阅读说明：本技术 一种高导热环氧树脂固化物及其制备方法 (High-thermal-conductivity epoxy resin cured product and preparation method thereof ) 是由 郝杰 桂起林 欧秋仁 邵明旺 董大为 于 2021-10-27 设计创作，主要内容包括：本发明提供了一种高导热环氧树脂固化物及其制备方法,应用于高分子复合材料技术领域,该方法包括：将环氧树脂、蒽醌型固化剂、促进剂和溶剂进行搅拌,得到树脂溶液；将所述树脂溶液进行干燥处理,得到树脂固体粉末；将所述树脂固体粉末进行加热处理,得到树脂液体；将所述树脂液体进行固化处理,得到所述高导热环氧树脂固化物。本发明制备的高导热环氧树脂固化物具备优异的导热性,且制备方法简单,易于实现工业化批量生产。(The invention provides a high-thermal-conductivity epoxy resin condensate and a preparation method thereof, which are applied to the technical field of polymer composite materials, and the method comprises the following steps: stirring epoxy resin, an anthraquinone curing agent, an accelerator and a solvent to obtain a resin solution; drying the resin solution to obtain resin solid powder; heating the resin solid powder to obtain resin liquid; and curing the resin liquid to obtain the high-thermal-conductivity epoxy resin cured product. The high-thermal-conductivity epoxy resin condensate prepared by the invention has excellent thermal conductivity, and the preparation method is simple and is easy to realize industrial mass production.)

1. The preparation method of the high-thermal-conductivity epoxy resin cured product is characterized by comprising the following steps of:

(1) stirring epoxy resin, an anthraquinone curing agent, an accelerator and a solvent to obtain a resin solution;

(2) and sequentially carrying out drying treatment, heating treatment and curing treatment on the resin solution to obtain the high-thermal-conductivity epoxy resin cured product.

2. The production method according to claim 1, wherein in step (1):

the high-thermal-conductivity epoxy resin condensate comprises the following raw materials in parts by weight: 100 parts of epoxy resin, 30-50 parts of anthraquinone curing agent, 10-20 parts of accelerator and 20-40 parts of solvent.

3. The production method according to claim 1 or 2, characterized in that:

the anthraquinone curing agent is at least one of 1, 2-diaminoanthraquinone, 1, 4-diaminoanthraquinone, 1, 5-diaminoanthraquinone and 2, 6-diaminoanthraquinone.

4. The production method according to any one of claims 1 to 3, characterized in that:

the epoxy resin is at least one of bisphenol A epoxy resin, bisphenol F epoxy resin and 3,3 ', 5, 5' -tetramethyl diphenol diglycidyl ether;

the accelerator is at least one of 2,4, 6-tri (dimethylaminomethyl) phenol, 2-ethyl-4-methylimidazole, 1, 2-dimethylimidazole, 1-methylimidazole, 1, 8-diazabicycloundecen-7-ene and N, N-dimethylbenzylamine; and/or

The solvent is one of acetone, dichloromethane and chloroform.

5. The method of claim 1, wherein:

in the step (1), the stirring temperature is 15-30 ℃, the stirring speed is 500-700 r/min, and the stirring time is 25-35 min.

6. The method of claim 1, wherein:

in the step (2), the drying process includes the substeps of:

(2.1) carrying out rotary evaporation treatment on the resin solution to obtain a resin mixture, wherein the temperature of the rotary evaporation treatment is 15-30 ℃, the pressure is-0.085 MPa, and the time is 10-15 min;

and (2.2) carrying out vacuum drying treatment on the resin mixture to obtain the resin solid powder, wherein the vacuum degree of the vacuum drying treatment is-0.085 MPa, the temperature is 35-45 ℃, and the time is 25-35 min.

7. The method of claim 1, wherein:

in the step (2), the heating treatment is to stir at a rotation speed of 500-700 r/min for 2-4 min at a temperature of 110-130 ℃.

8. The method of claim 1, wherein:

in the step (2), the curing treatment is carried out at 170-190 ℃ for 20-30 h.

9. The method of claim 1, wherein:

in the step (2), the curing treatment is carried out in a mold at 90-110 ℃.

10. A highly thermally conductive cured epoxy resin, characterized by being produced by the production method according to any one of claims 1 to 9.

Technical Field

The invention relates to the technical field of high polymer composite materials, in particular to a high-thermal-conductivity epoxy resin cured product and a preparation method thereof.

Background

When the electronic equipment operates, a large amount of heat energy can be generated, and if the heat energy is not dissipated in time, the heat energy can cause thermal fatigue, so that the performance release of the equipment is not facilitated, and the service life is prolonged. Thermal management is therefore an important factor affecting the performance of electronic devices. Epoxy resins have been widely used in the electronics industry, including electronics integration, energy storage and conversion systems, and light emitting diodes, due to their light weight, low cost, and good processability. Epoxy resin is a common thermosetting polymer, and is increasingly applied to electrical equipment due to strong adhesion to different materials and excellent electrical insulation performance. However, the low thermal conductivity (0.2W/(m · K)) of epoxy thermosets limits their further applications in the electronics industry.

The introduction of inorganic fillers is commonly used in the industry to improve the thermal conductivity of epoxy resins, such as boron nitride, and to improve the properties of epoxy thermosetting materials, such as thermal conductivity, optical effect, and flame retardancy. However, high proportions of filler have a strong negative impact on the mechanical properties of the composite and on the rheology control during processing (e.g. flow field control in injection moulding processes). In the prior art, the molecular structure and the chain segment structure of the material are usually changed through molecular design to obtain the intrinsic high-heat polymer, but the problems of complex preparation process, high difficulty and high cost still exist.

Disclosure of Invention

The embodiment of the invention provides a high-thermal-conductivity epoxy resin cured product and a preparation method thereof, and the high-thermal-conductivity epoxy resin cured product has excellent thermal conductivity and a simple preparation method.

In a first aspect, the present invention provides a method for preparing a cured high thermal conductive epoxy resin, the method comprising the steps of:

(1) stirring epoxy resin, an anthraquinone curing agent, an accelerator and a solvent to obtain a resin solution;

(2) and sequentially carrying out drying treatment, heating treatment and curing treatment on the resin solution to obtain the high-thermal-conductivity epoxy resin cured product.

Preferably, in the step (1), the mass parts of the raw materials in the cured high thermal conductive epoxy resin are as follows: 100 parts of epoxy resin, 30-50 parts of anthraquinone curing agent, 10-20 parts of accelerator and 20-40 parts of solvent.

Preferably, the anthraquinone curing agent is at least one of 1, 2-diaminoanthraquinone, 1, 4-diaminoanthraquinone, 1, 5-diaminoanthraquinone and 2, 6-diaminoanthraquinone.

Preferably, the epoxy resin is at least one of bisphenol A epoxy resin, bisphenol F epoxy resin and 3,3 ', 5, 5' -tetramethyl diphenol diglycidyl ether;

the accelerator is at least one of 2,4, 6-tri (dimethylaminomethyl) phenol, 2-ethyl-4-methylimidazole, 1, 2-dimethylimidazole, 1-methylimidazole, 1, 8-diazabicycloundecen-7-ene and N, N-dimethylbenzylamine.

Preferably, the solvent is one of acetone, dichloromethane and chloroform.

Preferably, in the step (1), the stirring temperature is 15-30 ℃, the stirring speed is 500-700 r/min, and the stirring time is 25-35 min.

Preferably, in the step (2), the drying process includes the substeps of:

(2.1) carrying out rotary evaporation treatment on the resin solution to obtain a resin mixture, wherein the temperature of the rotary evaporation treatment is 15-30 ℃, the pressure is-0.085 MPa, and the time is 10-15 min;

and (2.2) carrying out vacuum drying treatment on the resin mixture to obtain the resin solid powder, wherein the vacuum degree of the vacuum drying treatment is-0.085 MPa, the temperature is 35-45 ℃, and the time is 25-35 min.

Preferably, in the step (2), the heating treatment is stirring at a rotation speed of 500-700 r/min for 2-4 min at a temperature of 110-130 ℃.

Preferably, in the step (2), the curing treatment is curing at 170-190 ℃ for 20-30 h.

Preferably, in the step (2), the curing treatment is performed in a mold at 90-110 ℃.

In a second aspect, the invention provides a high thermal conductive epoxy resin cured product, which is prepared by the preparation method of any one of the first aspect.

Compared with the prior art, the invention at least has the following beneficial effects:

(1) in the invention, the anthraquinone compound containing naphthalene rings and amino groups is used as the curing agent, and the naphthalene ring structure in the anthraquinone curing agent has conjugated large pi bonds which are beneficial to conduction of heat flow, and the naphthalene ring structure is a rigid structure which is beneficial to heat dissipation through ring vibration, so that the anthraquinone compound containing naphthalene rings is selected as the curing agent, the thermal conductivity of the epoxy resin cured product can be obviously improved, and the prepared high-thermal-conductivity epoxy resin cured product has excellent thermal conductivity.

(2) The preparation method of the high-thermal-conductivity epoxy resin provided by the invention is simple, the raw materials can be mixed and stirred at normal temperature and normal pressure to react to obtain the resin solution, the reaction time is short, and the epoxy resin condensate can be obtained only by drying treatment and curing treatment after the resin solution is obtained, so that the application range is wider, and the industrial batch production of the high-thermal-conductivity epoxy resin is easy to realize.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer and more complete, the technical solutions of the present invention will be described below in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments, and all other embodiments obtained by a person of ordinary skill in the art without creative efforts based on the embodiments of the present invention belong to the protection scope of the present invention.

The invention provides a preparation method of a high-thermal-conductivity epoxy resin condensate, which comprises the following steps:

(1) stirring epoxy resin, an anthraquinone curing agent, an accelerator and a solvent to obtain a resin solution;

(2) and sequentially carrying out drying treatment, heating treatment and curing treatment on the resin solution to obtain the high-thermal-conductivity epoxy resin cured product.

In the invention, the anthraquinone compound containing naphthalene rings and amino groups is used as the curing agent, and the naphthalene ring structure in the anthraquinone curing agent has conjugated large pi bonds which are beneficial to conduction of heat flow, and the naphthalene ring structure is a rigid structure which is beneficial to heat dissipation through ring vibration, so that the anthraquinone compound containing naphthalene rings is selected as the curing agent, the thermal conductivity of the epoxy resin cured product can be obviously improved, and the prepared high-thermal-conductivity epoxy resin cured product has excellent thermal conductivity.

The amino group in the anthraquinone-based curing agent can undergo a ring-opening reaction with the epoxy group in the epoxy resin, and the anthraquinone compound containing a naphthalene ring can be combined with the epoxy resin by the ring-opening reaction to complete the modification of the epoxy resin, thereby obtaining an epoxy resin cured product having excellent thermal conductivity.

The preparation method of the high-thermal-conductivity epoxy resin provided by the invention is simple, the raw materials can be mixed and stirred at normal temperature and normal pressure to react to obtain the resin solution, the reaction time is short, and the epoxy resin condensate can be obtained only by drying treatment and curing treatment after the resin solution is obtained, so that the application range is wider, and the industrial batch production of the high-thermal-conductivity epoxy resin is easy to realize.

According to some preferred embodiments, in the step (1), the parts by weight of the raw materials in the cured high thermal conductive epoxy resin are as follows: 100 parts of the epoxy resin, 30 to 50 parts of the anthraquinone-based curing agent (for example, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts, 40 parts, 41 parts, 42 parts, 43 parts, 44 parts, 45 parts, 46 parts, 47 parts, 48 parts, 49 parts or 50 parts), 10 to 20 parts of the accelerator (for example, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts or 40 parts), and 20 to 40 parts of the solvent (for example, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts or 20 parts).

More specifically, for example, the mass parts of the raw materials in the cured high thermal conductive epoxy resin are as follows: 100 parts of epoxy resin, 30 parts of anthraquinone curing agent, 10 parts of accelerator and 20 parts of solvent; the high-thermal-conductivity epoxy resin condensate comprises the following raw materials in parts by weight: 100 parts of epoxy resin, 50 parts of anthraquinone curing agent, 20 parts of accelerator and 40 parts of solvent; the high-thermal-conductivity epoxy resin condensate comprises the following raw materials in parts by weight: 100 parts of epoxy resin, 45 parts of anthraquinone curing agent, 15 parts of accelerator and 40 parts of solvent.

Experiments prove that the epoxy resin condensate prepared from the epoxy resin and the anthraquinone curing agent in parts by mass has excellent thermal conductivity and mechanical property, and if the parts by mass of the anthraquinone curing agent is less than 30 parts, the prepared epoxy resin condensate has few naphthalene ring structures and poor thermal conductivity; if the mass part of the anthraquinone curing agent is more than 50 parts, the prepared cured epoxy resin has less three-dimensional network structure and poor mechanical property.

According to some preferred embodiments, the anthraquinone-based curing agent is at least one of 1, 2-diaminoanthraquinone, 1, 4-diaminoanthraquinone, 1, 5-diaminoanthraquinone, 2, 6-diaminoanthraquinone.

At least one of them is a mixture of any one or any several of them mixed in any ratio.

According to some preferred embodiments, the epoxy resin is at least one of bisphenol a type epoxy resin, bisphenol F type epoxy resin, 3 ', 5, 5' -tetramethylbiphenol diglycidyl ether;

the accelerator is at least one of 2,4, 6-tri (dimethylaminomethyl) phenol, 2-ethyl-4-methylimidazole, 1, 2-dimethylimidazole, 1-methylimidazole, 1, 8-diazabicycloundecen-7-ene and N, N-dimethylbenzylamine;

according to some preferred embodiments, the solvent is one of acetone, dichloromethane, chloroform.

In the invention, the accelerator can accelerate the curing of the epoxy resin, reduce the curing temperature and shorten the curing time. The organic solvent with low boiling point can dissolve the epoxy resin, the curing agent and the accelerator at room temperature (25 ℃) to obtain stable and uniform resin solution, and can be easily removed through rotary evaporation treatment.

According to some preferred embodiments, in the step (1), the stirring temperature of the stirring is 15 to 30 ℃ (for example, 15 ℃, 16 ℃, 17 ℃, 18 ℃, 19 ℃, 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃ or 30 ℃), the stirring speed is 500 to 700r/min (for example, 500r/min, 550r/min, 600r/min, 650r/min or 700r/min), and the stirring time is 25 to 35min (for example, 25min, 26min, 27min, 28min, 29min, 30min, 31min, 32min, 33min, 34min or 35 min).

In the invention, the resin solution can be obtained by stirring at normal temperature and normal pressure for 25-35 min, the preparation method is simple, the preparation conditions are loose, and complex equipment and technical support are not needed.

According to some preferred embodiments, in the step (2), the drying process includes the following sub-steps:

(2.1) performing rotary evaporation treatment on the resin solution to obtain a resin mixture, wherein the temperature of the rotary evaporation treatment is 15-30 ℃ (for example, 15 ℃, 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃ or 30 ℃), the pressure is-0.085 MPa, and the time is 10-15 min (for example, 10min, 11min, 12min, 13min, 14min or 15 min);

(2.2) subjecting the resin mixture to vacuum drying treatment to obtain the resin solid powder, wherein the vacuum degree of the vacuum drying treatment is-0.085 MPa, the temperature is 35-45 ℃ (for example, 35 ℃, 36 ℃, 37 ℃, 38 ℃, 39 ℃, 40 ℃, 41 ℃, 42 ℃, 43 ℃, 44 ℃ or 45 ℃) and the time is 25-35 min (for example, 25min, 26min, 27min, 28min, 29min, 30min, 31min, 32min, 33min, 34min or 35 min).

In the present invention, the solvent is used to sufficiently and uniformly mix the epoxy resin, the anthraquinone-based curing agent and the accelerator, and therefore, in order to ensure the properties of the finally produced resin, it is necessary to remove the solvent from the solution by a rotary evaporation treatment to obtain a resin mixture, and then further dry the resin mixture by a vacuum drying treatment to obtain a resin solid powder.

According to some preferred embodiments, in the step (2), the heating treatment is stirring at a rotation speed of 500 to 700r/min (for example, 500r/min, 550r/min, 600r/min, 650r/min or 700r/min) for 2 to 4min (for example, 2min, 3min or 4min) under a condition of 110 to 130 ℃ (for example, 110 ℃, 115 ℃, 120 ℃, 125 ℃ or 130 ℃).

In the present invention, the resin solid powder is converted from a solid phase to a liquid phase by a heating treatment to obtain a resin liquid, thereby facilitating the pouring thereof into a mold for a curing treatment.

According to some preferred embodiments, in the step (2), the curing treatment is performed at 170 to 190 ℃ (for example, 170 ℃, 175 ℃, 180 ℃, 185 ℃ or 190 ℃) for 20 to 30 hours (for example, 20 hours, 21 hours, 22 hours, 23 hours, 24 hours, 25 hours, 26 hours, 27 hours, 28 hours, 29 hours or 30 hours).

In the present invention, the curing process does not need to be performed in stages, and curing can be completed at a single temperature.

According to some preferred embodiments, in the step (2), the curing treatment is performed in a mold at 90 to 110 ℃ (for example, may be 90 ℃, 95 ℃, 100 ℃, 105 ℃ or 110 ℃).

In the invention, before the resin liquid is poured into the mold for curing, the mold needs to be preheated to 90-110 ℃ to ensure the fluidity of the resin liquid, and the mold is rapidly filled.

In a second aspect, the invention provides a high thermal conductive epoxy resin cured product, which is prepared by the preparation method of any one of the first aspect.

In order to more clearly illustrate the technical scheme and advantages of the present invention, a high thermal conductive epoxy resin cured product and a method for preparing the same are described in detail in the following examples

Example 1:

(1) 100g of 3,3 ', 5, 5' -tetramethylbiphenol diglycidyl ether, 45g of 1, 2-diaminoanthraquinone, 10g of 1-methylimidazole and 40g of acetone were stirred at 25 ℃ and a rotation speed of 600r/min for 30min to obtain a resin solution.

(2) Placing the resin solution in a rotary evaporator, and carrying out rotary evaporation at the rotating speed of 600r/min for 12min at the temperature of 25 ℃ and under the pressure of-0.085 KPa to obtain a resin mixture, and carrying out vacuum drying treatment on the resin mixture for 30min at the temperature of 40 ℃ and under the pressure of-0.085 KPa to obtain resin solid powder.

(3) And (3) placing the resin solid powder at 120 ℃, and stirring for 3min at the rotating speed of 600r/min to obtain resin liquid.

(4) Pouring the resin liquid into a mold preheated to 100 ℃ in advance, and then heating the mold to 180 ℃ and curing for 24 hours to obtain the cured epoxy resin.

Example 2:

(1) 100g of 3,3 ', 5, 5' -tetramethylbiphenol diglycidyl ether, 45g of 1, 4-diaminoanthraquinone, 10g of 1-methylimidazole and 40g of acetone were stirred at 25 ℃ and a rotation speed of 600r/min for 30min to obtain a resin solution.

(2) Placing the resin solution in a rotary evaporator, and carrying out rotary evaporation at the rotating speed of 600r/min for 12min at the temperature of 25 ℃ and under the pressure of-0.085 KPa to obtain a resin mixture, and carrying out vacuum drying treatment on the resin mixture for 30min at the temperature of 40 ℃ and under the pressure of-0.085 KPa to obtain resin solid powder.

(3) And (3) placing the resin solid powder at 120 ℃, and stirring for 3min at the rotating speed of 600r/min to obtain resin liquid.

(4) Pouring the resin liquid into a mold preheated to 100 ℃ in advance, and then heating the mold to 180 ℃ and curing for 24 hours to obtain the cured epoxy resin.

Example 3:

(1) 100g of 3,3 ', 5, 5' -tetramethylbiphenol diglycidyl ether, 45g of 1, 5-diaminoanthraquinone, 10g of 1-methylimidazole and 40g of acetone were stirred at 25 ℃ and a rotation speed of 600r/min for 30min to obtain a resin solution.

(2) Placing the resin solution in a rotary evaporator, and carrying out rotary evaporation at the rotating speed of 600r/min for 12min at the temperature of 25 ℃ and under the pressure of-0.085 KPa to obtain a resin mixture, and carrying out vacuum drying treatment on the resin mixture for 30min at the temperature of 40 ℃ and under the pressure of-0.085 KPa to obtain resin solid powder.

(3) And (3) placing the resin solid powder at 120 ℃, and stirring for 3min at the rotating speed of 600r/min to obtain resin liquid.

(4) Pouring the resin liquid into a mold preheated to 100 ℃ in advance, and then heating the mold to 180 ℃ and curing for 24 hours to obtain the cured epoxy resin.

Example 4:

(1) 100g of 3,3 ', 5, 5' -tetramethylbiphenol diglycidyl ether, 45g of 2, 6-diaminoanthraquinone, 10g of 1-methylimidazole and 40g of acetone were stirred at 25 ℃ and a rotation speed of 600r/min for 30min to obtain a resin solution.

(2) Placing the resin solution in a rotary evaporator, and carrying out rotary evaporation at the rotating speed of 600r/min for 12min at the temperature of 25 ℃ and under the pressure of-0.085 KPa to obtain a resin mixture, and carrying out vacuum drying treatment on the resin mixture for 30min at the temperature of 40 ℃ and under the pressure of-0.085 KPa to obtain resin solid powder.

(3) And (3) placing the resin solid powder at 120 ℃, and stirring for 3min at the rotating speed of 600r/min to obtain resin liquid.

(4) Pouring the resin liquid into a mold preheated to 100 ℃ in advance, and then heating the mold to 180 ℃ and curing for 24 hours to obtain the cured epoxy resin.

Example 5:

(1) 100g of 3,3 ', 5, 5' -tetramethylbiphenol diglycidyl ether, 30g of 1, 2-diaminoanthraquinone, 10g of 1-methylimidazole and 40g of acetone are stirred at 25 ℃ and the rotation speed of 600r/min for 30min to obtain a resin solution.

(2) Placing the resin solution in a rotary evaporator, and carrying out rotary evaporation at the rotating speed of 600r/min for 12min at the temperature of 25 ℃ and under the pressure of-0.085 KPa to obtain a resin mixture, and carrying out vacuum drying treatment on the resin mixture for 30min at the temperature of 40 ℃ and under the pressure of-0.085 KPa to obtain resin solid powder.

(3) And (3) placing the resin solid powder at 120 ℃, and stirring for 3min at the rotating speed of 600r/min to obtain resin liquid.

(4) Pouring the resin liquid into a mold preheated to 100 ℃ in advance, and then heating the mold to 180 ℃ and curing for 24 hours to obtain the cured epoxy resin.

Example 6:

(1) 100g of 3,3 ', 5, 5' -tetramethylbiphenol diglycidyl ether, 50g of 1, 2-diaminoanthraquinone, 10g of 1-methylimidazole and 40g of acetone were stirred at 25 ℃ and a rotation speed of 600r/min for 30min to obtain a resin solution.

(2) Placing the resin solution in a rotary evaporator, and carrying out rotary evaporation at the rotating speed of 600r/min for 12min at the temperature of 25 ℃ and under the pressure of-0.085 KPa to obtain a resin mixture, and carrying out vacuum drying treatment on the resin mixture for 30min at the temperature of 40 ℃ and under the pressure of-0.085 KPa to obtain resin solid powder.

(3) And (3) placing the resin solid powder at 120 ℃, and stirring for 3min at the rotating speed of 600r/min to obtain resin liquid.

(4) Pouring the resin liquid into a mold preheated to 100 ℃ in advance, and then heating the mold to 180 ℃ and curing for 24 hours to obtain the cured epoxy resin.

Comparative example 1:

(1) 100g of 3,3 ', 5, 5' -tetramethylbiphenol diglycidyl ether, 40g of dicyandiamide, 10g of 1-methylimidazole and 24g of acetone are stirred at 25 ℃ and the rotating speed of 600r/min for 30min to obtain a resin solution.

(2) Placing the resin solution in a rotary evaporator, and carrying out rotary evaporation at the rotating speed of 600r/min for 12min at the temperature of 25 ℃ and under the pressure of-0.085 KPa to obtain a resin mixture, and carrying out vacuum drying treatment on the resin mixture for 30min at the temperature of 40 ℃ and under the pressure of-0.085 KPa to obtain resin solid powder.

(3) And (3) placing the resin solid powder at 120 ℃, and stirring for 3min at the rotating speed of 600r/min to obtain resin liquid.

(4) Pouring the resin liquid into a mold preheated to 100 ℃ in advance, and then heating the mold to 180 ℃ and curing for 24 hours to obtain the cured epoxy resin.

Comparative example 2:

(1) 100g of 3,3 ', 5, 5' -tetramethylbiphenol diglycidyl ether, 10g of 1, 2-diaminoanthraquinone, 10g of 1-methylimidazole and 40g of acetone were stirred at 25 ℃ and a rotation speed of 600r/min for 30min to obtain a resin solution.

(2) Placing the resin solution in a rotary evaporator, and carrying out rotary evaporation at the rotating speed of 600r/min for 12min at the temperature of 25 ℃ and under the pressure of-0.085 KPa to obtain a resin mixture, and carrying out vacuum drying treatment on the resin mixture for 30min at the temperature of 40 ℃ and under the pressure of-0.085 KPa to obtain resin solid powder.

(3) And (3) placing the resin solid powder at 120 ℃, and stirring for 3min at the rotating speed of 600r/min to obtain resin liquid.

(4) Pouring the resin liquid into a mold preheated to 100 ℃ in advance, and then heating the mold to 180 ℃ and curing for 24 hours to obtain the cured epoxy resin.

Comparative example 3:

(1) 100g of 3,3 ', 5, 5' -tetramethylbiphenol diglycidyl ether, 80g of 1, 2-diaminoanthraquinone, 10g of 1-methylimidazole and 40g of acetone are stirred at 25 ℃ and the rotation speed of 600r/min for 30min to obtain a resin solution.

(2) Placing the resin solution in a rotary evaporator, and carrying out rotary evaporation at the rotating speed of 600r/min for 12min at the temperature of 25 ℃ and under the pressure of-0.085 KPa to obtain a resin mixture, and carrying out vacuum drying treatment on the resin mixture for 30min at the temperature of 40 ℃ and under the pressure of-0.085 KPa to obtain resin solid powder.

(3) And (3) placing the resin solid powder at 120 ℃, and stirring for 3min at the rotating speed of 600r/min to obtain resin liquid.

(4) Pouring the resin liquid into a mold preheated to 100 ℃ in advance, and then heating the mold to 180 ℃ and curing for 24 hours to obtain the cured epoxy resin.

The cured epoxy resins prepared in examples 1 to 4 and comparative examples 1 to 3 were subjected to performance tests, and the test results are shown in Table 1:

TABLE 1

From examples 1 to 4, it can be seen that the positions of two amino functional groups in the anthraquinone-based curing agent have an obvious effect on the mechanical properties of the high thermal conductive epoxy resin, and when two amino groups are concentrated on the same benzene ring of the anthraquinone compound (as in examples 1 and 2), the high thermal conductive epoxy resin is adversely affected due to the large steric hindrance, so that the finally obtained cured product has poor mechanical properties; however, when the amino groups are dispersed on different benzene rings of the anthraquinone compound (e.g., examples 3 and 4), the steric hindrance is reduced, which is advantageous for the crystallization of the highly thermally conductive epoxy resin, thereby providing the highly thermally conductive epoxy resin with excellent mechanical properties.

As shown in comparative example 1, the conventional curing agent has no naphthalene ring structure and no conjugated large pi bond, and thus does not have the effect of improving the thermal conductivity of the cured epoxy resin.

As can be seen from comparative example 2, when the mass part of the epoxy resin is 100 parts and the mass part of the anthraquinone-based curing agent is less than 30 parts, the cured product of the epoxy resin obtained has poor thermal conductivity.

As can be seen from comparative example 3, when the mass part of the epoxy resin is 100 parts and the mass part of the anthraquinone-based curing agent is more than 50 parts, the cured product of the epoxy resin obtained has poor mechanical properties.

Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.