阅读说明：本技术 一种绝缘导热橡胶复合材料及其制备方法 (Insulating heat-conducting rubber composite material and preparation method thereof ) 是由 常明伟 于 2020-12-22 设计创作，主要内容包括：本发明公开了一种绝缘导热橡胶复合材料,由如下重量份的各成分制备而成：端氨基超支化聚硅氧烷HPSi-NH-220-30份、环氧丁腈橡胶50-70份、氯醇橡胶15-25份、N,N’,N”-三-(四-(十六烷基)-三聚氰胺基乙基)-三聚氰胺5-8份、氧化铝纳米管4-7份、硼化硅纳米粉2-4份、碳化硅纤维3-7份、无机填料100-150份、荷负电偶联剂3-5份。本发明还提供了一种所述绝缘导热橡胶复合材料的制备方法。本发明公开的绝缘导热橡胶复合材料综合性能和性能稳定性佳,绝缘导热效果显著,机械力学性能和耐老化性能好。(The invention discloses an insulating heat-conducting rubber composite material which is prepared from the following components in parts by weight: amino-terminated hyperbranched polysiloxane HPSi-NH 2 20-30 parts of epoxy nitrile rubber, 50-70 parts of epichlorohydrin rubber, 15-25 parts of epichlorohydrin rubber, 5-8 parts of N, N' -tri- (tetra- (hexadecyl) -melamine-ethyl) -melamine, 4-7 parts of alumina nano-tube, 2-4 parts of silicon boride nano-powder, 3-7 parts of silicon carbide fiber, 100-150 parts of inorganic filler and 3-5 parts of negative charge coupling agent. The invention also provides a preparation method of the insulating heat-conducting rubber composite material. The insulating and heat-conducting rubber composite material disclosed by the invention is good in comprehensive performance and performance stability, remarkable in insulating and heat-conducting effect, and good in mechanical property and aging resistance.)

1. The insulating heat-conducting rubber composite material is characterized by being prepared from the following components in parts by weight: amino-terminated hyperbranched polysiloxane HPSi-NH₂20-30 parts of epoxy nitrile rubber, 50-70 parts of epichlorohydrin rubber, 15-25 parts of epichlorohydrin rubber, 5-8 parts of N, N' -tri- (tetra- (hexadecyl) -melamine-ethyl) -melamine, 4-7 parts of alumina nano-tube, 2-4 parts of silicon boride nano-powder, 3-7 parts of silicon carbide fiber, 100-150 parts of inorganic filler and 3-5 parts of negative charge coupling agent.

2. The insulating and heat-conducting rubber composite material as claimed in claim 1, wherein the negatively-charged coupling agent is at least one of triethoxysilylpropyl maleic acid, triethoxysilylacetic acid and N- (trimethoxysilylpropyl) ethylenediamine triacetic acid sodium salt.

3. The insulating and heat-conducting rubber composite material as claimed in claim 1, wherein the inorganic filler is at least one of aluminum nitride, magnesium oxide, aluminum oxide and silicon nitride.

4. The insulating and heat-conducting rubber composite material as claimed in claim 1, wherein the particle size of the inorganic filler is 400-800 mesh.

5. The insulating and heat-conducting rubber composite material as claimed in claim 1, wherein the silicon carbide fiber has a diameter of 10 μm and an average length of 320 μm.

6. The insulating and heat-conducting rubber composite material as claimed in claim 1, wherein the particle size of the silicon boride nano powder is 300-600 nm.

7. The insulating and heat-conducting rubber composite material according to claim 1, wherein the chlorohydrin rubber is at least one of T-65 chlorohydrin rubber, C-75 chlorohydrin rubber, and H-65 chlorohydrin rubber.

8. The insulating and heat-conducting rubber composite material as claimed in claim 1, wherein the epoxy nitrile rubber is at least one of ETBN1300X 40 epoxy nitrile rubber and ETBN1300X68 epoxy nitrile rubber.

9. The preparation method of the insulating and heat-conducting rubber composite material according to any one of claims 1 to 8, characterized by comprising the following steps: mixing the components according to the parts by weight to obtain a mixture, adding the mixture into a double-screw extruder for blending and extrusion, quickly placing the mixture on a die, and carrying out die pressing at the temperature of 190 ℃ and under the pressure of 25-35MPa for 10-15 minutes to obtain the insulating and heat-conducting rubber composite material.

Technical Field

The invention relates to the technical field of composite materials, in particular to an insulating heat-conducting rubber composite material and a preparation method thereof.

Background

With the rapid development of microelectronic integration and assembly technology, the circuit design of electronic products is more and more complex, and is in a trend of densification and miniaturization. The volumes of electronic components and logic circuits are reduced by tens of millions of times, the working frequency is increased rapidly, heat generated by electronic equipment is accumulated and increased rapidly at the moment, the temperature of a working environment is changed rapidly towards a high temperature direction, and if the heat cannot be discharged in time, the accumulated heat to a certain degree can certainly damage the components and equipment of the electronic equipment. Therefore, the development of high thermal conductive materials is imperative.

The heat conductive material for electronic components is also required to have good insulation properties. At present, the insulating heat conduction material on the market is full of precious, wherein the more common one is that insulating heat conduction material is insulating heat conduction rubber composite, and this kind of material is filled the heat conduction filler and is made in the rubber matrix material. Rubber itself has insulation properties, but a thermally conductive filler material generally affects its insulation properties. Non-insulating fillers such as metal powder, graphite, carbon fiber, carbon nanotube, and carbon fiber can improve the thermal conductivity of the rubber material, but also cause the insulation of the rubber material to be significantly reduced, and even convert the rubber material into a conductive material. The existing insulating heat-conducting rubber composite material has the defects that the heat conductivity, the physical property and the insulativity can not be simultaneously considered, the mechanical property is poor, the weather resistance and the ultraviolet resistance are poor, the service life is short, the composite material is easy to damage, the preparation cost is high, and the comprehensive property and the performance stability are required to be further improved.

The Chinese patent application with the application number of 201310372003.3 and the name of 'high-heat-conductivity insulating and heat-conducting silica gel gasket and a preparation method thereof' comprises the following raw materials in parts by weight: 1000 parts of spherical alumina 600-15 parts, methyl vinyl silicone rubber 5-15 parts, dimethyl silicone oil 30-70 parts, hydrogen-containing silicone oil 2-15 parts and catalyst 0.5-1.5 parts, which have good insulating property and heat conductivity, but because the dimethyl silicone oil with a larger proportion is used in the formula proportion, the silica gel gasket is easy to separate out in the using process, and the silica gel product has bad phenomena of cracking, hardening and the like.

Therefore, it is very important to develop an insulating and heat conducting rubber composite material with good comprehensive performance and performance stability, obvious insulating and heat conducting effect, and good mechanical property and aging resistance.

Disclosure of Invention

In order to overcome the defects in the prior art, the invention provides the insulating and heat-conducting rubber composite material which has good comprehensive performance and performance stability, obvious insulating and heat-conducting effect and good mechanical property and aging resistance. Meanwhile, the invention also provides a preparation method of the insulating heat-conducting rubber composite material, and the preparation method has the advantages of simple and feasible process, easily obtained raw materials, low requirements on equipment and reaction conditions, high preparation efficiency and low energy consumption, and is suitable for large-scale production.

In order to achieve the purpose, the invention adopts the technical scheme that the insulating heat-conducting rubber composite material is prepared from the following components in parts by weight: amino-terminated hyperbranched polysiloxane HPSi-NH₂20-30 parts of epoxy nitrile rubber, 50-70 parts of epichlorohydrin rubber, 15-25 parts of epichlorohydrin rubber, 5-8 parts of N, N' -tri- (tetra- (hexadecyl) -melamine-ethyl) -melamine, 4-7 parts of alumina nano-tube, 2-4 parts of silicon boride nano-powder, 3-7 parts of silicon carbide fiber, 100-150 parts of inorganic filler and 3-5 parts of negative charge coupling agent.

Preferably, the negatively charged coupling agent is at least one of triethoxysilylpropyl maleic acid, triethoxysilylacetic acid and N- (trimethoxysilylpropyl) ethylenediamine triacetic acid sodium salt.

Preferably, the inorganic filler is at least one of aluminum nitride, magnesium oxide, aluminum oxide and silicon nitride.

Preferably, the particle size of the inorganic filler is 400-800 meshes.

Preferably, the silicon carbide fibers have a diameter of 10 μm and an average length of 320 μm.

Preferably, the particle size of the silicon boride nano powder is 300-600 nm.

Preferably, the alumina nanotubes are prepared by the method of embodiment 1 of the chinese patent application No. 201710574181.2.

Preferably, the N, N ', N "-tris- (tetrakis- (hexadecyl) -cyanoethyl) -melamine is N, N', N" -tris- (tetrakis- (hexadecyl) -cyanoethyl) -melamine prepared by the method of example 4 of the chinese patent application No. 200910188561.8.

Preferably, the chlorohydrin rubber is at least one of T-65 chlorohydrin rubber, C-75 chlorohydrin rubber and H-65 chlorohydrin rubber.

Preferably, the epoxy nitrile rubber is at least one of ETBN1300X 40 epoxy nitrile rubber and ETBN1300X68 epoxy nitrile rubber.

Preferably, the amino-terminated hyperbranched polysiloxane HPSi-NH₂Is amino-terminated hyperbranched polysiloxane HPSi-NH prepared by the method of the invention patent example 1 of China with the application number of 201910338290.3₂。

Another objective of the present invention is to provide a preparation method of the insulating and heat conducting rubber composite material, which is characterized by comprising the following steps: mixing the components according to the parts by weight to obtain a mixture, adding the mixture into a double-screw extruder for blending and extrusion, quickly placing the mixture on a die, and carrying out die pressing at the temperature of 190 ℃ and under the pressure of 25-35MPa for 10-15 minutes to obtain the insulating and heat-conducting rubber composite material.

Adopt the produced beneficial effect of above-mentioned technical scheme to lie in:

(1) the preparation method of the insulating heat-conducting rubber composite material provided by the invention has the advantages of simple and feasible process, easily obtained raw materials, low requirements on equipment and reaction conditions, high preparation efficiency and low energy consumption, and is suitable for large-scale production.

(2) The insulating and heat-conducting rubber composite material provided by the invention overcomes the defects that the existing insulating and heat-conducting rubber composite material has the defects that the heat conductivity, the physical property and the insulativity can not be simultaneously considered, the mechanical property is poor, the weather resistance and the ultraviolet resistance are poor, the service life is short, the composite material is easy to damage, the preparation cost is high, and the comprehensive performance and the performance stability need to be further improved; through the synergistic effect of the components, the prepared insulating heat-conducting rubber composite material has the advantages of good comprehensive performance and performance stability, obvious insulating heat-conducting effect, good mechanical property and aging resistance.

(3) The insulating and heat-conducting rubber composite material provided by the invention combines excellent insulating properties, aging resistance and comprehensive properties of polysiloxane, nitrile rubber and chlorohydrin rubber, and the amino-terminated hyperbranched polysiloxane HPSi-NH₂The terminal amino group on the epoxy nitrile rubber and the epoxy group on the N, N '-tri- (tetra- (hexadecyl) -melamine aminoethyl) -melamine are easy to generate epoxy ring-opening reaction in the material forming stage, the chlorine group on the chlorohydrin rubber and the amino group on the N, N' -tri- (tetra- (hexadecyl) -melamine aminoethyl) -melamine can generate quaternization reaction to form a quaternary ammonium salt cation structure, the formed quaternary ammonium salt cation structure can be connected with the carboxyl group on the negative charge electric coupling agent in an ionic bond form, thereby leading the whole material to form a three-dimensional network cross-linking structure, effectively improving the comprehensive performance and the performance stability of the material, the filler with the heat conduction function and the rubber base material are uniformly dispersed to form a better heat conduction bridge, and the heat conduction performance of the composite material is effectively improved.

(4) The invention provides an insulating heat-conducting rubber composite material, namely amino-terminated hyperbranched polysiloxane HPSi-NH₂The structure and the structure of N, N' -tri- (tetra- (hexadecyl) -melamine aminoethyl) -melamine are introduced to act synergistically with nitrile groups and side group chlorine atoms, so that the heat aging performance, the ozone resistance, the bending resistance and the elasticity can be improved, the oil resistance, the solvent resistance and the flame retardant property of the material are better, and in addition, the insulating property can be improved.

(5) According to the insulating and heat-conducting rubber composite material provided by the invention, the addition of the alumina nano tube enables the heat-conducting property to be better, and the alumina nano tube, the silicon boride nano powder, the silicon carbide fiber and the inorganic filler are cooperated, so that the mechanical property can be improved, and the heat conduction and the insulation property can be improved.

Detailed Description

In order to make the technical solutions of the present invention better understood and make the above features, objects, and advantages of the present invention more comprehensible, the present invention is further described with reference to the following examples. The examples are intended to illustrate the invention only and are not intended to limit the scope of the invention.

The alumina nanotubes used in the following examples of the present invention were prepared by the method of example 1 of the chinese patent application No. 201710574181.2; the N, N '-tris- (tetrakis- (hexadecyl) -melamine-ethyl) -melamine is N, N' -tris- (tetrakis- (hexadecyl) -melamine-ethyl) -melamine prepared by the method in the Chinese patent application No. 200910188561.8, inventive example 4; the amino-terminated hyperbranched polysiloxane HPSi-NH₂Is amino-terminated hyperbranched polysiloxane HPSi-NH prepared by the method of the invention patent example 1 of China with the application number of 201910338290.3₂. Other raw materials were all purchased commercially.

Example 1

An insulating heat-conducting rubber composite material is prepared from the following components in parts by weight: amino-terminated hyperbranched polysiloxane HPSi-NH₂20 parts of epoxy nitrile rubber, 50 parts of epichlorohydrin rubber, 15 parts of N, N' -tris- (tetra- (hexadecyl) -melamine aminoethyl) -melamine, 4 parts of alumina nanotubes, 2 parts of silicon boride nano powder, 3 parts of silicon carbide fiber, 100 parts of inorganic filler and 3 parts of negative charge coupling agent.

The negative charge coupling agent is triethoxysilylpropyl maleic acid; the inorganic filler is aluminum nitride; the particle size of the inorganic filler is 400 meshes; the diameter of the silicon carbide fiber is 10 μm, and the average length of the silicon carbide fiber is 320 μm; the particle size of the silicon boride nano powder is 300 nm.

The chlorohydrin rubber is T-65 chlorohydrin rubber; the epoxy nitrile rubber is ETBN1300X 40 epoxy nitrile rubber.

The preparation method of the insulating heat-conducting rubber composite material is characterized by comprising the following steps: mixing the components in parts by weight to obtain a mixture, adding the mixture into a double-screw extruder for blending and extrusion, quickly placing the mixture on a die, and carrying out die pressing at the temperature of 170 ℃ and under the pressure of 25MPa for 10 minutes to obtain the insulating and heat-conducting rubber composite material.

Example 2

An insulating heat-conducting rubber composite material is prepared from the following components in parts by weight: amino-terminated hyperbranched polysiloxane HPSi-NH₂22 parts of epoxy nitrile rubber, 55 parts of epichlorohydrin rubber, 17 parts of chlorohydrin rubber, 6 parts of N, N' -tris- (tetra- (hexadecyl) -melamine-ethyl) -melamine, 5 parts of alumina nanotubes, 2.5 parts of silicon boride nano powder, 4 parts of silicon carbide fiber, 110 parts of inorganic filler and 3.5 parts of negative charge coupling agent.

The negative charge coupling agent is triethoxysilylacetic acid; the inorganic filler is magnesium oxide; the particle size of the inorganic filler is 500 meshes; the diameter of the silicon carbide fiber is 10 μm, and the average length of the silicon carbide fiber is 320 μm; the particle size of the silicon boride nano powder is 400 nm; the chlorohydrin rubber is C-75 chlorohydrin rubber; the epoxy nitrile rubber is ETBN1300X68 epoxy nitrile rubber.

The preparation method of the insulating heat-conducting rubber composite material is characterized by comprising the following steps: mixing the components in parts by weight to obtain a mixture, adding the mixture into a double-screw extruder for blending and extrusion, quickly placing the mixture on a die, and carrying out die pressing at the temperature of 175 ℃ and under the pressure of 27MPa for 12 minutes to obtain the insulating and heat-conducting rubber composite material.

Example 3

An insulating heat-conducting rubber composite material is prepared from the following components in parts by weight: amino-terminated hyperbranched polysiloxane HPSi-NH₂25 parts of epoxy nitrile rubber 60 parts, 20 parts of chlorohydrin rubber, 6.5 parts of N, N' -tri- (tetra- (hexadecyl) -melamine aminoethyl) -melamine, 5.5 parts of alumina nanotubes, 3 parts of silicon boride nano powder, 5 parts of silicon carbide fiber, 130 parts of inorganic filler and 4 parts of negative charge coupling agent.

The negative charge coupling agent is N- (trimethoxysilylpropyl) ethylenediamine triacetic acid sodium salt; the inorganic filler is alumina; the particle size of the inorganic filler is 600 meshes; the diameter of the silicon carbide fiber is 10 μm, and the average length of the silicon carbide fiber is 320 μm; the particle size of the silicon boride nano powder is 450 nm; the chlorohydrin rubber is H-65 chlorohydrin rubber; the epoxy nitrile rubber is ETBN1300X 40 epoxy nitrile rubber.

The preparation method of the insulating heat-conducting rubber composite material is characterized by comprising the following steps: mixing the components in parts by weight to obtain a mixture, adding the mixture into a double-screw extruder for blending and extrusion, quickly placing the mixture on a die, and carrying out die pressing at the temperature of 180 ℃ and under the pressure of 30MPa for 13 minutes to obtain the insulating and heat-conducting rubber composite material.

Example 4

An insulating heat-conducting rubber composite material is prepared from the following components in parts by weight: amino-terminated hyperbranched polysiloxane HPSi-NH₂28 parts of epoxy nitrile rubber 67 parts, 23 parts of chlorohydrin rubber, 7.5 parts of N, N' -tri- (tetra- (hexadecyl) -melamine-aminoethyl) -melamine, 6.5 parts of alumina nanotubes, 3.5 parts of silicon boride nano powder, 6.5 parts of silicon carbide fiber, 140 parts of inorganic filler and 4.5 parts of negative charge coupling agent.

The negative charge coupling agent is formed by mixing triethoxysilylpropyl maleic acid, triethoxysilylacetic acid and N- (trimethoxysilylpropyl) ethylenediamine triacetic acid sodium salt according to the mass ratio of 1:3: 2; the inorganic filler is formed by mixing aluminum nitride, magnesium oxide, aluminum oxide and silicon nitride according to the mass ratio of 1:2:1: 3; the particle size of the inorganic filler is 700 meshes; the diameter of the silicon carbide fiber is 10 μm, and the average length of the silicon carbide fiber is 320 μm; the particle size of the silicon boride nano powder is 550 nm; the chlorohydrin rubber is formed by mixing T-65 chlorohydrin rubber, C-75 chlorohydrin rubber and H-65 chlorohydrin rubber according to the mass ratio of 1:3: 2; the epoxy nitrile rubber is prepared by mixing ETBN1300X 40 epoxy nitrile rubber and ETBN1300X68 epoxy nitrile rubber according to the mass ratio of 3: 5.

The preparation method of the insulating heat-conducting rubber composite material is characterized by comprising the following steps: mixing the components in parts by weight to obtain a mixture, adding the mixture into a double-screw extruder for blending and extrusion, quickly placing the mixture on a die, and carrying out die pressing at 185 ℃ and 33MPa for 14 minutes to obtain the insulating and heat-conducting rubber composite material.

Example 5

An insulating heat-conducting rubber composite material is prepared from the following components in parts by weight: amino-terminated hyperbranched polysiloxane HPSi-NH₂30 parts of epoxy nitrile rubber, 70 parts of epichlorohydrin rubber, 25 parts of chlorohydrin rubber, 8 parts of N, N' -tris- (tetra- (hexadecyl) -melamine-aminoethyl) -melamine, 7 parts of alumina nanotubes, 4 parts of silicon boride nano powder, 7 parts of silicon carbide fiber, 150 parts of inorganic filler and 5 parts of negative charge coupling agent.

The negative charge coupling agent is triethoxysilylpropyl maleic acid; the inorganic filler is silicon nitride; the particle size of the inorganic filler is 800 meshes; the diameter of the silicon carbide fiber is 10 μm, and the average length of the silicon carbide fiber is 320 μm; the particle size of the silicon boride nano powder is 600 nm; the chlorohydrin rubber is T-65 chlorohydrin rubber; the epoxy nitrile rubber is ETBN1300X68 epoxy nitrile rubber.

The preparation method of the insulating heat-conducting rubber composite material is characterized by comprising the following steps: mixing the components in parts by weight to obtain a mixture, adding the mixture into a double-screw extruder for blending and extrusion, quickly placing the mixture on a die, and carrying out die pressing at the temperature of 190 ℃ and under the pressure of 35MPa for 15 minutes to obtain the insulating and heat-conducting rubber composite material.

Comparative example 1

The present example provides an insulating and heat conducting rubber composite material, whose formula and preparation method are substantially the same as those in example 1, except that: in which no alumina nanotubes were added.

Comparative example 2

The present example provides an insulating and heat conducting rubber composite material, whose formula and preparation method are substantially the same as those in example 1, except that: the silicon boride nanopowder and silicon carbide fiber were not added.

Comparative example 3

The present example provides an insulating and heat conducting rubber composite material, whose formula and preparation method are substantially the same as those in example 1, except that: no N, N', N "-tris- (tetrakis- (hexadecyl) -melamineaminoethyl) -melamine was added.

Comparative example 4

The present example provides an insulating and heat conducting rubber composite material, whose formula and preparation method are substantially the same as those in example 1, except that: in which no chlorohydrin rubber was added.

Comparative example 5

The present example provides an insulating and heat conducting rubber composite material, whose formula and preparation method are substantially the same as those in example 1, except that: wherein no amino-terminated hyperbranched polysiloxane HPSi-NH is added₂。

The insulating and heat-conducting rubber composite materials in the above examples 1 to 5 and comparative examples 1 to 5 were subjected to performance tests, the test results are shown in table 1, and the test methods are as follows: the thermal conductivity is tested according to GB/T11205-2009, the tensile strength is tested according to the standard of GB/T528-. The heat aging resistance is characterized by the change rate of tensile strength after aging at 70 ℃ for 96 hours, and the test standard is shown in GB-T3512-2001.

TABLE 1 Performance test results of the insulating and heat-conducting rubber composite

Detecting items	Thermal conductivity	Tensile strength	Thermal aging resistance	Volume resistivity
					Unit of	W/(m·K)	MPa	％	Ω·cm
Example 1	2.69	18.5	-7	3.1×1015
					Example 2	2.73	19.1	-5	3.4×1015
Example 3	2.77	19.8	-4	3.8×1015
					Example 4	2.82	20.4	-4	4.1×1015
Example 5	2.85	21.0	-3	4.3×1015
					Comparative example 1	1.97	12.3	-8	8.2×1014
Comparative example 2	1.82	11.6	-9	5.5×1014
					Comparative example 3	2.42	13.4	-18	3.6×1013
Comparative example 4	2.48	15.1	-14	2.3×1013
					Comparative example 5	2.37	12.5	-16	1.5×1013

As can be seen from table 1, the insulating and heat conducting rubber composite material disclosed in the embodiment of the present invention has more excellent insulating, heat conducting and thermal aging resistance properties, and has greater tensile strength, which is a result of the synergistic effect of the components.

The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.