JP6483481B2 - Torxic acid based polymer and its production intermediate - Google Patents

Description

  The present invention relates to a tolxic acid based polymer and its production intermediate. More specifically, the present invention relates to a tolxic acid-based polymer expected to be used as a heat-resistant resin in applications such as, for example, the aerospace field, the automobile industry, railway vehicles, ships and the like, and production intermediates thereof.

  In general, polymers such as polyimides and polyamides are produced from petroleum as a raw material. An α-truxillic acid derivative is prepared by photodimerization reaction of 4-aminocinnamic acid which is a compound derived from a microorganism as a biopolymer not using petroleum as a raw material, and a polymer is prepared using the α-truxillic acid derivative as a raw material Has been proposed (see, for example, Patent Document 1).

  The α-truxillic acid derivative has the formula:

(Wherein, X is -OR, -SR or -NHR, and R is alkyl, alkenyl or aryl)
Since two amino groups are aligned on a straight line, polymers such as polyamide, polyimide, polyurea and the like from which the .alpha.-truxillic acid derivative is used as a raw material are rigid. Excellent in thermodynamic properties.

  However, the polymer in which the α-truxillic acid derivative is used as a raw material is very rigid due to the fact that two amino groups are aligned on a straight line, and has a disadvantage of being inferior in solubility in various organic solvents. is there.

International Publication No. 2013/073519 brochure

  The present invention has been made in view of the above-mentioned prior art, and is excellent in solubility in various organic solvents as compared with a polymer in which an α-truxillic acid derivative is used as a raw material, and further flexible as compared with the polymer It is an object of the present invention to provide a tolxic acid-based polymer which is also excellent in sex and a production intermediate thereof.

The present invention
(1) Formula (I):

[Wherein, R ¹ and R ² each independently represent an —OR ³ group (R ³ represents an alkyl group, an alkenyl group or an aryl group), an —SR ³ group (R ³ is as defined above), or — NHR ³ group (R ³ is as defined above)
Tolxic acid based polymer characterized by containing a repeating unit having a group represented by
(2) Formula (Ia):

[Wherein, R ¹ and R ² each independently represent an —OR ³ group (R ³ represents an alkyl group, an alkenyl group or an aryl group), an —SR ³ group (R ³ is as defined above), or — NHR ³ group (R ³ is as defined above)
4,4'-diaminotruxic acid derivative represented by
(3) Formula (II):

[Wherein, R ¹ and R ² each independently represent an —OR ³ group (R ³ represents an alkyl group, an alkenyl group or an aryl group), an —SR ³ group (R ³ is as defined above), or — NHR ³ group (R ³ is as defined above)
And 4,4′-diamino-β-truxic acid derivatives represented by the formula (IV):

[Wherein, R ¹ and R ² each independently represent an —OR ³ group (R ³ represents an alkyl group, an alkenyl group or an aryl group), an —SR ³ group (R ³ is as defined above), or — NHR ³ group (R ³ is as defined above)
The 4,4'-diamino-.delta.-truxnic acid derivative represented by

  According to the present invention, a tolxic acid-based polymer which is excellent in solubility in various organic solvents as compared with a polymer in which an α-truxillic acid derivative is used as a raw material, and is also excellent in flexibility as compared with the polymer. And their production intermediates.

1 is a graph showing ¹ H-NMR (nuclear magnetic resonance) spectrum of 4-nitrocinnamic acid succinimide obtained in Example 1. FIG. 5 is a graph showing a ¹³ C-NMR (nuclear magnetic resonance) spectrum of 4-nitrocinnamic acid succinimide obtained in Example 1. FIG. 5 is a graph showing a mass spectrum of 4-nitrocinnamic acid succinimide obtained in Example 1. FIG. 5 is a graph showing ¹ H-NMR (nuclear magnetic resonance) spectrum of 4,4′-dinitro-δ-truxnic acid succinimide obtained in Example 1. FIG. 5 is a graph showing a ¹³ C-NMR (nuclear magnetic resonance) spectrum of 4,4′-dinitro-δ-truxnic acid succinimide obtained in Example 1. FIG. FIG. 6 is a graph showing a mass spectrum of 4,4′-dinitro-δ-truxnic acid succinimide obtained in Example 1. FIG. FIG. 6 is a graph showing ¹ H-NMR (nuclear magnetic resonance) spectrum of dimethyl 4,4′-dinitro-δ-truxinate obtained in Example 1. FIG. FIG. 7 is a graph showing a ¹³ C-NMR (nuclear magnetic resonance) spectrum of dimethyl 4,4′-dinitro-δ-truxinate obtained in Example 1. FIG. 5 is a graph showing a mass spectrum of dimethyl 4,4′-dinitro-δ-truxinate obtained in Example 1. FIG. FIG. 6 is a graph showing ¹ H-NMR (nuclear magnetic resonance) spectrum of dimethyl 4,4′-diamino-δ-truxinate obtained in Example 1. FIG.

FIG. 6 is a graph showing a ¹³ C-NMR (nuclear magnetic resonance) spectrum of dimethyl 4,4′-diamino-δ-truxinate obtained in Example 1. FIG. 5 is a graph showing a mass spectrum of dimethyl 4,4′-diamino-δ-truxinate obtained in Example 1. FIG. FIG. 6 is a graph showing ¹ H-NMR (nuclear magnetic resonance) spectrum of diethyl 4,4′-dinitro-δ-torxinate obtained in Example 2. FIG. FIG. 6 is a graph showing a ¹³ C-NMR (nuclear magnetic resonance) spectrum of diethyl 4,4′-dinitro-δ-truxinate obtained in Example 2. FIG. FIG. 6 is a graph showing ¹ H-NMR (nuclear magnetic resonance) spectrum of diethyl 4,4′-diamino-δ-truxinate obtained in Example 2. FIG. FIG. 7 is a graph showing a ¹³ C-NMR (nuclear magnetic resonance) spectrum of diethyl 4,4′-diamino-δ-truxinate obtained in Example 2. FIG. 7 is a graph showing ¹ H-NMR (nuclear magnetic resonance) spectrum of N, N′-diphenyl-4,4′-dinitro-δ-torxinamide obtained in Example 3. FIG. 7 is a graph showing a ¹³ C-NMR (nuclear magnetic resonance) spectrum of N, N′-diphenyl-4,4′-dinitro-δ-torxinamide obtained in Example 3. FIG. 7 is a graph showing ¹ H-NMR (nuclear magnetic resonance) spectrum of N, N′-diphenyl-4,4′-diamino-δ-torxinamide obtained in Example 3. FIG. 7 is a graph showing a ¹³ C-NMR (nuclear magnetic resonance) spectrum of N, N′-diphenyl-4,4′-diamino-δ-torxinamide obtained in Example 3. FIG.

7 is a graph showing ¹ H-NMR (nuclear magnetic resonance) spectrum of methyl 4-nitrocinnamate obtained in Example 4. FIG. 7 is a graph showing a ¹³ C-NMR (nuclear magnetic resonance) spectrum of methyl 4-nitrocinnamate obtained in Example 4. FIG. 15 is a graph showing a mass spectrum of methyl 4-nitrocinnamate obtained in Example 4. 7 is a graph showing ¹ H-NMR (nuclear magnetic resonance) spectrum of dimethyl 4,4′-dinitro-β-truxinate obtained in Example 4. FIG. 15 is a graph showing a ¹³ C-NMR (nuclear magnetic resonance) spectrum of dimethyl 4,4′-dinitro-β-truxinate obtained in Example 4. FIG. 7 is a graph showing a mass spectrum of dimethyl 4,4′-dinitro-β-truxinate obtained in Example 4. FIG. 7 is a graph showing ¹ H-NMR (nuclear magnetic resonance) spectrum of dimethyl 4,4′-diamino-β-truxinate obtained in Example 4. FIG. 7 is a graph showing ¹³ C-NMR (nuclear magnetic resonance) spectrum of dimethyl 4,4′-diamino-β-truxinate obtained in Example 4. FIG. 15 is a graph showing a mass spectrum of dimethyl 4,4′-diamino-β-truxinate obtained in Example 4. FIG. 6 is a graph showing ¹ H-NMR (nuclear magnetic resonance) spectrum of the β-truxic acid dimethyl-amic acid copolymer obtained in Example 5. FIG.

It is a graph which shows the result of the thermogravimetric-differential thermal analysis of (beta)-toluxic acid dimethyl-amic acid copolymer obtained in Example 5. FIG. FIG. 7 is a graph showing ¹ H-NMR (nuclear magnetic resonance) spectrum of the β-truxnic acid dimethyl-imide copolymer obtained in Example 5. FIG. FIG. 6 is a graph showing the results of thermogravimetric-differential thermal analysis of the β-truxnic acid dimethyl-imide copolymer obtained in Example 5. FIG. It is a graph which shows the < ¹ > H-NMR (nuclear magnetic resonance) spectrum of the (beta) -truxic acid dimethyl-amide copolymer obtained in Example 6. FIG. It is a graph which shows the result of the thermogravimetric-differential thermal analysis of (beta)-toluxic acid dimethyl-amide copolymer obtained in Example 6. FIG. It is a graph which shows the < ¹ > H-NMR (nuclear magnetic resonance) spectrum of the (beta)-toluxic acid dimethyl-urea copolymer obtained in Example 7. FIG. It is a graph which shows the result of the thermogravimetric-differential thermal analysis of (beta)-toluxic acid dimethyl-urea copolymer obtained in Example 7. FIG. It is a graph which shows the < ¹ > H-NMR (nuclear magnetic resonance) spectrum of the (delta)-toluxic acid dimethyl-amide copolymer obtained in Example 8. FIG. It is a graph which shows the result of the thermogravimetric-differential thermal analysis of (delta)-toluxic acid dimethyl-amide copolymer obtained in Example 8. FIG. It is a graph which shows the result of a differential scanning calorimetry analysis of (delta)-toluxic acid dimethyl-amide copolymer obtained in Example 8. FIG.

FIG. 16 is a graph showing ¹ H-NMR (nuclear magnetic resonance) spectrum of δ-truxnic acid amide-amic acid copolymer obtained in Example 9. FIG. FIG. 10 is a graph showing ¹ H-NMR (nuclear magnetic resonance) spectrum of δ-torxinamide-imide copolymer obtained in Example 9. FIG. It is a graph which shows the result of the thermogravimetric-differential thermal analysis of (delta)-toluxic acid amide-imide copolymer obtained in Example 9. FIG. It is a graph which shows the < ¹ > H-NMR (nuclear magnetic resonance) spectrum of (delta)-toluxic acid amide- (alpha)-tolyxic acid dimethyl-amic acid terpolymer obtained in Example 10. FIG. 16 is a graph showing the ¹ H-NMR (nuclear magnetic resonance) spectrum of the δ-torxinic acid amide-α-torxinic acid dimethyl-imide terpolymer obtained in Example 10. FIG. It is a graph which shows the result of the thermogravimetric-differential thermal analysis of (delta)-toluxic acid amide- (alpha)-toluxic acid dimethyl-imide terpolymer obtained in Example 10.

  As described above, the tolxic acid-based polymer of the present invention has the formula (I):

[Wherein, R ¹ and R ² each independently represent an —OR ³ group (R ³ represents an alkyl group, an alkenyl group or an aryl group), an —SR ³ group (R ³ is as defined above), or — NHR ³ group (R ³ is as defined above)
And a repeating unit having a group represented by

  As a raw material of the tolxic acid based polymer represented by the formula (I), the formula (Ia):

Wherein, R ¹ and R ² are each independently, -OR ³ group (R ³ is as defined above), - SR ³ group (R ³ is the same as) or -NHR ³ group (R ³ is Same as above) is shown]
The 4,4'-diaminotruxic acid derivative represented by can be used.

The 4,4′-diaminotruxic acid derivative represented by the formula (Ia) has a basic structure of a dimer of 4-aminocinnamic acid or its derivative. Protection to prevent the carboxyl group derived from the dimer of 4-aminocinnamic acid or its derivative from reacting with the amino group (—NH ₂ group) that the 4,4′-diaminotruxic acid derivative has. Protected as R ¹ and R ² as a group.

R ¹ and R ² are each independently, -OR ³ group (R ³ is as defined above), - SR ³ group (R ³ is the same as) or -NHR ³ group (R ³ is as defined above) Indicates As an alkyl group, a C1-C8 alkyl group is mentioned, for example. As an alkenyl group, a C2-C8 alkenyl group is mentioned, for example. Moreover, as an aryl group, a C6-C12 aryl group is mentioned, for example.

  Examples of 4,4′-diaminotorxine derivatives represented by the formula (Ia) include 4,4′-diamino-β-torxic acid diesters such as dimethyl 4,4′-diamino-β-torxinate; And 4,4'-diamino-δ-truxnic acid diester such as dimethyl 4'-diamino-δ-torxinate.

  In the following, methods for preparing 4,4'-diamino-β-truxnic acid diester and 4,4'-diamino-δ-truxic acid diester are described.

[Preparation of 4,4′-diamino-β-truxnic acid diester]
(1) Starting Material 4-Nitrocinnamic acid can be used as a starting material for 4,4'-diamino-β-truxic acid diester.

(2) Preparation of 4-nitrocinnamic acid derivative

  The 4-nitrocinnamic acid alkyl ester can be prepared by reacting 4-nitrocinnamic acid with an alcohol.

As the alcohol, for example, an alcohol represented by the formula: R ³ OH (R ³ is the same as above), a thioalcohol represented by the formula: R ³ SH (R ³ is the same as above), a formula: NHR ³ OH (R ³ like alcohol represented by the same) and the. These alcohols may be used alone or in combination of two or more.

  Hereinafter, the case of preparing 4-nitrocinnamic acid alkyl ester using monohydric aliphatic alcohol will be described as a representative example of the method of preparing 4-nitrocinnamic acid derivative, but the present invention will be described only by such an example. It is not limited.

  Examples of monohydric aliphatic alcohols include monohydric aliphatic alcohols having 1 to 8 carbon atoms such as methanol, ethanol and isopropanol. The carbon number of the monohydric aliphatic alcohol is 1 to 8, preferably 1 to 6, more preferably 1 to 4, and still more preferably 1 or 2.

  Since the reaction proceeds stoichiometrically with 4-nitrocinnamic acid and a monohydric aliphatic alcohol, 4-nitrocinnamic acid can be used in view of sufficiently esterifying the carboxyl group possessed by 4-nitrocinnamic acid. On the other hand, it is preferable to use a monovalent aliphatic alcohol in excess.

  In addition, when making 4-nitro cinnamic acid and monohydric aliphatic alcohol react, it is preferable to use acids, such as a sulfuric acid, in a suitable quantity from a viewpoint of promoting both reaction, for example.

  The reaction temperature of 4-nitrocinnamic acid and a monohydric aliphatic alcohol is not particularly limited, but is preferably from room temperature to reflux temperature from the viewpoint of promoting the reaction of both. Further, the atmosphere at the time of reaction may be the atmosphere, and may be, for example, an inert gas such as nitrogen gas or argon gas.

  The reaction time of 4-nitrocinnamic acid and a monohydric aliphatic alcohol varies depending on the reaction conditions such as the reaction temperature and can not be determined indiscriminately, but is usually about 1 to 5 hours.

  The 4-nitrocinnamic acid alkyl ester produced by the reaction of 4-nitrocinnamic acid and a monohydric aliphatic alcohol can be recovered by filtration, and if necessary, removing monohydric aliphatic alcohol under reduced pressure May be

(3) Preparation of 4,4'-Dinitro-β-torxic Acid Derivative By irradiating the above-obtained 4-nitrocinnamic acid alkyl ester with ultraviolet light having a wavelength of about 250 to 400 nm, 4,4'-dinitro is obtained. Dialkyl-β-truxinate can be prepared.

  When the 4-nitrocinnamic acid alkyl ester is irradiated with ultraviolet light, the 4-nitrocinnamic acid alkyl ester is preferably dispersed in an organic solvent in advance. As an organic solvent, although C6-C12 aliphatic hydrocarbon compounds, such as hexane, etc. are mentioned, for example, this invention is not limited only to this illustration. Further, the amount of the organic solvent is not particularly limited, and generally, it may be an amount capable of sufficiently dispersing the 4-nitrocinnamic acid alkyl ester.

  As a light source at the time of irradiating an ultraviolet-ray to 4-nitro cinnamate alkylester, although a high pressure mercury lamp etc. are mentioned, for example, this invention is not limited only to this illustration. The time for irradiating the 4-nitrocinnamic acid alkyl ester with ultraviolet light can not be determined uniquely because it varies depending on the type of light source, ultraviolet light intensity, etc., and thus the target 4,4'-dinitro-.beta.-truxic acid It is preferred to irradiate the 4-nitrocinnamic acid alkyl ester with ultraviolet light until the dialkyl is sufficiently formed.

  By irradiating the 4-nitrocinnamic acid alkyl ester with ultraviolet light as described above, dialkyl 4,4'-dinitro-β-truxinate can be obtained.

  When 4-nitrocinnamic acid alkyl ester is dispersed in an organic solvent, the produced dialkyl 4,4'-dinitro-β-truxinate can be recovered by filtration. The recovered dialkyl 4,4'-dinitro-β-truxinate may optionally be dried under reduced pressure.

(4) Preparation of 4,4'-diamino-β-torxic acid derivative Next, 4,4'-diamino- is obtained by reducing the dialkyl 4,4'-dinitro-β-torxinate obtained above. Dialkyl beta-truxinate can be obtained. The reduction of dialkyl 4,4'-dinitro-β-truxinate can be carried out, for example, by hydrogen reduction.

  The hydrogen reduction of dialkyl 4,4'-dinitro-β-truxinate can be carried out in an organic solvent such as methanol, ethanol, etc., in the presence of a catalyst such as, for example, a palladium on carbon catalyst. In addition, when hydrogen-reducing the 4,4'-dinitro-β-torxinic acid, from the viewpoint of promoting the reduction of the 4,4'-dinitro-β-torxinic acid, the temperature is about room temperature to 60 ° C. It is preferred to carry out hydrogen reduction.

  The hydrogen reduction of the dialkyl 4,4'-dinitro-.beta.-torxinate is generally preferably carried out until the dialkyl 4,4'-diamino-.beta.-torxinate is sufficiently formed.

  The dialkyl 4,4'-diamino-β-torxinate thus obtained may be separated from the organic solvent by means of filtration or the like and then dried under reduced pressure if necessary.

In the above description, the case where the 4,4′-diamino-β-torxic acid derivative is a dialkyl 4,4′-diamino-β-torxinate is described, but in the following formula (II), R ¹ and R ^The 4,4′-diamino-β-truxic acid derivative in which ² is a group other than an alkyloxy group can also be prepared in the same manner as described above.

  As described above, formula (II):

(Wherein, R ¹ and R ² are as defined above)
The 4,4′-diamino-β-truxic acid derivative represented by

[Preparation of 4,4′-Diamino-δ-truxnic Acid Derivative]
(1) Starting Material 4-Nitrocinnamic acid can be used as a starting material of dialkyl 4,4'-diamino-δ-torxinate.

(2) Preparation of 4-nitrocinnamic acid ester 4-nitrocinnamic acid ester can be prepared, for example, by reacting 4-nitrocinnamic acid with an alcohol in the presence of N, N'-diisopropylcarbodiimide .

  Examples of the alcohol include C6-C12 monovalent cycloalkyl alcohol such as cyclohexyl alcohol, C6-C12 monovalent aryl alcohol such as phenol, and hydroxyl group-containing succinic acid such as N-hydroxysuccinimide Although an acid imide etc. are mentioned, this invention is not limited only to this illustration. In the present specification, for convenience, a compound having a hydroxyl group is referred to as an alcohol.

  The amount of alcohol and N, N'-diisopropylcarbodiimide per mole of 4-nitrocinnamic acid is preferably about 1.5 to 2.5 moles or so.

  When reacting 4-nitrocinnamic acid with an alcohol, an organic solvent can be used. Examples of the organic solvent include, for example, 1,4-dioxane and the like, but the present invention is not limited to such examples. The amount of the solvent is not particularly limited, but generally, it is preferably about 200 to 500 parts by mass per 100 parts by mass of the total of 4-nitrocinnamic acid, alcohol and N, N'-diisopropylcarbodiimide.

  The reaction temperature of 4-nitrocinnamic acid and alcohol is not particularly limited, but from the viewpoint of promoting the reaction, it is preferably room temperature to reflux temperature. Further, the atmosphere at the time of reaction may be the atmosphere, and may be, for example, an inert gas such as nitrogen gas or argon gas.

  Although the reaction time of 4-nitrocinnamic acid and alcohol changes with reaction conditions, such as reaction temperature, etc., it can not generally be determined, but it is usually about 1 to 5 hours.

  By reacting 4-nitrocinnamic acid with an alcohol, for example, formula (III):

(Wherein, R ⁴ represents a monovalent cycloalkyloxy group having 6 to 12 carbon atoms, a monovalent aryloxy group having 6 to 12 carbon atoms, or an N-oxysuccinimide group)
The 4-nitrocinnamic acid derivative represented by these can be obtained.

  The 4-nitrocinnamic acid derivative obtained above can be recovered by filtration, and may optionally be washed with an organic solvent such as 2-propanol.

  The 4-nitrocinnamic acid derivative can be prepared as described above. For example, when 4-nitrocinnamic acid succinic acid derivative is prepared using N-hydroxy succinic acid derivative as alcohol, 4-nitrocinnamic acid succinimide ester may be obtained as 4-nitrocinnamic acid derivative it can.

  In the following, for convenience, the case where 4-nitrocinnamic acid succinimide ester is used as 4-nitrocinnamic acid ester will be described.

(3) Preparation of 4,4'-dinitro-δ-truxnic acid succinimide ester The 4-nitrocinnamic acid succinimide ester obtained above is irradiated with ultraviolet light having a wavelength of about 250 to 400 nm. 4,4'-Dinitro-δ-truxnic acid succinimide ester can be prepared.

  In irradiating ultraviolet light to 4-nitrocinnamic acid succinimide ester, 4-nitrocinnamic acid succinimide ester is preferably suspended in benzene as a solvent in advance. As an organic solvent, for example, benzene, toluene, xylene and the like are mentioned, but when benzene is used, it is surprising that 4,4'- such as 4,4'-dinitro-δ-torxinic acid succinimide ester etc. It has been found that dinitro-δ-truxnic acid diester can be prepared efficiently. The amount of benzene is not particularly limited, but from the viewpoint of sufficiently dispersing 4-nitrocinnamic acid succinimide ester, it is about 1000 to 2000 parts by mass per 100 parts by mass of 4-nitrocinnamic acid succinimide ester preferable.

  As a light source at the time of irradiating an ultraviolet-ray to 4-nitrocinnamic acid succinimide ester, a high pressure mercury lamp etc. are mentioned, for example, However, this invention is not limited only to this illustration. Since the time for irradiating ultraviolet light to 4-nitrocinnamic acid succinimide ester varies depending on the type of light source, ultraviolet light intensity, etc., it can not be determined indiscriminately, so the target 4,4'-dinitro-δ- It is preferable to irradiate ultraviolet light to 4-nitrocinnamic acid succinimide ester until tolquxine succinimide ester is sufficiently generated.

  By irradiating the ultraviolet light to 4-nitrocinnamic acid succinimide ester as described above, 4,4'-dinitro-δ-truxic acid succinimide ester can be obtained.

  When 4-nitrocinnamic acid succinimide ester is dispersed in an organic solvent, the generated 4,4'-dinitro-δ-torxic acid succinimide ester can be recovered by filtration. The recovered 4,4'-dinitro-δ-truxnic acid succinimide ester may optionally be dried under reduced pressure.

  In the above description, although the case of using N-hydroxysuccinimide as the alcohol has been described, the formula (IV) in the same manner as described above is used also when an alcohol other than N-hydroxysuccinimide is used.

(Wherein R ⁴ is the same as above)
The 4,4'-dinitro-delta-torxic acid derivative represented by these can be obtained.

In the formula (IV), as described above, R ⁴ is a monovalent cycloalkyloxy group having 6 to 12 carbon atoms, a monovalent aryloxy group having 6 to 12 carbon atoms, or an N-oxysuccinimide group It is. As the succinimide group, for example, formula (V):

And the like.

  The generated 4,4'-dinitro-δ-torxinic acid succinimide ester is recovered by filtration, and the recovered 4,4'-dinitro-δ-torxic acid succinimide ester is optionally reduced pressure It may be dried.

(4) Preparation of 4,4'-dinitro-δ-torxic acid derivative Next, the 4,4'-dinitro-δ-torxic acid succinimide ester obtained above and R ³ OH (R ³ is alkyl An alcohol represented by a group, an alkenyl group or an aryl group, a thioalcohol represented by the formula: R ³ SH (wherein R ³ is as defined above), a formula: R ³ NH ₂ (wherein R ³ is as defined above) The 4,4′-dinitro-δ-truxic acid derivative can be obtained by reaction with an aliphatic amine or an aromatic amine.

  Examples of the alcohol include monohydric aliphatic alcohol having a carbon number of 1 to 8, preferably 1 to 6, more preferably 1 to 4 such as methanol, ethanol, isopropanol, etc., substitution of a nitro group, an amino group, etc. Although C6-C12 aryl alcohol etc. which may have a group, etc. are mentioned, this invention is not limited only to this illustration.

  Examples of aromatic amines include aniline and the like, but the present invention is not limited to such examples.

  Since 4,4'-dinitro-δ-torxinic acid succinimide ester and alcohol, thioalcohol, aliphatic amine or aromatic amine proceed stoichiometrically, 4,4'-dinitro- From the viewpoint of sufficiently esterifying the ester group possessed by δ-truxnic acid succinimide ester, alcohol, thioalcohol, aliphatic amine or aromatic to 4,4′-dinitro-δ-truxic acid succinimide ester It is preferred to use the amine in excess.

  The reaction temperature of 4,4'-dinitro-δ-torxinic acid succinimide ester with alcohol, thioalcohol, aliphatic amine or aromatic amine is not particularly limited, but from the viewpoint of promoting the reaction of both, room temperature It is preferable that it is -reflux temperature. Further, the atmosphere at the time of reaction may be the atmosphere, and may be, for example, an inert gas such as nitrogen gas or argon gas.

  The reaction time of 4,4'-dinitro-δ-torxinic acid succinimide ester with alcohol, thioalcohol, aliphatic amine or aromatic amine varies depending on reaction conditions such as reaction temperature, etc. Although it can not, it is usually about 15 to 30 hours.

  The dialkyl 4,4'-dinitro-δ-torxinate formed by the reaction of 4,4'-dinitro-δ-torxinic acid succinimide ester with alcohol, thioalcohol, aliphatic amine or aromatic amine is filtered If necessary, the alcohol, thioalcohol, aliphatic amine or aromatic amine may be removed under reduced pressure.

  By reacting the 4,4'-dinitro-δ-truxnic acid succinimide ester with an alcohol, a thioalcohol, an aliphatic amine or an aromatic amine as described above, for example, a compound of the formula (VI):

[Wherein, R ¹ and R ² each independently represent an —OR ³ group (R ³ represents an alkyl group, an alkenyl group or an aryl group), an —SR ³ group (R ³ is as defined above), or — NHR ³ group (R ³ is as defined above)
The 4,4'-dinitro-delta-torxic acid derivative represented by these can be obtained.

(5) Preparation of 4,4'-diamino-δ-torxic acid derivative Next, 4,4'-diamino- is obtained by reducing the 4,4'-dinitro-δ-torxic acid derivative obtained above. δ-truxnic acid derivatives can be obtained. The reduction of the 4,4′-dinitro-δ-truxnic acid derivative can be carried out, for example, by hydrogen reduction and the like.

  The hydrogen reduction of the 4,4'-dinitro-δ-truxic acid derivative can be carried out, for example, in the presence of a catalyst such as a palladium on carbon catalyst, in an organic solvent such as, for example, methanol, ethanol or the like. In addition, when hydrogenating a 4,4'-dinitro-δ-torxic acid derivative, from the viewpoint of promoting the reduction reaction of the 4,4'-dinitro-δ-torxic acid derivative, it is about room temperature to about 80 ° C. Hydrogen reduction at temperature is preferred.

  The reduction of the 4,4'-dinitro-δ-torxic acid derivative is usually preferably carried out until the 4,4'-diamino-δ-torxic acid derivative is formed.

  The 4,4'-diamino-δ-torxic acid derivative obtained as described above may be separated from the organic solvent by means such as filtration, and then dried under reduced pressure if necessary.

  By hydrogen reduction of the 4,4'-dinitro-δ-torxic acid derivative as described above, the compound of formula (VII) is obtained.

(Wherein, R ¹ and R ² are as defined above)
The 4,4′-diamino-δ-truxnic acid diester represented by

Preparation of Torxic acid polymer
The tolxic acid based polymer contains a repeating unit having a group represented by formula (I).

  As a tolxic acid type polymer which has a group represented by a formula (I) as a constitutional unit, for example, a formula (VIII):

(Wherein, R ¹ and R ² are the same as above. R ⁷ and R ⁸ each independently represent a cycloalkyl group having 4 to 6 carbon atoms or an acetamide group)
A tolxic acid derivative-amide copolymer having a repeating unit represented by formula (IX):

(Wherein, R ¹ and R ² are as defined above)
A tolxic acid derivative-imide copolymer having a repeating unit represented by formula (X):

(Wherein, R ¹ and R ² are as defined above)
The torxic acid derivative-urea copolymer etc. which have a repeating unit represented by these, However, this invention is not limited only to this illustration.

The tolxic acid based polymer can be prepared, for example, as follows.
(1) Preparation of β-truxic acid derivative-imide copolymer β-truxic acid derivative-amic acid copolymer is prepared by, for example, converting 4,4′-diamino-β-torxic acid diester and cyclobutanetetracarboxylic acid dianhydride into dimethylacetamide. After dissolving, the obtained solution is stirred in an inert gas atmosphere such as nitrogen gas, and obtained by reacting 4,4'-diamino-β-truxnic acid diester with cyclobutanetetracarboxylic acid dianhydride. be able to.

  Reprecipitation can be performed by dropping the reaction solution obtained above into methanol to obtain a β-truxic acid derivative-amic acid copolymer.

  Next, the β-truxic acid derivative-amic acid copolymer obtained above is dissolved in an organic solvent such as, for example, dimethylacetamide, and the resulting solution is heated to a temperature of about 100 to 300 ° C. Torxic acid derivative-imide copolymers can be obtained.

(2) Preparation of .beta.-torxic acid derivative-amide copolymer [beta] -torxic acid derivative-amide copolymer is, for example, 4,4'-diamino-.beta.-torxic acid diester and 4,4'-diacetamido-.alpha.-truxic acid Can be obtained by polycondensation in the presence of triphenyl phosphite and pyridine in an organic solvent such as N-methyl pyrrolidone.

  The resulting reaction solution can be reprecipitated by dropping it into water, filtered, and if necessary, dried to recover the formed β-torxic acid derivative-amide copolymer.

(3) Preparation of β-torxinate ester-urea copolymer β-torxinate ester-urea copolymer is prepared, for example, by dissolving dimethyl 4,4′-diamino-β-torxinate and 1,3-phenylene diisocyanate in dimethylacetamide. It can be obtained by stirring in an inert gas atmosphere such as nitrogen gas and reacting dimethyl 4,4'-diamino-.beta.-truxinate with 1,3-phenylene diisocyanate. The resulting reaction solution is dropped into an organic solvent such as methanol to reprecipitate and recover the formed β-torxinate ester-urea copolymer, and the formed β-torxinate ester-urea copolymer is then dried. Can be recovered.

(4) Preparation of δ-torxinate ester-amide copolymer δ-torxinate ester-amide copolymer is, for example, 4,4′-diamino-δ-torxinate diester and 4,4′-diacetamido-α-truxic acid Can be obtained by polycondensation in N-methylpyrrolidone in the presence of triphenyl phosphite and pyridine. The resulting reaction solution can be reprecipitated by dropping it into water, and the resulting precipitate can be dried under reduced pressure to recover the δ-truxnic acid ester-amide copolymer.

(5) Preparation of δ-torxinamide / imide copolymer δ-torxinamide / amide acid copolymer is, for example, N, N′-diphenyl-4,4′-diamino-δ-torxinamide and cyclobutanetetracarboxylic acid After dissolving the dianhydride in dimethylacetamide, it is stirred in an inert gas atmosphere such as nitrogen gas, and N, N'-diphenyl-4,4'-diamino-.delta.-torxinamide and cyclobutanetetracarboxylic acid It can be obtained by reacting with an anhydride. The resulting reaction solution is dropped into ethanol and reprecipitated to recover the δ-truxnic acid amide-amic acid copolymer.

  Next, after dissolving the δ-truxnic acid amide-amic acid copolymer obtained above in an organic solvent such as dimethylacetamide, the resulting solution is heated to a temperature of about 100 to 300 ° C. Torxinamide-imide copolymers can be obtained.

(6) Preparation of δ-truxnic acid amide-α-truxylic acid diester-imide terpolymer δ-truxic acid amide-α-truxylic acid diester-amic acid terpolymer is, for example, N, N′-diphenyl-4,4 After dissolving '-diamino-δ-torxinamide, 4,4'-diamino-α-truxylic acid diester and cyclobutanetetracarboxylic acid dianhydride in an organic solvent such as dimethylacetamide, inert such as nitrogen gas Stir in a gas atmosphere to react N, N'-diphenyl-4,4'-diamino-δ-torxinamide, 4,4'-diamino-α-truxillic acid diester and cyclobutanetetracarboxylic acid dianhydride Can be obtained by The resulting reaction solution can be dropped into ethanol and recovered by reprecipitating the produced δ-torxinamide-α-truxillic acid diester-amic acid terpolymer.

  Next, the δ-truxnic acid amide-α-truxic acid diester-amic acid terpolymer obtained above is dissolved in an organic solvent such as dimethylacetamide, for example, and the obtained solution is heated to a temperature of about 100 to 300 ° C. By heating, δ-torxinic acid amide-α-truxillic acid diester-imide terpolymer can be obtained.

The presence of the repeating unit represented by the formula (I) of the tolxic acid based polymer of the present invention is, for example, ¹ H-nuclear magnetic resonance (NMR) spectrum, ¹³ C-nuclear magnetic resonance (NMR) spectrum, infrared absorption ( It can be easily confirmed by IR) spectrum, mass spectrometry or the like.

  The number average molecular weight of the tolxic acid-based polymer of the present invention is preferably from 10,000 to from the viewpoint of improving the solubility and flexibility in various organic solvents as compared with the polymer in which the α-truxillic acid derivative is used as the raw material. One million, more preferably 50,000 to 500,000. The number average molecular weight of the tolxic acid based polymer of the present invention is a value as measured based on the method described in the following examples.

  The tolxic acid-based polymer of the present invention obtained as described above is excellent in the solubility in various organic solvents as compared with the polymer in which the α-truxillic acid derivative is used as a raw material, and is further flexible as compared with the polymer It is expected to be used in applications such as, for example, the aerospace field, the automobile industry, railway vehicles, ships, etc., because of its excellent properties.

  Next, the present invention will be described in more detail based on examples, but the present invention is not limited to such examples.

In addition, the physical property of the compound obtained by the following each Example was investigated based on the following method.
[ ¹ H-NMR and ¹³ C-NMR]
・ Measurement device: Nuclear magnetic resonance spectrometer (made by Bruker, trade name: AVANCE III)

Gel Permeation Chromatography (GPC)
Measurement device: Showa Denko KK, trade name: Shodex-101
Measurement conditions Concentration at injection: 0.001% by mass
Injection volume: 25 μL
・ Flow rate: 0.5mL / min
Solvent: N, N-dimethylformamide Column: Showa Denko KK product name: Shodex KD-803 and trade name: Shodex KD-804
・ Column temperature: 40 ° C

Thermogravimetric-differential thermal analysis
Measuring device: Thermogravimetric-differential thermal simultaneous measuring device (manufactured by Hitachi High-Technologies Corp., trade name: STA7200)
The temperature was raised to 800 ° C. at a heating rate of 10 ° C./min in a nitrogen gas atmosphere, and the 5% weight loss temperature or the 10% weight loss temperature was measured.

Example 1 Preparation of Dimethyl 4,4'-Diamino-δ-torxinate (1)
The scheme to prepare dimethyl 4,4'-diamino-δ-truxinate using 4-nitrocinnamic acid as the starting material is shown below.

(1) Preparation of 4-nitrocinnamic acid succinimide (1) 25.17 g (0.130 mol) of 4-nitrocinnamic acid, 22.38 g (0.194 mol) of N-hydroxysuccinimide and N, N'- 30 mL (0.194 mol) of diisopropylcarbodiimide was added to 300 mL of 1,4-dioxane, and 4-nitrocinnamic acid was reacted with N-hydroxysuccinimide by heating under reflux at a temperature of 120 ° C. After completion of the reaction, 4-nitrocinnamic acid succinimide was recovered by filtration of the obtained reaction solution and washed with 2-propanol. The yield of the obtained 4-nitrocinnamic acid succinimide ester was 36.45 g, and the yield was 96.7%.

  In addition, it was confirmed from the measurement result of the following physical properties that 4-nitro cinnamic acid succinimide is the reaction product of 4-nitro cinnamic acid and N-hydroxy succinimide.

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 2.87 (s, 4 H, -CH ₂ -CH _2- ), 7.24 (d, 1 H, J = 16.1 Hz, -CH = CH-), 8.15 ( d, 2H, J = 8.8 Hz, aromatic ring), 8.30 (d, 2H, J = 8.8 Hz, aromatic ring)
¹³ C-NMR (100 MHz, DMSO-d ₆ ): δ 25.5, 116.2, 124.0, 130.3, 139.5, 147.2, 148.8, 161.9, 170.3.
FT-ICR MS (ESI): Calculated _{[M + Na, C 13 H} 10 N 2 O 6 Na] +: 313.0473, the value of experiment: 313.0431

The ¹ H-NMR spectrum, ¹³ C-NMR spectrum and mass spectrum of 4-nitrocinnamic acid succinimide obtained above are shown in FIG. 1, FIG. 2 and FIG. 3, respectively.

(2) Preparation of 4,4'-dinitro-δ-truxnic acid succinimide (2): 1.0 g (3.45 mmol) of 4-nitrocinnamic acid succinimide obtained above was suspended in 20 mL of benzene The resulting suspension was irradiated with ultraviolet light for 24 hours with a high pressure mercury lamp to form 4,4'-dinitro-.delta.-torxinic acid succinimide from 4-nitrocinnamic acid succinimide.

  Next, the resulting suspension was filtered to recover 4,4'-dinitro-δ-truxinic acid succinimide which was produced and dried under reduced pressure. The yield of the obtained 4,4'-dinitro-δ-truxnic acid succinimide was 0.63 g, and the yield was 63.0%.

  In addition, it was confirmed from the measurement result of the following physical properties that the produced | generated compound is 4,4'- dinitro- (delta)-toluxic acid succinimide.

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 2.81 (s, 8 H, -CH ₂ -CH _2- ), 4.21 (4 H, cyclobutane), 7.77 (d, 4 H, J = 8.8 Hz, aromatic ring ), 8.22 (d, 4H, J = 8.8 Hz, aromatic rings).
¹³ C-NMR (100 MHz, DMSO-d ₆ ): δ 26.0, 47.5, 124.3, 128.8, 146.0, 147.6, 167.1, 170.4.
FT-ICR MS (ESI): Calculated _{[M + Na, C 26 H} 20 N 4 O 12 -Na] +: 603.0975, the value of experiment: 603.0973.

The ¹ H-NMR spectrum, ¹³ C-NMR spectrum and mass spectrum of 4,4′-dinitro-δ-truxnic acid succinimide obtained above are shown in FIG. 4, FIG. 5 and FIG. 6 respectively.

(3) Preparation of dimethyl 4,4'-dinitro-δ-torxinate (3) 20 mL of methanol containing 0.93 g (1.60 mmol) of 4,4'-dinitro-δ-torxinate succinimide obtained above The solution was heated to reflux for 24 hours and then the methanol was evaporated under reduced pressure.

  Next, the reaction product obtained above was added to an extraction solvent consisting of 20 mL of ethyl acetate and 20 mL of water, liquid-liquid extraction was performed, and the organic layer was recovered. Sodium sulfate was added to the collected organic layer to dry it. After drying, sodium sulfate was removed by filtration from the organic layer, and ethyl acetate was removed under reduced pressure to recover dimethyl 4,4'-dinitro-δ-torxinate (3). The yield of the obtained dimethyl 4,4'-dinitro-δ-torxinate was 1.42 g, and the yield was 80.2%.

  In addition, it was confirmed from the measurement result of the following physical properties that the produced | generated compound is dimethyl 4, 4'- dinitro- (delta)-toluxic acid.

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 3.58-3.60 (m, 2 H, cyclobutane), 3.67 (s, 6 H, COOCH ₃ ), 3.91-3.94 (m, 2 H, cyclobutane), 7.64 (d , 4H, J = 8.8 Hz, aromatic ring), 8.21 (d, 4H, J = 8.8 Hz, aromatic ring).
¹³ C-NMR (100 MHz, DMSO-d ₆ ): δ 43.5, 46.1, 52.1, 123.8, 128.5, 146.7, 147.9, 171.7.
FT-ICR MS (ESI): Calculated _{[M + Na, C 20 H} 18 N 2 O 8 Na] +: 437.0961, the value of experiment: 437.0952.

The ¹ H-NMR spectrum, ¹³ C-NMR spectrum and mass spectrum of dimethyl 4,4′-dinitro-δ-torxinate obtained above are shown in FIGS. 7, 8 and 9 respectively.

(4) Preparation of dimethyl 4,4'-diamino-δ-torxinate (4) 2.57 g (6.20 mmol) of dimethyl 4,4'-dinitro-δ-torxinate obtained above and 10% palladium carbon By adding 0.66 g (0.01 mol%) of (Pd / C) catalyst to 50 mL of methanol and heating at a temperature of 50 ° C. for 4.5 hours, hydrogen of dimethyl 4,4′-dinitro-δ-torxinate A reduction reaction was performed. After completion of the reaction, the palladium carbon (Pd / C) catalyst is removed by filtering the resulting reaction solution, and dimethyl 4,4'-diamino-δ-torxinate formed by removing methanol under reduced pressure. (4) was recovered. The yield of the obtained dimethyl 4,4'-diamino-δ-torxinate (4) was 1.52 g, and the yield was 69.1%.

  In addition, it was confirmed from the measurement result of the following physical properties that the produced | generated compound is dimethyl 4, 4'- diamino- (delta)-toluxic acid.

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 3.17-3.31 (4H, m, cyclobutane), 3.64 (s, 6H, COOCH ₃ ), 5.01 (s, 4H, NH ₂ ), 6.50 (d, 4H, J = 8.4 Hz, aromatic ring), 6.92 (d, 4H, J = 8.4 Hz, aromatic ring).
¹³ C-NMR (100 MHz, DMSO-d ₆ ): δ 44.4, 47.6, 51.9, 113.9, 127.5, 147.7, 172.6.
FT-ICR MS (ESI): Calculated _{[M + Na, C 20 H} 22 N 2 O 4 -Na] +: 377.1477, the value of experiment: 377.1472.

The ¹ H-NMR spectrum, ¹³ C-NMR spectrum and mass spectrum of dimethyl 4,4′-diamino-δ-torxinate obtained above are shown in FIG. 10, FIG. 11 and FIG. 12 respectively.

Example 2 Preparation of diethyl 4,4'-diamino-δ-torxinate (6)
In the same manner as in Example 1 using 4-nitrocinnamic acid as a starting material, 4,4'-dinitro-δ-torxinic acid succinimide (2) was prepared and 4,4'-dinitro-δ was obtained. -Diethyl 4,4'-diamino-δ-truxinate was prepared as follows using toluxine succinimide (2).

  The scheme for preparing diethyl 4,4'-diamino-δ-truxinate using 4-nitrocinnamic acid is shown below.

(1) Preparation of diethyl 4,4'-dinitro-δ-torxinate (5) Dissolve 2.01 g (3.43 mmol) of 4,4'-dinitro-δ-torxinate succinimide in 20 mL of dehydrated ethanol, The resulting solution was heated to reflux for 40 hours, and then ethanol was distilled off under reduced pressure.

  Next, the reaction product obtained above was added to an extraction solvent consisting of 50 mL of ethyl acetate and 50 mL of water, liquid-liquid extraction was performed three times, and the organic layer was recovered. Sodium sulfate was added to the collected organic layer to dry it. After drying, sodium sulfate was removed from the organic layer by filtration, and diethyl 4,4'-dinitro-δ-torxinate (5) was recovered by removing ethyl acetate under reduced pressure. The yield of the obtained diethyl 4,4'-dinitro-δ-torxinate was 1.28 g, and the yield was 84.0%.

  In addition, it was confirmed from the measurement result of the following physical properties that the produced | generated compound is diethyl 4, 4'- dinitro- (delta)-toluxic acid.

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 1.18 (t, 6 H, J = 7.2 Hz, COOCH ₂ CH ₃ ), δ 3.49-3.51 (m, 2 H, cyclobutane), δ 3.92-3.95 (m , 2H, cyclobutane), 4.13 (q, 4H, J = 7.0 Hz, COOCH ₂ CH ₃ ), 7.64 (d, 4H, J = 8.8 Hz, aromatic ring), 8.20 (d, 4 H, J = 8.8 Hz, aroma ring).
¹³ C-NMR (100 MHz, DMSO-d ₆ ): δ 14.4, 44.3, 46.2, 61.1, 124.2, 178.9, 147.1, 148.3, 171.6

The ¹ H-NMR spectrum and ¹³ C-NMR spectrum of the diethyl 4,4'-dinitro-δ-torxinate obtained above are shown in FIG. 13 and FIG. 14 respectively.

(2) Preparation of diethyl 4,4'-diamino-δ-torxinate (6) 1.31 g (2.94 mmol) of diethyl 4,4'-dinitro-δ-torxinate obtained above and 10% palladium carbon 0.13 g (1.17 mmol) of (Pd / C) catalyst is added to 40 mL of methanol, and the hydrogen reduction reaction of diethyl 4,4'-dinitro-δ-torxinate is carried out by heating at a temperature of 50 ° C. for 24 hours I did. After completion of the reaction, the palladium carbon (Pd / C) catalyst is removed by filtering the obtained reaction solution, and diethyl 4,4'-diamino-δ-torxinate formed by removing methanol under reduced pressure. (6) was recovered. The yield of the obtained diethyl 4,4'-diamino-δ-torxinate was 1.05 g, and the yield was 92%.

  In addition, it was confirmed from the measurement result of the following physical properties that the produced | generated compound is a 4, 4'- diamino- (delta)-toluxic acid diethyl.

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 1.16 (t, 6 H, J = 7.2 Hz, COOCH ₂ CH ₃ ), δ 3.08-3.10 (m, 2 H, cyclobutane), δ 3.28-3. 30 (m , 2H, cyclobutane), 4.10 (q, 4H, J = 7.0 Hz, COOCH ₂ CH ₃ ), δ 4.97 (s, 4 H, NH ₂ ), 6.49 (d, 4 H, J = 8.4 Hz, aromatic ring), 8.40 (d, 4H, J = 8.4 Hz, aromatic ring).
¹³ C-NMR (100 MHz, DMSO-d ₆ ): δ 14.6, 45.2, 47.7, 60.8, 114.3, 127.9, 128.5, 148.1, 172.6.

The ¹ H-NMR and ¹³ C-NMR spectra of the diethyl 4,4'-diamino-δ-truxinate obtained above are shown in FIG. 15 and FIG. 16 respectively.

Example 3 Preparation of N, N′-Diphenyl-4,4′-Diamino-δ-truxnamide (8)
In the same manner as in Example 1 using 4-nitrocinnamic acid as a starting material, 4,4'-dinitro-δ-torxinic acid succinimide (2) was prepared and 4,4'-dinitro-δ was obtained. N, N'-Diphenyl-4,4'-diamino-.delta.-torxinamide was prepared using -truxin succinimide (2) as follows.

  The scheme up to preparation of N, N'-diphenyl-4,4'-diamino-δ-torxinamide using 4-nitrocinnamic acid is shown below.

(1) Preparation of N, N'-diphenyl-4,4'-dinitro-δ-torxinamide (7) 3.50 g (6.02 mmol) of 4,4'-dinitro-δ-torxinic acid succinimide and After dissolving 2.24 g (24.1 mmol) of aniline in 20 mL of dehydrated dimethylacetamide and stirring at room temperature for 14 hours, the precipitate is reprecipitated with diethylether and the obtained precipitate is dried to obtain N, N'-. Diphenyl-4,4'-dinitro-δ-torxinamide (7) was obtained. The yield of the obtained N, N′-diphenyl-4,4′-dinitro-δ-torxinamide (7) was 2.75 g, and the yield was 85%.

  In addition, it was confirmed from the measurement result of the following physical properties that the produced | generated compound is N, N'- diphenyl-4,4'- dinitro- delta-torxinamide.

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 3.67-3.69 (m, 2 H, cyclobutane), 4.07-4.09 (m, 2 H, cyclobutane), 7.05 (t, 2 H, J = 7.1 Hz, aromatic ring ), 7.30 (t, 4H, J = 7.1 Hz, aromatic ring), 7.64 (d, 8H, J = 7.1 Hz, aromatic ring), 8.26 (d, 4H, J = 8.9 Hz, aromatic ring), 10.26 (s , 2H, NH).
¹³ C-NMR (100 MHz, DMSO-d ₆ ): δ 45.7, 46.8, 119.8, 124.1, 124.4, 128.7, 129.2, 139.2, 147.1, 149.1, 169.7.

The ¹ H-NMR and ¹³ C-NMR spectra of the N, N′-diphenyl-4,4′-dinitro-δ-torxinamide obtained above are shown in FIGS. 17 and 18, respectively.

(2) Preparation of N, N'-diphenyl-4,4'-diamino-δ-torxinamide (8) N, N'-diphenyl-4,4'-dinitro-δ-torxine obtained above 2.50 g (4.66 mmol) of the amide and 0.17 g (1.63 mmol) of a 10% palladium on carbon (Pd / C) catalyst are added to 30 mL of dehydrated dimethylacetamide and N, N'-diphenyl-4,4 'at room temperature. The hydrogen reduction reaction of -dinitro-δ-torxinamide was carried out for 72 hours. After completion of the reaction, the palladium carbon (Pd / C) catalyst is removed by filtering the resulting reaction solution, and N, N'-diphenyl-4,4 'formed by removing dimethylacetamide under reduced pressure. -Diamino-δ-torxinamide (8) was recovered. The yield of the obtained N, N′-diphenyl-4,4′-diamino-δ-torxinamide (8) was 1.67 g, and the yield was 75%.

  In addition, it was confirmed from the measurement result of the following physical properties that the produced | generated compound is N, N'- diphenyl-4,4'- diamino- delta-torxinamide.

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 3.47-3.49 (m, 2 H, cyclobutane), 4.96 (s, 4 H, NH ₂ ), 6.50 (d, 4 H, J = 8.4 Hz, aromatic ring) , 6.94 (d, 4H, J = 8.3 Hz, aromatic ring), 7.01 (t, 2H, J = 7.4 Hz, aromatic ring), 7.26 (t, 4H, J = 7.9 Hz, aromatic ring), 7.63 (d, 4H, J = 7.9 Hz, aromatic ring), 10.06 (s, 2H, NH).
¹³ C-NMR (100 MHz, DMSO-d ₆ ): δ 46.9, 47.2, 114.3, 119.6, 123.7, 127.9, 129.1, 129.5, 139.5, 147.9, 171.1.

The ¹ H-NMR and ¹³ C-NMR spectra of the N, N′-diphenyl-4,4′-diamino-δ-torxinamide obtained above are shown in FIGS. 19 and 20, respectively.

Example 4 Preparation of dimethyl 4,4′-diamino-β-truxinate (11)
The scheme to prepare N, N'-diphenyl-4,4'-diamino-δ-torxinamide using 4-nitrocinnamic acid as a starting material is shown below.

(1) Preparation of methyl 4-nitrocinnamate (9) 9.98 g (51.7 mmol) of 4-nitrocinnamic acid, 100 mL of methanol and 2.5 mL of concentrated sulfuric acid are mixed, and the resulting mixed solution is heated for 3 hours. The mixture was refluxed with to give methyl 4-nitrocinnamate. The resulting reaction solution was filtered to recover methyl 4-nitrocinnamate, and the solvent was removed under reduced pressure to recover methyl 4-nitrocinnamate (9). The yield of the obtained methyl 4-nitrocinnamate (9) was 10.13 g, and the yield was 94.7%.

  In addition, it was confirmed from the measurement result of the following physical properties that the produced | generated compound is methyl 4-nitro cinnamate.

¹ H-NMR (400 MHz, DMSO-d ₆ ) δ 3.75 (s, 3 H, COOCH ₃ ), 6.85 (d, 1 H, J = 16.1 Hz, COCH = CH), 7.76 (d, 1 H, J = 16.1 Hz , COCH = CH), 8.00 (d, 2H, J = 8.80 Hz, aromatic ring), 8.23 (d, 2H, J = 8.80 Hz, aromatic ring).
¹³ C-NMR (100 MHz, DMSO-d ₆ ) δ 51.8, 122.1, 123.9, 129.5, 140.4, 142.0, 148.1, 166.2.
FT-ICR MS (SALDI): Calculated _{[M + Na, C 10 H} 9 NO 4 Na] +: 230.0422 real side value: 230.0422.

The ¹ H-NMR spectrum, ¹³ C-NMR spectrum and mass spectrum of methyl 4-nitrocinnamate obtained above are shown in FIG. 21, FIG. 22 and FIG. 23, respectively.

(2) Preparation of dimethyl 4,4'-dinitro-β-torxinate (10) 0.5 g (2.41 mmol) of the methyl 4-nitrocinnamate crystal obtained above was dispersed in 25 mL of hexane to obtain The dispersion was irradiated with ultraviolet light for 24 hours with a high pressure mercury lamp to form dimethyl 4,4'-dinitro-β-truxinate from methyl 4-nitrocinnamate.

  Next, the dispersion obtained above was filtered to recover the produced dimethyl 4,4'-dinitro-β-truxinate, which was dried under reduced pressure. The yield of the obtained dimethyl 4,4'-dinitro-β-torxinate was 0.48 g, and the yield was 96.0%.

  In addition, it was confirmed from the measurement result of the following physical properties that the produced | generated compound is dimethyl 4, 4'- dinitro- (beta) -truxic acid.

¹ H-NMR (400 MHz, DMSO-d ₆ ) δ 3.67 (s, 6 H, COOCH ₃ ), 4. 17 (m, 2 H, cyclobutane), 4.51 (m, 2 H, cyclobutane), 7. 39 (d, 4 H, J = 8.8 Hz, aromatic ring), 7.96 (d, 4H, J = 8.8 Hz, aromatic ring).
¹³ C-NMR (100 MHz, DMSO-d ₆ ) δ 41.6, 44.3, 52.0, 123.0, 129.2, 146.0, 146.3, 172.2.
FT-ICR MS (ESI): Calculated _{[M + Na, C 20 H} 18 N 2 O 8 Na] +: 437.0955 real side value: 437.0954.

The ¹ H-NMR spectrum, ¹³ C-NMR spectrum and mass spectrum of dimethyl 4,4′-dinitro-β-torxinate obtained above are shown in FIG. 24, FIG. 25 and FIG. 26, respectively.

(3) Preparation of dimethyl 4,4'-diamino-β-torxinate (11) 1.64 g (3.96 mmol) of dimethyl 4,4'-dinitro-β-torxinate obtained above and 10% palladium carbon Hydrogen of dimethyl 4,4'-dinitro-β-torxinate by adding 0.45 g (0.01 mol%) of (Pd / C) catalyst to 60 mL of methanol and heating at a temperature of 50 ° C. for 1.5 hours A reduction reaction was performed. After completion of the reaction, the palladium carbon (Pd / C) catalyst is removed by filtering the obtained reaction solution, and dimethyl 4,4'-diamino-β-torxinate formed by removing methanol under reduced pressure. (11) was recovered. The yield of the obtained dimethyl 4,4'-diamino-β-torxinate (11) was 1.30 g, and the yield was 92.9%.

  In addition, it was confirmed from the measurement result of the following physical properties that the produced | generated compound is dimethyl 4, 4'- diamino- (beta)-toluxic acid.

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 3.61 (s, 6 H, COOCH ₃ ), 3.74-3.95 (4 H, cyclobutane), 4. 76 (s, 4 H, NH ₂ ), 6.30 (d, 4 H, J = 8.3 Hz, aromatic ring), 6.66 (d, 4H, J = 8.4 Hz, aromatic ring).
¹³ C-NMR (100 MHz, DMSO-d ₆ ): δ 42.7, 44.3, 51.7, 113.5, 126.1, 128.5, 146.6, 173.1.
FT-ICR MS (ESI) calcd _{[M + H, C 20 H} 22 N 2 O 4 -H] +: 355.1658, actual side value 355.1651.

The ¹ H-NMR spectrum, ¹³ C-NMR spectrum and mass spectrum of dimethyl 4,4′-diamino-β-torxinate obtained above are shown in FIG. 27, FIG. 28 and FIG. 29, respectively.

Example 5 [Preparation of tolxic acid based polymer]
The scheme for preparing a tolxic acid based polymer (β-polyimide) using dimethyl 4,4′-diamino-β-torxinate and cyclobutanetetracarboxylic acid dianhydride is shown below.

(1) Preparation of .beta.-torxic acid dimethyl-amic acid copolymer 100 mg (0.28 mmol) of dimethyl 4,4'-diamino-.beta.-torxinate and 59 mg (0.28 mmol) of cyclobutanetetracarboxylic acid dianhydride dehydrated dimethylacetamide After dissolving in 0.2 mL, the resulting solution is stirred at room temperature for 48 hours in a nitrogen gas atmosphere to obtain dimethyl 4,4′-diamino-β-truxinate and cyclobutanetetracarboxylic acid dianhydride. Was made to react. The resulting reaction solution was reprecipitated by dropping it into methanol to obtain a β-truxnic acid dimethyl-amic acid copolymer as a white solid. The yield of the obtained β-truxnic acid dimethyl-amic acid copolymer was 61 mg, and the yield was 43.2%.

The number average molecular weight of the β-truxic acid dimethyl-amic acid copolymer obtained above was 1.03 × 10 ⁵ , and the weight average molecular weight was 1.42 × 10 ⁵ .

  In addition, the number average molecular weight and weight average molecular weight of the (beta)-toluxic acid dimethyl-amic acid copolymer obtained above were measured on the following measurement conditions by gel permeation chromatography (GPC). Also in the following examples, the number average molecular weight and the weight average molecular weight of the polymer were measured under the following measurement conditions.

〔Measurement condition〕
Device: Showa Denko KK product name: Shodex-101
· Concentration at injection: 0.001% by mass
Injection volume: 25 μL
・ Flow rate: 0.5mL / min
Solvent: N, N-dimethylformamide Column: Showa Denko KK trade name: Shodex KD-803 and trade name: Shodex KD-804
・ Column temperature: 40 ° C

The measurement result of < ¹ > H-NMR of the (beta)-toluxic acid dimethyl-amic acid copolymer obtained above is shown below. Also, ¹ H-NMR spectrum of the β-truxnic acid dimethyl-amic acid copolymer obtained above is shown in FIG.

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 3.92-4.15 (cyclobutane), 6.98-7.31 (aromatic ring), 9.95 (NH), 12.4 (COOH).

  From the above results, the β-truxnic acid dimethyl-amic acid copolymer obtained above has the formula:

(Wherein, Me represents a methyl group)
It was confirmed to have a repeating unit represented by

  Next, thermogravimetric-differential thermal analysis of the β-truxnic acid dimethyl-amic acid copolymer obtained above was performed. The results are shown in FIG. From the above results, it was confirmed that the 10% weight loss temperature of the β-truxnic acid dimethyl-amic acid copolymer obtained above was 339 ° C.

  In addition, the 10% weight loss temperature of the β-truxnic acid dimethyl-amic acid copolymer is as high as 800 ° C. by heating the tolxic acid dimethyl-amic acid copolymer in a nitrogen gas atmosphere at a heating rate of 5 ° C./min. The temperature at which the mass of the dimethyl-amic acid copolymer decreases by 10% by weight. Also in the following examples, the 10% weight loss temperature of the polymer was measured by the same method as described above.

(2) Preparation of .beta.-torxinic acid dimethyl-imide copolymer 100 mg of the above-obtained .beta.-torxic acid dimethyl-amic acid copolymer is dissolved in 0.2 mL of dimethylacetamide, and the obtained solution is cast on a glass plate, By gradually raising the temperature to 100 ° C., 150 ° C., 200 ° C. and 250 ° C. in a vacuum oven, a film of β-torxinate dimethyl-imide copolymer was formed.

The ¹ H-NMR spectrum of the β-truxnic acid dimethyl-imide copolymer obtained above is shown in FIG. As a result, the β-truxnic acid dimethyl-imide copolymer obtained above has the formula:

(Wherein, Me represents a methyl group)
It was confirmed to have a repeating unit represented by

  Next, thermogravimetric-differential thermal analysis of the β-truxnic acid dimethyl-imide copolymer obtained above was performed. The results are shown in FIG. From the above results, it was confirmed that the 10% weight loss temperature of the β-truxnic acid dimethyl-imide copolymer obtained above was 359 ° C.

Example 6 [Preparation of tolxic acid based polymer]
The scheme for preparing a tolxic acid based polymer (β-polyamide) using dimethyl 4,4′-diamino-β-torxinate and 4,4′-diacetamido-α-truxillic acid is shown below.

(1) Preparation of β-truxic acid dimethyl-amide copolymer Dimethyl 4,4'-diamino-β-truxinate (11) 301.07 mg (0.85 mmol) and 4,4'-diacetamido-α-truxic acid 343 .74 mg (0.84 mmol) were polycondensed in 0.7 mL of N-methylpyrrolidone in the presence of 0.24 mL (0.92 mmol) of triphenyl phosphite and 0.42 mL (5.2 mmol) of pyridine . Then, the obtained reaction solution was dropped into water to be reprecipitated, and the obtained precipitate was dried under reduced pressure to obtain a β-torxic acid dimethyl-amide copolymer (β-polyamide). The yield of the obtained β-truxnic acid dimethyl-amide copolymer was 0.62 g, and the yield was 96.1%.

In addition, the number average molecular weight of the β-truxnic acid dimethyl-amide copolymer obtained above was 4.63 × 10 ⁵ and the weight average molecular weight was 5.43 × 10 ⁵ .

The ¹ H-NMR spectrum of the β-truxnic acid dimethyl-amide copolymer obtained above is shown in FIG. As a result, the β-truxnic acid dimethyl-amide copolymer obtained above has the formula:

(Wherein, Me represents a methyl group and Ac represents an acetyl group)
It was confirmed to have a repeating unit represented by

  Next, the thermogravimetric-differential thermal analysis of the β-truxnic acid dimethyl-amide copolymer obtained above was performed. The results are shown in FIG. From the above results, it was confirmed that the 10% weight loss temperature of the β-truxnic acid dimethyl-amide copolymer obtained above was 330 ° C.

Example 7 [Preparation of tolxic acid based polymer]
The scheme for preparing a tolxic acid-based polymer (β-polyurea) using dimethyl 4,4′-diamino-β-torxinate and 1,3-phenylene diisocyanate is shown below.

(1) Preparation of .beta.-truxic acid dimethyl-urea copolymer 100 mg (0.28 mmol) of dimethyl 4,4'-diamino-.beta.-truxic acid and 51 mg (0.28 mmol) of 1,3-phenylene diisocyanate are dehydrated Dimethyl 4,4'-diamino-β-truxinate was reacted with 1,3-phenylene diisocyanate by dissolving in 0.2 mL of acetamide and stirring at room temperature in a nitrogen gas atmosphere for 48 hours. The resulting reaction solution was added dropwise to methanol to reprecipitate and recover the produced β-truxnic acid dimethyl-urea copolymer, and dried. The yield of the obtained β-torxinate dimethyl-urea copolymer was 120 mg, and the yield was 80.1%.

Also, beta-truxinic dimethyl obtained in the - number average molecular weight of the urea copolymer was 1.35 × 10 ^6, the weight average molecular weight was 2.00 × 10 ^6.

The ¹ H-NMR spectrum of the β-truxnic acid dimethyl-urea copolymer obtained above is shown in FIG. As a result, the β-truxidic acid dimethyl-urea copolymer obtained above has the formula:

(Wherein, Me represents a methyl group)
It was confirmed that it is a 4,4'-diamino- (beta)-toluxic acid dimethyl-urea copolymer which has a repeating unit represented by these.

  Next, the thermogravimetric-differential thermal analysis of the β-torxinate dimethyl-urea copolymer obtained above was performed. The results are shown in FIG. From the above results, it was confirmed that the 10% weight loss temperature of the β-torxinate dimethyl-urea copolymer obtained above was 271 ° C.

Example 8 [Preparation of tolxic acid based polymer]
The scheme for preparing a tolxic acid based polymer (δ-polyamide) using dimethyl 4,4′-diamino-δ-torxinate and 4,4′-diacetamido-α-truxillic acid is shown below.

(1) Preparation of δ-torxinate dimethyl-amide copolymer 99.39 mg (0.28 mmol) of dimethyl (4) 4,4'-diamino-δ-torxinate and 4,4'-diacetamido-α-truxillic acid 114 The polycondensation is carried out in 0.28 mL of N-methylpyrrolidone (NMP) in the presence of 80 .mu.L (0.305 mmol) of triphenyl phosphite and 0.14 mL (1.74 mmol) of pyridine.95 mg (0.28 mmol) The The reaction solution obtained above was dropped into methanol to reprecipitate the produced δ-truxnic acid dimethyl-amide copolymer, recovered by filtration, and then dried under reduced pressure. The yield of the obtained δ-truxnic acid dimethyl-amide copolymer was 0.12 g, and the yield was 56.6%.

In addition, the number average molecular weight of the δ-truxnic acid dimethyl-amide copolymer obtained above was 9.23 × 10 ⁴ , and the weight average molecular weight was 1.95 × 10 ⁵ .

The ¹ H-NMR spectrum of the δ-truxnic acid dimethyl-amide copolymer obtained above is shown in FIG. As a result, the δ-truxnic acid dimethyl-amide copolymer obtained above has the formula:

(Wherein, Me represents a methyl group and Ac represents an acetyl group)
It was confirmed that the 4,4'-diamino-δ-truxnic acid dimethyl-amide copolymer has a repeating unit represented by

  Next, the thermogravimetric-differential thermal analysis of the δ-truxnic acid dimethyl-amide copolymer obtained above was performed. The results are shown in FIG. From the above results, it was confirmed that the 10% weight loss temperature of the δ-truxnic acid dimethyl-amide copolymer obtained above was 430 ° C.

  Also, the differential scanning calorimetry (DSC) of the δ-truxnic acid dimethyl-amide copolymer obtained above was examined. The results are shown in FIG. From the results shown in FIG. 40, it was confirmed that the glass transition temperature of the δ-truxnic acid dimethyl-amide copolymer obtained above was 246 ° C.

Example 9 [Preparation of tolxic acid based polymer]
The scheme for preparing a tolxic acid based polymer (δ-polyimide) using N, N′-diphenyl-4,4′-diamino-δ-torxinamide and cyclobutanetetracarboxylic acid dianhydride is shown below.

(1) Preparation of δ-torxinamide / amide acid copolymer N, N'-diphenyl-4,4'-diamino-δ-torxinamide (8) 200 mg (0.42 mmol) and cyclobutanetetracarboxylic acid dianhydride After dissolving 82 mg (0.42 mmol) of (CBDA) in 0.7 mL of dehydrated dimethylacetamide, N, N'-diphenyl-4,4'-diamino is obtained by stirring at room temperature in a nitrogen gas atmosphere for 48 hours. -Δ-torxinamide was reacted with cyclobutanetetracarboxylic acid dianhydride. The resulting reaction solution was dropped into ethanol and reprecipitated to recover a white solid δ-torxinamide-amic acid copolymer. The yield of the δ-truxnic acid amide-amic acid copolymer obtained above was 245 mg, and the yield was 87%.

The number average molecular weight of the δ-truxnic acid amide-amic acid copolymer obtained above was 4.48 × 10 ⁵ , and the weight average molecular weight was 4.90 × 10 ⁵ .

The ¹ H-NMR spectrum of the δ-truxnic acid amide-amic acid copolymer obtained above was examined. The results are shown below.

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 3.84-3.51 (cyclobutane), 7.55-7.61 (aromatic ring), 10.16 (NH), 12.40 (COOH)

Also, ¹ H-NMR spectrum of the δ-truxnic acid amide-amic acid copolymer is shown in FIG. From the above results, the δ-truxnic acid amide-amic acid copolymer obtained above has the formula:

(Wherein, Ph represents a phenyl group)
It was confirmed that the copolymer was a δ-truxnic acid amide-amic acid copolymer having a repeating unit represented by

  Next, 200 mg of the δ-truxnic acid amide-amic acid copolymer obtained above is dissolved in 2 mL of dimethylacetamide, the obtained solution is cast on a glass plate, and 100 ° C., 150 ° C., 200 ° C. in a vacuum oven. And by gradually raising the temperature to 250 ° C., a film of δ-torxinamide-imide copolymer was formed.

The ¹ H-NMR spectrum of the δ-truxnic acid amide-imide copolymer obtained above is shown in FIG. As a result, the δ-truxnic acid amide-imide copolymer obtained above has the formula:

(Wherein, Ph represents a phenyl group)
It was confirmed to have a repeating unit represented by

  Next, thermogravimetric-differential thermal analysis of the δ-truxnic acid amide-imide copolymer obtained above was performed. The results are shown in FIG. From the above results, it was confirmed that the 10% weight loss temperature of the δ-torxinamide-imide copolymer obtained above was 384 ° C.

Example 10 [Preparation of δ-truxnic acid amide-α-truxillic acid diester-imide terpolymer]
N, N'-diphenyl-4,4'-diamino-δ-torxinamide (8), dimethyl 4,4'-diamino-α-truxyl acid, δ-torxic acid using cyclobutanetetracarboxylic acid dianhydride The scheme for preparing an amido-α-truxilic acid diester-imide terpolymer is shown below.

(1) Preparation of δ-torxinic acid amide-α-truxic acid dimethyl-amic acid terpolymer 121 mg (0.25 mmol) of N, N′-diphenyl-4,4′-diamino-δ-torxinamide (8), After dissolving 94 mg (0.25 mmol) of dimethyl 4,4'-diamino-α-truxyl acid and 100 mg (0.50 mmol) of cyclobutanetetracarboxylic acid dianhydride (CBDA) in 0.85 mL of dehydrated dimethylacetamide, nitrogen gas is used. By stirring for 48 hours at room temperature in the atmosphere, N, N'-diphenyl-4,4'-diamino-δ-torxinamide, dimethyl 4,4'-diamino-α-truxylate and cyclobutanetetracarboxylic acid The dianhydride was reacted. The resulting reaction solution is dropped into ethanol, and the formed δ-torxinic acid amide-α-truxic acid dimethyl-amic acid terpolymer is reprecipitated to obtain δ-torxic acid amide-α-torxylic acid as a white solid. The dimethyl-amic acid terpolymer was recovered. The yield of the δ-truxcinamide-α-truxillic acid dimethyl-amic acid terpolymer obtained above was 261 mg, and the yield was 83%.

In addition, the number average molecular weight of the δ-truxnic acid amide-α-truxillic acid dimethyl-amic acid terpolymer obtained above is It was 2.16 × 10 ⁵ and the weight average molecular weight was 3.39 × 10 ⁵ .

The ¹ H-NMR spectrum of the δ-truxcinamide-α-truxillic acid dimethyl-amic acid terpolymer obtained above was examined. The results are shown below.

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 3.54-4.27 (cyclobutane), 7.25-7.64 (aromatic ring), 10.22 (NH), 12.42 (COOH)

Further, ¹ H-NMR spectrum of the δ-truxnic acid ester-α-truxillic acid dimethyl-amic acid terpolymer is shown in FIG. From the above results, the δ-truxcinamide-α-truxillic acid dimethyl-amic acid terpolymer obtained above has the formula:

(Wherein, Ph represents a phenyl group and Me represents a methyl group)
It was confirmed to have a repeating unit represented by

(2) Preparation of δ-torxinamide-α-truxillic acid dimethyl-imide terpolymer The above-obtained δ-torxinamide-α-truxillic acid dimethyl-amide acid terpolymer is dissolved in dimethylacetamide to obtain The solution is cast on a glass plate, and δ-torxinamide-α-truxillic acid dimethyl-imide terpolymer is obtained by gradually raising the temperature to 100 ° C., 150 ° C., 200 ° C. and 250 ° C. in a vacuum oven. The film was formed.

The ¹ H-NMR spectrum of the δ-truxcinamide-α-truxillic acid dimethyl-imide terpolymer obtained above is shown in FIG. As a result, the δ-truxnic acid amide-α-truxillic acid dimethyl-imide terpolymer obtained above has the formula:

(Wherein, Ph represents a phenyl group and Me represents a methyl group)
It was confirmed to have a repeating unit represented by

  Next, the thermogravimetric-differential thermal analysis of the δ-truxnic acid amide-α-truxillic acid dimethyl-imide terpolymer obtained above was performed. The results are shown in FIG. From the above results, it was confirmed that the 10% weight loss temperature of the δ-truxcinamide-α-truxillic acid dimethyl-imide terpolymer obtained above was 385 ° C.

Comparative Example 1
The α-polyimide was prepared according to the “synthesis example of polyimide” described in WO 2013/073519.

Experimental Example The solubility of the polymer obtained in each Example or Comparative Example 1 in an organic solvent (25 ° C.) was examined, and the solubility was evaluated based on the following evaluation criteria. The results are shown in Table 1. The abbreviations shown in Table 1 mean the following.

MeOH: methanol THF: tetrahydrofuran DMSO: dimethylsulfoxide DMF: dimethylformamide NMP: N-methylpyrrolidone DMAc: dimethylacetamide TFA: trifluoroacetic acid

〔Evaluation criteria〕
++: excellent in solubility +: good in solubility-: insoluble

  From the results shown in Table 1, it can be seen that the polymers obtained in the respective examples are excellent in the solubility in various organic solvents as compared with the polymer obtained in the conventional Comparative Example 1. Therefore, the polymers obtained in the respective examples are expected to be used for applications such as resin films and coatings.

The tolxic acid-based polymer of the present invention is used in applications such as aerospace, for example, parts for aircraft, cars, parts for railway vehicles, parts for ships, parts for machines, electrical parts, electronic parts, parts for computers, etc. Is expected.

Claims (4)

Formula (I):

[Wherein, R ¹ and R ² each independently represent an —OR ³ group (R ³ represents an alkyl group, an alkenyl group or an aryl group), an —SR ³ group (R ³ is as defined above), or — NHR ³ group (R ³ is as defined above)
In a belt Rukishin acid polymer to contain a repeating unit having a group represented, the recurring unit has the formula (VIII):

(Wherein, R ¹ and R ² are the same as above. R ⁷ and R ⁸ each independently represent a cycloalkyl group having 4 to 6 carbon atoms or an acetamide group)
The repeating unit represented by, formula (IX):

(Wherein, R ¹ and R ² are as defined above)
Repeating unit represented by or formula (X):

(Wherein, R ¹ and R ² are as defined above)
A tolxic acid based polymer characterized by being a repeating unit represented by Formula (Ia):

[Wherein, R ¹ and R ² each independently represent an —OR ³ group (R ³ represents an alkyl group, an alkenyl group or an aryl group), an —SR ³ group (R ³ is as defined above), or — NHR ³ group (R ³ is as defined above)
4,4'-diaminotruxic acid derivative represented by Formula (II):

[Wherein, R ¹ and R ² each independently represent an —OR ³ group (R ³ represents an alkyl group, an alkenyl group or an aryl group), an —SR ³ group (R ³ is as defined above), or — NHR ³ group (R ³ is as defined above)
The 4,4'- diamino- (beta)-tolxic acid derivative represented by these. Formula (VII):

[Wherein, R ¹ and R ² each independently represent an —OR ³ group (R ³ represents an alkyl group, an alkenyl group or an aryl group), an —SR ³ group (R ³ is as defined above), or — NHR ³ group (R ³ is as defined above)
4,4'-Diamino-δ-truxic acid derivative represented by

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