CN102675594A - High-elasticity-modulus cyanate ester/bismaleimide resin compound - Google Patents

Abstract

The present invention relates to a kind of cyanate ester/bismaleimide resin combination of high elastic modulus, the raw material of described resin is by cyanate ester monomer, bismaleimide monomer, bisoxazoline compound , 3-functionality or 4-functionality glycidylamine epoxy compound composition, the 3-functionality or 4-functionality glycidylamine epoxy compound is introduced into cyanate/bismaleimide/bisoxazole In the phylloline resin, a thermosetting resin material with a high glass transition temperature and a high elastic modulus is obtained through a co-curing reaction. It can not only promote the curing reaction of the resin, but also improve the elastic modulus and glass transition temperature of the cured resin.

Description

Cyanate ester/bismaleimide resin composition with high elastic modulus

technical field

The invention relates to a cyanate ester/bismaleimide resin composition with high elastic modulus.

Background technique

Thermosetting resins are an important class of polymer materials, usually used as a matrix for the preparation of composite materials.

A performance disadvantage of composite materials is their low elastic modulus, which is generally about 10 times lower than that of metal materials. This is because in composite materials, the modulus of the matrix (thermosetting resin) is much smaller than that of the reinforcing materials (such as fibers, particles, etc.), which often cause large deformation due to insufficient stiffness when the composite material is stressed. When the composite material is subject to greater stress (such as compression, shearing), the matrix yields before the reinforcement material, resulting in microcracks, which cannot effectively support the fibers and transmit stress. If the stress continues to increase, the matrix will be destroyed before the reinforced material, resulting in a sharp decline in the mechanical properties of the composite until it fails. Therefore, to maintain or improve the performance of composite materials, the key is to increase the modulus of the matrix resin.

Ways and methods to increase the modulus of thermosetting resins are: (1) increase the rigidity of the molecular chain, mainly by introducing aromatic rings and heterocyclic groups into the chemical structure of the monomer resin; (2) increase the polarity of the molecular chain, mainly It is to introduce polar groups into the chemical structure of the monomer resin, such as amide groups, ester groups, etc.; (3) moderately increase the degree of crosslinking and weaken the relative slippage of molecular chains; (4) add nanoparticles. Among them, the first three ways are to increase the modulus of thermosetting resin by chemical means, and the latter way belongs to physical means.

In the previous research, the inventor proposed a "cyanate/bismaleimide co-curing resin" (cyanate/bismaleimide co-curing resin and its preparation method ZL200910052207.2), The resin is a high-performance thermosetting resin with high temperature resistance, high strength, low dielectric constant and low dielectric loss, and the flexural modulus of the cured resin is 4.5~4.7. For some harsh use environments, there is still the problem that the modulus is not large enough, which needs further improvement.

The inventors have found that multifunctional glycidylamine epoxy can be used as a crosslinking agent to increase the crosslinking density of the cured resin by reacting with components such as cyanate esters, thereby increasing its modulus of elasticity and glass transition Macroscopic physical properties such as temperature.

Contents of the invention

The object of the present invention is to propose a kind of high elastic modulus cyanate/bismaleimide resin composition.

The cyanate ester/bismaleimide/bisoxazoline co-curing resin proposed by the inventor in the ZL200910052207.2 patent is a class of resin with high glass transition temperature, high strength, low dielectric constant and low dielectric Loss of high performance thermosetting matrix resin. The inventors found that on the basis of the composition of the matrix resin, the macroscopic physical properties of the cured resin, especially the elastic modulus and heat resistance, can be effectively improved by introducing trifunctional and tetrafunctional epoxy components.

The epoxy compound itself can undergo a curing reaction with cyanate ester or bismaleimide to form a thermosetting resin material with a co-cured structure. The contriver finds, in cyanate ester/bismaleimide/bisoxazoline resin system, when adding glycidyl amine epoxy compound, the tertiary amine chemical structure in glycidyl amine epoxy is opposite to cyanate ester The curing reaction will play a certain catalytic role, which is beneficial to improve the conversion rate of the monomer in the curing process and promote the completion of the curing reaction. At the same time, the polyfunctional glycidylamine epoxy is a high-efficiency crosslinking agent, which can increase the crosslinking density of the cured resin, improve the elastic modulus, glass transition temperature and other properties of the resin.

The cyanate ester/bismaleimide resin composition of the high elastic modulus that the present invention proposes, the raw material of described resin is by cyanate ester monomer, bismaleimide monomer, bisoxazoline compound, The glycidyl amine epoxy compound of 3 functionalities or 4 functionalities is composed, and the weight percent of its component is:

Cyanate monomer 5-45%

Bismaleimide monomer 5-30%

Bisoxazoline Compounds 1-15%

The rest are trifunctional or quadrifunctional glycidylamine epoxy compounds, the total weight of which satisfies 100%.

In the present invention, the cyanate monomer includes: bisphenol A type cyanate (4,4'-dicyanatophenyl-propane, BADCy), bisphenol L type cyanate (4,4 '-dicyanatophenyl-ethane, BEDCy), bisphenol M-type cyanate (4,4'-[1,3-phenylbis(1-methyl-ethylene)]bisphenyl cyanate) or phenolic cyanate (PT), etc., or any of its prepolymers.

In the present invention, the bismaleimide monomer includes: 4,4'-diphenylmethane bismaleimide (BDM), N, N-m-phenylene bismaleimide, 4, Any of 4'-diphenyl ether bismaleimide, 4,4'-diphenylsulfone bismaleimide, and the like.

In the present invention, the bisoxazoline compounds include: 2,2'-(1,4-phenylene)-bisoxazoline, 2,2'-(1,3-phenylene)-diox Azoline, 2,2'-(1,4-phenylene)-4-methyl-bisoxazoline, 2,2'-(1,3-phenylene)-4-methyl-dioxa Azoline, 2,2'-(1,4-phenylene)-4,4'-dimethyl-bisoxazoline, 2,2'-(1,3-phenylene)-4,4 '-Dimethyl-bisoxazoline, 2,2'-ethylenebis(2-oxazoline), 2,2'-octylenebis(2-oxazoline), 2,2'-ethane Any of bis(4-methyl-2-oxazoline) or oxazoline-terminated polyether.

In the present invention, the 3-functionality or 4-functionality glycidylamine epoxy compound includes: triglycidyl p-aminophenol (such as AFG-90, etc.), 4,4'-diaminodiphenylmethane epoxy compound Resin (such as AG-80, SKE-3, etc.), tetraglycidyl-4,4'-diaminodiphenyl ether (4,4'-TGDDE, brand name SKE-1) or tetraglycidyl-3, More than one of 4'-diaminodiphenyl ether (3,4'-TGDDE, brand name SKE-2), etc.

The thermosetting resin composition with high elastic modulus proposed by the present invention can be prepared by melt mixing: after weighing each component according to the proportion, fully melt and mix at 80-120°C to obtain an uncured resin. The uncured resin is dissolved in a common solvent such as DMF, butanone or acetone, and formulated into a certain concentration of glue, which can be impregnated with reinforcing materials, such as glass cloth, carbon fiber cloth, etc., for forming composite materials.

The advantage of the present invention is that the glycidylamine epoxy compound with trifunctionality or quadrifunctionality is introduced into the cyanate/bismaleimide/bisoxazoline modified resin, which not only can accelerate the curing of the resin The reaction can also improve properties such as elastic modulus and glass transition temperature of the cured resin.

Detailed ways

The present invention is further illustrated below by way of examples.

Example 1

Weigh 40.0g of bisphenol A cyanate (BADCy) and 6.5g of tetraglycidyl-4,4'-diaminodiphenyl ether (4,4'-TGDDE) in a beaker, heat to melt, then add 15.0 g 4,4'-diphenylmethanebismaleimide, 8.5g 2,2'-(1,3-phenylene)-bisoxazoline, melt and stir at 80~120℃ Uniform, uncured modified resin is obtained.

The uncured resin is degassed in a vacuum oven at 80°C for 15 minutes, then poured into a mold coated with a silicone ester release agent, and cured in an electronic oven at 150°C/1h + 180°C/1h + 200°C/2h The curing process is carried out, and the post-curing condition is 240°C/3h. The obtained cured resin was a dark brown-red solid with a glass transition temperature of 294° C. (DMA method), a flexural strength of 142.3 MPa, and a flexural modulus of 5.7 GPa.

Example 2

Weigh 25g bisphenol A cyanate (BADCy), 15 g 4,4'-diphenylmethane bismaleimide, 10 g 2,2'-(1,3-phenylene)-diox Azoline, 20g tetraglycidyl-4,4'-diaminodiphenyl ether (4,4'-TGDDE), and the rest are the same as in Example 1.

The glass transition temperature of the cured resin is 288.4°C (DMA method), the flexural strength is 134.3MPa, and the flexural modulus is 5.6GPa.

Example 3

Weigh 35g phenolic cyanate (PT), 25 g 4,4'-diphenylmethane bismaleimide, 6 g 2,2'-(1,3-phenylene)-bisoxazoline , 35g4,4'-diaminodiphenylmethane epoxy resin, all the other are the same as embodiment 1.

The glass transition temperature of the cured resin is 335.5°C (DMA method), the flexural strength is 100.6MPa, and the flexural modulus is 6.2GPa.

Example 4

Weigh 35g 4,4'-dicyanatophenyl-ethane (BEDCy), 25g N,N-m-phenylene bismaleimide, 9 g 2,2'-(1,3- Phenyl)-bisoxazoline, 21g triglycidyl p-aminophenol, all the other are the same with embodiment 1.

The glass transition temperature of the cured resin is 263.4°C (DMA method), the flexural strength is 146.4MPa, and the flexural modulus is 4.9GPa.

Comparative example:

Weigh 90g bisphenol A type cyanate (BADCy) in a beaker, heat to melt, then add 10 g 4,4'-diphenylmethane bismaleimide, 9g 2,2'-(1,3 -phenylene)-bisoxazoline, the preparation process of resin is the same as embodiment 1. The obtained cured resin had a glass transition temperature of 286° C. (DMA method), a flexural strength of 111.8 MPa, and a flexural modulus of 4.5 GPa.

By the comparison of embodiment and comparative example, cyanate ester/bismaleimide/bisoxazoline/glycidylamine resin of the present invention cures and obtains the cured resin of high glass transition temperature, and its flexural modulus of elasticity is less The cured resin with glycidylamine epoxy crosslinking agent has been greatly improved.

Claims (5)

1. a cyanate ester/bismaleimide resin combination of high elastic modulus, it is characterized in that the raw material of described resin is made of cyanate ester monomer, bismaleimide monomer, bisoxazole The glycidyl amine epoxy compound of phylloline compound, 3 functionalities or 4 functionalities is composed, and the weight percent of its component is: Cyanate monomer 5-45% Bismaleimide monomer 5-30% Bisoxazoline compound 1-15% The rest are trifunctional or quadrifunctional glycidylamine epoxy compounds, the total weight of which satisfies 100%. 2. the cyanate/bismaleimide resin composition of high modulus of elasticity according to claim 1, is characterized in that described cyanate monomer comprises: bisphenol A type cyanate, bisphenol Any one of L-type cyanate, bisphenol M-type cyanate or novolak-type cyanate, or any one of their prepolymers. 3. the cyanate ester/bismaleimide resin composition of high modulus of elasticity according to claim 1, is characterized in that described bismaleimide monomer comprises: 4,4'-diphenyl Methane bismaleimide, N,N-m-phenylene bismaleimide, 4,4'-diphenyl ether bismaleimide or 4,4'-diphenylsulfone bismaleimide any of the amines. 4. the cyanate ester/bismaleimide resin composition of high modulus of elasticity according to claim 1, is characterized in that described bisoxazoline compound comprises: 2,2'-(1,4- phenylene)-bisoxazoline, 2,2'-(1,3-phenylene)-bisoxazoline, 2,2'-(1,4-phenylene)-4-methyl- Bisoxazoline, 2,2'-(1,3-phenylene)-4-methyl-bisoxazoline, 2,2'-(1,4-phenylene)-4,4'- Dimethyl-bisoxazoline, 2,2'-(1,3-phenylene)-4,4'-dimethyl-bisoxazoline, 2,2'-ethylene bis(2-oxa oxazoline), 2,2'-octylenebis(2-oxazoline), 2,2'-ethylenebis(4-methyl-2-oxazoline) or oxazoline-terminated polyether A sort of. 5. the cyanate ester/bismaleimide resin composition of high modulus of elasticity according to claim 1, is characterized in that described 3 functionalities or 4 functionalities glycidylamine epoxy compounds comprise: Triglycidyl p-aminophenol, 4,4'-diaminodiphenylmethane epoxy resin, tetraglycidyl-4,4'-diaminodiphenyl ether or tetraglycidyl-3,4'-diamino More than one of diphenyl ethers.