CN111500019A - Based on BN-Al2O3Modified high-thermal-conductivity insulating epoxy resin material and preparation method thereof - Google Patents

Based on BN-Al2O3Modified high-thermal-conductivity insulating epoxy resin material and preparation method thereof Download PDF

Info

Publication number
CN111500019A
CN111500019A CN202010395743.9A CN202010395743A CN111500019A CN 111500019 A CN111500019 A CN 111500019A CN 202010395743 A CN202010395743 A CN 202010395743A CN 111500019 A CN111500019 A CN 111500019A
Authority
CN
China
Prior art keywords
epoxy resin
nano
ultrasonic
thermal
modified
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
CN202010395743.9A
Other languages
Chinese (zh)
Inventor
韩永洲
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to CN202010395743.9A priority Critical patent/CN111500019A/en
Publication of CN111500019A publication Critical patent/CN111500019A/en
Withdrawn legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08—Materials not undergoing a change of physical state when used
    • C09K5/14—Solid materials, e.g. powdery or granular
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
    • C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers

Abstract

The invention relates to the technical field of epoxy resin, and discloses a BN-Al-based epoxy resin2O3The modified high-thermal-conductivity insulating epoxy resin material comprises the following formula raw materials and components: al (Al)2O3BN nano composite material, epoxy resin, curing agent and defoaming agent. Porous nanometer BN loaded Al with huge specific surface2O3The poly-dopamine is firmly combined on the surface of nano BN through pi-pi bond conjugation and van der Waals force interaction with a benzene ring structure of the poly-dopamine, and the 3-glycidyl ether oxypropyl trimethoxysilane reacts with rich phenolic hydroxyl of the poly-dopamine to ensure that Al reacts2O3the-BN nano composite material contains a large number of epoxy groups, polydopamine molecules and epoxy resin have good compatibility, and Al2O3Thermosetting and crosslinking epoxy group of-BN nano composite material and epoxy resin to obtain Al2O3the-BN nano composite material is grafted into the molecular chain of the epoxy resin, so that the nano Al is enhanced2O3And the compatibility and the dispersibility of BN and the epoxy resin, and the epoxy resin is endowed with excellent insulating property and heat-conducting property.

Description

Based on BN-Al2O3Modified high-thermal-conductivity insulating epoxy resin material and preparation method thereof
Technical Field
The invention relates to the technical field of epoxy resin, in particular to a BN-Al-based epoxy resin2O3Modified high-thermal-conductivity insulating epoxy resin material and a preparation method thereof.
Background
The insulating material is the foundation and guarantee of the development of electrical products, and has an important function on the development of the electrical motor industry, and the insulating material depends on the development of high polymer materials, so that the development and progress of the electrical products are directly restricted and influenced by the insulating high polymer materials, and the high polymer insulating materials mainly comprise materials such as phenolic resin, polyvinyl chloride, polyamide-imide, polymaleimide and the like, and relate to the industrial fields such as electricians, light industry, petrifaction, textile, building materials and the like.
The epoxy resin is a thermosetting resin, the product mainly comprises structural adhesive, low temperature resistant adhesive, conductive adhesive, foaming adhesive, civil engineering construction adhesive and the like, can be used as coating, adhesive, molding material, injection molding material and the like, is widely applied in the fields of sports goods, civil engineering construction, electronic appliances, automobile machinery and the like, has good insulating property, is widely applied to the aspects of insulation and encapsulation of high and low voltage electric appliances, motors and electronic components, but along with the rapid development of the electric motor industry, the traditional epoxy resin insulating material and the epoxy resin insulating material which can not meet the industrial requirements need to be developed, the epoxy resin material with more excellent insulating property and heat conducting property needs to be developed, alumina and boron nitride have very high heat conductivity and volume resistivity, the cost of the alumina is much cheaper than that of the boron nitride, therefore, the alumina can be used as a main additive, the boron nitride is used as a secondary additive, the composite material is compounded with epoxy resin to enhance the insulating property and the heat conducting property of the material, but the compatibility of nano aluminum oxide and nano boron nitride with the epoxy resin is poor, the nano aluminum oxide and the nano boron nitride are easy to agglomerate in the epoxy resin, and the mechanical property and the actual use performance of the epoxy resin material can be seriously influenced, so that the key for solving the problem is to improve the compatibility of the nano aluminum oxide and the nano boron nitride with the epoxy resin.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a BN-Al-based alloy2O3The modified high-thermal-conductivity insulating epoxy resin material and the preparation method thereof solve the problems of poor insulating property and thermal conductivity of the epoxy resin and poor compatibility of the nano aluminum oxide and the nano boron nitride with the epoxy resin.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: based on BN-Al2O3The modified high-thermal-conductivity insulating epoxy resin material comprises the following raw materials and components: al (Al)2O3The epoxy resin-BN nano composite material is prepared from BN nano composite material, epoxy resin, a curing agent and a defoaming agent according to the mass ratio of 5-35:100:40-80: 0.5-2.
Preferably, the BN-Al2O3The preparation method of the nano composite material comprises the following steps:
(1) distilled water and nano Al are added into a reaction bottle2O3Placing the solution in an ultrasonic dispersion instrument, adding boric acid and melamine after uniform ultrasonic dispersion, heating to 70-100 ℃, stirring at a constant speed for reaction for 5-10h, placing the solution in a liquid nitrogen atmosphere for freezing and cooling, performing freeze drying through a vacuum freeze dryer to remove a solvent, placing a solid product in an atmosphere resistance furnace, introducing argon, raising the temperature to 1080 and 1150 ℃ at a rate of 5-10 ℃/min, calcining for 3-5h, wherein the calcined product is nano porous BN loaded Al2O3。
(2) Adding distilled water solvent into a reaction bottle, adding Tris-HCl buffer solution to control the pH value of the solution to be 8-9, and adding nano porous BN modified Al2O3Adding dopamine hydrochloride after uniform ultrasonic dispersion, stirring at a constant speed at 50-70 ℃ for reaction for 15-25h, filtering the solution to remove the solvent, washing the solid product with distilled water and acetone, and fully drying to prepare the nano poly-dopamine modified BN loaded Al2O3。
(3) Adding a toluene solvent and nano poly dopamine modified BN loaded Al into a reaction bottle2O3Uniform ultrasonic dispersionThen adding a silane coupling agent, placing the mixture in an oil bath pot, heating to the temperature of 100 ℃ and 130 ℃, stirring at a constant speed for reaction for 6-12h, distilling the solution under reduced pressure to remove the solvent, washing the solid product by using distilled water and acetone, and fully drying to prepare the Al grafted with the silane coupling agent2O3-BN nanocomposite.
Preferably, the nano Al2O3The mass ratio of the boric acid to the melamine is 100:10-30:6-20, and the total mass fraction of the solution is controlled to be 0.5-3 g/L.
Preferably, the ultrasonic dispersion instrument comprises an ultrasonic chamber, an ultrasonic chamber upper part and two sides fixedly connected with regulators, wherein the regulators are movably connected with an ultrasonic emitter, a constant temperature heating box is fixedly connected below the ultrasonic chamber, and a reaction bottle and an ultrasonic chamber are fixedly connected with a sound insulation layer outside the ultrasonic chamber above the constant temperature heating box.
Preferably, the nanoporous BN modifies Al2O3The mass ratio of the dopamine hydrochloride to the dopamine hydrochloride is 8-15: 1.
Preferably, the silane coupling agent is 3-glycidyl ether oxypropyltrimethoxysilane and is modified with nano poly-dopamine to load BN with Al2O3The mass ratio of (A) to (B) is 1: 1.5-4.
Preferably, the base is based on BN-Al2O3The preparation method of the modified high-thermal-conductivity insulating epoxy resin material comprises the following steps:
(1) adding acetone solvent and Al into a reaction bottle2O3Uniformly dispersing the-BN nano composite material and the epoxy resin by ultrasonic, adding a curing agent and a defoaming agent, uniformly stirring, pouring the materials into a film forming die, and performing thermal curing to form a film to prepare the BN-Al-based nano composite material2O3Modified high heat-conducting insulating epoxy resin material.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
based on BN-Al2O3Modified high-thermal-conductivity insulating epoxy resin material prepared from nano Al2O3As carrier, by freeze drying and pyrolysisObtaining the porous nanometer BN loaded Al with huge specific surface2O3Loading Al on BN by in-situ polymerization2O3The surface of the porous nanometer BN is generated with nanometer polydopamine, B atoms and N atoms of the nanometer BN alternately form a hexagonal annular grid structure, the specific surface of the porous nanometer BN is very large, the porous nanometer BN is easy to interact with a benzene ring structure of the polydopamine through pi-pi bond conjugation and van der Waals force, the polydopamine is firmly combined on the surface of the nanometer BN, and then the Al reacts with rich phenolic hydroxyl of the polydopamine through 3-glycidyl ether oxypropyltrimethoxysilane, so that the Al reacts with rich phenolic hydroxyl of the polydopamine2O3the-BN nanocomposites contain a large number of epoxy groups.
Based on BN-Al2O3Modified high thermal conductive insulating epoxy resin material, Al2O3The poly-dopamine molecules on the surface of the-BN nano composite material have good compatibility with the epoxy resin, and in the process of curing the epoxy resin, the epoxy group and Al of the epoxy resin2O3Thermal curing and crosslinking a large number of epoxy groups of the-BN nanocomposite material to obtain Al2O3the-BN nano composite material is successfully grafted into the molecular chain of the epoxy resin, thereby enhancing the nano Al2O3And the compatibility and the dispersibility of BN and the epoxy resin, and the epoxy resin is endowed with excellent insulating property and heat-conducting property.
Drawings
Figure 1 is a schematic front view of an ultrasound chamber;
FIG. 2 is an enlarged schematic view of an ultrasonic transmitter;
fig. 3 is a schematic regulator regulation diagram.
1. An ultrasound chamber; 2. a regulator; 3. an ultrasonic transmitter; 4. a constant temperature heating box; 5. a reaction bottle; 6. and a sound insulation layer.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: based on BN-Al2O3The modified high-thermal-conductivity insulating epoxy resin material comprises the following raw materials and components: al (Al)2O3-BN nano composite material, epoxy resin, curing agent, defoaming agent and epoxy resinThe amount ratio is 5-35:100:40-80: 0.5-2.
BN-Al2O3The preparation method of the nano composite material comprises the following steps:
(1) distilled water and nano Al are added into a reaction bottle2O3The ultrasonic dispersion instrument comprises an ultrasonic chamber, an ultrasonic chamber upper part and two sides fixedly connected with regulators, wherein the regulators are movably connected with an ultrasonic emitter, a constant temperature heating box is fixedly connected with the lower part of the ultrasonic chamber, a reaction bottle and an outer side fixedly connected with sound insulation layer of the ultrasonic chamber are arranged above the constant temperature heating box, and boric acid and melamine are added after the ultrasonic dispersion is uniform2O3The mass ratio of the three is 100:10-30:6-20, the total mass fraction of the solution is controlled to be 0.5-3 g/L, the solution is heated to 70-100 ℃, the solution is stirred at a constant speed for reaction for 5-10h, the solution is placed in a liquid nitrogen atmosphere for freezing and cooling, a vacuum freeze dryer is used for freezing and drying to remove the solvent, the solid product is placed in an atmosphere resistance furnace, argon is introduced, the heating rate is 5-10 ℃/min, the temperature is raised to 1080-2O3。
(2) Adding distilled water solvent into a reaction bottle, adding Tris-HCl buffer solution to control the pH value of the solution to be 8-9, and adding nano porous BN modified Al2O3Adding dopamine hydrochloride with the mass ratio of 8-15:1 after ultrasonic dispersion is uniform, stirring at a constant speed at 50-70 ℃ for reaction for 15-25h, filtering the solution to remove the solvent, washing the solid product with distilled water and acetone, and fully drying to prepare the nano poly-dopamine modified BN loaded Al2O3。
(3) Adding a toluene solvent and nano poly dopamine modified BN loaded Al into a reaction bottle2O3Adding silane coupling agent 3-glycidyl ether oxypropyltrimethoxysilane after ultrasonic dispersion is uniform, and modifying BN loaded with Al with nano poly-dopamine2O3The mass ratio of the components is 1:1.5-4, the mixture is placed in an oil bath pot and heated to 100-130 ℃, the mixture is stirred at a constant speed for reaction for 6-12h, the solution is decompressed and distilled to remove the solvent, distilled water and acetone are used for washing a solid product, and the solid product is fully dried to prepare the Al grafted by the silane coupling agent2O3-BN nanocomposite.
Based on BN-Al2O3The preparation method of the modified high-thermal-conductivity insulating epoxy resin material comprises the following steps:
(1) adding an acetone solvent, an Al2O3-BN nano composite material and epoxy resin into a reaction bottle, adding a curing agent and a defoaming agent after uniform ultrasonic dispersion, uniformly stirring, pouring the materials into a film forming die, and performing thermal curing to form a film to obtain the BN-Al-based nano composite material2O3Modified high heat-conducting insulating epoxy resin material.
Example 1
(1) Preparation of nano porous BN loaded Al2O3Component 1: distilled water and nano Al are added into a reaction bottle2O3The ultrasonic dispersion instrument comprises an ultrasonic chamber, an ultrasonic chamber upper part and two sides fixedly connected with regulators, wherein the regulators are movably connected with an ultrasonic emitter, a constant temperature heating box is fixedly connected with the lower part of the ultrasonic chamber, a reaction bottle and an outer side fixedly connected with sound insulation layer of the ultrasonic chamber are arranged above the constant temperature heating box, and boric acid and melamine are added after the ultrasonic dispersion is uniform2O3The mass ratio of the three is 100:10-30:6-20, the total mass fraction of the solution is controlled to be 0.5-3 g/L, the solution is heated to 70-100 ℃, the solution is stirred at a constant speed for reaction for 5-10h, the solution is placed in a liquid nitrogen atmosphere for freezing and cooling, a vacuum freeze dryer is used for freezing and drying to remove the solvent, the solid product is placed in an atmosphere resistance furnace, argon is introduced, the heating rate is 5-10 ℃/min, the temperature is raised to 1080-2O3And (3) component 1.
(2) Preparation of nanometer polydopamine modified BN loaded Al2O3Component 1: adding distilled water solvent into a reaction bottle, adding Tris-HCl buffer solution to control the pH value of the solution to be 8-9, and adding nano porous BN modified Al2O3Uniformly dispersing the component 1 by ultrasonic, adding dopamine hydrochloride with the mass ratio of 8-15:1, uniformly stirring the mixture at 50-70 ℃ for reaction for 15-25h, filtering the solution to remove the solvent, washing the solid product by using distilled water and acetone, and fully drying the solid product to prepare the nano poly-dopaAmine modified BN loaded Al2O3And (3) component 1.
(3) Preparation of silane coupling agent grafted Al2O3BN nanocomposite 1: adding a toluene solvent and nano poly dopamine modified BN loaded Al into a reaction bottle2O3The component 1 is added with silane coupling agent 3-glycidyl ether oxypropyl trimethoxy silane after being dispersed uniformly by ultrasonic, and modified BN loaded with Al with nano poly dopamine2O3The mass ratio of the components is 1:1.5-4, the mixture is placed in an oil bath pot and heated to 100-130 ℃, the mixture is stirred at a constant speed for reaction for 6-12h, the solution is decompressed and distilled to remove the solvent, distilled water and acetone are used for washing a solid product, and the solid product is fully dried to prepare the Al grafted by the silane coupling agent2O3BN nanocomposite 1.
(4) Preparation based on BN-Al2O3Modified high thermal conductive insulating epoxy resin material 1: adding acetone solvent and Al into a reaction bottle2O3Uniformly dispersing the-BN nano composite material 1 and the epoxy resin by ultrasonic, adding a curing agent and a defoaming agent, uniformly stirring, pouring the materials into a film forming die, and performing thermosetting film forming to obtain the BN-Al-based nano composite material based on BN-Al, wherein the mass ratio of the curing agent to the defoaming agent is 5-35:100:40-80:0.5-22O3Modified high thermal conductivity insulating epoxy resin material 1.
Example 2
(1) Preparation of nano porous BN loaded Al2O3And (2) component: distilled water and nano Al are added into a reaction bottle2O3The ultrasonic dispersion instrument comprises an ultrasonic chamber, an ultrasonic chamber upper part and two sides fixedly connected with regulators, wherein the regulators are movably connected with an ultrasonic emitter, a constant temperature heating box is fixedly connected with the lower part of the ultrasonic chamber, a reaction bottle and an outer side fixedly connected with sound insulation layer of the ultrasonic chamber are arranged above the constant temperature heating box, and boric acid and melamine are added after the ultrasonic dispersion is uniform2O3The mass ratio of the three is 100:10-30:6-20, the total mass fraction of the solution is controlled to be 0.5-3 g/L, the solution is heated to 70-100 ℃, the solution is stirred at a constant speed for reaction for 5-10h, the solution is put in a liquid nitrogen atmosphere for freezing and cooling, a vacuum freeze dryer is used for freezing and drying to remove the solvent, the solid product is put in airIntroducing argon into an atmosphere resistance furnace, raising the temperature to 1080-1150 ℃ at the rate of 5-10 ℃/min, calcining for 3-5h, wherein the calcined product is the nano porous BN loaded Al2O3And (3) component 2.
(2) Preparation of nanometer polydopamine modified BN loaded Al2O3And (2) component: adding distilled water solvent into a reaction bottle, adding Tris-HCl buffer solution to control the pH value of the solution to be 8-9, and adding nano porous BN modified Al2O3And (2) adding dopamine hydrochloride into the component 2 after ultrasonic dispersion, wherein the mass ratio of the dopamine hydrochloride to the component 2 is 8-15:1, uniformly stirring the mixture at 50-70 ℃ for reaction for 15-25h, filtering the solution to remove the solvent, washing the solid product by using distilled water and acetone, and fully drying the washed solid product to prepare the nano poly-dopamine modified BN loaded Al2O3And (3) component 2.
(3) Preparation of silane coupling agent grafted Al2O3BN nanocomposite 2: adding a toluene solvent and nano poly dopamine modified BN loaded Al into a reaction bottle2O3The component 2 is added with silane coupling agent 3-glycidyl ether oxypropyl trimethoxy silane after being dispersed uniformly by ultrasonic, and modified BN loaded with Al with nano poly dopamine2O3The mass ratio of the components is 1:1.5-4, the mixture is placed in an oil bath pot and heated to 100-130 ℃, the mixture is stirred at a constant speed for reaction for 6-12h, the solution is decompressed and distilled to remove the solvent, distilled water and acetone are used for washing a solid product, and the solid product is fully dried to prepare the Al grafted by the silane coupling agent2O3BN nanocomposite 2.
(4) Preparation based on BN-Al2O3Modified high thermal conductivity insulating epoxy resin material 2: adding acetone solvent and Al into a reaction bottle2O3Uniformly dispersing the-BN nano composite material 1 and the epoxy resin by ultrasonic, adding a curing agent and a defoaming agent, uniformly stirring, pouring the materials into a film forming die, and performing thermosetting film forming to obtain the BN-Al-based nano composite material based on BN-Al, wherein the mass ratio of the curing agent to the defoaming agent is 5-35:100:40-80:0.5-22O3And 2, a modified high-thermal-conductivity insulating epoxy resin material.
Example 3
(1) Preparation of nano porous BN loaded Al2O3And (3) component: adding distilled water into the reaction bottleAnd nano Al2O3The ultrasonic dispersion instrument comprises an ultrasonic chamber, an ultrasonic chamber upper part and two sides fixedly connected with regulators, wherein the regulators are movably connected with an ultrasonic emitter, a constant temperature heating box is fixedly connected with the lower part of the ultrasonic chamber, a reaction bottle and an outer side fixedly connected with sound insulation layer of the ultrasonic chamber are arranged above the constant temperature heating box, and boric acid and melamine are added after the ultrasonic dispersion is uniform2O3The mass ratio of the three is 100:10-30:6-20, the total mass fraction of the solution is controlled to be 0.5-3 g/L, the solution is heated to 70-100 ℃, the solution is stirred at a constant speed for reaction for 5-10h, the solution is placed in a liquid nitrogen atmosphere for freezing and cooling, a vacuum freeze dryer is used for freezing and drying to remove the solvent, the solid product is placed in an atmosphere resistance furnace, argon is introduced, the heating rate is 5-10 ℃/min, the temperature is raised to 1080-2O3And (3) component.
(2) Preparation of nanometer polydopamine modified BN loaded Al2O3And (3) component: adding distilled water solvent into a reaction bottle, adding Tris-HCl buffer solution to control the pH value of the solution to be 8-9, and adding nano porous BN modified Al2O3Uniformly dispersing the component 1 by ultrasonic, adding dopamine hydrochloride in a mass ratio of 8-15:1, uniformly stirring the mixture at 50-70 ℃ for reaction for 15-25h, filtering the solution to remove the solvent, washing the solid product by using distilled water and acetone, and fully drying to prepare the nano poly-dopamine modified BN loaded Al2O3And (3) component.
(3) Preparation of silane coupling agent grafted Al2O3BN nanocomposite 3: adding a toluene solvent and nano poly dopamine modified BN loaded Al into a reaction bottle2O3After the component 3 is uniformly dispersed by ultrasonic, adding a silane coupling agent 3-glycidyl ether oxypropyltrimethoxysilane and modifying BN (boron nitride) loaded Al with nano poly-dopamine2O3The mass ratio of the components is 1:1.5-4, the mixture is placed in an oil bath pot and heated to 100-130 ℃, the mixture is stirred at a constant speed for reaction for 6-12h, the solution is decompressed and distilled to remove the solvent, distilled water and acetone are used for washing a solid product, and the solid product is fully dried to prepare the Al grafted by the silane coupling agent2O3-BN nanocompositesAnd (3) feeding.
(4) Preparation based on BN-Al2O3Modified high thermal conductive insulating epoxy resin material 3: adding acetone solvent and Al into a reaction bottle2O3Uniformly dispersing the-BN nano composite material 1 and the epoxy resin by ultrasonic, adding a curing agent and a defoaming agent, uniformly stirring, pouring the materials into a film forming die, and performing thermosetting film forming to obtain the BN-Al-based nano composite material based on BN-Al, wherein the mass ratio of the curing agent to the defoaming agent is 5-35:100:40-80:0.5-22O3And 3, a modified high-thermal-conductivity insulating epoxy resin material.
Example 4
(1) Preparation of nano porous BN loaded Al2O3And (4) component: distilled water and nano Al are added into a reaction bottle2O3The ultrasonic dispersion instrument comprises an ultrasonic chamber, an ultrasonic chamber upper part and two sides fixedly connected with regulators, wherein the regulators are movably connected with an ultrasonic emitter, a constant temperature heating box is fixedly connected with the lower part of the ultrasonic chamber, a reaction bottle and an outer side fixedly connected with sound insulation layer of the ultrasonic chamber are arranged above the constant temperature heating box, and boric acid and melamine are added after the ultrasonic dispersion is uniform2O3The mass ratio of the three is 100:10-30:6-20, the total mass fraction of the solution is controlled to be 0.5-3 g/L, the solution is heated to 70-100 ℃, the solution is stirred at a constant speed for reaction for 5-10h, the solution is placed in a liquid nitrogen atmosphere for freezing and cooling, a vacuum freeze dryer is used for freezing and drying to remove the solvent, the solid product is placed in an atmosphere resistance furnace, argon is introduced, the heating rate is 5-10 ℃/min, the temperature is raised to 1080-2O3And (4) component.
(2) Preparation of nanometer polydopamine modified BN loaded Al2O3And (4) component: adding distilled water solvent into a reaction bottle, adding Tris-HCl buffer solution to control the pH value of the solution to be 8-9, and adding nano porous BN modified Al2O3And (4) adding dopamine hydrochloride into the component 4 after ultrasonic dispersion, wherein the mass ratio of the dopamine hydrochloride to the component 4 is 8-15:1, uniformly stirring the mixture at 50-70 ℃ for reaction for 15-25h, filtering the solution to remove the solvent, washing the solid product by using distilled water and acetone, and fully drying the washed solid product to prepare the nano poly-dopamine modified BN loaded Al2O3And (4) component.
(3) Preparation of silane coupling agent grafted Al2O3BN nanocomposite 4: adding a toluene solvent and nano poly dopamine modified BN loaded Al into a reaction bottle2O3And 4, adding a silane coupling agent 3-glycidyl ether oxypropyltrimethoxysilane after ultrasonic dispersion is uniform, and modifying BN (boron nitride) loaded Al with nano poly-dopamine2O3The mass ratio of the components is 1:1.5-4, the mixture is placed in an oil bath pot and heated to 100-130 ℃, the mixture is stirred at a constant speed for reaction for 6-12h, the solution is decompressed and distilled to remove the solvent, distilled water and acetone are used for washing a solid product, and the solid product is fully dried to prepare the Al grafted by the silane coupling agent2O3BN nanocomposite 4.
(4) Preparation based on BN-Al2O3Modified high thermal conductive insulating epoxy resin material 4: adding acetone solvent and Al into a reaction bottle2O3Uniformly dispersing the-BN nano composite material 4 and the epoxy resin by ultrasonic, adding a curing agent and a defoaming agent, uniformly stirring, pouring the materials into a film forming die, and performing thermosetting film forming to obtain the BN-Al-based nano composite material based on BN-Al, wherein the mass ratio of the curing agent to the defoaming agent is 5-35:100:40-80:0.5-22O3And (4) a modified high-thermal-conductivity insulating epoxy resin material.
Example 5
(1) Preparation of nano porous BN loaded Al2O3And (5) component: distilled water and nano Al are added into a reaction bottle2O3The ultrasonic dispersion instrument comprises an ultrasonic chamber, an ultrasonic chamber upper part and two sides fixedly connected with regulators, wherein the regulators are movably connected with an ultrasonic emitter, a constant temperature heating box is fixedly connected with the lower part of the ultrasonic chamber, a reaction bottle and an outer side fixedly connected with sound insulation layer of the ultrasonic chamber are arranged above the constant temperature heating box, and boric acid and melamine are added after the ultrasonic dispersion is uniform2O3The mass ratio of the three is 100:10-30:6-20, the total mass fraction of the solution is controlled to be 0.5-3 g/L, the solution is heated to 70-100 ℃, the solution is stirred at a constant speed for reaction for 5-10h, the solution is placed in a liquid nitrogen atmosphere for freezing and cooling, a vacuum freeze dryer is used for freezing and drying to remove the solvent, the solid product is placed in an atmosphere resistance furnace, argon is introduced into the atmosphere resistance furnace, and the solvent is removedHeating to 1080-1150 ℃ at the heating rate of 5-10 ℃/min, calcining for 3-5h, wherein the calcined product is the nano porous BN loaded Al2O3And (5) component.
(2) Preparation of nanometer polydopamine modified BN loaded Al2O3And (5) component: adding distilled water solvent into a reaction bottle, adding Tris-HCl buffer solution to control the pH value of the solution to be 8-9, and adding nano porous BN modified Al2O3Uniformly dispersing the component 1 by ultrasonic, adding dopamine hydrochloride in a mass ratio of 8-15:1, uniformly stirring the mixture at 50-70 ℃ for reaction for 15-25h, filtering the solution to remove the solvent, washing the solid product by using distilled water and acetone, and fully drying to prepare the nano poly-dopamine modified BN loaded Al2O3And (5) component.
(3) Preparation of silane coupling agent grafted Al2O3BN nanocomposite 5: adding a toluene solvent and nano poly dopamine modified BN loaded Al into a reaction bottle2O3And 5, adding a silane coupling agent 3-glycidyl ether oxypropyltrimethoxysilane after uniform ultrasonic dispersion and modifying BN (boron nitride) loaded Al with nano poly-dopamine2O3The mass ratio of the components is 1:1.5-4, the mixture is placed in an oil bath pot and heated to 100-130 ℃, the mixture is stirred at a constant speed for reaction for 6-12h, the solution is decompressed and distilled to remove the solvent, distilled water and acetone are used for washing a solid product, and the solid product is fully dried to prepare the Al grafted by the silane coupling agent2O3-BN nanocomposite 5.
(4) Preparation based on BN-Al2O3Modified high thermal conductive insulating epoxy resin material 5: adding acetone solvent and Al into a reaction bottle2O3Uniformly dispersing the-BN nano composite material 5 and the epoxy resin by ultrasonic, adding a curing agent and a defoaming agent, uniformly stirring, pouring the materials into a film forming die, and performing thermosetting film forming to obtain the BN-Al-based nano composite material based on BN-Al, wherein the mass ratio of the curing agent to the defoaming agent is 5-35:100:40-80:0.5-22O3And 5, a modified high-thermal-conductivity insulating epoxy resin material.
Examples insulation Performance testing
Figure BDA0002487468480000101
Examples Heat transfer Performance testing
Figure BDA0002487468480000111
In summary, the one is based on BN-Al2O3Modified high-thermal-conductivity insulating epoxy resin material prepared from nano Al2O3As a carrier, preparing the porous nanometer BN loaded Al with huge specific surface by freeze drying and high-temperature thermal decomposition2O3Loading Al on BN by in-situ polymerization2O3The surface of the porous nanometer BN is generated with nanometer polydopamine, B atoms and N atoms of the nanometer BN alternately form a hexagonal annular grid structure, the specific surface of the porous nanometer BN is very large, the porous nanometer BN is easy to interact with a benzene ring structure of the polydopamine through pi-pi bond conjugation and van der Waals force, the polydopamine is firmly combined on the surface of the nanometer BN, and then the Al reacts with rich phenolic hydroxyl of the polydopamine through 3-glycidyl ether oxypropyltrimethoxysilane, so that the Al reacts with rich phenolic hydroxyl of the polydopamine2O3the-BN nanocomposites contain a large number of epoxy groups.
Al2O3The poly-dopamine molecules on the surface of the-BN nano composite material have good compatibility with the epoxy resin, and in the process of curing the epoxy resin, the epoxy group and Al of the epoxy resin2O3Thermal curing and crosslinking a large number of epoxy groups of the-BN nanocomposite material to obtain Al2O3the-BN nano composite material is successfully grafted into the molecular chain of the epoxy resin, thereby enhancing the nano Al2O3And the compatibility and the dispersibility of BN and the epoxy resin, and the epoxy resin is endowed with excellent insulating property and heat-conducting property.

Claims (7)

1. Based on BN-Al2O3The modified high-thermal-conductivity insulating epoxy resin material comprises the following raw materials and components, and is characterized in that: al (Al)2O3The epoxy resin-BN nano composite material is prepared from BN nano composite material, epoxy resin, a curing agent and a defoaming agent according to the mass ratio of 5-35:100:40-80: 0.5-2.
2. BN-Al based on according to claim 12O3The modified high-thermal-conductivity insulating epoxy resin material is characterized in that: the BN-Al2O3The preparation method of the nano composite material comprises the following steps:
(1) adding nano Al into distilled water2O3Placing the solution in an ultrasonic dispersion instrument, adding boric acid and melamine after ultrasonic dispersion is uniform, heating to 70-100 ℃ for reaction for 5-10h, freeze-drying the solution to remove the solvent, placing the solid product in an atmosphere resistance furnace, introducing argon, raising the temperature to 1080-1150 ℃ at the rate of 5-10 ℃/min, calcining for 3-5h, wherein the calcined product is the nano porous BN loaded Al2O3；
(2) Adding Tris-HCl buffer solution into distilled water solvent to control the pH value of the solution to be 8-9, and then adding nano porous BN modified Al2O3Adding dopamine hydrochloride after ultrasonic dispersion is uniform, reacting for 15-25h at 50-70 ℃, filtering, washing and drying to prepare the nanometer polydopamine modified BN loaded Al2O3；
(3) Adding nano poly dopamine modified BN loaded Al into toluene solvent2O3Adding a silane coupling agent after uniform ultrasonic dispersion, heating to 100-130 ℃, reacting for 6-12h, removing the solvent, washing and drying to prepare the silane coupling agent grafted Al2O3-BN nanocomposite.
3. BN-Al based on according to claim 22O3The modified high-thermal-conductivity insulating epoxy resin material is characterized in that: the nano Al2O3The mass ratio of the boric acid to the melamine is 100:10-30:6-20, and the total mass fraction of the solution is controlled to be 0.5-3 g/L.
4. BN-Al based on according to claim 22O3The modified high-thermal-conductivity insulating epoxy resin material is characterized in that: the ultrasonic dispersion instrument comprises an ultrasonic chamber, a tone fixedly connected to the upper part and the two sides of the ultrasonic chamberThe section device and the regulator are movably connected with an ultrasonic emitter and a constant temperature heating box which is fixedly connected below the ultrasonic chamber, and a reaction bottle and a sound insulation layer which is fixedly connected outside the ultrasonic chamber are arranged above the constant temperature heating box.
5. BN-Al based on according to claim 22O3The modified high-thermal-conductivity insulating epoxy resin material is characterized in that: the nano-porous BN modified Al2O3The mass ratio of the dopamine hydrochloride to the dopamine hydrochloride is 8-15: 1.
6. BN-Al based on according to claim 22O3The modified high-thermal-conductivity insulating epoxy resin material is characterized in that: the silane coupling agent is 3-glycidyl ether oxypropyltrimethoxysilane and is modified with nanometer polydopamine to load BN with Al2O3The mass ratio of (A) to (B) is 1: 1.5-4.
7. BN-Al based on according to claim 12O3The modified high-thermal-conductivity insulating epoxy resin material is characterized in that: based on BN-Al2O3The preparation method of the modified high-thermal-conductivity insulating epoxy resin material comprises the following steps:
(1) adding Al to acetone solvent2O3Uniformly dispersing the-BN nano composite material and the epoxy resin by ultrasonic, adding a curing agent and a defoaming agent, uniformly stirring, pouring the materials into a film forming die, and performing thermal curing to form a film to prepare the BN-Al-based nano composite material2O3Modified high heat-conducting insulating epoxy resin material.
CN202010395743.9A 2020-05-12 2020-05-12 Based on BN-Al2O3Modified high-thermal-conductivity insulating epoxy resin material and preparation method thereof Withdrawn CN111500019A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010395743.9A CN111500019A (en) 2020-05-12 2020-05-12 Based on BN-Al2O3Modified high-thermal-conductivity insulating epoxy resin material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010395743.9A CN111500019A (en) 2020-05-12 2020-05-12 Based on BN-Al2O3Modified high-thermal-conductivity insulating epoxy resin material and preparation method thereof

Publications (1)

Publication Number Publication Date
CN111500019A true CN111500019A (en) 2020-08-07

Family

ID=71871841

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010395743.9A Withdrawn CN111500019A (en) 2020-05-12 2020-05-12 Based on BN-Al2O3Modified high-thermal-conductivity insulating epoxy resin material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN111500019A (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113636529A (en) * 2021-07-15 2021-11-12 西安理工大学 Preparation method of boron nitride and aluminum oxide heat-conducting filler
CN113698736A (en) * 2021-10-09 2021-11-26 深圳市鑫奕龙达电子有限公司 Halogen-free flame-retardant heat-conducting wire insulating layer and preparation method thereof
CN114015338A (en) * 2021-11-18 2022-02-08 北京世纪航凯电力科技股份有限公司 Durable weather-proof insulating heat-conducting heat-reflecting coating and preparation method thereof
CN114806081A (en) * 2022-03-11 2022-07-29 华中科技大学 Polymer composite material based on aromatic compound modified heat-conducting and insulating composite powder and preparation thereof
CN115850913A (en) * 2022-12-02 2023-03-28 西南石油大学 Preparation method of environment-friendly nano intumescent flame retardant mBN @ LDH @ PATP and epoxy resin nano composite material
CN116622283A (en) * 2023-07-24 2023-08-22 广东优冠生物科技有限公司 Fireproof flame-retardant shell substrate coating and preparation method thereof
WO2024004528A1 (en) * 2022-06-30 2024-01-04 パナソニックＩｐマネジメント株式会社 Composite material, application product thereof, and composite material manufacturing method
WO2024004527A1 (en) * 2022-06-30 2024-01-04 パナソニックＩｐマネジメント株式会社 Composite material, product resulting from applying said composite material, and method for producing composite material

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113636529A (en) * 2021-07-15 2021-11-12 西安理工大学 Preparation method of boron nitride and aluminum oxide heat-conducting filler
CN113698736A (en) * 2021-10-09 2021-11-26 深圳市鑫奕龙达电子有限公司 Halogen-free flame-retardant heat-conducting wire insulating layer and preparation method thereof
CN113698736B (en) * 2021-10-09 2023-09-12 深圳市永杰诚电子有限公司 Halogen-free flame-retardant heat-conducting wire insulating layer and preparation method thereof
CN114015338A (en) * 2021-11-18 2022-02-08 北京世纪航凯电力科技股份有限公司 Durable weather-proof insulating heat-conducting heat-reflecting coating and preparation method thereof
CN114806081A (en) * 2022-03-11 2022-07-29 华中科技大学 Polymer composite material based on aromatic compound modified heat-conducting and insulating composite powder and preparation thereof
WO2024004528A1 (en) * 2022-06-30 2024-01-04 パナソニックＩｐマネジメント株式会社 Composite material, application product thereof, and composite material manufacturing method
WO2024004527A1 (en) * 2022-06-30 2024-01-04 パナソニックＩｐマネジメント株式会社 Composite material, product resulting from applying said composite material, and method for producing composite material
CN115850913A (en) * 2022-12-02 2023-03-28 西南石油大学 Preparation method of environment-friendly nano intumescent flame retardant mBN @ LDH @ PATP and epoxy resin nano composite material
CN115850913B (en) * 2022-12-02 2024-03-08 西南石油大学 Preparation method of environment-friendly nano intumescent flame retardant mBN@LDH@PATP and epoxy resin nanocomposite
CN116622283A (en) * 2023-07-24 2023-08-22 广东优冠生物科技有限公司 Fireproof flame-retardant shell substrate coating and preparation method thereof
CN116622283B (en) * 2023-07-24 2023-11-07 广东优冠生物科技有限公司 Fireproof flame-retardant shell substrate coating and preparation method thereof

Similar Documents

Publication Publication Date Title
CN111500019A (en) Based on BN-Al2O3Modified high-thermal-conductivity insulating epoxy resin material and preparation method thereof
Wang et al. Thermal conductivity improvement of epoxy composite filled with expanded graphite
CN110054864B (en) High-thermal-conductivity composite filler and preparation method of polymer-based composite material thereof
CN105860315B (en) A kind of preparation method of hexagonal boron nitride/poly styrene composite material
CN110903608A (en) High-thermal-conductivity epoxy composite material and preparation method thereof
CN113004474B (en) Multi-walled carbon nanotube/barium titanate/polydicyclopentadiene composite material based on front-end ring-opening metathesis polymerization and preparation method thereof
CN112608565A (en) High-thermal-conductivity graphene heat dissipation film and preparation method thereof
CN107868465A (en) A kind of heat conductive insulating composite with anisotropic structure and preparation method thereof
CN112225986B (en) High-thermal-conductivity flame-retardant polyolefin-based composite material and preparation method thereof
CN112812318A (en) High-dielectric nano boron nitride modified epoxy resin composite material and preparation method thereof
CN113881190A (en) Epoxy resin composite material for packaging power electronic transformer and preparation method thereof
CN106146866A (en) A kind of polyimide composite film and preparation method thereof
CN111334001A (en) High-thermal-conductivity boron nitride modified epoxy resin insulating material and preparation method thereof
CN106753213A (en) A kind of PCB organic silicon electronic potting adhesive with excellent moistureproof and waterproof performance
CN111621253A (en) Graphite-based high-strength heat-conducting epoxy resin adhesive and preparation method thereof
CN111484626A (en) Modified boron nitride grafted waterborne acrylic resin insulating material and preparation method thereof
CN108264765B (en) Preparation method of toughened heat-conducting insulating cyanate resin-based composite material
CN107266864A (en) It is a kind of for insulating materials of LED package and preparation method thereof
CN112662313B (en) Preparation method of polyphosphazene modified polyesterimide water-based heat-conducting coating
CN106751477A (en) A kind of high-molecular-weight epoxy Heat Conduction Material and preparation method thereof
Weng et al. Improved thermal conductivities of epoxy resins containing surface functionalized BN nanosheets
Zhang et al. Preparation of poly glycidyl methacrylate (PGMA) chain-grafted boron nitride/epoxy composites and their thermal conductivity properties
CN113416510A (en) Epoxy resin pouring sealant and preparation method thereof
CN113278290A (en) High-temperature-resistant silicon rubber and preparation method thereof
Zheng et al. Improved thermal conductivity and excellent electrical insulation properties of polysiloxane nanocomposite-incorporated functional boron nitride sheets via in situ polymerization

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WW01 Invention patent application withdrawn after publication

Application publication date: 20200807

WW01 Invention patent application withdrawn after publication