JP2010053070A - Bisimide phenol compound, method for producing the same, and polymer compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a bisimide phenol compound useful as a starting monomer of a heat resistant polymeric material, having an imide group expected to improve heat resistance of a resulting resin, solubility sufficient for a reaction in a common ketonic solvent, and a sufficient content of the imide group by virtue of the simplified molecular structure thereof. <P>SOLUTION: The bisimide phenol compound is represented by formula (I) (in the formula, R<SB>1</SB>represents a functional group of ¾α¾ of ≥45° and ≤90° with ¾α¾ being an absolute value of a dihedral angle α formed by a pair of conjugate planes, according to the theoretical calculation of the most stable structure; R<SB>5</SB>represents a hydrogen atom or a functional group of ¾α¾ of ≥0° and <45°; R<SB>2</SB>, R<SB>3</SB>, R<SB>4</SB>each represents a hydrogen atom, a hydroxy group or a 1-10C organic group; R<SB>6</SB>represents a 1-10C organic group; X represents a single bond, a 1-20C organic group, -O- or -SO<SB>2</SB>-; n is 0 to 3; provided that none of R<SB>1</SB>to R<SB>6</SB>is a halogen atom and one of R<SB>2</SB>to R<SB>5</SB>is a hydroxy group). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a novel bisimidephenol compound, a method for producing the same, and a polymer compound obtained by polymerizing the bisimidephenol compound as at least a part of a monomer.

  An imide compound is known to have excellent heat resistance, and an imide phenol compound into which an imide group has been introduced is useful as a raw material for a polymer material that requires heat resistance. A typical heat-resistant polymer material is an aromatic polyimide resin, but it has a very high melting point and very low solubility in common organic solvents (eg, ketones), making it workable and workable. There are many problems. For example, in order to use polyimide as a solution, a highly polar solvent such as N-methylpyrrolidone is required, but a highly polar solvent such as N-methylpyrrolidone has a very high boiling point and is difficult to remove. There are problems such as being likely to cause blisters in the subsequent process.

  As a countermeasure against this, a method is known in which a solution of polyamic acid, which is a precursor of polyimide, is used, and after removing the solvent, the imide ring is closed by heating or a chemical method to form a polyimide resin (Non-Patent Document 1). However, this method has problems such as warping due to volumetric shrinkage during ring closure.

  On the other hand, the method of using a bisimide phenol compound as a monomer is also disclosed (patent documents 1 to 4). However, the bisimide phenol compounds known so far are not sufficiently soluble in common organic solvents such as ketone solvents, and the molecular structure is complicated to impart solubility. The concentration of the imide group may decrease.

In addition, there is an example in which an ester group is introduced into the main chain to increase the solubility (Patent Document 5), but the ester group is not preferable because of the problem of hydrolysis.
JP-A-1-319528 Japanese Patent Laid-Open No. 2-70722 Japanese Patent Laid-Open No. 3-209858 JP 2007-91799 A JP 2003-82101 A "Development of heat-resistant polymer electronic materials", CMC Publishing, 2008, p. 92

  The present invention has been made in view of such circumstances, and the problem is that it contains an imide group that is expected to improve the heat resistance of the resin, and has sufficient solubility for reactions in general ketone solvents. Another object of the present invention is to provide an aromatic bisimidephenol compound useful as a raw material monomer for a heat-resistant polymer material having a sufficient imide group content due to a simplified molecular structure.

  As a result of intensive studies, the present inventors have found a bisimidephenol compound that exhibits a sufficient solubility in a ketone solvent by having a specific structure. Moreover, it discovered that this bisimide phenol compound could be manufactured by making a specific aminophenol compound and aromatic carboxylic dianhydride react.

  That is, the gist of the present invention resides in a bisimidephenol compound represented by the following general formula (I).

(In general formula (I), R ₁ represents a monovalent functional group in which | α | defined below is 45 ° or more and 90 ° or less, and R ₅ is a hydrogen atom or defined below. | Α | represents a monovalent functional group with 0 ° or more and less than 45 °.
R ₂ , R _3, and R ₄ each independently represent a hydrogen atom, a hydroxyl group, or an organic group having 1 to 10 carbon atoms. A ring may be formed.
R ₆ represents an organic group having 1 to 10 carbon atoms, but two adjacent groups may be bonded to form a ring having 20 or less carbon atoms condensed with a benzene ring.
X represents a single bond, an optionally substituted divalent organic group having 1 to 20 carbon atoms, —O— or —SO ₂ —.
n is an integer of 0-3.
The plurality of R _{1 to} R ₆ may be the same as or different from each other. However, R _{1 to} R ₆ are not halogen atoms, and any one of R _{2 to} R ₅ is a hydroxyl group, so that the compound has two hydroxyl groups. )

{Definition of ||
| Α | is the absolute value of the dihedral angle α formed by two conjugate planes when the most stable structure based on theoretical calculation is calculated in the structure represented by the following formula (I-1).

（式中、ＲはＲ_１又はＲ_５に該当する。）

(In the formula, R corresponds to R ₁ or R _5. )

Here, the theoretical calculation of the dihedral angle is performed using the AM1 method using “Microsoft Windows XP Professional Version 2002 Service Pack 2” as the OS and “Gaussian 03 x86-Win32 version Rev.B.05” as the software. This is done by calculating the most stable structure by specifying “opt = verytight” as an option).
α is the following four types (1) to (4) consisting of four adjacent atoms, C (carbonyl carbon of imide) -N (imide nitrogen) -C (aromatic ring) -C (aromatic ring) Of the dihedral angles, the absolute value is the smallest. C ^{1 to} C ⁵ are represented by the following formula (I-Ia).
^{(1) C 1 -C 2 -N} -C 4
(2) C ¹ -C ² -N-C ^{5
(3) C 3 -C 2 -N} -C 4
^{(4) C 3 -C 2 -N} -C 5

（式中、ＲはＲ_１又はＲ_５に該当する。）

(In the formula, R corresponds to R ₁ or R _5. )

  Another gist of the present invention is characterized by dehydrating condensation of an aminophenol represented by the following general formula (II) and an aromatic carboxylic dianhydride represented by the following general formula (III): The manufacturing method of the said bisimide phenol compound exists.

（一般式（II）において、Ｒ_１〜Ｒ_５はそれぞれ一般式（Ｉ）におけると同義である。）

(In general formula (II), R _{1 to} R ₅ have the same meanings as in general formula (I).)

（一般式(III)において、Ｘ、Ｒ_６及びｎはそれぞれ一般式（Ｉ）におけると同義である。）

(In general formula (III), X, R ₆ and n have the same meanings as in general formula (I).)

  Still another subject matter of the present invention resides in a polymer compound obtained by polymerizing the bisimidephenol compound as at least a part of a monomer.

According to the present invention, it is a bisimide phenol compound containing an imide group that is expected to improve the heat resistance of a resin, has sufficient solvent solubility for reaction in a general ketone solvent, and is simple. Provided is a novel aromatic bisimidephenol compound useful as a raw material monomer for a heat-resistant polymer material having a sufficient imide group content due to the converted molecular structure.
Moreover, since the bisimidephenol compound of the present invention is a non-halogen compound containing no halogen atom, it is very suitable in the recent dehalogenation flow.

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

[Bisimidophenol compounds]
The bisimidophenol compound of the present invention is represented by the following general formula (I), and has high solubility in a ketone solvent, so that it is excellent in handling property in polymerization reaction and the like, and the imide group concentration in the molecule Therefore, it is useful as a raw material monomer for imparting heat resistance to epoxy resins, polyester resins, polycarbonate resins, phenol resins and the like.

(In general formula (I), R ₁ represents a monovalent functional group in which | α | defined below is 45 ° or more and 90 ° or less, and R ₅ is a hydrogen atom or defined below. | Α | represents a monovalent functional group with 0 ° or more and less than 45 °.
R ₂ , R _3, and R ₄ each independently represent a hydrogen atom, a hydroxyl group, or an organic group having 1 to 10 carbon atoms. A ring may be formed.
R ₆ represents an organic group having 1 to 10 carbon atoms, but two adjacent groups may be bonded to form a ring having 20 or less carbon atoms condensed with a benzene ring.
X represents a single bond, an optionally substituted divalent organic group having 1 to 20 carbon atoms, —O— or —SO ₂ —.
n is an integer of 0-3.
The plurality of R _{1 to} R ₆ may be the same as or different from each other. However, R _{1 to} R ₆ are not halogen atoms, and any one of R _{2 to} R ₅ is a hydroxyl group, so that the compound has two hydroxyl groups. )

{Definition of ||
| Α | is the absolute value of the dihedral angle α formed by two conjugate planes when the most stable structure based on theoretical calculation is calculated in the structure represented by the following formula (I-1).

（式中、ＲはＲ_１又はＲ_５に該当する。）

(In the formula, R corresponds to R ₁ or R _5. )

Here, the theoretical calculation of the dihedral angle is performed using the AM1 method using “Microsoft Windows XP Professional Version 2002 Service Pack 2” as the OS and “Gaussian 03 x86-Win32 version Rev.B.05” as the software. This is done by calculating the most stable structure by specifying “opt = verytight” as an option).
α is the following four types (1) to (4) consisting of four adjacent atoms, C (carbonyl carbon of imide) -N (imide nitrogen) -C (aromatic ring) -C (aromatic ring) Of the dihedral angles, the absolute value is the smallest. C ^{1 to} C ⁵ are represented by the following formula (I-Ia).
^{(1) C 1 -C 2 -N} -C 4
(2) C ¹ -C ² -N-C ^{5
(3) C 3 -C 2 -N} -C 4
^{(4) C 3 -C 2 -N} -C 5

（式中、ＲはＲ_１又はＲ_５に該当する。）

(In the formula, R corresponds to R ₁ or R _5. )

  In the present invention, “organic group” is a group containing a carbon atom, and “functional group” is a general term for an organic group and an inorganic group such as a hydroxyl group.

<Explanation of solubility expression>
Imide group-containing compounds, especially aromatic imide compounds, have excellent physical properties due to strong cohesion due to stacking of conjugated planes containing imide groups, but have very low solvent solubility and are difficult to handle. .

Although the details of the reason why the bisimidephenol compound of the present invention is excellent in solubility in a solvent are not clear, it is estimated as follows.
(1) By having the substituent R ₁ having an appropriate size at the ortho position of the imide group, the conjugate plane containing the imide group has a twist, and stacking between molecules is appropriately inhibited.
(2) Both ortho positions of the imide group are asymmetric (R ₁ ≠ R ₅ ), so that the crystallinity is lowered.

In the bisimide phenol compound of the present invention, good solvent solubility is exhibited by these factors acting in concert.
However, if the substituent R ₁ that causes twisting is too large, stacking between molecules, which is a feature of the imide compound, may be completely inhibited, and sufficient physical properties may not be obtained. R ₁ is preferably kept at an appropriate size.

<R ₁ >
R ₁ is a monovalent functional group other than a halogen atom having the above | α | of 45 ° or more and 90 ° or less. Of R ₁ | α | lower limit, since the overlapping solvent solubility decreases hardly occurs due to the intermolecular, preferably 48 °, more preferably 51 °. On the other hand, the upper limit of | α | is preferably 75 °, more preferably 60 °, because the substituent has an appropriate size at which stacking between molecules, which is a characteristic of an imide compound, occurs.

R ₁ satisfies the above | α | and easily develops the imide group concentration in the carbon imide phenol molecule and the physical properties expected of the imide compound, that is, the molecular weight is not excessively large. The organic group having 1 to 10 carbon atoms is considered to have sufficient group content and the physical properties expected of the imide compound are not impaired by the intermolecular interaction being inhibited by steric hindrance. Is preferable, an organic group having 1 to 3 carbon atoms is more preferable, and an organic group having 1 to 2 carbon atoms is particularly preferable.

Specific examples of R ₁ include a hydrocarbon group, an aromatic group, an acyl group (aldehyde, ketone), a carboxyl group, an alkoxycarbonyl group (ester), an alkoxyl group, an allyloxyl group, an optionally substituted amino group, An optionally substituted carboxamide group, mercapto group, alkylthio group, arylthio group, sulfinyl group, sulfonyl group, sulfo group, trialkylsilyl group and the like can be mentioned. Among them, since | α | is a suitable range, it is a linear or secondary hydrocarbon group, acyl group (aldehyde, ketone), carboxyl group, alkoxycarbonyl group (ester), alkoxyl group, aryloxyl group, substituted Amino group, substituted carboxamide group, mercapto group, alkylthio group, arylthio group, sulfinyl group, sulfonyl group, sulfo group are preferred, and in particular, linear hydrocarbon group, acyl group excluding formyl group, carboxyl group, Alkoxycarbonyl groups (esters), substituted amino groups, sulfonyl groups and sulfo groups are preferred.

In addition, the functional groups having | α | of 45 to 90 ° are shown in Table 1, and among these functional groups particularly suitable as R ₁ (| α | = 48 to 75 °), Table 2 together with the | α | (In the following, Ph represents a phenyl group, Me represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, and Bu represents a butyl group).

Of the functional groups shown in Table 2, R ₁ is particularly preferably those shown in Table 3 below (| α | = 51-60 °).

<R ₅ >
R ₅ is a hydrogen atom or a monovalent functional group other than a halogen atom having the above | α | of 0 ° or more and less than 45 °. | Α | is 0 ° when R ₅ is a substituent having Lewis acidity that strongly interacts with the carbonyl oxygen of the imide group. In such a case, the formation of a dihedral angle by R ₁ is R ₅ inhibits, since there may not be enough solubility, | alpha | lower limit is preferably 10 °, more preferably 20 °. In addition, since a substituent that causes a large twist may further increase the dihedral angle generated by R ₁ and deviate from the preferred range, the upper limit of | α | is preferably 43 °.

Specific examples of R ₅ include sterically small hydrogen atoms or functional groups such as hydrogen atoms or functional groups represented by | α | in Table 4 below. Among these, steric ones such as hydrogen atoms or hydroxyl groups And a hydrogen atom or a functional group having a small Lewis acidity is preferable.

<R _{2 to} R ₄ >
R _{2 to} R ₄ each independently represent a hydrogen atom, a hydroxyl group, or a monovalent organic group other than a halogen atom having 1 to 10 carbon atoms, but among R _{2 to} R ₄ , two adjacent groups are A ring having 20 or less carbon atoms that is bonded to each other and condensed to a benzene ring may be formed.
The organic group having 1 to 10 carbon atoms as R ₂ to R _4, is not particularly limited, since the relative imide group content the molecular weight of each group is large is reduced, is the number 3 or less organic group having a carbon It is preferable.

Specific examples of R _{2 to} R ₄ are each independently a hydrogen atom, a hydrocarbon group, an aromatic group (including a heterocyclic group), a carbonyl group (aldehyde, ketone, ester, amide, etc.), an alkoxy group, or an acyloxy group. Group, alkylthio group, aryloxy group, dialkylamino group. When R _{2 to} R ₄ are hydrocarbon groups, they may have a substituent as long as the carbon number is 10 or less. Examples of the substituent include a heterocyclic group, a carbonyl group, a dialkylamino group, an alkoxy group, Examples include an acyloxy group, an alkylthio group, an aryloxy group, and a silyl group.

R _{2 to} R ₄ are each independently preferably a hydrogen atom, a hydroxyl group or a methyl group.

<Hydroxyl group of R _{2 to} R ₅ >
In the bisimide phenol compound of the present invention, any one of R _{2 to} R ₅ needs to be a hydroxyl group.
This is because, when the bisimidephenol compound of the present invention is used as a raw material monomer and polymerized, it cannot be polymerized without a reactive substituent, and the most versatile reactive substituent is a hydroxyl group. It depends.
However, there hydroxyl groups or three in one molecule, 3 since the gel becomes more than functional, a one by one either R ₂ to R ₅ is a hydroxyl group, two bonded to the imide groups in one molecule It is sufficient that one hydroxyl group is bonded to each benzene ring.

<R ₆ >
R ₆ each independently represents a monovalent organic group other than a halogen atom having 1 to 10 carbon atoms, and when R ₆ is adjacent to each other on one benzene ring, the two adjacent R ₆ are A ring having 20 or less carbon atoms that is bonded and condensed to a benzene ring may be formed.
R ₆ is not particularly limited as long as it is an organic group other than a halogen atom having 1 to 10 carbon atoms. However, since the relative imide group content decreases as the molecular weight of each group increases, the number of carbon atoms is 3 or less. An organic group is preferred.

Specific examples of R ₆ each independently include a hydrocarbon group, an aromatic group (including a heterocyclic group), a carbonyl group (aldehyde, ketone, ester, amide, etc.), and a dialkylamino group. When R ₆ is a hydrocarbon group, it may have a substituent as long as it has 10 or less carbon atoms. Examples of the substituent include a heterocyclic group, a carbonyl group, a dialkylamino group, an alkoxy group, an acyloxy group, An alkylthio group, an aryloxy group, and a silyl group are mentioned.

<X>
X represents a single bond, an optionally substituted divalent organic group having 1 to 20 carbon atoms, —O—, or —SO ₂ —. In the case where X is a divalent organic group, the imide group content is relatively lowered when the molecular weight is increased. Therefore, an organic group having 1 to 10 carbon atoms is preferable, and an organic group having 1 to 3 carbon atoms. It is preferable. Specific examples of the divalent organic group having 1 to 3 carbon atoms include a methylene group, a 2,2-propylidene group, and an oxymethylene group.

X is particularly preferably a single bond, an oxymethylene group, —O—, or —SO ₂ —.

<N>
n is an integer of 0 to 3. However, when n is large and the molecular weight of the bisimidephenol compound is increased, the relative imide group content is decreased. Therefore, n is preferably 0 or 1.

<Symmetry>
In the bisimide phenol compound of the present invention, R _{1 to} R ₆ bonded to the benzene ring portion of the left and right ring structures connected by the linking group X and n representing the number of R ₆ are the same or different on the left and right. However, the same is preferable because the symmetry of the molecule is good and the cohesive force that is characteristic of the imide is not impaired when the molecular weight is increased.

<Molecular weight>
The lower limit of the molecular weight of the bisimidephenol compound of the present invention is 504, and the upper limit is preferably 1000 or less, particularly 800 or less, and particularly 600 or less.
If the molecular weight of the bisimide phenol compound of the present invention is excessively small, the molecular design of the bisimide phenol compound of the present invention is impossible, and conversely if excessively large, the imide group content in the bisimide phenol compound is small. Is not preferable.

<Imido group content>
The imide group content of the bisimidephenol compound of the present invention (molar amount of imide group per gram of the bisimidephenol compound of the present invention) is a bisimidephenol useful as a raw material monomer for heat-resistant polymer materials having a large imide group content. Since it can become a compound, it is preferably 0.22 mmol / g or more, particularly 1.0 mmol / g or more, particularly 2.0 mmol / g or more. The maximum value of the imide group content is theoretically 4.0 mmol / g.

The structure of the bisimidephenol compound of the present invention such as imide group content is confirmed by ¹ H-NMR (nuclear magnetic resonance spectrum analysis: heavy dimethyl sulfoxide solvent), IR (infrared absorption spectroscopy), MS (mass spectrometry). can do.

<Solubility in solvents>
The bisimide phenol compound of the present invention has high solubility in ketone solvents. Specifically, among the bisimidephenol compounds of the present invention, a preferable one shows a solubility of 0.5% by weight or more at 60 ° C. in a ketone solvent, and a more preferable one is 1.0% by weight or more. In particular, the solubility is 2.0% by weight or more, and the most preferable is 3.0% by weight or more.

  Here, the ketone solvent refers to a liquid having a ketone group. Among them, it is desirable that it is aprotic so as not to interfere with the reaction of bisimidephenol, for example, acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), diisopropyl ketone, di-tert-butyl ketone, cyclopentanone, cyclohexanone. Cyclohexyl methyl ketone, acetophenone, acetylacetone and the like.

  Even if the solubility in these solvents is very slight, the reaction proceeds by taking time or time if it is partially dissolved, but it is preferable that the solubility is high in consideration of actual workability.

  In addition, the measuring method of the solubility with respect to the solvent of the bisimide phenol compound of this invention is as follows.

{Solubility measurement method}
A bisimidephenol compound and a solvent are put into a sample bottle, and the solubility when heated in an oil bath at 60 ° C. for 2 hours is visually confirmed while occasionally shaking by hand. Start measurement from a high concentration. If there is any undissolved material, add a small amount of solvent to lower the concentration, and use the concentration at the time of complete dissolution as solubility.

<Application>
As a use of the bisimide phenol compound of this invention, it is useful as a manufacturing raw material monomer etc., such as an epoxy resin excellent in heat resistance, a polyester resin, a polycarbonate resin, a phenol resin, etc., for example.

[Method for producing bisimidephenol compound]
The production method of the bisimidephenol compound of the present invention is not particularly limited. For example, an aminophenol represented by the following general formula (II) and an aromatic carboxylic acid dianhydride represented by the following general formula (III) It can be produced by the production method of the present invention wherein the product is dehydrated and condensed.

（一般式（II）において、Ｒ_１〜Ｒ_５はそれぞれ一般式（Ｉ）におけると同義である。）

(In general formula (II), R _{1 to} R ₅ have the same meanings as in general formula (I).)

（一般式(III)において、Ｘ、Ｒ_６及びｎはそれぞれ一般式（Ｉ）におけると同義である。）

(In general formula (III), X, R ₆ and n have the same meanings as in general formula (I).)

  An aminophenol represented by the general formula (II) (hereinafter simply referred to as “aminophenol”) and an aromatic carboxylic dianhydride represented by the general formula (III) (hereinafter simply referred to as “aromatic carboxylic acid”). The dehydration condensation of “acid dianhydride”) is carried out by converting these raw materials into an amic acid under a temperature condition in which imide ring closure (dehydration) does not occur from the viewpoint of minimizing a side reaction of ester formation by a phenolic hydroxyl group Hereinafter, it may be referred to as “first-stage reaction”), and the reaction temperature is preferably raised to form an imide ring (hereinafter sometimes referred to as “second-stage reaction”).

When an amic acid is generated, if an active proton is present, a side reaction with an acid anhydride group occurs, which inhibits the formation of the amic acid. Therefore, the amic acid is generated by heating in an aprotic organic solvent. Is preferred.
The dehydration reaction for forming an imide ring from an amic acid may be carried out by further heating the produced amic acid or using a dehydrating agent. This dehydration reaction may be performed in the presence or absence of a solvent.

  Hereinafter, the manufacturing method of the bisimide phenol compound of this invention by the dehydration condensation reaction of aminophenol and aromatic carboxylic dianhydride is demonstrated in detail.

<Aminophenol>
Examples of aminophenols represented by the general formula (II) include the following.

(| Α | = 51 ° -60 °)
<Benzoic acids: R ₁ = COOH>
2-amino-3-hydroxybenzoic acid, 2-amino-3-hydroxy-4-methylbenzoic acid, 2-amino-3-hydroxy-4-ethylbenzoic acid, 2-amino-3-hydroxy-4-propylbenzoic acid Acid, 2-amino-3-hydroxy-5-methylbenzoic acid, 2-amino-3-hydroxy-4-methoxybenzoic acid, 2-amino-3-hydroxy-4-ethoxybenzoic acid, 2-amino-3- Hydroxy-5-methoxybenzoic acid, 2-amino-3-hydroxy-4-acetylaminobenzoic acid, 2-amino-3-hydroxy-4,5-dimethylbenzoic acid, 2-amino-3-hydroxy-4,6 -Dimethylbenzoic acid, 2-amino-3-hydroxy-4-ethylthiobenzoic acid, 2-amino-4-hydroxybenzoic acid, 5-acetyl-2-amino-4-hydride Xylbenzoic acid, 6-acetyl-2-amino-4-hydroxybenzoic acid, 2-amino-4-hydroxy-5-methoxybenzoic acid, 2-amino-5-ethoxy-4-hydroxybenzoic acid, 2-amino- 5-benzyloxy-4-hydroxybenzoic acid, 2-amino-5-hydroxybenzoic acid, 2-amino-4-methyl-5-hydroxybenzoic acid, 2-amino-4-methoxy-5-hydroxybenzoic acid, 2- Amino-6-hydroxybenzoic acid, 2-amino-6-hydroxy-4-methylbenzoic acid, 6-amino-3-ethyl-2-hydroxybenzoic acid

<Methyl benzoates: R ₁ = COOMe>
Methyl 2-amino-3-hydroxybenzoate, methyl 2-amino-3-hydroxy-4-methylbenzoate, methyl 2-amino-3-hydroxy-5-methylbenzoate, 2-amino-3-hydroxy-5 -Methyl methoxybenzoate, methyl 2-amino-5-ethoxy-3-hydroxybenzoate, 3,4-methoxycarbonyl-2-aminophenol, methyl 2-amino-3-hydroxy-4-acetylaminobenzoate, 2 -Amino-3-hydroxy-6-[(2-trimethylsilylethoxy) methoxy] methyl benzoate, methyl 2-amino-4-hydroxybenzoate, methyl 5-acetyl-2-amino-4-hydroxybenzoate, 2- Methyl amino-4-hydroxy-5-methoxybenzoate, 2-amino-4-hydroxy-5-methoxycarbo Methyl benzoate, methyl 2-amino-5-hydroxybenzoate, methyl 2-amino-4-methoxycarbonyl-5-hydroxybenzoate, methyl 2-amino-4-benzoyloxy-5-hydroxybenzoate, 2- Methyl amino-4-methoxy-5-hydroxybenzoate, methyl 2-amino-6-hydroxybenzoate, methyl 6-amino-3-ethyl-2-hydroxybenzoate

_{<Acetophenones:} R 1 = COMe>
2-amino-3-hydroxyacetophenone, 2-amino-3-hydroxy-5-methylacetophenone, 2-amino-3-hydroxy-6-methylacetophenone, 2-amino-3-hydroxy-4,6-dimethylacetophenone, 2-amino-4-hydroxyacetophenone, 2-amino-4-hydroxy-5-propylacetophenone, 2-amino-4-hydroxy-6-phenylacetophenone, 2-amino-5-hydroxyacetophenone, 2-amino-3- Methoxy-5-hydroxyacetophenone, 2-amino-5-hydroxy-6-methylacetophenone, 2-amino-6-hydroxyacetophenone, 2-amino-6-hydroxy-4-methylacetophenone

<Dimethylanilines: R ₁ = NMe ₂ >
2-amino-3-hydroxy-N, N-dimethylaniline, 2-amino-4-hydroxy-N, N-dimethylaniline, 2-amino-5-hydroxy-N, N-dimethylaniline, 2-amino-6 -Hydroxy-N, N-dimethylaniline

<Acetylanilines: R ₁ = NHCOMe>
2-amino-3-hydroxy-N-acetylaniline, 2-amino-4-hydroxy-N-acetylaniline, 2-amino-5-hydroxy-N-acetylaniline, 2-amino-4-carboxy-5-hydroxy -N-acetylaniline, 2-amino-4-ethoxycarbonyl-5-hydroxy-N-acetylaniline, 2-amino-4-acetyl-5-hydroxy-N-acetylaniline, 2-amino-6-hydroxy-N -Acetylaniline

<Methyl sulfonates: R ₁ = SO ₃ Me>
Methyl 2-amino-3-hydroxyphenylsulfonate, methyl 2-amino-4-hydroxyphenylsulfonate, methyl 2-amino-5-hydroxyphenylsulfonate, methyl 2-amino-6-hydroxyphenylsulfonate

<Methyl sulfones: R ₁ = SO ₂ Me>
(2-amino-3-hydroxyphenyl) methylsulfone, (2-amino-4-hydroxyphenyl) methylsulfone, (2-amino-5-hydroxyphenyl) methylsulfone, (2-amino-6-hydroxyphenyl) methyl Sulfone

<Aminophenols: R ₁ = Me>
4-amino-3-methylphenol, 4-amino-2,3-dimethylphenol, 4-amino-2,5-dimethylphenol, 4-amino-2,3,6-trimethylphenol, 3-amino-2- Methylphenol, 3-amino-4-methylphenol, 3-amino-2,6-dimethylphenol, 3-amino-2,5-dimethylphenol, 5-amino-2,4-dimethylphenol, 5-amino-3 , 4-dimethylphenol, 5-amino-2,3,4-trimethylphenol, 5-amino-2,3,6-trimethylphenol, 2-amino-3-methylphenol, 2-amino-3,6-dimethyl Phenol, 2-amino-3,4-dimethylphenol, 2-amino-3,5-dimethylphenol, 2-amino-3,4,6-trimethyl Phenol, 2-amino-3,5,6-trimethylphenol, 2-amino-3,4,5-trimethylphenol, 2-amino-3,4,5,6-tetramethylphenol 2-amino-6-isopropyl -3-methylphenol, 2-amino-4,6-di-tert-butyl-3-methylphenol, 2-amino-3-methyl-6- (1,1,3,3-tetramethylbutyl) phenol, 2-amino-2,3-dimethyl-6- (1,1,3,3-tetramethylbutyl) phenol, 2-amino-3-methyl-5- (2-tolyl) phenol, 2- (1-adamantyl) ) -5-amino-4-methylphenol, 4-amino-2-isopropyl-5-methylphenol, 4-amino-2-tert-butyl-5-methylphenol, 4-amino 2-cyclohexyl-5-methylphenol, 4-amino-2- (1,1-dimethylpropyl) -5-methylphenol, 4-amino-5-methyl-2- (1,1,3,3-tetramethyl) Butyl) phenol, 4-amino-2- (4-cyclohexylbutyl) -5-methylphenol, 4-amino-6-ethyl-2,3-dimethylphenol, 2-hydroxy-6-methyl-3-anisidine, 2 -Hydroxy-3,4-dimethyl-5-anisidine, 2-hydroxy-6-methyl-4-anisidine, 3-hydroxy-2-methyl-4-anisidine, 5-hydroxy-3-methyl-4-anisidine, 5 -Hydroxy-2,3-dimethyl-4-anisidine, 2-amino-5-hexadecyloxy-4-isobutyl-3-methylphenol, 3-a No-5-hydroxy-2-methylbenzoic acid, 3-amino-5-hydroxy-4-methylbenzoic acid, 5-amino-2-hydroxy-4-methylbenzoic acid, 5-amino-2-hydroxy-3, 6-dimethylbenzoic acid, 5-amino-2-hydroxy-3-isopropyl-6-methylbenzoic acid, 4-amino-2-hydroxy-3-methylbenzoic acid, 4-amino-2-hydroxy-5-methylbenzoic acid Acid, 4-amino-2-hydroxy-3,6-dimethylbenzoic acid, methyl 3-amino-2-hydroxy-4-methylbenzoate, methyl 4-amino-2-hydroxy-5-methylbenzoate, 4- Amino-2-hydroxy-3-methylacetophenone, 4-amino-3-hydroxy-5-methylacetophenone, 2-amino-4-cyano-3,5-dimethylphen Nol, N, N-dimethyl-3-amino-4,5-dimethyl-2-hydroxybenzamide, N, N-dimethyl-3-amino-2-hydroxy-4-methylbenzamide, 2-amino-5- (tert -Butoxycarbonylmethyl) -3-methylphenol, 4-amino-2-hydroxy-3-methylbenzophenone, 4-amino-2-hydroxy-5-methylbenzophenone, 2-acetoxy-4-amino-6-isopropyl-3 -Methylphenol, 2-acetylamino-4-amino-5-methylphenol, 4-acetylamino-2-amino-3-methylphenol, 6-acetylamino-2-amino-3-methylphenol, N, N- Dibenzyl-2- (4-amino-2-hydroxy-5-methylphenyl) propanamide, 2-a No-3-methyl-4,6-bis (N-piperidinylmethyl) phenol, 4-amino-3-methyl-2,6-bis (N-piperidinylmethyl) phenol, 2-amino-3- Methyl-4,6-bis (N-pyrrolidinylmethyl) phenol, 4-amino-3-methyl-2- (3-thiophenyl) phenol, 4-amino-3-methyl-6- (3-thiophenyl) phenol 4-amino-3-methyl-6- (3-thiophenylmethyl) phenol

(| Α | = 48 ° -75 °)
<R ₁ = Et>
3-amino-2-ethylphenol, 4-amino-3-ethylphenol, 4-amino-3-ethyl-2,6-dimethylphenol, 4-amino-2,3-diethylphenol, 3-amino-4- Ethylphenol, 5-amino-4-ethyl-2-methoxycarbonylphenol, 2-amino-3-ethylphenol, 2-amino-3,5-diethylphenol

<R ₁ = iPr>
3-amino-2-isopropylphenol, 4-amino-3-isopropylphenol, 4-amino-3-isopropyl-6-methylphenol, 2-acetyl-4-amino-3-isopropyl-6-methylphenol, 4- Amino-6-carboxy-3-isopropylphenol, 4-amino-2,5-diisopropylphenol, 3-amino-4-isopropylphenol, 2-amino-3-isopropylphenol, 2-amino-3-isopropyl-6 Methylphenol

<R ₁ = OMe>
3-hydroxy-2-anisidine, 4-hydroxy-2-anisidine, 4-hydroxy-5-methyl-2-anisidine, 4-hydroxy-2,5-dimethoxyaniline, 5-acetyl-4-hydroxy-2-anisidine 4-hydroxy-5-ethoxycarbonyl-2-anisidine, 4-hydroxy-3-methyl-2,5-dimethoxyaniline, 4-hydroxy-5-benzoyl-2-anisidine, 5-acetyl-4-hydroxy-3 -Methyl-2-anisidine, 4-amino-2,3-dimethoxy-6-methylphenol, 4-amino-2,3-dimethoxyphenol, 4-hydroxy-5-tert-butyl-2-anisidine, 5-hydroxy -2-anisidine, 5-hydroxy-4-methyl-2-anisidine, 5-hydroxy-2,4- Methoxyaniline, 5-hydroxy-3-methyl-2,4-dimethoxyaniline, 5-hydroxy-4-benzoylamino-2-anisidine, 5-hydroxy-4-acetylamino-2-anisidine, 6-hydroxy-2- Anisidine, 6-hydroxy-5-methyl-2-anisidine, 6-hydroxy-5-acetyl-2-anisidine, 6-hydroxy-5-benzoyl-2-anisidine, 6-hydroxy-5-methoxycarbonyl-2-anisidine 6-hydroxy-5- [2- (N, N-dipropylamino) ethyl] -2-anisidine, 2-hydroxy-3-carboxymethyl-4,6-dimethoxyaniline, 6-hydroxy-2,4- Dimethoxyaniline, 3-hydroxy-2,4-dimethoxyaniline, 2,3,4-trimethoxy 6-amino-phenol

<R ₁ = SMe>
2-methylthio-3-aminophenol, 3-methylthio-4-aminophenol, 4-methylthio-3-aminophenol, 2-methoxy-4-methylthio-5-aminophenol, 2,4-methylthio-5-aminophenol , 3-methylthio-2-aminophenol

_<R 1 = CONH _2>
2-amino-6-hydroxybenzamide, 2-amino-5-hydroxybenzamide, 2-amino-4-hydroxybenzamide, 5-acetyl-2-amino-4-hydroxybenzamide, 2-amino-4-hydroxy-5- Methoxycarbonylbenzamide, 2-amino-4-hydroxy-5-ethoxycarbonylbenzamide, 2-amino-3-hydroxybenzamide, 2-amino-3-hydroxy-4-methylbenzamide

(| Α | = 45 ° ~ 90 °)
<R ₁ = tBu>
3-amino-2-tert-butylphenol, 3-amino-2,5-di-tert-butylphenol, 3-amino-2,6-di-tert-butylphenol, 4-amino-3-tert-butylphenol, 4- Amino-2,5-di-tert-butylphenol, 3-amino-4-tert-butylphenol, 5-amino-2,4-di-tert-butylphenol, 2-amino-3-tert-butylphenol, 2-amino- 3,5-di-tert-butylphenol, 2-amino-3,6-di-tert-butylphenol

<R ₁ = Ph>
3-amino-2-phenylphenol, 4-amino-3-phenylphenol, 4-amino-2,5-diphenylphenol, 3-amino-4-phenylphenol, 5-amino-2-methoxycarbonyl-4-phenyl Phenol, 2-amino-3-phenylphenol

<R ₁ = SiMe ₃ >
3-amino-2-trimethylsilylphenol, 4-amino-3-trimethylsilylphenol, 3-amino-4-trimethylsilylphenol, 2-amino-3-trimethylsilylphenol

<R ₁ = CONHMe>
2-amino-6-hydroxy-N-methylbenzamide, 2-amino-5-hydroxy-N-methylbenzamide, 2-amino-4-hydroxy-N-methylbenzamide, 2-amino-3-hydroxy-N-methyl Benzamide

Among these, since the molecular weight is small and the reactivity of the substituent is low, the following are preferable.
<R ₁ = NMe ₂ >
2-amino-3-hydroxy-N, N-dimethylaniline, 2-amino-4-hydroxy-N, N-dimethylaniline, 2-amino-5-hydroxy-N, N-dimethylaniline, 2-amino-6 -Hydroxy-N, N-dimethylaniline

<R ₁ = Me>
4-amino-3-methylphenol, 4-amino-2,3-dimethylphenol, 4-amino-2,5-dimethylphenol, 4-amino-2,3,6-trimethylphenol, 3-amino-2- Methylphenol, 3-amino-4-methylphenol, 3-amino-2,6-dimethylphenol, 3-amino-2,5-dimethylphenol, 5-amino-2,4-dimethylphenol, 5-amino-3 , 4-dimethylphenol, 5-amino-2,3,4-trimethylphenol, 5-amino-2,3,6-trimethylphenol, 2-amino-3-methylphenol, 2-amino-3,6-dimethyl Phenol, 2-amino-3,4-dimethylphenol, 2-amino-3,5-dimethylphenol, 2-amino-3,4,6-trimethyl Phenol, 2-amino-3,5,6-trimethylphenol, 2-amino-3,4,5-trimethylphenol, 2-amino-3,4,5,6-tetramethylphenol, 2-amino-6- Isopropyl-3-methylphenol, 4-amino-2-isopropyl-5-methylphenol, 4-amino-6-ethyl-2,3-dimethylphenol, 2-hydroxy-6-methyl-3-anisidine, 2-hydroxy -3,4-dimethyl-5-anisidine, 2-hydroxy-6-methyl-4-anisidine, 3-hydroxy-2-methyl-4-anisidine, 5-hydroxy-3-methyl-4-anisidine, 5-hydroxy -2,3-dimethyl-4-anisidine, 3-amino-5-hydroxy-2-methylbenzoic acid, 3-amino-5-hydroxy- -Methylbenzoic acid, 5-amino-2-hydroxy-4-methylbenzoic acid, 5-amino-2-hydroxy-3,6-dimethylbenzoic acid, 5-amino-2-hydroxy-3-isopropyl-6-methyl Benzoic acid, 4-amino-2-hydroxy-3-methylbenzoic acid, 4-amino-2-hydroxy-5-methylbenzoic acid, 4-amino-2-hydroxy-3,6-dimethylbenzoic acid, 3-amino Methyl 2-hydroxy-4-methylbenzoate, methyl 4-amino-2-hydroxy-5-methylbenzoate

<R ₁ = Et>
3-amino-2-ethylphenol, 4-amino-3-ethylphenol, 4-amino-3-ethyl-2,6-dimethylphenol, 4-amino-2,3-diethylphenol, 3-amino-4- Ethylphenol, 2-amino-3-ethylphenol, 2-amino-3,5-diethylphenol

<R ₁ = iPr>
3-amino-2-isopropylphenol, 4-amino-3-isopropylphenol, 4-amino-3-isopropyl-6-methylphenol, 2-acetyl-4-amino-3-isopropyl-6-methylphenol, 4- Amino-2,5-diisopropylphenol, 3-amino-4-isopropylphenol, 2-amino-3-isopropylphenol, 2-amino-3-isopropyl-6-methylphenol

<R ₁ = OMe>
3-hydroxy-2-anisidine, 4-hydroxy-2-anisidine, 4-hydroxy-5-methyl-2-anisidine, 4-hydroxy-5-methoxy-2-anisidine, 5-acetyl-4-hydroxy-2- Anisidine, 4-hydroxy-3-methyl-5-methoxy-2-anisidine, 5-acetyl-4-hydroxy-3-methyl-2-anisidine, 4-amino-2,3-dimethoxy-6-methylphenol, 4 -Amino-2,3-dimethoxyphenol, 5-hydroxy-2-anisidine, 5-hydroxy-4-methyl-2-anisidine, 5-hydroxy-4-methoxy-2-anisidine, 5-hydroxy-4-methoxy- 3-methyl-2-anisidine, 6-hydroxy-2-anisidine, 6-hydroxy-5-methyl-2-anisidine 6-hydroxy-5-acetyl-2-anisidine, 6-hydroxy-5- [2- (N, N-dipropylamino) ethyl] -2-anisidine, 6-hydroxy-2,4-dimethoxyaniline, 3- Hydroxy-2,4-dimethoxyaniline, 2,3,4-trimethoxy-6-aminophenol

  Among these, in particular, 4-amino-3-methylphenol, 4-amino-2,3-dimethylphenol, 3-amino-2-methylphenol, 2-amino-3-methylphenol, and the like are obtained. It is preferable from the viewpoint of the balance between the solubility and cohesive force of the phenol compound and availability.

  These aminophenols may be used singly or in combination of two or more, but preferably only one is used for producing a symmetric bisimidephenol compound.

<Aromatic carboxylic dianhydride>
Examples of the aromatic carboxylic dianhydride represented by the general formula (III) include 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 2,3 ′, 3,4′- Tetracarboxylic dianhydrides such as biphenyltetracarboxylic dianhydride (a-BPDA), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (s-BPDA); 2,2 ′, 3 , 3′-diphenylmethane tetracarboxylic dianhydride, 2,3 ′, 3,4′-diphenylmethane tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylmethane tetracarboxylic dianhydride, etc. Tetracarboxylic dianhydride; 2,2 ′, 3,3 ′-(2,2-diphenylpropane) tetracarboxylic dianhydride, 2,3 ′, 3,4 ′-(2,2-diphenylpropane) Tetracarboxylic dianhydride, 3,3 ', 4 (2,2-diphenylpropane) tetracarboxylic dianhydride such as 4 ′-(2,2-diphenylpropane) tetracarboxylic dianhydride; 2,2 ′, 3,3′-benzophenonetetracarboxylic dianhydride 2,3 ′, 3,4′-benzophenone tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride such as 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride; ', 3,3'-Diphenyl ether tetracarboxylic dianhydride, 2,3', 3,4'-diphenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride Diphenyl ether tetracarboxylic dianhydride such as 2,2 ′, 3,3′-diphenylsulfone tetracarboxylic dianhydride, 2,3 ′, 3,4′-diphenylsulfonetetra Carboxylic acid dianhydride, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride diphenyl tetracarboxylic acid dianhydride and the like. Among them, the symmetry of the molecule itself is good, the symmetry of the bisimidephenol compound as a whole is improved, the properties of the imide are fully exhibited, and the necessary solubility can be obtained by setting the above | α | appropriately. 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (s-BPDA), 3,3 ′, 4,4′-benzophenone tetra Carboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride and the like are preferable.
In addition, these may be used individually by 1 type and may be used in mixture of 2 or more types.

<Solvent>
As described above, an aprotic organic solvent is preferable as the solvent used in the first-stage reaction because it may react with an acid anhydride group in the presence of active protons and hinder the formation of amic acid. When a solvent is used for the second stage reaction, the solvent is not particularly limited. In this case, the solvent used in the first-stage reaction for generating an amic acid and the second-stage reaction for generating an imide ring may be the same or different, but in terms of simplicity, the same solvent is used to avoid complication of solvent exchange. In the case of using a different solvent, it is preferable to add another solvent in the second stage reaction.

  The organic solvent used for producing the first stage amic acid is an aprotic organic solvent that can partially dissolve the aromatic carboxylic dianhydride and aminophenol and does not react with the raw material under the reaction conditions. Well, for example, amide solvents such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ethyl acetate, butyl acetate, etc. Ester solvents; ether solvents such as 1,4-dioxane, tetrahydrofuran, diethyl ether, dibutyl ether, methyl-t-butyl ether, diphenyl ether; aromatic solvents such as toluene, xylene, mesitylene, ethylbenzene, cumene, anisole, etc. Can be mentioned. These may be used alone or in combination of two or more. When mixed and used, it may be mixed from the beginning of the reaction or may be added during the reaction.

<Raw material ratio / Raw material temperature>
The molar ratio of the aromatic carboxylic dianhydride and aminophenol to be subjected to the reaction is most preferably 1: 2 of the reaction equivalent in which both raw materials do not remain. However, the aminophenol which can be easily removed may be more than the necessary amount (2 mol or more per 1 mol of the aromatic carboxylic dianhydride) relative to the aromatic carboxylic dianhydride. That is, since aminophenol is water-soluble by acid treatment, it can be easily removed even if it remains after the reaction. On the other hand, the acid anhydride group can be converted into an alkali salt of a dicarboxylic acid by alkali treatment and water-solubilized, but the bisimidephenol produced also becomes an alkali salt. The dianhydride is difficult to separate and purify. The molar ratio of the aromatic carboxylic dianhydride and aminophenol used in the reaction is preferably 1: 2 to 1: 4, more preferably 1: 2 to 1: 3 of aromatic carboxylic dianhydride: aminophenol. 1: 2 is particularly preferred.

When the first-stage reaction and the second-stage reaction are performed using a solvent, the concentration of aminophenol in the reaction solution may be 0.2 to 95% by weight, particularly 1 to 55% by weight, especially 3 to 35% by weight. preferable. The concentration of the aromatic carboxylic dianhydride in the reaction solution is preferably 0.02 to 88% by weight, particularly 2 to 64% by weight, and particularly 5 to 50% by weight.
Further, the total concentration of the aromatic carboxylic dianhydride and aminophenol in the reaction solution is not particularly limited. However, from the viewpoint of workability, it is preferably 8 to 85% by weight in the first stage reaction for generating an amic acid, and the imide ring In the second-stage reaction for producing, 5% by weight or more is preferable. Note that this second-stage reaction may be performed without a solvent.

<Catalyst>
In both the first-stage reaction and the second-stage reaction, the reaction proceeds satisfactorily even without a catalyst, but a catalyst may be used if necessary. Examples of the catalyst include aromatic amines such as pyridine and N, N-dimethylaminopyridine; triethylamine, tributylamine, triphenylamine, N, N′-dimethylbenzylamine, N-methylmorpholine, N-methylpiperidine, 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,8-diazabicyclo [5.4.0] -7-undecene (DBU), urotropine, N, N, N′N′-tetramethyl Tertiary amine compounds such as ethylenediamine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine; acetic acid, trifluoroacetic acid, phenolic compounds, benzenesulfonic acid, toluenesulfonic acid, boric acid, phosphoric acid and the like Bronsted acidic compounds; alkali metals, alkaline earth metals, boron, aluminum, Gallium, indium, silicon, germanium, tin, antimony, bismuth, lanthanoids, titanium, zirconium, hafnium, vanadium, niobium, tantalum, manganese, rhenium, iron, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver Lewis acidic compounds containing gold, zinc and the like, and these may be used alone or in combination of two or more.

Although there is no restriction | limiting in particular in the usage-amount of a catalyst, It is preferable to set it as about 10 mol% or less with respect to the acid anhydride group used as a reaction point, for example, about 1-5 mol%.
The reaction conditions described below need not be changed depending on the presence or absence of a catalyst.

<Dehydrating agent>
When the dehydration reaction of the second stage reaction is performed by a chemical method using a dehydrating agent, for example, a method of using an acid anhydride and a base together, such as acetic anhydride and pyridine, or an acid halide and a base are used in combination. And a method using a carbodiimide compound such as N, N′-dicyclohexylcarbodiimide or a phosphoric acid-based dehydration condensing agent.

Although there is no restriction | limiting in particular as the usage-amount of these dehydrating agents, For example, it is preferable to set it as about 1.0-2.0 molar equivalent with respect to an acid anhydride group.
When these dehydrating agents are used, after the completion of the first stage reaction, the appropriate amount of the dehydrating agent may be added to the reaction system to carry out the second stage reaction.

<Reaction conditions>
The reaction conditions such as reaction temperature and reaction time may be any conditions that allow an imide ring to be generated, but are preferably within the following ranges from the viewpoint of workability.

That is, in the first-stage reaction for producing an amic acid, the reaction temperature is preferably a condition that does not cause a ring-closing reaction (dehydration) of the imide. Therefore, the upper limit is preferably 110 ° C, more preferably 100 ° C, and particularly preferably 95 ° C. 90 ° C. is most preferred. The lower limit is preferably 5 ° C., more preferably 40 ° C., and particularly preferably 60 ° C., because if it is too low, the reaction rate becomes slow and the efficiency decreases. The reaction time of the first-stage amic acid production reaction depends on the temperature, but the lower limit is usually 0.5 hours, preferably 1 hour, and the upper limit is usually 12 hours, preferably 6 hours.
The reaction pressure is preferably normal pressure or increased pressure, more preferably normal pressure.

  In the first-stage reaction, it is preferable to stir the reaction system in order to prevent bumping during heating, and a mechanical stirrer or a magnetic stirrer can be used for stirring. The stirring speed is not particularly limited.

  The reaction temperature when performing dehydration by heating in the stage of formation of the imide ring in the second stage reaction requires a sufficient temperature for water to volatilize and be removed from the reaction system, so the lower limit is preferably 120 ° C., more preferably 130 ° C., particularly preferably 140 ° C. The upper limit is preferably 250 ° C., more preferably 200 ° C. from the viewpoint of preventing thermal decomposition of the product. The dehydration reaction is carried out until the amount of water removed reaches the theoretical amount, most often within 24 hours.

The reaction temperature when dehydration is carried out by a chemical method using a dehydrating agent is usually 5 to 100 ° C. because it is not necessary to distill off water by heating.
When dehydrating using a dehydrating agent, a solvent is required. However, when dehydrating by heating, the solvent may or may not be present. For example, after the amic acid is generated in a certain solvent, another solvent is required. It is also possible to carry out heat dehydration by substituting with a solvent having a high boiling point, or heat dihydration without solvent by distilling off the solvent from the amic acid.

In the second stage reaction, when a solvent is used, the reaction pressure may be normal pressure, and when no solvent is used, normal pressure or reduced pressure may be used. However, in order to allow dehydration to proceed smoothly, reduced pressure is preferred. Moreover, when using a solvent, in order to prevent bumping at the time of a heating similarly to the 1st step reaction, it is preferable to stir the reaction system, and a mechanical stirrer or a magnetic stirrer can be used for stirring. The stirring speed is not particularly limited.
When the second stage reaction is carried out without solvent, continuous stirring is not necessary.

<Other additives>
In the method of the present invention, an additive such as an antioxidant or a surfactant may be added to the reaction system as long as the reaction of the present invention is not significantly hindered. When these additives are added, the amount added is preferably 5% by weight or less of the raw material.
These additives are preferably substances other than primary amines other than raw materials, secondary amines, alcohols other than phenols, acid anhydrides other than raw materials, isocyanate compounds and the like from the viewpoint of imide ring formation.

<Confirmation of reaction progress>
The progress of the reaction can be confirmed by monitoring the consumption of the raw material by thin layer chromatography (TLC), gas chromatography (GC), liquid chromatography (LC) or the like. In addition, in the heat dehydration method, the progress of the reaction can be confirmed more simply by the amount of water removed. For example, in the method using a solvent, the amount of water can be measured by using a Dean-Stark tube, and in the method using no solvent, the amount of water removed by weight reduction can be known. Thus, the progress of the reaction can be confirmed.

<Product recovery and purification>
The bisimidophenol compound produced through the first-stage reaction and the second-stage reaction becomes a solution or precipitates to form a dispersion or a precipitate when a solvent is used. When it is in solution, it can be obtained as a solid by evaporating and removing the solvent, or by precipitating by mixing with a poor solvent in which the bisimidephenol compound does not dissolve. If it is a dispersion or a precipitate, it can be filtered as it is, or it can be further easily filtered by mixing with a poor solvent. Any one of pressurization, normal pressure, and vacuum filtration may be used for the filtration.

  The filtered bisimidephenol can be obtained with sufficient purity if the ratio of the raw materials is appropriate, but can be further purified if impurities such as residual aminophenol or a small amount of coloring components are a problem.

  As the purification method, a method of washing and removing using a solvent in which bisimidephenol does not dissolve and impurities are dissolved is the simplest. In this case, examples of the solvent used include alcohols such as methanol, ethanol, and isopropanol; Aromatics such as toluene and xylene; ethers such as diethyl ether, dibutyl ether, tetrahydrofuran and 1,4-dioxane. Which solvent is suitable depends on the bisimide phenol. Moreover, residual aminophenol can be more efficiently removed by washing with an acid such as hydrochloric acid, sulfuric acid, nitric acid, or phosphoric acid.

  The recrystallization method is effective when impurities are taken into the crystal and are difficult to remove by washing. Recrystallization can be carried out by dissolving the filtered bisimidephenol in a solvent, adding a poor solvent to precipitate again, and then filtering. The combination of the solvent for dissolving bisimidephenol and the poor solvent is not particularly limited, and examples thereof include acetone / water, N-methylpyrrolidone / water, N-methylpyrrolidone / toluene and the like. Further, the above-mentioned washing may be performed after filtering this.

  The drying method of bisimide phenol is not particularly limited, and it may or may not be heated and may or may not be decompressed.

  If the reaction and purification are carried out under the above-mentioned preferable conditions, the yield is good. Usually, according to the method of the present invention, the desired bisimidephenol compound can be obtained at a yield of 80 to 100%.

  Examples of substances that may be mixed as impurities include unreacted raw materials, imide oligomers formed by reaction of impurity diamines contained in aminophenol, residual solvents, amine oxides, and the like. .

[Polymer compound]
The polymer compound of the present invention is obtained by polymerizing the above-described bisimide phenol compound of the present invention as at least a part of the raw material monomer, or copolymerizing it with other monomers, specifically May be an epoxy resin, a polyester resin, a polycarbonate resin, a phenol resin, or the like.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded.

In the following, all “%” indicating purity is “wt%”.
Further, ¹ H-NMR of the synthesized compound was measured at room temperature in a heavy DMSO (dimethyl sulfoxide) solvent using a Bruker AV400M. In addition, IR was measured by a permeation method by preparing KBr tablets using FT / IR-230 (manufactured by JASCO Corporation). MS was Polaris Q (manufactured by Hitachi High-Technologies Corporation), the ion source temperature was 200 ° C., the ionization method was EI, and the ionization energy was 70 eV.

[Example 1]
To a 2 L flask equipped with a mechanical stirrer, Dean-Stark tube, and reflux condenser, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (s-BPDA, manufactured by Mitsubishi Chemical Corporation, purity 99) .8%) 100 g (340 mmol) and N-methylpyrrolidone (NMP, Mitsubishi Chemical Corporation, purity 99.9%) 300 ml were added and stirred, 4-amino-m-cresol (product name) (or 4 84 g (680 mmol) of -amino-3-methylphenol (alias)) (manufactured by Wako Pure Chemical Industries, Ltd., purity of 98% or more) was added. This was heated in an oil bath at 80 ° C. for 2 hours, 150 ml of toluene was added, and the oil bath temperature was raised to 160 ° C. Three hours after toluene began to reflux, it was confirmed that almost the theoretical amount of water had distilled into the Dean-Stark tube, and the oil bath was removed and the mixture was cooled to room temperature with stirring. When 1.5 L of distilled water was added thereto, the product was precipitated. This was filtered with a Buchner funnel, washed with 3 L of water and 1 L of ethanol, and then dried under reduced pressure at 135 ° C. to remove the solvent, and a pale yellow N, represented by the following formula (A1-1): N′-bis (2-methyl-4-hydroxyphenyl) -4,4′-diphthalimide was obtained. Yield 167 g (332 mmol, 98% yield). In this compound, | α | of the methyl group (Me) corresponding to R ₁ of the general formula (I) is 55.8 °.

The analysis results of this compound are as follows.
¹ H NMR (400 MHz, DMSO-d ₆ ): δ 2.05 (6H, s, —CH ₃ ), 6.72 (2H, dd, J = 2.8, 8.0 Hz, Ar—H), 6.79 (2H, d, J = 2.8Hz, Ar-H), 7.15 (2H, d, J = 8.0Hz, Ar-H), 8.09 (2H, d, J = 8.0Hz, Ar-H), 8.38 (2H, d, J = 8.0 Hz, Ar-H), 8.41 (2H, s, Ar-H), 9.71 (2H, s, -OH)
IR (KBr): 3448,1774,1709,1618,1504,1460,1421,1383,1300,1257,1111,744,546cm ^-1
MS: m / z 504 ([M ⁺ ], 100%), 505 ([M ⁺ ] +1, 31%), 506 ([M ⁺ ] + 2,6.2%)

[Example 2]
4-Amino-3-methylphenol was converted to 4-amino-2,3-xylenol (product name) (or 4-amino-2,3-dimethylphenol (alias)) (Tokyo Chemical Industry Co., Ltd., purity 97% N) N′-bis (2,3-dimethyl-4-) of the product represented by the following formula (A1-2), except that the amount was changed to 93 g (680 mmol). Hydroxyphenyl) -4,4′-diphthalimide was obtained. Yield 169 g (317 mmol, 93% yield). In this compound, | α | of the methyl group (Me) corresponding to R ₁ of the general formula (I) is 55.8 °.

The analysis results of this compound are as follows.
¹ H NMR (400 MHz, DMSO-d ₆ ): δ 1.97 (3H, s, —CH ₃ ), 2.13 (3H, s, —CH ₃ ), 6.79 (2H, d, J = 8.4 Hz, Ar—H) , 7.00 (2H, d, J = 8.4Hz, Ar-H), 8.09 (2H, d, J = 8.0Hz, Ar-H), 8.38 (2H, d, J = 8.0Hz, Ar-H), 8.41 (2H, s, Ar-H), 9.64 (2H, s, -OH)
IR (KBr): 3417,1770,1716,11628,1591,1491,1423,1383,1284,1236,1109,814,746,548cm ^-1
MS: m / z 532 ([M ⁺ ], 100%), 533 ([M ⁺ ] ⁺ 1,39.3%), 534 ([M ⁺ ] + 2,8.6%)

[Example 3]
4-amino-3-methylphenol was converted to 3-amino-o-cresol (product name) (or 3-amino-2-methylphenol (also known as)) (manufactured by Tokyo Chemical Industry Co., Ltd., purity 98% or more) 84 g ( N, N′-bis (2-methyl-3-hydroxyphenyl) -4,4′-diphthalimide represented by the following formula (A2), except that it was changed to 680 mmol). Got. Yield 170 g (337 mmol, 99% yield). In this compound, | α | of the methyl group (Me) corresponding to R ₁ of the general formula (I) is 55.8 °.

The analysis results of this compound are as follows.
¹ H NMR (400 MHz, DMSO-d ₆ ): δ 1.94 (6H, s, —CH ₃ ), 6.83 (2H, d, J = 8.0 Hz, Ar—H), 6.95 (2H, d, J = 8.0 Hz, Ar-H), 7.15 (2H, dd, J = 8.0,8.0Hz, Ar-H), 8.11 (2H, d, J = 8.0Hz, Ar-H), 8.39 (2H, d, J = 8.0 Hz, Ar-H), 8.44 (2H, s, Ar-H), 9.77 (2H, s, -OH)
IR (KBr): 3442,1770,1718,1610,1593,1473,1423,1377,1336,1282,1228,1115,897,781,742,717cm ^-1
MS: m / z 504 ([M ⁺ ], 100%), 505 ([M ⁺ ] +1, 32.9%), 506 ([M ⁺ ] + 2,7.4%)

[Example 4]
4-amino-3-methylphenol was converted to 2-amino-m-cresol (product name) (or 2-amino-3-methylphenol (alias)) (manufactured by Tokyo Chemical Industry Co., Ltd., purity 95%) 84 g (680 mmol) ), Except that N, N′-bis (2-methyl-6-hydroxyphenyl) -4,4′-diphthalimide represented by the following formula (A3) is used. Obtained. Yield 165 g (326 mmol, yield 96%). In this compound, | α | of the methyl group (Me) corresponding to R ₁ of the general formula (I) is 55.8 °, and | α | of the hydroxyl group (OH) corresponding to R ₅ is 42.3 °. It is.

The analysis results of this compound are as follows.
¹ H NMR (400 MHz, DMSO-d ₆ ): δ 2.10 (6H, s, —CH ₃ ), 6.84 (2H, d, J = 8.0 Hz, Ar—H), 7.23 (2H, dd, J = 8.0 , 8.0Hz, Ar-H), 8.13 (2H, d, J = 8.0Hz, Ar-H), 8.41 (2H, d, J = 8.0Hz, Ar-H), 8.46 (2H, s, Ar-H ), 9.86 (2H, s, -OH)
IR (KBr): 3401,330,1772,1709,1618,1591,1508,1473,1387,1294,1209,1105,891,852,779,746,696,546cm ^-1
MS: m / z 504 ([M ⁺ ], 100%), 505 ([M ⁺ ] +1, 39.5%), 506 ([M ⁺ ] + 2,6.4%)

[Example 5]
3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride is converted to 4,4′-oxydiphthalic anhydride (product name) (or 3,3 ′, 4,4′-diphenyl ether tetracarboxylic anhydride ( Alias)) (Tokyo Chemical Industry Co., Ltd., purity 98%) 100 g (322 mmol), 4-amino-m-cresol (product name) (or 4-amino-3-methylphenol (alias)) (Wako Jun N, N′-bis (2) represented by the following formula (A4) is carried out in the same manner as in Example 1 except that the amount of Yakuhin Kogyo Co., Ltd. (purity 98% or more) is 79 g (644 mmol). -Methyl-4-hydroxyphenyl) -4,4'-oxydiphthalimide was obtained. Yield 164 g (316 mmol, 98% yield). In this compound, | α | of the methyl group (Me) corresponding to R ₁ of the general formula (I) is 55.8 °.

The analysis results of this compound are as follows.
¹ H NMR (400 MHz, DMSO-d ₆ ): δ 2.03 (6H, s, —CH ₃ ), 6.70 (2H, dd, J = 2.4, 8.4 Hz, Ar—H), 6.76 (2H, d, J = 2.4Hz, Ar-H), 7.11 (2H, d, J = 8.4Hz, Ar-H), 7.63 (2H, d, J = 2.4Hz, Ar-H), 7.64 (2H, dd, J = 2.4 , 8.8Hz, Ar-H), 8.50 (2H, d, J = 8.8Hz, Ar-H), 9.70 (2H, s, -OH)
IR (KBr): 3413,1772,1716,1608,1508,1464,1437,1385,1300,1259,1201,1107,1084,852,752,553cm ^-1
MS: m / z 520 ([M ⁺ ], 100%), 521 ([M ⁺ ] +1, 36.4%), 522 ([M ⁺ ] + 2,8.9%)

[Example 6]
3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride is converted to 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd., purity 96% or more). 100 g (279 mmol) and 69 g of 4-amino-m-cresol (product name) (or 4-amino-3-methylphenol (alias)) (manufactured by Wako Pure Chemical Industries, Ltd., purity 98% or more) (N, N′-bis (2-methyl-4-hydroxyphenyl) -4,4′-sulfonyldibenzene represented by the following formula (A5)), except that (558 mmol) was used. Phthalimide was obtained. Yield 136 g (240 mmol, 86% yield). In this compound, | α | of the methyl group (Me) corresponding to R ₁ of the general formula (I) is 55.8 °.

The analysis results of this compound are as follows.
¹ H NMR (400 MHz, DMSO-d ₆ ): δ2.00 (6H, s, —CH ₃ ), 6.70 (2H, dd, J = 2.4, 8.8 Hz, Ar—H), 6.75 (2H, d, J = 2.4Hz, Ar-H), 7.10 (2H, d, J = 8.8Hz, Ar-H), 8.20 (2H, d, J = 8.8Hz, Ar-H), 8.63 (2H, dd, J = 0.8 , 8.8Hz, Ar-H), 8.65 (2H, d, J = 0.8Hz, Ar-H), 9.72 (2H, s, -OH)
IR (KBr): 3424,1778,1718,1608,1504,1460,1431,1383,1327,1302,1259,1221,1180,1155,1107,673,638,565cm ^-1
MS: m / z 568 ([M ⁺ ], 100%), 569 ([M ⁺ ] ⁺ 1,35.6%), 570 ([M ⁺ ] ⁺ 2,11.6%), 571 ([M ⁺ ] +3, (3.0%)

[Example 7]
3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride is converted to 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (Wako Pure Chemical Industries, Ltd., purity 96% or more) 100 g (310 mmol) and the amount of 4-amino-m-cresol (product name) (or 4-amino-3-methylphenol (alias)) (manufactured by Wako Pure Chemical Industries, Ltd., purity 98% or more) is 76 g. (N, N′-bis (2-methyl-4-hydroxyphenyl) -4,4′-oxomethylene represented by the following formula (A6)) except that (620 mol) was used. Diphthalimide was obtained. Yield 164 g (309 mmol, 99% yield). In this compound, | α | of the methyl group (Me) corresponding to R ₁ of the general formula (I) is 55.8 °.

The analysis results of this compound are as follows.
¹ H NMR (400 MHz, DMSO-d ₆ ): δ 2.05 (6H, s, —CH ₃ ), 6.72 (2H, dd, J = 2.8, 8.4 Hz, Ar—H), 6.78 (2H, d, J = 2.8Hz, Ar-H), 7.15 (2H, d, J = 8.4Hz, Ar-H), 8.17 (2H, dd, J = 0.4,8.0Hz, Ar-H), 8.18 (2H, dd, J = 0.8,8.0Hz, Ar-H), 8.27 (2H, dd, J = 0.8,8.0Hz, Ar-H), 9.72 (2H, s, -OH)
IR (KBr): 3363,1772,1718,1658,1608,1508,1466,1439,1377,1290,1238,1165,1128,1103,854,725,546cm ^-1
MS: m / z 532 ([M ⁺ ], 100%), 533 ([M ⁺ ] +1, 33.8%), 534 ([M ⁺ ] + 2,6.2%)

[Comparative Example 1]
Except that 4-amino-3-methylphenol was changed to 74 g (680 mmol) of p-aminophenol (product name) (manufactured by Wako Pure Chemical Industries, Ltd., purity 98%), the same procedure as in Example 1 was carried out. N, N′-bis (4-hydroxyphenyl) -4,4′-diphthalimide (CAS No. 128764-43-3) represented by the following formula (B1-1) was obtained. Yield 159 g (335 mmol, 98% yield).

[Comparative Example 2]
The same procedure as in Example 1 was carried out except that 4-amino-3-methylphenol was changed to 93 g (680 mmol) of 4-amino-3,5-xylenol (manufactured by Tokyo Chemical Industry Co., Ltd., purity 98% or more). N, N′-bis (2,6-dimethyl-4-hydroxyphenyl) -4,4′-diphthalimide represented by the following formula (B1-2) was obtained. Yield 177 g (333 mmol, 98% yield). In this compound, | α | of the methyl group (Me) corresponding to R ₁ and R ₅ in the general formula (I) is 55.8 °.

The analysis results of this compound are as follows.
¹ H NMR (400 MHz, DMSO-d ₆ ): δ2.00 (12H, s, —CH ₃ ), 6.63 (4H, s, Ar—H), 8.12 (2H, d, J = 8.0 Hz, Ar—H ), 8.40 (2H, dd, J = 0.8,8.0Hz, Ar-H), 8.44 (2H, d, J = 0.8Hz, Ar-H), 9.64 (2H, s, -OH)
IR (KBr): 3371, 1770, 1707, 1597, 1475, 1423, 1377, 1321, 1271, 1161, 1113, 1028, 889, 847, 748, 692, 557, 538cm ^-1
MS: m / z 532 ([M ⁺ ], 100%), 533 ([M ⁺ ] ⁺ 1,38.1%), 534 ([M ⁺ ] ⁺ 2,7.5%), 535 ([M ⁺ ] +3, 1.0%)

[Comparative Example 3]
The same procedure as in Example 1 was conducted except that 4-amino-3-methylphenol was changed to 74 g (680 mmol) of m-aminophenol (product name) (manufactured by Wako Pure Chemical Industries, Ltd., purity 98.5%). Thus, N, N′-bis (3-hydroxyphenyl) -4,4′-diphthalimide (CAS No. 295348-32-2) represented by the following formula (B2-1) was obtained. Yield 152 g (319 mmol, 94% yield).

[Comparative Example 4]
The same procedure as in Example 1 was conducted except that 4-amino-3-methylphenol was changed to 84 g (680 mmol) of 5-amino-o-cresol (manufactured by Wako Pure Chemical Industries, Ltd., purity 97% or more), N, N′-bis (4-methyl-3-hydroxyphenyl) -4,4′-diphthalimide represented by the following formula (B2-2) was obtained. Yield 151 g (300 mmol, yield 88%).

The analysis results of this compound are as follows.
¹ H NMR (400 MHz, DMSO-d ₆ ): δ 2.19 (6H, s, —CH ₃ ), 6.80 (2H, dd, J = 2.0, 8.0 Hz, Ar—H), 6.89 (2H, d, J = 2.0Hz, Ar-H), 7.20 (2H, d, J = 8.0Hz, Ar-H), 8.08 (2H, d, J = 7.6Hz, Ar-H), 8.37 (2H, dd, J = 1.2 , 7.6Hz, Ar-H), 8.41 (2H, d, J = 1.2Hz, Ar-H), 9.67 (2H, s, -OH)
IR (KBr): 3471,1770,1718,1618,1599,1523,1427,1369,1281,1265,1232,1186,1128,1095,796,741,553cm ^-1
MS: m / z 504 ([M ⁺ ], 100%), 505 ([M ⁺ ] +1, 34.0%), 506 ([M ⁺ ] + 2,6.9%)

[Comparative Example 5]
Except for changing 4-amino-3-methylphenol to 74 g (680 mmol) of o-aminophenol (product name) (manufactured by Wako Pure Chemical Industries, Ltd., purity 97%), the same procedure as in Example 1 was carried out. N, N′-bis (4-hydroxyphenyl) -4,4′-diphthalimide represented by the following formula (B3-1) was obtained. Yield 160 g (337 mmol, yield 99%). In this compound, | α | of the hydroxyl group (OH) corresponding to R ₁ of the general formula (I) is 42.3 °.

The analysis results of this compound are as follows.
¹ H NMR (400 MHz, DMSO-d ₆ ): δ 6.94 (2H, ddd, J = 1.2, 7.6, 7.6 Hz, Ar—H), 7.01 (2H, dd, J = 1.2, 7.6 Hz, Ar—H ), 7.30 (2H, dd, J = 1.6, 7.6Hz, Ar-H), 7.34 (2H, ddd, J = 1.2, 7.6, 7.6Hz, Ar-H), 8.01 (2H, d, J = 8.0Hz) , Ar-H), 8.44 (2H, dd, J = 1.6,8.0Hz, Ar-H), 8.44 (2H, d, J = 1.6Hz, Ar-H), 9.90 (2H, s, -OH)
IR (KBr): 3317,1768,1701,1620,1601,1512,1464,1425,1389,1300,1286,1198,1111,1090,893,872,758,744,631cm ^-1
MS: m / z 476 ([M ⁺ ], 100%), 477 ([M ⁺ ] ⁺ 1,33.0%), 478 ([M ⁺ ] + 2,6.5%)

[Comparative Example 6]
Except that 4-amino-3-methylphenol was changed to 84 g (680 mmol) of 6-amino-m-cresol (manufactured by Wako Pure Chemical Industries, Ltd., purity 90% or more), the same procedure as in Example 1 was carried out. N, N′-bis (4-methyl-2-hydroxyphenyl) -4,4′-diphthalimide represented by the following formula (B3-2) was obtained. Yield 168 g (333 mmol, 98% yield). In this compound, | α | of the hydroxyl group (OH) corresponding to R ₁ of the general formula (I) is 42.3 °.

The analysis results of this compound are as follows.
¹ H NMR (400 MHz, DMSO-d ₆ ): δ 2.26 (6H, s, —CH ₃ ), 6.90 (2H, d, J = 8.4 Hz, Ar—H), 7.09 (2H, d, J = 2.4 Hz, Ar-H), 7.14 (2H, dd, J = 2.4, 8.4 Hz, Ar-H), 8.09 (2H, d, J = 8.0 Hz, Ar-H), 8.39 (2H, d, J = 8.0 Hz, Ar-H), 8.43 (2H, s, Ar-H), 9.62 (2H, s, -OH)
IR (KBr): 3398,1774,1718,1618,1512,1425,1375,1336,1292,1277,1188,1140,1109,1088,820,768,742,557cm ^-1
MS: m / z 504 ([M ⁺ ], 100%), 505 ([M ⁺ ] +1, 34.6%), 506 ([M ⁺ ] + 2,7.3%)

[Comparative Example 7]
The same procedure as in Example 1 was carried out except that 4-amino-3-methylphenol was changed to 84 g (680 mmol) of 2-amino-p-cresol (manufactured by Tokyo Chemical Industry Co., Ltd., purity 98%). N, N′-bis (5-methyl-2-hydroxyphenyl) -4,4′-diphthalimide represented by (B3-3) was obtained. Yield 158 g (313 mmol, 92% yield). In this compound, | α | of the hydroxyl group (OH) corresponding to R ₁ of the general formula (I) is 42.3 °.

The analysis results of this compound are as follows.
¹ H NMR (400 MHz, DMSO-d ₆ ): δ 2.32 (6H, s, —CH ₃ ), 6.75 (2H, d, J = 7.6 Hz, Ar—H), 6.82 (2H, s, Ar—H) ), 7.15 (2H, d, J = 7.6Hz, Ar-H), 8.08 (2H, d, J = 7.6Hz, Ar-H), 8.38 (2H, dd, J = 1.6, 7.6Hz, Ar-H) ), 8.42 (2H, d, J = 1.6Hz, Ar-H), 9.73 (2H, s, -OH)
IR (KBr): 3556,3473,1768,1707,1616,1527,1427,1383,1304,1279,1171,1117,891,808,746,559cm ^-1
MS: m / z 504 ([M ⁺ ], 100%), 505 ([M ⁺ ] +1, 33.9%), 506 ([M ⁺ ] + 2,7.0%)

[Comparative Example 8]
3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride is converted to 4,4′-oxydiphthalic anhydride (product name) (or 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride. (Alias)) (Tokyo Chemical Industry Co., Ltd., purity 98%) 100 g (322 mmol), 4-amino-3-methylphenol was p-aminophenol (product name) (manufactured by Wako Pure Chemical Industries, Ltd., N, N′-bis (4-hydroxyphenyl) -4,4 ′ represented by the following formula (B4-1), except that the purity is 98 g) and 70 g (644 mmol). -Oxydiphthalimide (CAS No. 95576-73-1) was obtained. Yield 157 g (320 mmol, 99% yield).

[Comparative Example 9]
3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride is converted to 4,4′-oxydiphthalic anhydride (product name) (or 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride. (Alias)) (Tokyo Chemical Industry Co., Ltd., purity 98%) 100 g (322 mmol), 4-amino-3-methylphenol was m-aminophenol (product name) (manufactured by Wako Pure Chemical Industries, Ltd., N, N′-bis (3-hydroxyphenyl) -4 represented by the following formula (B4-2), except that the purity was 98.5% and 70 g (644 mmol). 4'-oxydiphthalimide (CAS No. 50444-30-9) was obtained. Yield 157 g (320 mmol, 99% yield).

[Comparative Example 10]
3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride is converted to 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd., purity 96% or more). Example 1 except that 100 g (279 mmol) and 4-amino-3-methylphenol were replaced with 61 g (558 mmol) of p-aminophenol (product name) (manufactured by Wako Pure Chemical Industries, Ltd., purity 98%). In the same manner, N, N′-bis (4-hydroxyphenyl) -4,4′-sulfonyldiphthalimide represented by the following formula (B5-1) was obtained. Yield 149 g (276 mmol, 99% yield).

The analysis results of this compound are as follows.
¹ H NMR (400 MHz, DMSO-d ₆ ): δ 6.88 (4H, dd, J = 2.0, 6.8 Hz, Ar—H), 7.20 (4H, dd, J = 2.0, 6.8 Hz, Ar—H), 8.17 (2H, dd, J = 0.8,8.0Hz, Ar-H), 8.61 (2H, dd, J = 1.6,8.0Hz, Ar-H), 8.63 (2H, dd, J = 0.8,1.6Hz, Ar -H), 9.79 (2H, s, -OH)
IR (KBr): 3450,1778,1711,1599,1518,1452,1389,1319,1242,1178,1149,1119,1095,1059,837,742,675,638,598,563,526cm ^-1
MS: m / z 540 ([M ⁺ ], 100%), 541 ([M ⁺ ] ⁺ 1,31.3%), 542 ([M ⁺ ] ⁺ 2,12.0%), 543 ([M ⁺ ] +3, 2.6%)

[Comparative Example 11]
3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride is converted to 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd., purity 96% or more). 100 g (279 mmol) and 4-amino-3-methylphenol was changed to m-aminophenol (product name) (manufactured by Wako Pure Chemical Industries, Ltd., purity 98.5%) 61 g (558 mmol). 1 and N, N′-bis (3-hydroxyphenyl) -4,4′-sulfonyldiphthalimide (CAS No. 129209-40-1) represented by the following formula (B5-2) Obtained. Yield 149 g (276 mmol, 99% yield).

[Comparative Example 12]
3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride becomes 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (manufactured by Wako Pure Chemical Industries, Ltd., purity 96% or more) Example 1 except that 100 g (310 mmol) and 4-amino-3-methylphenol were changed to p-aminophenol (product name) (Wako Pure Chemical Industries, Ltd., purity 98%) 68 g (620 mol). In the same manner, N, N′-bis (4-hydroxyphenyl) -4,4′-oxomethylenediphthalimide (CAS No. 53417-18-8) represented by the following formula (B6-1) is obtained. It was. Yield 155 g (307 mmol, 99% yield).

[Comparative Example 13]
3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride becomes 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (manufactured by Wako Pure Chemical Industries, Ltd., purity 96% or more) 100 g (310 mmol), and 4-amino-3-methylphenol was m-aminophenol (manufactured by Wako Pure Chemical Industries, Ltd., purity 98.5%) 68 g (620 mol). And N, N′-bis (3-hydroxyphenyl) -4,4′-oxomethylenediphthalimide (CAS No. 54492-20-0) represented by the following formula (B6-2) was obtained. Yield 150 g (298 mmol, 96% yield).

[Solubility comparison]
Using cyclohexanone (manufactured by Wako Pure Chemical Industries, Ltd., grade S, purity 99% or more) as a solvent, the solubility in a state heated to 60 ° C. was measured visually according to the above-described solubility measurement method. The results are shown in Tables 5 and 6.

The following can be understood from the above results.
Table 5 summarizes the raw material aromatic carboxylic dianhydrides that are 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydrides. In Tables 5 and 6, “position of methyl group” and “position of OH group” represent positions on the benzene ring of the phenol moiety, respectively, and are positions relative to N of the imide group.

  The compounds A1-1, A1-2, A2, and A3 in the examples all had a methyl group at one of the ortho positions and exhibited a solubility of 1% by weight or more. In particular, the compounds A1-1 and A3 are 5% by weight and 10% by weight, respectively, and it is understood that the bisimide phenol having a rigid structure has very high solubility.

  On the other hand, B1-2 having a methyl group at both ortho positions dissolves only 0.5% by weight, which is very poor in solubility as compared with compound A1-1. Moreover, compared with compound A1-2, although it had two methyl groups similarly, compound B1-2 with high symmetry was bad in solubility. Further, compounds B2-2, B3-2 and B3-3 having a methyl group other than the ortho position, and compounds B1-1, B2-1 and B3-1 having no methyl group are all less than 0.5% by weight. Met.

  Table 6 summarizes the results using other aromatic carboxylic dianhydrides, but in this case as well, all of compounds A4, A5, and A6 having a methyl group only at one ortho position correspond. It showed higher solubility than the unsubstituted bisimidephenol.

Claims (3)

Bisimide phenol compound represented by the following general formula (I).

(In general formula (I), R ₁ represents a monovalent functional group in which | α | defined below is 45 ° or more and 90 ° or less, and R ₅ is a hydrogen atom or defined below. | Α | represents a monovalent functional group with 0 ° or more and less than 45 °.
R ₂ , R _3, and R ₄ each independently represent a hydrogen atom, a hydroxyl group, or an organic group having 1 to 10 carbon atoms. A ring may be formed.
R ₆ represents an organic group having 1 to 10 carbon atoms, but two adjacent groups may be bonded to form a ring having 20 or less carbon atoms condensed with a benzene ring.
X represents a single bond, an optionally substituted divalent organic group having 1 to 20 carbon atoms, —O— or —SO ₂ —.
n is an integer of 0-3.
The plurality of R _{1 to} R ₆ may be the same as or different from each other. However, R _{1 to} R ₆ are not halogen atoms, and any one of R _{2 to} R ₅ is a hydroxyl group, so that the compound has two hydroxyl groups. )
{Definition of ||
| Α | is the absolute value of the dihedral angle α formed by two conjugate planes when the most stable structure based on theoretical calculation is calculated in the structure represented by the following formula (I-1).

(In the formula, R corresponds to R ₁ or R _5. )
Here, the theoretical calculation of the dihedral angle is performed using the AM1 method using “Microsoft Windows XP Professional Version 2002 Service Pack 2” as the OS and “Gaussian 03 x86-Win32 version Rev.B.05” as the software. This is done by calculating the most stable structure by specifying “opt = verytight” as an option).
α is the following four types (1) to (4) consisting of four adjacent atoms, C (carbonyl carbon of imide) -N (imide nitrogen) -C (aromatic ring) -C (aromatic ring) Of the dihedral angles, the absolute value is the smallest. C ^{1 to} C ⁵ are represented by the following formula (I-Ia).
^{(1) C 1 -C 2 -N} -C 4
(2) C ¹ -C ² -N-C ^{5
(3) C 3 -C 2 -N} -C 4
^{(4) C 3 -C 2 -N} -C 5

(In the formula, R corresponds to R ₁ or R _5. ) The bisimide according to claim 1, wherein the aminophenol represented by the following general formula (II) and the aromatic carboxylic dianhydride represented by the following general formula (III) are dehydrated and condensed. A method for producing a phenol compound.

(In general formula (II), R _{1 to} R ₅ have the same meanings as in general formula (I).)

(In general formula (III), X, R ₆ and n have the same meanings as in general formula (I).)   A polymer compound obtained by polymerizing the bisimidephenol compound according to claim 1 as at least a part of a monomer.