CN115710461B - High-performance heat-conducting silicone grease and preparation method and application thereof - Google Patents
High-performance heat-conducting silicone grease and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides high-performance heat-conducting silicone grease and a preparation method and application thereof. The high-performance heat-conducting silicone grease comprises the following components in parts by weight: 100 parts of silicone oil, 1000-2000 parts of heat-conducting filler, 0.5-10 parts of silane coupling agent, 0.5-10 parts of filler modifier and 0.1-5 parts of thixotropic agent; wherein the filler modifier comprises long-chain fatty acid with carbon number more than or equal to 20 and acrylic ester copolymer which are activated by carbonyl; and the filler modifier is grafted to the silane coupling agent on the surface of the heat-conducting filler. According to the invention, the surface of the small-particle-size insulating heat-conducting filler is modified by the specific auxiliary agent, so that the interface compatibility between the filler and the organic silicon is improved, and the heat-conducting property of the organic silicon grease is improved.
Description
Technical Field
The invention relates to the technical field of thermal interface heat conduction, in particular to high-performance heat conduction silicone grease, and a preparation method and application thereof.
Background
Along with the development of society and technology, electronic components are continuously developed towards high power, miniaturization and densification, which causes a great amount of heat to be accumulated in a limited space when the components are operated, and the working efficiency and the service life of the components are seriously affected. How to quickly conduct the excess heat away from the electronic components is a challenge. The heat conduction silicone grease is composite silica gel composed of at least one of dimethyl silicone oil, long-chain alkyl silicone oil, phenyl dimethyl silicone oil and fluoro dimethyl silicone oil, a heat conduction filler, an auxiliary agent and the like, has good wettability to the surface of a component, has the advantages of easiness in operation, excellent high and low temperature stability, extremely low heat resistance and the like, is mainly applied between a heating component and a radiator, fills an uneven gap between the heating component and the radiator, replaces air which is a poor conductor with extremely low heat conductivity, effectively reduces the heat resistance of the gap, and achieves an excellent heat conduction effect.
The heat conduction silicone grease is used as one common heat conduction material, has extremely low heat resistance, small consumption, good heat conduction effect, good insulativity, excellent high and low temperature resistance and good operability, and is widely favored by customers. However, the electrical insulation of thermally conductive silicone grease is also very important for electronic components. The patents CN112876849A, CN102634212A, CN109370227A, CN103756325A and CN108373592a disclose a method for preparing heat conduction silicone grease from carbon materials (such as graphene, carbon nanotubes, etc.) and silicone oil, but the carbon materials have excellent heat conduction performance and good electric conduction performance, which makes the prepared heat conduction silicone grease have poor insulating performance and limits the application of the heat conduction silicone grease in some important occasions.
The electronic components are designed to have a longer service life at high temperatures, and the thermally conductive interface materials that match the electronic components are also required. Patent CN105111740a discloses a heat-conducting silicone grease for a high-power light-emitting diode, which comprises a plurality of parts of 4-isopropyl cyclohexanol and 2-methyl octanoate in materials, wherein the two materials have lower boiling points, and the viscosity of the prepared heat-conducting silicone grease can be effectively diluted, so that better operability is achieved, but under a high-temperature environment, along with volatilization of the two materials, a cavity is formed at the volatilized position inside the heat-conducting silicone grease, and the heat resistance is rapidly increased.
The thermal resistance and the thermal conductivity coefficient are key indexes for measuring the heat conduction performance of the heat conduction silicone grease. Wherein, the thermal resistance is in direct proportion to the coating thickness, and the thicker the thickness is, the larger the thermal resistance is. This requires that the thermally conductive silicone grease prepared be fine and smooth, and that the filler particle size not be too large. Patent CN111019351a discloses a heat conductive silicone grease for heat dissipation of a high-power LED, which has a relatively high heat conductivity, but uses a heat conductive filler with a particle size of 15.1-30 μm and a relatively large particle size, and specific thermal resistance performance indexes are not listed in the patent.
From the thermal resistance point of view, the smaller the particle size of the filler, the smaller the thickness of the coating, and the smaller the thermal resistance; however, the smaller the particle diameter of the filler, the larger the specific surface area, and the more interfaces with the silicone matrix are generated, resulting in an increase in interface thermal resistance. The ideal filler has small particle size, good compatibility with the organosilicon matrix and low interface thermal resistance, so that the surface modification of the heat conduction filler with small particle size is needed to improve the interface compatibility of the inorganic filler and the organosilicon matrix, and further reduce the thermal resistance and high-temperature aging resistance of the heat conduction silicone grease.
Disclosure of Invention
The invention aims to overcome the defect of higher interfacial thermal resistance of small-particle-size heat conducting filler and an organosilicon matrix in the prior art, and provides high-performance heat conducting silicone grease with excellent interfacial thermal resistance and high-temperature aging resistance. According to the invention, the surface of the small-particle-size insulating heat-conducting filler is modified by the specific auxiliary agent, so that the interface compatibility between the filler and the organic silicon is improved, and the heat-conducting property of the organic silicon grease is improved.
The invention further aims at providing a preparation method of the high-performance heat-conducting silicone grease.
The invention further aims to provide an application of the high-performance heat-conducting silicone grease in preparing electronic components.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the high-performance heat-conducting silicone grease comprises the following components in parts by weight:
wherein the filler modifier comprises long-chain fatty acid with carbon number more than or equal to 20 and acrylic ester copolymer which are activated by carbonyl; and the filler modifier is grafted to the silane coupling agent on the surface of the heat-conducting filler.
In the heat conduction silicone grease system, a silane coupling agent is firstly connected to the surface of a heat conduction filler, then a macromolecular filler modifier is grafted to the organic end of the silane coupling agent, long-chain alkyl in long-chain fatty acid activated by carbonyl in the macromolecular filler modifier can be wound and coated on the surface of an inorganic heat conduction filler, and chemical coating and physical coating are simultaneously carried out on the inorganic heat conduction filler; meanwhile, the acrylic ester copolymer is introduced, so that the grafting rate of the surface of the inorganic heat conducting filler is improved, the coating area is increased, the compatibility with polar silicone oil is improved, and the organic-inorganic interface thermal resistance is effectively reduced; and the acrylate copolymer forms a cross-linked network structure in the polymerization process and a cross-linked structure formed by physical winding action between the acrylate copolymer and carbonyl activated long-chain fatty acid, which is beneficial to the penetration of long-chain fatty acid chain segments into a macromolecular cross-linked structure, so that the coating fastness of the macromolecular modifier to inorganic heat-conducting filler is greatly improved, and the heat-conducting stability of the heat-conducting silicone grease is further improved.
Preferably, in the filler modifier, the weight ratio of long-chain fatty acid: acrylate copolymer = 1: (0.1-0.3). In the modifier, long-chain fatty acid activated by carbonyl mainly forms chemical coating on the surface of the inorganic heat-conducting filler, and fatty acid long chains which are not fully reacted form physical coating on the surface of the inorganic heat-conducting filler; the acrylate copolymer and the carbonyl activated long chain fatty acid then form a cross-linked structure through physical entanglement, which can increase the grafting ratio and provide a stable coating structure. However, since the acrylic ester copolymer is easy to generate ether micromolecules in the polymerization process, and a monofunctional acrylic ester micromolecule reactive diluent is required to be added in the polymerization process, the micromolecules are easy to migrate in the heat-conducting silicone grease, and oil and VOC volatilization easily occur at high temperature, so that the heat stability of the heat-conducting silicone grease is reduced, and the stability of the heat-conducting property can be kept for a long time at high temperature in order to reduce the oil yield and VOC volatilization rate of the heat-conducting silicone grease, the addition amount of the acrylic ester copolymer is not excessive. In the above mixing ratio range, the high-performance heat-conducting silicone grease with excellent comprehensive performance can be prepared.
Preferably, the long chain fatty acid has 20 to 30 carbon atoms. The chain segment of the fatty acid is too short to be coated on the surface of the inorganic heat conducting filler; the chain segment of the fatty acid is too long, and a compact and firm coating layer can be formed on the surface of the inorganic heat conducting filler, but the molecular chain is too long, so that the molecular chain is easy to wind and gather, easy to disperse and uneven, and has larger viscosity, thereby being unfavorable for processing.
Preferably, the long chain fatty acid is at least one of arachidic acid, behenic acid or decyltetradecanoic acid.
Silicone oils conventional in the art can be used in the present invention. The silicone oil includes, but is not limited to, at least one of a dimethyl silicone oil, a phenyl dimethyl silicone oil, a long chain alkyl silicone oil, or a fluoromethyl silicone oil.
Preferably, the viscosity of the silicone oil is 20-1000 cps, the viscosity is too small, the content of siloxane small molecules is more, the oil yield and VOC volatilization rate of the obtained heat conduction silicone grease are higher, and the heat stability of the silicone grease can be reduced; too high a viscosity, difficult processing, poor dispersibility of the filler in the silicone oil matrix, and poor spreadability of the silicone grease, and poor handleability. Therefore, the viscosity of the silicone oil is more preferably 100 to 500cps.
Preferably, the silicone oil contains 3-20 polymers (D3-D20) with a content of silane small molecules of not more than 100ppm.
Preferably, the silane coupling agent is at least one of 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane (KH 550), 3-aminopropyl methyldiethoxysilane, 3-methacryloxypropyl trimethoxysilane (KH 570), 3-methacryloxypropyl triethoxysilane, or 3-methacryloxypropyl methyldiethoxysilane.
Further preferably, the silane coupling agent is 3-aminopropyl triethoxysilane.
Conventional thermally conductive fillers in the art may be used in the present invention including, but not limited to, at least one of alumina, zinc oxide, magnesium oxide, silica, aluminum nitride, boron nitride, aluminum carbide, silicon carbide, aluminum hydroxide, magnesium hydroxide, boehmite, or diamond.
Preferably, the median particle diameter (D 50 Particle size) of 0.3 to 10 mu m.
Thixotropic agents conventional in the art, including but not limited to at least one of hydrogenated castor oil, organobentonite, attapulgite or methylcellulose, may be used in the present invention.
The invention also provides a preparation method of the high-performance heat-conducting silicone grease, which comprises the following steps:
s1, preparation of raw materials
Mixing the raw materials for synthesizing the long-chain fatty acid and acrylic ester copolymer activated by carbonyl into a first part of silicone oil, stirring and reacting at 40-120 ℃, and obtaining a filler modifier after the reaction is completed;
simultaneously, after uniformly mixing the silane coupling agent and the second part of silicone oil, adding a heat conducting filler, heating to 60-120 ℃ and reacting to obtain a mixture 1;
s2, adding the filler modifier obtained in the step S1 into the mixture 1 obtained in the step S1, and stirring and reacting at 40-100 ℃ and/or under ultraviolet light, so as to obtain a mixture 2 after the reaction is completed;
s3, adding the rest third part of silicone oil added with the thixotropic agent into the mixture 2 obtained in the step S2, stirring and reacting at the temperature of 80-180 ℃ under the negative pressure condition, obtaining a crude product after the reaction is complete, and grinding the crude product to obtain the high-performance heat-conducting silicone grease.
Preferably, the stirring speed in the step S1 is 700-1500 r/min.
Preferably, the stirring speed in step S2 and step S3 is independently 2000-3500 r/min, more preferably 3000r/min.
Preferably, the synthetic raw materials of the acrylic ester copolymer in the step S1 comprise an initiator and acrylic ester monomers.
Preferably, the synthetic raw materials of the carbonyl-activated long-chain fatty acid in step s1 include long-chain fatty acid and an activator. The activator is at least one of N, N-carbonyl diimidazole and dicyclohexyl carbodiimide.
Conventional initiators may be used in the present invention. The initiator includes, but is not limited to, at least one of a peroxide initiator, an azo-type initiator, or a photoinitiator.
Preferably, the peroxide initiator is at least one of benzoyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate or tert-butyl peroxyvalerate; the azo initiator is at least one of azodiisobutyronitrile, azodiisoheptonitrile or dimethyl azodiisobutyrate; the photoinitiator is at least one of 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl acetone or bis (2, 4, 6-trimethylbenzoyl) phenyl phosphine oxide.
Preferably, the initiator is added in an amount of 100 to 1000ppm based on the total weight of the synthetic monomers. The molecular weight and the distribution of the polymerization product (polyacrylate or polyurethane) can be reasonably controlled by controlling the addition amount of the initiator, so that the obtained filler modifier has moderate molecular weight and moderate viscosity, and is convenient to process.
Preferably, the acrylic monomer is at least one of butyl acrylate, isooctyl acrylate, lauryl acrylate, butyl methacrylate, isooctyl methacrylate or lauryl methacrylate.
Preferably, the adding of the heat conducting filler in the step S1 is multiple times, and the multiple times of adding can enable the filler to fully react with the silane coupling agent and the filler modifier and facilitate uniform dispersion between the modified filler and the silicone oil.
The application of the high-performance heat-conducting silicone grease in the preparation of electronic components is also within the protection scope of the invention.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the surface of the small-particle-size insulating heat-conducting filler is modified by the specific auxiliary agent, so that the interface compatibility between the filler and the organic silicon is improved, and the heat-conducting property of the organic silicon grease is improved. The thermal resistance of the high-performance heat-conducting silicone grease is 0.12 ℃ in cm 2 below/W, can be as low as 0.064 ℃ cm 2 W; the oil yield is below 0.35%, the viscosity is below 250000cps, the thermal resistance is still kept at a lower level after being placed at 150 ℃ for 1000 hours, and the rise rate of the thermal resistance in a high-temperature environment is lower than 15% and can be as low as 4.42% compared with the initial thermal resistance.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples, which are not intended to limit the present invention in any way. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art. The reagents and materials used in the present invention are commercially available unless otherwise specified.
Example 1
The embodiment provides a high-performance heat-conducting silicone grease, which is prepared by the following steps:
s1, preparing a filler modifier
8 parts of simethicone (viscosity 100cps, D3-D20 silane micromolecule content 100ppm, which is tested under the condition of 25 ℃ and 50RH percent according to the standard GB/T10247-2008), 3 parts of long-chain fatty acid (eicosane, with 20 carbon atoms) and 2.5 parts of N, N-carbonyl diimidazole are uniformly stirred and mixed, and then the mixture is heated to 80 ℃ and stirred and reacted for 3 hours at the speed of 700r/min to obtain a filler modifier 1 (namely, long-chain fatty acid activated by carbonyl);
stirring and reacting 2 parts of simethicone, 0.55 part of acrylic ester monomer (butyl acrylate) and 150ppm of initiator (benzoyl peroxide) of the total weight of the monomers at 80 ℃ at a speed of 700r/min for 1h, and obtaining a filler modifier 2 (acrylic ester copolymer);
namely, the weight ratio of the long chain fatty acid activated by carbonyl: acrylic copolymer = 1:0.1;
s2, adding 1.5 parts of silane coupling agent (1 part of 3-aminopropyl triethoxysilane and 0.5 part of 3-methacryloxypropyl trimethoxysilane) into 85 parts of simethicone, stirring and mixing uniformly, adding 1000 parts of heat conducting filler (mixed heat conducting filler formed by zinc oxide, aluminum oxide and aluminum nitride in a weight ratio of 1:5:4, wherein the D50 particle size of the heat conducting filler is 5 mu m) three times, and stirring and reacting at 75 ℃ for 1.5 hours at 700r/min to obtain a mixture 1;
s3, adding the filler modifier 1 prepared in the step S1 into the mixture 1 obtained in the step S2, stirring for 1h at 90 ℃ under 500r/min, adding the filler modifier 2 into the mixture 1, and reacting for 2h under the dual actions of 80 ℃ and 365nm ultraviolet light to obtain a mixture 2;
s4, adding 0.3 part of thixotropic agent (organic bentonite) into 5 parts of dimethyl silicone oil, stirring for 0.5h at a speed of 3000r/min, standing for 0.5h, stirring for 1.5h at a speed of 3000r/min, uniformly dispersing the thixotropic agent into the dimethyl silicone oil to form thixotropic agent-dimethyl silicone oil mixed solution, adding the thixotropic agent-dimethyl silicone oil mixed solution into the mixture 2, stirring for 8h at 180 ℃ under a negative pressure of 1000r/min (not more than-0.1 Mpa), obtaining a crude product, and grinding to a particle size of <30 mu m to obtain the high-performance heat-conducting silicone grease.
Example 2
The present example provides a high-performance heat-conducting silicone grease, which is prepared by the preparation method of example 1, and is different from example 1 in that the amount of the synthetic raw materials is adjusted so that the total weight of the modifier obtained in step s1 is unchanged, but the weight ratio of the modifier to the long-chain fatty acid activated by carbonyl is: acrylate copolymer = 1:0.3.
example 3
The present example provides a high-performance heat-conductive silicone grease, which is prepared by the preparation method of example 1, and is different from example 1 in that the eicosanoic acid (with 20 carbon atoms) in step s1 is replaced by behenic acid (with 22 carbon atoms) in an equivalent amount.
Example 4
This example provides a high performance heat conductive silicone grease prepared according to the preparation method of example 1, which differs from example 1 in that eicosanoic acid (20 carbon atoms) in step s1 is replaced with decyltetradecanoic acid (24 carbon atoms) in equal amount.
Example 5
The present example provides a high-performance heat-conducting silicone grease, which is prepared by the preparation method of example 1, and is different from example 1 in that the silane coupling agent in step s2 is replaced by KH570 with the same amount of KH 550.
Example 6
The present example provides a high performance heat conductive silicone grease prepared according to the preparation method of example 1, which is different from example 1 in that the silane coupling agent in step s2 is replaced by 3-methacryloxypropyl methyltriethoxysilane with the same amount from KH 550.
Example 7
The present example provides a high-performance heat-conducting silicone grease, which is prepared by the preparation method of example 1, and is different from example 1 in that the acrylic ester monomer in step s1 is replaced by isooctyl acrylate with equal amount from butyl acrylate.
Example 8
The embodiment provides a high-performance heat-conducting silicone grease, which is prepared by the preparation method of the embodiment 1, and is different from the embodiment 1 in that the acrylic ester monomer in the step S1 is replaced by lauryl methacrylate with the same amount of butyl acrylate.
Example 9
The present example provides a high performance heat conductive silicone grease prepared according to the preparation method of example 1, which is different from example 1 in that N, N carbonyl diimidazole in step s1 is replaced with dicyclohexylcarbodiimide of the same quality.
Example 10
This example provides a high performance heat conductive silicone grease prepared according to the preparation method of example 1, which differs from example 1 in that the heat conductive filler in step s2 is replaced by aluminum hydroxide (median particle size of 1 μm) in equal amount.
Example 11
This example provides a high performance heat conductive silicone grease prepared according to the method of example 1, which differs from example 1 in that the silicone oil is replaced with phenyl dimethyl silicone oil (viscosity 500cps, content of small silane molecules D3-D20 80ppm, measured at 25 ℃ and 50RH% according to standard GB/T10247-2008).
Comparative example 1
The comparative example provides a heat-conducting silicone grease prepared by the preparation method of example 1, which is different from example 1 in that the amount of synthetic raw materials is adjusted so that the total weight of the modifier obtained in step s1 is unchanged, but the weight ratio of the modifier to the long-chain fatty acid activated by carbonyl group is: acrylate copolymer = 0:1: i.e. only containing an acrylate copolymer in a too large ratio.
Comparative example 2
The comparative example provides a heat conductive silicone grease prepared by the preparation method of example 1, which is different from example 1 in that the mass of the carbonyl activator in step s1 is replaced by eicosanoic acid, namely long chain fatty acid is not carbonyl activated.
Comparative example 3
The comparative example provides a heat-conducting silicone grease prepared by the preparation method of the example 1, which is different from the example 1 in that the acrylic monomer in the step S1 is replaced by eicosane in equal amount, namely the filler modifier of the comparative example does not contain acrylic ester copolymer.
Comparative example 4
The comparative example provides a heat-conducting silicone grease prepared by the preparation method of the embodiment 1, which is different from the embodiment 1 in that long-chain fatty acid in the step S1 is replaced by succinic acid with shorter fatty chain segment.
Performance testing
The properties of the heat-conducting silicone grease obtained in the above examples and comparative examples were characterized, and specific test items, test methods and results are as follows:
1. thermal resistance: specific test methods refer to standard ASTM D5470.
2. Viscosity: specific test methods refer to standard GB/T10247.
3. Oil yield: glass beaker with caliber of 75cm is taken and weighed m 1 The method comprises the steps of carrying out a first treatment on the surface of the Placing 10g (accurate to +/-0.001 g) of heat conduction silicone grease in a glass beaker, placing the glass beaker in a precise oven at 125 ℃ for 7d, taking out, cooling to room temperature, and weighing m 2 Calculating the oil ratio:
4. high temperature resistance and heat conduction stability: preparing a copper plate with the thickness of 25.4mm and 25.4mm (the surface roughness Ra of the copper plate is not more than 2.5), scrubbing the surface of the copper plate with acetone for 3 times, and airing for later use; and uniformly coating heat-conducting silicone grease between the two copper plates, fixing the two copper plates by using a clamp, placing the copper plates into a precise oven at 150 ℃ for 1000 hours, taking out the copper plates for cooling, testing the thermal resistance, and recording the thermal resistance value.
Table 1 test results of heat conductive silicone grease obtained in examples and comparative examples
From the above results, it can be seen that:
the thermal resistance of the high-performance heat-conducting silicone grease prepared by the invention is 0.12 ℃ cm 2 below/W, can be as low as 0.064 ℃ cm 2 W; the oil yield is below 0.35%, the viscosity is below 250000cps, the thermal resistance is still kept at a lower level after being placed at 150 ℃ for 1000 hours, and the rise rate of the thermal resistance in a high-temperature environment is lower than 15% and can be as low as 4.42% compared with the initial thermal resistance.
The results of examples 1-2 and comparative examples 1 and 3 show that the thermal stability of the resulting thermally conductive silicone grease decreases and the oil yield increases as the ratio of the acrylate copolymer in the filler modifier increases. In the proper proportion range, the high-performance heat-conducting silicone grease with excellent heat stability at high temperature can be obtained.
The results of examples 1, 3-4 and comparative example 4 show that the thermal resistance of the obtained heat conductive silicone grease tends to decrease and then increase with the increase of the length of the fatty chain segment in the long chain fatty acid activated by the carbonyl group, because the heat conductive filler can be wrapped more firmly with the increase of the fatty chain in a certain length range with the increase of the fatty chain segment, but when the length of the fatty chain segment is increased to a certain value, the molecular chain is too long, so that the heat conductive silicone grease is easy to wind and gather, is easy to disperse unevenly, and has larger viscosity, thereby being unfavorable for processing. However, when the molecular chain is too short (as in comparative example 4), the carbonyl long chain compound grafted to the heat conductive powder is insufficient for the coating surface of the heat conductive powder, so that more heat conductive powder surface is directly contacted with silicone oil, the contact thermal resistance is large, the overall viscosity is also large, and therefore, the thermal resistance of the obtained heat conductive silicone grease is high and the heat conductive stability is also poor.
The results of examples 1 and 5 to 6 show that the selection of the silane coupling agent has less influence on the performance of the obtained heat conductive silicone grease, but the modification effect of the silane coupling agent KH550 (example 6) is better.
The results of examples 1 and 7 to 11 show that the type of the acrylate copolymer, the type of the carbonyl activator, the type of the heat conductive filler, and the type of the silicone oil have little influence on the performance of the heat conductive silicone grease.
The results of example 1 and comparative examples 1 to 3 show that there is a synergistic effect between the carbonyl-activated long-chain fatty acid and the acrylate copolymer in the filler modifier, which together improve the heat conducting property and the heat conducting stability of the heat conducting silicone grease, and that none of them is lacking, high-performance heat conducting silicone grease with excellent heat conducting property and heat conducting stability can not be prepared. When the acrylate copolymer (like comparative example 3) is absent, the physical and chemical coating of the surface of the heat conducting powder is poor, so that the viscosity is increased, and the thermal resistance is also increased; if the acrylate copolymer is too much (as in comparative example 1), the finally prepared high-performance heat-conducting silicone grease has too high oil yield and poor high-temperature aging performance.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (9)
1. The high-performance heat-conducting silicone grease is characterized by comprising the following components in parts by weight:
wherein the filler modifier comprises long-chain fatty acid with carbon number more than or equal to 20 and acrylic ester copolymer which are activated by carbonyl; and the filler modifier is grafted to a silane coupling agent on the surface of the heat-conducting filler;
in the filler modifier, the weight ratio of the long-chain fatty acid activated by carbonyl is as follows: acrylate copolymer = 1: (0.1-0.3).
2. The high performance heat conductive silicone grease according to claim 1, wherein the activator used for carbonyl activation is at least one of N, N' -carbonyldiimidazole and dicyclohexylcarbodiimide.
3. The high performance heat conductive silicone grease of claim 1, wherein the silicone oil is at least one of a dimethyl silicone oil, a phenyl dimethyl silicone oil, a long chain alkyl silicone oil, or a fluoromethyl silicone oil.
4. The high performance, thermally conductive silicone grease of claim 3, wherein the silicone oil has a viscosity of 50 to 1000cps; the content of silane small molecules of 3-20 polymers in the silicone oil is not more than 100ppm.
5. The high performance, thermally conductive silicone grease of claim 1, wherein the silane coupling agent is at least one of 3-aminopropyl trimethoxysilane, 3-aminopropyl diethoxysilane, 3-aminopropyl methyltriethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl triethoxysilane, or 3-methacryloxypropyl methyldiethoxysilane.
6. The high performance, thermally conductive silicone grease of claim 1, wherein the thermally conductive filler is at least one of alumina, zinc oxide, magnesium oxide, silica, aluminum nitride, boron nitride, aluminum carbide, silicon carbide, aluminum hydroxide, magnesium hydroxide, boehmite, or diamond.
7. The high performance heat conductive silicone grease of claim 6, wherein the median particle size of the heat conductive filler is 0.3 to 10 μm.
8. The method for preparing the high-performance heat-conducting silicone grease according to any one of claims 1 to 7, which is characterized by comprising the following steps:
s1, preparation of raw materials
Mixing the raw materials for synthesizing the long-chain fatty acid and acrylic ester copolymer activated by carbonyl into a first part of silicone oil, stirring and reacting at 40-120 ℃, and obtaining a filler modifier after the reaction is completed;
simultaneously, after uniformly mixing the silane coupling agent and the second part of silicone oil, adding a heat conducting filler, heating to 60-120 ℃ and reacting to obtain a mixture 1;
s2, adding the filler modifier obtained in the step S1 into the mixture 1 obtained in the step S1, and stirring and reacting at 40-100 ℃ and/or under ultraviolet light, so as to obtain a mixture 2 after the reaction is completed;
s3, adding the rest third part of silicone oil added with the thixotropic agent into the mixture 2 obtained in the step S2, stirring and reacting at the temperature of 80-180 ℃ under the negative pressure condition, obtaining a crude product after the reaction is complete, and grinding the crude product to obtain the high-performance heat-conducting silicone grease.
9. Use of the high-performance heat-conducting silicone grease according to any one of claims 1-7 for preparing electronic components.
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012052137A (en) * | 2011-11-28 | 2012-03-15 | Shin-Etsu Chemical Co Ltd | Heat conductive silicone grease composition |
| WO2020077333A1 (en) * | 2018-10-12 | 2020-04-16 | Ppg Industries Ohio, Inc. | Compositions containing thermally conductive fillers |
| CN109438987A (en) * | 2018-10-31 | 2019-03-08 | 深圳联腾达科技有限公司 | High thermal-conductive silicone grease and preparation method thereof |
| WO2022126383A1 (en) * | 2020-12-15 | 2022-06-23 | 万华化学集团股份有限公司 | Asymmetric silicone oil, preparation method therefor, and application thereof |
| CN114410113A (en) * | 2021-11-08 | 2022-04-29 | 佛山金戈新材料股份有限公司 | Flowing type fine heat-conducting silicone grease and preparation method thereof |
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