CN113646302A - Method for producing tetracarboxylic dianhydride - Google Patents
Method for producing tetracarboxylic dianhydride Download PDFInfo
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- CN113646302A CN113646302A CN202080025972.XA CN202080025972A CN113646302A CN 113646302 A CN113646302 A CN 113646302A CN 202080025972 A CN202080025972 A CN 202080025972A CN 113646302 A CN113646302 A CN 113646302A
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- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
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- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
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Abstract
The present invention addresses the problem of providing a method for producing a tetracarboxylic dianhydride having any of biphenylene, terphenylene, tetrabiphenylene, and naphthylene as a main skeleton, which has an improved reaction selectivity, high purity, high yield, and is industrially advantageous. As a solution, a method for producing a tetracarboxylic dianhydride represented by the general formula (1) is provided, which is characterized in that a diol compound represented by the general formula (2) and a trimellitic anhydride halide are reacted in the presence of a lactone or/and a nitrile having a relative dielectric constant of 25 or more.
Description
Technical Field
The present invention relates to a method for producing a tetracarboxylic dianhydride useful as a raw material for a heat-resistant resin such as a polyesterimide resin, a heat-resistant curing agent such as an epoxy resin, or a resin modifier.
Background
Polyimide has not only excellent heat resistance but also excellent chemical resistance, radiation resistance, electrical insulation, excellent mechanical properties, and the like, and is therefore widely used in various electronic devices such as FPC substrates, TAB substrates, protective films for semiconductor elements, and interlayer insulating films for integrated circuits. In addition to these characteristics, polyimide has recently been gaining increasing importance due to its simplicity of production, extremely high film purity, ease of physical property improvement using various available monomers, and the like.
Among them, as a raw material of a novel polyesterimide having a high glass transition temperature, a low linear thermal expansion coefficient equivalent to that of a metal foil, an extremely low water absorption rate, a high elastic modulus, sufficient toughness, and sufficient adhesion to a metal foil, tetracarboxylic dianhydrides represented by the following general formula (1-1) are known (for example, patent document 1).
[ chemical formula 1]
(in the formula, R1Represents a linear or branched alkyl group having 1 to 6 carbon atoms, m represents an integer of 2 to 4, and n represents an integer of 0 to 4. )
Further, naphthalene bis (trimellitic monoester dianhydride) is also known as a raw material of polyimide which can be suitably used for a base film for a flexible printed circuit board, a carrier tape for TAB, a resin for a laminate, and the like (for example, patent document 2).
On the other hand, various methods are known for producing tetracarboxylic dianhydrides, and among these methods, various methods have been studied for reacting diol compounds with trimellitic anhydride halides, because the halides of trimellitic anhydride, which is a raw material, can be easily obtained.
Patent document 3 describes a method of using p-toluenesulfonyl chloride, which is an acid halogenating agent, in combination in order to obtain a target compound at a high yield and a low temperature in a short time by using N, N-dimethylacetamide as a solvent during the reaction.
Patent document 4 describes a method in which toluene is used as a solvent in the reaction.
Patent document
Patent document 1: international publication No. 2008/091011
Patent document 2: japanese patent laid-open publication No. 2004-285364
Patent document 3: japanese laid-open patent publication No. 63-303976
Patent document 4: japanese laid-open patent publication No. 10-070157
Disclosure of Invention
In these known production methods, it is necessary to additionally use an acid halide, and as shown in the comparative examples described later, it is clear that a large amount of oligomer impurities is by-produced in addition to the tetracarboxylic dianhydride which is the target compound, and the purity of the target compound is lowered. It is common technical knowledge that if a polyesterimide resin is produced using a raw material having a low purity, the resin characteristics are poor.
The present invention has been made in view of the above circumstances, and an object thereof is to provide a method for producing a tetracarboxylic dianhydride having any of biphenylene, terphenylene, quaterphenylene, and naphthylene as a main skeleton, which has an improved reaction selectivity, a high purity, a high yield, and an industrially advantageous effect.
The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that the above problems can be solved by reacting a diol compound with a trimellitic anhydride halide in the presence of a specific solvent, and have completed the present invention.
The present invention is as follows.
1. A process for producing a tetracarboxylic dianhydride represented by the following general formula (1), characterized by reacting a diol compound represented by the following general formula (2) with a trimellitic anhydride halide in the presence of a lactone or/and nitrile having a relative dielectric constant of 25 or more,
[ chemical formula 2]
HO-X-OH (2)
Wherein X represents a divalent group represented by the following general formula (3-1) or the following general formula (3-2);
[ chemical formula 3]
In the formula, R1Represents a linear or branched alkyl group having 1 to 6 carbon atoms, m represents an integer of 2 to 4, n represents an integer of 0 to 4, and represents a bonding position;
[ chemical formula 4]
Wherein, represents a bonding site;
[ chemical formula 5]
Wherein X is the same as X in the general formula (2).
According to the present invention, the reaction selectivity of the tetracarboxylic dianhydride represented by the general formula (1) is improved, the production of impurity oligomers is suppressed, and a method for producing a tetracarboxylic dianhydride, which is rapid in reaction, high in purity, high in yield, and industrially advantageous, can be provided.
Detailed Description
The present invention will be described in detail below.
< starting materials: diol compound represented by the general formula (2) >
One of the starting materials used in the production method of the present invention is a diol compound represented by the following general formula (2).
[ chemical formula 6]
HO-X-OH (2)
(wherein X represents a divalent group represented by the following general formula (3-1) or the following general formula (3-2))
[ chemical formula 7]
(in the formula, R1Represents a linear or branched alkyl group having 1 to 6 carbon atoms, m represents an integer of 2 to 4, n represents an integer of 0 to 4, and represents a bonding position. )
[ chemical formula 8]
(wherein, represents a bonding position.)
R in the general formula (3-1)1The alkyl group represents a linear or branched alkyl group having 1 to 6 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group, a 2-methylpentyl group and a hexyl group. Among them, a linear or branched alkyl group having 1 to 4 carbon atoms is preferable, a methyl group or a butyl group is more preferable, and a methyl group is particularly preferable.
In the general formula (3-1), m represents an integer of 2 to 4, and m is preferably 2.
N in the general formula (3-1) represents an integer of 0 to 4, and n is preferably 1 to 4 from the viewpoint of solubility of the diol and the derivative thereof in a solvent.
Examples of the positions of the 2 bonding positions of the naphthalene ring of the formula (3-2) include the 1, 4-position, 1, 5-position, 1, 8-position, 2, 3-position, 2, 6-position, 2, 7-position and 2, 8-position. The position of the bonding position is preferably 1, 4-position, 1, 5-position, 2, 6-position, 2, 7-position, 2, 8-position, more preferably 1, 5-position, 2, 6-position, 2, 7-position, further preferably 2, 6-position, 2, 7-position, particularly preferably 2, 6-position.
In the diol compound represented by the general formula (2), X is represented by the following general formula (2-1) when X is represented by the general formula (3-1).
[ chemical formula 9]
(in the formula, R1M, n and R in the general formula (3-1)1M and n are the same. )
Specific examples of the diol having m ═ 2 include biphenyl-4, 4 ' -diol, 3,3 ' -dimethyl-biphenyl-4, 4 ' -diol, 3,3 ' -diethyl-biphenyl-4, 4 ' -diol, 3,3 ' -diisopropyl-biphenyl-4, 4 ' -diol, 3,3 ', 5,5 ' -tetramethyl-biphenyl-4, 4 ' -diol, 3,3 ', 6,6 ' -tetramethyl-biphenyl-4, 4 ' -diol, 2 ', 3,3 ', 5,5 ' -hexamethyl-biphenyl-4, 4 ' -diol, 3 ' -dimethyl-5, 5 ' -di-tert-butyl-biphenyl-4, 4 ' -diol.
Examples of the diol compound of m ═ 3 include 4,4 ″ -dihydroxy-p-terphenyl, 4 ″ -dihydroxy-3-methyl-p-terphenyl, 4 ″ -dihydroxy-3-ethyl-p-terphenyl, 4 ″ -dihydroxy-3-n-propyl-p-terphenyl, 4 ″ -dihydroxy-3-isopropyl-p-terphenyl, 4 ″ -dihydroxy-3, 5-dimethyl-p-terphenyl, and 4,4 ″ -dihydroxy-3, 3 ″ -dimethyl-p-terphenyl.
As the diol of m ═ 4, for example, 4 '"-dihydroxy-p-quaterphenyl, 4'" -dihydroxy-3-methyl-p-quaterphenyl, 4 '"-dihydroxy-3-ethyl-p-quaterphenyl, 4'" -dihydroxy-3-n-propyl-p-quaterphenyl, 4 '"-dihydroxy-3, 5-dimethyl-p-quaterphenyl, 4'" -dihydroxy-3, 3 '"-diethyl-p-quaterphenyl, 4'" -dihydroxy-3, 3 '"-di-n-propyl-p-quaterphenyl, 4'" -dihydroxy-3, 3' -diisopropyl-p-quaterphenyl.
Preferred examples of the diol compound represented by the general formula (2-1) include biphenyl-4, 4 ' -diol, 3,3 ' -dimethyl-biphenyl-4, 4 ' -diol, 3,3 ', 5,5 ' -tetramethyl-biphenyl-4, 4 ' -diol, 2 ', 3,3 ', 5,5 ' -hexamethyl-biphenyl-4, 4 ' -diol, 3,3 ' -dimethyl-5, 5 ' -di-tert-butyl-biphenyl-4, 4 ' -diol, 4 ' -dihydroxy-p-terphenyl, 4 ' -dihydroxy-p-terphenyl, and the like, from the viewpoints of easiness of synthesis of the diol compound as a raw material, availability of raw materials and cost of raw materials for synthesizing the diol compound, and solubility of the diol compound and its derivative in a solvent, 4,4 "-dihydroxy-3-methyl-p-terphenyl, 4" -dihydroxy-3-isopropyl-p-terphenyl, 4 ' "-dihydroxy-p-quaterphenyl, 4 '" -dihydroxy-3, 3 ' "-dimethyl-p-quaterphenyl.
In the diol compound represented by the general formula (2), when X is represented by the general formula (3-2), it is represented by the following general formula (2-2).
[ chemical formula 10]
Specific examples thereof include 1, 4-dihydroxynaphthalene, 1, 5-dihydroxynaphthalene, 1, 8-dihydroxynaphthalene, 2, 3-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, 2, 7-dihydroxynaphthalene and 2, 8-dihydroxynaphthalene.
Preferable examples of the diol compound represented by the general formula (2-2) include 1, 4-dihydroxynaphthalene, 1, 5-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, 2, 7-dihydroxynaphthalene and 2, 8-dihydroxynaphthalene. Among the diol compounds represented by the general formula (2-2), 1, 5-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene and 2, 7-dihydroxynaphthalene are more preferable, 2, 6-dihydroxynaphthalene and 2, 7-dihydroxynaphthalene are further preferable, and 2, 6-dihydroxynaphthalene is particularly preferable.
< starting materials: trimellitic anhydride halide
One of the starting materials used in the production process of the present invention is a trimellitic anhydride halide.
Examples of the trimellitic anhydride halide used in the present invention include trimellitic anhydride chloride, trimellitic anhydride bromide, trimellitic anhydride iodide, and trimellitic anhydride fluoride, and among these trimellitic anhydride halides, trimellitic anhydride chloride is preferably used from the viewpoint of low cost and good availability. The amount of the trimellitic anhydride halide used is usually 2 to 3 moles, preferably 2.1 to 2.5 moles, based on 1 mole of the diol compound represented by the general formula (2).
< As the reaction solvent >
The production method of the present invention is characterized in that the reaction is carried out in the presence of a lactone or/and nitrile having a relative dielectric constant of 25 or more. Among these solvents, the presence of lactones or nitriles is preferable from the viewpoint of reaction rate, and the presence of lactones or nitriles is more preferable from the viewpoint of reaction rate and reduction in the amount of oligomers produced as impurities. The relative dielectric constant of these solvents is preferably 30 or more, and more preferably 35 or more.
That is, when lactones having a relative dielectric constant of 25 or more are used, lactones having a relative dielectric constant of 30 or more are preferable, and lactones having a relative dielectric constant of 35 or more are more preferable. The upper limit value is preferably 55 or less, and more preferably 50 or less.
When nitriles having a relative dielectric constant of 25 or more are used, nitriles having a relative dielectric constant of 30 or more are preferable, and nitriles having a relative dielectric constant of 35 or more are more preferable. The upper limit value is preferably 55 or less, and more preferably 50 or less.
When lactones and nitriles having a relative dielectric constant of 25 or more are used, those having a relative dielectric constant of 30 or more are preferable, and those having a relative dielectric constant of 35 or more are more preferable. The upper limit value is preferably 55 or less, and more preferably 50 or less.
Specific examples of the lactone having a relative dielectric constant of 25 or more include γ -butyrolactone (relative dielectric constant: 42) and γ -valerolactone (relative dielectric constant: 34).
Examples of nitriles having a relative dielectric constant of 25 or more include acetonitrile (relative dielectric constant: 37.5), propionitrile (relative dielectric constant: 29.7), benzonitrile (relative dielectric constant: 25.2), methoxypropionitrile (relative dielectric constant: 25), and dimethoxypropionitrile (relative dielectric constant: 28).
The weight ratio of lactone and nitrile when the lactone and nitrile having a relative dielectric constant of 25 or more are used is 90/10 to 10/90, preferably 80/20 to 20/80, and more preferably 70/30 to 30/70.
Examples of the aprotic polar solvent having a relative dielectric constant of 25 or more include amides such as dimethylformamide (relative dielectric constant: 37) and dimethylacetamide (relative dielectric constant: 37.8), and lactams such as N-methylpyrrolidone (relative dielectric constant: 32.2). However, as specifically shown in the following comparative examples, it was confirmed that these aprotic polar solvents produced many impurities in the reaction of the diol compound represented by the above general formula (2) and the trimellitic anhydride halide. It is considered that the formation of the impurities is caused by the reaction of the polar aprotic solvent with the trimellitic acid halide or the acceleration of the decomposition of the trimellitic acid halide. That is, the production method using an amide or a lactam in an aprotic polar solvent having a relative dielectric constant of 25 or more is inferior to the production method of the present invention in terms of reaction selectivity.
The reaction solvent in the present invention may be used in combination with an organic solvent other than lactones or nitriles having a relative dielectric constant of 25 or more, as long as the effects of the present invention are not impaired, but is preferably composed of lactones, nitriles, or lactones and nitriles having a relative dielectric constant of 25 or more.
The amount of the reaction solvent used in the present invention is in the range of 4 to 30 times the weight of the diol compound represented by the general formula (2). The reaction solvent may be added during the reaction.
< about the base >
In the production method of the present invention, since the diol compound represented by the above general formula (2) reacts with the trimellitic anhydride halide to generate hydrogen chloride, a base that traps the hydrogen chloride is used. Such a base is not particularly limited, and organic tertiary amines such as pyridine, triethylamine and N, N-dimethylaniline, epoxies such as propylene oxide, and inorganic bases such as potassium carbonate and sodium hydroxide can be used. Among them, pyridine is preferably used from the viewpoint of separation operation after the reaction, cost, harmfulness, and the like.
< target compound: tetracarboxylic dianhydride represented by the general formula (1)
The target compound in the production method of the present invention is a tetracarboxylic dianhydride represented by the following general formula (1).
[ chemical formula 11]
(wherein X is the same as X in the general formula (2))
In the tetracarboxylic dianhydride represented by the general formula (1), X is represented by the following general formula (1-1) when X is represented by the general formula (3-1).
[ chemical formula 12]
(in the formula, R1M, n and R of the formula (3-1)1M and n are the same. )
R in the general formula (1-1)1Specific examples or preferable examples of m and n are the same as those of the above general formula (3-1).
Examples of the tetracarboxylic dianhydride represented by the general formula (1-1), specifically the tetracarboxylic dianhydride represented by m ═ 2, include biphenyl-4, 4 ' -biphenol-bis (trimellitic anhydride), 3 ' -dimethyl-biphenyl-4, 4 ' -biphenol-bis (trimellitic anhydride), 3 ' -diethyl-biphenyl-4, 4 ' -biphenol-bis (trimellitic anhydride), 3 ' -diisopropyl-biphenyl-4, 4 ' -biphenol-bis (trimellitic anhydride), 3 ', 5,5 ' -tetramethyl-biphenyl-4, 4 ' -biphenol-bis (trimellitic anhydride), 3 ', 6,6 ' -tetramethyl-biphenyl-4, 4 ' -biphenol-bis (trimellitic anhydride), 2,2 ', 3,3 ', 5,5 ' -hexamethyl-biphenyl-4, 4 ' -diol-bis (trimellitic anhydride), 3,3 ' -dimethyl-5, 5 ' -di-tert-butyl-biphenyl-4, 4 ' -diol-bis (trimellitic anhydride).
Examples of the tetracarboxylic dianhydride with m ═ 3 include 4,4 ″ -dihydroxy-p-terphenyl-bis (trimellitic anhydride), 4 ″ -dihydroxy-3-methyl-p-terphenyl-bis (trimellitic anhydride), 4 ″ -dihydroxy-3-ethyl-p-terphenyl-bis (trimellitic anhydride), 4 ″ -dihydroxy-3-n-propyl-p-terphenyl-bis (trimellitic anhydride), 4 ″ -dihydroxy-3-isopropyl-p-terphenyl-bis (trimellitic anhydride), 4 ″ -dihydroxy-3, 5-dimethyl-p-terphenyl-bis (trimellitic anhydride), 4 ″ -dihydroxy-3, 3' -dimethyl-p-terphenyl-bis (trimellitic anhydride).
As the tetracarboxylic dianhydride of m ═ 4, for example, 4 '"-dihydroxy-p-quaterphenyl-bis (trimellitic anhydride), 4'" -dihydroxy-3-methyl-p-quaterphenyl-bis (trimellitic anhydride), 4 '"-dihydroxy-3-ethyl-p-quaterphenyl-bis (trimellitic anhydride), 4'" -dihydroxy-3-n-propyl-p-quaterphenyl-bis (trimellitic anhydride), 4 '"-dihydroxy-3, 5-dimethyl-p-quaterphenyl-bis (trimellitic anhydride), 4'" -dihydroxy-3, 3 '"-dimethyl-p-quaterphenyl-bis (trimellitic anhydride), 4'" -dihydroxy-3, 3 ' -diethyl-p-quaterphenyl-bis (trimellitic anhydride), 4 ' -dihydroxy-3, 3 ' -di-n-propyl-p-quaterphenyl-bis (trimellitic anhydride), 4 ' -dihydroxy-3, 3 ' -diisopropyl-p-quaterphenyl-bis (trimellitic anhydride).
Preferred examples of the tetracarboxylic dianhydride represented by the general formula (1-1) include biphenyl-4, 4 ' -biphenol-bis (trimellitic anhydride), 3,3 ' -dimethyl-biphenyl-4, 4 ' -biphenol-bis (trimellitic anhydride), 3,3 ', 5,5 ' -tetramethyl-biphenyl-4, 4 ' -biphenol-bis (trimellitic anhydride), 2 ', 3,3 ', 5,5 ' -hexamethyl-biphenyl-4, 4 ' -biphenol-bis (trimellitic anhydride), and 3,3 ' -dimethyl-5 from the viewpoints of easiness of synthesis of the diol as a raw material, availability of raw materials and cost of raw materials for synthesizing the diol, and solubility of the diol and its derivative in a solvent, 5 '-di-tert-butyl-biphenyl-4, 4' -diol-bis (trimellitic anhydride), 4 "-dihydroxy-p-terphenyl-bis (trimellitic anhydride), 4" -dihydroxy-3-methyl-p-terphenyl-bis (trimellitic anhydride), 4 "-dihydroxy-3-isopropyl-p-terphenyl-bis (trimellitic anhydride), 4" -dihydroxy-p-quaterphenyl-bis (trimellitic anhydride), 4 '"-dihydroxy-3, 3'" -dimethyl-p-quaterphenyl-bis (trimellitic anhydride).
In the tetracarboxylic dianhydride represented by the general formula (1), X is represented by the following general formula (1-2) when X is represented by the general formula (3-2).
[ chemical formula 13]
Specific examples of the tetracarboxylic dianhydride represented by the general formula (1-2) include 1, 4-naphthalenediol-bis (trimellitic anhydride), 1, 5-naphthalenediol-bis (trimellitic anhydride), 1, 8-naphthalenediol-bis (trimellitic anhydride), 2, 3-naphthalenediol-bis (trimellitic anhydride), 2, 6-naphthalenediol-bis (trimellitic anhydride), 2, 7-naphthalenediol-bis (trimellitic anhydride), 2, 8-naphthalenediol-bis (trimellitic anhydride), and the like.
Among the tetracarboxylic dianhydrides represented by the general formula (1-2), 1, 4-naphthalenediol-bis (trimellitic anhydride), 1, 5-naphthalenediol-bis (trimellitic anhydride), 2, 6-naphthalenediol-bis (trimellitic anhydride), 2, 7-naphthalenediol-bis (trimellitic anhydride) are preferable, 2, 8-naphthalenediol-bis (trimellitic anhydride), more preferably 1, 5-naphthalenediol-bis (trimellitic anhydride), 2, 6-naphthalenediol-bis (trimellitic anhydride) and 2, 7-naphthalenediol-bis (trimellitic anhydride), further preferably 2, 6-naphthalenediol-bis (trimellitic anhydride), 2, 7-naphthalenediol-bis (trimellitic anhydride), and particularly preferably 2, 6-naphthalenediol-bis (trimellitic anhydride).
< regarding the reaction conditions >
The reaction is started by mixing a solution of a lactone or/and a nitrile having a relative dielectric constant of 25 or more of a diol compound represented by the general formula (2) with a trimellitic anhydride chloride dissolved in the lactone or/and nitrile having a relative dielectric constant of 25 or more. In this case, a base such as pyridine is contained in the mixed solution, that is, the solution on the side of the diol compound represented by the general formula (2). In contrast to the mixing method described above, when a trimellitic anhydride chloride solution is mixed with a solution of a diol compound represented by the general formula (2), by-products are more easily produced than in the mixing method described above. Therefore, the former mixing method is preferable.
The molar ratio of the starting material to the base used in the reaction is preferably in the range of 1.0/2.1 to 2.5/3.0 to 5.0 for the diol compound represented by the general formula (2)/trimellitic anhydride chloride/base.
The mixing of the above solutions is performed at low temperature. The temperature in the reaction system is preferably in the range of-10 to 10 ℃, more preferably in the range of-5 to 7 ℃, and particularly preferably in the range of 0 to 5 ℃. The time for mixing is not limited, and preferably 2 to 4 hours.
The stirring immediately after the completion of the mixing (hereinafter, sometimes referred to as "post-stirring 1") is continued at a low temperature, preferably at a temperature within the reaction system of-10 to 10 ℃, more preferably at a temperature within the range of-5 to 7 ℃, and particularly preferably at a temperature within the range of 0 to 5 ℃. The "post-stirring 1" is preferably carried out at such a temperature range for approximately 5 hours or less, more preferably 2 to 3 hours.
After the "post-stirring 1", the reaction may be completed by further continuing the stirring at a temperature higher than that of the "post-stirring 1" (hereinafter, sometimes referred to as "post-stirring 2") in order to promote the reaction. The "post-stirring 2" is preferably carried out at a temperature within the reaction system within a range of 20 to 75 ℃, more preferably within a range of 20 to 70 ℃, and particularly preferably within a range of 25 to 65 ℃. The "post-stirring 2" is preferably carried out at such a temperature range for approximately 5 hours or less, more preferably 2 to 3 hours.
After the completion of the reaction, a conventionally known method can be used to isolate the target compound, and examples thereof include a method in which a precipitate existing after the completion of the reaction or precipitated after cooling is collected by filtration and the precipitate is washed with water, an organic solvent, or the like.
Examples
The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.
The reaction selectivity in the following examples was analyzed by the following method.
< analytical method >
1. Gel permeation chromatography
The device comprises the following steps: high-speed GPC apparatus HLC-8320GPC manufactured by Tosoh corporation
A chromatographic column: TSKgel guardcolum HXL-L1 branch,
TSKgel G2000HXL 2 branch,
TSKgel G3000HXL 1 branch,
TSKgel G4000HXL 1 branch,
Mobile phase solvent: tetrahydrofuran (THF)
Flow rate: pump Sam.1.0ml/min, Ref.Sam. 1/3
Temperature of the column: fixation at 40 deg.C
A detector: RI (Ri)
< reaction selectivity >
(1) Reaction selectivity of target Compound
Reaction selectivity ═ area% of the target compound (tetracarboxylic dianhydride represented by general formula (1))/(100 [% ] - (area% of diol compound represented by general formula (2) + area% of trimellitic anhydride halide +% of trimellitic acid)) × 100 ×
(2) Reaction selectivity of impurity oligomers
Reaction selectivity ═ area% of impurity oligomer/(% area of 100- (diol compound represented by general formula (2) + area% of trimellitic anhydride halide + area% of trimellitic acid)) × 100
< example 1 >
[ chemical formula 14]
A four-necked flask equipped with a thermometer, a stirrer and a cooling tube was charged with 48.4g (0.23mol) of trimellitic anhydride chloride (b) and 143.0g of acetonitrile (relative dielectric constant: 37.5), and the mixture was cooled to 5 ℃ or lower by replacing nitrogen in the flask while stirring and dissolving. Then, while keeping the temperature in the flask at 5 ℃ or lower, the mixture was used for 2 hours, and a preparation solution in which 27.0g (0.10mol) of the diol compound (a), 182.2g of acetonitrile, and 39.8g (0.50mol) of pyridine in the reaction formula were dissolved was added dropwise into the flask at a constant rate. After completion of the dropwise addition, the mixture was stirred at 5 ℃ or lower for 2 hours (after-stirring 1). The reaction solution at this time was analyzed by Gel Permeation Chromatography (GPC), and as a result, the objective compound (c) in the above reaction formula was 92.2% (RI area% reaction selectivity by GPC: the same applies hereinafter), and the impurity oligomer was 1.2%.
Then, the temperature was raised to 65 ℃ and stirred for 3 hours (poststirring 2). The reaction solution was analyzed by Gel Permeation Chromatography (GPC), and as a result, the target compound (c) was 95.9% and the impurity oligomer was 1.6% in the above reaction formula.
The impurities formed as by-products in the above reaction are estimated to be oligomers having the following chemical structures, as is clear from the results of Gel Permeation Chromatography (GPC) analysis, since they have a higher molecular weight than the target compound (c).
[ chemical formula 15]
< example 2 >
The reaction was carried out in the same manner as in example 1 except that the solvent was changed to γ -butyrolactone (relative dielectric constant: 42).
When the reaction solution after completion of the post-stirring 1 was analyzed by Gel Permeation Chromatography (GPC), the target compound (c) was 97.3% and the impurity oligomer was 2.6% in the above reaction formula.
Further, the reaction-completed liquid after the stirring 2 was analyzed by Gel Permeation Chromatography (GPC), and as a result, the target compound (c) was 96.9% and the impurity oligomer was 2.8% in the above reaction formula.
< example 3 >
The reaction was carried out in the same manner as in example 1 except that the solvent was changed to a mixed solvent in which the weight ratio of acetonitrile (relative dielectric constant: 37.5) to γ -butyrolactone (relative dielectric constant: 42) was 1 to 1.
When the reaction solution after completion of the post-stirring 1 was analyzed by Gel Permeation Chromatography (GPC), the target compound (c) was 96.8% and the impurity oligomer was 2.0% in the above reaction formula.
Further, the reaction-completed liquid after the stirring 2 was analyzed by Gel Permeation Chromatography (GPC), and as a result, the target compound (c) was 96.8% and the impurity oligomer was 2.0% in the above reaction formula.
< comparative example 1 >
The reaction was carried out in the same manner as in example 1 except that the solvent was changed to tetrahydrofuran (relative dielectric constant: 7.6).
When the reaction solution after completion of the post-stirring 1 was analyzed by Gel Permeation Chromatography (GPC), the target compound (c) was 57.4% and the impurity oligomer was 4.1% in the above reaction formula.
Further, the reaction-completed liquid after the post-stirring 2 was analyzed by Gel Permeation Chromatography (GPC), and as a result, the target compound (c) was 88.1% and the impurity oligomer was 9.8% in the above reaction formula.
< comparative example 2 >
The reaction was carried out in the same manner as in example 1 except that the solvent was changed to toluene (relative dielectric constant: 2.4).
When the reaction solution after completion of the post-stirring 1 was analyzed by Gel Permeation Chromatography (GPC), the target compound (c) was 67.3% and the impurity oligomer was 7.1% in the above reaction formula.
Further, the reaction-completed liquid after the post-stirring 2 was analyzed by Gel Permeation Chromatography (GPC), and as a result, the target compound (c) was 81.5% and the impurity oligomer was 12.4% in the above reaction formula.
< comparative example 3 >
The reaction was carried out in the same manner as in example 1 except that the solvent was changed to N-methylpyrrolidone (relative dielectric constant: 32.2).
When the reaction solution after completion of the post-stirring 1 was analyzed by Gel Permeation Chromatography (GPC), the target compound (c) was 73.6% and the impurity oligomer was 4.6% in the above reaction formula.
Further, the reaction-completed liquid after the stirring 2 was analyzed by Gel Permeation Chromatography (GPC), and as a result, the target compound (c) was 88.9% and the impurity oligomer was 9.2% in the above reaction formula.
< comparative example 4 >
The reaction was carried out in the same manner as in example 1 except that the solvent was changed to dimethylacetamide (relative dielectric constant: 37.8), and after completion of the dropwise addition, the mixture was stirred at 5 ℃ or lower for 2 hours.
The reaction solution at this time was analyzed by Gel Permeation Chromatography (GPC), and as a result, the target compound (c) was 49.4% and the impurity oligomer was 5.7% in the above reaction formula.
< investigation on reaction Selectivity >
From the results of examples 1 to 3 and comparative examples 1 to 4, it was confirmed that the production method of the present invention, in which the reaction is carried out in the presence of lactones or/and nitriles having a relative dielectric constant of 25 or more, is an industrially advantageous production method because the reaction selectivity of the tetracarboxylic dianhydride represented by the general formula (1) is high, the production of impurity oligomers is suppressed, and the like. It is clear that the reaction in the presence of nitriles having a relative dielectric constant of 25 or more (example 1) is excellent in suppressing the formation of oligomers as impurities, and the reaction in the presence of lactones having a relative dielectric constant of 25 or more (example 2) is excellent in the effect of increasing the reaction rate. In particular, it was confirmed that when the reaction is carried out in the presence of lactones and nitriles having a relative dielectric constant of 25 or more (example 3), a very excellent effect of increasing the reaction rate and suppressing the formation of impurity oligomers can be obtained.
On the other hand, it is also clear that when the reaction is carried out in the presence of a solvent other than lactones or nitriles having a relative dielectric constant of 25 or more, the reaction rate is slow, the production of impurity oligomers is not suppressed, and the reaction selectivity is low, and therefore, it is inferior as an industrial production method.
< example 4 >
[ chemical formula 16]
A four-necked flask equipped with a thermometer, a stirrer and a cooling tube was charged with 48.4g (0.23mol) of trimellitic anhydride chloride (b) and 112.6g of acetonitrile (relative dielectric constant: 37.5), and the mixture was dissolved with stirring and nitrogen-substituted in the vessel, followed by cooling to 5 ℃ or lower. Then, 16.0g (0.10mol) of the diol compound (d) in the above reaction formula, 143.4g of acetonitrile (relative dielectric constant: 37.5) and 39.6g (0.50mol) of pyridine were dissolved in the flask, and the mixture was dropped into the flask at a constant rate over a period of 2 hours while keeping the temperature in the flask at 5 ℃ or lower. After completion of the dropwise addition, the mixture was stirred at 5 ℃ or lower for 2 hours (after-stirring 1). The reaction solution at this time was analyzed by Gel Permeation Chromatography (GPC), and as a result, the objective compound (e) in the above reaction formula was 98.2% (RI area% reaction selectivity by GPC: the same applies hereinafter), and the impurity oligomer was 0.7%. Then, the temperature was raised to 65 ℃ and stirred for 2 hours (poststirring 2). The reaction solution was analyzed by Gel Permeation Chromatography (GPC), and as a result, the target compound (e) was 98.5% and the impurity oligomer was 0.7% in the above reaction formula.
The impurities formed as by-products in the above reaction are estimated to be oligomers having the following chemical structures, as is clear from the results of Gel Permeation Chromatography (GPC) analysis, since they have a higher molecular weight than the target compound (e).
[ chemical formula 17]
< example 5 >
The reaction was carried out in the same manner as in example 4 except that the solvent was changed to a mixed solvent in which the weight ratio of acetonitrile (relative dielectric constant: 37.5) to γ -butyrolactone (relative dielectric constant: 42) was 1 to 1.
When the reaction solution after completion of the post-stirring 1 was analyzed by Gel Permeation Chromatography (GPC), the target compound (e) was 98.6% and the impurity oligomer was 0.5% in the above reaction formula.
Further, the reaction-completed liquid after the stirring 2 was analyzed by Gel Permeation Chromatography (GPC), and as a result, the target compound (e) was 98.9% and the impurity oligomer was 0.5% in the above reaction formula.
< comparative example 5 >
The reaction was carried out in the same manner as in example 4 except that the solvent was changed to tetrahydrofuran (relative dielectric constant: 7.6).
When the reaction solution after completion of the post-stirring 1 was analyzed by Gel Permeation Chromatography (GPC), the target compound (e) was 95.4% and the impurity oligomer was 1.5% in the above reaction formula.
Further, the reaction-completed liquid after the post-stirring 2 was analyzed by Gel Permeation Chromatography (GPC), and as a result, the target compound (e) was 97.8% and the impurity oligomer was 1.5% in the above reaction formula.
< investigation on reaction Selectivity >
As is clear from the results of examples 4 and 5 and comparative example 5, the production method of the present invention in which the reaction is carried out in the presence of lactones or/and nitriles having a relative dielectric constant of 25 or more was confirmed to be an industrially advantageous production method because the reaction selectivity of tetracarboxylic dianhydride represented by the general formula (1) is high, the production of impurity oligomers is suppressed, and the reaction rate-improving effect is excellent, even when the diol compound represented by the general formula (2) is changed to the diol compound (d). In particular, it was confirmed that when the reaction is carried out in the presence of lactones and nitriles having a relative dielectric constant of 25 or more (example 5), a very excellent effect of increasing the reaction rate and suppressing the formation of impurity oligomers can be obtained.
On the other hand, it was also confirmed that when the reaction is carried out in the presence of a solvent other than lactones or nitriles having a relative dielectric constant of 25 or more (comparative example 5), the reaction rate is slow, the production of impurity oligomers is not suppressed, and the reaction selectivity is low, and therefore, the method is inferior as an industrial production method.
< example 6 >
[ chemical formula 18]
A four-necked flask equipped with a thermometer, a stirrer and a cooling tube was charged with 112.6g of a mixed solvent of trimellitic anhydride chloride (b)48.4g (0.23mol) and acetonitrile (relative dielectric constant: 37.5) and γ -butyrolactone (relative dielectric constant: 42) in a weight ratio of 1 to 1, and the mixture was cooled to 5 ℃ or lower while stirring and dissolving the mixed solvent in the vessel with nitrogen substitution. Then, while keeping the temperature in the flask at 5 ℃ or lower, the mixture was used for 2 hours, and a mixed solvent of 16.0g (0.10mol) of the diol compound (f) in the reaction formula, 143.4g of a mixed solvent of acetonitrile (relative dielectric constant: 37.5) and γ -butyrolactone (relative dielectric constant: 42) in a weight ratio of 1 to 1, and 39.6g (0.50mol) of pyridine were dissolved in the flask, and the mixture was added dropwise thereto at a constant rate. After completion of the dropwise addition, the mixture was stirred at 5 ℃ or lower for 2 hours (after-stirring 1). The reaction solution at this time was analyzed by Gel Permeation Chromatography (GPC), and as a result, the objective compound (g) in the above reaction formula was 98.3% (RI area% reaction selectivity by GPC: the same applies hereinafter), and the impurity oligomer was 0.9%. Then, the temperature was raised to 65 ℃ and stirred for 2 hours (poststirring 2). The reaction solution was analyzed by Gel Permeation Chromatography (GPC), and as a result, the target compound (g) in the reaction formula was 98.4% and the impurity oligomer was 0.8%.
The impurities formed as by-products in the above reaction are estimated to be oligomers having the following chemical structures, as is clear from the results of Gel Permeation Chromatography (GPC) analysis, since they have a larger molecular weight than the target compound (g).
[ chemical formula 19]
< comparative example 6 >
A reaction was carried out in the same manner as in example 6 except that the solvent was changed to tetrahydrofuran (relative dielectric constant: 7.6).
When the reaction solution after completion of the post-stirring 1 was analyzed by Gel Permeation Chromatography (GPC), the target compound (g) in the reaction formula was 95.7%, and the impurity oligomer was 2.0%.
Further, the reaction-completed liquid after the post-stirring 2 was analyzed by Gel Permeation Chromatography (GPC), and as a result, the target compound (g) in the reaction formula was 97.1% and the impurity oligomer was 1.9%.
< investigation on reaction Selectivity >
From the results of example 6 and comparative example 6, it was confirmed that when the reaction is carried out in the presence of lactones and nitriles having a relative dielectric constant of 25 or more (example 6), extremely excellent effects of increasing the reaction rate and suppressing the production of impurity oligomers can be obtained.
On the other hand, it was also confirmed that when the reaction is carried out in the presence of a solvent other than lactones or nitriles having a relative dielectric constant of 25 or more (comparative example 6), the reaction rate is slow, the production of impurity oligomers is not suppressed, and the reaction selectivity is low, and therefore, the method is inferior as an industrial production method.
Claims (1)
1. A process for producing a tetracarboxylic dianhydride represented by the following general formula (1), characterized by reacting a diol compound represented by the following general formula (2) with a trimellitic anhydride halide in the presence of a lactone or/and nitrile having a relative dielectric constant of 25 or more,
[ chemical formula 1]
HO-X-OH (2)
Wherein X represents a divalent group represented by the following general formula (3-1) or the following general formula (3-2);
[ chemical formula 2]
In the formula, R1Represents a linear or branched alkyl group having 1 to 6 carbon atoms, m represents an integer of 2 to 4, n represents an integer of 0 to 4, and represents a bonding position;
[ chemical formula 3]
Wherein, represents a bonding site;
[ chemical formula 4]
Wherein X is the same as X in the general formula (2).
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| PCT/JP2020/016653 WO2020218134A1 (en) | 2019-04-24 | 2020-04-16 | Method for producing tetracarboxylic acid dianhydride |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090306329A1 (en) * | 2007-01-26 | 2009-12-10 | Honshu Chemical Industry Co., Ltd. | Novel ester group-containing tetracarboxylic acid dianhydride, novel polyesterimide precursor derived therefrom, and polyesterimide |
| JP2010001250A (en) * | 2008-06-20 | 2010-01-07 | Air Water Inc | METHOD FOR PRODUCING p-PHENYLENE-BIS (TRIMELLITIC ACID MONOESTER ACID ANHYDRIDE) |
| JP2011006330A (en) * | 2009-06-23 | 2011-01-13 | Air Water Inc | Method for producing aromatic carboxylic acid dianhydride having ester group |
| WO2015151924A1 (en) * | 2014-03-31 | 2015-10-08 | 日産化学工業株式会社 | Acid dianhydride and use thereof |
| JP2017173454A (en) * | 2016-03-22 | 2017-09-28 | Jsr株式会社 | Liquid crystal aligning agent, liquid crystal alignment film and production method of the same, liquid crystal element, polymer and compound |
| JP2017203005A (en) * | 2016-05-12 | 2017-11-16 | 田岡化学工業株式会社 | Manufacturing method of tetracarboxylic acid dianhydride having ester group |
| CN109305949A (en) * | 2017-07-28 | 2019-02-05 | 三星电子株式会社 | Monomer, polymer, compensation film, optical film and display equipment |
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| JPH0745485B2 (en) | 1987-06-05 | 1995-05-17 | 東洋インキ製造株式会社 | Process for producing ester carboxylic acid anhydrides |
| DE19548453A1 (en) * | 1995-12-22 | 1997-06-26 | Bayer Ag | Process for the preparation of polycyclic compounds |
| JPH1036506A (en) * | 1996-07-18 | 1998-02-10 | Kanegafuchi Chem Ind Co Ltd | New polyimide composition and polyimide film |
| JP2004285364A (en) | 2004-06-07 | 2004-10-14 | Kaneka Corp | Base film for flexible printed circuit board, polyimide film usable for carrier tape for tab |
-
2020
- 2020-04-16 CN CN202080025972.XA patent/CN113646302A/en active Pending
- 2020-04-16 KR KR1020217031843A patent/KR20220004021A/en not_active Application Discontinuation
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090306329A1 (en) * | 2007-01-26 | 2009-12-10 | Honshu Chemical Industry Co., Ltd. | Novel ester group-containing tetracarboxylic acid dianhydride, novel polyesterimide precursor derived therefrom, and polyesterimide |
| JP2010001250A (en) * | 2008-06-20 | 2010-01-07 | Air Water Inc | METHOD FOR PRODUCING p-PHENYLENE-BIS (TRIMELLITIC ACID MONOESTER ACID ANHYDRIDE) |
| JP2011006330A (en) * | 2009-06-23 | 2011-01-13 | Air Water Inc | Method for producing aromatic carboxylic acid dianhydride having ester group |
| WO2015151924A1 (en) * | 2014-03-31 | 2015-10-08 | 日産化学工業株式会社 | Acid dianhydride and use thereof |
| JP2017173454A (en) * | 2016-03-22 | 2017-09-28 | Jsr株式会社 | Liquid crystal aligning agent, liquid crystal alignment film and production method of the same, liquid crystal element, polymer and compound |
| JP2017203005A (en) * | 2016-05-12 | 2017-11-16 | 田岡化学工業株式会社 | Manufacturing method of tetracarboxylic acid dianhydride having ester group |
| CN109305949A (en) * | 2017-07-28 | 2019-02-05 | 三星电子株式会社 | Monomer, polymer, compensation film, optical film and display equipment |
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| TW202104200A (en) | 2021-02-01 |
| WO2020218134A1 (en) | 2020-10-29 |
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