JP7127622B2 - Aromatic bismaleimide compound and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to an aromatic bismaleimide compound and a method for producing the same.

Bismaleimide resin is known to be one of high heat-resistant resins, and has been studied as a material capable of closing the difference in heat resistance between epoxy resin and polyimide. New bismaleimide compounds have also been reported in recent years (Patent Documents 1 and 2). A bismaleimide compound having very low dielectric properties has also been reported (Patent Document 3). These are often used as resins for substrates, and are widely used in impregnated varnishes, laminates, molded articles, and the like. However, in many cases, even if the bismaleimide compound itself is attempted to form a film, it does not form a film. Therefore, although the bismaleimide compound is used together with a film-forming agent, the properties of the bismaleimide compound itself cannot be effectively utilized in some cases.

Many of the bismaleimide compounds are low-molecular-weight compounds or monomers with a molecular weight of 2,000 or less. There are very few reports of high-molecular-weight bismaleimide compounds having a chain-like polymer skeleton and maleimide groups at both ends of the molecule.

In addition, many aromatic bismaleimide compounds have drawbacks such as being soluble only in high-boiling aprotic polar solvents such as NMP (N-methyl-2-pyrrolidone) and DMAc (N,N-dimethylacetamide). It is desired to dissolve in other general-purpose solvents.

JP 2011-219539 A JP 2018-012671 A JP 2014-194021 A JP 2012-036233 A

Accordingly, an object of the present invention is to provide a novel aromatic bismaleimide compound which can be formed into a film without using a filming agent and which is soluble in solvents other than high-boiling aprotic polar solvents, and a method for producing the same. That is.

The present inventors have made intensive studies to solve the above problems, and as a result, have found that the following aromatic bismaleimide compounds can achieve the above objects, and completed the present invention.

（式中、Ｘ¹は独立して、下記式

（ａは１～６の数である）

から選ばれる２価の基であり、ｍは１～３０の数であり、ｎは１～５の数であり、Ａ¹及びＡ²はそれぞれ独立して、下記式（２）

（式中、Ｘ²は独立して、下記式

（ａは１～６の数である）

から選ばれる２価の基であり、Ｒ¹は独立して、水素原子、塩素原子、または非置換又は置換の炭素数１～６の脂肪族炭化水素基である）
または下記式（３）

（式中、Ｘ¹は前記と同じものを示す）

で示される２価の芳香族基である）

＜２＞
前記式（１）の芳香族ビスマレイミド化合物の数平均分子量が３，０００～５０，０００であることを特徴とする＜１＞に記載の芳香族ビスマレイミド化合物。

＜３＞
前記式（１）のＸ¹と前記式（３）のＸ¹とが同じ２価の基を有することを特徴とする＜１＞または＜２＞に記載の芳香族ビスマレイミド化合物。

＜４＞
前記式（１）において、Ａ¹が前記式（２）のとき、Ａ²が前記式（３）であるか、またはＡ¹が前記式（３）のとき、Ａ²が前記式（２）であることを特徴とする＜１＞から＜３＞のいずれか１つに記載の芳香族ビスマレイミド化合物。

＜５＞
下記式（４）

（式中、Ｘ¹は独立して、下記式

（ａは１～６の数である）

から選ばれる２価の基である）

で示される芳香族ジフタル酸無水物と下記式（５）

（式中、Ｒ¹は独立して、水素原子、塩素原子、または非置換又は置換の炭素数１～６の脂肪族炭化水素基であり、Ｘ²は独立して、下記式

（ａは１～６の数である）

から選ばれる２価の基である）

で示される芳香族ジアミンとを、モル比で芳香族ジフタル酸無水物／芳香族ジアミン＝１．０１～１．５０／１．０で反応させて、アミック酸を合成し、閉環脱水する工程Ａと、
該工程Ａに次いで、前記工程Ａで得られた反応物と下記式（６）

（式中、Ｘ¹は前記と同じ）

で示される芳香族ジアミンとでアミック酸を合成し、閉環脱水する工程Ｂと、
該工程Ｂに次いで、前記工程Ｂで得られた反応物と無水マレイン酸を反応させ、マレアミック酸を合成し、閉環脱水することによって分子鎖末端をマレイミド基で封鎖する工程Ｃとを有することを特徴とする＜１＞から＜４＞のいずれか１つに記載の芳香族ビスマレイミド化合物の製造方法。

＜６＞
下記式（４）

（式中、Ｘ¹は独立して、下記式

（ａは１～６の数である）

から選ばれる２価の基である）

で示される芳香族ジフタル酸無水物と下記式（６）

（式中、Ｘ¹は独立して、下記式

（ａは１～６の数である）

から選ばれる２価の基である）

で示される芳香族ジアミンとを、モル比で芳香族ジフタル酸無水物／芳香族ジアミン＝１．０１～１．５０／１．０で反応させて、アミック酸を合成し、閉環脱水する工程Ａ’と、
該工程Ａ’に次いで、前記工程Ａ’で得られた反応物と下記式（５）

（式中、Ｒ¹は独立して、水素原子、塩素原子、または非置換又は置換の炭素数１～６の脂肪族炭化水素基であり、Ｘ²は独立して、下記式

（ａは１～６の数である）

から選ばれる２価の基である）

で示される芳香族ジアミンとでアミック酸を合成し、閉環脱水する工程Ｂ’と、
該工程Ｂ’に次いで、前記工程Ｂ’で得られた反応物と無水マレイン酸を反応させ、マレアミック酸を合成し、閉環脱水することによって分子鎖末端をマレイミド基で封鎖する工程Ｃ’を有することを特徴とする＜１＞から＜４＞のいずれか１つに記載の芳香族ビスマレイミド化合物の製造方法。
<1>
An aromatic bismaleimide compound represented by the following formula (1).

(Wherein, X ¹ is independently represented by the following formula

(a is a number from 1 to 6)

is a divalent group selected from m is a number of 1 to 30, n is a number of 1 to 5, A ¹ and A ² are each independently represented by the following formula (2)

(Wherein, X ² is independently represented by the following formula

(a is a number from 1 to 6)

and R ¹ is independently a hydrogen atom, a chlorine atom, or an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 6 carbon atoms)
or the following formula (3)

(Wherein, X ¹ is the same as above)

is a divalent aromatic group represented by

<2>
The aromatic bismaleimide compound according to <1>, wherein the aromatic bismaleimide compound of formula (1) has a number average molecular weight of 3,000 to 50,000.

<3>
The aromatic bismaleimide compound according to <1> or <2>, wherein X ¹ in formula (1) and X ¹ in formula (3) have the same divalent group.

<4>
In the above formula (1), when A ¹ is the above formula (2), A ² is the above formula (3), or when A ¹ is the above formula (3), A ² is the above formula (2) The aromatic bismaleimide compound according to any one of <1> to <3>, characterized in that:

<5>
Formula (4) below

(Wherein, X ¹ is independently represented by the following formula

(a is a number from 1 to 6)

is a divalent group selected from

and the aromatic diphthalic anhydride represented by the following formula (5)

(In the formula, R ¹ is independently a hydrogen atom, a chlorine atom, or an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 6 carbon atoms, and X ² is independently the following formula

(a is a number from 1 to 6)

is a divalent group selected from

is reacted with the aromatic diamine represented by the molar ratio of aromatic diphthalic anhydride/aromatic diamine = 1.01 to 1.50/1.0 to synthesize an amic acid, and ring-closing dehydration step A When,
Following the step A, the reactant obtained in the step A and the following formula (6)

(Wherein, X ¹ is the same as above)

A step B of synthesizing an amic acid with an aromatic diamine represented by and ring-closing dehydration;
Step B is followed by Step C of reacting the reactant obtained in Step B with maleic anhydride to synthesize maleamic acid, and ring-closing dehydration to block the ends of the molecular chains with maleimide groups. A method for producing an aromatic bismaleimide compound according to any one of <1> to <4>.

<6>
Formula (4) below

(Wherein, X ¹ is independently represented by the following formula

(a is a number from 1 to 6)

is a divalent group selected from

and the aromatic diphthalic anhydride represented by the following formula (6)

(Wherein, X ¹ is independently represented by the following formula

(a is a number from 1 to 6)

is a divalent group selected from

is reacted with the aromatic diamine represented by the molar ratio of aromatic diphthalic anhydride/aromatic diamine = 1.01 to 1.50/1.0 to synthesize an amic acid, and ring-closing dehydration step A 'When,
Following the step A', the reactant obtained in the step A' and the following formula (5)

(In the formula, R ¹ is independently a hydrogen atom, a chlorine atom, or an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 6 carbon atoms, and X ² is independently the following formula

(a is a number from 1 to 6)

is a divalent group selected from

A step B' of synthesizing an amic acid with an aromatic diamine represented by and ring-closing dehydration;
Step B' is followed by step C' of reacting the reactant obtained in step B' with maleic anhydride to synthesize maleamic acid, followed by ring-closing dehydration to block the molecular chain ends with maleimide groups. The method for producing an aromatic bismaleimide compound according to any one of <1> to <4>, characterized by:

The aromatic bismaleimide compound of the present invention can be formed into a film without using a filming agent, and dissolves in solvents other than high-boiling aprotic polar solvents. The aromatic bismaleimide compound of the present invention having such characteristics is useful as adhesives, primers, coating materials and the like.

¹ H-NMR spectrum chart of the aromatic bismaleimide compound synthesized in Example 1. FIG. 4 is an IR spectrum chart of the aromatic bismaleimide compound synthesized in Example 1. FIG.

Specific embodiments of the present invention are described below.

（式中、Ｘ¹は独立して、下記式

（ａは１～６の数である）

から選ばれる２価の基であり、ｍは１～３０、好ましくは２～２０の数であり、ｎは１～５、好ましくは１～３、より好ましくは１の数であり、Ａ¹及びＡ²はそれぞれ独立して、下記式（２）

（式中、Ｘ²は独立して、下記式

（ａは１～６の数である）

から選ばれる２価の基であり、Ｒ¹は独立して、水素原子、塩素原子、または非置換又は置換の炭素数１～６の脂肪族炭化水素基である）
または下記式（３）

（式中、Ｘ¹は前記と同じものを示す）

で示される２価の芳香族基である。）
<Aromatic bismaleimide compound>
The bismaleimide compound of the present invention is a novel aromatic bismaleimide compound represented by the following formula (1).

(Wherein, X ¹ is independently represented by the following formula

(a is a number from 1 to 6)

is a divalent group selected from m is a number of 1 to 30, preferably 2 to 20, n is a number of 1 to 5, preferably 1 to 3, more preferably 1, A ¹ and A ² is independently represented by the following formula (2)

(Wherein, X ² is independently represented by the following formula

(a is a number from 1 to 6)

and R ¹ is independently a hydrogen atom, a chlorine atom, or an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 6 carbon atoms)
or the following formula (3)

(Wherein, X ¹ is the same as above)

is a divalent aromatic group represented by )

X ¹ is preferably -CH ₂ - or -C(CH ₃ ) ₂ - from the viewpoint of availability of raw materials. m is a number of 1-30, preferably a number of 2-20. When m is within this range, a good balance is achieved between the uncured solubility of the aromatic bismaleimide compound in a solution and the ability to form a film, and the toughness and heat resistance of the resulting cured product. n is a number from 1 to 5, preferably from 1 to 3, more preferably 1;

X ² is preferably -CH ₂ - or -C(CH ₃ ) ₂ - from the viewpoint of availability of raw materials. Also, R ¹ is independently a hydrogen atom, a chlorine atom, or an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 6 carbon atoms. Examples of unsubstituted or substituted aliphatic hydrocarbon groups having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, cyclohexyl group and the like. Groups in which some or all of the hydrogen atoms in these groups have been substituted with halogen atoms such as F, Cl, Br, etc., such as trifluoromethyl groups, can be mentioned. R ¹ is preferably a hydrogen atom or an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 3 carbon atoms, and A ¹ and A ² may be different from the viewpoint of availability of raw materials. more preferred.

The aromatic bismaleimide compound of formula (1) preferably has a number average molecular weight of 3,000 to 50,000, more preferably 5,000 to 40,000. When the number-average molecular weight is within this range, the aromatic bismaleimide compound is stably dissolved in a solvent and the film-forming ability is improved.
The number average molecular weight referred to in the present invention refers to the number average molecular weight measured by gel permeation chromatography (GPC) under the following conditions using polystyrene as a standard substance.

[Measurement conditions for GPC]
Developing solvent: tetrahydrofuran Flow rate: 0.35 mL/min
Detector: RI
Column: TSK-GEL H type (manufactured by Tosoh Corporation)
Column temperature: 40°C
Sample injection volume: 5 μL

Moreover, X ¹ in the formula (1) and X ¹ in the formula (3) have the same divalent group. The aromatic bismaleimide compound of the present invention is produced using a divalent acid anhydride and a diamine having the same bisphenol skeleton. The manufacturing method thereof will be described in detail below.

<Method for Producing Aromatic Bismaleimide Compound>
The method for producing the aromatic bismaleimide compound of the present invention is not particularly limited, but it can be produced efficiently by, for example, either method shown below.

（式中、Ｘ¹は上記と同じであり、独立して、下記式

（ａは１～６の数である）

から選ばれる２価の基である）

で示される芳香族ジフタル酸無水物と下記式（５）

（式中、Ｒ¹、Ｘ²は上記と同じであり、Ｒ¹は独立して、水素原子、塩素原子、または非置換又は置換の炭素数１～６の脂肪族炭化水素基であり、Ｘ²は独立して、下記式

（ａは１～６の数である）

から選ばれる２価の基である）

で示される芳香族ジアミンとでアミック酸を合成し、閉環脱水する工程Ａと、
該工程Ａに次いで、前記工程Ａで得られた反応物と下記式（６）

（式中、Ｘ¹は上記と同じ）

で示される芳香族ジアミンとでアミック酸を合成し、閉環脱水する工程Ｂと、
該工程Ｂに次いで、前記工程Ｂで得られた反応物と無水マレイン酸を反応させ、マレアミック酸を合成し、閉環脱水することによって分子鎖末端をマレイミド基で封鎖する工程Ｃとを有する芳香族ビスマレイミド化合物の製造方法である。 As one method, the following formula (4)

(Wherein, X ¹ is the same as above, independently, the following formula

(a is a number from 1 to 6)

is a divalent group selected from

and the aromatic diphthalic anhydride represented by the following formula (5)

(wherein R ¹ and X ² are the same as above, R ¹ is independently a hydrogen atom, a chlorine atom, or an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 6 carbon atoms; ² is independent of the following formula

(a is a number from 1 to 6)

is a divalent group selected from

A step A of synthesizing an amic acid with an aromatic diamine represented by and ring-closing dehydration;
Following the step A, the reactant obtained in the step A and the following formula (6)

(Wherein, X ¹ is the same as above)

A step B of synthesizing an amic acid with an aromatic diamine represented by and ring-closing dehydration;
After step B, the reaction product obtained in step B is reacted with maleic anhydride to synthesize maleamic acid, and ring-closing dehydration is performed to block the end of the molecular chain with a maleimide group. A method for producing a bismaleimide compound.

（式中、Ｘ¹は上記と同じであり、独立して、下記式

（ａは１～６の数である）

から選ばれる２価の基である）

で示される芳香族ジフタル酸無水物と下記式（６）

（式中、Ｘ¹は上記と同じ）

で示される芳香族ジアミンとでアミック酸を合成し、閉環脱水する工程Ａ’と、
該工程Ａ’に次いで、前記工程Ａ’で得られた反応物と下記式（５）

（式中、Ｒ¹、Ｘ²は上記と同じであり、Ｒ¹は独立して、水素原子、塩素原子、または非置換又は置換の炭素数１～６の脂肪族炭化水素基であり、Ｘ²は独立して、下記式

（ａは１～６の数である）

から選ばれる２価の基である）

で示される芳香族ジアミンとでアミック酸を合成し、閉環脱水する工程Ｂ’と、
該工程Ｂ’に次いで、前記工程Ｂ’で得られた反応物と無水マレイン酸を反応させ、マレアミック酸を合成し、閉環脱水することによって分子鎖末端をマレイミド基で封鎖する工程Ｃ’を有する芳香族ビスマレイミド化合物の製造方法である。 Another method is the following formula (4)

(Wherein, X ¹ is the same as above, independently, the following formula

(a is a number from 1 to 6)

is a divalent group selected from

and the aromatic diphthalic anhydride represented by the following formula (6)

(Wherein, X ¹ is the same as above)

A step A' of synthesizing an amic acid with an aromatic diamine represented by and ring-closing dehydration;
Following the step A', the reactant obtained in the step A' and the following formula (5)

(wherein R ¹ and X ² are the same as above, R ¹ is independently a hydrogen atom, a chlorine atom, or an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 6 carbon atoms; ² is independent of the following formula

(a is a number from 1 to 6)

is a divalent group selected from

A step B' of synthesizing an amic acid with an aromatic diamine represented by and ring-closing dehydration;
Step B' is followed by step C' of reacting the reactant obtained in step B' with maleic anhydride to synthesize maleamic acid, followed by ring-closing dehydration to block the molecular chain ends with maleimide groups. A method for producing an aromatic bismaleimide compound.

The above two production methods are shown, but the basic flow is to synthesize an amic acid with an aromatic diphthalic acid and an aromatic diamine, and through a step A (or step A') of ring-closing dehydration, step A (or After step A′), an aromatic diamine different from the previous step A (or step A′) is added to synthesize an amic acid, and further through step B (or step B′) of ring-closing dehydration, step B (or After step B'), maleic anhydride is reacted to synthesize maleamic acid, and finally ring-closing dehydration is performed to block the molecular chain ends with maleimide groups. A maleimide compound can be obtained, and the main difference between the above two production methods is the order of the types of aromatic diamines to be added.
The reaction can be broadly classified into two, that is, reaction for synthesizing amic acid or maleamic acid and ring-closing dehydration reaction, which will be described in detail below.

In step A (or step A'), first, a specific aromatic diphthalic anhydride and a specific aromatic diamine are reacted to synthesize an amic acid. This reaction generally proceeds at room temperature (25°C) to 100°C in a high-boiling aprotic polar solvent. Anisole and its derivatives (eg, o-methylanisole, p-methylanisole, etc.) can be used as solvents rather than aprotic polar solvents.
Subsequently, the ring-closing dehydration reaction of the amic acid is carried out under the conditions of 120 to 180° C., and then proceeds while removing the water by-produced by the condensation reaction from the system. A high-boiling aprotic polar solvent or an acid catalyst may be added to promote the ring-closing dehydration reaction. High-boiling aprotic polar solvents include N,N-dimethylformamide (DMF), dimethylsulfoxide (DMSO) and the like. These may be used individually by 1 type, and may use 2 or more types together. Acid catalysts include sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid and the like. These may be used individually by 1 type, and may use 2 or more types together.

The blending ratio of the aromatic diphthalic anhydride and the aromatic diamine is preferably aromatic diphthalic anhydride/aromatic diamine = 1.01 to 1.50/1.0 in terms of molar ratio. More preferably, the ratio of anhydride/aromatic diamine is 1.01 to 1.15/1.0. By blending in this ratio, a copolymer containing both terminal imide groups can be synthesized as a result.

In step B (or step B'), first, the copolymer containing imide groups at both ends obtained in step A (or step A') is reacted with a specific aromatic diamine to synthesize an amic acid. This reaction also generally proceeds at room temperature (25° C.) to 100° C. in a high-boiling aprotic polar solvent. It is preferable to use anisole and its derivatives (eg, o-methylanisole, p-methylanisole, etc.) as solvents rather than high-boiling aprotic polar solvents. These may be used individually by 1 type, and may use 2 or more types together.
Similarly, the subsequent ring-closure dehydration reaction of amic acid is carried out under conditions of 120 to 180° C., and then proceeds while removing water produced as a by-product of the condensation reaction from the system. A high boiling aprotic polar solvent acid catalyst can also be added to promote the ring-closing dehydration reaction. High-boiling aprotic polar solvents include N,N-dimethylformamide (DMF), dimethylsulfoxide (DMSO) and the like. These may be used individually by 1 type, and may use 2 or more types together. Acid catalysts include sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid and the like. These may be used individually by 1 type, and may use 2 or more types together.

The blending ratio of the copolymer containing imide groups at both ends and the aromatic diamine is preferably 1.0:1.6 to 2.5, more preferably 1.0:1.8 to 2.2 in terms of molar ratio. is more preferred.

In step C (or step C′), the diamine having amino groups at both ends obtained in step B (or step B′) is reacted with maleic anhydride at room temperature (25° C.) to 100° C. After synthesizing maleamic acid, ring-closing dehydration is performed at 120 to 180° C. while removing water in the system by-produced, thereby blocking the ends of the molecular chains with maleimide groups to obtain the desired aromatic bismaleimide compound. be able to.

The molar ratio of the diamine having amino groups at both ends and maleic anhydride is preferably 1.0:1.6 to 2.5, more preferably 1.0:1.8 to 2.2. is more preferable.

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the examples and comparative examples, "room temperature" means 25°C.

ｍ＝５、ｎ＝１（それぞれ平均値）


¹Ｈ－ＮＭＲ（４００ＭＨｚ、ＣＤＣｌ₃）δ１．２６－１．２８（－Ｃ₆Ｈ₂（－ＣＨ₂－ＣＨ ₃）₂、１２Ｈ）、１．７２－１．７８（－Ｃ（ＣＨ ₃）₂－、１２Ｈ）、２．４５－２．５２（－Ｃ₆Ｈ₂（－ＣＨ ₂－ＣＨ₃）₂、８Ｈ）、３．７（－Ｃ₆Ｈ₂－ＣＨ ₂－Ｃ₆Ｈ₂－、２Ｈ）、４．１４（－ＣＨ＝ＣＨ－、４Ｈ）、６．６５‐７．０５（芳香族環由来、１４Ｈ）、７．０６‐７．１４（芳香族環由来、８Ｈ）、７．２８‐７．４８（芳香族環由来、２４Ｈ）、７．９２‐７．９５（芳香族環由来、２Ｈ）
Example 1
Preparation of Bismaleimide Compound (Formula 7) Into a 1 L glass 4-neck flask equipped with a stirrer, Dean-Stark tube, cooling condenser and thermometer, 2,2-bis[4-(2,3-dicarboxyphenoxy) was added. Add 65.06 g (0.125 mol) of phenyl]propane dianhydride, 35.26 g (0.115 mol) of 4,4-methylenebis(2,6-diethylaniline) and 250 g of anisole, and stir at 80° C. for 3 hours. Amic acid was synthesized by Thereafter, the temperature was raised to 150° C. as it was, and the mixture was stirred for 2 hours while distilling off by-produced moisture to synthesize a copolymer.
Then, 7.05 g (0.015 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane is added to the flask containing the copolymer solution cooled to room temperature, and stirred at 80°C for 3 hours. synthesized amic acid. Thereafter, the temperature was raised to 150° C. as it was, and the mixture was stirred for 2 hours while distilling off by-produced moisture to synthesize a diamine compound at both ends.
After cooling the flask containing the resulting solution of both terminal diamines to room temperature, 1.45 g (0.015 mol) of maleic anhydride was added and stirred at 80° C. for 3 hours to synthesize maleamic acid. Thereafter, the temperature was raised to 150° C. as it was, and the mixture was stirred for 2 hours while distilling off by-produced moisture to obtain a varnish of the desired aromatic bismaleimide compound. Thereafter, anisole was distilled off at 130° C. under reduced pressure (10 mmHg or less) to obtain a dark brown solid. From the ¹ H-NMR and IR spectra of the obtained product, it was found to have a structure represented by the following formula 7. The ¹ H-NMR spectrum is shown in FIG. 1, and the IR spectrum is shown in FIG. Moreover, the number average molecular weight of the obtained product was 11,600.

m = 5, n = 1 (mean value for each)


¹ H-NMR (400 MHz, CDCl ₃ ) δ 1.26-1.28 (--C ₆ H ₂ (--CH ₂ --CH ₃ ) ₂ , 12H), 1.72-1.78 (--C(C H ₃ ) _2- , 12H), 2.45-2.52 (--C ₆ H ₂ (--C H ₂ --CH ₃ ) ₂ , 8H), 3.7 (--C ₆ H ₂ --CH ₂ --C ₆ H ₂ —, 2H), 4.14 (—C H ═C H —, 4H), 6.65-7.05 (derived from aromatic ring, 14H), 7.06-7.14 (aromatic ring derived from aromatic ring, 8H), 7.28-7.48 (derived from aromatic ring, 24H), 7.92-7.95 (derived from aromatic ring, 2H)

ｍ＝５、ｎ＝１（それぞれ平均値）
Example 2
Preparation of Bismaleimide Compound (Formula 8) Into a 1 L glass 4-neck flask equipped with a stirrer, Dean-Stark tube, cooling condenser and thermometer, 2,2-bis[4-(2,3-dicarboxyphenoxy) was added. 65.06 g (0.125 mol) of phenyl]propane dianhydride, 54.05 g (0.115 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane and 250 g of anisole were added, and the temperature was maintained at 80°C. and stirred for 6 hours to synthesize an amic acid. Thereafter, the temperature was raised to 150° C. as it was, and the mixture was stirred for 2 hours while distilling off by-produced moisture to synthesize a copolymer.
After that, 4.60 g (0.015 mol) of 4,4-methylenebis(2,6-diethylaniline) was added to the flask containing the copolymer solution cooled to room temperature, and the amic acid was removed by stirring at 80°C for 3 hours. Synthesized. Thereafter, the temperature was raised to 150° C. as it was, and the mixture was stirred for 2 hours while distilling off by-produced moisture to synthesize a diamine compound at both ends.
After cooling the flask containing the resulting solution of both terminal diamines to room temperature, 1.45 g (0.015 mol) of maleic anhydride was added and stirred at 80° C. for 3 hours to synthesize maleamic acid. Thereafter, the temperature was raised to 150° C. as it was, and the mixture was stirred for 2 hours while distilling off by-produced moisture to obtain a varnish of the desired aromatic bismaleimide compound. Thereafter, anisole was distilled off at 130° C. under reduced pressure (10 mmHg or less) to obtain a dark brown solid having a structure represented by Formula 8 below. Also, the number average molecular weight of the obtained product was 15,100.

m = 5, n = 1 (mean value for each)

ｍ＝５、ｎ＝１（それぞれ平均値）
Example 3
Preparation of Bismaleimide Compound (Formula 9) Into a 1 L glass 4-neck flask equipped with a stirrer, Dean-Stark tube, cooling condenser and thermometer, 2,2-bis[4-(2,3-dicarboxyphenoxy) was added. 65.06 g (0.125 mol) of phenyl]propane dianhydride, 40.78 g (0.115 mol) of 4,4-methylenebis(2,6-dipropylaniline) and 250 g of anisole were added, and the mixture was heated at 80° C. for 3 hours. Amic acid was synthesized by stirring. Thereafter, the temperature was raised to 150° C. as it was, and the mixture was stirred for 2 hours while distilling off by-produced moisture to synthesize a copolymer.
Then, 7.05 g (0.015 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane is added to the flask containing the copolymer solution cooled to room temperature, and stirred at 80°C for 3 hours. synthesized amic acid. Thereafter, the temperature was raised to 150° C. as it was, and the mixture was stirred for 2 hours while distilling off the generated water to synthesize a diamine compound at both ends.
After cooling the flask containing the resulting solution of both terminal diamines to room temperature, 1.45 g (0.015 mol) of maleic anhydride was added and stirred at 80° C. for 3 hours to synthesize maleamic acid. Thereafter, the temperature was raised to 150° C. as it was, and the mixture was stirred for 2 hours while distilling off by-produced moisture to obtain a varnish of the desired aromatic bismaleimide compound. Thereafter, anisole was distilled off at 130° C. under reduced pressure (10 mmHg or less) to obtain a dark brown solid having a structure represented by Formula 9 below. Moreover, the number average molecular weight of the obtained product was 12,500.

m = 5, n = 1 (mean value for each)

The obtained bismaleimide compounds (Examples 1 to 3) and the following bismaleimide compounds (Comparative Examples 1 to 3) were examined for solubility in various organic solvents and film forming ability by the following methods. Table 1 shows the results.

Comparative Example 1: 4,4'-diphenylmethanebismaleimide (manufactured by Keiai Kasei Co., Ltd.)
Comparative Example 2: 2,2'-bis-[4-(4-maleimidophenoxy)phenyl]propane (Kei Kasei)
Comparative Example 3: Long-chain alkyl group-containing bismaleimide compound (BMI-1500, Designer Molecules Inc.)

Solubility test Each bismaleimide compound was dissolved in 100 g of an organic solvent (anisole, tetrahydrofuran (THF), N-methyl-2-pyrrolidone (NMP), or N,N-dimethylformamide (DMF)) at 25°C. , the dissolution amount (g/100 g solvent) was measured.

Evaluation method of film forming ability An N,N-dimethylformamide (DMF) solution (50% by mass of active ingredient) of each bismaleimide compound was applied to a polyethylene terephthalate (PET) film (G2) having a thickness of 38 μm using a Baker applicator. -38, manufactured by Teijin) to a thickness of 30 μm and an A4 size (210 mm×297 mm), and dried at 150° C. After drying, the appearance was clean and the film was formed without problems, and the film was not formed due to repelling, or the bismaleimide precipitated and aggregated to cause poor appearance. .

Claims (5)

It is represented by the following formula (1), and when A ¹ is the following formula (2), A ² is the following formula (3), or when A ¹ is the following formula (3), A ² is the following formula ( 2) Aromatic bismaleimide compound.

(Wherein, X ¹ is independently represented by the following formula

(a is a number from 1 to 6)

is a divalent group selected from m is a number of 1 to 30, n is a number of 1 to 5, A ¹ and A ² are each independently represented by the following formula (2)

(Wherein, X ² is independently represented by the following formula

(a is a number from 1 to 6)

and R ¹ is independently a hydrogen atom, a chlorine atom, or an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 6 carbon atoms)
or the following formula (3)

(Wherein, X ¹ is the same as above)

is a divalent aromatic group represented by
2. The aromatic bismaleimide compound according to claim 1, wherein the aromatic bismaleimide compound of formula (1) has a number average molecular weight of 3,000 to 50,000.
3. The aromatic bismaleimide compound according to claim ¹ , wherein X1 in formula ( ¹ ) and X1 in formula (3) have the same divalent group.
Formula (4) below

(Wherein, X ¹ is independently represented by the following formula

(a is a number from 1 to 6)

is a divalent group selected from

and the aromatic diphthalic anhydride represented by the following formula (5)

(In the formula, R ¹ is independently a hydrogen atom, a chlorine atom, or an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 6 carbon atoms, and X ² is independently the following formula

(a is a number from 1 to 6)

is a divalent group selected from

is reacted with the aromatic diamine represented by the molar ratio of aromatic diphthalic anhydride/aromatic diamine = 1.01 to 1.50/1.0 to synthesize an amic acid, and ring-closing dehydration step A When,
Following the step A, the reactant obtained in the step A and the following formula (6)

(Wherein, X ¹ is the same as above)

A step B of synthesizing an amic acid with an aromatic diamine represented by and ring-closing dehydration;
Step B is followed by Step C of reacting the reactant obtained in Step B with maleic anhydride to synthesize maleamic acid, and ring-closing dehydration to block the ends of the molecular chains with maleimide groups. 4. A method for producing an aromatic bismaleimide compound according to any one of claims 1 to 3 .
Formula (4) below

(Wherein, X ¹ is independently represented by the following formula

(a is a number from 1 to 6)

is a divalent group selected from

and the aromatic diphthalic anhydride represented by the following formula (6)

(Wherein, X ¹ is independently represented by the following formula

(a is a number from 1 to 6)

is a divalent group selected from

is reacted with the aromatic diamine represented by the molar ratio of aromatic diphthalic anhydride/aromatic diamine = 1.01 to 1.50/1.0 to synthesize an amic acid, and ring-closing dehydration step A 'When,
Following the step A', the reactant obtained in the step A' and the following formula (5)

(In the formula, R ¹ is independently a hydrogen atom, a chlorine atom, or an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 6 carbon atoms, and X ² is independently the following formula

(a is a number from 1 to 6)

is a divalent group selected from

A step B' of synthesizing an amic acid with an aromatic diamine represented by and ring-closing dehydration;
Step B' is followed by step C' of reacting the reactant obtained in step B' with maleic anhydride to synthesize maleamic acid, followed by ring-closing dehydration to block the molecular chain ends with maleimide groups. The method for producing an aromatic bismaleimide compound according to any one of claims 1 to 3 , characterized in that:

Images