JPH03243606A - Resin composition for composite material - Google Patents

Abstract

PURPOSE:To obtain the subject composition having excellent processability, heat-resistance, durability, mechanical properties, etc., and suitable as a heat- resistant material for aerospace use, etc., by using a specific bismaleimide (mixture) and a specific alkenylphenol as essential components. CONSTITUTION:The objective composition can be produced by compounding (A) a bismaleimide of formula I (Y is -O-, etc.; Z is group of formula II, etc.) produced by condensation dehydration reaction of a diamine with maleic anhydride or mixture of the bismaleimide and other bismaleimide (e.g. 1,2- bismaleimidoethane) with (B) an alkenylphenol produced by compounding (i) an alkenylphenol of formula III and/or formula IV produced by the Claisen rearrangement of a reaction product of a dihydroxynaphthalene and an allyl halide with (ii) preferably diallylbisphenol A and/or diallylbisphenol F. The amount of the component B is 0.1-2.0 equivalent per 1 equivalent of the component A.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel resin composition for composite materials that has excellent processability and provides excellent heat resistance, durability, and mechanical properties.

[Prior art and problems to be solved by the invention] As matrix resins for composite materials, conventional resins themselves have excellent mechanical properties, especially strength and elongation, as well as good adhesion to reinforcing materials. Epoxy resins have been widely used because of their excellent strength development properties. However, epoxy resins have limitations in terms of heat resistance, mechanical properties at high temperatures, water resistance, etc., and meet the demands for higher performance, especially heat resistance and water resistance, which have been increasing in recent years mainly for aerospace applications. It's becoming impossible.

Thermosetting resin compositions containing polyimide and alkenylphenol and/or alkenylphenol ether are known to meet these requirements (Japanese Patent Publication No. 55
(Refer to Publication No.-39242).

The alkenylphenol used in the WA production of this resin composition is diallybisphenol A or diallybisphenol F, and the aromatic bismaleimide is a compound containing 1 m or 2 relatively short chain phenyl rings.
These include bismaleimidodiphenylmethane, 4.4'-bismaleimidodiphenyl ether, 2.4'-bismaleimidotoluene, and 1.3'-bismaleimidobenzene. Therefore, the crosslink density in the cured resin is high,
Only a cured product that is relatively brittle and lacks elongation and toughness can be obtained, and when made into a composite material, the impact resistance is insufficient, and improvements are needed. Furthermore, the cured resin had a high water absorption rate and poor water resistance and hot water resistance. Furthermore, since these bismaleimides have a relatively high melting point and are crystalline, it is difficult to mix them, and even after they are made into prepregs, recrystallization occurs, resulting in difficulties in handling and processability.

In order to improve these performances, it is known to use relatively long-chain compounds containing three or four phenyl rings as bismaleimides. However, although the elongation, brittleness, and water absorption of the cured product can be improved to some extent by using these long-chain bismaleimides, the heat resistance generally tends to decrease and does not satisfy all requirements. do not have. Therefore, there is a need for a resin composition with an excellent balance of heat resistance, toughness, elongation, and water resistance of the cured product.

[Means for solving the problem] The present inventors have developed a resin composition for composite materials that has high impact resistance, FFt thermal resistance, water resistance, and mechanical properties, and also has excellent processability. As a result of research, it was discovered that a resin composition suitable for the above purpose can be obtained by using a specific bismaleimide compound and a specific alkenylphenol, and the present invention was achieved.

The present invention relates to a composite material comprising a general formula compound and an alkenylphenol represented by a bismaleimide represented by the following formula and/or (S) or a bismaleimide mixture containing the bismaleimide of the formula I as one component. The composition of the present invention, which is a resin composition, further contains diallylbisphenol A and/or as alkenylphenol.
Alternatively, it is preferable to contain diallylbisphenol F.

The bismaleimide of formula I used in the present invention can be produced by a known method of subjecting the corresponding diamine to a condensation-dehydration reaction with 2 equivalents of maleic anhydride. Examples of corresponding diamines include the following compounds. 1.3-bis(
3-aminophenoxy)benzene, 1,4-bis(3-
Aminophenoxy)benzene, 1.3-bisoxy)benzene, 1.4-bis(cy)benzene, 1.3-bis(s)) nanotalene, 1.4-bis(s))naphthalene, 2.3-bis(s))naphthalene, 1.5 - bisun) naphthalene, 1. ．． 6-bis-di) naphthalene, 1,7-bis-di) naphthalene, 2,7-bis-di) naphthalene, 2,6-bis-di) naphthalene, 1,4-bis-di)-2-phenylbenzene, (4-aminophenokyaminophenoamino) Phenoaminophenoxyaminophenoxyaminophenoxyaminophenoxyaminophenoxyaminophenoxyaminophenoxyaminophenoxy4,4'-bis(4-aminophenoxy)biphenyl, 2,2-bis[4(4)
-aminophenoxy)phenyl 1-propane, bis(4-
(4-Aminophenoxy)phenyl 1-sulfone, bis[
4-(3-aminophenoxy)phenyl 1-sulfone, 9
．． 9-bis[4-(4-aminophenoxy)phenyl 1
Fluorene, 9.9-bis[4(3-aminophenoxy)phenyl-1 fluorene, 1.3-bis(p-aminocumyl)benzene, 1.4-bis(p-aminocumyl)benzene, etc.

The above-mentioned diamine is available as a commercial product, and can also be produced by a known method, for example, the method described in JP-A-59-170122.

The resin composition of the present invention has the formula I as the bismaleimide component.
In addition to bismaleimide, other bismaleimides may be contained. Examples of other bismaleimides include the following compounds. 1.2-bismaleimidoethane,
1.6-bismaleimide hexane, 1.12-bismaleimide dodecane, 1.6-bismaleimide (2,2,4
-trimethyl)hexadi, 1.3-bismaleimidobenzene, 1.4 bismaleimidobenzene, 4.4'-bismaleimidodiphenylmethane, 4.4'-bismaleimidodiphenyl ether, 3.4'-bismaleimidodiphenyl ether, 4.4 '-Bismaleimidodiphenyl sulfide, 33'-bismaleimidodiphenylsulfone, 4.4'-bismaleimidodiphenylsulfone, 4.4'-bismaleimidodicyclohexylmethane, 2.4-bismaleimidotoluene', 2
．． 6-bismaleimide toluene, 2,4-bismaleimide anisole, N, N'm-xylene bismaleimide, N, N' = p-xylene bismaleimide. The content of other bismaleimides is 10 equivalents or less relative to the equivalent of bismaleimide I of formula (1).

The alkenyl ales represented by the formula (■) and the formula (■) are dihydroxynaphthalene, i.e., 16-dihydroxynaphthalene,
1.7-dihydroxynaphthalene, 2.7-dihydroxynaphthalene or 2.6-dihydroxynaphthalene and 9.9-bis(4-hydroxyphenyl)fluorene and allyl halide, i.e. allyl chloride, allyl bromide are reacted to obtain an alkenyl ether; Furthermore, it can be obtained by a known method of Claisen rearrangement of an alkenyl ether (see Japanese Patent Publication No. 39242/1983).

Among the alkenylphenols represented by formulas ① and ⑐
may contain an alkenyl ether represented by 2C+, +=CH,).

Furthermore, diallylbisphenol A is added as alkenylphenol for the purpose of adjusting various properties of uncured resin and cured resin.
It is effective to blend and/or diallylbisphenol F with the alkenylphenol of formula (1) and/or formula (2). The amount of diallyl bisphenol A and/or diallyl bisphenol F to be blended may be determined as desired, taking into account that when the amount of diallyl bisphenol A and/or diallyl bisphenol F increases, the heat resistance of the cured product tends to decrease.

In the resin composition of the present invention, the mixing ratio of the bismaleimide component and alkenylphenol is 1 part of the bismaleimide component.
It is preferable to range from 01 to 20 equivalents of alkenylphenol. If the amount of the latter is less than 1.1 equivalent, the cured product will become brittle and the viscosity of the resin composition will also increase, which is unfavorable for processing. There is a tendency for a large amount of unreacted alkenyl groups to remain, resulting in a decrease in heat resistance.

The bismaleimide component may be reacted with the alkenylphenol in advance to an extent that gelation does not occur. Although the resin composition of the present invention can be easily cured by heat, a polymerization catalyst may be added for the purpose of imparting desired properties to the cured product or adjusting the thermosetting properties of the resin.

As polymerization catalysts, imidazoles, tertiary amines,
Examples include ionic catalysts such as quaternary ammonium salts, boron trifluoride amine salts, organophosphines, and organophosphonium salts, and radical polymerization initiators such as known organic peroxides, hydroperoxides, and azoisobutyronitrile. The amount of catalyst added may be determined depending on the purpose, but from the viewpoint of stability of the resin composition, it is preferably 0.01 to 3% by weight based on the total resin solid components.

If desired, other known thermosetting resins such as epoxy resins, unsaturated polyester resins, phenol resins, silicone resins, triazine resins, other allyl resins, etc., and thermoplastic resins such as polyether sulfone, polyester, polyether ether ketone, etc. Polyetherimide etc. may be added.

The resin composition for composite materials of the present invention can be blended with various fillers and reinforcing materials using a mixer, kneader roll, etc. at a relatively low temperature, and can be easily prepared into a casting or molding material.

When impregnating reinforcing materials with the resin composition of the present invention, a prepolymer is produced by pre-reacting the composition at a temperature of 50 to 150°C, and in many cases, the viscosity is sufficiently low at low temperatures, so it is melted at a relatively low temperature. Can be impregnated in any state. Acetone, methyl ethyl ketone, methylene chloride, chloroform, if desired.
It may be dissolved and impregnated in a solvent such as tetrahydrofuran.

Reinforcing materials include glass fiber, carbon fiber, boron fiber,
Inorganic fibers such as silicon carbide fibers, p') -p-
Chopped, yarn, tape, sheet, knitted, matted, paper-like materials made of organic fibers such as phenylene terephthalimide, poly-p-benzamide, polyamide hydrazide, etc., asbestos, mica, talc, etc., and 2 of these. Mixtures of more than one species are used. Further, depending on the purpose, flow control agents such as fine silicon oxide powder, pigments, dyes, stabilizers, plasticizers, lubricants, tar, asphalt, etc. may be used alone or in combination with other reinforcing agents. The content of the reinforcing agent is preferably 5 to 80% by volume.

Hereinafter, the present invention will be explained in more detail with reference to Examples, Reference Examples, and Comparative Examples.

"Viscosity of uncured resin" was measured at 50°C using a dynamic mechanical spectrometer manufactured by Rheometrics.

The glass transition point fTgl of the cured product is PerkinElmer D
It was measured by the TMA method using a model TMS-2 equipped with an SC-2.

The water absorption rate was determined from the rate of weight change after a 2 cm thick, 5 cm square cured resin plate was left in hot water at 95° C. for 24 hours. Further, the bending elongation was determined in accordance with JIS K6911.

The "hot water resistance" of a composite material is defined as a 0° 16-layer laminate composite that is left in water at 95°C for 14 days (wetl) and then heated to room temperature according to ASTM D-2344 at 177°C.
Determined by measuring the interlaminar shear strength [ILSS1] at 232°C.

"Impact resistance" is based on NASA RP 1092, in which a 25-inch board with dimensions of 4 x 6 x O is fixed on a stand with a 3 x 5-inch hole, and a 4.9 kg nose with an inch radius is attached in the center. It was determined by dropping a weight and applying an impact of 10,001 bins per inch of plate thickness, and then subjecting the plate to a compression test.

All composite data shows fiber content of 60% by volume.
This is a converted value.

Reference Example 1 Synthesis of 1.3-bis(4-maleimidophenoxy)benzene: In a three-necked flask, 196 gf (2.0 moles) of maleic anhydride was dissolved in 300+off acetone. 1.3-bis(4-aminophenoxy)benzene 292g fl,
0 mol) was dissolved in 300 ml of acetone and added dropwise to the above droplet over 2 hours. After the dropwise addition was completed, the mixture was further stirred at room temperature for 2 hours. The resulting maleamic acid precipitate was filtered and dried to obtain 450 g of maleamic acid.

Maleamic acid 450g, triethylamine 50m
β, 2.0 g of nickel acetate tetrahydrate and 500 g of acetone
mff was mixed and stirred, and 170 g of acetic anhydride was added dropwise at room temperature. After the dropwise addition, the mixture was gradually heated and reacted under reflux for 5 hours. After cooling to room temperature, the reaction solution was poured into methanol, and the resulting precipitate was filtered off. The mixture was further washed with methanol and then dried to obtain 380 g (084 mol) of 1.3-bis(4-maleimidophenoxy)benzene. Melting temperature is 152℃
Met.

Reference Example 2 Synthesis of 2.2-bis(4-(4-maleimidophenoxy)phenyl 1-propane): In the same manner as in Reference Example 1 using 2.2-bis[4-(4-aminophenoxy)phenyl 1-propane, 2.2-bis(4-(4-maleimidophenoxy)phenyl 1-propane) was obtained.The melting temperature was 88°C.

Reference Example 3 Synthesis of 1.3-bis(p-maleimidocumyl)benzene: Using 1.3-bis(p-aminocumyl)benzene, 1.3-bis(p-maleimidocumyl)benzene was synthesized in the same manner as in Reference Example 1. mil) benzene was obtained. The melting temperature was 138°C.

Reference example 4 9.9-bis(3-allyl-4-hydroxyphenyl)
Synthesis of fluorene: 9.9-bis(4-hydroxyphenyl)fluorene 3
50 g of NaOH, 182.5 g of NaOH and 1 g of n-propanol are heated to reflux. After all the components had been dissolved, 200 mj2 of allyl chloride was added dropwise over 2 hours. The reaction mixture was further refluxed for 6 hours. After cooling to room temperature, the precipitated Na
C12 was filtered off, and n-propertool was further distilled off. The obtained crude diallyl ether was mixed with chloroform, washed with water, dried over sodium sulfate, and then chloroform was distilled off. The obtained diallyl ether was subjected to Claisen rearrangement at 200°C under a nitrogen stream to form 9.9-bis(3-allyl-4
-Hydroxyphenyl)fluorene (385 g) was obtained.

Reference Example 5 Synthesis of 1,5-dihydroxy-2,6-diallylnaphthalene: 1,5-dihydroxy-2,6-diallylnaphthalene was obtained in the same manner as in Reference Example 4 using 1,5-dihydroxynaphthalene.

Example 1 1 obtained in Reference Example 1 as a bismaleimide component,
Using 3-bis(4-maleimidophenoxy)benzene (hereinafter abbreviated as BMI-1), 9,9-bis(3-allyl-4 obtained from Reference Example 4) was used as alkenylphenol.
-hydroxyphenyl)fluorene (hereinafter abbreviated as AHPF) was used.

These compounds were mixed and stirred at 140° C. for 30 minutes in the proportions (equivalent ratio) shown in the table to obtain a prepolymer. This prepolymer is sandwiched between glass plates to a predetermined thickness, and 18
A cured resin plate was obtained by curing at 0°C for 4 hours and further post-curing at 243°C for 4 hours. Further, this prepolymer was stretched into a thin film on release paper at 80°C, and carbon fiber (Pyrofilm MR50 manufactured by Mitsubishi Rayon Co., Ltd.) was coated on a drum.
K) was wound and impregnated. Then, by cutting it open, a unidirectional prepreg (thread bone 140 g/m", resin content 33% by weight) was obtained. This prepreg was
[+45°10°/-45°/90°1
4. The composite materials were laminated in a quasi-isotropic manner, cured at 180°C for 4 hours, and further cured at 243°C for 4 hours to obtain a composite material.

Various tests were conducted on uncured resins, cured resins, and composite materials. The results are shown in the table.

Examples 2 and 3 2 obtained in Reference Example 2 as the bismaleimide component,
A cured resin plate and a composite material were obtained in the same manner as in Example 1 except that 2-r4-(4-maleimidophenoxy)phenyl]propane (abbreviated as BMI-2 under 1,,I) was used. The test results are shown in the table.

Example 4 1 obtained in Reference Example 3 as a bismaleimide component,
3-bis(p-maleimidocumyl)benzene (hereinafter B
A cured resin plate and a composite material were obtained in the same manner as in Example 1, except that a cured resin plate (abbreviated as M I 3) was used. The test results are shown in the table.

Example 5 BMI-2 was used as the bismaleimide component, and 1,5-dihydroxy-2,6-diallylnaphthalene (hereinafter referred to as DHA) obtained in Reference Example 5 was used as the alkenylphenol.
A cured resin plate and a composite material were obtained in the same manner as in Example 1 except that a cured resin plate and a composite material were used. The test results are shown in the table.

Example 6 BMI-2 as the bismaleimide component, AHP F as the alkenylphenol, and diallylbisphenol A synthesized by the method described in Japanese Patent Publication No. 5539242.
A cured resin plate and a composite material were obtained in the same manner as in Example 1 except that an equimolar mixture of FU (abbreviated as ABPA) was used. The test results are shown in the table.

Example 7 BMI-2 and 4.4′ of clay plate as bismaleimide components
- Equimolar mixture of bismaleimidiphenylmethane (hereinafter abbreviated as BMPM), A as alkenylphenol
A cured resin plate and a composite material were obtained in the same manner as in Example 1 using HPF. The test results are shown in the table.

Comparative Example 1 A cured resin plate and a composite material were obtained in the same manner as in Example 1 except that BMPM was used as the bismaleimide component and ABPA was used as the alkenylphenol. The test results are shown in the table.

[Effects of the invention] The cured products and composite materials of the resin composition of the present invention have excellent heat resistance, impact resistance, and balance, and are also excellent in water resistance and mechanical properties. have. The resin composition of the present invention is useful as a casting, impregnating and laminating molding material, particularly as a heat-resistant material for aerospace applications.

Claims (1)

[Claims] 1. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, when Y is -O-, Z is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Numerical formulas, There are chemical formulas, tables, etc.▼,▲mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, where R_1 is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -SO_2- or ▲Mathematical formulas, chemical formulas, When Y is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, Z means ▲There are mathematical formulas, chemical formulas, tables, etc.▼) or bismaleimide of formula I A bismaleimide mixture containing as one component and an alkenylphenol represented by the following formula: Characteristic resin composition for composite materials.