Method for preparing organic/inorganic hybrid high thermally conductive and insulating two-component adhesive and method for using the same

Patent metadata

Field	Value
Publication number	US-12570881-B2
Application number	US-202418640216-A
Country	US
Kind code	B2
Filing date	Apr 19, 2024
Priority date	Apr 20, 2023
Publication date	Mar 10, 2026
Grant date	Mar 10, 2026

Abstract

Provided are a method for preparing an organic/inorganic hybrid thermally conductive and insulating two-component adhesive and a method for using the same. The purpose is to solve the problem that thermally conductive adhesives in the prior art cannot meet the requirements of thermal conductivity, good bonding performance and insulation characteristics at the same time. The method includes: 1. preparing an organic phase aluminum dihydrogen phosphate; 2. treating a diamond thermally conductive filler; 3. modifying polyurethane compatible with aluminum dihydrogen phosphate; and 4. preparing an organic/inorganic hybrid insulating two-component adhesive. The use method includes: coating the adhesive onto a surface of a material to be bonded, and bonding; and subjecting a resulting member to be bonded to defoaming, heating, and holding.

First claim

What is claimed is:

1 . A method for preparing an organic/inorganic hybrid thermally conductive and insulating two-component adhesive, comprising the following steps:
1) Preparing an organic phase aluminum dihydrogen phosphate: in parts by mass, weighing 100 parts of an aluminum dihydrogen phosphate aqueous solution, 50-100 parts of ethyl acetate and 0.1-1 part of chromium chloride; subjecting the 100 parts of the aluminum dihydrogen phosphate aqueous solution to reduced pressure distillation to obtain a distilled aluminum dihydrogen phosphate solution; adding the 50-100 parts of the ethyl acetate to the distilled aluminum dihydrogen phosphate solution and stirring; adding the 0.1-1 part of the chromium chloride to a resulting system and stirring until the chromium chloride is dissolved to obtain a first mixture; and finally storing the first mixture in a sealed manner to obtain the organic phase aluminum dihydrogen phosphate; 2) Treating a diamond thermally conductive filler: subjecting diamond particles to sintering and acid treatment in sequence to obtain acid-treated diamond particles; adding the acid-treated diamond particles to a solution of lithium aluminum hydride and sodium borohydride in tetrahydrofuran; subjecting a resulting system to a reflux reaction; and finally washing and air drying a resulting reaction product to obtain a treated diamond thermally conductive filler; wherein in the solution of lithium aluminum hydride and sodium borohydride in tetrahydrofuran, a mass ratio of the lithium aluminum hydride to the sodium borohydride is in a range of 1:1 to 1:3, and a total mass percentage of the lithium aluminum hydride and the sodium borohydride is in a range of 5% to 10%; 3) Modifying a polyurethane compatible with aluminum dihydrogen phosphate: 3.1) mixing spherical aluminum oxide particles with an isopropanol solution to obtain a second mixture; adding a mixed solution of sodium tetrahydroaluminate and hydrogen peroxide to the second mixture; subjecting a resulting mixed system to reaction; and finally cleaning and drying a resulting reaction product to obtain a pretreated aluminum oxide; wherein in the mixed solution of sodium tetrahydroaluminate and hydrogen peroxide, a mass ratio of the sodium tetrahydroaluminate to the hydrogen peroxide is in a range of 1:1 to 1:3, and a total mass percentage of the sodium tetrahydroaluminate and the hydrogen peroxide is in a range of 10% to 20%; and 3.2) in parts by mass, weighing 100 parts of a polyurethane adhesive isocyanate A component and 2-5 parts of the pretreated aluminum oxide; and mixing the 2-5 parts of the pretreated aluminum oxide and the 100 parts of the polyurethane adhesive isocyanate A component under ultrasound to obtain the polyurethane compatible with aluminum dihydrogen phosphate; 4) Preparing an organic/inorganic hybrid insulating two-component adhesive: 4.1) in parts by mass, weighing 100 parts of the organic phase aluminum dihydrogen phosphate and 50-400 parts of the polyurethane compatible with aluminum dihydrogen phosphate; adding the 50-400 parts of the polyurethane compatible with aluminum dihydrogen phosphate to the 100 parts of the organic phase aluminum dihydrogen phosphate, and mixing; and finally packaging a resulting mixture separately to obtain an organic/inorganic hybrid insulating adhesive A component; and 4.2) in parts by mass, weighing 100 parts of a polyurethane adhesive hydroxyl-terminated curing agent B component and 50-200 parts of the treated diamond thermally conductive filler; adding the 50-200 parts of the treated diamond thermally conductive filler to the 100 parts of the polyurethane adhesive hydroxyl-terminated curing agent B component, and mixing to obtain a third mixture; and finally packaging the third mixture separately to obtain an organic/inorganic hybrid insulating adhesive B component; and forming the organic/inorganic hybrid thermally conductive and insulating two-component adhesive from the organic/inorganic hybrid insulating adhesive A component and the organic/inorganic hybrid insulating adhesive B component.

2 . The method of claim 1 , wherein in step 1), a mass percentage of the aluminum dihydrogen phosphate aqueous solution is in a range of 40% to 60%; and
in step 1), subjecting the aluminum dihydrogen phosphate aqueous solution to the reduced pressure distillation is performed at a pressure of 0.1 Pa to 1 Pa, a rotating speed of 60 r/min to 80 r/min and a temperature of 75° C. to 80° C. in a rotary evaporator, until no water is evaporated out.

3 . The method of claim 1 , wherein the diamond particles have an average particle size of 5 μm to 20 μm; and in step 3.1), the spherical aluminum oxide particles have an average particle size of 30 nm to 50 nm.

4 . The method of claim 1 , wherein in step 2), subjecting diamond particles to sintering and acid treatment in sequence is performed as follows: subjecting the diamond particles to the sintering at a temperature of 350° C. to 400° C. in an air atmosphere for 20 min to 30 min to obtain sintered diamond particles; adding the sintered diamond particles into a mixed acid, and subjecting a resulting system to reaction at a temperature of 100° C. to 120° C. for 12 h to 16 h; washing a resulting reaction product with a 5% to 10% of lithium hydroxide solution and anhydrous ethanol under ultrasound at a power of 400 w to 600 w for 1 h to 2 h; and finally drying a resulting washed product to obtain the acid-treated diamond particles.

5 . The method of claim 4 , wherein the mixed acid is a mixture of sulfuric acid, chromic acid and nitric acid, and a volume ratio of the sulfuric acid to the chromic acid is in a range of 1:0.5 to 1:1 and a volume ratio of the sulfuric acid to the nitric acid is in a range of 1:1 to 1:2; and a mass percentage of the sulfuric acid is in a range of 80% to 98.4%, a mass percentage of the chromic acid is in a range of 50% to 65%, and a mass percentage of the nitric acid is in a range of 50% to 65%.

6 . The method of claim 1 , wherein in step 2), the reflux reaction is performed at a temperature of 40° C. to 50° C. for 2 h to 4 h.

7 . The method of claim 1 , wherein in step 3.1), a ratio of a mass of the spherical aluminum oxide particles to a volume of the isopropanol solution is in a range of 1 g: 50 mL to 1 g: 100 mL; in step 3.1), a ratio of the mass of the spherical aluminum oxide particles to a volume of the mixed solution of sodium tetrahydroaluminate and hydrogen peroxide is in a range of 1 g: 5 mL to 1 g: 10 mL; and in step 3.1), the reaction is performed at a temperature of 60° C. to 80° C. under stirring for 1 h to 2 h.

8 . A method for using the organic/inorganic hybrid thermally conductive and insulating two-component adhesive prepared by the method of claim 1 , comprising the following steps:
in parts by mass, weighing 100 parts of the organic/inorganic hybrid insulating adhesive A component and 50-100 parts of the organic/inorganic hybrid insulating adhesive B component; adding the 50-100 parts of the organic/inorganic hybrid insulating adhesive B component to the 100 parts of the organic/inorganic hybrid insulating adhesive A component, and mixing to obtain the organic/inorganic hybrid thermally conductive and insulating two-component adhesive; coating the organic/inorganic hybrid thermally conductive and insulating two-component adhesive onto a surface of a material to be bonded, and bonding to obtain a member to be bonded; subjecting the member to be bonded to defoaming by standing under conditions of vacuum pressure not less than 10-1 Pa and ambient temperature for 5 min to 10 min to obtain a defoamed member to be bonded; and heating the defoamed member to be bonded to a temperature of 80° C. to 100° C. at a heating rate of 5° C./h to

Assignees

• Harbin Inst Technology
• Hit Zhengzhou Res Institute

Inventors

• Cao Wenxin
• Zhu Jiaqi
• Gao Ge
• Zhao Yuwei
• Wang Zhuochao
• Zhao Kunlong
• Liu Yingqi
• Zhang Tianyu
• Li Xiaohui

Classifications

• C09J2475/00

  Presence of polyurethane · CPC title

• C09J5/00

  Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers · CPC title

• C08K2201/005

  Additives being defined by their particle size in general · CPC title

• C08K2201/001

  Conductive additives · CPC title

• C08K2003/327

  Aluminium phosphate · CPC title