CN106146842A - A kind of 13BDAPB type siliceous epoxy acid imide matrix resin and preparation method thereof - Google Patents

Abstract

The invention relates to a 13BDAPB type silicon-containing epoxyimide matrix resin and a preparation method thereof. The matrix resin is 1,3-bis(2,4-diaminophenoxy)benzene, epoxy resin, 3-aminopropyl Trialkoxysilane, imide oligomer and curing agent. The preparation method comprises the following steps: (1) preparing an imide oligomer; (2) putting 1,3-bis(2,4-diaminophenoxy)benzene and epoxy resin into a reaction kettle, stirring and mixing After the reaction, add the imide oligomer to continue the stirring reaction, then add 3-aminopropyltrialkoxysilane to stir the reaction, then add the curing agent and stir to mix evenly. The present invention can be widely used in the bonding between metals such as steel, copper, aluminum, ceramics, glass, and resin-based composite materials, as well as the preparation of glass fiber, aramid fiber, and carbon fiber-reinforced composite materials, and has good industrial prospects.

Description

A kind of 13BDAPB type silicon-containing epoxy imide matrix resin and preparation method thereof

technical field

The invention belongs to the field of polymer matrix resin and its preparation, in particular to a 13BDAPB silicon-containing epoxyimide matrix resin and its preparation method.

Background technique

As we all know, epoxy resin has many excellent properties: (1) Good bonding performance: high bonding strength, wide bonding surface, it is compatible with many metals (such as iron, steel, copper, aluminum, metal alloys, etc.) The bonding strength of metal materials (such as glass, ceramics, resin-based composite materials, wood, plastics, etc.) is very high, and some even exceed the strength of the bonded material itself, so it can be used in many stressed structural parts. One of the main components of the mixture; (2) good processing performance: the flexibility of epoxy resin formula, the diversity of processing technology and product performance are the most prominent among polymer materials; (3) good stability performance: ring The curing of epoxy resin mainly depends on the ring-opening addition polymerization of epoxy groups, so no low molecular weight is produced during the curing process, and its curing shrinkage rate is one of the lowest varieties of thermosetting resins, generally 1%-2%, if Selecting appropriate fillers can reduce the shrinkage rate to about 0.2%; the main chain of the cured epoxy resin is ether bond, benzene ring, and three-dimensional cross-linked structure, so it has excellent acid and alkali resistance.

Therefore, epoxy resin is widely used in various fields of national economy: whether it is high-tech field or general technology field, whether it is national defense industry or civilian industry, and even people's daily life can see its traces.

At present, epoxy resin systems also have some problems, such as low heat resistance, far inferior to aromatic heterocyclic polymer systems (such as polyimide, polybenzimidazole, polybenzoxazole, polyphenylquinone, etc.) oxaline, polybenzothiazole, etc.).

Polyimide was developed in the 1960s, and the most commonly used one is made from pyromellitic dianhydride and aromatic diamine. Polyimide molecules contain multiple aromatic heterocyclic structural units, so polyimide resin is a class of polymer materials with extremely excellent heat resistance. Conventional polyimide structure, its thermal decomposition temperature is generally above 500 ℃, and it also has toughness. Therefore, it is also often used as a heat-resistant toughening modifier for thermosetting resins, such as epoxy resins and bismaleimide resins.

Chinese invention patent CN103146330A discloses a 2,2-bis[4-(2,4-diaminophenoxy)phenyl]hexafluoropropane type high temperature resistant epoxy adhesive and its preparation method, the mass ratio is 1: 1-2 consists of component A and component B, wherein component A is the reaction of 2,2-bis[4-(2,4-diaminophenoxy)phenyl]hexafluoropropane and epoxy resin Copolymer formed; component B is composed of 2,2-bis[4-(2,4-diaminophenoxy)phenyl]hexafluoropropane and aromatic dibasic acid anhydride in a strong polar aprotic organic solvent It reacts with toluene to form a homogeneous transparent solution with a solid content of 15%-30%. The preparation method includes: stirring and mixing components A and B at a mass ratio of 1:1-2 at room temperature.

Chinese invention patent CN103131369A discloses a 4,4'-bis(2,4-diaminophenoxy)diphenylsulfone type high temperature resistant epoxy adhesive and its preparation method, which consists of A with a mass ratio of 1:1-2 Component and B component, wherein A component is a copolymer formed by the reaction of 4,4'-bis(2,4-diaminophenoxy)diphenyl sulfone and epoxy resin; B component is composed of 4,4'-bis(2,4-diaminophenoxy)diphenyl sulfone reacts with aromatic dibasic acid anhydride in strong polar aprotic organic solvent and toluene, with a solid content of 15%-30% Homogeneous clear solution. The preparation method includes: stirring and mixing components A and B at a mass ratio of 1:1-2 at room temperature.

Chinese invention patent CN103146331A discloses a 4,4'-bis(2,4-diaminophenoxy)biphenyl type high temperature resistant epoxy adhesive and its preparation method, which consists of group A with a mass ratio of 1:1-2 Component and B component, wherein A component is a copolymer formed by the reaction of 4,4'-bis(2,4-diaminophenoxy)biphenyl and epoxy resin; B component is composed of 4, 4'-bis(2,4-diaminophenoxy)biphenyl reacts with aromatic dibasic acid anhydride in strong polar aprotic organic solvent and toluene to form a homogeneous transparent solid content of 15%-30% solution. The preparation method includes: stirring and mixing components A and B at a mass ratio of 1:1-2 at room temperature.

Yan Rui, Yu Xinhai et al [Research on Preparation and Properties of New Epoxy Adhesives, Insulating Materials, 2012, 45(2): 12-14,18] disclosed a new type of epoxy resin adhesive and its preparation method, and its performance has been systematically studied.

Yu Xinhai et al [Preparation and Performance Research of Silicone Epoxy System Adhesive, Insulating Materials, 2012,45(2):1-3,11] disclosed a silicone resin modified epoxy resin adhesive system, and its performance was studied, and an adhesive with superior comprehensive performance was obtained.

Yu Xinhai and others applied for the Chinese invention patent CN102220102A, disclosing a high temperature resistant adhesive and its preparation method.

Chinese invention patent CN102260480A discloses a high temperature resistant modified epoxy resin adhesive and a preparation method thereof.

Chinese invention patent CN102181251A discloses an epoxy resin adhesive modified by unsaturated polyimide and a preparation method thereof.

Chinese invention patent CN102031082A discloses a benzimidazole diamine curable epoxy adhesive and a preparation method thereof.

Chinese invention patent CN101649174A discloses a high temperature resistant one-component solvent-free epoxy adhesive and its preparation method.

Chinese invention patent CN101544879A discloses a preparation method of a high-strength solvent-free epoxy adhesive.

Wu Min et al. [Development of a new high-strength one-component epoxy resin adhesive, Adhesive, 2009, 30(9): 54-57] disclosed a one-component epoxy adhesive with excellent comprehensive performance, especially with Very high tensile shear strength.

Chen Hongjiang et al [Study on curing kinetics of new epoxy resin adhesive system, Bonding, 2009, 30(8): 43-45] disclosed an epoxy resin adhesive system and studied its curing kinetics .

[Research on curing kinetics of polyimide-epoxy resin adhesive, Chemistry and Adhesion, 2011, 33(2): 17-20] disclosed a polyimide-epoxy resin adhesive, and The solidification kinetics study was carried out.

Chinese invention patent CN101148656A discloses a method for preparing a high-temperature-resistant solvent-free epoxy adhesive. Solvent-free epoxy adhesive. However, its high temperature resistance performance still has great limitations, which cannot meet the practical application in many high temperature environments.

Chinese invention patent CN101397486A discloses a preparation method of a two-component solvent-free epoxy resin adhesive. Epoxy resin and carboxyl-terminated nitrile rubber; component B is 1,3-bis(2,4-diaminophenoxy)benzene aromatic polyamine curing agent. The addition amount of alicyclic epoxy resin and carboxyl-terminated nitrile rubber is respectively 20-35% and 12% (mass percentage) of the novolac epoxy resin. The addition amount of the 1,3-bis(2,4-diaminophenoxy)benzene aromatic polyamine curing agent is 15-20% (mass percentage) of the novolac epoxy resin, and the obtained adhesive system has good manufacturability. But its heat resistance is not ideal enough.

Chinese invention patent CN1927908A discloses a preparation method of polyimide powder containing phenolic hydroxyl groups. Due to the existence of phenolic hydroxyl groups, the polyimide powder can react with epoxy groups to form covalent bonds, thereby improving the thermoplastic polyimide. The compatibility of imide resin and epoxy resin can further make the epoxy resin system achieve good toughening effect.

Yu Xinhai et al [Development of High Temperature Resistant One-Component Epoxy Adhesive [J]. Bonding, 2008, 29(12): 16-19] disclosed a preparation method of high temperature resistant one-component epoxy adhesive, the main It is characterized in that: maleic anhydride (MA) is used as the end-capping agent, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (BAHPFP), 2,2-bis[4-(4- The phenolic hydroxyl Polyetherimide resin (HPEI); the synthesized HPEI is used as a high-temperature toughening agent, and N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane ( TGDDM), hydrogenated bisphenol A epoxy resin (HBPAE), latent curing agent, etc., to prepare a high temperature resistant one-component epoxy adhesive with excellent comprehensive performance.

Contents of the invention

The technical problem to be solved by the present invention is to provide a 13BDAPB silicon-containing epoxyimide matrix resin and its preparation method. The preparation process of the present invention is simple, environmentally friendly, and has excellent comprehensive performance, and can be widely used in steel, copper, aluminum, etc. The bonding between metals and substrates such as ceramics, glass, and resin-based composite materials, as well as the preparation of glass fiber, aramid fiber, and carbon fiber-reinforced composite materials, have good industrialization prospects.

A kind of 13BDAPB type silicon-containing epoxy imide matrix resin of the present invention is made of 1,3-bis(2,4-di Aminophenoxy) benzene, epoxy resin, 3-aminopropyltrialkoxysilane, imide oligomer and curing agent; wherein, the imide oligomer is 2:1 by molar ratio: 2 of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride and maleic Anhydride reaction derived.

The 3-aminopropyltrialkoxysilane is selected from one or a mixture of 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane.

Described epoxy resin is selected from E-51 epoxy resin, E-44 epoxy resin, ES216 epoxy resin, ECC202 epoxy resin, CE793 epoxy resin, glycidyl amine type epoxy resin, glycidyl ether type epoxy resin One or more of resins, alicyclic epoxy resins, novolac epoxy resins, and glycidyl ester epoxy resins.

The glycidylamine type epoxy resin is selected from N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane epoxy resin, N,N,N',N'- Tetraglycidyl-3,3'-dimethyl-4,4'-diaminodiphenylmethane epoxy resin, N,N,N',N'-tetraglycidyl-3,3'-diethyl Base-4,4'-diaminodiphenylmethane epoxy resin, N,N,N',N'-tetraglycidyl-3,3'-dichloro-4,4'-diaminodiphenylmethane ring Oxygen resin, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenyl ether epoxy resin, N,N,N',N'-tetraglycidyl-4,4 '-Diaminodiphenylsulfone epoxy resin, N,N,N',N'-tetraglycidyl-3,4'-diaminodiphenyl ether epoxy resin, N,N,N',N'- Tetraglycidyl-3,3'-diaminodiphenylsulfone epoxy resin, N,N,N',N'-tetraglycidyl-4,4'-diaminobiphenyl epoxy resin, N,N ,N',N'-tetraglycidyl p-phenylenediamine epoxy resin, N,N,N',N'-tetraglycidyl m-phenylenediamine epoxy resin, N,N,N',N' -Tetraglycidyl-1,4-bis(4-aminophenoxy)benzene epoxy resin, N,N,N',N'-tetraglycidyl-1,4-bis(3-aminophenoxy base) benzene epoxy resin, N,N,N',N'-tetraglycidyl-1,3-bis(4-aminophenoxy) benzene epoxy resin, N,N,N',N'- Tetraglycidyl-1,3-bis(3-aminophenoxy)benzene epoxy resin, N,N,N',N'-tetraglycidyl-1,4-bis(2-trifluoromethyl -4-aminophenoxy)benzene epoxy resin, N,N,N',N'-tetraglycidyl-1,3-bis(2-trifluoromethyl-4-aminophenoxy)benzene ring Oxygen resin, N,N,N',N',O-pentaglycidyl-4,4'-diamino-4"-hydroxytriphenylmethane epoxy resin, N,N,N',N'-tetra Glycidyl-2,2-bis[4-(4-aminophenoxy)phenyl]propane epoxy resin, N,N,N',N'-tetraglycidyl-2,2-bis[4 -(4-aminophenoxy)phenyl]hexafluoropropane epoxy resin, N,N,N',N'-tetraglycidyl-2,2-bis[4-(3-aminophenoxy) Phenyl]propane epoxy resin, N,N,N',N'-tetraglycidyl-2,2-bis[4-(2-trifluoromethyl-4-aminophenoxy)phenyl]propane Epoxy resin, N,N,N',N'-tetraglycidyl-2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane epoxy resin, N,N,N ',N'-tetraglycidyl-2,2-bis[4-(2-trifluoromethyl-4-aminophenoxy)phenyl]hexafluoropropane epoxy resin, N,N,N', N'-tetraglycidyl-4,4'-bis(4-aminophenoxy)diphenyl ether epoxy resin, N,N,N',N '-Tetraglycidyl-4,4'-bis(2-trifluoromethyl-4-aminophenoxy)diphenyl ether epoxy resin, N,N,N',N'-tetraglycidyl- 4,4'-bis(4-aminophenoxy)diphenylsulfone epoxy resin, N,N,N',N'-tetraglycidyl-4,4'-bis(2-trifluoromethyl- 4-aminophenoxy)diphenylsulfone epoxy resin, N,N,N',N'-tetraglycidyl-4,4'-bis(4-aminophenoxy)diphenylsulfone epoxy resin , N,N,N',N'-tetraglycidyl-4,4'-bis(2-trifluoromethyl-4-aminophenoxy) diphenyl sulfide epoxy resin, N,N,N ',N'-tetraglycidyl-4,4'-bis(4-aminophenoxy)diphenylmethane epoxy resin, N,N,N',N'-tetraglycidyl-4,4' -Bis(2-trifluoromethyl-4-aminophenoxy)diphenylmethane epoxy resin, N,N,N',N'-tetraglycidyl-4,4'-bis(4-aminobenzene oxy)benzophenone epoxy resin, N,N,N',N'-tetraglycidyl-4,4'-bis(2-trifluoromethyl-4-aminophenoxy)benzidine Ketone epoxy resin, N,N,N',N'-tetraglycidyl-4,4'-bis(4-aminophenoxy)biphenyl epoxy resin, N,N,N',N'- Tetraglycidyl-4,4'-bis(2-trifluoromethyl-4-aminophenoxy)biphenyl epoxy resin, N,N,N',N',O,O'-hexaglycidyl Base-2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane epoxy resin, N,N,O-triglycidyl p-aminophenol epoxy resin, N,N,O-triglycidyl One or more of glyceryl m-aminophenol epoxy resins.

The glycidyl ether type epoxy resin is selected from 1,3-diglycidyl resorcinol, 1,4-diglycidyl hydroquinone, 4,4'-diglycidyl bisphenol S, 2,2-bis(4-glycidylphenyl)hexafluoropropane, 2,2-bis(4-glycidylcyclohexyl)propane, bisphenol F diglycidyl ether, hydrogenated bisphenol A diglycidyl ether , one or more of bisphenol A diglycidyl ether, fatty alcohol polyglycidyl ether.

The alicyclic epoxy resin is selected from 3,4-epoxy cyclohexanoic acid-3',4'-epoxy cyclohexyl methyl ester, 3,4-epoxy group-6-methyl cyclohexanoic acid -One or more of 3',4'-epoxy-6'-methylcyclohexylmethyl ester and dipentene dioxide.

Described novolac type epoxy resin is selected from phenol-formaldehyde novolac resin type epoxy resin, orthocresol-formaldehyde novolac resin type epoxy resin, resorcinol-formaldehyde novolac resin type epoxy resin, m-cresol-formaldehyde novolac resin Resin type epoxy resin, catechol-formaldehyde novolac resin type epoxy resin, bisphenol A-formaldehyde novolac resin type epoxy resin, bisphenol S-formaldehyde novolac resin type epoxy resin, bisphenol AF-formaldehyde novolac resin One or several types of epoxy resins, biphenol-formaldehyde novolac resins, o-phenylphenol-formaldehyde novolac epoxy resins, naphthol-formaldehyde novolac epoxy resins.

Described glycidyl ester type epoxy resin is selected from diglycidyl terephthalate epoxy resin, diglycidyl isophthalate epoxy resin, diglycidyl phthalate epoxy resin, endomethine Diglycidyl Tetrahydrophthalate Epoxy Resin, 4,5-Epoxycyclohexane-1,2-Diglycidyl Dicarboxylate Epoxy Resin, Diglycidyl Phthalate Epoxy Resin One or more of the resins.

The curing agent is selected from hexahydrophthalic anhydride, K-12 curing agent, tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, dodecenyl succinic anhydride, methyl hexahydrophthalic anhydride, tung oil anhydride, dicyclopentadiene and butadiene 80 acid anhydride formed by the reaction of olefinic anhydride, acid anhydride formed by the reaction of terpene and maleic anhydride, liquid anhydride formed by the reaction of turpentine oil and maleic anhydride, N,N-dimethylaniline, N,N-dimethyl-p-methylaniline, N,N-dimethylbenzylamine, 2-ethyl-4-methylimidazole, imidazole, 2,4,6-tris(dimethylaminomethyl)phenol , 1,8-diaza-bicyclo[5.4.0]undecene-7 or one or more.

A kind of preparation method of 13BDAPB type silicon-containing epoxyimide matrix resin of the present invention, comprises the steps:

(1) 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, o-cresol, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl] Put propane dianhydride and maleic anhydride into the reaction kettle, feed nitrogen, stir, heat up to 80°C, add isoquinoline dropwise, heat to 100°C-110°C, stir for 5-12 hours, then cool to 60°C ℃, pour the reactant into a precipitating kettle filled with a precipitating agent, stir at a high speed, precipitate solid matter, filter, and vacuum-dry at 80 ℃ for 10 hours to obtain an imide oligomer;

(2) Put 1,3-bis(2,4-diaminophenoxy)benzene (13BDAPB) and epoxy resin into the reaction kettle, stir and mix at 80°C-100°C for 0.5-1 hour, then add The imide oligomer continues to stir and react for 1-2 hours, then add 3-aminopropyltrialkoxysilane to stir and react for 5-15 minutes, cool to room temperature, then add curing agent, stir and mix evenly.

The mass ratio of isoquinoline to 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane described in step (1) is 1-4:20.

The precipitation agent described in step (1) is selected from methanol, ethanol, propanol, isopropanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol One or more of alcohol diethyl ether, acetone, butanone; wherein, the mass ratio of precipitating agent to 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane is 20-40:1 .

The mass ratio of o-cresol to 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane described in step (1) is 10-20:1.

Beneficial effect

(1) The viscosity of the present invention has good controllability, can be adjusted in a wider range, has simple preparation process, is environmentally friendly, and has excellent comprehensive performance, and can be widely used in metals such as steel, copper, aluminum, and ceramics, glass, and resin-based composites. The bonding between base materials such as materials, and the preparation of glass fiber, aramid fiber, and carbon fiber reinforced composite materials have good industrialization prospects; (2) the present invention can complete the preparation process in general-purpose equipment, which is conducive to realizing industrialization Production.

detailed description

Below in conjunction with specific embodiment, further illustrate the present invention. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the teachings of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.

Example 1

73.2 grams (0.2 moles) of 2,2-bis(3-amino-4-hydroxyphenyl) hexafluoropropane (BAHPFP, 366 g/mol), 735.0 grams of o-cresol, 52.0 grams (0.1 moles) of 2,2- Bis[4-(3,4-dicarboxyphenoxy)phenyl]propanedianhydride (BPADA, 520g/mol) and 19.6 grams (0.2mol) of maleic anhydride (MA, 98g/mol) were placed in the reactor , feed nitrogen, stir, heat up to 80°C, add 3.8 grams of isoquinoline dropwise, heat to 100°C, stir and react for 5 hours, then cool to 60°C, pour the reactant into a precipitate containing 1500 grams of methanol Stir in the kettle at high speed to precipitate solid matter, filter, and vacuum-dry at 80°C for 10 hours to obtain 308.3 g of imide oligomer (theoretical yield: 314.0 g), with a yield of 98.2%, which is designated as BBMO-1.

Example 2

73.2 g (0.2 mol) of 2,2-bis(3-amino-4-hydroxyphenyl) hexafluoropropane (BAHPFP, 366 g/mol), 1460 g of o-cresol, 52.0 g (0.1 mol) of 2,2- Bis[4-(3,4-dicarboxyphenoxy)phenyl]propanedianhydride (BPADA, 520g/mol) and 19.6 grams (0.2mol) of maleic anhydride (MA, 98g/mol) were placed in the reactor , feed nitrogen, stir, heat up to 80°C, add 14.0 grams of isoquinoline dropwise, heat to 110°C, stir and react for 12 hours, cool to 60°C, pour the reactant into 2000 grams of ethanol and 920 grams of In the settling tank of ethylene glycol monomethyl ether, high-speed stirring, the solid matter was precipitated, filtered, and vacuum-dried at 80°C for 10 hours to obtain 313.4 grams of imide oligomers (theoretical yield: 314.0 grams), with a yield of 99.8%. Denoted as BBMO-2.

Example 3

1.0 g of 1,3-bis(2,4-diaminophenoxy)benzene (13BDAPB), 30.0 g of 3,4-epoxycyclohexanoic acid-3',4'-epoxycyclohexylmethyl ester , 20.0 grams of CE793 epoxy resin and 50.0 grams of N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane epoxy resin were put into the reaction kettle, stirred and mixed at 100°C After 0.5 hours, add 2.0 grams of BBMO-1 imide oligomer and continue to stir for 1 hour, then add 3.0 grams of 3-aminopropyltrimethoxysilane and stir for 5 minutes, cool to room temperature, then add 5.0 grams of 1, 8-diaza-bicyclo[5.4.0]undecene-7 and 45.0 grams of methyltetrahydrophthalic anhydride were stirred and mixed uniformly to obtain 156.0 grams of 13BDAPB type silicon-containing epoxyimide matrix resin, denoted as M-1 .

Example 4

Mix 3.0 g of 1,3-bis(2,4-diaminophenoxy)benzene (13BDAPB), 20.0 g of diglycidyl isophthalate epoxy resin, 20.0 g of ES216 epoxy resin and 60.0 g of N,N ,N',N'-tetraglycidyl-4,4'-diaminodiphenyl ether epoxy resin was put into the reaction kettle, stirred and mixed for 1 hour at 80°C, then added 1.0 g BBMO-1 and 4.0 g The imide oligomer of BBMO-2 continued to stir for 2 hours, then added 3.0 g of 3-aminopropyltrimethoxysilane and 5.0 g of 3-aminopropyltriethoxysilane, stirred for 5 minutes, and cooled to room temperature , then add 25.0 grams of 2-ethyl-4-methylimidazole and 5.0 grams of 2,4,6-tris(dimethylaminomethyl)phenol, stir and mix evenly to obtain 146.0 grams of 13BDAPB type silicon-containing epoxy imide Base resin, denoted as M-2.

Example 5

5.0 grams of 1,3-bis(2,4-diaminophenoxy)benzene (13BDAPB), 10.0 grams of o-cresol-formaldehyde novolac type epoxy resin, 30.0 grams of hydrogenated bisphenol A diglycidyl ether and 60.0 Put gram of N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane epoxy resin into the reaction kettle, stir and mix for 1 hour at 80°C, then add 3.0 grams of BBMO- The imide oligomer of 2 continued to stir and react for 2 hours, then added 2.0 grams of 3-aminopropyltrimethoxysilane and stirred for 15 minutes, cooled to room temperature, and then added 30.0 grams of 2-ethyl-4-methylimidazole With 15.0 grams of tung oil anhydride, stir and mix uniformly to obtain 155.0 grams of 13BDAPB type silicon-containing epoxyimide matrix resin, denoted as M-3.

Example 6

Take an appropriate amount of the 13BDAPB silicon-containing epoxyimide matrix resin of Examples 3 to 5, namely M-1 to M-3, and apply them evenly on standard stainless steel test pieces, stack them, and clamp them , Put it into a blast oven for curing: start from room temperature to 80°C, keep it for 2 hours, then continue to heat up to 120°C, keep it for 1 hour, continue to heat up to 150°C, keep it for 0.5 hours, and then naturally cool to room temperature. Using an electronic tensile machine, it was tested for tensile shear strength at room temperature (25°C) and high temperature (180°C), and the results are shown in Table 1.

Take an appropriate amount of the 13BDAPB silicon-containing epoxyimide matrix resins of Examples 3 to 5, namely M-1 to M-3, and apply them evenly on the flat glass test pieces, stack them, and clamp them , Put it into a blast oven for curing: start from room temperature to 80°C, keep it for 2 hours, then continue to heat up to 120°C, keep it for 1 hour, continue to heat up to 150°C, keep it for 0.5 hours, and then naturally cool to room temperature. Using an electronic tensile machine, it was tested for tensile shear strength at room temperature (25°C) and high temperature (180°C), and the results are shown in Table 1.

Take an appropriate amount of the 13BDAPB silicon-containing epoxyimide matrix resins of Examples 3 to 5, namely M-1 to M-3, and soak them evenly on the glass cloth, and laminate them with standard stainless steel test pieces Clamp and put in a blast oven for curing: start from room temperature to 80°C, keep it for 2 hours, then continue to heat up to 120°C, keep it for 1 hour, continue to heat up to 150°C, keep it for 0.5 hours, then cool naturally to room temperature. Using an electronic tensile machine, it was tested for tensile shear strength at room temperature (25°C) and high temperature (180°C), and the results are shown in Table 1.

Table 1 Tensile shear strength, unit: MPa

Claims (10)

1. a 13BDAPB type silicon-containing epoxy imide matrix resin, characterized in that: by mass ratio of 1,3-bis(2, 4-diaminophenoxy)benzene 13BDAPB, epoxy resin, 3-aminopropyl trialkoxy silane, imide oligomer and curing agent; wherein, the imide oligomer is composed of a molar ratio of 2:1:2 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane di Anhydride and maleic anhydride reaction. 2. A kind of 13BDAPB type silicon-containing epoxy imide matrix resin according to claim 1, characterized in that: the 3-aminopropyltrialkoxysilane is selected from 3-aminopropyltrimethoxysilane , 3-aminopropyltriethoxysilane or a mixture of two. 3. A kind of 13BDAPB type silicon-containing epoxy imide matrix resin according to claim 1, characterized in that: the epoxy resin is selected from E-51 epoxy resin, E-44 epoxy resin, ES216 ring Oxygen resin, ECC202 epoxy resin, CE793 epoxy resin, glycidyl amine epoxy resin, glycidyl ether epoxy resin, alicyclic epoxy resin, phenolic epoxy resin, glycidyl ester epoxy resin one or more of. 4. A 13BDAPB type silicon-containing epoxyimide matrix resin according to claim 3, characterized in that: said glycidylamine epoxy resin is selected from N, N, N', N'-tetraglycid Glyceryl-4,4'-diaminodiphenylmethane epoxy resin, N,N,N',N'-tetraglycidyl-3,3'-dimethyl-4,4'-diaminodiphenyl Methane epoxy resin, N,N,N',N'-tetraglycidyl-3,3'-diethyl-4,4'-diaminodiphenylmethane epoxy resin, N,N,N', N'-tetraglycidyl-3,3'-dichloro-4,4'-diaminodiphenylmethane epoxy resin, N,N,N',N'-tetraglycidyl-4,4'- Diaminodiphenyl ether epoxy resin, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylsulfone epoxy resin, N,N,N',N'-tetraglycidyl Glyceryl-3,4'-diaminodiphenyl ether epoxy resin, N,N,N',N'-tetraglycidyl-3,3'-diaminodiphenylsulfone epoxy resin, N,N, N',N'-tetraglycidyl-4,4'-diaminobiphenyl epoxy resin, N,N,N',N'-tetraglycidyl p-phenylenediamine epoxy resin, N,N, N',N'-tetraglycidyl m-phenylenediamine epoxy resin, N,N,N',N'-tetraglycidyl-1,4-bis(4-aminophenoxy)phenylene epoxy resin , N,N,N',N'-tetraglycidyl-1,4-bis(3-aminophenoxy)benzene epoxy resin, N,N,N',N'-tetraglycidyl-1 ,3-bis(4-aminophenoxy)benzene epoxy resin, N,N,N',N'-tetraglycidyl-1,3-bis(3-aminophenoxy)benzene epoxy resin, N,N,N',N'-tetraglycidyl-1,4-bis(2-trifluoromethyl-4-aminophenoxy)benzene epoxy resin, N,N,N',N'- Tetraglycidyl-1,3-bis(2-trifluoromethyl-4-aminophenoxy)benzene epoxy resin, N,N,N',N',O-pentaglycidyl-4,4 '-Diamino-4"-hydroxytrityl epoxy resin, N,N,N',N'-tetraglycidyl-2,2-bis[4-(4-aminophenoxy)phenyl] Propane epoxy resin, N,N,N',N'-tetraglycidyl-2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane epoxy resin, N,N, N',N'-tetraglycidyl-2,2-bis[4-(3-aminophenoxy)phenyl]propane epoxy resin, N,N,N',N'-tetraglycidyl- 2,2-bis[4-(2-trifluoromethyl-4-aminophenoxy)phenyl]propane epoxy resin, N,N,N',N'-tetraglycidyl-2,2- Bis[4-(3-aminophenoxy)phenyl]hexafluoropropane epoxy resin, N,N,N',N'-tetraglycidyl-2,2-bis[4-(2-trifluoro Methyl-4-aminophenoxy)phenyl]hexafluoropropane epoxy resin, N,N,N',N '-tetraglycidyl-4,4'-bis(4-aminophenoxy)diphenyl ether epoxy resin, N,N,N',N'-tetraglycidyl-4,4'-bis( 2-trifluoromethyl-4-aminophenoxy)diphenyl ether epoxy resin, N,N,N',N'-tetraglycidyl-4,4'-bis(4-aminophenoxy) Diphenylsulfone epoxy resin, N,N,N',N'-tetraglycidyl-4,4'-bis(2-trifluoromethyl-4-aminophenoxy)diphenylsulfone epoxy resin, N,N,N',N'-tetraglycidyl-4,4'-bis(4-aminophenoxy)diphenyl sulfide epoxy resin, N,N,N',N'-tetraglycidyl Base-4,4'-bis(2-trifluoromethyl-4-aminophenoxy)diphenyl sulfide epoxy resin, N,N,N',N'-tetraglycidyl-4,4' -Bis(4-aminophenoxy)diphenylmethane epoxy resin, N,N,N',N'-tetraglycidyl-4,4'-bis(2-trifluoromethyl-4-aminobenzene oxy)diphenylmethane epoxy resin, N,N,N',N'-tetraglycidyl-4,4'-bis(4-aminophenoxy)benzophenone epoxy resin, N,N ,N',N'-tetraglycidyl-4,4'-bis(2-trifluoromethyl-4-aminophenoxy)benzophenone epoxy resin, N,N,N',N' -Tetraglycidyl-4,4'-bis(4-aminophenoxy)biphenyl epoxy resin, N,N,N',N'-tetraglycidyl-4,4'-bis(2- Trifluoromethyl-4-aminophenoxy)biphenyl epoxy resin, N,N,N',N',O,O'-hexaglycidyl-2,2-bis(3-amino-4- One or more of hydroxyphenyl) hexafluoropropane epoxy resin, N,N,O-triglycidyl p-aminophenol epoxy resin, N,N,O-triglycidyl m-aminophenol epoxy resin kind. 5. a kind of 13BDAPB type silicon-containing epoxy imide matrix resin according to claim 3, is characterized in that: described glycidyl ether type epoxy resin is selected from 1,3-diglycidyl resorcinol , 1,4-diglycidyl hydroquinone, 4,4'-diglycidyl bisphenol S, 2,2-bis(4-glycidylphenyl) hexafluoropropane, 2,2-bis One or more of (4-glycidylcyclohexyl)propane, bisphenol F diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol A diglycidyl ether, fatty alcohol polyglycidyl ether. 6. A 13BDAPB type silicon-containing epoxyimide matrix resin according to claim 3, characterized in that: the alicyclic epoxy resin is selected from 3,4-epoxy cyclohexanoic acid-3' ,4'-epoxycyclohexylmethyl ester, 3,4-epoxy-6-methylcyclohexanoic acid-3',4'-epoxy-6'-methylcyclohexylmethyl ester, dioxide One or more of dipentene. 7. a kind of 13BDAPB type silicon-containing epoxy imide base resin according to claim 3, is characterized in that: described novolak type epoxy resin is selected from phenol-formaldehyde novolac type epoxy resin, o-cresol- Formaldehyde novolac resin type epoxy resin, resorcinol-formaldehyde novolac resin type epoxy resin, m-cresol-formaldehyde novolac resin type epoxy resin, catechol-formaldehyde novolac resin type epoxy resin, bisphenol A- Formaldehyde novolac resin type epoxy resin, bisphenol S-formaldehyde novolac resin type epoxy resin, bisphenol AF-formaldehyde novolac resin type epoxy resin, biphenol-formaldehyde novolac resin type epoxy resin, o-phenylphenol- One or more of formaldehyde novolac resin type epoxy resin and naphthol-formaldehyde novolac resin type epoxy resin. 8. a kind of 13BDAPB type silicon-containing epoxy imide matrix resin according to claim 3, is characterized in that: described glycidyl ester type epoxy resin is selected from diglycidyl terephthalate epoxy resin, Diglycidyl Isophthalate Epoxy Resin, Diglycidyl Phthalate Epoxy Resin, Endomethylene Tetrahydrophthalate Diglycidyl Epoxy Resin, 4,5-Epoxycyclohexane One or more of diglycidyl alkane-1,2-dicarboxylate epoxy resin and diglycidyl phthalate epoxy resin. 9. a kind of 13BDAPB type silicon-containing epoxy imide matrix resin according to claim 1, is characterized in that: described curing agent is selected from hexahydrophthalic anhydride, K-12 curing agent, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride Hydrophthalic anhydride, dodecenyl succinic anhydride, methyl hexahydrophthalic anhydride, tung oil anhydride, 80 acid anhydride formed by the reaction of dicyclopentadiene and maleic anhydride, formed by the reaction of terpene and maleic anhydride acid anhydride, liquid anhydride formed by the reaction of turpentine oil and maleic anhydride, N,N-dimethylaniline, N,N-dimethyl-p-methylaniline, N,N-dimethylbenzylamine, 2 One of -ethyl-4-methylimidazole, imidazole, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diaza-bicyclo[5.4.0]undecene-7 species or several. 10. a kind of preparation method of 13BDAPB type silicon-containing epoxyimide matrix resin as claimed in claim 1, comprises the steps: (1) 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, o-cresol, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl] Put propane dianhydride and maleic anhydride into the reaction kettle, feed nitrogen, stir, heat up to 80°C, add isoquinoline dropwise, heat to 100°C-110°C, stir for 5-12 hours, then cool to 60°C °C, pour the reactant into a settling kettle filled with a precipitating agent, stir, and precipitate a solid, filter, and dry in vacuum to obtain an imide oligomer; (2) Put 1,3-bis(2,4-diaminophenoxy)benzene 13BDAPB and epoxy resin into the reaction kettle, stir and mix at 80°C-100°C for 0.5-1 hour, then add acyl The amine oligomer continues to stir and react for 1-2 hours, then add 3-aminopropyltrialkoxysilane to stir and react for 5-15 minutes, cool to room temperature, then add curing agent, stir and mix evenly.