials is colored in a dark amber color, and therefore, has a problem in applications where high transparency is required. On the other hand, a polyimide resin obtained by forming a polyimide precursor by a polycondensation reaction of an alicyclic tetracarboxylic dianhydride and an aromatic diamine and imidizing the precursor is known to have less coloration and high transparency (see patent documents 1 and 2).
As a raw material of the polyimide having less coloring and high transparency, namely 1 kind of alicyclic tetracarboxylic acid dianhydride, namely alkylcyclobutanedioic acid dianhydride, patent document 3 discloses: as shown in the following scheme, a mixture of 1, 3-dimethylcyclobutane-1, 2,3, 4-tetracarboxylic acid-1, 2:3, 4-dianhydride (1,3-DMCBDA) and 1, 2-dimethylcyclobutane-1, 2,3, 4-tetracarboxylic acid-1, 2:3, 4-dianhydride (1,2-DMCBDA) can be obtained by photodimerization of citraconic anhydride (abbreviated as MMA).
On the other hand, it is known that: when 1,3-DMCBDA and 1,2-DMCBDA are compared, the former 1,3-DMCBDA, which is an isomer having a highly symmetrical structure, can produce a polyimide having a high molecular weight, and is more useful than the latter 1, 2-DMCBDA.
However, patent document 3 describes that a mixture of 1,3-DMCBDA and 1,2-DMCBDA can be obtained, but does not describe that an isomer having a highly symmetrical structure and high usefulness, i.e., the former 1,3-DMCBDA, can be selectively produced in a high yield.
Documents of the prior art
Patent document
Patent document 1: japanese examined patent publication (Kokoku) No. 2-24294
Patent document 2: japanese laid-open patent publication No. 58-208322
Patent document 3: japanese laid-open patent publication No. 4-106127
Disclosure of Invention
Problems to be solved by the invention
An object of the present invention is to provide a novel production method which uses a specific maleic anhydride compound as a raw material and, by virtue of a photodimerization reaction thereof, improves the selectivity of 1, 3-dialkylcyclobutane-1, 2,3, 4-tetracarboxylic acid-1, 2:3, 4-dianhydride (hereinafter also referred to as 1, 2-DACBDA.) which is a highly symmetrical and highly useful isomer having a structure higher than that of 1, 2-dialkylcyclobutane-1, 2,3, 4-tetracarboxylic acid-1, 2:3, 4-dianhydride (hereinafter also referred to as 1, 3-DACBDA.) as compared with conventional methods, and which can produce the compound at a high yield.
Means for solving the problems
The present inventors have conducted extensive studies to solve the above problems, and as a result, have found a novel production method for achieving the above object, and have completed the present invention.
The present invention has the following gist.
1. A process for producing a 1,2,3, 4-cyclobutanetetracarboxylic acid-1, 2:3, 4-dianhydride (1,3-DACBDA) derivative represented by the formula (2), characterized by causing a photodimerization reaction of a maleic anhydride compound represented by the following formula (1) in a reaction solvent which is 100 times or more by mass relative to the maleic anhydride compound.
(wherein R represents an alkyl group having 1 to 20 carbon atoms.)
2. The production method according to 1, wherein R is a methyl group.
3. The production process according to the above 1 or 2, wherein the photodimerization reaction is carried out in a reaction solvent in an amount of 100 to 300 times by mass relative to the maleic anhydride compound.
4. The production process according to the above 1 or 2, wherein the photodimerization reaction is carried out in a reaction solvent in which the amount of the reaction solvent used is 150 to 250 times by mass relative to the maleic anhydride compound.
5. The production process according to any one of the above 1 to 4, wherein the reaction solvent is an organic carboxylic acid ester, an organic carboxylic acid anhydride, or a carbonate.
6. The production method according to any one of the above 1 to 5, wherein the reaction solvent is ethyl acetate or dimethyl carbonate.
7. The production method according to any one of the above 1 to 6, wherein the reaction is carried out in the presence of a sensitizer comprising benzophenone, acetophenone, benzaldehyde, benzophenone substituted with an electron-withdrawing group, acetophenone substituted with an electron-withdrawing group, benzaldehyde substituted with an electron-withdrawing group, or anthraquinone.
8. The production method according to 7, wherein the electron-withdrawing group is at least 1 selected from the group consisting of a fluoro group, a chloro group, a bromo group, an iodo group, a nitro group, a cyano group and a trifluoromethyl group.
9. The production method according to 7 or 8, wherein the number of the electron-withdrawing groups is 1 to 5.
10. The production method according to any one of the above 6 to 9, wherein the sensitizer is used in an amount of 0.1 to 20 mol% based on the maleic anhydride compound.
11. The production method according to any one of the above 1 to 10, wherein the reaction temperature is 0to 20 ℃.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a mixture of 1,3-DACBDA and 1,2-DACBDA is provided by the photodimerization reaction of a specific maleic anhydride compound, but the 1,3-DACBDA, which is a more useful isomer having a highly symmetrical structure, has a higher selectivity than conventional methods, and the conversion rate of the photodimerization reaction of the maleic anhydride compound is increased, so that the 1,3-DACBDA can be obtained with a high yield.
Detailed Description
The method for producing 1,2,3, 4-cyclobutanetetracarboxylic acid-1, 2:3, 4-dianhydride (1,3-DACBDA) represented by formula (2) by photodimerization reaction of the maleic anhydride compound represented by formula (1) is represented by the following reaction scheme.
Wherein R represents an alkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, and particularly preferably 1 to 6 carbon atoms.
The alkyl group having 1 to 20 carbon atoms may be either a linear or branched saturated alkyl group or a linear or branched unsaturated alkyl group.
Specific examples thereof include saturated alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1-dimethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 1-dimethyl-n-butyl, 1-ethyl-n-butyl, 1, 2-trimethyl-n-propyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, and n-eicosyl; unsaturated alkyl groups such as 1-methylvinyl, 2-allyl, 1-ethylvinyl, 2-methylallyl, 2-butenyl, 2-methyl-2-butenyl, 3-methyl-3-butenyl, 2-hexenyl, 4-methyl-3-pentenyl, 4-methyl-4-pentenyl, 2, 3-dimethyl-2-butenyl, 1-ethyl-2-pentenyl, 3-dodecenyl, propargyl, 3-butynyl, 3-methyl-2-propynyl, and 9-decynyl groups.
N represents positive, i represents iso, s represents secondary, and t represents tertiary.
Examples of the maleic anhydride compound represented by the formula (1) include citraconic anhydride, 2-ethylmaleic anhydride, 2-isopropylmaleic anhydride, 2-n-butylmaleic anhydride, 2-tert-butylmaleic anhydride, 2-n-pentylmaleic anhydride, 2-n-hexylmaleic anhydride, 2-n-heptylmaleic anhydride, 2-n-octylmaleic anhydride, 2-n-nonylmaleic anhydride, 2-n-decylmaleic anhydride, 2-n-dodecylmaleic anhydride, 2-n-eicosylmaleic anhydride, 2- (1-methylvinyl) maleic anhydride, 2- (2-allyl) maleic anhydride, 2- (1-ethylvinyl) maleic anhydride, 2- (2-methylallyl) maleic anhydride, 2- (2-butenyl) maleic anhydride, 2-n-butylmaleic anhydride, 2-n-pentylmaleic anhydride, 2-n-hexylmaleic anhydride, 2-n-heptylmaleic anhydride, 2-octylmaleic anhydride, 2-, 2- (2-hexenyl) maleic anhydride, 2- (1-ethyl-2-pentenyl) maleic anhydride, 2- (3-dodecenyl) maleic anhydride, 2-propargyl maleic anhydride, 2- (3-butynyl) maleic anhydride, 2- (3-methyl-2-propynyl) maleic anhydride, 2- (9-decynyl) maleic anhydride, and the like. Among them, since the photoreaction proceeds efficiently, citraconic anhydride, 2-ethylmaleic anhydride, 2-isopropylmaleic anhydride, 2-n-butylmaleic anhydride, 2-tert-butylmaleic anhydride, 2-n-pentylmaleic anhydride, 2-n-hexylmaleic anhydride, 2-n-heptylmaleic anhydride, 2-n-octylmaleic anhydride, 2-n-nonylmaleic anhydride, 2-n-decylmaleic anhydride, or 2-n-dodecylmaleic anhydride is preferable, and citraconic anhydride, 2-ethylmaleic anhydride, 2-isopropylmaleic anhydride, 2-n-butylmaleic anhydride, 2-tert-butylmaleic anhydride, 2-n-pentylmaleic anhydride, or 2-n-hexylmaleic anhydride is more preferable.
As the reaction solvent, an organic solvent generally used in photochemical reactions can be used. On the other hand, as a solvent that can be industrially used, the following conditions must be satisfied: (1) is a carbonyl compound having a high photosensitizing effect; (2) the solubility of the raw material maleic anhydride compound is high, and the solubility of the CBDA derivative compound is low in order to suppress the decomposition reaction of the produced CBDA derivative compound; (3) the solubility of the by-product is high, and the CBDA derivative compound can be purified only by washing with the same solvent; (4) a compound having a boiling point of about 50 to 150 ℃ so as not to have a low boiling point which is at risk of ignition and not to remain in the CBDA derivative compound; (5) is safe with respect to the environment; (6) is also stable in photoreaction; (7) low cost and the like. From these viewpoints, hexane, heptane, acetonitrile, acetone, chloroform, etc. may be used as the reaction solvent. The reaction solvent is preferably an organic carboxylic acid ester, an organic carboxylic acid anhydride, or a carbonate.
As organic carboxylic acid esters, suitable are those of the formula R1COOR2(wherein, R1Is hydrogen or an alkyl group having 1 to 4 carbon atoms, preferably 1 or 2 carbon atoms, R2An alkyl group having 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms. ) Fatty acid alkyl esters are shown.
Preferred examples of the organic carboxylic acid ester include methyl formate, ethyl formate, n-propyl formate, isopropyl formate, n-butyl formate, isobutyl formate, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, isopropyl propionate, n-butyl propionate, and isobutyl propionate. Further, ethylene glycol dicarbamate, ethylene glycol diacetate, ethylene glycol dipropionate, and the like can be used.
The organic carboxylic acid anhydride is preferably represented by the general formula (R)1CO)2O (wherein, R1Including the preferred embodiments, are as defined above. ) Carboxylic acid anhydrides shown. Preferred examples thereof are propionic anhydride, butyric anhydride, trifluoroacetic anhydride or acetic anhydride. Among these, acetic anhydride is preferable from the viewpoint that 1,3-DACBDA can be obtained at a higher yield.
In addition, as the carbonate ester, a dialkyl carbonate ester in which the number of carbons of the alkyl group is preferably 1 to 3, more preferably 1 or 2 is suitable. Preferable examples thereof include dimethyl carbonate, diethyl carbonate, dipropyl carbonate, and a mixture thereof.
Among them, the reaction solvent is preferably ethyl formate, methyl acetate, ethyl acetate, isopropyl acetate, isobutyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, isopropyl propionate, ethylene glycol dicarbamate, ethylene glycol diacetate, dimethyl carbonate or diethyl carbonate, and the solvent is most preferably ethyl acetate or dimethyl carbonate.
The above solvents can be used alone in 1 kind, or in combination of 2 or more, when used alone, has the advantage of easy processing after the reaction.
In the present invention, when the reaction solvent contains ethyl acetate, dimethyl carbonate, diethyl carbonate or ethylene glycol diacetate, the solubility of the maleic anhydride compound as the raw material is high, but the solubility of the produced 1,3-DACBDA is low, and the target compound precipitates as crystals during the reaction, so that side reactions such as the reverse reaction of converting DACBDA to a maleic anhydride compound and the production of oligomers can be suppressed.
In the present invention, the amount of the reaction solvent is important, and it was found that: by maximizing the amount of the reaction solvent, the selectivity of 1,3-DACBDA in the resulting mixture of 1,3-DACBDA and 1,2-DACBDA becomes greater. That is, by the presence of the reaction solvent in an amount of 100 times by mass or more, preferably 100 to 300 times by mass, and more preferably 150 to 250 times by mass based on the raw material maleic anhydride compound, a product having a high 1,3-DACBDA content and a high 1,3-DACBDA selectivity can be obtained as compared with the conventional method.
In the photoreaction of the present invention, the wavelength of light is 200 to 400nm, more preferably 250 to 350nm, and particularly preferably 280 to 330 nm. As the light source, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, an electrodeless lamp, a light-emitting diode, or the like is preferably used because the CBDA derivative compound is specifically provided at a high yield.
Further, as the photochemical reaction apparatus, by changing the light source cooling tube from quartz glass to Pyrex (registered trademark) glass, the colored polymer and impurities adhering to the light source cooling tube were reduced, and the yield of the CBDA derivative compound was observed to be improved.
When the reaction temperature is high, the polymer is by-produced, and when the reaction temperature is low, the solubility of the maleic anhydride compound is lowered and the production efficiency is reduced, so that the reaction is preferably carried out at-20 to 80 ℃ and more preferably at-10 to 50 ℃. Especially at 0-20 ℃, the generation of byproducts is obviously inhibited, and the 1,3-DACBDA can be obtained with high selectivity and yield.
The reaction time varies depending on the amount of the maleic anhydride compound, the type of the light source, and the irradiation amount, and may be carried out until the unreacted maleic anhydride compound reaches 0to 40%, preferably 0to 10%.
The reaction time is, specifically, usually 1 to 200 hours, preferably 1 to 100 hours, and more preferably 1 to 60 hours.
The conversion rate can be easily determined by analyzing the reaction solution by gas chromatography or the like.
When the reaction time becomes long, the conversion of the maleic anhydride compound increases, and the amount of the CBDA derivative compound deposited increases, the CBDA derivative compound produced starts to adhere to the outer wall (reaction solution side) of the light source cooling tube, and the crystal coloration and the decrease in light efficiency (yield per unit power x unit time) due to the simultaneous decomposition reaction are observed. Therefore, in order to increase the conversion of the maleic anhydride compound, it is not preferable because it takes a long time for 1 lot, which is accompanied by a decrease in production efficiency in practical use.
The reaction may be carried out by a batch method or a flow-through method, and a batch method is preferably used. The pressure during the reaction may be either normal pressure or elevated pressure, and is preferably normal pressure.
The production method of the present invention may be carried out by adding a sensitizer. Examples of the sensitizer include benzophenone, acetophenone, benzaldehyde, anthraquinone, benzophenone substituted with an electron-withdrawing group, acetophenone substituted with an electron-withdrawing group, benzaldehyde substituted with an electron-withdrawing group, and the like.
Examples of the electron-withdrawing group include at least 1 selected from the group consisting of a fluoro group, a chloro group, a bromo group, an iodo group, a nitro group, a cyano group, and a trifluoromethyl group, and preferably a fluoro group, a chloro group, a bromo group, a cyano group, and a trifluoromethyl group. Particularly preferred electron-withdrawing groups are fluoro groups and chloro groups.
The number of electron-withdrawing groups is 1 to 10, preferably 1 to 5, and particularly preferably 1 to 3.
The substitution position of the electron-withdrawing group includes an ortho position, a meta position, and a para position of the carbonyl group, and is preferably an ortho position or a para position.
When the number of electron-withdrawing groups is 2 or more, the electron-withdrawing groups may be the same or different from each other. In addition, anthraquinone in which carbonyl groups having an electron-withdrawing effect are crosslinked in the ortho position may be used.
Specific examples of the benzophenone and the benzophenone substituted with the electron-withdrawing group include benzophenone, 2-fluorobenzophenone, 3-fluorobenzophenone, 4-fluorobenzophenone, 2-chlorobenzophenone, 3-chlorobenzophenone, 4-chlorobenzophenone, 2-cyanobenzophenone, 3-cyanobenzophenone, 4-cyanobenzophenone, 2-nitrobenzophenone, 3-nitrobenzophenone, 4-nitrobenzophenone, 2,4 ' -dichlorobenzophenone, 4 ' -difluorobenzophenone, 4 ' -dichlorobenzophenone, 4 ' -dibromobenzophenone, 3 ' -bis (trifluoromethyl) benzophenone, 3,4 ' -dinitrobenzophenone, 3 ' -dinitrobenzophenone, mixtures thereof, 4, 4' -dinitrobenzophenone, 2-chloro-5-nitrobenzophenone, 1, 3-bis (4-fluorobenzoyl) benzene, 1, 3-bis (4-chlorobenzoyl) benzene, 2, 6-dibenzoylbenzonitrile, 1, 3-dibenzoyl-4, 6-dinitrobenzene, anthraquinone and the like. Among them, 4 '-difluorobenzophenone or 4, 4' -dichlorobenzophenone is preferable.
Specific examples of the acetophenone and acetophenone substituted with an electron-withdrawing group include acetophenone, 2 ' -fluoroacetophenone, 3 ' -fluoroacetophenone, 4 ' -fluoroacetophenone, 2 ' -chloroacetophenone, 3 ' -chloroacetophenone, 4 ' -chloroacetophenone, 2 ' -cyanoacetophenone, 3 ' -cyanoacetophenone, 4 ' -cyanoacetophenone, 2 ' -nitroacetophenone, 3 ' -nitroacetophenone, 4 ' -nitroacetophenone, 2 ', 4 ' -difluoroacetophenone, 3 ', 4 ' -difluoroacetophenone, 2 ', 4 ' -dichloroacetophenone, 3 ', 4 ' -dichloroacetophenone, 4 ' -chloro-3 ' -nitroacetophenone, 4 ' -bromo-3 ' -nitroacetophenone, 4 ' -fluoro-3 ' -nitroacetophenone and the like. Among them, 4 ' -fluoroacetophenone, 2 ', 4 ' -difluoroacetophenone, 3 ', 4 ' -difluoroacetophenone, 2 ', 4 ' -dichloroacetophenone or 3 ', 4 ' -dichloroacetophenone is preferable.
Examples of the benzaldehyde and benzaldehyde substituted with an electron-withdrawing group include benzaldehyde, 2-fluorobenzaldehyde, 3-fluorobenzaldehyde, 4-fluorobenzaldehyde, 2-chlorobenzaldehyde, 3-chlorobenzaldehyde, 4-chlorobenzaldehyde, 2-cyanobenzaldehyde, 3-cyanobenzaldehyde, 4-cyanobenzaldehyde, 2-nitrobenzaldehyde, 3-nitrobenzaldehyde, 4-nitrobenzaldehyde, 2, 4-difluorobenzaldehyde, 3, 4-difluorobenzaldehyde, 2, 4-dichlorobenzaldehyde, 3, 4-dichlorobenzaldehyde, 2-chloro-5-nitrobenzaldehyde, 4-chloro-2-nitrobenzaldehyde, 4-chloro-3-nitrobenzaldehyde, 5-chloro-2-nitrobenzaldehyde, 5-chloro-3-nitrobenzaldehyde, 4-nitrobenzaldehyde, and the like, 2-fluoro-5-nitrobenzaldehyde, 4-fluoro-3-nitrobenzaldehyde, 5-fluoro-2-nitrobenzaldehyde, and the like. Among them, preferred is 4-fluorobenzaldehyde, 4-chlorobenzaldehyde, 2, 4-difluorobenzaldehyde, 3, 4-difluorobenzaldehyde, 2, 4-dichlorobenzaldehyde or 3, 4-dichlorobenzaldehyde.
The amount of the sensitizer to be used is not particularly limited as long as it is an amount that accelerates the photoreaction rate, and is preferably 0.1 to 20 mol%, more preferably 0.1 to 5 mol%, based on the maleic anhydride compound.
The above benzophenone derivative, acetophenone derivative or benzaldehyde derivative may be used alone or 1 or more of them may be used in combination, and when used alone, the treatment after the reaction is easy.
The target compound is obtained by filtering precipitates in the reaction solution after the photoreaction, washing the filtrate with an organic solvent, and drying under reduced pressure.
The amount of the organic solvent used for washing the filtrate may be an amount that allows transfer of the precipitate remaining in the reaction tank to the filter, and when the amount of the organic solvent is large, the target compound is transferred to the filtrate, and the recovery rate is lowered. Therefore, the amount of the organic solvent used for washing the filtrate is preferably 0.5 to 10 times by weight, more preferably 1 to 2 times by weight, based on the maleic anhydride compound used in the reaction.
The organic solvent used for washing the filtrate is not particularly limited, and it is not preferable to use a solvent having high solubility of the product because: the target compound is transferred to the filtrate to cause a decrease in recovery. Therefore, examples of the organic solvent used for washing the filtrate include methyl formate, ethyl formate, n-propyl formate, isopropyl formate, n-butyl formate, isobutyl formate, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, isopropyl propionate, n-butyl propionate, isobutyl propionate, ethylene glycol diformate, ethylene glycol diacetate, ethylene glycol dipropionate, dimethyl carbonate, and diethyl carbonate, which are used as reaction solvents for the photodimerization reaction; a solvent which does not dissolve the product and does not react with the product, such as toluene, hexane, heptane, acetonitrile, acetone, chloroform, acetic anhydride, a mixed solvent thereof, and the like. Among them, ethyl acetate, dimethyl carbonate, acetic anhydride and the like are preferable, and ethyl acetate or dimethyl carbonate is more preferable.
Examples
The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In addition, the analysis method used in the examples is as follows.
< GC analysis conditions >
The device comprises the following steps: GC-2010Plus (manufactured by Shimadzu corporation),
Column: DB-1 (manufactured by GL Sciences Inc.) diameter 0.25mm X length 30m, film thickness 0.25 μm, carrier gas: he. A detector: FID, sample injection amount: 1 μ L, injection port temperature: 160 ℃, detector temperature: 220 ℃ and column temperature: 70 ℃ (20min) -40 ℃/min-220 ℃ (15min), split ratio: 1:50, internal standard substance: butyl lactate.
<1H NMR analysis conditions>
The device comprises the following steps: fourier transform type superconducting Nuclear magnetic resonance apparatus (FT-NMR) INOVA-400 (manufactured by Varian corporation) at 400MHz,
Solvent: DMSO-d6, internal standard substance: tetramethylsilane (TMS).
< conditions for melting Point analysis >
The device comprises the following steps: DSC1 (manufactured by Mettler Toledo International Inc.),
Temperature: 35-5 ℃/min-400 ℃, and the temperature of the pot is as follows: au (sealed).
Example 1
Into a 30mL Pyrex (registered trademark) glass test tube, 0.10g (0.89mmol) of Citraconic Anhydride (CA) and carbonic acid bis (ester) were put under a nitrogen atmosphere20g (222mmol, 200 times by weight relative to Citraconic Anhydride (CA)) of methyl ester was dissolved by stirring with a magnetic stirrer. Thereafter, the mixture was irradiated with a 100W high-pressure mercury lamp for 4 hours while stirring at 10 to 15 ℃. Thereafter, 2g of the reaction solution in the reactor was collected, and the solvent was distilled off with an evaporator at 70 to 80 Torr. By passing1H NMR analysis confirmed: the crude product obtained was a mixture comprising 1,3-DM-CBDA and 1,2-DM-CBDA (1,3-DM-CBDA:1,2-DM-CBDA ═ 48.3: 51.7).
1H NMR(DMSO-d6,δppm)(1,3-DM-CBDA)：1.38(s,6H),3.89(s,2H).
1H NMR(DMSO-d6,δppm)(1,2-DM-CBDA)：1.37(s,6H),3.72(s,2H).
mp.(1,3-DM-CBDA)：316-317℃
Examples 2 to 7 and comparative examples 1 to 5
A series of operations were performed in the same manner as in example 1 using the solvents shown in table 1 below, and the amounts of 4, 4' -dichlorobenzophenone (DClBP) and Citraconic Anhydride (CA) charged and the amounts of the solvents added. In addition, the production ratio of 1,3-DM-CBDA to 1,2-DM-CBDA (1,3-DM-CBDA:1,2-DM-CBDA) was calculated in the same manner as in example 1.
The solvents, whether or not DClBP was added, the amount of CA charged, the amount of solvent and the results are shown in the following table. The production ratio of 1,3-DM-CBDA to 1,2-DM-CBDA in the reaction mixture obtained here was calculated and shown in the table together with the results obtained in example 1. In table 1, Neat indicates that the reaction is performed in the absence of a solvent. Also, 0.1 to 10 mol% of DClBP based on citraconic anhydride was used.
[ Table 1]
Industrial applicability
The 1,3-DACBDA obtained by the present invention is a compound useful as a raw material of polyamic acid, polyimide, and the like, which are industrially widely used as resin compositions used for electronic materials such as liquid crystal display elements, protective materials in semiconductors, insulating materials, and the like.
The entire contents of the specification, claims and abstract of japanese patent application 2014-007185 applied on 1/17/2014 are incorporated herein by reference as the disclosure of the present invention.

Claims (11)

1. A process for producing a 1,2,3, 4-cyclobutanetetracarboxylic acid-1, 2:3, 4-dianhydride derivative represented by the formula (2), which comprises subjecting a maleic anhydride compound represented by the following formula (1) to a photodimerization reaction in a reaction solvent which is 100 times or more by mass relative to the maleic anhydride compound,
wherein R represents an alkyl group having 1 to 20 carbon atoms.
2. The production method according to claim 1, wherein R is a methyl group.
3. The production method according to claim 1 or 2, wherein the photodimerization reaction is carried out in a reaction solvent which is 100 to 300 times by mass relative to the maleic anhydride compound.
4. The production process according to claim 1 or 2, wherein the photodimerization reaction is carried out in a reaction solvent in which the amount of the reaction solvent used is 150 to 250 times by mass relative to the maleic anhydride compound.
5. The production process according to any one of claims 1 to 4, wherein the reaction solvent is an organic carboxylic acid ester, an organic carboxylic acid anhydride, or a carbonate.
6. The production process according to any one of claims 1 to 5, wherein the reaction solvent is ethyl acetate or dimethyl carbonate.
7. The production method according to any one of claims 1 to 6, wherein the reaction is carried out in the presence of a sensitizer comprising benzophenone, acetophenone, benzaldehyde, benzophenone substituted with an electron-withdrawing group, acetophenone substituted with an electron-withdrawing group, benzaldehyde substituted with an electron-withdrawing group, or anthraquinone.
8. The production method according to claim 7, wherein the electron-withdrawing group is at least 1 selected from the group consisting of a fluoro group, a chloro group, a bromo group, an iodo group, a nitro group, a cyano group, and a trifluoromethyl group.
9. The production process according to claim 7 or 8, wherein the number of the electron-withdrawing groups is 1 to 5.
10. The production method according to any one of claims 7 to 9, wherein the sensitizer is used in an amount of 0.1 to 20 mol% based on the maleic anhydride compound.
11. The production method according to any one of claims 1 to 10, wherein the reaction temperature is 0to 20 ℃.
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59212495A (en) * 1983-05-19 1984-12-01 Nissan Chem Ind Ltd Preparation of 1,2,3,4-cyclobutanetetracarboxylic acid-1, 2:3,4-dianhydride
US20060089505A1 (en) * 2004-10-20 2006-04-27 Eternal Chemical Co., Ltd. Cyclobutanetetracarboxylate compound and preparation method thereof
WO2008153287A1 (en) * 2007-06-13 2008-12-18 Korea Research Institute Of Chemical Technology Low temperature processable substituted alicyclic polyimide photo-alignment layers and method for preparing liquid crystal cells
CN101925851A (en) * 2008-01-25 2010-12-22 日产化学工业株式会社 Liquid-crystal alignment material and liquid-crystal display element
CN102361849A (en) * 2009-02-12 2012-02-22 日产化学工业株式会社 Tetracarboxylic acid derivatives, processes for producing same, and liquid-crystal alignment material
CN105916867A (en) * 2014-01-17 2016-08-31 日产化学工业株式会社 Method for producing cyclobutane tetracarboxylic acid derivative
CN105916864A (en) * 2014-01-17 2016-08-31 日产化学工业株式会社 Method for producing cyclobutane tetracarboxylic acid derivative
CN105916866A (en) * 2014-01-17 2016-08-31 日产化学工业株式会社 Method for producing cyclobutane tetracarboxylic acid derivative

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4017313A (en) * 1974-09-30 1977-04-12 E. I. Du Pont De Nemours And Company Photosensitive composition containing a leuco dye, a photosensitizer, an aromatic aldehyde and a secondary or tertiary amine and the use thereof in a direct-print process
JPS58208322A (en) 1982-05-31 1983-12-05 Japan Synthetic Rubber Co Ltd Polyimide compound
JPS60188427A (en) 1984-03-09 1985-09-25 Nissan Chem Ind Ltd Novel polyimide resin and its production
JPH0224294Y2 (en) 1984-10-25 1990-07-03
JP2923007B2 (en) 1990-08-28 1999-07-26 チッソ株式会社 Solvent-soluble polyimide, method for producing the same, and material for color filter
JP4852206B2 (en) * 2001-12-26 2012-01-11 日産化学工業株式会社 Method for producing cyclobutanetetracarboxylic dianhydride compound
JP2006328027A (en) * 2005-05-30 2006-12-07 Nof Corp Method for producing cyclobutanetetracarboxylic acid dianhydrides
JP2006347931A (en) * 2005-06-15 2006-12-28 Nissan Chem Ind Ltd Dialkylcyclobutanoic acid dianhydride and method for producing the same
JP5027556B2 (en) 2006-07-28 2012-09-19 株式会社カネカ Polyimide resin, polyimide resin layer using the same, laminate, method for producing laminate, optical compensation member
JP4928347B2 (en) 2007-05-09 2012-05-09 株式会社カネカ Polyimide, polyimide varnish, optical compensation film, polyimide, and method for producing optical compensation film.

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59212495A (en) * 1983-05-19 1984-12-01 Nissan Chem Ind Ltd Preparation of 1,2,3,4-cyclobutanetetracarboxylic acid-1, 2:3,4-dianhydride
US20060089505A1 (en) * 2004-10-20 2006-04-27 Eternal Chemical Co., Ltd. Cyclobutanetetracarboxylate compound and preparation method thereof
WO2008153287A1 (en) * 2007-06-13 2008-12-18 Korea Research Institute Of Chemical Technology Low temperature processable substituted alicyclic polyimide photo-alignment layers and method for preparing liquid crystal cells
CN101925851A (en) * 2008-01-25 2010-12-22 日产化学工业株式会社 Liquid-crystal alignment material and liquid-crystal display element
CN102361849A (en) * 2009-02-12 2012-02-22 日产化学工业株式会社 Tetracarboxylic acid derivatives, processes for producing same, and liquid-crystal alignment material
CN105916867A (en) * 2014-01-17 2016-08-31 日产化学工业株式会社 Method for producing cyclobutane tetracarboxylic acid derivative
CN105916864A (en) * 2014-01-17 2016-08-31 日产化学工业株式会社 Method for producing cyclobutane tetracarboxylic acid derivative
CN105916866A (en) * 2014-01-17 2016-08-31 日产化学工业株式会社 Method for producing cyclobutane tetracarboxylic acid derivative

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MASATOSHI HASEGAWA 等，: ""Colorless polyimides with low coefficient of thermal expansion derived from alkyl-substituted cyclobutanetetracarboxylic dianhydrides"", 《POLYMER INTERNATIONAL》 *

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