WO2018108028A1

WO2018108028A1 - High-strength thermally conductive insulation material

Info

Publication number: WO2018108028A1
Application number: PCT/CN2017/115070
Authority: WO
Inventors: 顾建强
Original assignee: 顾建强
Priority date: 2016-12-13
Filing date: 2017-12-07
Publication date: 2018-06-21
Also published as: DE202017006842U1; CN106751506A

Abstract

A high-strength thermally conductive insulation material, comprising a thermally conductive insulation material base and a high-strength system, the amount of high-strength system added being 3.2-3.4% of the weight of the thermally conductive insulation material; the thermally conductive insulation material base comprises the following components in parts by weight: 12.5-12.7 parts of aluminium oxide, 5.5-5.7 parts of magnesium oxide, 2.1-2.3 parts of silicon carbide, 3.1-3.3 parts of silane coupling agent, 2.4-2.6 parts of calcium nitrate, 4.1-4.3 parts of hydroquinone, 3.8-4 parts of nickel acetate, 12-14 parts of ethanol, 14-16 parts of epoxy resin, 5.1-5.3 parts of dimethyl acrylamide, 2.2-2.4 parts of sodium metasilicate, and 6.1-6.3 parts of benzotriazole. The addition of the high-strength system in the high-strength thermally conductive insulation material improves the tensile strength, bending strength, notched impact strength, thermal conduction coefficient, heat resistance, and anti-static properties of the thermally conductive insulation material.

Description

[Name of invention established by ISA in accordance with Rule 37.2] High-strength thermally conductive insulation material

Technical field

The invention belongs to the technical field of polymer materials, and particularly relates to a high-strength heat-conductive insulating material.

Background technique

The thermally conductive polymer-based composite material is a multi-phase composite system having a certain heat conduction function obtained by using a polymer as a matrix and a thermally conductive substance as a filler. It has both thermal conductivity and many excellent properties of polymer materials. It can adjust the thermal conductivity, electrical conductivity and mechanical properties of materials in a wide range, so it has broad application prospects.

Traditional thermal materials are mostly metals and metal oxides, as well as other non-metallic materials (such as graphite, carbon black, AlN, SiC, etc.). With the development of science and technology and industrial production, many special heat conduction occasions put forward higher requirements for thermal conductive materials, and it is expected to have more excellent comprehensive properties, such as light weight, strong chemical resistance, excellent electrical insulation, and impact resistance. Easy processing and so on. Due to the excellent corrosion resistance, mechanical properties and electrical insulation properties of polymer materials, polymer materials are gradually used to replace traditional thermal materials. However, polymer materials are mostly poor conductors of heat, with low thermal conductivity, but with thermal conductivity. After the substance, it will become a heat conductive material.

Thermally conductive and insulating polymer matrix composites have received more and more attention and competition research and development due to their excellent comprehensive performance and their special applications in electromagnetic shielding, electronic information, thermal measurement technology, chemical engineering, mechanical engineering and other fields.

Summary of the invention

The technical problem to be solved by the present invention is:

(1) How to increase the tensile strength, bending strength and notched impact strength of the thermally conductive insulating material by adding a high-strength system;

(2) How to improve the technical problem of lowering the thermal conductivity of the thermally conductive insulating material due to the addition of the high-strength system.

The technical solution of the present invention to solve the above technical problems is:

A high-strength thermal conductive insulating material comprising a thermally conductive insulating material matrix and a high-strength system, wherein the high-strength system is added in an amount of 3.2-3.4% by weight of the thermally conductive insulating material; and the thermally conductive insulating material matrix comprises: alumina 12.5-12.7 parts, 5.5-5.7 parts of magnesium oxide, 2.1-2.3 parts of silicon carbide, 3.1-3.3 parts of silane coupling agent, 2.4-2.6 parts of calcium nitrate, 4.1-4.3 parts of hydroquinone, 3.8-4 parts of nickel acetate , 12-14 parts of ethanol, 14-16 parts of epoxy resin, 5.1-5.3 parts of dimethyl acrylamide, 2.2-2.4 parts of sodium metasilicate, 6.1-6.3 parts of benzotriazole; parts by weight of high strength system Including: 8.7-8.9 parts of nano-silica, 21-33 parts of ethoxylated alkylamine, 61-63 parts of methyl hydrogen silicone oil, 4.7-4.9 parts of hydroxypolydimethylsiloxane, vinyl trimethoxy 8.7-8.9 parts of silane, 2.5-2.7 parts of ammonium polyphosphate, 3.2-3.4 parts of nano montmorillonite, 3.5-3.7 parts of fumed silica, 2.6-2.8 parts of γ-aminopropyltriethoxysilane, alkane Phenolic polyoxyethylene ether 5.1-5.3 parts, toughening agent 1.7-1.9 parts, reactive diluent 1.1-1.3 parts, compatibilizer 2.5-2.7 parts, coupling agent 1.2-1.4 parts, leveling agent 1.1-1.3 parts ,mixing 0.3-0.5 parts of a rare earth; nanosilica particle diameter 20-30nm, nanoclays a particle size of 20-30nm.

The preparation method of the high-strength thermal conductive insulating material of the invention is:

(1) Alumina, magnesia, silicon carbide, silane coupling agent, calcium nitrate, hydroquinone, nickel acetate, ethanol, epoxy resin, dimethyl acrylamide, sodium metasilicate, in a set by weight , the benzotriazole is added to the mixer, heated and stirred, and cooled to room temperature; the heating temperature is 40-60 ° C, and the stirring speed is 300-500 rpm;

(2) heating and stirring the components of the high-strength system according to the set weight parts to obtain a high-strength system; the heating temperature is 85-87 ° C, and the stirring speed is 250-300 rpm;

(3) mixing the base of the heat-conducting insulating material with the high-strength system according to the set ratio, heating and stirring under vacuum conditions, cooling to room temperature, curing, that is, obtaining a vacuum degree of 0.08-0.1 MPa, heating temperature of 50-70 ° C .

The technical solution further defined by the present invention is:

The high-strength thermally conductive insulating material, the toughening agent is one or more of a styrene-butadiene thermoplastic elastomer, a chlorinated polyethylene or an ethylene-vinyl acetate copolymer; and the reactive diluent is an alkyl group. One or more mixtures of glycidyl ether, glycidyl octanoate, trimethylolpropane triglycidyl ether, toluene glycidyl ether, castor oil polyglycidyl ether; compatibilizer is maleic anhydride Branch modified polypropylene; the coupling agent is one or one of a vinyl tributyl sulfonyl silane coupling agent, a methyl vinyl dichloro silane coupling agent, a methyl tributyl ketone silane coupling agent Above mixture; leveling agent is isophorone, diacetone alcohol, fluorine modified acrylic acid, phosphate modified acrylic acid, acrylic acid, polydimethylsiloxane, polymethylalkylsiloxane, organic modification One or more mixtures of polysiloxanes.

The beneficial effects of the invention are that the thermally conductive insulating material provided by the invention has the advantages of high strength and good insulation performance. The experimental results show that the high-strength system of the present invention can effectively enhance the tensile strength, bending strength and notched impact strength of the thermally conductive insulating material, and the tensile strength of the thermally conductive insulating material of the present invention can be obtained when the high-strength system is added to the thermally conductive insulating material substrate. Increase by at least 1.5 times, increase bending strength by at least 1.3 times, increase notched impact strength by at least 1.3 times, tensile strength up to 95-98 MPa, flexural strength up to 120-128 MPa, and notched impact strength of 5.5-6 MPa. But "nano silica, ethoxylated alkylamine, methyl hydrogen silicone oil, hydroxy polydimethylsiloxane, vinyl trimethoxysilane, ammonium polyphosphate, chopped glass fiber, nano montmorillonite After the high-strength system consisting of fumed silica, γ-aminopropyltriethoxysilane, alkylphenol ethoxylate and toughening agent, the structure of the thermally conductive insulating material is damaged and collapsed, and the thermal conductivity is The addition of reactive diluents, compatibilizers, coupling agents, leveling agents and mixed rare earth chlorides can improve the compatibility with the thermally conductive insulating material matrix, and make the structure of the thermal conductive insulating material more regular, thermal conductivity Improved, thermal conductivity of 7.5 ~ 7.9. The comprehensive results show that when the high-strength system of the present invention is added in an amount of 3.2-3.4% of the weight of the thermally conductive insulating material, the tensile strength, bending strength, notched impact strength and thermal conductivity of the thermally conductive insulating material can reach an equilibrium point. The tensile strength, bending strength, notched impact strength and thermal conductivity are superior. In addition, the experimental results show that the addition of the high-strength system of the present invention can effectively improve the high temperature resistance of the thermal conductive insulating material, and the heat resistance grade can reach 200-230 ° C; in addition, the antistatic property of the thermal conductive insulating material can be effectively improved, and the obtained Unexpected technical effects. In summary, the present invention can improve the tensile strength, bending strength, notched impact strength, thermal conductivity, high temperature resistance and antistatic property of the thermally conductive insulating material by adding a high strength system.

detailed description

Example 1

This embodiment is a high-strength thermal conductive insulating material comprising a thermally conductive insulating material matrix and a high-strength system. The high-strength system is added in an amount of 3.2% by weight of the thermally conductive insulating material.

The parts by weight of the thermally conductive insulating material substrate include: 12.5 parts of alumina, 5.5 parts of magnesium oxide, 2.1 parts of silicon carbide, 3.1 parts of silane coupling agent, 2.4 parts of calcium nitrate, 4.1 parts of hydroquinone, 3.8 parts of nickel acetate, 12 parts of ethanol, 14 parts of epoxy resin, 5.1 parts of dimethyl acrylamide, 2.2 parts of sodium metasilicate, and 6.1 parts of benzotriazole.

The parts by weight of the high strength system include: 8.7 parts of nano silica, 21 parts of ethoxylated alkylamine, 61 parts of methyl hydrogen silicone oil, 4.7 parts of hydroxypolydimethylsiloxane, vinyl trimethoxy 8.7 parts of silane, 2.5 parts of ammonium polyphosphate, 3.2 parts of nano montmorillonite, 3.5 parts of fumed silica, 2.6 parts of γ-aminopropyltriethoxysilane, 5.1 parts of alkylphenol ethoxylate Toughener 1.7 parts, reactive diluent 1.1 parts, compatibilizer 2.5 parts, coupling agent 1.2 parts, leveling agent 1.1 parts, mixed rare earth chloride 0.3 parts; nano silica particle size 20nm, nano montmorillonite The particle size is 20 nm.

Wherein the toughening agent is a styrene-butadiene thermoplastic elastomer; the reactive diluent is an alkyl glycidyl ether; the compatibilizing agent is a maleic anhydride graft modified polypropylene; and the coupling agent is vinyltributyl ketone oxime a silane coupling agent; the leveling agent is isophorone.

(1) Alumina, magnesia, silicon carbide, silane coupling agent, calcium nitrate, hydroquinone, nickel acetate, ethanol, epoxy resin, dimethyl acrylamide, sodium metasilicate, in a set by weight , the benzotriazole is added to the mixer, heated and stirred, and cooled to room temperature; the heating temperature is 40 ° C, and the stirring speed is 300 rpm;

(2) heating and stirring the components of the high-strength system according to the set weight parts to obtain a high-strength system; the heating temperature is 85 ° C, and the stirring speed is 250 rpm;

(3) Mixing the base of the heat-conducting insulating material with the high-strength system according to the set ratio, heating and stirring under vacuum conditions, cooling to room temperature, and solidifying, that is, the vacuum degree is 0.08 MPa, and the heating temperature is 50 °C.

Example 2

This embodiment is a high-strength thermally conductive insulating material comprising a thermally conductive insulating material matrix and a high-strength system, and the high-strength system is added in an amount of 3.3% by weight of the thermally conductive insulating material.

The parts by weight of the thermally conductive insulating material substrate include: 12.6 parts of alumina, 5.6 parts of magnesium oxide, 2.2 parts of silicon carbide, 3.2 parts of silane coupling agent, 2.5 parts of calcium nitrate, 4.2 parts of hydroquinone, 3.9 parts of nickel acetate, 13 parts of ethanol, 15 parts of epoxy resin, 5.2 parts of dimethyl acrylamide, 2.3 parts of sodium metasilicate, and 6.2 parts of benzotriazole.

The parts by weight of the high strength system include: 8.8 parts of nano silica, 22 parts of ethoxylated alkylamine, 62 parts of methyl hydrogen silicone oil, 4.8 parts of hydroxypolydimethylsiloxane, vinyl trimethoxy 8.8 parts of silane, 2.6 parts of ammonium polyphosphate, 3.3 parts of nano montmorillonite, 3.6 parts of fumed silica, 2.7 parts of γ-aminopropyltriethoxysilane, 5.2 parts of alkylphenol ethoxylate 1.8 parts of toughener, 1.2 parts of reactive diluent, 2.6 parts of compatibilizer, 1.3 parts of coupling agent, 1.2 parts of leveling agent, mixed 0.4 parts of rare earth chloride; particle size of nano-silica is 25nm, nano-montmorillonite The particle size is 25 nm.

Wherein, the toughening agent is chlorinated polyethylene; the reactive diluent is glycidyl octanoate; the compatibilizing agent is maleic anhydride graft modified polypropylene; the coupling agent is methyl vinyl dichlorosilane coupling agent The leveling agent is diacetone alcohol.

(1) Alumina, magnesia, silicon carbide, silane coupling agent, calcium nitrate, hydroquinone, nickel acetate, ethanol, epoxy resin, dimethyl acrylamide, sodium metasilicate, in a set by weight , the benzotriazole is added to the mixer, heated and stirred, and cooled to room temperature; the heating temperature is 50 ° C, and the stirring speed is 400 rpm;

(2) heating and stirring the components of the high-strength system according to the set weight parts to obtain a high-strength system; the heating temperature is 86 ° C, and the stirring speed is 280 rpm;

(3) mixing the base of the heat-conductive insulating material and the high-strength system according to the set ratio, heating and stirring under vacuum conditions, cooling to room temperature, and solidifying, that is, the vacuum degree is 0.09 MPa, and the heating temperature is 60 °C.

Example 3

This embodiment is a high-strength thermally conductive insulating material comprising a thermally conductive insulating material matrix and a high-strength system. The high-strength system is added in an amount of 3.4% by weight of the thermally conductive insulating material.

The parts by weight of the thermally conductive insulating material substrate include: 12.7 parts of alumina, 5.7 parts of magnesium oxide, 2.3 parts of silicon carbide, 3.3 parts of silane coupling agent, 2.6 parts of calcium nitrate, 4.3 parts of hydroquinone, 4 parts of nickel acetate, 14 parts of ethanol, 16 parts of epoxy resin, 5.3 parts of dimethyl acrylamide, 2.4 parts of sodium metasilicate, and 6.3 parts of benzotriazole.

The parts by weight of the high strength system include: 8.9 parts of nano silica, 33 parts of ethoxylated alkylamine, 63 parts of methyl hydrogen silicone oil, 4.9 parts of hydroxypolydimethylsiloxane, vinyl trimethoxy 8.7 parts of silane, 2.7 parts of ammonium polyphosphate, 3.4 parts of nano montmorillonite, 3.7 parts of fumed silica, 2.8 parts of γ-aminopropyltriethoxysilane, 5.3 parts of alkylphenol ethoxylate Toughener 1.9 parts, reactive diluent 1.3 parts, compatibilizer 2.7 parts, coupling agent 1.4 parts, leveling agent 1.3 parts, mixed rare earth chloride 0.5 parts; nano silica particle size 30nm, nano montmorillonite The particle size is 30 nm.

Wherein the toughening agent is an ethylene-vinyl acetate copolymer; the reactive diluent is trimethylolpropane triglycidyl ether; the compatibilizing agent is maleic anhydride graft modified polypropylene; the coupling agent is methyl tributyl Keto mercapto silane coupling agent; leveling agent is polydimethylsiloxane.

(1) Alumina, magnesia, silicon carbide, silane coupling agent, calcium nitrate, hydroquinone, nickel acetate, ethanol, epoxy resin, dimethyl acrylamide, sodium metasilicate, in a set by weight , the benzotriazole is added to the mixer, heated and stirred, and cooled to room temperature; the heating temperature is 60 ° C, and the stirring speed is 500 rpm;

(2) heating and stirring the components of the high-strength system according to the set weight parts to obtain a high-strength system; the heating temperature is 87 ° C, and the stirring speed is 300 rpm;

(3) Mixing the heat conductive insulating material substrate with the high strength system according to the set ratio, heating and stirring under vacuum conditions, cooling to room temperature, and solidifying, that is, the vacuum degree is 0.1 MPa, and the heating temperature is 70 °C.

The materials obtained in Examples 1-5 were subjected to performance tests, and the results were as follows:

Other than the above-described embodiments, the present invention may have other embodiments. Any technical solution formed by equivalent replacement or equivalent transformation falls within the protection scope of the present invention.

Claims

A high-strength thermal conductive insulating material, comprising: a thermally conductive insulating material base and a high-strength system, wherein the high-strength system is added in an amount of 3.2-3.4% by weight of the thermally conductive insulating material;

The parts by weight of the thermally conductive insulating material matrix comprises: 12.5-12.7 parts of alumina, 5.5-5.7 parts of magnesium oxide, 2.1-2.3 parts of silicon carbide, 3.1-3.3 parts of silane coupling agent, 2.4-2.6 parts of calcium nitrate, 4.1-4.3 parts of hydroquinone, 3.8-4 parts of nickel acetate, 12-14 parts of ethanol, 14-16 parts of epoxy resin, 5.1-5.3 parts of dimethyl acrylamide, 2.2-2.4 parts of sodium metasilicate, benzene Triazole 6.1-6.3 parts;

The parts by weight of the high-strength system include: 8.7-8.9 parts of nano-silica, 21-33 parts of ethoxylated alkylamine, 61-63 parts of methyl-containing hydrogen silicone oil, hydroxypolydimethylsiloxane 4.7-4.9 parts of alkane, 8.7-8.9 parts of vinyltrimethoxysilane, 2.5-2.7 parts of ammonium polyphosphate, 3.2-3.4 parts of nano-montmorillonite, 3.5-3.7 parts of fumed silica, γ-aminopropyl three 2.6-2.8 parts of ethoxysilane, 5.1-5.3 parts of alkylphenol ethoxylate, 1.7-1.9 parts of toughening agent, 1.1-1.3 parts of reactive diluent, 2.5-2.7 parts of compatibilizer, 1.2-2.7 coupling agent 1.4 parts, leveling agent 1.1-1.3 parts, mixed rare earth chloride 0.3-0.5 parts; said nano-silica has a particle diameter of 20-30 nm, and said nano-montmorillonite has a particle diameter of 20-30 nm.
The high-strength thermally conductive insulating material according to claim 1, wherein the toughening agent is one of a styrene-butadiene thermoplastic elastomer, a chlorinated polyethylene or an ethylene-vinyl acetate copolymer. More than one mixture; the reactive diluent is one of alkyl glycidyl ether, glycidyl octanoate, trimethylolpropane triglycidyl ether, toluene glycidyl ether, castor oil polyglycidyl ether or a mixture of more than one; the compatibilizing agent is a maleic anhydride graft-modified polypropylene; the coupling agent is a vinyltributyl ketone-based silane coupling agent, a methylvinyldichlorosilane coupling agent, One or more mixtures of methyl tributyl ketone silane coupling agents; the leveling agent is isophorone, diacetone alcohol, fluorine modified acrylic acid, phosphate modified acrylic acid, acrylic acid, poly One or more mixtures of dimethylsiloxane, polymethylalkylsiloxane, organomodified polysiloxane.
The high-strength thermally conductive insulating material according to claim 1 or 2, comprising: a thermally conductive insulating material substrate and a high-strength system, wherein the high-strength system is added in an amount of 3.2% by weight of the thermally conductive insulating material;

The parts by weight of the thermally conductive insulating material substrate include: 12.5 parts of alumina, 5.5 parts of magnesium oxide, 2.1 parts of silicon carbide, 3.1 parts of silane coupling agent, 2.4 parts of calcium nitrate, 4.1 parts of hydroquinone, and 3.8 of nickel acetate. a portion, 12 parts of ethanol, 14 parts of epoxy resin, 5.1 parts of dimethyl acrylamide, 2.2 parts of sodium metasilicate, and 6.1 parts of benzotriazole;

The parts by weight of the high-strength system include: 8.7 parts of nano-silica, 21 parts of ethoxylated alkylamine, 61 parts of methyl-containing silicone oil, 4.7 parts of hydroxypolydimethylsiloxane, vinyl 8.7 parts of trimethoxysilane, 2.5 parts of ammonium polyphosphate, 3.2 parts of nano-montmorillonite, 3.5 parts of fumed silica, 2.6 parts of γ-aminopropyltriethoxysilane, 5.1 parts of alkylphenol ethoxylate , 1.7 parts of toughening agent, 1.1 parts of reactive diluent, 2.5 parts of compatibilizer, 1.2 parts of coupling agent, 1.1 parts of leveling agent, 0.3 parts of mixed rare earth chloride; the particle size of the nano-silica is 20 nm The nano montmorillonite has a particle diameter of 20 nm.
The high-strength thermally conductive insulating material according to claim 1 or 2, comprising: a thermally conductive insulating material substrate and a high-strength system, wherein the high-strength system is added in an amount of 3.3% by weight of the thermally conductive insulating material;

The parts by weight of the thermally conductive insulating material matrix comprises: 12.6 parts of alumina, 5.6 parts of magnesium oxide, 2.2 parts of silicon carbide, 3.2 parts of a silane coupling agent, 2.5 parts of calcium nitrate, 4.2 parts of hydroquinone, and 3.9 of nickel acetate. Parts, 13 parts of ethanol, 15 parts of epoxy resin, 5.2 parts of dimethyl acrylamide, 2.3 parts of sodium metasilicate, 6.2 parts of benzotriazole;

The parts by weight of the high-strength system include: 8.8 parts of nano-silica, 22 parts of ethoxylated alkylamine, 62 parts of methyl-containing silicone oil, 4.8 parts of hydroxypolydimethylsiloxane, vinyl 8.8 parts of trimethoxysilane, 2.6 parts of ammonium polyphosphate, 3.3 parts of nano montmorillonite, 3.6 parts of fumed silica, 2.7 parts of γ-aminopropyltriethoxysilane, 5.2 parts of alkylphenol ethoxylate , 1.8 parts of toughening agent, 1.2 parts of reactive diluent, 2.6 parts of compatibilizer, 1.3 parts of coupling agent, 1.2 parts of leveling agent, mixed 0.4 parts of rare earth chloride; the particle size of the nano silica is 25 nm The nano montmorillonite has a particle size of 25 nm.
The high-strength thermally conductive insulating material according to claim 1 or 2, comprising: a thermally conductive insulating material substrate and a high-strength system, wherein the high-strength system is added in an amount of 3.4% by weight of the thermally conductive insulating material;

The parts by weight of the thermally conductive insulating material matrix comprises: 12.7 parts of alumina, 5.7 parts of magnesium oxide, 2.3 parts of silicon carbide, 3.3 parts of silane coupling agent, 2.6 parts of calcium nitrate, 4.3 parts of hydroquinone, nickel acetate 4 Parts, 14 parts of ethanol, 16 parts of epoxy resin, 5.3 parts of dimethyl acrylamide, 2.4 parts of sodium metasilicate, 6.3 parts of benzotriazole;

The parts by weight of the high-strength system include: 8.9 parts of nano-silica, 33 parts of ethoxylated alkylamine, 63 parts of methyl-containing silicone oil, 4.9 parts of hydroxypolydimethylsiloxane, vinyl 8.9 parts of trimethoxysilane, 2.7 parts of ammonium polyphosphate, 3.4 parts of nano montmorillonite, 3.7 parts of fumed silica, 2.8 parts of γ-aminopropyltriethoxysilane, 5.3 parts of alkylphenol ethoxylate , 1.9 parts of toughening agent, 1.3 parts of reactive diluent, 2.7 parts of compatibilizer, 1.4 parts of coupling agent, 1.3 parts of leveling agent, mixed 0.5 parts of rare earth chloride; the particle size of the nano-silica is 30 nm The nano montmorillonite has a particle diameter of 30 nm.