High-performance non-silicone thermal grease and preparation method therefor

Abstract

The present invention belongs to the field of thermally conductive materials, and specifically relates to the field of A61L24, more specifically to a high-performance non-silicone thermal grease and a preparation method therefor. The raw materials for preparing the high-performance non-silicone thermal grease comprise, in parts by mass, 5-6 parts of a non-silicone oil, 90-95 parts of a thermally conductive compound filler, 0.1-1 part of a treatment agent, and 0.1-0.5 parts of an antioxidant, wherein the non-silicone oil is aviation lubricating oil, and the thermally conductive compound filler comprises a 10 µm aluminum powder, a 2 µm aluminum powder, 1 µm aluminum oxide and 0.1 µm zinc oxide. The prepared non-silicone thermal grease has a high thermal conductivity, low thermal resistance, good high-temperature resistance, and a good practical use effect.

Description

A high-performance non-silicone thermal grease and its preparation method Technical Field

[0001] The present invention belongs to the field of thermal conductive materials, in particular to the field of A61L24, and more specifically to a high-performance non-silicon thermal grease and a preparation method thereof. Background Art

[0002] With technological advancements and the advent of the electronic information technology era, electronic products are becoming increasingly miniaturized. The heat generated by electronic products can damage the body, causing device aging, shortening lifespan, and malfunctioning. Therefore, rapid heat conduction and dissipation is a critical technical challenge facing electronic products. Commonly used thermal conductive materials include thermal grease. Thermal grease is typically made from silicone oil as the primary raw material, with fillers such as metal oxides added. Through a series of processing steps, thermal grease offers low thermal resistance and high thermal conductivity, providing both insulation and sealing properties. It can also transfer heat through gaps in heating and cooling areas, making it an excellent thermal conductor. However, the introduction of silicone oil can lead to overflow at high temperatures. For example, when applied to electronic products, such overflow can cause short circuits, freezing, and even fire. Non-silicone thermal grease, by using a non-silicone oil-based system, effectively avoids these issues. The addition of functional additives such as treatment agents and antioxidants to non-silicone systems can improve the high-temperature resistance of non-silicone materials.

[0003] The prior art CN108676212A discloses a non-silicon thermally conductive gasket suitable for use in optical components. The raw materials for its preparation include a base resin, a composite thermally conductive filler, a halogen-free flame retardant, and a functional additive. The thermal conductivity coefficient is high, which can reach above 1W / m·K, and the heat resistance effect is good. The prior art CN110105638A discloses a low-density, high-thermal-conductivity non-silicon material. The raw materials include a thermally conductive filler, a carrier, etc., which has excellent thermal conductivity and insulation properties. However, the above-mentioned prior art adopts a technical solution of compounding a polymer organic resin and a thermally conductive filler, which is not conducive to reducing the thermal resistance and improving the heat resistance of the non-silicon thermally conductive material.

[0004] Summary of the Invention

[0005] In order to solve the above technical problems, the first aspect of the present invention provides a high-performance non-silicone thermal grease, the raw materials for its preparation, calculated by mass, include: 5-6 parts of non-silicone oil, 90-95 parts of thermal conductive compound filler, 0.1-1 part of treatment agent, and 0.1-0.5 part of antioxidant.

[0006] Preferably, the non-silicone oil includes one of aviation lubricating oil, aviation gear oil, engine lubricating oil, aviation hydraulic oil, and general lubricating oil for power transmission.

[0007] Further preferably, the non-silicone oil includes aviation lubricating oil.

[0008] Preferably, the aviation lubricant has a kinematic viscosity of 10-24 cst at 40°C and a usable range of -40 to 180°C; as an implementable case, the aviation lubricant has a kinematic viscosity of 13 cst at 40°C and a usable range of -40 to 180°C, and the model is Shell W15W-50 aviation lubricant.

[0009] Preferably, the aviation lubricant has a kinematic viscosity of 4-17 cst at 100°C and a usable range of -40 to 204°C. As an implementable case, the aviation lubricant has a kinematic viscosity of 5.05 cst at 100°C and a usable range of -40 to 204°C, and the model is Sinopec Petrochemical Research Institute 4050 high-temperature synthetic aviation lubricant.

[0010] Preferably, the thermally conductive composite filler includes at least two of: alumina, zinc oxide, boron nitride, aluminum nitride, aluminum powder, silver powder, graphene, aluminum nitride, silicon carbide, and quartz powder.

[0011] Further preferably, the thermally conductive composite filler includes aluminum powder, aluminum oxide and zinc oxide.

[0012] Preferably, the particle size of the aluminum powder is 1 to 10 μm; as an implementable case, the particle size of the aluminum powder includes at least one of 1 μm, 2 μm, 3 μm, 5 μm, and 10 μm.

[0013] More preferably, the aluminum powder has a particle size of 2 μm and 10 μm.

[0014] Preferably, the particle size of the aluminum oxide is 1-2 μm.

[0015] More preferably, the particle size of the aluminum oxide is 1 μm.

[0016] Preferably, the particle size of the zinc oxide is less than 1 μm.

[0017] More preferably, the particle size of the zinc oxide is 0.1 μm.

[0018] Preferably, the mass ratio of the 10 μm aluminum powder, 2 μm aluminum powder, 1 μm aluminum oxide and 0.1 μm zinc oxide is (40-50): (15-25): (15-25): (10-15).

[0019] Further preferably, the mass ratio of the 10 μm aluminum powder, 2 μm aluminum powder, 1 μm aluminum oxide and 0.1 μm zinc oxide is (40-45): (15-20): (20-25): (10-12).

[0020] The preparation method of the thermal conductive composite filler is to uniformly mix 10 μm aluminum powder, 2 μm aluminum powder, 1 μm aluminum oxide and 0.1 μm zinc oxide.

[0021] Preferably, the treating agent includes one or more of a silane coupling agent, a titanate coupling agent, and an aluminate coupling agent.

[0022] Further preferably, the treating agent includes a silane coupling agent; as an implementable case, the silane coupling agent includes one of KBM-3, KH-550, KH-560, KH-570, KH-580, KH-590, and A-151.

[0023] More preferably, the silane coupling agent is KBM-3.

[0024] The present invention does not further limit the components of the antioxidant. Any auxiliary agent that can play an antioxidant role can be used, including but not limited to: one or more of antioxidant 1010, antioxidant 1076, antioxidant 168, antioxidant 264, antioxidant 7501, and anti-aging agent B125.

[0025] A second aspect of this embodiment provides a method for preparing high-performance non-silicone thermal grease, comprising at least the following steps:

[0026] S1. Add non-silicone oil and antioxidant into a planetary mixer and stir evenly at 60-80℃;

[0027] S2. Add thermal conductive composite filler and treatment agent in sequence, and stir at 60-80°C for 1-2 hours;

[0028] S3, heating to 90-120℃, vacuuming for 0.5-1h;

[0029] S4. Cool to room temperature and discharge. Beneficial effects

[0030] (1) In order to solve the technical defect of existing silicone oil system thermal conductive materials that silicone oil is easy to overflow at high temperature and thus damage the product, the present invention uses non-silicone oil as the preparation raw material, which can effectively improve the high temperature resistance of thermal grease. At the same time, the inventors found that the selection of non-silicone oil with moderate dynamic viscosity and wide application range, especially Shell W15W-5 aviation lubricant with a kinematic viscosity of 13 cst at 40°C and a range of application of -40 to 180°C, and Sinopec Petrochemical Institute of Petroleum 4050 high-temperature synthetic aviation lubricant with a kinematic viscosity of 5.05 cst at 100°C and a range of application of -40 to 204°C, can not only ensure that the non-silicone thermal grease has low thermal resistance, but also can withstand high temperatures of 125°C.

[0031] (2) While the use of non-silicone oil can improve the high-temperature resistance of thermal grease to a certain extent, the inventors discovered during actual formulation testing that the amount of non-silicone oil used needs to be strictly controlled. In this preparation system, 5-6 parts of non-silicone oil are preferred. Excessive amounts of non-silicone oil can affect the uniformity of the thermally conductive composite filler in the system, reduce the viscosity of the non-silicone thermal grease, and reduce the adhesion strength of the thermal grease to electronic products, affecting normal use.

[0032] (3) As the core component for improving the thermal conductivity of thermal grease, the selection of thermally conductive compound filler is of vital importance. First, in order to improve the thermal conductivity and material density of thermal grease, the inventors preferred 2μm and 10μm aluminum powders. Then, in order to improve the corrosion resistance and high temperature resistance of the thermally conductive compound filler, the inventors added and used 1μm aluminum oxide, which can effectively fill the space gaps formed by stacking aluminum powders of different particle sizes. However, the inventors found that there are still certain gaps between the thermally conductive compound fillers. Since the thermal resistance of air is relatively large, it is not conducive to the low thermal resistance performance of non-silicon thermal grease. The inventors found that zinc oxide with a particle size of less than 1μm, especially 0.2μm zinc oxide, can be used to further fill the gaps in the thermally conductive compound filler, further reducing the thermal resistance of non-silicon thermal grease, while increasing the density of its material and improving the high temperature resistance and stability of the thermal grease.

[0033] (IV) The inventors also discovered that when the mass ratio of 10 μm aluminum powder, 2 μm aluminum powder, 1 μm aluminum oxide, and 0.1 μm zinc oxide is controlled to be (40-50): (15-25): (15-25): (10-15), the density of the non-silicone thermal grease can be effectively increased, thereby reducing the thermal conductivity of the material; if the mass fractions of 10 μm aluminum powder, 2 μm aluminum powder, and 1 μm aluminum oxide are not within the optimal implementation range, due to their relatively large particle sizes, more space gaps are formed, which is not conducive to the tight filling of 0.1 μm zinc oxide in the non-silicone thermal grease, thereby affecting the thermal conductivity of the product.

[0034] (5) The present invention performs heating and vacuuming operations after preparing the non-silicone thermal grease, which can effectively reduce impurities such as water and air in the thermal grease, thereby improving the aging resistance of the non-silicone thermal grease. The product can pass the 125°C high temperature resistance, double 85 standard test, and high and low temperature cycle test of -40 to 125°C, and has excellent actual use effect. DETAILED DESCRIPTION

[0035] Example 1

[0036] The first aspect of this embodiment provides a high-performance non-silicone thermal grease, the raw materials for its preparation are, in parts by mass: 5 parts of aviation lubricating oil; 84 parts of thermally conductive composite filler, including 42 parts of 10μm aluminum powder, 20 parts of 2μm aluminum powder, 20 parts of 1μm aluminum oxide and 12 parts of 0.1μm zinc oxide; 0.7 parts of silane coupling agent, and 0.3 parts of antioxidant.

[0037] The preparation method of the thermal conductive composite filler is to uniformly mix 10 μm aluminum powder, 2 μm aluminum powder, 1 μm aluminum oxide and 0.1 μm zinc oxide.

[0038] The aviation lubricant is Shell W15W-50 aviation lubricant and Sinopec Petrochemical Institute 4050 high-temperature synthetic aviation lubricant, with a mass ratio of 1:1; the silane coupling agent is KBM-3; the antioxidant is antioxidant 1010; the aluminum powder, zinc oxide, aluminum oxide, silane coupling agent, and antioxidant are all commercially available products.

[0039] A second aspect of this embodiment provides a method for preparing high-performance non-silicone thermal grease, which specifically includes the following steps:

[0040] S1. Add non-silicone oil and antioxidant into a planetary mixer and stir evenly at 60°C;

[0041] S2. Add thermal conductive composite filler and treatment agent in sequence, and stir at 60°C for 1 hour;

[0042] S3, heating to 100℃ and vacuuming for 1h;

[0043] S4. Cool to room temperature 25°C and discharge.

[0044] Example 2

[0045] The first aspect of this embodiment provides a high-performance non-silicone thermal grease, the raw materials for its preparation are, in parts by mass: 6 parts of aviation lubricating oil; 93 parts of thermally conductive composite filler, including 42 parts of 10μm aluminum powder, 20 parts of 2μm aluminum powder, 20 parts of 1μm aluminum oxide and 11 parts of 0.1μm zinc oxide; 0.7 parts of silane coupling agent; and 0.3 parts of antioxidant.

[0046] The preparation method of the thermal conductive composite filler is to uniformly mix 10 μm aluminum powder, 2 μm aluminum powder, 1 μm aluminum oxide and 0.1 μm zinc oxide.

[0047] The aviation lubricant is Shell W15W-50 aviation lubricant; the silane coupling agent is KBM-3; the antioxidant is antioxidant 1010; the aluminum powder, zinc oxide, aluminum oxide, silane coupling agent, and antioxidant are all commercially available products.

[0048] A second aspect of this embodiment provides a method for preparing high-performance non-silicone thermal grease, which specifically includes the following steps:

[0049] S1. Add non-silicone oil and antioxidant into a planetary mixer and stir evenly at 60°C;

[0050] S2. Add thermal conductive composite filler and treatment agent in sequence, and stir at 60°C for 1 hour;

[0051] S3, heating to 100℃ and vacuuming for 1h;

[0052] S4. Cool to room temperature 25°C and discharge.

[0053] Example 3

[0054] The first aspect of this embodiment provides a high-performance non-silicone thermal grease, the raw materials for its preparation are, in parts by mass: 6 parts of aviation lubricating oil; 93 parts of thermally conductive composite filler, including 42 parts of 10μm aluminum powder, 20 parts of 2μm aluminum powder, 20 parts of 1μm aluminum oxide and 11 parts of 0.1μm zinc oxide; 0.7 parts of silane coupling agent; and 0.3 parts of antioxidant.

[0055] The preparation method of the thermal conductive composite filler is to uniformly mix 10 μm aluminum powder, 2 μm aluminum powder, 1 μm aluminum oxide and 0.1 μm zinc oxide.

[0056] The aviation lubricant is Sinopec Petrochemical Institute of Petroleum 4050 high-temperature synthetic aviation lubricant; the silane coupling agent is KBM-3; the antioxidant is antioxidant 1010; the aluminum powder, zinc oxide, aluminum oxide, silane coupling agent, and antioxidant are all commercially available products.

[0057] A second aspect of this embodiment provides a method for preparing high-performance non-silicone thermal grease, which specifically includes the following steps:

[0058] S1. Add non-silicone oil and antioxidant into a planetary mixer and stir evenly at 60°C;

[0059] S2. Add thermal conductive composite filler and treatment agent in sequence, and stir at 60°C for 1 hour;

[0060] S3, heating to 100℃ and vacuuming for 1h;

[0061] S4. Cool to room temperature 25°C and discharge.

[0062] Example 4

[0063] The first aspect of this embodiment provides a high-performance non-silicone thermal grease, the raw materials for its preparation are, in parts by mass: 5 parts of aviation lubricating oil; 94 parts of thermally conductive composite filler, including 42 parts of 10μm aluminum powder, 20 parts of 2μm aluminum powder, 20 parts of 1μm aluminum oxide and 12 parts of 0.1μm zinc oxide; 0.7 parts of silane coupling agent; and 0.3 parts of antioxidant.

[0064] The preparation method of the thermal conductive composite filler is to uniformly mix 10 μm aluminum powder, 2 μm aluminum powder, 1 μm aluminum oxide and 0.1 μm zinc oxide.

[0065] The aviation lubricant is Shell W15W-50 aviation lubricant; the silane coupling agent is KBM-3; the antioxidant is antioxidant 1010; the aluminum powder, zinc oxide, aluminum oxide, silane coupling agent, and antioxidant are all commercially available products.

[0066] A second aspect of this embodiment provides a method for preparing high-performance non-silicone thermal grease, which specifically includes the following steps:

[0067] S1. Add non-silicone oil and antioxidant into a planetary mixer and stir evenly at 60°C;

[0068] S2. Add thermal conductive composite filler and treatment agent in sequence, and stir at 60°C for 1 hour;

[0069] S3, heating to 100℃ and vacuuming for 1h;

[0070] S4. Cool to room temperature 25°C and discharge.

[0071] Comparative Example 1

[0072] The first aspect of this comparative example provides a high-performance non-silicone thermal grease, and the raw materials for its preparation are, in parts by mass: 6 parts of aviation lubricating oil; 93 parts of thermally conductive composite filler, including 52 parts of 10μm aluminum powder, 10 parts of 2μm aluminum powder, 20 parts of 1μm aluminum oxide and 11 parts of 0.1μm zinc oxide; 0.7 parts of silane coupling agent; and 0.3 parts of antioxidant.

[0073] The preparation method of the thermal conductive composite filler is to uniformly mix 10 μm aluminum powder, 2 μm aluminum powder, 1 μm aluminum oxide and 0.1 μm zinc oxide.

[0074] The aviation lubricant is Shell W15W-50 aviation lubricant; the silane coupling agent is KBM-3; the antioxidant is antioxidant 1010; the aluminum powder, zinc oxide, aluminum oxide, silane coupling agent, and antioxidant are all commercially available products.

[0075] The second aspect of this comparative example provides a method for preparing high-performance non-silicone thermal grease, which specifically comprises the following steps:

[0076] S1. Add non-silicone oil and antioxidant into a planetary mixer and stir evenly at 60°C;

[0077] S2. Add thermal conductive composite filler and treatment agent in sequence, and stir at 60°C for 1 hour;

[0078] S3, heating to 100℃ and vacuuming for 1h;

[0079] S4. Cool to room temperature 25°C and discharge.

[0080] Comparative Example 2

[0081] The first aspect of this comparative example provides a high-performance non-silicone thermal grease, and the raw materials for its preparation are, in parts by mass: 6 parts of aviation lubricating oil; 93 parts of thermally conductive composite filler, including 52 parts of 10μm aluminum powder, 20 parts of 2μm aluminum powder, 10 parts of 1μm aluminum oxide and 11 parts of 0.1μm zinc oxide; 0.7 parts of silane coupling agent; and 0.3 parts of antioxidant.

[0082] The preparation method of the thermal conductive composite filler is to uniformly mix 10 μm aluminum powder, 2 μm aluminum powder, 1 μm aluminum oxide and 0.1 μm zinc oxide.

[0083] The aviation lubricant is Shell W15W-50 aviation lubricant; the silane coupling agent is KBM-3; the antioxidant is antioxidant 1010; the aluminum powder, zinc oxide, aluminum oxide, silane coupling agent, and antioxidant are all commercially available products.

[0084] The second aspect of this comparative example provides a method for preparing high-performance non-silicone thermal grease, which specifically comprises the following steps:

[0085] S1. Add non-silicone oil and antioxidant into a planetary mixer and stir evenly at 60°C;

[0086] S2. Add thermal conductive composite filler and treatment agent in sequence, and stir at 60°C for 1 hour;

[0087] S3, heating to 100℃ and vacuuming for 1h;

[0088] S4. Cool to room temperature 25°C and discharge.

[0089] Comparative Example 3

[0090] The first aspect of this comparative example provides a high-performance non-silicone thermal grease, and the raw materials for its preparation are, in parts by mass: 7 parts of aviation lubricating oil; 92 parts of thermally conductive composite filler, including 52 parts of 10μm aluminum powder, 10 parts of 2μm aluminum powder, 20 parts of 1μm aluminum oxide and 10 parts of 0.1μm zinc oxide; 0.7 parts of silane coupling agent; and 0.3 parts of antioxidant.

[0091] The preparation method of the thermal conductive composite filler is to uniformly mix 10 μm aluminum powder, 2 μm aluminum powder, 1 μm aluminum oxide and 0.1 μm zinc oxide.

[0092] The aviation lubricant is Shell W15W-50 aviation lubricant; the silane coupling agent is KBM-3; the antioxidant is antioxidant 1010; the aluminum powder, zinc oxide, aluminum oxide, silane coupling agent, and antioxidant are all commercially available products.

[0093] The second aspect of this comparative example provides a method for preparing high-performance non-silicone thermal grease, which specifically comprises the following steps:

[0094] S1. Add non-silicone oil and antioxidant into a planetary mixer and stir evenly at 60°C;

[0095] S2. Add thermal conductive composite filler and treatment agent in sequence, and stir at 60°C for 1 hour;

[0096] S3, heating to 100℃ and vacuuming for 1h;

[0097] S4. Cool to room temperature 25°C and discharge.

[0098] Comparative Example 4

[0099] The first aspect of this comparative example provides a high-performance non-silicone thermal grease, and the raw materials for its preparation are, in parts by mass: 7 parts of aviation lubricating oil; 93 parts of thermally conductive composite filler, including 52 parts of 10μm aluminum powder, 20 parts of 2μm aluminum powder, 10 parts of 1μm aluminum oxide and 11 parts of 0.1μm zinc oxide; 0.7 parts of silane coupling agent; and 0.3 parts of antioxidant.

[0100] The preparation method of the thermal conductive composite filler is to uniformly mix 10 μm aluminum powder, 2 μm aluminum powder, 1 μm aluminum oxide and 0.1 μm zinc oxide.

[0101] The aviation lubricant is Shell W15W-50 aviation lubricant; the silane coupling agent is KBM-3; the antioxidant is antioxidant 1010; the aluminum powder, zinc oxide, aluminum oxide, silane coupling agent, and antioxidant are all commercially available products.

[0102] The second aspect of this comparative example provides a method for preparing high-performance non-silicone thermal grease, which specifically comprises the following steps:

[0103] S1. Add non-silicone oil and antioxidant into a planetary mixer and stir evenly at 60°C;

[0104] S2. Add thermal conductive composite filler and treatment agent in sequence, and stir at 60°C for 1 hour;

[0105] S3, heating to 100℃ and vacuuming for 1h;

[0106] S4. Cool to room temperature 25°C and discharge.

[0107] Performance evaluation

[0108] Test objects and test results are detailed in Table 1 and Table 2

[0109] Table 1

[0110] Table 2

Claims

1. A high-performance non-silicone thermal grease, characterized by: The raw materials for preparation include at least 5-6 parts of non-silicone oil, 90-95 parts of thermal conductive composite filler, 0.1-1 part of treatment agent and 0.1-0.5 part of antioxidant in parts by mass.

2. The high-performance non-silicone thermal grease according to claim 1, characterized in that: The non-silicone oil includes one of aviation lubricating oil, aviation gear oil, engine lubricating oil, aviation hydraulic oil, and general lubricating oil for power transmission.

3. The high-performance non-silicone thermal grease according to claim 2, characterized in that: The non-silicone oil includes aviation lubricating oil.

4. The high-performance non-silicone thermal grease according to claim 1, characterized in that: The thermally conductive composite filler comprises at least two of aluminum oxide, zinc oxide, boron nitride, aluminum nitride, aluminum powder, silver powder, graphene, aluminum nitride, silicon carbide, and quartz powder.

5. The high-performance non-silicone thermal grease according to claim 4, characterized in that: The thermally conductive composite filler comprises aluminum powder, aluminum oxide and zinc oxide; the preparation method of the thermally conductive composite filler is to mix the aluminum powder, aluminum oxide and zinc oxide.

6. The high-performance non-silicone thermal grease according to claim 5, characterized in that: The particle size of the aluminum powder is 1 to 10 μm.

7. The high-performance non-silicone thermal grease according to claim 5, characterized in that: The particle size of the aluminum oxide is 1-2 μm.

8. The high-performance non-silicone thermal grease according to claim 5, characterized in that: The particle size of the zinc oxide is less than 1 μm.

9. The high-performance non-silicone thermal grease according to claim 1, characterized in that: The treating agent comprises one or more of a silane coupling agent, a phthalate coupling agent and an aluminate coupling agent.

10. A method for preparing a high-performance non-silicone thermal grease according to any one of claims 1 to 9, characterized in that: At least the following steps are included: S1. Add non-silicone oil and antioxidant into a planetary mixer and stir evenly at 60-80℃; S2. Add thermal conductive composite filler and treatment agent in sequence, and stir at 60-80°C for 1-2 hours; S3, heating to 90-120℃, vacuuming for 0.5-1h; S4. Cool to room temperature and discharge.

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