JPS63255263A - Bismaleimide and production thereof - Google Patents

Abstract

NEW MATERIAL:2,2-Bis[ 4-(3-maleimidophenoxy)phenyl ]-1,1,1,3,3,3-hexafluoro propane shown by formula I. USE:A raw material monomer for polymaleimide resins and polyamine modified polymaleimide resins having excellent heat resistance and flexibility. Useful as resin materials such as electrical and electronic insulating materials, heat- resistant adhesives and aerospace industrial materials requiring specific functions. PREPARATION:An ether bond-containing diamine shown by formula II is reacted with maleic anhydride in an organic solvent such as acetone, a prepared bismaleamic acid shown by formula III is reacted with acetic anhydride as a dehydrating agent in an organic solvent such as acetone in the presence of a base such as triethylamine and a catalyst such as MgO and cobalt (II) acetate at 20-80 deg.C for 0.5-9hr and subjected to ring formation through dehydration to readily give a compound shown by formula I of light yellow crystal.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a bismaleimide compound useful as a monomer for heat-resistant polymers and a method for producing the same. More specifically, bismaleimide represented by the formula (I) and this compound represented by the formula (I
I) It relates to a method of manufacturing by reacting a diamine having an ether bond represented by formula I with maleic anhydride.

(Prior art) Conventionally, resins having an imide structure have exhibited excellent performance in electrical insulation, heat resistance, and dimensional stability of molded products, and have been widely used in industry. As heat-resistant thermosetting resins, polyimide resins, polyamino bismaleimide resins, and the like are known, and are widely used in impregnated varnishes, Sada Naka, molded products, and the like.

However, although these conventional resins are generally excellent in terms of heat resistance, they have the disadvantage that molded products are brittle, making them impractical for the purpose of molding resins.

On the other hand, as a bismaleimide compound, 2,2-bis(4
-(4-aminophenoxy)phenyl-1゜1.1,3
, 3.3-Hexafluoropropane as a diamine component has been described to potentially impart flexibility to polyamino bismaleimide resin (JP-A-56-103162). ).

(Problems to be Solved by the Invention) The problem of the present invention is to take advantage of the characteristics of a bismaleimide compound, represented by N,N''-(4,4'-methylene diphenylene) bismaleimide, as a thermosetting resin. , and 2
,2-bis(4-(3-aminophenoxy)phenyl-
Bis represented by the above formula (I), which is a raw material monomer for a resin with good heat resistance and flexibility, incorporating a 1,1,1,3,3,3-hexafluoropropane structure into maleimide. An object of the present invention is to provide maleimide compounds.

(Means for Solving the Problems) Based on this idea, the present inventors have made extensive studies to solve the problems of the present invention. As a result, the formula (I)
It has been discovered that a novel bismaleimide compound represented by has excellent heat resistance, and that this compound can be easily produced by subjecting the diamine represented by (ff) above and maleic anhydride to a condensation/dehydration reaction, and the present invention was completed.

That is, the present invention is a novel bismaleimide compound and a method for its use.

The compound of the present invention is 2,2-bis(4-(3-maleimidophenoxy)phenyl)-1,1,1,3,3,3-hexafluoropropane represented by formula (I).

An example of the performance that indicates the heat resistance of a compound is the 5% weight loss hot water temperature, and the temperature of this compound (I) is at a very high level of 460°C in air.

The method for producing the compound of the present invention will be explained.

The diamine used as a raw material is a 2,2-bis(4-(3-aminophenoxy)phenyl)-1,1,1,3,3,3-hexafluoropropane compound represented by formula (If) . This diamine is manufactured by condensation and reduction of 2.2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane and m-dinitrobenzene. (Japanese Patent Application Laid-Open No. 60-59560).

The method for producing the compound of the present invention is not particularly limited, but usually, in the first step, diamines represented by formula (■) and maleic anhydride are reacted in a medium containing 11Af''j! , to produce bismaleamic acid represented by the formula (I [ , ketones such as acetone, methyl ethyl ketone, cyclohexanone, diisopropyl ketone, ethers such as ether, tetrahydrofuran, dioxane, β-oxyethyl methyl ether, aromatic compounds such as benzene, toluene, chlorobenzene, acetonitrile, N,N-dimethylformamide , N,N-dimethylacetamide, dimethylsulfoxide, 1-methyl-
Examples include aprotic polar solvents such as 2-pyrrolidinone and 1,3-dimethyl-2-imidazolidinone.

The amount of these solvents to be used is not particularly limited, but usually 1 to 10 times the weight of the raw materials is sufficient.

Next, in the second step, bismaleamic acid is cyclized and dehydrated to produce bismaleimide represented by the general formula A known method is used for this in an organic solvent (Japanese Patent Publication No. 46-23250, Japanese Patent Publication No. 46-23250,
9-40231, Special Publication No. 59-52660).

At this time, the amount of acetic anhydride used is not particularly limited to an upper limit, but is usually in the range of 2 to 4 times the molar amount of bismaleamic acid.

The catalysts used are alkaline earth metal oxides, iron (■
and III), nickel (■), manganese (■ and I [[), copper (I and ■) or cobalt (■ and ■) carbonates, sulfates, phosphates, acetates, etc.
Particularly preferred are nickel acetate (■) and cobalt acetate (
■) is magnesium oxide. These catalysts exhibit sufficient effects when used alone, but two or more types may be used in combination.

The amount used is 5X10-' to 0.1 for bismaleamic acid.
It is in the molar range.

The bases used are alkali metal acetates or tertiary amines. Specific examples include sodium acetate, potassium acetate, trimethylamine, triethylamine, and tributylamine. The amount used is in the range of 0.05 to 1.1 mol based on bismaleamic acid.

Implementation of the method of the invention,! There are no particular restrictions for Mr. Ji,
The intermediate bismaleamic acid produced in the first step does not necessarily need to be isolated in order to produce bismaleimide, and can be directly subjected to the second step cyclization and dehydration reaction in the same solvent. At this time, the reaction temperature was 20 to 80°C.
The reaction time is in the range of 0.5 to 9 hours.

After the reaction is completed, the precipitated crystals are filtered and discharged into water or methanol to obtain the desired crystals.

(Functions and Effects) The compound of the present invention is useful as a raw material monomer for polymaleimide resins and polyamine-modified polymaleimide resins that have excellent heat resistance and flexibility.

Therefore, it has a wide range of uses as a material for resins that require unique functions, such as electrical and electronic insulating materials, heat-resistant adhesives, and base materials for the aerospace industry.

(Example) Hereinafter, the present invention will be explained in more detail using Examples.

Example 1 4.32 g (0,044 mol) of maleic anhydride and 4.32 g of acetone were placed in a reaction flask equipped with a stirrer and a thermometer.
2.2-bis(4-(3-aminophenoxy)phenyl)-1,1,1,3,3,3
- A solution of 10.37 g (0.02 mol) of hexafluoropropane dissolved in 31.0 g of acetone is added dropwise at room temperature, and the mixture is further stirred at 23-27°C for 3 hours.

After the reaction was completed, the resulting crystals were filtered, washed with acetone, and dried to obtain bismaleamic acid as pale yellow crystals.

Yield 14.2g (yield 99.3%) mp, 18
6-188℃ Elemental analysis (%) HNF Calculated value 58.83 3.37 3.92 15.9
4 analysis value 59.21 3.50 3.76 15.
20IR (KBr, C11-'): 3220.
3280 (NH) 1705 (amide bond) 1245 (ether bond) 7.14 g of bismaleamic acid thus obtained (
0.01 mol) is suspended in 21.4 g of acetone, 0.48 g of triethylamine is added, and the mixture is stirred at room temperature for 30 minutes.

Magnesium oxide (I[) 20mg, cobalt acetate (
■)・4) After adding 2 mg of 1.0, 2.6 g of acetic anhydride
was added dropwise over 30 minutes at 25°C and further stirred at room temperature for 3 hours. After completion of the reaction, the resulting crystals were filtered, washed and dried to obtain bismaleimide as pale yellow crystals.

Yield 6.4g (yield 94.3%) mp, 135-138°C Elemental analysis (%) HNF Calculated value 61.95 2.97 4.13 16.8
0 analysis value 61.97 2.74 4.17 16.
26IR (KBr, cm-Re: 1780 and 172
0 (imide bond) 1245 (ether bond) 5% weight-'! Decreasing temperature 1: i): 460°C Example 2 4.32 g (0,044 mol) of maleic anhydride and 4.32 g of acetone were placed in a reaction flask equipped with a stirrer and a temperature needle.
Charge and dissolve. To this, 2,2-bis(4-(3-aminophenoxy)phenyl) -1,1,1,3,3,
A solution prepared by dissolving 10.37 g (0.02 mol) of 3-hexafluoropropane in 31.0 g of acetone is added dropwise at room temperature, and the mixture is further stirred at 23 to 27° C. for 3 hours, causing crystals to precipitate.

After adding 0.96 g of triethylamine to this, the mixture was stirred at room temperature for 30 minutes. Magnesium oxide (n) 4hg
After adding 4 mg of cobalt (II) acetate.4Hz, 5.2 g of acetic anhydride was added dropwise at 25°C over 30 minutes, and the mixture was further stirred at room temperature for 3 hours.

After the reaction was completed, the resulting crystals were filtered, washed, and dried to obtain bismaleimide as pale yellow crystals.

Yield 1- 13.1g (Yield 96.5%) 鵠p, 1
35~138°C

Claims (1)

[Claims] 1) Bismaleimide represented by formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) 2) Formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) A method for producing bismaleimide represented by the formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I), which is characterized by reacting the diamine represented by the formula with maleic anhydride.