JP2011219539A - Bisimide compound, bisamic acid compound and method for producing those - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new bisimide compound serving as a raw material for a resin having good transparency.SOLUTION: The bisimide compound is represented by general formula (1), wherein Xand Xrepresent general formula (2-1) or (2-2). In general formulae (2-1) and (2-2), Rto Rmay be the same or different and are selected from the group consisting of hydrogen atom, halogen atom and 1-3C alkyl; and Ris selected from the group consisting of -O-, -S-, -CH-, -C(CH)- and -CO-.

Description

  The present invention relates to bisimide compounds and bisamidic acid compounds, and methods for producing them.

  Conventionally, it is known that polymaleimide resins using bismaleimide as a monomer represented by N, N′-diphenylmethane bismaleimide have excellent heat resistance (see Patent Documents 1 and 2). Polymaleimide resins, which are homopolymers of bismaleimide compounds, and polymaleimide / polyamine resins in which bismaleimide compounds are copolymerized with amines are widely used in impregnated varnishes, laminates, molded articles and the like. A polyimide resin using bismaleimide as a curing agent is also known (see Patent Document 3).

  However, most conventional bismaleimides have a structure in which an imide group is bonded to a benzene ring. For this reason, it has been difficult to achieve a high level of both heat resistance and transparency of resins (such as polymaleimide resins, polymaleimide / polyamine resins, and polyimide resins) containing bismaleimide as a resin component. .

JP-A-47-8644 JP 47-11500 A Japanese Patent Laid-Open No. 2004-209962

  An object of the present invention is to provide a novel bisimide compound; the bisimide compound is used as a resin component to impart transparency to the resin. Preferably, the bisimide compound which provides transparency without impairing the heat resistance of the resin by using it as a resin component is provided. For example, a bisimide compound that imparts transparency to a polyimide resin without deteriorating the excellent heat resistance is provided by originally using a resin component of a polyimide resin having excellent heat resistance.

  In order to achieve the above-described problems, the present inventors have intensively studied, and as a result, completed the present invention. That is, the first of the present invention relates to the following bisimide compounds and the like.

式（１）において、−Ｒ_１−部分はあってもなくてもよく、−Ｒ_１−部分がある場合、−Ｒ_１−は、−Ｏ−、−Ｓ−、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−及び−ＣＯ−から選ばれる。ｎは０〜３の整数を表す。また、Ｘ_１、Ｘ_２は、それぞれ同一であっても異なっていてもよく、下記一般式（２−１）または（２−２）を表す。

一般式（２−１）および（２−２）において、Ｒ_２〜Ｒ_５は、それぞれ同一であっても異なっていてもよく、水素原子、ハロゲン原子及び炭素数１〜３のアルキル基から選ばれる。Ｒ_６は−Ｏ−、−Ｓ−、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−及び−ＣＯ−から選ばれる。 [1] A bisimide compound represented by the following general formula (1).

In formula (1), the —R ₁ — moiety may or may not be present. When there is an —R ₁ — moiety, —R ₁ — represents —O—, —S—, —CH ₂ —, —C. It is selected from (CH ₃ ) ₂ — and —CO—. n represents an integer of 0 to 3. X ₁ and X ₂ may be the same as or different from each other, and represent the following general formula (2-1) or (2-2).

In the general formulas (2-1) and (2-2), R _{2 to} R ₅ may be the same or different and are selected from a hydrogen atom, a halogen atom, and an alkyl group having 1 to 3 carbon atoms. It is. R ₆ is selected from —O—, —S—, —CH ₂ —, —C (CH ₃ ) ₂ —, and —CO—.

一般式（２）におけるＸ_１、Ｘ_２は、前記一般式（１）における定義と同じである。 [2] The bisimide compound according to [1], which is a bisimide compound represented by the following general formula (2) in which —R ₁ — in the general formula (1) is —CH ₂ — and n = 1. .

X ₁ and X ₂ in the general formula (2) are the same as defined in the general formula (1).

一般式（３）におけるＸ_１、Ｘ_２は、前記一般式（１）における定義と同じである。 [3] The bisimide compound according to [1], which is a bisimide compound represented by the following general formula (3) having no —R ₁ — moiety in the general formula (1) and n = 1.

X ₁ and X ₂ in the general formula (3) are the same as defined in the general formula (1).

一般式（４）におけるＸ_１、Ｘ_２は前記一般式（１）における定義と同じである。 [4] The bisimide compound according to [1], which is a bisimide compound represented by the following general formula (4) having no —R ₁ — moiety in the general formula (1) and having n = 0.

X ₁ and X ₂ in the general formula (4) are the same as defined in the general formula (1).

[5] Any one of [1] to [4], wherein X ₁ and X ₂ in the general formula (1) are bisimide compounds represented by the following formula (2-3) or (2-4): Bisimide compound.

一般式（５）における、Ｒ_１、ｎ、Ｘ_１およびＸ_２は前記一般式（１）における定義と同じである。 [6] The method for producing a bisimide compound according to [1], comprising a step of subjecting the bisamidic acid compound represented by the general formula (5) to a dehydration ring-closing reaction.

In the general formula (5), R ₁ , n, X ₁ and X ₂ are the same as defined in the general formula (1).

  The second of the present invention relates to the following bisamic acid compounds and the like.

一般式（５）において、−Ｒ_１−部分はあってもなくてもよく、−Ｒ_１−部分がある場合、−Ｒ_１−は、−Ｏ−、−Ｓ−、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−及び−ＣＯ−からなる群から選ばれる。ｎは、それぞれ独立して０〜３の整数を表す。Ｘ_１、Ｘ_２は、それぞれ同一であっても異なっていてもよく、下記一般式（２−１）または（２−２）を表す。

一般式（２−１）および（２−２）において、Ｒ_２〜Ｒ_５は、それぞれ同一であっても異なっていてもよく、水素原子、ハロゲン原子及び炭素数１〜３のアルキル基からなる群から選ばれる。Ｒ_６は−Ｏ−、−Ｓ−、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−及び−ＣＯ−からなる群から選ばれる。 [7] A bisamic acid compound represented by the general formula (5).

In the general formula (5), a —R ₁ — moiety may or may not be present. When there is a —R ₁ — moiety, —R ₁ — represents —O—, —S—, —CH ₂ —, — It is selected from the group consisting of C (CH ₃ ) ₂ — and —CO—. n represents the integer of 0-3 each independently. X ₁ and X ₂ may be the same as or different from each other, and represent the following general formula (2-1) or (2-2).

In the general formulas (2-1) and (2-2), R _{2 to} R ₅ may be the same as or different from each other, and are each composed of a hydrogen atom, a halogen atom, and an alkyl group having 1 to 3 carbon atoms. Selected from the group. R ₆ is selected from the group consisting of —O—, —S—, —CH ₂ —, —C (CH ₃ ) ₂ —, and —CO—.

一般式（６）におけるＸ_１およびＸ_２は、前記一般式（５）における定義と同じである。 [8] The bisamide according to [7], which is a bisamidic acid compound represented by the following general formula (6) in which —R ₁ — in the general formula (5) is —CH ₂ — and n = 1. Acid compound.

X ₁ and X ₂ in the general formula (6) are the same as defined in the general formula (5).

一般式（７）におけるＸ_１およびＸ_２は、前記一般式（５）における定義と同じである。 [9] The bisamidic acid compound according to [7], which is a bisamidic acid compound represented by the following general formula (7) having no —R ₁ — moiety in the general formula (5) and n = 1.

X ₁ and X ₂ in the general formula (7) are the same as defined in the general formula (5).

一般式（８）におけるＸ_１およびＸ_２は、前記一般式（５）における定義と同じである。 [10] The bisamidic acid compound according to [7], which is a bisamidic acid compound represented by the following general formula (8) having no —R ₁ — moiety in the general formula (5) and n = 0.

X ₁ and X ₂ in the general formula (8) are the same as defined in the general formula (5).

[11] Any one of [7] to [10], wherein X ₁ and X ₂ in the general formula (5) are bisamidic acid compounds represented by the following formula (2-3) or (2-4): The bisamidic acid compound according to item.

一般式（９）におけるＲ_１およびｎは、前記一般式（５）における定義と同じである。

一般式（１０）におけるＹは、下記一般式（２−１）または（２−２）で表される。

上記式（２−１）および（２−２）におけるＲ_２〜Ｒ_６は、前記一般式（５）における定義と同じである。 [12] The production of the bisamidic acid compound according to [7], comprising a step of subjecting an alicyclic diamine compound represented by the general formula (9) to an acid anhydride represented by the general formula (10). Method.

R ₁ and n in the general formula (9) are the same as defined in the general formula (5).

Y in the general formula (10) is represented by the following general formula (2-1) or (2-2).

R _{2 to} R ₆ in the above formulas (2-1) and (2-2) are the same as defined in the general formula (5).

  By using the bisimide compound of the present invention containing a specific alicyclic diamine structure as a resin component, it is possible to impart excellent transparency to the resin as compared with conventional aromatic bismaleimides. Moreover, the bisimide compound of the present invention is less likely to lower the heat resistance of the resin than the conventional aromatic bismaleimide.

一般式（１）中、−Ｒ_１−部分はあってもなくてもよい。−Ｒ_１−部分がない場合には、シクロヘキサン骨格に架橋基が導入されず、非架橋シクロヘキサン構造となる。−Ｒ_１−部分がある場合、−Ｒ_１−は、−Ｏ−、−Ｓ−、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−及び−ＣＯ−から選ばれる。Ｒ_１が−ＣＨ_２−であるか（ノルボルナン構造）、または−Ｒ_１−部分を有さない構造（非架橋シクロヘキサン構造）であることが好ましい。 1. Bisimide compound The bisimide compound of this invention is represented by following General formula (1).

In general formula (1), the -R ₁ -moiety may or may not be present. When there is no —R ₁ — moiety, no crosslinking group is introduced into the cyclohexane skeleton, resulting in a non-crosslinked cyclohexane structure. When there is a —R ₁ — moiety, —R ₁ — is selected from —O—, —S—, —CH ₂ —, —C (CH ₃ ) ₂ — and —CO—. R ₁ is preferably —CH ₂ — (norbornane structure) or a structure having no —R ₁ — moiety (non-crosslinked cyclohexane structure).

As shown by the general formula (1), the imide-containing group containing X ₁ may be bonded to any part of the cyclohexane ring, but preferably in the following formulas (1 ′) and (1 ″) Combined as shown.

  N in the general formula (1) represents an integer of 0 to 3, and is preferably 0 or 1.

X ₁ and X ₂ in the general formula (1) may be the same or different, and represent the following general formula (2-1) or (2-2).

R _{2 to} R ₅ in the general formulas (2-1) and (2-2) may be the same or different and are selected from a hydrogen atom, a halogen atom, and an alkyl group having 1 to 3 carbon atoms. . Examples of the halogen atom represented by R _{2 to} R ₅ include a fluorine atom, a chlorine atom, and a bromine atom. Examples of the alkyl group having 1 to 3 carbon atoms represented by R _{2 to} R ₅ include a methyl group, an ethyl group, an n-propyl group, and an i-propyl group.

R ₆ in the general formulas (2-1) and (2-2) is selected from —O—, —S—, —CH ₂ —, —C (CH ₃ ) ₂ —, and —CO—, and —CH _2. -Is preferred.

X ₁ and X ₂ in the general formula (1) are particularly preferably groups represented by the following formula (2-3) or (2-4).

  The bisimide compound of the present invention may not necessarily be isolated depending on the application. For example, it may be a mixture of positional isomers or a mixture of stereoisomers.

  Although the bisimide compound of this invention can be used for various uses, it can be used as a resin component, for example. Using as a resin component includes using as a monomer component or as a curing agent. For example, the bisimide compound of the present invention can be used as a curing agent for polyimide resins.

  The bisimide compound of the present invention has a cut-off wavelength of 20 to 40 nm lower than that of a conventional aromatic bismaleimide by an ultraviolet-visible absorption spectrum in a solution. For example, the cutoff wavelength of 1,4-bismaleimide cyclohexane, which is a compound of the present invention, is lower than that of N, N′-diphenylmethane bismaleimide, which is a typical aromatic bisimide compound. That is, the bisimide compound of the present invention can transmit light having a lower wavelength (ultraviolet-visible region) and more light in the entire visible region as compared to the conventional aromatic bismaleimide. For this reason, transparency specific to alicyclic can be imparted to the resin composition containing the bisimide compound of the present invention as a resin component and the cured product thereof.

The light transmission characteristics (cutoff wavelength) of the bisimide compound of the present invention can be controlled mainly by adjusting the structures of X ₁ and X ₂ in the general formula (1).

  Furthermore, although the bisimide compound of the present invention contains an alicyclic diamine structure, it can have the same thermal stability as a conventional aromatic bismaleimide. Therefore, alicyclic specific transparency can be imparted to the resin composition containing the bisimide compound of the present invention as a resin component and the cured product thereof without impairing heat resistance.

一般式（５）におけるＲ_１、ｎ、Ｘ_１およびＸ_２は、前記一般式（１）における定義と同じである。 2. Production method of bisimide compound The bisimide compound of the present invention represented by the general formula (1) can be produced, for example, by subjecting the bisamidic acid compound represented by the general formula (5) to a dehydration ring-closing reaction.

R ₁ , n, X ₁ and X ₂ in the general formula (5) are the same as defined in the general formula (1).

一般式（９）におけるＲ_１およびｎは、前記一般式（５）における定義と同じである。

式（１０）におけるＹは、下記一般式（２−１）または（２−２）で表される。

上記式におけるＲ_２〜Ｒ_６は、前記一般式（１）における定義と同じである。 The bisamic acid compound of the general formula (5) can be produced by addition reaction of an alicyclic diamine compound represented by the general formula (9) and an acid anhydride represented by the general formula (10). .

R ₁ and n in the general formula (9) are the same as defined in the general formula (5).

Y in Formula (10) is represented by the following general formula (2-1) or (2-2).

R _{2 to} R ₆ in the above formula are the same as defined in the general formula (1).

  Examples of the alicyclic diamine compound of the general formula (9) include 2,5-diaminomethyl-7-oxabicyclo [2.2.1] heptane, 2,6-diaminomethyl-7-oxabicyclo [2. 2.1] Heptane, 2,5-diaminomethyl-7-thiabicyclo [2.2.1] heptane, 2,6-diaminomethyl-7-thiabicyclo [2.2.1] heptane, 2,5-diaminomethyl -7,7-dimethylnorbornane, 2,6-diaminomethyl-7,7-dimethylnorbornane, 2,5-diaminomethyl-7-oxonorbornane, 2,6-diaminomethyl-7-oxonorbornane, 2,5- Diaminomethylnorbornane, 2,6-diaminomethylnorbornane, 2,5-diaminonorbornane, 2,6-diaminonorbornane, 1,3-bisaminomethylcyclohexane, 1,4-bisaminomethylcyclohexane, 1,3-diaminocycl Hexane, 1,4-diaminocyclohexane, and the like. In these diamine compounds, when a stereoisomer exists, it may be an isolate of the isomer or a mixture of isomers.

  Examples of the acid anhydride represented by the general formula (10) include maleic anhydride, 3-methylmaleic anhydride, 3-ethylmaleic anhydride, 3,4-dimethylmaleic anhydride, and 3,4-diethylanhydride. Maleic acid, 3,4,5,6-tetrahydrophthalic anhydride, 3-chloromaleic anhydride, 3,4-dichloromaleic anhydride, nadic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride Examples include 3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride, bicyclo [2,2,2] oct-5-ene-2,3-dicarboxylic anhydride, and the like.

  The bisimide compound of the present invention is obtained by reacting an alicyclic diamine compound of the general formula (9) with an acid anhydride of the general formula (10) to obtain a bisamide acid compound represented by the general formula (5), It can be obtained by imidization. The bisamidic acid compound represented by the general formula (5) may be once isolated and further imidized to form a bisimide compound; without isolating the bisamidic acid compound represented by the general formula (5). In the reaction system, imidization may be performed.

  Although there exist the following methods, for example in the method of obtaining a bisimide compound from the alicyclic diamine compound of General formula (9) and the acid anhydride of General formula (10), it is not specifically limited.

(1) A method of obtaining an imide compound by synthesizing a bisamic acid compound at 120 ° C. or lower and then imidizing by raising the temperature to 100 to 200 ° C. (thermal imidization)
(2) Method of synthesizing a bisamidic acid compound in the same manner as in (1) above, and then chemically imidizing using an imidizing agent such as acetic anhydride (chemical imidization)
(3) A method of synthesizing a bisamidic acid compound in the same manner as in the above (1) and then imidating in the presence of a solvent for azeotropic dehydration in the presence or absence of a catalyst (azeotropic dehydration ring closure method)
(4) Method of imidizing by mixing diamine and dicarboxylic anhydride and then immediately heating in the presence or absence of catalyst and / or azeotropic dehydration solvent (direct thermal imidization)

  With respect to 1 mol of the alicyclic diamine compound represented by the general formula (9), the acid anhydride represented by the general formula (10) is usually 1.5 to 3.0 times mol, more preferably 1. The reaction is carried out in the range of 8 to 2.2 moles.

  In the reaction between the alicyclic diamine compound represented by the general formula (9) and the acid anhydride represented by the general formula (10), the acid anhydride and the alicyclic diamine compound may be charged in total from the beginning. Since the reaction between the diamine compound and the acid anhydride is an exothermic reaction, it is preferable to carry out the reaction while suppressing excessive heat generation by adding one of them little by little.

  More preferably, the acid anhydride is dissolved in a solvent, and the alicyclic amine compound is dropped while stirring so that the temperature in the reaction kettle is 100 ° C. or lower, preferably 30 to 100 ° C. of. At this time, the raw material amine to be dropped may be dissolved in the same solvent as the reaction solvent. The dropping time of the raw material amine is preferably 5 to 180 minutes, but more preferably the whole amount is dropped in the range of 30 to 120 minutes.

  Immediately after the addition of the raw material amine, the produced bisamidic acid compound may be subjected to a dehydration ring-closing reaction, but preferably the bisamidic acid compound is aged at 30 to 120 ° C. for about 0.5 to 3.0 hours. More preferably, after aging at 50 to 100 ° C. for about 1.0 to 2.0 hours, the dehydration ring-closing reaction is carried out.

  The reaction of the alicyclic diamine compound of the general formula (9) and the acid anhydride of the general formula (10) is preferably performed in an organic solvent. The organic solvent used is not limited as long as it does not adversely affect the desired reaction. For example, saturated hydrocarbons such as pentane, hexane, heptane, cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene; Halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, dichloroethane, chlorobenzene, dichlorobenzene; diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis ( Ethers such as 2-methoxyethoxy) ethane, bis [2- (2-methoxyethoxy) ethyl] ether, tetrahydrofuran, 1,3-dioxane, 1,4-dioxane, anisole; phenol, o-chlorophenol , M-chlorophenol, p-chloropheno O-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4- Phenols such as xylenol and 3,5-xylenol; N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, hexamethylphosphoramide Amides such as: Lactams such as N-methyl-2-pyrrolidone and N-methylcaprolactam; Sulfur-containing solvents such as dimethyl sulfoxide, diphenyl sulfoxide, dimethyl sulfone, diphenyl sulfone, and sulfolane; 1,3-dimethyl-2- Examples include imidazolidinone. These organic solvents may be used alone or in combination of two or more.

  Furthermore, the organic solvent for the reaction of the alicyclic diamine compound of the general formula (9) and the acid anhydride of the general formula (10) may coexist with the following solvent. Examples of organic solvents that can coexist include benzene, toluene, o-xylene, m-xylene, p-xylene, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, o-bromotoluene, m-bromotoluene, Examples thereof include p-bromotoluene, chlorobenzene, bromobenzene and the like. These can act as an azeotropic solvent for removing (dehydrating) water generated in the reaction solution.

  The amount of reaction solvent used is not particularly limited and varies depending on the solvent type and composition used, but is usually 1 to 1000 weights per 1 part by weight of raw material (total of alicyclic diamine compound or acid dianhydride). Parts, preferably 3 to 100 parts by weight. The reaction solvent is preferably a solution by dissolving the raw material, but the reaction may be performed in a slurry state.

  The dehydration ring closure reaction for obtaining bisimide from the obtained bisamic acid is not particularly limited, and a method known per se is employed. As described above, the produced bisamic acid may or may not be isolated and purified.

  Specifically, the dehydration ring closure reaction may be performed in the presence of an organic base catalyst, an acid catalyst, or an imidizing agent as necessary. Examples of organic base catalysts include triethylamine, tributylamine, tripentylamine, N, N-dimethylaniline, N, N-diethylaniline, pyridine, α-picoline, β-picoline, γ-picoline, 2,4-lutidine 2,6-lutidine, quinoline, isoquinoline and the like are included, and pyridine and γ-picoline are preferable.

  Examples of acid catalysts include hydrochloric acid, hydrogen bromide, hydrogen iodide, sulfuric acid, sulfuric anhydride, nitric acid, phosphoric acid, phosphorous acid, phosphotungstic acid, phosphomolybdic acid, etc .; methanesulfonic acid, ethanesulfonic acid Sulfonic acids such as trifluoromethanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid; carboxylic acids such as acetic acid and oxalic acid; halogens such as chloroacetic acid, dichloroacetic acid, trichloroacetic acid, fluoroacetic acid, difluoroacetic acid and trifluoroacetic acid Carboxylic acids; solid acids such as silica, alumina and activated clay; and cation-type ion exchange resins. In particular, sulfuric acid, phosphoric acid, and p-toluenesulfonic acid are suitable. These catalysts may be used alone or in combination of two or more. These acid catalysts may be salts with diamine compounds.

  The amount of these catalysts used is not particularly limited as long as the reaction rate of the dehydration ring closure reaction is substantially improved, but is 0.001 to 10 times mol, preferably 0.005 mol to 5 mol, relative to the raw material diamine compound. Double mole, more preferably 0.01 to 1 mole.

  Examples of the imidizing agent are not particularly limited, and a known method in which acetic anhydride or the like is used as a dehydrating agent and the reaction is performed in an organic solvent in the presence of a base and a catalyst (Japanese Examined Patent Publication Nos. 46-232250 and 49-40231). JP-B-59-52660) or a condensing agent such as polyphosphoric acid or dicyclohexylcarbodiimide can be used.

  The amount of the dehydrating agent (such as acetic anhydride) used as the imidizing agent is not particularly limited with respect to the upper limit, but it is preferably 1.0 to 10 times the mole of the diamine compound as a starting material, and more preferably The range is 1.8 to 6.0 times mole.

  Examples of catalysts used in combination when acetic anhydride is used as the dehydrating agent for the imidizing agent include alkaline earth metal oxides, iron (II and III), nickel (II), manganese (II and III ), Copper (I and II) or cobalt (II and III) carbonates, sulfates, phosphates, acetates and the like. These catalysts exhibit a sufficient effect even when used alone, but they may be used in combination of two or more.

The amount of the catalyst used as the imidizing agent is in the range of 5 × 10 ^{−4 to} 0.1 mol with respect to 1 mol of the bisamidic acid compound. Examples of the base as an imidizing agent include sodium acetate, potassium acetate, trimethylamine, triethylamine, tributylamine and the like. The usage-amount of a base is the range of 0.05-1.1 mol with respect to 1 mol of bisamide acid compounds.

  The reaction temperature and reaction time in the dehydration ring-closing reaction vary depending on the type of raw material used, the type of solvent, the type of catalyst, the type and amount of azeotropic dehydration solvent, the type and amount of imidizing agent, etc. It is 1 to 24 hours in the range of 20 to 180 ° C. When performing direct thermal imidation, as a guide, the reaction is carried out until the distilled water reaches a theoretical amount (usually not all are recovered, so the recovery rate is 50 to 90%). Usually about several hours. In this case, a method of removing water generated by imidization with an azeotropic agent such as toluene is general and effective.

  The reaction pressure in the dehydration cyclization reaction is not particularly limited, but is usually set to atmospheric pressure. Although the reaction atmosphere is not particularly limited, the reaction is usually performed in an atmosphere of air, nitrogen, helium, neon, or argon, preferably in an inert gas such as nitrogen or argon.

  The method for isolating the target bisimide compound from the reaction mixture containing the bisimide compound is not particularly limited, but when the target product is precipitated from the reaction solvent, it may be isolated by filtration or centrifugation. On the other hand, when the target product is dissolved in the reaction solvent, the solvent is distilled off under reduced pressure, or an appropriate poor solvent is added to the reaction mixture, or the reaction mixture is discharged into the poor solvent to cause precipitation. It may be filtered or centrifuged.

  When it is necessary to further purify the isolated imide compound, it may be purified by adopting a method known as a conventional method. Examples of the method include distillation purification method, recrystallization method, column chromatography. Process, sludge treatment and activated carbon treatment.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the scope of the present invention is not limited by this.

  Each physical property in the examples was measured and evaluated by the following methods.

  Transparency: A DMAc solution having a concentration of 0.01 mol / L of each bisimide compound was prepared. Using a Shimadzu UV2550 as a measuring device, the ultraviolet-visible absorption spectrum of this solution was measured. At this time, the wavelength at which the transmittance becomes 70% (λ @ 70 nm) and the wavelength at which the transmittance becomes 1% (λ @ 1 nm: cut-off wavelength) were used as indices.

  Thermophysical properties: melting start temperature, melting point, endothermic start temperature, endothermic peak temperature, exothermic start temperature, and exothermic peak temperature of each bisimide compound were measured by DSC method, using Shimadzu DCC-60A as a measuring device, with a temperature rising rate of 5 ° C / Measured in minutes.

  Heat resistance: Each bisimide compound was heated to 350 ° C. at a rate of 5 ° C./min in a nitrogen atmosphere and kept for 2 hours to produce a cured resin. The thermogravimetric decrease of the produced cured resin was measured using Shimadzu TGA-50 at a heating rate of 10 ° C./min. At this time, the case where the 5 wt% weight reduction temperature was 400 ° C. or higher was evaluated as “◯”, and the case where it was lower than 400 ° C. was evaluated as “X”.

[Example 1]
(Production of norbornane-bismethylmaleimide (NBDA-BMI))
A 1000 ml glass four-necked flask equipped with a stirrer, cooling condenser, thermometer, nitrogen gas inlet tube and dropping funnel was charged with 25.6 g (0.26 mol) of maleic anhydride and 200 g of DMF, and the temperature was raised to 60 ° C. Dissolve completely while warm. Into this, 20 g (0.13 mol) of a mixture of 2,5-diaminomethylnorbornane and 2,6-diaminomethylnorbornane was dropped over 1 hour while paying attention to the reaction temperature (maintaining at 60 ° C.), Further, aging was performed at 60 ° C. for 2 hours. Subsequently, 120 g of polyphosphoric acid was charged under stirring while paying attention to the reaction temperature (maintaining at 60 ° C.). Thereafter, the temperature was slowly raised to 90 ° C., and a dehydration ring-closing reaction was performed at 90 to 95 ° C. for 12 hours.

  After completion of the reaction, the reaction mixture was cooled to room temperature and charged with 200 g of methanol and 200 g of water. After stirring for 1 hour, the precipitate was separated by filtration. Thereafter, the operation of slugging with 400 g of water for 1 hour at room temperature was repeated twice to remove the acid component. Three times the amount of DMF and 2% by weight of activated carbon were added to the obtained crude NBDA-BMI, and the activated carbon treatment was performed at 70 to 75 ° C. for 30 minutes, followed by filtration after heating and cooling. The resulting crystals were washed with methanol to obtain the desired product (yield: 35%). The purity was> 99%. The transmittance measurement results are shown in Table 1, and the thermophysical property / heat resistance test results are shown in Table 2.

The result of ¹ H-NMR is shown below.
¹ H-NMR (DMSO-d6): δ = 0.50-2.25 (m, 10H), 3.04-3.39 (m, 4H), 7.00 (m, 4H)

[Example 2]
(Production of 1,3-bismaleimidomethylcyclohexane (1,3BAC-BMI))
In the same procedure as in Example 1, except that the alicyclic diamine compound was changed to 1,3-bisaminomethylcyclohexane and the recrystallization solvent was changed to ethanol (30 times the amount / crude pair, reflux), , 3-Bismaleimidomethylcyclohexane (1,3BAC-BMI) was obtained. The transmittance measurement results are shown in Table 1, and the thermophysical property / heat resistance test results are shown in Table 2.

The result of ¹ H-NMR is shown below.
¹ H-NMR (DMSO-d6): δ = 0.56 (m, 1H), 0.78 (m, 2H), 0.98-1.23 (m, 1H), 1.35-1.77 (M, 6H), 3.22 (d, 4H), 6.97 (s, 4H)

[Example 3]
(Production of 1,4-bismaleimidomethylcyclohexane (1,4BAC-BMI))
Except that the alicyclic diamine compound was changed to 1,4-bisaminomethylcyclohexane and the recrystallization solvent was changed to DMAc (25 times amount / crude, 90 ° C.), the same procedure as in Example 1 was carried out. 1,4-Bismaleimidomethylcyclohexane (1,4BAC-BMI) was obtained. The transmittance measurement results are shown in Table 1, and the thermophysical property / heat resistance test results are shown in Table 2.

The result of ¹ H-NMR is shown below.
¹ H-NMR (DMSO-d6): δ = 0.74-0.98 (m, 4H), 1.43-1.69 (m, 6H), 3.23 (d, 4H), 6.92 (S, 4H)

[Example 4]
(Production of 1,4-bismaleimide cyclohexane (CHDA-BMI))
In the same procedure as in Example 1, except that the alicyclic diamine compound was changed to 1,4-diaminocyclohexane and the recrystallization solvent was changed to DMAc (50 times amount / crude, 90 ° C.), 4-Bismaleimide cyclohexane (CHDA-BMI) was obtained. The transmittance measurement results are shown in Table 1, and the thermophysical property / heat resistance test results are shown in Table 2.

The result of ¹ H-NMR is shown below.
¹ H-NMR (DMSO-d6): δ = 1.65-1.83 (m, 4H), 1.97-2.19 (m, 4H), 3.84 (m, 2H), 6.90 (S, 4H)

[Comparative Example 1]
The transmittance measurement results of N, N′-diphenylmethane bismaleimide (MDA-BMI) are shown in Table 1, and the thermophysical property / heat resistance test results are shown in Table 2.

[Example 5]
(Production of norbornane-bismethylnadicimide (NBDA-BNI))
14. Mixture of 2,5-diaminomethylnorbornane and 2,6-diaminomethylnorbornane in a 500 ml glass four-necked flask equipped with a stirrer, Dean Stark, cooling condenser, thermometer, nitrogen gas inlet tube and dropping funnel 4 g (0.1 mol) and DMAc 200 g were charged and dissolved. To the stirred reaction solution, 36.1 g (0.22 mol) of nadic anhydride was added all at once at room temperature. After stirring at room temperature for 1 hour, the temperature was raised to 60 ° C. and aging was further performed for 2 hours.

  Subsequently, 3.8 g (0.02 mol) of p-toluenesulfonic acid monohydrate and 200 g of toluene were charged into the obtained solution. While heating at 130 to 140 ° C., the reaction solution was allowed to react for 8 hours while distilling off the water generated in the reaction solution using a Dean Stark. After completion of the reaction, toluene and DMAc were distilled off from the obtained reaction mixture under reduced pressure. The precipitate was washed with 500 ml of 3% by weight aqueous sodium hydroxide solution, filtered and dried to obtain a compositional organism. To the obtained crude NBDA-BMI, 2% by weight of activated carbon was added, and acetone or methanol was charged, and the activated carbon treatment was performed for 30 minutes under heating and refluxing, and then filtered by heating and cooled. The resulting crystals were filtered and dried to obtain the desired product (yield: 50%). The purity was> 99%. The transmittance measurement results are shown in Table 3, and the thermophysical property / heat resistance test results are shown in Table 4.

The result of ¹ H-NMR is shown below.
¹ H-NMR (CDCl ₃ ): δ = 0.53-2.20 (m, 14H) 3.00-3.46 (m, 12H), 6.02-6.16 (m, 4H)

[Example 6]
(Production of 1,3-bisnadicimidomethylcyclohexane (1,3BAC-BNI))
The same procedure as in Example 5 except that the alicyclic diamine compound was changed to 1,3-bisaminomethylcyclohexane and the recrystallization solvent was changed to 2-propanol (7.5 times amount / crude, reflux). To obtain 1,3-bisnadicimidomethylcyclohexane (1,3BAC-BNI). The transmittance measurement results are shown in Table 3, and the thermophysical property / heat resistance test results are shown in Table 4.

The result of ¹ H-NMR is shown below.
¹ H-NMR (DMSO-d6): δ = 0.44 (q, 1H), 0.58-0.81 (m, 2H), 0.93-1.16 (m, 1H), 1.26 -1.72 (m, 10H), 3.01 (d, 4H), 3.24 (s, 4H), 3.31 (s, 4H), 6.04 (q, 4H)

[Example 7]
(Production of 1,4-bisnadicimidomethylcyclohexane (1,4BAC-BNI))
The reaction was performed in the same procedure as in Example 5 except that the alicyclic diamine compound was changed to 1,4-bisaminomethylcyclohexane. After the completion of the reaction, crystals were precipitated by cooling to room temperature, and this was filtered and dried to obtain 1,4-bisnadicimidomethylcyclohexane (1,4BAC-BNI). The transmittance measurement results are shown in Table 3, and the thermophysical property / heat resistance test results are shown in Table 4.

The result of ¹ H-NMR is shown below.
¹ H-NMR (DMSO-d6): δ = 0.76 (m, 4H), 1.37 (m, 2H), 1.45 to 1.66 (m, 8H), 3.02 (d, 4H) ), 3.23 (s, 4H), 3.29 (s, 4H) 6.02 (q, 4H)

[Example 8]
(Production of 1,4-bisnadicimidocyclohexane (CHDA-BNI))
Example 5 except that the alicyclic diamine compound was changed to 1,4-diaminocyclohexane, the reaction solvent was changed to NMP, and the recrystallization solvent was changed to NMP (20 times amount / crude, 100 ° C.). The reaction was carried out in the same manner to obtain 1,4-bisnadicimidocyclohexane (CHDA-BNI). Table 3 shows the transmittance measurement results, and Table 4 shows the thermophysical / heat resistance test results.

The result of ¹ H-NMR is shown below.
¹ H-NMR (DMSO-d6): δ = 1.37-1.59 (m, 8H), 1.88-2.11 (m, 4H), 3.22 (s, 8H), 3.65 (M, 2H) 6.02 (q, 4H)

[Comparative Example 2]
Table 3 shows the transmittance measurement results of 1,3-bis (3-nadicimidophenoxy) benzene (APB-BNI), and Table 4 shows the thermal properties and heat resistance test results.

  As shown in Table 4, it can be seen that an endothermic reaction and an exothermic reaction occur. The endothermic reaction is derived from the reverse Diels-Alder reaction of the norbornene ring, and the exothermic reaction is presumed to be derived from the crosslinking reaction of the bisimide compound.

  As shown in the transmittance measurement results in Tables 1 and 3, the compounds of the present invention (Examples) have λ @ 70% and λ @ 1% on the short wavelength side as compared with the compounds of Comparative Examples. That is, light in the entire visible light region including the ultraviolet visible region is transmitted. Therefore, transparency can be imparted to a high molecular weight material using the compound of the present invention as a raw material for a monomer or a crosslinking agent.

  Further, as shown in the heat resistance test results of Table 2 and Table 4, the thermogravimetric decrease temperature of the cured resin of the compound of the present invention (Example) is kept as high as the thermogravimetric decrease temperature of the comparative cured resin. I'm leaning. Therefore, the heat resistance of the high molecular weight material made from the compound of the present invention is also excellent.

  In addition to being useful as a raw material for thermosetting resins, the imide compound of the present invention can be used as a heat-resistant adhesive for use in the electronic field or as an additive to thermoplastic resins.

Claims (12)

A bisimide compound represented by the following general formula (1):

[In general formula (1),
The —R ₁ — moiety may or may not be present. When the —R ₁ — moiety is present, —R ₁ — represents —O—, —S—, —CH ₂ —, —C (CH ₃ ) ₂ —. And selected from the group consisting of -CO-;
n independently represents an integer of 0 to 3;
X ₁ and X ₂ may be the same as or different from each other, and represent the following general formula (2-1) or (2-2).

(In the general formulas (2-1) and (2-2),
R _{2 to} R ₅ may be the same or different and are selected from the group consisting of a hydrogen atom, a halogen atom and an alkyl group having 1 to 3 carbon atoms;
R ₆ is selected from the group consisting of —O—, —S—, —CH ₂ —, —C (CH ₃ ) ₂ —, and —CO—. )] The bisimide compound according to claim 1, which is a bisimide compound represented by the following general formula (2) in which —R ₁ — in the general formula (1) is —CH ₂ — and n = 1.

(X ₁ and X ₂ in the general formula (2) are the same as defined in the general formula (1).) The bisimide compound according to claim 1, which is a bisimide compound represented by the following general formula (3) having no —R ₁ — moiety in the general formula (1) and n = 1.

(X ₁ and X ₂ in the general formula (3) are the same as defined in the general formula (1).) The bisimide compound according to claim 1, which is a bisimide compound represented by the following general formula (4) having no —R ₁ — moiety in the general formula (1) and n = 0.

(X ₁ and X ₂ in the general formula (4) are the same as defined in the general formula (1).) The bisimide compound according to any one of claims 1 to 4, wherein X ₁ and X ₂ in the general formula (1) are bisimide compounds represented by the following formula (2-3) or (2-4): .

The manufacturing method of the bisimide compound of Claim 1 including the process of carrying out dehydration ring-closing reaction of the bisamide acid compound represented by General formula (5).

(R ₁ , n, X ₁ and X ₂ in the general formula (5) are the same as defined in the general formula (1).) A bisamidic acid compound represented by the general formula (5):

[In general formula (5),
The —R ₁ — moiety may or may not be present. When the —R ₁ — moiety is present, —R ₁ — represents —O—, —S—, —CH ₂ —, —C (CH ₃ ) ₂ —. And selected from the group consisting of -CO-;
n independently represents an integer of 0 to 3;
X ₁ and X ₂ may be the same as or different from each other, and represent the following general formula (2-1) or (2-2).

(In the general formulas (2-1) and (2-2),
R _{2 to} R ₅ may be the same or different and are selected from the group consisting of a hydrogen atom, a halogen atom and an alkyl group having 1 to 3 carbon atoms;
R ₆ is selected from the group consisting of —O—, —S—, —CH ₂ —, —C (CH ₃ ) ₂ —, and —CO—. )] R ₁ in the general formula (5) is -CH 2 _-, and a bisamide acid compound represented by the following general formula is n = 1 (6), bisamide acid compound according to claim 7.

(X ₁ and X ₂ in the general formula (6) are the same as defined in the general formula (5).) The bisamidic acid compound according to claim 7, which is a bisamidic acid compound represented by the following general formula (7) having no —R ₁ — moiety in the general formula (5) and n = 1.

(X ₁ and X ₂ in the general formula (7) are the same as defined in the general formula (5).) The bisamidic acid compound according to claim 7, which is a bisamidic acid compound represented by the following general formula (8) having no —R ₁ — moiety in the general formula (5) and n = 0.

(X ₁ and X ₂ in the general formula (8) are the same as defined in the general formula (5).) Is _{X 1} and _{X 2} is represented by the following formula in the formula (5) (2-3) or bisamide acid compound represented by (2-4), bisamide acid according to any one of claims 7 to 10 Compound.

The manufacturing method of the bisamide acid compound of Claim 7 including the process with which an alicyclic diamine compound represented by General formula (9) and the acid anhydride represented by General formula (10) are addition-reacted.

(R ₁ and n in the general formula (9) are the same as defined in the general formula (5).)

[Y in Formula (10) is the following general formula (2-1) or (2-2)

(R _{2 to} R ₆ in the above formulas (2-1) and (2-2) are the same as defined in the general formula (5)). ]