JPH0413661A - Bisimide - Google Patents

Abstract

NEW MATERIAL:The bisimide of formula I (D is 2-24C alkylene having at least one polymerizable unsaturated double bond; R is H, halogen, 1-4C alkyl or alkoxy; n is 2-15). USE: Useful as a resin material for laminated sheet, fiber-reinforced composite material, sliding material, molding material, sealant and protective paint for electronic parts, resist material, electrically conductive paste, etc., suitable for improving the flexibility and solvent solubility of a resin. PREPARATION: The objective compound of formula I can be produced by adding 1mol of a diamine compound of formula II to 2-2.6mol of an unsaturated dicarboxylic acid anhydride in a mixture of an aromatic hydrocarbon solvent or a halogenated hydrocarbon solvent and an aprotic polar solvent and subjecting the resultant diamic acid of formula IV to dehydrative cyclization reaction in the presence of an acidic catalyst at 80-200 deg.C for 0.5-10hr.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention is applicable to laminates, fiber-reinforced composite materials, sliding materials, molding materials, electronic component sealants and protective coatings, resist materials, conductive pastes, etc. The present invention provides a novel bisimide compound with excellent visibility that is useful as a resin material.

[Prior art and issues]

Bismaleimide obtained from 4,4'-diaminodiphenylmethane and maleic anhydride has conventionally been used as an addition polymerization type bisimide that is easy to mold. However, although this bismaleimide is generally excellent in terms of heat resistance, the molded product is brittle and is not practical as a molding resin.

Furthermore, it has drawbacks such as poor workability because it is difficult to dissolve in general-purpose solvents. In addition, in recent years, various bismaleimides with improved flexibility have been proposed (Japanese Patent Application Laid-Open No. 1677-1989
No. 60, No. 62-167777).

[Problem to be solved by the invention]

However, although the visibility of the bismaleimides is improved, their solubility in solvents is the same as that of conventional bismaleimides, so their use has naturally been limited.

The present invention was made to solve these problems, and aims to improve flexibility and solubility in solvents.

[Means to solve the problem]

As a result of intensive studies to achieve the above object, the present inventors found that the following new imide compound is preferable for improving flexibility and solvent solubility compared to conventional bismaleimide. It was discovered that it is a raw material for resin.

That is, the present invention provides a bisimide compound represented by the following general formula (1).

[In the formula, D has at least one polymerizable unsaturated double bond
It is an alkylene group having 2 to 24 carbon atoms, and R represents a hydrogen atom, a halogen atom, or an alkyl group or an alkoxy group having 1 to 4 carbon atoms.

n is an integer from 2 to 15] The present invention will be explained in more detail below.

The present invention provides a bisimide represented by the above general formula (I).
f) [In the formula, R and n are the same as above] A diamine represented by the following general formula (III) δ [In the formula, D is the same as above] A diamine represented by the following general formula (III) δ [In the formula, D is the same as above] An addition reaction is carried out to obtain a bisamic acid represented by the following general formula (IV) [wherein R, D and n are the same as above], and this bisamic acid is dehydrated and ring-closed to obtain the general formula (IV).
The bisimide compound shown in 1) can be obtained.

(Diamine) Used in the bisimide compound of the present invention, the general formula (
Examples of the diamine compound represented by It) include dimethylene-bis(4-aminobenzoate), trimethylene-bis(4-aminobenzoate), hexamethylene-bis(4-aminobenzoate), and decamethylene-bis(4-aminobenzoate).
Bis(4-aminobenzoate), tetramethylene(3
~aminobenzoate), tetramethylene (2-aminobenzoate), tetramethylene (3-methyl-4-aminobenzoate), and the like.

(Unsaturated dicarboxylic anhydride) The unsaturated dicarboxylic anhydride represented by the general formula (1) includes maleic anhydride, itaconic anhydride, pyrosiconic anhydride, citraconic anhydride, dichloromaleic anhydride, and these unsaturated carboxylic anhydrides. Diels-Alder reaction products of acid anhydrides and dienes, such as cyclopentadiene,
These include Diels-Alder reaction product hydrates of furan, allocimene, and terpinene with maleic anhydride.

(Production of imide) The bisimide compound of the present invention can be produced by a known method of imidization using a conventional dehydrating agent such as acetic anhydride, but the method described in JP-A-1-211563 is preferable.

Specifically, 2 to 2.6 moles of unsaturated dicarboxylic acid anhydride are used for 1 mole of an aromatic diamine compound, and an addition reaction is carried out in a mixed solvent of an aromatic hydrocarbon solvent and an aprotic polar solvent. The dehydration ring-closing reaction is carried out in the presence of a catalyst at a temperature range of 80 to 200°C for 0.5 to 10 hours.

As the aromatic hydrocarbon solvent, for example, benzene, toluene, xylene, etc. are used, and as the halogenated hydrocarbon solvent, for example, chloroform, 1,2-dichloroethane, chlorobenzene, etc. are used. As the aprotic polar solvent, N,N-dimethylformamide, N,N-
Dimethylacetamide, dimethyl sulfoxide, N-methyl-2- and lolidone, etc. can be used. In the mixed solvent, the aromatic hydrocarbon solvent or halogenated hydrocarbon solvent and the aprotic solvent are mixed at a ratio of about 50:50 to 99:1. This mixed solvent is usually 1 to 10%
Used in double weight.

After the reaction is completed, a poor solvent is added to the reaction product to precipitate bisimide, followed by separation, washing, and drying to obtain a product.

[Use of the bisimide compound of the present invention]

The bisimide obtained by carrying out the present invention gives a tough cured product by heating and melting it alone. Furthermore, various polymerization initiators and catalysts can be added for the purpose of promoting the crosslinking reaction.

It can also be used in combination with known maleimides,
It can be modified according to the purpose by curing through addition reactions with amines and allylphenols, or by blending with epoxy resins, vinyl compounds, acrylates, cyanate esters, etc., and is used in a wide range of applications. be able to.

〔Example〕

Hereinafter, the present invention will be specifically explained with reference to Examples.

1"L"2 5 with dropping funnel, thermometer, stirrer and water separator
Add trimethylene-bis(
4-aminobenzoate) and 260 g of chlorobenzene were charged and stirred.

On the other hand, 30.2 y (0,308 mol) of maleic anhydride was dissolved in 50 g of chlorobenzene and 11 g of N-methyl-2-pyrrolidone, and 20 to 40
The mixture was added dropwise over a period of 30 minutes at a temperature range of .degree.

After the dropwise addition was completed, 2.7 g of para-toluenesulfonic acid was added, and the temperature was raised, and the reaction was carried out for 4 hours while maintaining the temperature at 132°C. The water produced during this time was distilled out of the system together with chlorobenzene.

Thereafter, chlorobenzene was distilled off under reduced pressure in a temperature range of 40 to 80°C. Add 400 g of methanol to the precipitated bismaleimide, take out the slurry, separate, wash with water,
Dry, yellow-brown bismaleimide62. I got it. Yield 9
3.4%, melting point 127-131°C.

The infrared absorption spectrum of this compound is shown in FIG. 1, and the nuclear magnetic resonance spectrum is shown in FIG. 2.

In FIG. 1, there is an absorption derived from the imide ring at 1710 cw-'.

δ In Figure 2, there is a spectrum derived from the vinyl proton of the imide ring at 6.8p9-.

Bismaleimide 23.79 and 4 obtained in Example 1 with bis≧dom
．． 4.0 g of 4'-diaminodiphenylmethane at a temperature of 14
The mixture was stirred at 0°C until homogeneous.

Next, it was poured into a metal mold and cured at 180°C for 5 hours and then at 250°C for 5 hours.
．． A tough cured product with a time of 7 ms and a thickness of 6.4+ui was obtained.

The same procedure as in Example 1 was performed except that m-nidiamine was changed to hexamethylene-bis(3-aminobenzoate) to obtain yellow bismaleimide 66.19.

The yield was 91.5%, and the melting point was 81-84°C.

〔Effect of the invention〕

The bisimide obtained by carrying out the present invention gives a tough cured product by heating and melting it alone.

Furthermore, various polymerization initiators and catalysts can be added for the purpose of promoting the crosslinking reaction. In addition, it can be used in combination with known maleimides, and can be modified according to the purpose by curing by addition reaction with amines and allylphenols, or by blending with epoxy resins, vinyl compounds, acrylates, cyanate esters, etc. It is also possible to do this.

[Brief explanation of drawings]

FIG. 1 is an infrared absorption spectrum of bismaleimide obtained in Example 1, and FIG. 2 is a nuclear magnetic resonance spectrum.

Claims (1)

[Claims] General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, D represents at least one polymerizable unsaturated double bond]
It is an alkylene group having 2 to 24 carbon atoms, and R represents a hydrogen atom, a halogen atom, or an alkyl group or an alkoxy group having 1 to 4 carbon atoms. n is an integer of 2 to 15] A bisimide represented by: