Long-life high-thermal-conductivity two-component gel as well as preparation method and application thereof

Abstract

The invention discloses a bi-component gel with long service life and high thermal conductivity. By regulating and controlling the physicochemical properties of the components and combining the microstructure design of the filler, the prepared bi-component heat-conducting gel has the characteristics of high stability, low heat conductivity coefficient change in high-temperature, low-temperature and high-humidity environments, unobvious oil outlet condition, long service life and high heat conductivity.

Description

Technical Field

[0001] The invention belongs to the technical field of thermal conductive materials, and specifically relates to a two-component gel, and in particular to a long-life high thermal conductive 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. Electronic components generate a lot of heat when working, which affects the performance and life of the components. Therefore, heat dissipation is an important issue that electronic products need to consider. Thermal interface materials can effectively improve the heat dissipation effect and are a necessity in many heat dissipation systems. Thermal conductive gel is a high-performance thermal conductive interface material. Compared with thermal conductive gaskets and thermal conductive silicone grease, thermal conductive gel has the advantages of low thermal resistance, low assembly thickness, stable state after vulcanization, not easy to oil, and crack. 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 silicone grease. Thermal conductive gel is mainly divided into single-component thermal conductive gel and two-component thermal conductive gel. Among them, the two-component thermal conductive gel is formed by mixing the 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 it is necessary to select appropriate silicone oil and thermally conductive fillers during preparation. Commonly used thermally conductive fillers are mainly metals (silver, copper, aluminum, etc.); metal oxides (aluminum oxide, magnesium oxide, zinc oxide, etc.); non-metallic materials (aluminum nitride, silicon carbide, graphite, etc.). The shapes of fillers can be divided into granular, flake, spherical and fibrous. Thermally conductive gel products on the market still have poor aging resistance and obvious oil release, which not only affects the thermal conductivity but also affects the usage, and is not conducive to the efficient heat dissipation of electronic components.

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

[0005] CN111876135A discloses a thermally conductive gel and a preparation method thereof. By selecting thermally conductive fillers of different particle sizes, different shapes and high thermal conductivity for compounding and preparing under a special production process, the thermally conductive gel prepared has a thermal conductivity of 7.6 to 9.2 W / mK and good thermal conductivity, but the thermally conductive gel prepared by this technical solution has poor high temperature resistance.

[0006] CN110330947A discloses a thermally conductive gel containing carbon nanotubes and its preparation and application. By using carbon nanotubes and conventional fillers as thermally conductive fillers, the high thermal conductivity of carbon nanotubes and the large amount of filling of conventional fillers are fully utilized, and the silicone oil is cross-linked by pre-curing, which improves the anti-aging performance of the thermally conductive gel and also makes the thermal conductivity stable.

[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: In view of the problem that the current thermal conductive gel is easy to age in high and low temperature environments, especially the oil leakage phenomenon after long-term use, the present invention provides a long-life high thermal conductivity two-component gel and a preparation method thereof. The present invention controls the physicochemical properties of each component and combines the filler microstructure design to prepare a two-component thermal conductive gel with high stability. In high and low temperature and high humidity environments, the thermal conductivity coefficient changes little, and the oil leakage is not obvious, showing the characteristics of 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, the two-component gel comprising component A and 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 parts, second modified silicone oil 0.05-0.3 parts, treatment agent 0.06-0.08 parts, dispersant 0.4-0.8 parts, modifier 0.05-0.3 parts, thickener 0.06-0.15 parts;

[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 structure 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 hexadecyl trimethoxysilane, 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 with a boron-containing five-membered heterocyclic group.

[0019] The filler Y is partially deoxidized tin oxide in vacuum, 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 them.

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

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

[0025] (1) Preparation of component A:

[0026] 1) adding the modifier to the first modified silicone oil and stirring 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 four;

[0032] b) adding the second modified silicone oil to the intermediate 4, stirring evenly, adding filler Y, and stirring under vacuum for 40-60 minutes to obtain the intermediate 5;

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

[0034] The thermally conductive gel of component A and the thermally conductive gel of component B obtained above are mixed in a required proportion to obtain the two-component thermally 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 two-component thermally conductive gel prepared by the present invention has high stability by regulating the physicochemical properties of each component and combining the filler microstructure design. The thermal conductivity of the prepared thermally conductive gel is above 4W / (m*K) and 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 is further described in detail below in conjunction with specific implementation modes.

[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 (ie, SnOx).

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

[0041] The two-component thermally 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 the first modified silicone oil, 0.05 parts of the 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 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, add the dispersant and filler X, and stir for 40 minutes to obtain the intermediate 2;

[0048] 3) adding the second modified silicone oil and the treating agent to the intermediate 2 in sequence, stirring with ultrasound for 20 min, 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 four;

[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 B component thermal conductive gel.

[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 thermally conductive gel of component A and the thermally conductive gel of component B obtained above are mixed in a ratio of 1:1 to obtain the two-component thermally 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 includes 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 hexadecyl 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) while stirring the intermediate 1, add the dispersant and filler X, and stir for 30 minutes to obtain the intermediate 2;

[0065] 3) adding the second modified silicone oil and the treating agent to the intermediate 2 in sequence, stirring with ultrasound for 15 min, 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 four;

[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 B component thermal conductive gel.

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

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

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

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

[0075] Component A contains the following components 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 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 hexadecyl trimethoxysilane 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; 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, add the dispersant and filler X, and stir for 35 minutes to obtain the intermediate 2;

[0083] 3) adding the second modified silicone oil and the treating agent to the intermediate 2 in sequence, stirring with ultrasound for 25 min, 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 and stirring for 20 minutes, then adding the modifier and stirring for 8 minutes to obtain intermediate four;

[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 B component thermal conductive gel.

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

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

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

[0096] The thermal conductivity and viscosity results of the embodiments and comparative examples of the present application are shown in Table 1. Viscosity: measured with reference to ASTM D2196 using a 96# rotor of a Bollfeld viscometer, at 25°C, the thermal grease was introduced into the rotational viscometer and rotated continuously at 20 rpm for 2 minutes; Thermal conductivity: tested with reference to ASTM D5470.

[0097] Table 1 Thermal conductivity and viscosity results of the embodiments and comparative examples

[0098]

[0099]

[0100] It can be seen from Table 1 that the thermally conductive gel prepared by the method of the present invention has a higher thermal conductivity 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 tests at 150°C every other week.

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

[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 the high and 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, the dispersant and the thickener, and the control of the process flow, which is beneficial to prolonging 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 only for illustrating the technical concept and features of the present invention, and are only used to help understand the method and core idea of ​​the present application, and cannot be used to limit the protection scope of the present invention. Any equivalent changes or modifications made according to the spirit of the present invention should be included in the protection scope 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 parts, second modified silicone oil 0.05-0.3 parts, treatment agent 0.06-0.08 parts, dispersant 0.4-0.8 parts, modifier 0.05-0.3 parts, thickener 0.06-0.15 parts; 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 structure 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 hexadecyl trimethoxysilane, 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.

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; the second modified silicone oil is a mixed silicone oil of polyether modified silicone oil and hexadecyl trimethoxysilane in a mass ratio of 13.5 to 20:

1.

3. 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 with a boron-containing five-membered heterocyclic group.

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

5. The long-life high thermal conductivity two-component gel according to claim 1, characterized in that: 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 them.

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 them.

7. The long-life high thermal conductivity two-component gel according to claim 1, characterized in that: The modifier is any one of methyl butynol, propynol, tributylamine and dimethyl fumarate or a mixture of two thereof; the thickener is any one of saponin gum and glyceryl monostearate or a mixture of two thereof.

8. The method for preparing the long-life high thermal conductivity two-component gel according to any one of claims 1 to 7, 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 thickener while stirring intermediate 3, stir evenly and then stir under vacuum for 30-50 minutes to obtain component A; (2) Preparation of component B: 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; 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 thermally conductive gel of component A and the thermally conductive gel of component B obtained above are mixed in a required proportion to obtain the two-component thermally conductive gel.

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

10. Use of the long-life high thermal conductivity two-component gel according to any one of claims 1 to 7 as a thermal interface material.

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