阅读说明：本技术 二胺化合物、二胺化合物的制造方法和聚酰亚胺 (Diamine compound, process for producing diamine compound, and polyimide ) 是由 佐藤义昌 高桥浩司 青山悟 柏原徹也 于 2018-04-24 设计创作，主要内容包括：由H<Sub>2</Sub>NH<Sub>2</Sub>C-Ro<Sup>2</Sup>-CH<Sub>2</Sub>NH<Sub>2</Sub>(式中,Ro<Sup>2</Sup>表示树脂酸二聚体残基)表示的二胺化合物。(From H 2 NH 2 C‑Ro 2 ‑CH 2 NH 2 (wherein, Ro 2 Representing a residue of a resin acid dimer).)

1. A diamine compound consisting of H₂NH₂C-Ro²-CH₂NH₂Is represented by the formula, wherein²Represents a residue of a resin acid dimer.

2. The diamine compound according to claim 1, which is a diamine compound of the following structure:

3. a method for producing a diamine compound, comprising the steps of: by reacting N ≡ C-Ro²-C ≡ N, to produce the diamine compound according to claim 1 or 2, wherein Ro²Represents a residue of a resin acid dimer.

4. The method for producing a diamine compound according to claim 3, further comprising the step of: make Ro from¹A mono-nitrile compound represented by-C.ident.N, wherein Ro is used as the raw material, to produce the dinitrile compound¹Represents a resin acid residue.

5. The method for producing a diamine compound according to claim 3, further comprising the step of: from R-OOC-Ro²Reacting a diester compound represented by-COO-R with ammonia to produce the dinitrile compound, wherein Ro²Represents a residue of a resin acid dimer, and R represents an alkyl group having 1 to 10 carbon atoms.

6. A polyimide comprising a monomer unit derived from the diamine compound according to claim 1 or 2 and a monomer unit derived from a tetracarboxylic dianhydride.

Technical Field

The present invention relates to a diamine compound, a method for producing a diamine compound, and a polyimide. More specifically, the present invention relates to a diamine compound having a resin acid dimer residue as a main skeleton, a process for producing the diamine compound, and a polyimide.

Background

Diamine compounds are compounds widely used in the fields of organic chemistry and polymer chemistry, and are particularly useful as monomers of polyimide resins used in fibers, electronic materials, automobile materials, aerospace materials, and the like. Polyimide resins are known to be excellent in heat resistance, mechanical properties, and chemical resistance. With the expansion of applications, polyimide resins are required to have higher heat resistance and higher mechanical properties than ever before. Among them, polyimide having a bulky skeleton is excellent in heat resistance (see patent document 1).

Disclosure of Invention

It is considered that a diamine compound having an alicyclic structure in the molecule and a rigid and bulky skeleton not only imparts a polymer having more excellent heat resistance, but also expands applications that have not been achieved heretofore. Accordingly, an object of the present invention is to provide a diamine compound which has more excellent heat resistance and can be extended to various new uses, a method for producing the diamine compound, and a polyimide.

The diamine compound according to one embodiment of the present invention to solve the above problems is represented by H₂NH₂C-Ro²-CH₂NH₂(wherein, Ro²Representing a residue of a resin acid dimer).

Solve the problem ofA method for producing a diamine compound according to one aspect of the present invention to solve the above problems is a method for producing a diamine compound, comprising: by reacting N ≡ C-Ro²-C ≡ N (in the formula, Ro)²Representing a resin acid dimer residue) to produce the diamine compound.

A polyimide according to an embodiment of the present invention to solve the above problems is a polyimide comprising a monomer unit derived from the diamine compound and a monomer unit derived from a tetracarboxylic dianhydride.

Drawings

FIG. 1 is an infrared absorption spectrum of dimerized rosin diamine obtained in example 1.

FIG. 2 is a DI/MS diagram of dimerized rosin diamine obtained in example 1.

FIG. 3 is a GPC chart of dimerized rosin diamine obtained in example 1.

FIG. 4 is an infrared absorption spectrum of dimerized rosin diamine obtained in example 3.

FIG. 5 shows the dimerized rosin diamine obtained in example 3¹HNMR map.

FIG. 6 is a GPC chart of dimerized rosin diamine obtained in example 3.

FIG. 7 is an infrared absorption spectrum chart of a polyimide obtained in example 4.

Detailed Description

The diamine compound of one embodiment of the present invention is represented by H₂NH₂C-Ro²-CH₂NH₂(wherein, Ro²Represents a residue of a resin acid dimer. Hereinafter, abbreviated as formula) are described. An example of the structure is shown below.

(Structure I)

(Structure II)

The resin acid dimer which is a precursor of the diamine compound of the present embodiment is composed of HOOC-Ro²-COOH (formula, Ro)²Represents a residue of a resin acid dimer. The following is illustrated in the omitted drawings. ) And (4) showing. In the present specification, the term "residue of a resin acid dimer" refers to a portion obtained by removing two carboxyl groups from the resin acid dimer. For Ro²And is not particularly limited. Ro²Can be exemplified by Ro¹-L₁-Ro¹(wherein, Ro¹Is a resin acid residue, L₁Represents a single bond or a methylene group). In the present specification, the term "resin acid residue" refers to a residue derived from Ro¹-COOH, the portion of the resin acid from which the carboxyl group has been removed. An example of the structure of the resin acid dimer is shown below.

The diamine compound of the present embodiment can be prepared by reacting N.ident.C-Ro²-C ≡ N (in the formula, Ro)²Represents a residue of a resin acid dimer. Hereinafter, abbreviated as the formula) is reduced.

Dinitrile compounds can be employed such that the compound has Ro¹-C ≡ N (in the formula, Ro)¹Represents a resin acid residue. The following is illustrated in the omitted drawings. ) The method of dimerization of the mononitrile compound (hereinafter, also referred to as method [1]]) Or, made by ROOC-Ro²-COOR (in the formula, Ro)²Represents a residue of a resin acid dimer, and R represents an alkyl group having 1 to 10 carbon atoms. The following is illustrated in the omitted drawings. ) A method of reacting the diester compound with ammonia (hereinafter, also referred to as method [2]]) And (4) manufacturing.

< method [1] >)

The mononitrile compound as the starting material in the process [1] is obtained by cyanating a resin acid with ammonia by various known methods.

Examples of the resin acids include abietic acid, neoabietic acid, balacetric acid, levopimaric acid, dehydroabietic acid, dihydroabietic acid, tetrahydroabietic acid, pimaric acid, isopimaric acid, sandaracopimaric acid, and dehydroabietic acid.

Resin acids are contained in various rosins. Specifically, examples of the various rosins include natural rosins (gum rosin, tall oil rosin, wood rosin) derived from masson pine, marsh pine (slash pine), メ ル ク シ pine, pinus sylvestris, loblolly pine, king pine, etc., purified rosins obtained by purifying natural rosins, hydrogenated rosins obtained by hydrogenating natural rosins, and disproportionated rosins obtained by disproportionating natural rosins.

The method and conditions for the above-mentioned cyanation reaction are not particularly limited. The method and conditions for the cyanation reaction can be any of various known methods. Specifically, the cyanation reaction may be carried out by, for example, heating and melting the rosin and blowing ammonia gas into the melt by various known means. The blowing conditions are not particularly limited. Generally, the blowing conditions are about 0.5 to 20 mol/hr of ammonia per 1 mol of resin acid contained in the rosin, the reaction temperature is about 140 to 360 ℃, and the reaction time is about 1 to 50 hours. In the cyanation reaction, a catalyst such as zinc oxide, calcium hydroxide, or magnesium hydroxide can be used. The amount of the catalyst used is not particularly limited. The amount of the catalyst used is usually about 0.1 to 50 parts by mass, preferably about 1 to 20 parts by mass, based on 100 parts by mass of the rosin.

To Ro contained in the product (rosin nitrile) obtained above¹The amount of the mononitrile compound represented by-C.ident.N is not particularly limited. The amount of the mononitrile compound is usually 80% by weight or more, preferably 85% by weight or more, and more preferably 90% by weight or more and less than about 99.9% by weight. The product can be purified by various known means. The content of the mononitrile compound can be quantified by various known means. Specifically, the content of the mononitrile compound was determined by GC/MS based on the sum of the total peak areas of the rosin nitriles and the corresponding mononitrificationThe ratio of the peak area of the compound was determined.

Next, the mononitrile compound is dimerized. The dimerization reaction is not particularly limited. The dimerization reaction can be carried out by various known methods. Specifically, examples of the dimerization reaction include a method of heating the rosin nitrile in the presence or absence of a catalyst and an organic solvent (hereinafter referred to as method [1] -1), and a method of reacting the rosin nitrile in the presence of formaldehyde, an acid catalyst and an organic solvent (hereinafter referred to as method [1] -2).

Examples of the catalyst of the method [1] -1 include acid catalysts such as sulfuric acid, formic acid, acetic acid, phosphoric acid, p-toluenesulfonic acid, methanesulfonic acid and solid acids having sulfonic acid groups, Lewis acid catalysts such as hydrogen fluoride, zinc chloride, aluminum chloride, titanium tetrachloride, boron trifluoride and boron trifluoride phenol complex, boron trifluoride derivatives such as boron trifluoride dimethyl ether complex and boron trifluoride diethyl ether complex, and polymers having pendant sulfonic acid groups such as polystyrenesulfonic acid, polyvinylsulfonic acid and fluorine-based polymers having sulfonic acid type functional groups. The catalysts of the processes [1] -1 may be used in combination. In terms of ease of removal, the catalyst is particularly preferably at least one selected from the group consisting of sulfuric acid, formic acid, phosphoric acid, p-toluenesulfonic acid, methanesulfonic acid, a solid acid having a sulfonic acid group, and zinc chloride. The amount of the catalyst used is not particularly limited. The amount of the catalyst used is usually about 0.1 to 90 parts by weight, preferably about 1 to 20 parts by weight, based on 100 parts by weight of the rosin nitrile. In addition, the heating conditions in the above method are not particularly limited. The heating conditions are usually about 0 to 200 ℃ and about 0.5 to 24 hours.

Examples of the organic solvent used in the method [1] -1 include aromatic hydrocarbons such as toluene, xylene and tetrahydronaphthalene: aliphatic hydrocarbons such as heptane, octane, and the like: ketone hydrocarbons such as methyl ethyl ketone and methyl isopropyl ketone: ester hydrocarbons such as ethyl acetate and butyl acetate: halogen-based hydrocarbons such as carbon tetrachloride, ethylene dichloride, trichloroethane and tetrachloroethane: and carboxylic group-containing organic acids such as acetic acid, propionic acid, butyric acid and anhydrides thereof, formic acid, chloroacetic acid, and lactic acid. The organic solvents of the methods [1] -1 can be used in combination. Further, in the case of using formic acid or acetic acid, since these also function as a polymerization catalyst, the above-mentioned catalyst may not be used. The organic solvent used in the method [1] -1 is preferably the above aromatic hydrocarbon and/or aliphatic hydrocarbon, particularly preferably xylene, heptane, octane or the like, from the viewpoint of easiness of recovery and reuse. The amount of the organic solvent used is not particularly limited. The amount of the organic solvent used is usually about 1 to 900 parts by weight, preferably about 1 to 500 parts by weight, based on 100 parts by weight of the rosin nitrile.

The acid catalyst of the method [1] -2 is, for example, the acid catalyst of the method [1] -1, or the like. The acid catalysts of the methods [1] -2 can be used in combination. The amount of the catalyst used is not particularly limited. The amount of the catalyst used is usually about 0.1 to 200 parts by weight, preferably about 1 to 50 parts by weight, based on 100 parts by weight of the rosin nitrile. The reaction conditions in the method [1] -2 are also not particularly limited. The reaction conditions are usually about-30 to 200 ℃, preferably about 0 to 100 ℃ and about 0.5 to 24 hours.

The organic solvent of the method [1] -2 can be exemplified by the organic solvent of the method [1] -1, and the like. The organic solvents of the methods [1] -2 can be used in combination. The organic solvent used in the method [1] to [2] is preferably an aromatic hydrocarbon and/or an ester hydrocarbon, and particularly preferably ethyl acetate, butyl acetate, or the like, from the viewpoint of high solubility of the raw material. The amount of the organic solvent used is not particularly limited. The amount of the organic solvent used is usually about 1 to 500 parts by weight, preferably about 1 to 200 parts by weight, based on 100 parts by weight of the rosin nitrile.

The formaldehyde used in the method [1] -2 is not particularly limited. Examples of the formaldehyde used in the methods [1] -2 include paraformaldehyde and formalin. The formaldehyde of the process [1] -2 may be used in combination. The formaldehyde used in the method [1] -2 is preferably paraformaldehyde from the viewpoint of solubility. The amount of formaldehyde used is not particularly limited. The amount of formaldehyde used is usually about 1 to 100 parts by weight, preferably about 1 to 30 parts by weight, based on 100 parts by weight of the rosin nitrile.

Method [1]-1 and [1]2, after the dimerization reaction is completed, the product is produced by washing with water, neutralization with an alkali, filtration, distillation under reduced pressure, or the likeThe product (dimerized rosin dinitrile) is optionally freed from the above-mentioned solvent, catalyst, unreacted mononitrile compound, decomposition product, etc. to obtain a resin composed of N.ident.C-Ro²-a dinitrile compound represented by-C ≡ N. The conditions for the distillation under reduced pressure are not particularly limited. The reduced pressure distillation is usually carried out at about 200 to 290 ℃ and about 60 to 8000 Pa. The content of the dinitrile compound in the dimerized rosin dinitrile is not particularly limited. The content of the dinitrile compound is usually 80% by weight or more, preferably 85% by weight or more, more preferably 90% by weight or more and less than 99.9% by weight. The content of the dinitrile compound can be quantified by various known means. Specifically, the content of the dinitrile compound can be determined by the method of measurement using GC/MS described above.

< method [2] >)

Shown below as method [2]Of the starting material of (a) by ROOC-Ro²Examples of the structure of diester compounds represented by-COOR.

(wherein R represents an alkyl group having 1 to 10 carbon atoms.)

(wherein R represents an alkyl group having 1 to 10 carbon atoms.)

The diester compound can be produced by various known methods. Specifically, the diester compound can be prepared, for example, by the method described in International publication No. 2014/030652.

The method for producing the diester compound is not particularly limited. The diester compound can be produced by various known methods. Specifically, examples of the diester compound include a method of dimerizing a rosin ester obtained by esterification of the above rosin or its chloride with a monohydric alcohol having about 1 to 10 carbon atoms (hereinafter referred to as method [2] -1), and a method of esterifying a dimerized rosin obtained by dimerization of the rosin with a monohydric alcohol (hereinafter referred to as method [2] -2).

Examples of the monohydric alcohol include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, and pentanol. The monohydric alcohol is preferably a monohydric alcohol having about 1 to 5 carbon atoms, and particularly preferably methanol, from the viewpoint of the yield of the diester compound.

The esterification reaction in the method [2] -1 is not particularly limited. The esterification reaction of Process [2] -1 can be carried out by various known methods. Specifically, the esterification reaction in the method [2] -1 is carried out by, for example, a method of esterifying the rosin with the monohydric alcohol. Specifically, the esterification reaction in the method [2] -1 is exemplified by a method of reacting the resin acid contained in the rosin with the monohydric alcohol by converting the resin acid into a resin acid chloride by, for example, a thionyl chloride method; and a method in which a resin acid is reacted with the monohydric alcohol under pressure, then a mixed solution of the monohydric alcohol and water is removed from the reaction system, and then a new monohydric alcohol is further charged and subjected to esterification reaction again.

In the method [2]The rosin ester obtained in (1) contains Ro¹-COOR (in the formula, Ro)¹Represents a resin acid residue, and R represents an alkyl group having 1 to 10 carbon atoms. The following is illustrated in the omitted drawings. ) The monoester compound shown.

The dimerization reaction of the monoester according to the method [2] -1 can be carried out by the same method and conditions as those for the dimerization reaction of the mononitrile compound described above. After the dimerization reaction is completed, the organic solvent, the catalyst, the unreacted monoester and the decomposed product can be removed from the product by the above-mentioned means and conditions, if necessary.

In the method [2]The product (dimerized rosin diester) obtained in (1) contains ROOC-Ro²A diester compound represented by-COOR. The amount of the diester compound is not particularly limited. The content of the diester compound is usually 80% by weight or more, preferably 85% by weight or more, more preferably 90% by weight or more and less than 99.9% by weight. The content of the diester compound can be determined by various known means. Specifically, the content of the diester compound is measured by Gel Permeation Chromatography (GPC) based on dimerized rosinThe ratio of the total peak area of the diester to the peak area corresponding to the diester compound was determined.

The dimerization reaction of rosins in the method [2] -2 can be carried out by the above dimerization reaction and conditions thereof.

In the method [2]The product (dimerized rosin) obtained in (1) contains HOOC-Ro²-resin acid dimer represented by-COOH. The content of the resin acid dimer is not particularly limited. The content of the resin acid dimer is usually 80% by weight or more, preferably 85% by weight or more, more preferably 90% by weight or more and less than 99.9% by weight. The content of the resin acid dimer can be quantified by various known means. Specifically, the content of the resin acid dimer is determined by the method of measurement using the Gel Permeation Chromatography (GPC) described above.

The esterification reaction of the dimerized rosin with the monohydric alcohol in the method [2] -2 can be carried out by the above-mentioned esterification method and conditions. Specifically, the esterification reaction includes, for example, a method of reacting dimerized rosin with the monohydric alcohol by producing an acid chloride by, for example, a thionyl chloride method; a method in which dimerized rosin is reacted with the monohydric alcohol under pressure, and then a mixed solution of the monohydric alcohol and water is removed from the reaction system, and then a new monohydric alcohol is further charged, and the esterification reaction is performed again.

In the method [2]The product (dimerized rosin diester) obtained in (E) -2 contains ROOC-Ro²A diester compound represented by-COOR. The content of the diester compound is not particularly limited. The content of the diester compound is usually 80% by weight or more, preferably 85% by weight or more, more preferably 90% by weight or more and less than 99.9% by weight. The content of the diester compound can be determined by various known means. Specifically, the content of the diester compound can be determined by the method of measurement using Gel Permeation Chromatography (GPC) as described above.

As the method for reacting the dimerized rosin diester obtained in the methods [2] -1 and [2] -2 with ammonia, the same method and conditions as those of the above-mentioned cyanation reaction can be employed. Specifically, for example, the dimerized rosin diester is melted by heating, and an ammonia gas is blown into the melt under the above conditions. In addition, the above-mentioned cyanation catalyst can be used in the reaction.

After completion of the above-mentioned cyanation reaction, the product (dimerized rosin dinitrile) is optionally subjected to removal of the catalyst, unreacted mononitrile compound, decomposition product and the like by washing with water, neutralization with an alkali, filtration, distillation under reduced pressure or the like to obtain a resin composed of N.ident.C-Ro²-a dinitrile compound represented by-C ≡ N. The content of the dinitrile compound in the dimerized rosin dinitrile is not particularly limited. The content of the dinitrile compound is usually 80% by weight or more, preferably 85% by weight or more, more preferably 90% by weight or more and less than 99.9% by weight.

Dimerized rosin dinitriles consisting of N ≡ C-Ro²The identification and quantification of dinitrile compounds represented by-C.ident.N can be carried out by various known means. Specifically, examples of means for identifying and quantifying the dinitrile compound include an infrared spectroscopy method, a nuclear magnetic resonance method, a Gas Chromatography (GC) analysis method, a GC/MS method, and the like.

The diamine compound of the present embodiment can be produced by subjecting the dinitrile compound obtained in the above-described methods [1] and [2] to a reduction reaction. The method and conditions for the reduction reaction are not particularly limited. The method and conditions for the reduction reaction can be various known means. Specifically, examples of the method and conditions for the reduction reaction include a method (hydrogenation reduction) in which a dinitrile compound is reduced in the presence of a reducing agent and a solvent, and a method (hydrogenation) in which the dinitrile compound is reduced by heating under pressure of hydrogen in the presence of a hydrogenation catalyst.

The method and conditions for the hydrogenation reduction are not particularly limited. The method and conditions for the hydrogenation reduction can be various known means. The reducing agent is not particularly limited. Examples of the reducing agent include a boron hydride-based reducing agent such as lithium borohydride, sodium tetrahydroborate, sodium cyanoborohydride, lithium triethylborohydride, sodium triacetoxyborohydride, and lithium tris (sec-butyl) borohydride, and an aluminum hydride reducing agent such as lithium aluminum hydride, diisobutylaluminum hydride, lithium triethoxyaluminum hydride, and sodium bis (2-methoxyethoxy) aluminum hydride (SMEAH). The amount of the reducing agent used is not particularly limited. The amount of the reducing agent used is usually about 0.1 to 500 parts by weight, preferably about 1 to 300 parts by weight, based on 100 parts by weight of the dinitrile. The solvent is not particularly limited. Examples of the solvent include aromatic hydrocarbons such as toluene, xylene, and tetralin: aliphatic hydrocarbons such as heptane, octane, and the like: ketone hydrocarbons such as methyl ethyl ketone and methyl isopropyl ketone: ester hydrocarbons such as ethyl acetate and butyl acetate: and halogen-based hydrocarbons such as carbon tetrachloride, ethylene dichloride, trichloroethane, and tetrachloroethane. The above solvents may be used in combination. In addition, the amount of the solvent used is not particularly limited. The amount of the solvent used is usually about 1 to 800 parts by weight, preferably about 1 to 500 parts by weight, based on 100 parts by weight of the dinitrile compound. Further, the reaction temperature is not particularly limited. The reaction temperature is about-30 ℃ to 200 ℃, and the reaction time is about 0.5 to 24 hours.

The method and conditions for the hydrogenation are also not particularly limited. The method and conditions for the hydrogenation can be various known means. The hydrogenation is carried out, for example, by heating the dinitrile compound in the presence of a hydrogenation catalyst under a hydrogen pressure of usually about 1 to 100MPa, preferably about 1 to 20MPa for about 0.5 to 24 hours. The hydrogenation catalyst is not particularly limited, and various known catalysts can be used. The hydrogenation catalyst can preferably be exemplified by nickel-based, cobalt-based, palladium-based, rhodium-based, ruthenium-based, and platinum-based catalysts. The hydrogenation catalyst is usually used by being supported on a carrier such as carbon, silica or alumina. The amount of the hydrogenation catalyst used is usually about 0.1 to 100 parts by weight, preferably about 0.1 to 40 parts by weight, based on 100 parts by weight of the dinitrile compound. The hydrogenation temperature is about 0 to 300 ℃, preferably about 10 to 200 ℃. The hydrogenation may be carried out in a state where the dinitrile compound is dissolved in a solvent, if necessary. The solvent used is not particularly limited. The solvent is preferably a solvent which is inactive to the reaction and easily dissolves the starting materials and the product. Examples of the solvent include cyclohexane, n-hexane, n-heptane, decalin, tetrahydrofuran, dioxane, and the like. The solvents may be used in combination. The amount of the solvent used is not particularly limited. The solvent is generally used so that the solid content is about 10% by weight or more of the dinitrile compound. The amount of the solid component is preferably in the range of 10 to 70 wt%. In addition, ammonia, an aqueous alkali solution, a solid base, or the like may be added as a solvent in order to suppress the by-production of the secondary amine and the tertiary amine. The amount to be added is not particularly limited. The amount of the compound to be added is preferably 1 to 60 parts by weight based on 100 parts by weight of the dinitrile compound.

The diamine compound of the present embodiment can also be obtained by subjecting the dimerized rosin dinitrile obtained in methods [1] and [2] to a reduction reaction instead of the dinitrile compound. The above-mentioned reduction or hydrogenation can be carried out in the same manner and under the same conditions for the reduction of the dimerized rosin dinitrile.

After the completion of the reduction reaction, the catalyst, unreacted monoamine compound, decomposed product and the like are removed from the product (dimerized rosin diamine) by means of washing with water, neutralization with an alkali, filtration, distillation under reduced pressure or the like as necessary to obtain a product composed of H₂NH₂C-Ro²-CH₂NH₂The diamine compound represented. The content of the diamine compound in the dimerized rosin diamine is not particularly limited. The content of the diamine compound is usually 60% by weight or more, preferably 80% by weight or more, and more preferably 99% by weight or more.

H in the dimerized rosin diamine of the present embodiment₂NH₂C-Ro²-CH₂NH₂The diamine compound represented can be identified and quantified by various known means. Specifically, examples of the identification and quantification of the diamine compound include an infrared spectroscopy method, a nuclear magnetic resonance method, Gel Permeation Chromatography (GPC), Gas Chromatography (GC) analysis, and DI/MS method.

The polyimide of the present embodiment is a reaction product containing a reaction component (α) (hereinafter referred to as the (α) component) of the diamine compound (a1) (hereinafter referred to as the (a1) component) of the present embodiment and a tetracarboxylic dianhydride (a2) (hereinafter referred to as the (a2) component). That is, the component (α) contains a monomer unit derived from the diamine compound (a1) and a monomer unit derived from the tetracarboxylic dianhydride (a 2).

As the component (a2), various known tetracarboxylic dianhydrides can be used without particular limitation. Specifically, examples of the component (a2) include aliphatic tetracarboxylic acid dianhydride, aromatic tetracarboxylic acid dianhydride, and the like.

Examples of the aliphatic tetracarboxylic acid dianhydride include 1, 2, 3, 4-butanetetracarboxylic acid dianhydride, 1, 2, 3, 4-cyclobutanetetracarboxylic acid dianhydride, 1, 2, 3, 4-cyclopentanetetracarboxylic acid dianhydride, 1, 2, 4, 5-cyclohexanetetracarboxylic acid dianhydride, bicyclo (2, 2, 2) oct-7-ene-2, 3, 5, 6-tetracarboxylic acid dianhydride, bicyclo (2, 2, 2) octane-2, 3, 5, 6-tetracarboxylic acid dianhydride, 2, 3, 5-tricarboxycyclopentylacetic acid dianhydride, 3, 5, 6-tricarboxynorbornane-2-acetic acid dianhydride, 4, 5-tetrahydrofurantetracarboxylic acid dianhydride, 3-carboxymethyl-1, 2, 4-cyclopentanetricarboxylic acid-1, 4: 2, 3-dianhydride, and the like. Aliphatic tetracarboxylic dianhydrides may be used in combination.

Examples of the aromatic tetracarboxylic acid dianhydride include pyromellitic dianhydride, 4, 4 ' -oxydiphthalic dianhydride, 3, 3 ', 4, 4 ' -benzophenonetetracarboxylic acid dianhydride, 3, 3 ', 4, 4 ' -diphenylethertetracarboxylic acid dianhydride, 3, 3 ', 4, 4 ' -diphenylsulfonetetracarboxylic acid dianhydride, 1, 2, 3, 4-benzenetetracarboxylic acid dianhydride, 1, 4, 5, 8-naphthalenetetracarboxylic acid dianhydride, 2, 3, 6, 7-naphthalenetetracarboxylic acid dianhydride, 3, 3 ', 4, 4 ' -biphenyltetracarboxylic acid dianhydride, 2 ', 3, 3 ' -biphenyltetracarboxylic acid dianhydride, 2, 3, 3 ', 4 ' -benzophenonetetracarboxylic acid dianhydride, 2, 3, 3 ', 4 ' -diphenylethertetracarboxylic acid dianhydride, 2, 3, 3 ', 4' -diphenylsulfone tetracarboxylic dianhydride, 2-bis (3, 3 ', 4, 4' -tetracarboxyphenyl) tetrafluoropropane dianhydride, 2 '-bis (3, 4-dicarboxyphenoxyphenyl) sulfone dianhydride, 2-bis (2, 3-dicarboxyphenyl) propane dianhydride, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, and 4, 4' - [ propane-2, 2-diylbis (1, 4-phenyleneoxy) ] diphthalic dianhydride, and the like. Aromatic tetracarboxylic dianhydrides may be used in combination.

The component (. alpha.) may contain various known diaminopolysiloxanes (a3) (hereinafter referred to as component (a 3)). Specifically, the component (a3) is, for example, α, ω -bis (2-aminoethyl) polydimethylsiloxane, α, ω -bis (3-aminopropyl) polydimethylsiloxane, α, ω -bis (4-aminobutyl) polydimethylsiloxane, α, ω -bis (5-aminopentyl) polydimethylsiloxane, α, ω -bis [3- (2-aminophenyl) propyl ] polydimethylsiloxane, α, ω -bis [3- (4-aminophenyl) propyl ] polydimethylsiloxane, or the like. The component (a3) can be used in combination.

The component (α) may contain a diamine other than the component (a1) and the component (a3) (hereinafter, also referred to as a component (a 4)) as required. Specifically, the component (a4) is an alicyclic diamine such as diaminocyclohexane, diaminodicyclohexylmethane, dimethyl-diaminodicyclohexylmethane, tetramethyl-diaminodicyclohexylmethane, diaminodicyclohexylpropane, diaminobicyclo [2.2.1] heptane, bis (aminomethyl) -bicyclo [2.2.1] heptane, 3(4), 8(9) -bis (aminomethyl) -tricyclo [5.2.1.02, 6] decane, 1, 3-bisaminomethylcyclohexane, isophorone diamine, or the like; bisaminophenoxyphenylpropanes such as 2, 2-bis [4- (3-aminophenoxy) phenyl ] propane and 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane; diaminodiphenyl ethers such as 3, 3 ' -diaminodiphenyl ether, 3, 4 ' -diaminodiphenyl ether and 4, 4 ' -diaminodiphenyl ether; phenylenediamines such as p-phenylenediamine and m-phenylenediamine; diaminodiphenyl sulfides such as 3, 3 ' -diaminodiphenyl sulfide, 3, 4 ' -diaminodiphenyl sulfide and 4, 4 ' -diaminodiphenyl sulfide; diaminodiphenyl sulfones such as 3, 3 ' -diaminodiphenyl sulfone, 3, 4 ' -diaminodiphenyl sulfone and 4, 4 ' -diaminodiphenyl sulfone; diaminobenzophenones such as 3, 3 ' -diaminobenzophenone, 4 ' -diaminobenzophenone, and 3, 4 ' -diaminobenzophenone; diaminodiphenylmethane such as 3, 3 ' -diaminodiphenylmethane, 4 ' -diaminodiphenylmethane, and 3, 4 ' -diaminodiphenylmethane; diaminophenylpropanes such as 2, 2-bis (3-aminophenyl) propane, 2-bis (4-aminophenyl) propane and 2- (3-aminophenyl) -2- (4-aminophenyl) propane; diaminophenylhexafluoropropanes such as 2, 2-bis (3-aminophenyl) -1, 1, 1, 3, 3, 3-hexafluoropropane, 2-bis (4-aminophenyl) -1, 1, 1, 3, 3, 3-hexafluoropropane and 2- (3-aminophenyl) -2- (4-aminophenyl) -1, 1, 1, 3, 3, 3-hexafluoropropane; diaminophenylethanes such as 1, 1-bis (3-aminophenyl) -1-phenylethane, 1-bis (4-aminophenyl) -1-phenylethane and 1- (3-aminophenyl) -1- (4-aminophenyl) -1-phenylethane; bisaminophenoxybenzenes such as 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1, 4-bis (3-aminophenoxy) benzene, and 1, 4-bis (4-aminophenoxy) benzene; bis-aminobenzoylbenzenes such as 1, 3-bis (3-aminobenzoyl) benzene, 1, 3-bis (4-aminobenzoyl) benzene, 1, 4-bis (3-aminobenzoyl) benzene, 1, 4-bis (4-aminobenzoyl) benzene, and the like; bisaminodimethylbenzenes such as 1, 3-bis (3-amino- α, α -dimethylbenzyl) benzene, 1, 3-bis (4-amino- α, α -dimethylbenzyl) benzene, 1, 4-bis (3-amino- α, α -dimethylbenzyl) benzene, and 1, 4-bis (4-amino- α, α -dimethylbenzyl) benzene; bisaminobis (trifluoromethyl) benzyl benzenes such as 1, 3-bis (3-amino- α, α -bis (trifluoromethyl) benzyl) benzene, 1, 3-bis (4-amino- α, α -bis (trifluoromethyl) benzyl) benzene, 1, 4-bis (3-amino- α, α -bis (trifluoromethyl) benzyl) benzene, and 1, 4-bis (4-amino- α, α -bis (trifluoromethyl) benzyl) benzene; aminophenoxy biphenyls such as 2, 6-bis (3-aminophenoxy) benzonitrile, 2, 6-bis (3-aminophenoxy) pyridine, 4 '-bis (3-aminophenoxy) biphenyl, and 4, 4' -bis (4-aminophenoxy) biphenyl; aminophenoxyphenyl ketones such as bis [4- (3-aminophenoxy) phenyl ] ketone and bis [4- (4-aminophenoxy) phenyl ] ketone; aminophenoxyphenyl sulfides such as bis [4- (3-aminophenoxy) phenyl ] sulfide and bis [4- (4-aminophenoxy) phenyl ] sulfide; aminophenoxy phenyl sulfones such as bis [4- (3-aminophenoxy) phenyl ] sulfone and bis [4- (4-aminophenoxy) phenyl ] sulfone; aminophenoxy phenyl ethers such as bis [4- (3-aminophenoxy) phenyl ] ether and bis [4- (4-aminophenoxy) phenyl ] ether; aminophenoxyphenylpropanes such as 2, 2-bis [4- (3-aminophenoxy) phenyl ] propane, 2-bis [3- (3-aminophenoxy) phenyl ] -1, 1, 1, 3, 3, 3-hexafluoropropane, 2-bis [4- (4-aminophenoxy) phenyl ] -1, 1, 1, 3, 3, 3-hexafluoropropane and the like; and 1, 3-bis [4- (3-aminophenoxy) benzoyl ] benzene, 1, 3-bis [4- (4-aminophenoxy) benzoyl ] benzene, 1, 4-bis [4- (3-aminophenoxy) benzoyl ] benzene, 1, 4-bis [4- (4-aminophenoxy) benzoyl ] benzene, 1, 3-bis [4- (3-aminophenoxy) - α, α -dimethylbenzyl ] benzene, 1, 3-bis [4- (4-aminophenoxy) - α, α -dimethylbenzyl ] benzene, 1, 4-bis [4- (3-aminophenoxy) - α, α -dimethylbenzyl ] benzene, 1, 4-bis [4- (4-aminophenoxy) - α, alpha-dimethylbenzyl ] benzene, 4 ' -bis [4- (4-aminophenoxy) benzoyl ] diphenyl ether, 4 ' -bis [4- (4-amino-alpha, alpha-dimethylbenzyl) phenoxy ] benzophenone, 4 ' -bis [4- (4-amino-alpha, alpha-dimethylbenzyl) phenoxy ] diphenylsulfone, 4 ' -bis [4- (4-aminophenoxy) phenoxy ] diphenylsulfone, 3 ' -diamino-4, 4 ' -diphenoxybenzophenone, 3 ' -diamino-4, 4 ' -biphenoxybenzophenone, 3 ' -diamino-4-phenoxybenzophenone, 3 ' -diamino-4-diphenoxybenzophenone, 4-phenoxybenzophenone, 4 ' -di-amino-4-phenoxybenzophenone, 4-phenoxy, 6, 6 '-bis (3-aminophenoxy) 3, 3, 3,' 3, '-tetramethyl-1, 1' -spirobiindane, 6 '-bis (4-aminophenoxy) 3, 3, 3,' 3, '-tetramethyl-1, 1' -spirobiindane, 1, 3-bis (3-aminopropyl) tetramethyldisiloxane, 1, 3-bis (4-aminobutyl) tetramethyldisiloxane, bis (aminomethyl) ether, bis (2-aminoethyl) ether, bis (3-aminopropyl) ether, bis (2-aminomethoxy) ethyl ] ether, bis [2- (2-aminoethoxy) ethyl ] ether, bis [2- (3-aminopropoxy) ethyl ] ether, 1, 2-bis (aminomethoxy) ethane, 1, 2-bis (2-aminoethoxy) ethane, 1, 2-bis [2- (aminomethoxy) ethoxy ] ethane, 1, 2-bis [2- (2-aminoethoxy) ethoxy ] ethane, ethylene glycol bis (3-aminopropyl) ether, diethylene glycol bis (3-aminopropyl) ether, triethylene glycol bis (3-aminopropyl) ether, ethylenediamine, 1, 3-diaminopropane, 1, 4-diaminobutane, 1, 5-diaminopentane, 1, 6-diaminohexane, 1, 7-diaminoheptane, 1, 8-diaminooctane, 1, 9-diaminononane, 1, 10-diaminodecane, 1, 11-diaminoundecane, 1, 12-diaminododecane, and the like. The component (a4) can be used in combination.

The molar ratio of the component (a2) as an acid component to the component (a1), the component (a3) and the component (a4) as a diamine component [ (a2)/[ (a1) + (a3) + (a4) ] ] is not particularly limited. From the viewpoint of heat resistance, the molar ratio [ (a2)/[ (a1) + (a3) + (a4) ] ] is usually about 1 to 1.5, preferably about 1 to 1.2.

The ratio of the (a1) component, the (a3) component and the (a4) component in the diamine component is not particularly limited. From the viewpoint of heat resistance, the ratio is generally as follows.

(a1) The components: about 10 to 100 mol%, preferably about 30 to 100 mol%

(a3) The components: about 50 to 0 mol%, preferably about 5 to 0 mol%

(a4) The components: about 90 to 0 mol%, preferably about 70 to 0 mol%

The polyimide of the present embodiment can be produced by various known methods. Specifically, for example, the component (a1), the component (a2), and optionally the component (a3) and/or the component (a4) are subjected to addition polymerization in the presence of an organic solvent at a temperature of about room temperature (25 ℃) to 120 ℃ and preferably about room temperature (25 ℃) to 80 ℃ for about 1 to 24 hours to synthesize a polyamic acid solution. Then, the polyamic acid solution obtained as it is can be further subjected to imidization (dehydration ring-closure reaction) at a temperature of about 80 to 250 ℃, preferably about 100 to 200 ℃ for about 0.5 to 50 hours. Alternatively, the imidization reaction may be carried out by casting or coating the polyamic acid solution on a support such as a glass plate, a metal plate (e.g., SUS), or a plastic film (e.g., polyethylene terephthalate film or polyimide film), and then heating the polyamic acid solution at a temperature of about 80 to 300 ℃, preferably about 150 to 300 ℃, for about 0.5 to 50 hours.

Examples of the organic solvent include amide solvents such as N-methyl-2-pyrrolidone, N-dimethylacetamide, N-diethylacetamide, and N, N-dimethylformamide, lactone solvents such as γ -butyrolactone, ketone solvents such as methylisobutylketone, ether solvents such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and dipropylene glycol dimethyl ether, alicyclic solvents such as cyclohexanone and methylcyclohexane, alcohol solvents such as methanol, ethanol, propanol, benzyl alcohol, and cresol, and aromatic solvents such as toluene and xylene. An organic solvent may be used in combination. Among these, the organic solvent is preferably an aprotic polar solvent.

In the imidization reaction, various known catalysts can be used. Specifically, the catalyst is, for example, an aliphatic tertiary amine such as triethylamine, an aromatic tertiary amine such as dimethylaniline, or a heterocyclic tertiary amine such as pyridine, picoline or isoquinoline. The catalyst may be used in combination.

Various known dehydrating agents can be used in the imidization reaction. Specific examples of the dehydrating agent include aliphatic acid anhydrides such as acetic anhydride and aromatic acid anhydrides such as benzoic anhydride. The dehydrating agents may be used in combination.

The polyimide of the present embodiment can be identified by various known means. Specifically, examples of the means for identifying the polyimide include an infrared spectroscopy, a nuclear magnetic resonance method, and Gel Permeation Chromatography (GPC). The physical properties of the polyimide of the present embodiment are not particularly limited. From the viewpoint of heat resistance, the polyimide has a weight average molecular weight (which is a polystyrene equivalent value obtained by the Gel Permeation Chromatography (GPC)) of usually about 5000 to 50000 in terms of physical properties.

As described above, the diamine compound of the present embodiment has a structure of a resin acid dimer residue having a rigid and bulky skeleton in the molecule. Therefore, the monomer can be suitably used for a process plastic having heat resistance and abrasion resistance. For example, the diamine compound of the present embodiment is considered to be useful as a monomer for polyimide in applications requiring heat resistance and mechanical properties. Specifically, the diamine compound of the present embodiment is expected to be used as a raw material for polyimide used in applications such as aerospace industrial parts (satellites and the like), automobile parts, semiconductor materials (resists and the like), military aircraft, electric and electronic parts, heat-resistant fibers, and industrial equipment. Further, it is considered that the polyimide can be used for applications other than the above-described applications requiring heat resistance and mechanical properties.

One embodiment of the present invention has been described above. However, the present invention is not limited to the above embodiments. The above-described embodiment is an embodiment of the invention having the following configuration.

(1) From H₂NH₂C-Ro²-CH₂NH₂(wherein, Ro²Representing a residue of a resin acid dimer).

With such a configuration, the diamine compound has more excellent heat resistance than the conventional diamine compound. Therefore, the diamine compound can be expanded to various new uses.

(2) The diamine compound according to (1), which is a diamine compound having the following structure.

With such a configuration, the diamine compound having the above structure can be easily synthesized into a polyimide compound. Therefore, such diamine compounds are easily further expanded to various new uses.

(3) A method for producing a diamine compound, comprising the steps of: by reacting N ≡ C-Ro²-C ≡ N (in the formula, Ro)²Represents a resin acid dimer residue) to produce the diamine compound of (1) or (2).

With such a constitution, the process for producing the diamine compound and the use of Ro¹-CH₂NH₂(wherein, Ro¹Representing a resin acid residue) is used in a higher yield than a method for producing a diamine compound by dimerization of a monoamine represented by the following formula.

(4) The process for producing a diamine compound according to (3), further comprising the steps of: make Ro from¹-C ≡ N (in the formula, Ro)¹Representing a resin acid residue) to produce the dinitrile compound.

With such a constitution, the process for producing the diamine compound comprises Ro, since the production is omitted¹The step of producing the monoester compound represented by-COO-R is shortened.

(5) The process for producing a diamine compound according to (3), further comprising the steps of: from R-OOC-Ro²-COO-R (in the formula, Ro)²A resin acid dimer residue, and R represents an alkyl group having 1 to 10 carbon atoms) with ammonia, to produce the dinitrile compound.

With this configuration, in the method for producing the diamine compound, the diester compound having high purity is used as a starting material, and therefore, the obtained diamine compound can be easily purified.

(6) A polyimide comprising a monomer unit derived from the diamine compound described in (1) or (2) and a monomer unit derived from a tetracarboxylic dianhydride.

With such a configuration, the polyimide obtained contains monomer units derived from the diamine compound, and therefore can be used in applications where heat resistance and abrasion resistance are required.