WO2019095397A1

WO2019095397A1 - Highly thermally and electrically conductive environmentally-friendly adhesive and preparation method therefor

Info

Publication number: WO2019095397A1
Application number: PCT/CN2017/112000
Authority: WO
Inventors: 杨定宽
Original assignee: 苏州锐特捷化工制品有限公司
Priority date: 2017-11-17
Filing date: 2017-11-21
Publication date: 2019-05-23
Also published as: CN107699179A

Abstract

Disclosed is a highly thermally and electrically conductive environmentally-friendly adhesive comprising the following components: a modified epoxy resin, konjak glucomannan, chitosan, a thermally conductive filler, an electrically conductive filler, a diluent, a curing agent, a curing accelerator, and a rheology controller. The adhesive effectively improves the compatibility between the fillers and the resin as a matrix, and improves the dispersion effect and the environmental protection properties.

Description

High thermal conductivity conductive environment-friendly adhesive and preparation method thereof

Technical field

The invention relates to the field of chemical products, in particular to a high thermal conductivity conductive environmentally friendly adhesive.

Background technique

Conductive and thermal conductive adhesive is a special conductive polymer composite material which can effectively bond various materials and has electrical and thermal conductivity. The conductive and thermal conductive adhesives on the market are usually composed of conductive and thermally conductive filler materials and polymer resins. . However, the existing conductive and thermal conductive adhesives have poor filling and dispersing properties due to the aggregation of the conductive and thermally conductive fillers, which limits the electrical and thermal conductivity, especially the thermal conductivity, and the thermal conductivity is usually lower than 2w/(m·K). Above and below 0.2w/(m·K), the thermal conductivity is low and cannot meet the needs of use. Further, the polymer resin has disadvantages such as poor toughness and environmental protection.

Summary of the invention

The technical problem mainly solved by the invention is to provide a high thermal conductivity conductive environment-friendly adhesive and a preparation method thereof, which can solve the above problems of the existing heat conductive conductive adhesive.

In order to solve the above technical problem, a technical solution adopted by the present invention is to provide a high thermal conductivity conductive environmentally friendly adhesive, comprising the following components by weight: 40-50 parts of modified epoxy resin, konjac glucomannan 20~ 30 parts, 15-20 parts of chitosan, 15-25 parts of heat conductive filler, 10-15 parts of conductive filler, 5-8 parts of diluent, 5-8 parts of curing agent, 1-3 parts of curing accelerator, rheology control 3 to 5 parts of the agent.

In a preferred embodiment of the present invention, the modified epoxy resin is a nitrile rubber toughened modified epoxy Resin.

In a preferred embodiment of the invention, the thermally conductive filler comprises Ag-AIN particles, aluminum nitride and aluminum oxide in a mass ratio of 5 to 7:3 to 5:1 to 3.

In a preferred embodiment of the present invention, the conductive filler comprises silver-plated multi-walled carbon nanotubes and micron silver powder in a mass ratio of 2 to 3:2 to 4.

In order to solve the above technical problem, another technical solution adopted by the present invention is to provide a method for preparing a high thermal conductivity conductive environmentally friendly adhesive, comprising the following steps:

(1) Preparation of Ag-AIN particles: The A1N particles are first placed in a muffle furnace for high temperature treatment, then washed with an acidic cleaning solution, rinsed with cooled deionized water, dried, and finally deposited on the surface by palladium-free electroless plating. a layer of dense metal Ag plating to obtain the Ag-AIN particles;

(2) Preparation of thermally conductive mixed components: weigh 1/4 to 1/3 of the modified amount of modified epoxy resin, Ag-AIN particles prepared in step (1) and other thermally conductive fillers of formula amount and 1/4~ 1/3 of the formula amount of diluent is added to a vacuum mixing agitator, and stirred and mixed under a certain degree of vacuum to obtain a thermally conductive mixed component;

(3) Preparation of silver-plated carbon nanotubes: Weigh a formula of multi-walled carbon nanotubes into a flask containing an acidified solution, sonicate, wash to neutrality and dry, and finally use palladium-free electroless plating on the surface. And depositing a dense metal Ag plating layer in the tube to obtain the silver-plated carbon nanotube;

(4) Preparation of conductive mixed components: weigh 1/4 to 1/3 of the modified amount of modified epoxy resin, silver-plated carbon nanotubes prepared in step (3) and other conductive fillers of the formula and 1/4 ~ 1/3 of the formula amount of diluent is added to a vacuum mixing agitator, stirred and mixed under a certain degree of vacuum to obtain a conductive mixed component;

(5) Preparation of adhesive: weighing the remaining formula of the modified epoxy resin, the thermally conductive mixed component prepared in the step (2), the conductive mixed component prepared in the step (3), and the formula amount of konjac glucomannan Glycan, formula amount of chitosan, formula amount of rheology control agent and remaining formula amount of diluent, stirring under vacuum The mixture is uniformly mixed, and then a formula amount of a curing agent and a curing accelerator are added, and the mixture is stirred under vacuum to obtain the adhesive.

In a preferred embodiment of the present invention, in the step (1), the high temperature treatment conditions are: temperature 600 to 800 ° C, time 3 to 5 h; the acidic cleaning liquid is potassium perchromate and high manganese A mixture of potassium acid in a molar volume of 1:0.5.

In a preferred embodiment of the present invention, in the step (2), the conditions of the vacuum stirring and mixing are: a vacuum degree of 0.1 to 0.3 MPa, a stirring rate of 300 to 400 r/min, and a stirring time of 35 to ～ at room temperature. 45min.

In a preferred embodiment of the present invention, in the step (3), the acidifying solution is a mixed acid of concentrated sulfuric acid and concentrated hydrochloric acid having a mass concentration of 55-65%; the ultrasonic treatment method is: 70~ Ultrasonic treatment at 80 ° C for 1.5 ~ 2h.

In a preferred embodiment of the present invention, in the step (4), the conditions of the vacuum stirring and mixing are: a vacuum degree of 0.1 to 0.3 MPa, a stirring rate of 300 to 400 r/min, and a stirring time of 35 to ～ at room temperature. 45min.

In a preferred embodiment of the present invention, in the step (5), the conditions of the vacuum stirring and mixing are: a vacuum degree of 0.1 to 0.3 MPa, a stirring rate of 600 to 1000 r/min, and a stirring time of 20 at room temperature. ~40min.

The invention has the beneficial effects that the invention selects the heat conductive filler and the conductive multi-wall carbon nanotube by electroless silver plating through reasonable raw material selection and formulation design, especially the selection of the heat conductive filler and the conductive filler, and then electrically conductive filler and conductive The filler is distributed in a part of the matrix resin and mixed into a mixed component, and the other matrix components are mixed, thereby effectively improving the compatibility between the nano-scale thermal conductive filler and the conductive filler and the matrix resin, thereby improving the dispersion effect, thereby maximizing the functionality thereof. ; through epoxy resin and konjac glucomannan The combination with chitosan broadens the performance of the substrate while improving environmental friendliness.

Detailed ways

The preferred embodiments of the present invention are described in detail below, so that the advantages and features of the present invention can be more readily understood by those skilled in the art.

Embodiments of the invention include:

Example 1

A high thermal conductivity conductive environmentally friendly adhesive comprising the following components by weight: 40 parts of modified epoxy resin, 20 parts of konjac glucomannan, 15 parts of chitosan, 15 parts of thermally conductive filler, 10 parts of conductive filler, diluted 5 parts of the agent, 5 parts of the curing agent, 1 part of the curing accelerator, and 3 parts of the rheology control agent.

Wherein, the modified epoxy resin is a nitrile rubber toughened modified epoxy resin.

The thermally conductive filler includes Ag-AIN particles, aluminum nitride, and aluminum oxide in a mass ratio of 5:3:1.

The conductive filler includes silver-plated multi-walled carbon nanotubes and micron silver powder in a mass ratio of 2:2.

The preparation method of the above high thermal conductivity conductive environment-friendly adhesive comprises the following steps:

(1) Preparation of Ag-AIN particles: First, the A1N particles were placed in a muffle furnace at 600 ° C for 5 h, then washed with an acidic cleaning solution and rinsed with cooled deionized water, vacuum dried, and finally palladium-free electroless plating. The method deposits a dense metal Ag plating on the surface thereof to obtain the Ag-AIN particles;

The acidic cleaning solution is a mixture of potassium perchromate and potassium permanganate in a molar volume of 1:0.5;

(2) Preparation of thermally conductive mixed components: weigh 1/4 to 1/3 of the amount of modified epoxy resin, step (1) The Ag-AIN particles prepared in the formula and other thermally conductive fillers of the formula amount and the diluent of 1/4 to 1/3 of the formula amount are added to the vacuum mixing stirrer at room temperature at a vacuum of 0.1 to 0.3 MPa at 300 r/min. Stirring and mixing for 45 min at a rate to obtain a thermally conductive mixed component;

Wherein, the acidification liquid is a mixed acid of concentrated sulfuric acid and concentrated hydrochloric acid having a mass concentration of 55%; the ultrasonic treatment method is: ultrasonic treatment at 70 ° C for 2 h;

(4) Preparation of conductive mixed components: weigh 1/4 to 1/3 of the modified amount of modified epoxy resin, silver-plated carbon nanotubes prepared in step (3) and other conductive fillers of the formula and 1/4 ～ 3% of the formula amount of diluent is added to a vacuum mixer, and the mixture is stirred and mixed at a rate of 300 r/min for 45 min at room temperature under a vacuum of 0.1 to 0.3 MPa to obtain a conductive mixed component;

(5) Preparation of adhesive: weighing the remaining formula of the modified epoxy resin, the thermally conductive mixed component prepared in the step (2), the conductive mixed component prepared in the step (3), and the formula amount of konjac glucomannan The polysaccharide, the formula amount of chitosan, the formula amount of the rheology control agent and the remaining formula amount of the diluent are stirred and mixed at a rate of 600 r/min for 40 min at room temperature under a vacuum of 0.1 to 0.3 MPa until homogeneous, and then added. A formulation amount of a curing agent and a curing accelerator are stirred and mixed under the same vacuum conditions to obtain the adhesive.

Example 2

A high thermal conductivity conductive environmentally friendly adhesive comprising the following components by weight: 50 parts of modified epoxy resin, 30 parts of konjac glucomannan, 20 parts of chitosan, 25 parts of thermally conductive filler, 15 parts of conductive filler, diluted 8 parts of the agent, 8 parts of the curing agent, 3 parts of the curing accelerator, and 5 parts of the rheology control agent.

The thermally conductive filler includes Ag-AIN particles, aluminum nitride, and aluminum oxide in a mass ratio of 7:5:3.

The conductive filler includes silver-plated multi-walled carbon nanotubes and micron silver powder in a mass ratio of 3:4.

(1) Preparation of Ag-AIN particles: First, the A1N particles were placed in a muffle furnace at 800 ° C for 3 h, then washed with an acidic cleaning solution and rinsed with cooled deionized water, vacuum dried, and finally palladium-free electroless plating. The method deposits a dense metal Ag plating on the surface thereof to obtain the Ag-AIN particles;

(2) Preparation of thermally conductive mixed components: weigh 1/4 to 1/3 of the modified amount of modified epoxy resin, Ag-AIN particles prepared in step (1) and other thermally conductive fillers of formula amount and 1/4~ 1/3 of the formula amount of diluent is added to a vacuum mixing agitator, and stirred at a rate of 400 r/min under a vacuum of 0.1 to 0.3 MPa for 35 minutes at room temperature to obtain a thermally conductive mixed component;

Wherein the acidification liquid is a mixed acid of concentrated sulfuric acid and concentrated hydrochloric acid having a mass concentration of 65%; the ultrasonic treatment method is: ultrasonic treatment at 80 ° C for 1.5 h;

(4) Preparation of conductive mixed components: weigh 1/4 to 1/3 of the modified amount of modified epoxy resin, silver-plated carbon nanotubes prepared in step (3) and other conductive fillers of the formula and 1/4 ～ 3% of the formula amount of diluent is added to a vacuum mixer, and the mixture is stirred and mixed at a rate of 400 r/min for 35 min at room temperature under a vacuum of 0.1 to 0.3 MPa to obtain a conductive mixed component;

(5) Preparation of adhesive: weighing the remaining formula of the modified epoxy resin, the thermally conductive mixed component prepared in the step (2), the conductive mixed component prepared in the step (3), and the formula amount of konjac glucomannan The polysaccharide, the formula amount of chitosan, the formula amount of the rheology control agent and the remaining formula amount of the diluent are stirred and mixed at a rate of 1000 r/min for 20 min at room temperature under a vacuum of 0.1 to 0.3 MPa until homogeneous, and then added. A formulation amount of a curing agent and a curing accelerator are stirred and mixed under the same vacuum conditions to obtain the adhesive.

The high thermal conductivity conductive environmentally friendly adhesive obtained by the above method has been tested to have a conductivity higher than 8.9 S/cm, a thermal conductivity higher than 3.8 W/(m·K), high bonding strength, and excellent overall performance. .

The invention combines the heat conductive filler and the conductive multi-wall carbon nanotube by electroless silver plating through reasonable raw material selection and formula design, especially the selection of the heat conductive filler and the conductive filler, and then distributes the heat conductive filler and the conductive filler to the partial matrix resin. The mixed component is mixed with other matrix components, which effectively improves the compatibility between the nano-scale thermal conductive filler and the conductive filler and the matrix resin, and improves the dispersion effect, thereby maximizing its functionality; through epoxy resin and konjac The combination of glucomannan and chitosan broadens the performance of the matrix while improving environmental friendliness.

The above description is only the preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes can be made to the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and scope of the present invention are intended to be included within the scope of the present invention.

Claims

A high thermal conductivity conductive environment-friendly adhesive characterized by comprising the following components by weight: 40-50 parts of modified epoxy resin, 20-30 parts of konjac glucomannan, 15-20 parts of chitosan, heat conduction 15 to 25 parts of the filler, 10 to 15 parts of the conductive filler, 5 to 8 parts of the diluent, 5 to 8 parts of the curing agent, 1 to 3 parts of the curing accelerator, and 3 to 5 parts of the rheology control agent.
The high thermal conductivity conductive environmentally friendly adhesive according to claim 1, wherein the modified epoxy resin is a nitrile rubber toughened modified epoxy resin.
The high thermal conductivity conductive environment-friendly adhesive according to claim 1, wherein the thermally conductive filler comprises Ag-AIN particles, aluminum nitride and aluminum oxide in a mass ratio of 5 to 7:3 to 5:1 to 3 .
The high thermal conductivity conductive environmentally friendly adhesive according to claim 1, wherein the conductive filler comprises silver-plated multi-walled carbon nanotubes and micron silver powder in a mass ratio of 2 to 3:2 to 4.
A method for preparing a high thermal conductivity conductive environmentally friendly adhesive according to claim 1, comprising the steps of:

(1) Preparation of Ag-AIN particles: The A1N particles are first placed in a muffle furnace for high temperature treatment, then washed with an acidic cleaning solution, rinsed with cooled deionized water, dried, and finally deposited on the surface by palladium-free electroless plating. a layer of dense metal Ag plating to obtain the Ag-AIN particles;

(2) Preparation of thermally conductive mixed components: weigh 1/4 to 1/3 of the modified amount of modified epoxy resin, Ag-AIN particles prepared in step (1) and other thermally conductive fillers of formula amount and 1/4~ 1/3 of the formula amount of diluent is added to a vacuum mixing agitator, and stirred and mixed under a certain degree of vacuum to obtain a thermally conductive mixed component;

(3) Preparation of silver-plated carbon nanotubes: Weigh a formula of multi-walled carbon nanotubes into a flask containing an acidified solution, sonicate, wash to neutrality and dry, and finally use palladium-free electroless plating on the surface. And depositing a dense metal Ag plating layer in the tube to obtain the silver-plated carbon nanotube;

(4) Preparation of conductive mixed components: weigh 1/4 to 1/3 of the amount of modified epoxy resin, step (3) The silver-plated carbon nanotubes prepared in the formula and the other conductive fillers of the formula amount and the diluent of 1/4 to 1/3 of the formula amount are added into a vacuum mixing agitator, and stirred and mixed under a certain degree of vacuum to obtain a conductive mixed component;

(5) Preparation of adhesive: weighing the remaining formula of the modified epoxy resin, the thermally conductive mixed component prepared in the step (2), the conductive mixed component prepared in the step (3), and the formula amount of konjac glucomannan The polysaccharide, the formula amount of chitosan, the formula amount of the rheology control agent and the remaining formula amount of the diluent are stirred and mixed uniformly under vacuum, and then the formula amount of the curing agent and the curing accelerator are added, and the mixture is stirred under vacuum to obtain a solution. Adhesive.
The method for preparing a high thermal conductivity conductive environment-friendly adhesive according to claim 5, wherein in the step (1), the high temperature treatment condition is: a temperature of 600 to 800 ° C, and a time of 3 to 5 h; The acidic cleaning solution is a mixture of potassium perchromate and potassium permanganate in a molar volume of 1:0.5.
The method for preparing a high thermal conductivity conductive environment-friendly adhesive according to claim 5, wherein in the step (2), the vacuum agitation mixing condition is: at room temperature, the degree of vacuum is 0.1 to 0.3 MPa, The stirring rate is 300-400 r/min, and the stirring time is 35-45 min.
The method for preparing a high thermal conductivity conductive environment-friendly adhesive according to claim 5, wherein in the step (3), the acidifying solution is a mixture of concentrated sulfuric acid and concentrated hydrochloric acid having a mass concentration of 55-65%. The method of sonication is: ultrasonic treatment at 70-80 ° C for 1.5 to 2 h.
The method for preparing a high thermal conductivity conductive environment-friendly adhesive according to claim 5, wherein in the step (4), the vacuum agitation mixing condition is: a vacuum degree of 0.1 to 0.3 MPa at room temperature, The stirring rate is 300-400 r/min, and the stirring time is 35-45 min.
The method for preparing a high thermal conductivity conductive environment-friendly adhesive according to claim 5, wherein in the step (5), the vacuum agitation mixing condition is: a vacuum degree of 0.1 to 0.3 MPa at room temperature. The stirring rate is 600-1000 r/min, and the stirring time is 20-40 min.