A long-life high-thermal-conductivity two-component gel and its preparation method and application

Abstract

The present invention discloses a long-life, high-thermal-conductivity two-component gel. By regulating the physicochemical properties of each component and combining it with filler microstructure design, the resulting two-component thermally conductive gel exhibits high stability, minimal thermal conductivity fluctuations, and minimal oil leakage in high- and low-temperature, high-humidity environments, demonstrating its long life and high thermal conductivity.

Description

Technical Field

[0001] The present invention belongs to the technical field of thermal conductive materials, and specifically relates to a two-component gel, and more particularly to a long-life, high-thermal-conductivity two-component gel, and a preparation method and application thereof. Background Art

[0002] With the advancement of science and technology, a large number of electronic products have developed rapidly. When electronic components are working, they generate a lot of heat, which affects the performance and life of the components. Therefore, heat dissipation is an important issue that needs to be considered in electronic products. Thermal interface materials can effectively improve the heat dissipation effect and are essential in many heat dissipation systems. Thermal conductive gel is a high-performance thermal conductive interface material. Compared with thermal conductive gaskets and thermal conductive grease, thermal conductive gel has the advantages of low thermal resistance, low assembly thickness, stable state after vulcanization, and is not prone to oil release and cracking. It can maintain a stable shape like a thermal conductive gasket and is not easy to flow out from the interface gap like thermal conductive grease. Thermal conductive gel is mainly divided into single-component thermal conductive gel and two-component thermal conductive gel. Among them, two-component thermal conductive gel is formed by mixing two components and vulcanizing them to form a stable shape.

[0003] Thermally conductive gel is a composite of thermally conductive fillers and silicone oil, so its preparation requires the selection of appropriate silicone oil and fillers. Commonly used thermally conductive fillers include metals (silver, copper, aluminum, etc.); metal oxides (aluminum oxide, magnesium oxide, zinc oxide, etc.); and non-metallic materials (aluminum nitride, silicon carbide, graphite, etc.). Fillers can be granular, flake, spherical, or fibrous. Thermally conductive gel products currently on the market still suffer from poor aging resistance and significant oil release, which not only affects thermal conductivity but also hinders performance and performance, hindering efficient heat dissipation from electronic components.

[0004] CN114106564A discloses an oriented thermally conductive gel, preparation method, and application. By orienting spherical fillers and anisotropic thermally conductive fillers, the resulting oriented thermally conductive gel exhibits ultra-high thermal conductivity in the axial direction of the anisotropic thermally conductive fillers while maintaining a stable extrusion rate.

[0005] CN111876135A discloses a thermally conductive gel and its preparation method. By selecting and compounding thermally conductive fillers with different particle sizes, shapes, and high thermal conductivity, and preparing them using a special production process, the resulting thermally conductive gel has a thermal conductivity of 7.6 to 9.2 W / mK, demonstrating excellent thermal conductivity. However, the resulting thermally conductive gel exhibits poor high-temperature resistance.

[0006] CN110330947A discloses a thermally conductive gel containing carbon nanotubes, its preparation, and its application. By combining carbon nanotubes with conventional fillers, the thermally conductive gel leverages the high thermal conductivity of the carbon nanotubes and the large-volume filling capacity of conventional fillers. Furthermore, pre-curing cross-links the silicone oil, improving the thermally conductive gel's aging resistance and stabilizing its thermal conductivity.

[0007] Therefore, how to provide a highly stable thermally conductive gel has become a technical problem that urgently needs to be solved. Summary of the Invention

[0008] Purpose of the Invention: To address the problem of current thermally conductive gels aging easily in high and low temperature environments, particularly the tendency to release oil after prolonged use, the present invention provides a long-life, high-thermal-conductivity two-component gel and its preparation method. By manipulating the physicochemical properties of each component and incorporating filler microstructure design, the resulting two-component thermally conductive gel exhibits high stability, minimal thermal conductivity fluctuations, and minimal oil release in high- and low-temperature, high-humidity environments, demonstrating long life and high thermal conductivity.

[0009] In order to solve the above technical problems, the present invention discloses a long-life, high-thermal-conductivity two-component gel, wherein the two-component gel comprises a component A and a component B, wherein the component A comprises the following components in parts by weight:

[0010] Filler X 80-88 parts, first modified silicone oil 0.3-1 part, second modified silicone oil 0.05-0.3 part, treating agent 0.06-0.08 part, dispersant 0.4-0.8 part, modifier 0.05-0.3 part, thickener 0.06-0.15 part;

[0011] The B component comprises the following components in parts by weight:

[0012] Filler Y 86-92 parts, first modified silicone oil 1.5-3.5 parts, second modified silicone oil 0.05-0.2 parts, modifier 0.3-0.5 parts, third modified silicone oil 0.05-0.18 parts;

[0013] Filler X is one or a mixture of spinel-structured aluminum titanium silicate and whisker-shaped potassium sodium titanate;

[0014] Filler Y is partially deoxidized tin oxide (i.e., SnOx);

[0015] The first modified silicone oil is a mixture of phenyl polytrimethylsiloxane and polydimethylsiloxane, the second modified silicone oil is a mixture of polyether modified silicone oil and hexadecyltrimethoxysilane, and the third modified silicone oil is a linear polydimethylsiloxane terminated with a hydroxyl-terminated silicone oil and a boron-containing five-membered heterocyclic group.

[0016] Wherein, the first modified silicone oil is a mixed silicone oil of phenyl polytrimethylsiloxane and polydimethylsiloxane in a mass ratio of 1 to 3.7:1.

[0017] The second modified silicone oil is a mixed silicone oil of polyether modified silicone oil and hexadecyltrimethoxysilane in a mass ratio of 13.5 to 20:1.

[0018] The third modified silicone oil is a hydroxyl-terminated silicone oil with a branching factor of 0.35 to 0.75 and a linear polydimethylsiloxane terminated by a boron-containing five-membered heterocyclic group.

[0019] The filler Y is vacuum partially deoxidized tin oxide, the treatment pressure is -0.03MPa to -0.12MPa, and the vacuum treatment time is 1.5 to 2.5h.

[0020] The treatment agent is any one of cobalt acetate, nickel oxalate, manganese citrate, dibutyltin dilaurate, and ammonium ferric citrate, or a mixture of two of the two.

[0021] The dispersant is any one of pentaerythritol isostearate, isononyl isostearate and isodecyl hexadecanoate, or a mixture of two of the two.

[0022] The modifier is any one of methyl butynol, propynol, tributylamine and dimethyl fumarate or a mixture of two thereof.

[0023] The thickener is any one of saponin gum and glyceryl monostearate or a mixture of both.

[0024] This application further proposes a method for preparing the above-mentioned long-life and high-thermal-conductivity two-component gel, comprising the following steps:

[0025] (1) Preparation of component A:

[0026] 1) Add the modifier to the first modified silicone oil and stir for 8-12 minutes to obtain an intermediate 1;

[0027] 2) Add dispersant and filler X while stirring intermediate 1, and stir for 30-40 minutes to obtain intermediate 2;

[0028] 3) Add the second modified silicone oil and the treating agent to the intermediate 2 in sequence, and stir ultrasonically for 15-25 minutes to obtain the intermediate 3;

[0029] 4) Add the thickener while stirring the intermediate 3, stir evenly, and then stir under vacuum for 30-50 minutes to obtain component A;

[0030] (2) Preparation of component B:

[0031] a) heating the first modified silicone oil to 60-80 degrees and stirring for 20 minutes, then adding the modifier and stirring for 5-10 minutes to obtain intermediate 4;

[0032] b) adding the second modified silicone oil to the intermediate four, stirring evenly, adding filler Y, and stirring under vacuum for 40-60 minutes to obtain the intermediate five;

[0033] c) adding the third modified silicone oil to the obtained intermediate V while stirring, and stirring evenly to obtain component B;

[0034] The thermal conductive gel of component A and the thermal conductive gel of component B obtained above are mixed in a required proportion to obtain the two-component thermal conductive gel.

[0035] The vacuum degree of the above vacuum conditions is -0.02 MPa to -0.06 MPa, for example, it can be -0.02 MPa, -0.03 MPa, -0.04 MPa, -0.05 MPa or -0.06 MPa.

[0036] The present invention further proposes the use of the long-life high thermal conductivity two-component gel as a thermal interface material.

[0037] Beneficial effects: The present invention regulates the physicochemical properties of each component and combines it with the filler microstructure design to prepare a two-component thermal conductive gel with high stability. The thermal conductivity of the prepared thermal conductive gel is above 4W / (m*K) and it has very high stability. After continuous high-temperature aging, high and low temperature shock, high temperature and high humidity, it still has excellent stability and no oil leakage. DETAILED DESCRIPTION

[0038] The present invention will be further described in detail below with reference to specific embodiments.

[0039] The filler Y used in the following examples is commercially available tin oxide placed in a high-temperature vacuum sintering furnace at 1600°C in vacuum (-0.03MPa to -0.12MPa) for 95 minutes to obtain partially deoxidized tin oxide (i.e., SnOx).

[0040] Example 1: Preparation method of long-life high thermal conductivity two-component gel.

[0041] Two-component thermal conductive gel includes component A and component B;

[0042] Component A comprises the following components in parts by weight: 88 parts of filler X, 0.3 parts of a first modified silicone oil, 0.05 parts of a second modified silicone oil, 0.08 parts of cobalt acetate, 0.4 parts of pentaerythritol isostearate, 0.05 parts of methyl butynol, and 0.15 parts of saponin gum, wherein filler X is a commercially available spinel structure aluminum titanium silicate;

[0043] The B component comprises the following components in parts by weight: 86 parts of filler Y, 1.5 parts of the first modified silicone oil, 0.2 parts of the second modified silicone oil, 0.3 parts of the modifier, and 0.18 parts of the third modified silicone oil.

[0044] Among them, the first modified silicone oil is a mixed silicone oil of phenyl polytrimethylsiloxane and polydimethylsiloxane in a mass ratio of 1:1; the second modified silicone oil is a mixed silicone oil of polyether modified silicone oil and hexadecyltrimethoxysilane in a mass ratio of 20:1; the third modified silicone oil is a hydroxyl-terminated silicone oil with a branching factor of 0.35 and a linear polydimethylsiloxane terminated with a boron-containing five-membered heterocyclic group;.

[0045] The specific preparation process of component A is as follows:

[0046] 1) Adding the modifier to the first modified silicone oil and stirring for 8 minutes to obtain an intermediate 1;

[0047] 2) While stirring the intermediate 1, dispersant and filler X were added and stirred for 40 minutes to obtain the intermediate 2;

[0048] 3) Add the second modified silicone oil and the treating agent to the intermediate 2 in sequence, and stir ultrasonically for 20 minutes to obtain the intermediate 3;

[0049] 4) Add the thickener while stirring the intermediate 3, stir evenly, and then stir under vacuum for 40 minutes to obtain the thermal conductive gel of component A.

[0050] The specific preparation process of component B is as follows:

[0051] a) heating the first modified silicone oil to 60 degrees and stirring for 20 minutes, then adding the modifier and stirring for 10 minutes to obtain intermediate 4;

[0052] b) adding the second modified silicone oil to the intermediate 4, stirring evenly, adding filler Y, and stirring under vacuum for 40 minutes to obtain the intermediate 5;

[0053] c) adding the third modified silicone oil to the obtained intermediate V while stirring, and stirring evenly to obtain the thermal conductive gel of component B.

[0054] The vacuum degree of the above vacuum conditions is -0.02MpaMPa.

[0055] The preparation process of the two-component thermal conductive gel is as follows:

[0056] The thermal conductive gel of component A and the thermal conductive gel of component B obtained above are mixed in a ratio of 1:1 to obtain the two-component thermal conductive gel.

[0057] Example 2: Preparation method of long-life high thermal conductivity two-component gel.

[0058] The two-component thermally conductive gel comprises component A and component B, wherein:

[0059] Component A comprises the following components in parts by weight: 80 parts of filler X, 1 part of first modified silicone oil, 0.15 parts of second modified silicone oil, 0.06 parts of treating agent, 0.8 parts of dispersant, 0.18 parts of modifier, and 0.09 parts of thickener;

[0060] Component B comprises the following components in parts by weight: 92 parts of filler Y, 3.5 parts of the first modified silicone oil, 0.05 parts of the second modified silicone oil, 0.5 parts of the modifier, and 0.05 parts of the third modified silicone oil.

[0061] Among them, filler X is whisker-like potassium sodium titanate; the first modified silicone oil is a mixed silicone oil of phenyl polytrimethylsiloxane and polydimethylsiloxane in a mass ratio of 1:1; the second modified silicone oil is a mixed silicone oil of polyether-modified silicone oil and hexadecyltrimethoxysilane in a mass ratio of 20:1; the third modified silicone oil is a hydroxyl-terminated silicone oil with a branching factor of 0.35 and a linear polydimethylsiloxane terminated with a boron-containing five-membered heterocyclic group; the treating agent is a mixture of nickel oxalate and manganese citrate in a mass ratio of 0.3:1; the dispersant is a mixture of isononyl isostearate and isodecyl hexadecanoate in a mass ratio of 7:1; the modifier is a mixture of propargyl alcohol and tributylamine in a mass ratio of 1:2; and the thickener is glyceryl monostearate.

[0062] The specific preparation process of component A is as follows:

[0063] 1) Adding the modifier to the first modified silicone oil and stirring for 12 minutes to obtain an intermediate 1;

[0064] 2) Add dispersant and filler X while stirring intermediate 1, and stir for 30 minutes to obtain intermediate 2;

[0065] 3) Add the second modified silicone oil and the treating agent to the intermediate 2 in sequence, and stir ultrasonically for 15 minutes to obtain the intermediate 3;

[0066] 4) Add the thickener while stirring the intermediate 3, stir evenly, and then stir under vacuum for 50 minutes to obtain the thermal conductive gel of component A.

[0067] The specific preparation process of component B is as follows:

[0068] a) heating the first modified silicone oil to 80 degrees and stirring for 20 minutes, then adding the modifier and stirring for 5 minutes to obtain intermediate 4;

[0069] b) adding the second modified silicone oil to the intermediate 4, stirring evenly, adding filler Y, and stirring under vacuum for 60 minutes to obtain the intermediate 5;

[0070] c) adding the third modified silicone oil to the obtained intermediate V while stirring, and stirring evenly to obtain the thermal conductive gel of component B.

[0071] The vacuum degree of the above vacuum conditions is -0.06 MPa.

[0072] The preparation process of the two-component thermal conductive gel is as follows:

[0073] The thermal conductive gel of component A and the thermal conductive gel of component B obtained above are mixed in a ratio of 1:1 to obtain the two-component thermal conductive gel.

[0074] Example 3: The two-component thermally conductive gel includes component A and component B.

[0075] Component A contains the following components in parts by weight:

[0076] Filler X84 parts, first modified silicone oil 0.65 parts, second modified silicone oil 0.3 parts, treating agent 0.07 parts, dispersant 0.6 parts, modifier 0.3 parts, thickener 0.06 parts;

[0077] Component B contains the following components in parts by weight:

[0078] Filler Y 89 parts, first modified silicone oil 2 parts, second modified silicone oil 0.13 parts, modifier 0.4 parts, third modified silicone oil 0.11 parts.

[0079] Among them, filler X is a mixture of spinel structure aluminum titanium silicate and whisker-like potassium sodium titanate (mixing ratio 2:1); the first modified silicone oil is a mixed silicone oil of phenyl polytrimethylsiloxane and polydimethylsiloxane in a mass ratio of 1:1; the second modified silicone oil is a mixed silicone oil of polyether modified silicone oil and hexadecyltrimethoxysilane in a mass ratio of 20:1; the third modified silicone oil is a hydroxyl-terminated silicone oil with a branching factor of 0.35 and a linear polydimethylsiloxane terminated with a boron-containing five-membered heterocyclic group; filler Y is 1600 degrees vacuum partially deoxidized tin oxide (i.e., SnOx); the treating agent is a mixture of dibutyltin dilaurate and ammonium ferric citrate in a mass ratio of 1:1.8; the dispersant is isodecyl hexadecanoate; the modifier is dimethyl fumarate; and the thickener is a mixture of saponin gum and glyceryl monostearate in a mass ratio of 3.5:1.

[0080] The specific preparation process of component A is as follows:

[0081] 1) Adding the modifier to the first modified silicone oil and stirring for 10 minutes to obtain an intermediate 1;

[0082] 2) While stirring the intermediate 1, dispersant and filler X were added and stirred for 35 minutes to obtain the intermediate 2;

[0083] 3) Add the second modified silicone oil and the treating agent to the intermediate 2 in sequence, and stir ultrasonically for 25 minutes to obtain the intermediate 3;

[0084] 4) Add the thickener while stirring the intermediate 3, stir evenly, and then stir under vacuum for 30 minutes to obtain the thermal conductive gel of component A.

[0085] The specific preparation process of component B is as follows:

[0086] a) heating the first modified silicone oil to 70 degrees Celsius and stirring for 20 minutes, then adding the modifier and stirring for 8 minutes to obtain intermediate 4;

[0087] b) adding the second modified silicone oil to the intermediate 4, stirring evenly, adding filler Y, and stirring under vacuum for 50 minutes to obtain the intermediate 5;

[0088] c) adding the third modified silicone oil to the obtained intermediate V while stirring, and stirring evenly to obtain the thermal conductive gel of component B.

[0089] The vacuum degree of the above vacuum conditions is -0.04 MPa.

[0090] The preparation process of the two-component thermal conductive gel is as follows:

[0091] The thermal conductive gel of component A and the thermal conductive gel of component B obtained above were mixed in a ratio of 1:0.95 to obtain the two-component thermal conductive gel.

[0092] Comparative Example 1:

[0093] The main components of similar international products on the market are vinyl silicone oil, alumina, catalyst and inhibitor.

[0094] Comparative Example 2:

[0095] The main components of similar domestic products on the market are vinyl silicone oil, alumina, catalyst and inhibitor.

[0096] The thermal conductivity and viscosity results for the Examples and Comparative Examples are shown in Table 1. Viscosity: measured in accordance with ASTM D2196 using a 96# spindle in a Bollefy viscometer. The thermal grease was introduced into the rotational viscometer and rotated continuously at 20 rpm for 2 minutes at 25°C. Thermal conductivity: measured in accordance with ASTM D5470.

[0097] Table 1 Thermal conductivity and viscosity results of Examples and Comparative Examples

[0098]

[0099]

[0100] It can be seen from Table 1 that the thermal conductive gel prepared by the method of the present invention has a higher thermal conductivity coefficient and its performance is better than similar products at home and abroad.

[0101] The Example 1 was subjected to continuous high temperature aging, high temperature and high humidity, and high and low temperature impact tests. The results are shown in Table 2.

[0102] High temperature aging: The thermal conductive gel is subjected to performance testing at 150°C every week.

[0103] High temperature and high humidity: The thermal conductive gel is tested at a temperature of 85°C and a humidity of 85% every other week.

[0104] High and low temperature aging: The thermal conductive gel is kept at 150℃ for 30 minutes, then kept at -40℃ for 30 minutes, and the cycle is repeated. The performance test is performed every other week.

[0105] Table 2 High temperature aging, high temperature and high humidity, and high and low temperature impact test results of Example 1

[0106]

[0107] The above tests show that the present invention achieves high-low temperature and high-humidity resistance of the thermally conductive gel through the composition and microstructure design of the filler, the molecular structure design of the silicone oil, the organic regulation of the treating agent, dispersant, and thickener, and the control of the process flow, which is beneficial to extending the service life of the thermally conductive gel.

[0108] Finally, it should be noted that, in this article, relational terms such as first and second, etc. are merely used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations.

[0109] The above embodiments are intended only to illustrate the technical concepts and features of the present invention and are only used to help understand the method and core concept of the present application, and are not intended to limit the scope of protection of the present invention. Any equivalent changes or modifications made based on the spirit of the present invention should be included in the scope of protection of the present invention.

Claims

1. A long-life high thermal conductivity two-component gel, characterized in that: The two-component gel comprises component A and component B, wherein component A comprises the following components in parts by weight: Filler X 80-88 parts, first modified silicone oil 0.3-1 part, second modified silicone oil 0.05-0.3 part, treating agent 0.06-0.08 part, dispersant 0.4-0.8 part, modifier 0.05-0.3 part, thickener 0.06-0.15 part; The B component comprises the following components in parts by weight: Filler Y 86-92 parts, first modified silicone oil 1.5-3.5 parts, second modified silicone oil 0.05-0.2 parts, modifier 0.3-0.5 parts, third modified silicone oil 0.05-0.18 parts; Filler X is one or a mixture of spinel-structured aluminum titanium silicate and whisker-shaped potassium sodium titanate; Filler Y is partially deoxidized tin oxide; The first modified silicone oil is a mixture of phenyl polytrimethylsiloxane and polydimethylsiloxane, the second modified silicone oil is a mixture of polyether modified silicone oil and hexadecyltrimethoxysilane, and the third modified silicone oil is a hydroxyl-terminated silicone oil and a linear polydimethylsiloxane terminated with a boron-containing five-membered heterocyclic group; The treating agent is any one of cobalt acetate, nickel oxalate, manganese citrate, dibutyltin dilaurate, and ammonium ferric citrate, or a mixture of two of them; the modifier is any one of methylbutynol, propynol, tributylamine, and dimethyl fumarate, or a mixture of two of them; and the thickener is any one of saponin gum and glyceryl monostearate, or a mixture of two of them.

2. The long-life high thermal conductivity two-component gel according to claim 1, characterized in that: The first modified silicone oil is a mixed silicone oil of phenyl polytrimethylsiloxane and polydimethylsiloxane in a mass ratio of 1 to 3.7:

1.

3. The long-life high thermal conductivity two-component gel according to claim 1, characterized in that: The second modified silicone oil is a mixed silicone oil of polyether modified silicone oil and hexadecyltrimethoxysilane in a mass ratio of 13.5 to 20:

1.

4. The long-life high thermal conductivity two-component gel according to claim 1, characterized in that: The third modified silicone oil is a hydroxyl-terminated silicone oil with a branching factor of 0.35 to 0.75 and a linear polydimethylsiloxane terminated by a boron-containing five-membered heterocyclic group.

5. The long-life high thermal conductivity two-component gel according to claim 1, characterized in that: The filler Y is vacuum partially deoxidized tin oxide, the treatment pressure is -0.03MPa to -0.12MPa, and the vacuum treatment time is 1.5 to 2.5h.

6. The long-life high thermal conductivity two-component gel according to claim 1, characterized in that: The dispersant is any one of pentaerythritol isostearate, isononyl isostearate and isodecyl hexadecanoate, or a mixture of two of the two.

7. The method for preparing the long-life high thermal conductivity two-component gel according to any one of claims 1 to 6, characterized in that: The steps include: (1) Preparation of component A: 1) Add the modifier to the first modified silicone oil and stir for 8-12 minutes to obtain intermediate 1; 2) Add dispersant and filler X while stirring intermediate 1, and stir for 30-40 minutes to obtain intermediate 2; 3) Add the second modified silicone oil and the treating agent to the intermediate 2 in sequence, and stir ultrasonically for 15-25 minutes to obtain the intermediate 3; 4) Add the thickener while stirring the intermediate 3, stir evenly, and then stir under vacuum for 30-50 minutes to obtain component A; (2) Preparation of component B: a) Heat the first modified silicone oil to 60-80 degrees Celsius and stir for 20 minutes, then add the modifier and stir for 5-10 minutes to obtain intermediate 4; b) Add the second modified silicone oil to the intermediate 4, stir evenly, then add filler Y, and stir under vacuum for 40-60 minutes to obtain the intermediate 5; c) adding the third modified silicone oil to the obtained intermediate V while stirring, and stirring evenly to obtain component B; The thermal conductive gel of component A and the thermal conductive gel of component B obtained above are mixed in a required proportion to obtain the two-component thermal conductive gel.

8. The preparation method according to claim 7, characterized in that The vacuum degree of the vacuum condition is -0.02MPa to -0.06Mpa.

9. Use of the long-life, high-thermal-conductivity two-component gel according to any one of claims 1 to 6 as a thermal interface material.

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