阅读说明：本技术 一种有机无机杂化的本征型液晶环氧树脂及其制备方法与应用 (Organic-inorganic hybrid intrinsic liquid crystal epoxy resin and preparation method and application thereof ) 是由 吴昆� 刘迎春 吕茂萍 史珺 吕满庚 于 2020-12-15 设计创作，主要内容包括：本发明提供一种有机无机杂化的本征型液晶环氧树脂及其制备方法与应用。本发明的有机无机杂化的本征型液晶环氧树脂的制备方法首先引入席夫碱结构基元,而后通过双酚-环氧氯丙烷法制备得到。本发明的有机无机杂化的本征型液晶环氧树脂导热系数达0.7～1.6W m～(-1)K～(-1),相比于普通的树脂基体,其具有较高的导热系数。本发明有机无机杂化的本征型液晶环氧经热固化之后可在电子封装材料和导热材料等领域应用。(The invention provides an organic-inorganic hybrid intrinsic liquid crystal epoxy resin and a preparation method and application thereof. The preparation method of the organic-inorganic hybrid intrinsic liquid crystal epoxy resin firstly introduces Schiff base structural elements and then prepares the organic-inorganic hybrid intrinsic liquid crystal epoxy resin by a bisphenol-epichlorohydrin method. The heat conductivity coefficient of the organic-inorganic hybrid intrinsic liquid crystal epoxy resin reaches 0.7-1.6W m ‑1 K ‑1 Compared with the common resin matrix, the heat conduction coefficient of the composite material is higher. The organic-inorganic hybrid intrinsic liquid crystal epoxy can be applied to the fields of electronic packaging materials, heat conducting materials and the like after being thermally cured.)

1. An organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer is characterized in that: the chemical structure is as follows:

wherein R1, R2 and R3 can be selected from one of the following structural units in an identical or different way: h, wherein H represents a bonding site.

2. The method for preparing the organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer according to claim 1, wherein the method comprises the following steps: the method comprises the following steps:

(1) synthesis of bisphenol structural intermediate: adding o-phenylenediamine, a catalyst, vanillin or o-vanillin or m-hydroxybenzaldehyde or p-hydroxybenzaldehyde or o-hydroxybenzaldehyde and a solvent into a reactor, and refluxing and stirring for 8-24 hours at 40-80 ℃; washing the solid obtained by the reaction, and then drying at 50-80 ℃ for 20-30 h to obtain a bisphenol structure intermediate;

(2) synthesizing a liquid crystal type epoxy resin monomer: adding the bisphenol structure intermediate synthesized in the step (1), a solvent, a catalyst and epichlorohydrin into a reactor, reacting for 2-4 h at 70-90 ℃ in a nitrogen atmosphere, cooling to 10-25 ℃, and adding 20-40% (w/w) NaOH aqueous solution to continue reacting for 30-90 min; washing the solid obtained by the reaction, and then drying at 50-80 ℃ for 20-30 h to obtain a liquid crystal epoxy resin monomer;

(3) adding the liquid crystal epoxy resin monomer obtained in the step (2) and a solvent into a reactor, then adding silver nitrate, stirring for 1-3 h, adding a reducing agent, reacting for 3-8 h at 25-60 ℃, adding water for recrystallization, and then drying for 20-30 h at 50-80 ℃ to obtain the organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer.

3. The method for preparing the organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer according to claim 2, wherein:

the catalyst in the step (1) is one of stannous chloride, glacial acetic acid and concentrated sulfuric acid; when the catalyst is a solid catalyst, the dosage of the catalyst is 2.5-5 wt% of the total reactants, and when the catalyst is a liquid catalyst, the dosage of the catalyst is calculated by adding 50-150 mu L of the catalyst per 100mL of a reaction system;

the use amount ratio of the o-phenylenediamine to vanillin or o-vanillin or m-hydroxybenzaldehyde or p-hydroxybenzaldehyde and o-hydroxybenzaldehyde in the step (1) is 1: 2-2.5;

the solvent in the step (1) is acetonitrile, trichloromethane, absolute ethyl alcohol or N, N-dimethylformamide, and the dosage of the solvent is calculated according to the concentration of vanillin, o-vanillin, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde or o-hydroxybenzaldehyde in a system of 0.2-0.5 mol/L;

the washing solvent in the step (1) is absolute ethyl alcohol or deionized water.

4. The method for preparing the organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer according to claim 2, wherein:

the epichlorohydrin is used in the step (2) according to the ratio of the bisphenol structural intermediate: epichlorohydrin is in a molar ratio of 1:4 to 10;

the catalyst in the step (2) is tetrabutylammonium bromide or tetrabutylammonium chloride, and the using amount of the catalyst is 2.5-5 wt% of the total reactants;

the solvent in the step (2) is acetonitrile, N-dimethylformamide or dimethyl sulfoxide, and the using amount is controlled to be 0.2-0.4 mol/L according to the concentration of the bisphenol structure intermediate in a system;

the amount of the NaOH aqueous solution in the step (2) is calculated according to the bisphenol structure intermediate: and NaOH is in a molar ratio of 1: 1-2.

5. The method for preparing the organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer according to claim 2, wherein:

the using amount of the silver nitrate in the step (3) is 0.1-1: 1 in terms of the molar ratio of the silver nitrate to the liquid crystal type epoxy resin monomer, and the silver nitrate is prepared into a silver nitrate aqueous solution with the concentration of 1-2 mol/L by using deionized water before use;

the reducing agent in the step (3) is N, N-dimethylformyl, ascorbic acid or ethanol, and the using amount of the reducing agent is the same as that of the silver nitrate substance;

the solvent in the step (3) is acetonitrile, acetone or dimethyl sulfoxide, and the dosage is controlled to be 0.1-0.5 mol/L according to the concentration of the liquid crystal type epoxy resin monomer in the system.

6. Use of the organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer according to claim 1 for preparing an organic-inorganic hybrid intrinsic liquid crystal epoxy resin.

7. Use according to claim 6, characterized in that:

the preparation method comprises the following specific steps: taking the organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer of claim 1, adding a curing agent, an accelerator and a solvent, removing the solvent in vacuum, degassing bubbles, and then carrying out thermal curing to obtain the organic-inorganic hybrid intrinsic liquid crystal epoxy resin.

8. Use according to claim 7, characterized in that:

the curing agent is 4,4 '-diaminodiphenylmethane or 4, 4' -diaminodicyclohexylmethane, and the use amount of the curing agent is 1: 3-4 in terms of the molar ratio of the curing agent to the organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer;

the accelerant is 2-ethyl-4-methylimidazole or 2-methylimidazole, and the using amount of the accelerant is 0.5-1 wt% of the total amount of the organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer and the curing agent;

the solvent is acetone or dichloromethane, and the dosage is controlled to be 2-2.5 mol/L according to the concentration of the organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer in the system;

the heat curing conditions are as follows: 4, 4' -diaminodiphenylmethane is adopted for curing at 120 ℃ for 3h, at 150 ℃ for 3h and at 170 ℃ for 2 h; or 4, 4' -diaminodiphenylmethane is adopted for curing at 110 ℃ for 4h, at 155 ℃ for 3h and at 160 ℃ for post-curing for 2 h.

9. An organic-inorganic hybrid intrinsic liquid crystal epoxy resin is characterized in that: prepared by the process as claimed in claim 7 or 8.

10. The organic-inorganic hybrid intrinsic liquid crystal epoxy resin as claimed in claim 9, which is used in the fields of electronic packaging materials and thermal conduction.

Technical Field

The invention belongs to the technical field of high-thermal-conductivity high polymer materials, and particularly relates to organic-inorganic hybrid intrinsic liquid crystal epoxy resin and a preparation method and application thereof.

Background

With rapid progress of science and technology, electronic equipment and devices are continuously developed towards light, thin, short and direction, so that the power is greatly increased when the electronic equipment and devices work, the dissipated power density per unit area is rapidly increased, and researches indicate that the dissipated power density of the current high-power electronic devices can reach 1000W cm when the electronic equipment and devices work^-2Thereby causing a serious heat dissipation problem. In addition, whether the heat dissipation problem can be effectively solved or not is a key factor for continuation of moore's law, and is a bottleneck for development of electronic equipment. The ideal heat conducting material has the properties of high heat conductivity, high insulation, excellent mechanical property, easy processing and forming and the like. Compared with traditional heat conducting materials such as inorganic materials, metal materials and the like, the polymer heat conducting materials and the excellent characteristics of good electrical insulation, corrosion resistance, excellent mechanical strength, low cost, easy processing and the like are widely applied to the field of heat conducting. Currently, the research on polymer heat conduction materials mainly involves the following two aspects: the high heat-conducting polymer composite material is prepared by adding high heat-conducting particles and an intrinsic polymer with high heat-conducting property is synthesized. The high heat-conducting composite material is obviously improved only when the content of the heat-conducting particles reaches a threshold value, but other excellent characteristics of the polymer, such as mechanics, electric insulation and the like, are often sacrificed, and the high heat-conducting composite material is also poor in type, particle size and dispersibility of the heat-conducting particlesAnd thus reduce its thermal conductivity. Therefore, the intrinsic type heat conductive polymer has received a great deal of attention, and it is far more effective to increase the thermal conductivity of the system by improving the thermal conductivity of the polymer continuous phase matrix than to increase the amount of the heat conductive particles. For example, chinese publications CN110229318A and CN109180979A disclose that mesogens are introduced into the main chain and the side chain of a polymer, respectively, and the thermal conductivity of the polymer matrix is improved by adjusting the microscopic order of the polymer and forming a regularly arranged mesomorphic structure.

However, in the prior art, the thermal conductivity of the material is not improved by constructing mesomorphic elements and inorganic nano particles to prepare organic-inorganic hybrid intrinsic polymers.

Disclosure of Invention

In order to overcome the defect of low thermal conductivity of the existing polymer-based material, the invention mainly aims to provide an organic-inorganic hybrid intrinsic liquid crystal epoxy resin.

The invention also aims to provide a preparation method of the organic-inorganic hybrid intrinsic liquid crystal epoxy resin.

The invention further aims to provide application of the organic-inorganic hybrid intrinsic liquid crystal epoxy resin.

Compared with the common epoxy resin structure, the organic-inorganic hybrid intrinsic liquid crystal epoxy resin structure has the advantages that the ordering and high-degree conjugate structure of the central liquid crystal element and the network structure formed by the Schiff base structure complexing silver provide effective channels for phonon transmission, the silver dispersibility is greatly improved compared with a silver/epoxy composite material, and the prepared organic-inorganic hybrid intrinsic liquid crystal epoxy resin has lower thermal resistance.

The purpose of the invention is realized by the following technical scheme:

an organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer has the following chemical structure:

wherein R1, R2 and R3 can be selected from one of the following structural units in an identical or different way: wherein denotes the attachment position.

The preparation method of the organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer comprises the following steps:

(1) synthesis of bisphenol structural intermediate: adding o-phenylenediamine, a catalyst, vanillin or o-vanillin or m-hydroxybenzaldehyde or p-hydroxybenzaldehyde or o-hydroxybenzaldehyde and a solvent into a reactor, and refluxing and stirring for 8-24 hours at 40-80 ℃; washing the solid obtained by the reaction, and then drying at 50-80 ℃ for 20-30 h to obtain a bisphenol structure intermediate;

(2) synthesizing a liquid crystal type epoxy resin monomer: adding the bisphenol structure intermediate synthesized in the step (1), a solvent, a catalyst and epichlorohydrin into a reactor, reacting for 2-4 h at 70-90 ℃ in a nitrogen atmosphere, cooling to 10-25 ℃, and adding 20-40% (w/w) NaOH aqueous solution to continue reacting for 30-90 min; washing the solid obtained by the reaction, and then drying at 50-80 ℃ for 20-30 h to obtain a liquid crystal epoxy resin monomer;

(3) adding the liquid crystal epoxy resin monomer obtained in the step (2) and a solvent into a reactor, then adding silver nitrate, stirring for 1-3 h, adding a reducing agent, reacting for 3-8 h at 25-60 ℃, adding water for recrystallization, and then drying for 20-30 h at 50-80 ℃ to obtain the organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer.

The organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer is applied to the preparation of the organic-inorganic hybrid intrinsic liquid crystal epoxy resin.

The preparation method comprises the following specific steps: and adding a curing agent, an accelerator and a solvent into the organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer, removing the solvent in vacuum, removing bubbles, and then thermally curing to obtain the organic-inorganic hybrid intrinsic liquid crystal epoxy resin.

The catalyst in the step (1) is preferably one of stannous chloride, glacial acetic acid and concentrated sulfuric acid; when the catalyst is a solid catalyst, the dosage of the catalyst is 2.5-5 wt% of the total reactants, and when the catalyst is a liquid catalyst, the dosage of the catalyst is calculated by adding 50-150 mu L of the catalyst per 100mL of a reaction system.

The use amount ratio of the o-phenylenediamine to vanillin or o-vanillin or m-hydroxybenzaldehyde or p-hydroxybenzaldehyde and o-hydroxybenzaldehyde in the step (1) is 1: 2-2.5;

the solvent in the step (1) is acetonitrile, trichloromethane, absolute ethyl alcohol or N, N-dimethylformamide, and the dosage of the solvent is calculated according to the concentration of vanillin, o-vanillin, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde or o-hydroxybenzaldehyde in a system of 0.2-0.5 mol/L.

The washing solvent in the step (1) is absolute ethyl alcohol or deionized water.

The epichlorohydrin is used in the step (2) according to the ratio of the bisphenol structural intermediate: the epichlorohydrin is in a molar ratio of 1:4 to 10.

The catalyst in the step (2) is tetrabutylammonium bromide or tetrabutylammonium chloride, and the dosage of the catalyst is 2.5-5 wt% of the total reactants.

The solvent in the step (2) is acetonitrile, N-dimethylformamide or dimethyl sulfoxide, and the using amount is controlled to be 0.2-0.4 mol/L according to the concentration of the bisphenol structure intermediate in a system.

The amount of the NaOH aqueous solution in the step (2) is preferably determined according to the bisphenol structure intermediate: and NaOH is in a molar ratio of 1: 1-2.

And (4) the using amount of the silver nitrate in the step (3) is 0.1-1: 1 of the molar ratio of the silver nitrate to the liquid crystal type epoxy resin monomer, and the silver nitrate is prepared into an aqueous solution of the silver nitrate with the concentration of 1-2 mol/L by using deionized water before use.

The reducing agent in the step (3) is N, N-dimethylformyl, ascorbic acid or ethanol, and the using amount of the reducing agent is the same as that of the silver nitrate substance.

The solvent in the step (3) is acetonitrile, acetone or dimethyl sulfoxide, and the dosage is controlled to be 0.1-0.5 mol/L according to the concentration of the liquid crystal type epoxy resin monomer in the system.

In application, the curing agent is 4,4 '-diaminodiphenylmethane or 4, 4' -diaminodicyclohexylmethane, and the use amount of the curing agent is calculated according to the molar ratio of the curing agent to the organic-inorganic hybrid liquid crystal epoxy resin monomer of 1: 3-4.

In application, the accelerant is 2-ethyl-4-methylimidazole or 2-methylimidazole, and the using amount of the accelerant is 0.5-1 wt% of the total amount of the organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer and the curing agent.

In the application, the solvent is acetone or dichloromethane, and the dosage is controlled to be 2-2.5 mol/L according to the concentration of the organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer in the system.

In application, the heat curing conditions are as follows: 4, 4' -diaminodiphenylmethane is adopted for curing at 120 ℃ for 3h, at 150 ℃ for 3h and at 170 ℃ for 2 h; or 4, 4' -diaminodiphenylmethane is adopted for curing at 110 ℃ for 4h, at 155 ℃ for 3h and at 160 ℃ for post-curing for 2 h.

An organic-inorganic hybrid intrinsic liquid crystal epoxy resin is prepared by the method.

The organic-inorganic hybrid intrinsic liquid crystal epoxy resin is applied to the fields of electronic packaging materials and heat conduction.

Compared with the prior art, the invention has the following advantages and beneficial effects:

(1) the invention adopts the Schiff base structure to synthesize the liquid crystal epoxy resin with high planarization, and silver nano particles are synthesized in situ between mesomorphic elements based on the complexing effect of Schiff base and metal ions, so that the organic-inorganic hybrid high-thermal-conductivity liquid crystal epoxy resin is synthesized.

(2) The order of the resin can be effectively increased by introducing the Schiff base structure and in-situ synthesis of the silver nanoparticles, and in addition, the introduction of the silver can greatly reduce the interface thermal resistance of the resin matrix and provide an effective heat conduction network for phonon transmission.

(3) The organic-inorganic hybrid high-thermal conductivity liquid crystal epoxy resin phase prepared by the inventionCompared with pure epoxy resin (0.19-0.21W m)^-1K^-1) The heat-conducting property of the material is greatly enhanced (0.7-1.6W m)^-1K^-1) The thermal conductivity coefficient of the polymer is 3.7-8.4 times that of the traditional polymer matrix.

(4) Compared with pure epoxy resin (60-80 MPa), the organic-inorganic hybrid high-thermal-conductivity liquid crystal epoxy resin prepared by the invention has the advantage that the tensile strength of the material is greatly enhanced and can reach 100 MPa.

Detailed Description

The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1

(1) 0.01mol of o-phenylenediamine, 0.02mol of vanillin, 50 mu L of glacial acetic acid and 100ml of acetonitrile are added into a three-neck flask provided with a condenser tube, and the mixture is heated to 40 ℃ in a magnetic stirring oil bath kettle and refluxed for 8 hours. Then washing with water, and drying in a vacuum oven at 50 ℃ for 24h to obtain the bisphenol structure compound.

(2) In a three-necked flask under nitrogen atmosphere, 0.01mol of bisphenol structural intermediate, 2.5 wt% of total reactants of tetrabutylammonium bromide, 0.04mol of epichlorohydrin and 50ml of acetonitrile were reacted at 70 ℃ for 2 hours, cooled to 10 ℃, and 2g of aqueous NaOH (20% (w/w)) solution was added to continue the reaction for 30 minutes. And washing the obtained solid with deionized water for 3 times, and then placing the solid in a vacuum oven to dry for 24 hours at 50 ℃ to obtain the liquid crystal epoxy resin monomer.

(3) Adding 0.01mol of the prepared liquid crystal epoxy resin and 100mL of acetonitrile into a single-neck flask in nitrogen atmosphere, then adding 10mL of 1mol/L silver nitrate aqueous solution, stirring for 1h, adding 0.01mol of N, N-dimethyl formyl, reacting for 3h at 25 ℃, adding a large amount of water for recrystallization, and then drying for 24h at 50 ℃ in a vacuum oven, thus obtaining the organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer.

(4) 0.01mol of organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer, 0.0025mol of 4, 4' -diaminodiphenylmethane, and 2-ethyl-4-methylimidazole with the mass fraction of 0.5 percent of the total amount of the organic-inorganic hybrid liquid crystal epoxy resin monomer and the curing agent are added with 5ml of dichloromethane to be uniformly mixed, bubbles are pumped in vacuum for 10min, the mixture is cured for 3h at 120 ℃, cured for 3h at 150 ℃ and cured for 2h at 170 ℃, and the high-thermal-conductivity epoxy resin material is obtained.

The organic-inorganic hybrid intrinsic liquid crystal epoxy resin prepared by the scheme has the thermal conductivity coefficient reaching 0.7W m^-1K^-1。

Example 2

(1) 0.01mol of o-phenylenediamine, 0.021mol of o-vanillin, 50 mu L of concentrated sulfuric acid and 42ml of N, N-dimethylformamide are added into a three-neck flask provided with a condensing tube, and the mixture is heated to 50 ℃ in a magnetic stirring oil bath kettle and refluxed for 12 hours. Then washing with water, and drying in a vacuum oven at 55 ℃ for 24h to obtain the bisphenol structure compound.

(2) In a three-necked flask under nitrogen atmosphere, 0.01mol of bisphenol structural intermediate, 3 wt% tetrabutylammonium chloride, 0.05mol of epichlorohydrin and 50ml of N, N-dimethylformamide were added and reacted at 80 ℃ for 2.5 hours, cooled to 15 ℃, and 3g of NaOH (20% (w/w)) aqueous solution was added and the reaction was continued for 40 minutes. And washing the obtained solid with deionized water for 3 times, and then placing the solid in a vacuum oven to dry for 24 hours at 55 ℃ to obtain the liquid crystal epoxy resin monomer.

(3) Adding 0.01mol of the prepared liquid crystal epoxy resin and 80mL of acetone into a single-neck flask in nitrogen atmosphere, then adding 30mL of a 2mol/L silver nitrate solution, stirring for 1.5h, adding 0.006mol of ascorbic acid, reacting for 5h at 40 ℃, adding a large amount of water for recrystallization, and then drying for 24h at 60 ℃ in a vacuum oven to obtain the organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer.

(4) 0.01mol of organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer, 0.0025mol of 4, 4' -diaminodiphenylmethane, and 2-ethyl-4-methylimidazole with the mass fraction of 1% of the total amount of the organic-inorganic hybrid liquid crystal epoxy resin monomer and the curing agent are added with 5ml of acetone to be uniformly mixed, air bubbles are pumped in vacuum for 10min, the mixture is cured for 3h at 120 ℃, cured for 3h at 150 ℃ and cured for 2h at 170 ℃, and the high-thermal-conductivity epoxy resin material is obtained.

The organic-inorganic hybrid intrinsic liquid crystal epoxy resin prepared by the scheme has the thermal conductivity coefficient reaching 0.85W m^-1K^-1Tensile strength of 85MPa。

Example 3

(1) 0.01mol of o-phenylenediamine, 0.025mol of m-hydroxybenzaldehyde, 2.5 wt% of stannous chloride and 80ml of trichloromethane are added into a three-neck flask provided with a condenser tube, and the mixture is heated to 80 ℃ in a magnetic stirring oil bath kettle and refluxed for 24 hours. Then washing with absolute ethyl alcohol, and drying in a vacuum oven at 80 ℃ for 24h to obtain the bisphenol structure compound.

(2) 0.01mol of bisphenol structure intermediate, 5 wt% tetrabutylammonium chloride, 0.08mol of epichlorohydrin and 50ml of N, N-dimethylformamide were added to a three-necked flask under nitrogen atmosphere to react at 80 ℃ for 4 hours, cooled to 18 ℃, and 2g of NaOH (40% (w/w)) aqueous solution was added to continue the reaction for 80 minutes. And washing the obtained solid with deionized water for 3 times, and then placing the solid in a vacuum oven to dry for 24 hours at the temperature of 80 ℃ to obtain the liquid crystal epoxy resin monomer.

(3) Adding 0.01mol of the prepared liquid crystal epoxy resin and 20mL of dimethyl sulfoxide into a single-neck flask in nitrogen atmosphere, then adding 10mL of 1mol/L silver nitrate solution, stirring for 3h, adding 0.01mol of ascorbic acid, reacting for 6h at 60 ℃, adding a large amount of water for recrystallization, and then drying for 24h at 80 ℃ in a vacuum oven, thus obtaining the organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer.

(4) Taking 0.01mol of organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer, 0.0025mol of 4, 4' -diaminodicyclohexylmethane and 2-methylimidazole with the mass fraction of 1% of the total amount of the organic-inorganic hybrid liquid crystal epoxy resin monomer and the curing agent, adding 5ml of acetone, uniformly mixing, vacuumizing for 10min, curing at 110 ℃ for 4h, curing at 155 ℃ for 3h, and curing at 160 ℃ for 2h to obtain the high-thermal-conductivity epoxy resin material.

The organic-inorganic hybrid intrinsic liquid crystal epoxy resin prepared by the scheme has the thermal conductivity coefficient reaching 1.2W m^-1K^-1The tensile strength was 70 MPa.

Example 4

(1) 0.01mol of o-phenylenediamine, 0.023mol of o-hydroxybenzaldehyde, 4 wt% of stannous chloride and 70ml of trichloromethane are added into a three-neck flask provided with a condenser tube, and the temperature is raised to 65 ℃ in a magnetic stirring oil bath kettle and the reflux is carried out for 24 hours. Then washing with absolute ethyl alcohol, and drying in a vacuum oven at 65 ℃ for 24h to obtain the bisphenol structure compound.

(2) In a three-necked flask under nitrogen atmosphere, 0.01mol of bisphenol structural intermediate, 3.5 wt% tetrabutylammonium chloride, 0.1mol of epichlorohydrin and 40ml of N, N-dimethylformamide were added and reacted at 90 ℃ for 3 hours, cooled to 25 ℃, and 2g of NaOH (30% (w/w)) aqueous solution was added and the reaction was continued for 90 minutes. And washing the obtained solid with deionized water for 3 times, and then placing the solid in a vacuum oven to dry for 24 hours at the temperature of 80 ℃ to obtain the liquid crystal epoxy resin monomer.

(3) Adding 0.01mol of the prepared liquid crystal epoxy resin and 25mL of dimethyl sulfoxide into a single-neck flask in nitrogen atmosphere, then adding 35mL of 2mol/L silver nitrate aqueous solution, stirring for 2h, adding 0.007mol of ascorbic acid, reacting for 8h at 50 ℃, adding a large amount of water for recrystallization, and then drying for 24h at 80 ℃ in a vacuum oven, thus obtaining the organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer.

(4) 0.01mol of organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer, 0.0025mol of 4, 4' -diaminodicyclohexylmethane and 2-methylimidazole with the mass fraction of 0.5 percent of the total amount of the organic-inorganic hybrid liquid crystal epoxy resin monomer and the curing agent are added with 5ml of dichloromethane to be uniformly mixed, air bubbles are pumped in vacuum for 10min, the mixture is cured for 3h at 120 ℃, cured for 3h at 150 ℃ and cured for 2h at 170 ℃ to obtain the high-thermal-conductivity epoxy resin material.

The organic-inorganic hybrid intrinsic liquid crystal epoxy resin prepared by the scheme has the thermal conductivity coefficient reaching 0.92W m^-1K^-1The tensile strength was 92 MPa.

Example 5

(1) 0.01mol of o-phenylenediamine, 0.024mol of p-hydroxybenzaldehyde, 5 wt% of stannous chloride and 80ml of absolute ethyl alcohol are added into a three-neck flask provided with a condenser pipe, and the mixture is heated to 60 ℃ in a magnetic stirring oil bath kettle and refluxed for 24 hours. Then washing with absolute ethyl alcohol, and drying in a vacuum oven at 65 ℃ for 24h to obtain the bisphenol structure compound.

(2) In a three-necked flask under nitrogen atmosphere, 0.01mol of a bisphenol structural intermediate, 4 wt% of tetrabutylammonium bromide, 0.06mol of epichlorohydrin and 50ml of N, N-dimethylformamide were reacted at 90 ℃ for 3 hours, cooled to 20 ℃, and 2g of an aqueous NaOH (20% (w/w)) solution was added to continue the reaction for 60 minutes. And washing the obtained solid with deionized water for 3 times, and then placing the solid in a vacuum oven to dry for 24 hours at the temperature of 80 ℃ to obtain the liquid crystal epoxy resin monomer.

(3) Adding 0.01mol of the prepared liquid crystal epoxy resin and 50mL of dimethyl sulfoxide into a single-neck flask in nitrogen atmosphere, then adding 10mL of 2mol/L silver nitrate aqueous solution, stirring for 3h, adding 0.02mol of N, N-dimethyl formyl, reacting for 8h at 60 ℃, adding a large amount of water for recrystallization, and then drying for 24h at 80 ℃ in a vacuum oven, thus obtaining the organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer.

(4) Taking 0.01mol of organic-inorganic hybrid intrinsic liquid crystal epoxy resin monomer, 0.0025mol of 4, 4' -diaminodicyclohexylmethane and 2-methylimidazole with the mass fraction of 1% of the total amount of the organic-inorganic hybrid liquid crystal epoxy resin monomer and the curing agent, adding 5ml of acetone, uniformly mixing, vacuumizing for 10min, curing at 120 ℃ for 3h, curing at 150 ℃ for 3h, and curing at 170 ℃ for 2h to obtain the high-thermal-conductivity epoxy resin material.

The organic-inorganic hybrid intrinsic liquid crystal epoxy resin prepared by the scheme has the thermal conductivity coefficient reaching 1.6W m^-1K^-1The tensile strength was 100 MPa.

Comparative example 1

The thermal conductivity of a common resin matrix is shown in table 1 below:

TABLE 1 thermal conductivity of conventional resin matrices

The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.