CN114907699B - Heat conduction interface material and preparation method and application thereof - Google Patents
Heat conduction interface material and preparation method and application thereof Download PDFInfo
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- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
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Abstract
The invention provides a heat-conducting interface material, a preparation method and application thereof, which belong to the technical field of heat-conducting materials and are prepared from the following raw materials in parts by weight: 100 parts of polysiloxane resin with a silicon vinyl structure, 1-20 parts of reaction auxiliary agent, 2-40 parts of hydrogen-containing silicone oil, 0.1-1600 ppm of platinum catalyst calculated by platinum, 100-4000 parts of heat conduction filler and 0.001-1.6 parts of polymerization inhibitor. The invention adopts polysiloxane resin with silicon vinyl structure to react with hydrogen-containing silicone oil to prepare interface material, controls the composition of the polysiloxane resin with silicon vinyl structure, adds reaction auxiliary agent with reactive functional group, controls the dosage of each component, adjusts the structure of the interface material, further improves the reliability of the interface material, does not generate slipping, cracking or pulverization phenomenon after mechanical vibration, impact and aging experiments, and has small change of thermal resistance and thermal conductivity coefficient before and after aging.
Description
Technical Field
The invention relates to the technical field of heat conduction materials, in particular to a heat conduction interface material and a preparation method and application thereof.
Background
With the increasing high integration of 3C digital products, automatic driving, intelligent equipment, 5G communication and the like, the power of a chip is increased by times, and thermal management has become a key link of chip design and development. Heat dissipation from heat-generating electronic components generally requires a heat sink to ensure stable and long-term reliable operation of the chip and other components. In order to smoothly transfer heat from a heat-generating electronic component to a heat sink, it is generally necessary to fill a thermally conductive interface material between the electronic component and the heat sink.
At present, a heat-conducting gasket or a heat-conducting silicone resin material is generally used as a heat-conducting interface material, however, the heat-conducting gasket has poor plasticity, cannot be applied to the surface with irregular size, has poor adhesion with a heat-conducting interface, has large thermal contact thermal resistance, and generally adopts a heat-conducting interface material with liquid fluidity and plasticity, such as heat-conducting silicone grease. However, after the silicone grease prepared in the prior art is used for a long time, the problems of oil precipitation, pulverization and the like are easy to occur; and with the wide popularization of 5G communication and new energy automobiles, the heat conduction interface material between the chip and the radiator is likely to be in a vertical placement state, so that the reliability of the heat conduction interface material is reduced in the long-term outdoor vibration, temperature and humidity change process, the phenomena of material slippage, cracking and the like occur, and the heat conductivity coefficient and the heat resistance of the material are greatly changed.
Therefore, there is a need for a thermally conductive interface material with high reliability.
Disclosure of Invention
The invention aims to provide a heat conduction interface material, a preparation method and application thereof. The interface material provided by the invention has excellent reliability, and can not slip, crack or chalk after mechanical vibration, impact and aging.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a heat-conducting interface material which is prepared from the following raw materials in parts by weight: 100 parts of polysiloxane resin with a silicon vinyl structure, 1-20 parts of reaction auxiliary agent, 2-40 parts of hydrogen-containing silicone oil, 0.1-1600 ppm of platinum catalyst calculated by platinum, 100-4000 parts of heat conduction filler and 0.001-1.6 parts of polymerization inhibitor;
the polysiloxane resin with the silicon vinyl structure comprises compounds shown in a formula 1, a formula 2 and a formula 3; the mass ratio of the compounds shown in the formula 1, the formula 2 and the formula 3 is (30-90): (10-30): (0-20);
in the formula 1, m is more than or equal to 20 and less than or equal to 150, me is methyl, and Vi is vinyl;
in the formula 2, y is more than or equal to 1 and less than or equal to 5, x+y is more than or equal to 20 and less than or equal to 150, me is methyl, and Vi is vinyl;
in the formula 3, n is more than or equal to 20 and less than or equal to 65, me is methyl, and Vi is vinyl;
the structure of the reaction auxiliary agent is shown as a formula 4:
in the formula 4, R 1 Is hydrogen, ethenyl, propenyl or butenyl, R 2 Is methyl, ethyl or propyl, R 3 Is methyl, ethyl or propyl, Z is methylene, ethylene or propylene, x is an integer of 0-2, p is more than or equal to 3 and less than or equal to 7, q is more than or equal to 1 and less than or equal to 3, and o+p+q is more than or equal to 10 and less than or equal to 20.
Preferably, the hydrogen-containing silicone oil comprises compounds shown in formula 5 and formula 6;
in the formula 5, s+t is more than or equal to 20 and less than or equal to 100, and t/(74s+60t+162) is more than or equal to 0.05% and less than or equal to 0.5%;
in the formula 6, 1500 is less than or equal to 74r+134 is less than or equal to 4000, and 0.05 percent is less than or equal to 2/(74r+162) is less than or equal to 0.13 percent.
Preferably, the mass ratio of the compounds shown in the formula 5 and the formula 6 in the hydrogen-containing silicone oil is (1-20): (1-20).
Preferably, the heat conductive filler includes one or more of aluminum oxide, zinc oxide, silicon dioxide, silicon carbide, silicon nitride, magnesium oxide, aluminum nitride, boron nitride, graphite and derivatives thereof, aluminum powder, silver powder, nickel powder, and iron powder.
Preferably, the particle size of the heat conductive filler is 0.1 to 120 μm.
Preferably, the polymerization inhibitor includes one of 1-ethynyl cyclohexanol, 3, 5-dimethyl-1-hexyn-3-ol, 1,3,5, 7-tetramethyl-1, 3,5, 7-tetravinyl cyclotetrasiloxane, and diethyl fumarate.
The invention provides a preparation method of the heat conduction interface material, which comprises the following steps:
(1) Mixing polysiloxane resin with a silicon vinyl structure, a reaction auxiliary agent, hydrogen-containing silicone oil, a polymerization inhibitor and a platinum catalyst for addition reaction to obtain base oil;
(2) And (3) mixing the base oil obtained in the step (1) with a heat-conducting filler to obtain the heat-conducting interface material.
Preferably, the temperature of the addition reaction in the step (1) is 0-300 ℃, and the time of the addition reaction is 0.2-24 h.
Preferably, the mixing time in the step (2) is 0.5 to 24 hours.
The invention also provides an application of the heat conduction interface material in the heat conduction material or the heat conduction interface material prepared by the preparation method according to the technical scheme.
The invention provides a heat-conducting interface material which is prepared from the following raw materials in parts by weight: 100 parts of polysiloxane resin with a silicon vinyl structure, 1-20 parts of reaction auxiliary agent, 2-40 parts of hydrogen-containing silicone oil, 0.1-1600 ppm of platinum catalyst calculated by platinum, 100-4000 parts of heat conduction filler and 0.001-1.6 parts of polymerization inhibitor. The invention adopts polysiloxane resin with silicon vinyl structure to react with hydrogen-containing silicone oil to prepare interface material, controls the composition of the polysiloxane resin with silicon vinyl structure, adds reaction auxiliary agent with reactive functional group, controls the dosage of each component, adjusts the structure of the product, and improves the reliability of the interface material. The results of the examples show that the interface material provided by the invention does not slip, crack or pulverize after mechanical vibration, impact and aging experiments, has excellent reliability, and has small change of thermal resistance and thermal conductivity before and after aging.
Drawings
FIG. 1 is a physical diagram of a test flow observation fixture in an embodiment of the invention.
Detailed Description
The invention provides a heat-conducting interface material which is prepared from the following raw materials in parts by weight: 100 parts of polysiloxane resin with a silicon vinyl structure, 1-20 parts of reaction auxiliary agent, 2-40 parts of hydrogen-containing silicone oil, 0.1-1600 ppm of platinum catalyst calculated by platinum, 100-4000 parts of heat conduction filler and 0.001-1.6 parts of polymerization inhibitor.
The sources of the components are not particularly limited in the present invention unless otherwise specified, and may be commercially available products known to those skilled in the art or products prepared by conventional preparation methods.
The raw materials for preparing the heat-conducting interface material comprise 100 parts of polysiloxane resin with a silicon vinyl structure according to parts by weight.
In the present invention, the silicone resin having a silicon vinyl structure includes formula 1, formula 2 and formula
A compound of formula 3:
in the formula 1, m is more than or equal to 20 and less than or equal to 150, me is methyl, and Vi is vinyl;
in the formula 2, y is more than or equal to 1 and less than or equal to 5, x+y is more than or equal to 20 and less than or equal to 150, me is methyl, and Vi is vinyl;
in the formula 3, n is more than or equal to 20 and less than or equal to 65, me is methyl, and Vi is vinyl.
In the present invention, the silicone resin having a silicon vinyl structure includes a compound having a structure shown in formula 1. In the invention, the compound with the structure shown in the formula 1 reacts with hydrogen-containing silicone oil to form an interface material, and the structure of the compound with the structure shown in the formula 1 is controlled, so that the structure of the interface material is regulated, and the reliability of the interface material is improved.
In the present invention, in the formula 1, 20.ltoreq.m.ltoreq.150, preferably 30.ltoreq.m.ltoreq.120, more preferably 30.ltoreq.m.ltoreq.80. In the invention, the m value is limited in the range, if the m value is too low, the molecular weight of the compound in the formula 1 is too small, the content of volatile substances is too high, the possibility of cracking of the interface material in the high-temperature aging process is higher, if the m value is too high, the molecular weight of the compound in the formula 1 is too high, gelation easily occurs in the mixing reaction process, the viscosity is too high, the addition of the heat conducting filler is not facilitated, and the improvement of the heat conducting coefficient is influenced.
In the present invention, the silicone resin having a silicon vinyl structure includes a compound having a structure represented by formula 2. In the invention, the compound with the structure shown in the formula 2 reacts with hydrogen-containing silicone oil to form an interface material, the structure of the compound with the formula 2 contains a silicon vinyl functional group which reacts with silicon hydrogen, and the two ends of the compound are also of a structure of full-silicon methyl, so that the surface energy is low, the wetting of the filler surface and the heat dissipation substrate surface is facilitated, and the contact thermal resistance is reduced.
In the invention, in the formula 2, y is more than or equal to 1 and less than or equal to 5, preferably y is more than or equal to 2 and less than or equal to 4, and more preferably y is more than or equal to 3 and less than or equal to 4; x+y is 20 to 150, preferably 40 to 120, more preferably 40 to 80.
The invention limits the x and y values to the above range, the y value is less than 1, which is unfavorable for the hydrosilylation reaction in the mixing process, and too large y value leads to larger crosslinking density after the mixing reaction, gelation easily occurs, and the mixed interface material has larger hardness and low extrusion property, which is unfavorable for construction; when the value of x+y is too low, the molecular weight of the compound of formula 2 is too small, the content of volatile substances is too high, so that the possibility of cracking of the interface material in the high-temperature aging process is higher, when the value of x+y is too high, the molecular weight of the compound of formula 2 is too large, gelation easily occurs in the mixing reaction process, the viscosity is too large, the addition of the heat conducting filler is not facilitated, and the improvement of the heat conducting coefficient is influenced.
In the present invention, the silicone resin having a silicon vinyl structure includes a compound having a structure represented by formula 3. In the invention, the compound with the structure shown in the formula 3 reacts with hydrogen-containing silicone oil to form an interface material, one end of the compound in the formula 3 is vinyl, and the other end is trimethylsilyl, so that the purpose of reaction plasticization is mainly achieved, oil precipitation of the interface material in the storage and application processes is avoided, and the crosslinking density of the interface material can be adjusted to control the extrudability.
In the present invention, in the formula 3, 20.ltoreq.n.ltoreq.65, preferably 20.ltoreq.n.ltoreq.50, more preferably 20.ltoreq.n.ltoreq.30.
The n value of the invention is limited in the range, if the n value is too low, the molecular weight of the compound of the formula 3 is too small, the content of volatile substances is too high, the possibility of cracking of the interface material in the high-temperature aging process is higher, and if the n value is too high, the molecular weight of the compound of the formula 3 is too high, so that the aim of adjusting the extrudability by reactive plasticization cannot be fulfilled.
In the present invention, the mass ratio of the compounds represented by the formula 1, the formula 2 and the formula 3 is (30 to 90): (10-30): (0 to 20), preferably (40 to 80): (15-25): (5 to 15), more preferably (50 to 70): 20:10. the present invention can further improve the reliability of the interface material by limiting the mass ratio of the compounds represented by formulas 1, 2 and 3 to the above-described range.
The raw materials for preparing the heat conductive interface material according to the present invention include 1 to 20 parts, preferably 5 to 15 parts, and more preferably 10 parts of a reaction auxiliary agent based on 100 parts by mass of a polysiloxane resin having a silicon vinyl structure.
In the invention, the structure of the reaction auxiliary agent is shown as a formula 4:
in the formula 4, R 1 Is hydrogen, ethenyl, propenyl or butenyl, R 2 Is methyl, ethyl or propyl, R 3 Is methyl, ethyl or propyl, Z is methylene, ethylene or propylene, x is an integer of 0-2, p is more than or equal to 3 and less than or equal to 7, q is more than or equal to 1 and less than or equal to 3, and o+p+q is more than or equal to 10 and less than or equal to 20. In the invention, the compound with the structure shown in the formula 4 has q chain segments which interact with the filler, can improve the dispersibility of the heat-conducting filler, and contains R which can participate in the reaction in the molecule 1 The functional groups can prevent excessive volatilization of small molecular substances under high-temperature aging, improve the reliability of the interface material, and avoid the phenomena of sliding cracking and the like of the interface material.
In the present invention, in the formula 4, x is an integer of 0 to 2, preferably 0 or 1; p is more than or equal to 3 and less than or equal to 7, preferably 4 and less than or equal to 6, and more preferably p=5; 1.ltoreq.q.ltoreq.3, preferably q=2; 10.ltoreq.o+p+q.ltoreq.20, preferably 12.ltoreq.o+p+q.ltoreq.18, more preferably 14.ltoreq.o+p+q.ltoreq.16.
The x, o, p, q value is limited to the above range, so that the interface material has certain viscosity and molecular weight, and the reliability of the interface material is further improved.
The raw materials for preparing the heat conduction interface material comprise 2-40 parts, preferably 5-35 parts, more preferably 10-30 parts and most preferably 15-20 parts of hydrogen silicone oil based on 100 parts by mass of polysiloxane resin with a silicon vinyl structure.
In the present invention, the hydrogen-containing silicone oil preferably includes compounds represented by formula 5 and formula 6:
in the formula 5, s+t is more than or equal to 20 and less than or equal to 100, and t/(74s+60t+162) is more than or equal to 0.05% and less than or equal to 0.5%;
in the formula 6, 1500 is less than or equal to 74r+134 is less than or equal to 4000, and 0.05 percent is less than or equal to 2/(74r+162) is less than or equal to 0.13 percent.
In the present invention, the hydrogen-containing silicone oil preferably includes a compound having a structure represented by formula 5. In the present invention, the compound having the structure shown in the above item 5 reacts with a polysiloxane resin having a silicon vinyl structure to form an interface material.
In the invention, in the formula 5, 20.ltoreq.s+t.ltoreq.100, preferably 30.ltoreq.s+t.ltoreq.80, more preferably 40.ltoreq.s+t.ltoreq.60; 0.05% or less t/(74s+60t+162) or less than 0.5%, preferably 0.1% or less t/(74s+60t+162) or less than 0.4%, more preferably 0.2% or less t/(74s+60t+162) or less than 0.3%.
The invention limits the s and t values within the above range, so that the compound has proper hydrogen content, and the interface material is easy to gel in the mixing process due to the too high hydrogen content, and the compound of the formula 5 is easy to participate in the reaction to a low degree, and is easy to produce oil separation in the storage and application processes.
In the present invention, the hydrogen-containing silicone oil preferably includes a compound having a structure represented by formula 6. In the present invention, the compound of formula 6 is mainly used for improving the extrudability and flexibility of the thermally conductive interface material.
In the invention, in the formula 6, 1500 is less than or equal to 74r+134 is less than or equal to 4000, preferably 2000 is less than or equal to 74r+134 is less than or equal to 3500, more preferably 2500 is less than or equal to 74r+134 is less than or equal to 3000;0.05% or less than 2/(74 r+162) or less than 0.13%, preferably 0.06% or less than 2/(74 r+162) or less than 0.10%, more preferably 0.07% or less than 2/(74 r+162) or less than 0.09%.
The r value is limited in the range, so that the compound has proper molecular weight, the molecular weight is too low, the content of volatile substances is too high, the possibility of cracking of the material during high-temperature aging is higher, the viscosity is too high, and the aim of adjusting the extrudability and softness of the material cannot be fulfilled.
In the present invention, the mass ratio of the compounds represented by formula 5 and formula 6 in the hydrogen-containing silicone oil is preferably (1 to 20): (1 to 20), more preferably (5 to 15): (5-15). The invention limits the mass ratio of the compounds shown in the formula 5 and the formula 6 in the hydrogen-containing silicone oil in the above range, and can further improve the reliability of the interface material.
In the present invention, the ratio of the total hydrosilylation functional groups to the total silylhydride functional groups in the compounds of formulas 1 to 6 is preferably 0.05 to 0.5. In the invention, the ratio of the total silicon-hydrogen functional groups to the total silicon-vinyl functional groups in the compounds of the formulas 1-6 is limited in the range, and the ratio of the silicon-hydrogen functional groups to the silicon-vinyl functional groups is too low, so that the interface material is easy to be oil-separated in the storage and application processes, and the interface material is easy to crack, slip and the like in the aging process; the ratio is too high, and the viscosity of the prepolymer generated after the mixing reaction is too high or gel appears, which is unfavorable for the addition of the heat conducting filler.
The raw materials for preparing the heat conductive interface material according to the present invention include 0.1 to 1600ppm, preferably 1 to 1000ppm, more preferably 100 to 500ppm of platinum catalyst based on 100 parts by mass of polysiloxane resin having a silicon vinyl structure. In the invention, the amount of the platinum catalyst is calculated by the mass content of platinum in the platinum catalyst accounting for the heat conduction interface material. In the present invention, the platinum catalyst is preferably platinum black, chloroplatinic acid or a reaction product of chloroplatinic acid and a monohydric alcohol, a complex of chloroplatinic acid and 1,3,5, 7-tetramethyl-1, 3,5, 7-tetravinylcyclotetrasiloxane or a complex of chloroplatinic acid and 1, 3-tetramethyl-1, 3-divinyldisiloxane. The invention limits the dosage of the platinum catalyst in the above range, and can lead polysiloxane resin with silicon vinyl structure to fully react with hydrogen-containing silicone oil.
The raw materials for preparing the heat conductive interface material comprise 100 to 4000 parts of heat conductive filler, preferably 500 to 3000 parts, and more preferably 1000 to 2000 parts, based on 100 parts by mass of polysiloxane resin with a silicon vinyl structure. The invention limits the use amount of the heat conducting filler in the range, can improve the heat conducting property of the interface material, can ensure that the interface material is uniformly filled with the heat conducting filler, and avoids agglomeration.
In the present invention, the heat conductive filler preferably includes one or more of aluminum oxide, zinc oxide, silicon dioxide, silicon carbide, silicon nitride, magnesium oxide, aluminum nitride, boron nitride, graphite and derivatives thereof, aluminum powder, silver powder, nickel powder, and iron powder.
In the present invention, the particle diameter of the heat conductive filler is preferably 0.1 to 120. Mu.m, more preferably 1 to 100. Mu.m, most preferably 30 to 80. Mu.m. The invention limits the particle size of the heat conducting filler in the range, so that the heat conducting filler has proper particle size, the state of the interface material is thicker if the particle size is too small, the application of processes such as extrusion dispensing and the like is not facilitated, the state stability of the interface material is insufficient if the particle size is too large, and the contact thermal resistance is too high.
The shape of the heat conducting filler is not particularly limited, and the shape of the heat conducting filler known to those skilled in the art can be adopted. In the present invention, the morphology of the heat conductive filler is preferably spherical. In the invention, the spherical morphology can reduce the specific surface area of the filler and increase the filling amount of the filler.
The raw materials for preparing the heat conductive interface material of the present invention include 0.001 to 1.6 parts of polymerization inhibitor, preferably 0.01 to 1.5 parts, more preferably 0.1 to 1 part, based on 100 parts by mass of polysiloxane resin having a silicon vinyl structure. In the present invention, the polymerization inhibitor is used to control the hydrosilylation reaction rate when the components are mixed. The invention limits the dosage of the polymerization inhibitor to the above range, and can lead the hydrosilation reaction to have a proper speed.
In the present invention, the polymerization inhibitor preferably includes one of 1-ethynyl cyclohexanol, 3, 5-dimethyl-1-hexyn-3-ol, 1,3,5, 7-tetramethyl-1, 3,5, 7-tetravinyl cyclotetrasiloxane and diethyl fumarate.
The invention adopts polysiloxane resin with silicon vinyl structure to react with hydrogen-containing silicone oil to prepare interface material, controls the composition of the polysiloxane resin with silicon vinyl structure, adds reaction auxiliary agent with reactive functional group, controls the dosage of each component, adjusts the structure of the product, and improves the reliability of the interface material.
The invention provides a preparation method of the heat conduction interface material, which comprises the following steps:
(1) Mixing polysiloxane resin with a silicon vinyl structure, a reaction auxiliary agent, hydrogen-containing silicone oil, a polymerization inhibitor and a platinum catalyst for addition reaction to obtain base oil;
(2) And (3) mixing the base oil obtained in the step (1) with a heat-conducting filler to obtain the heat-conducting interface material.
The invention mixes polysiloxane resin with silicon vinyl structure, reaction auxiliary agent, hydrogen-containing silicone oil, polymerization inhibitor and platinum catalyst to carry out addition reaction to obtain base oil.
In the present invention, the temperature of the addition reaction is preferably 0 to 300 ℃, more preferably 25 to 150 ℃, and most preferably 50 to 100 ℃; the time of the addition reaction is preferably 0.2 to 24 hours, more preferably 3 to 8 hours. In the present invention, the addition reaction is preferably carried out under stirring; the stirring rate is preferably 50 to 1000rpm, more preferably 100 to 800rpm, most preferably 200 to 500rpm. In the invention, in the addition reaction process, the hydrosilylation reaction between the hydrosilylation functional group and the silicon vinyl functional group in each component takes place under the catalysis of a platinum catalyst.
After the base oil is obtained, the base oil is mixed with the heat conducting filler to obtain the heat conducting interface material.
The operation of mixing the base oil and the heat conductive filler is not particularly limited, and a mixing technical scheme well known to those skilled in the art may be adopted. In the present invention, the mixing is preferably performed under stirring conditions, and the stirring speed is preferably 30 to 1000rpm, more preferably 100 to 800rpm, and most preferably 300 to 500rpm. In the present invention, the mixing time is preferably 0.5 to 24 hours, more preferably 3 to 12 hours; the temperature of the mixing is preferably 20 to 80 ℃, more preferably 20 to 50 ℃.
After the mixing is completed, the mixed product is preferably defoamed to obtain the heat-conducting interface material.
In the present invention, the deaeration is preferably vacuum deaeration; the vacuum degree of the vacuum defoamation is preferably less than or equal to-0.085 MPa; the time for the vacuum degassing is preferably 1 to 8 hours, more preferably 3 to 6 hours.
The invention controls the technological parameters such as reaction temperature, reaction time and the like, can fully react the components, and further improves the performance of the product.
The invention also provides an application of the heat conduction interface material in the heat conduction material or the heat conduction interface material prepared by the preparation method according to the technical scheme.
The operation of the application of the heat conduction interface material in the heat conduction material is not particularly limited, and the technical scheme of the application of the heat conduction interface material in the heat conduction material, which is well known to the person skilled in the art, can be adopted.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The heat-conducting interface material is prepared from the following raw materials in parts by weight: 100 parts of polysiloxane resin with a silicon vinyl structure (m=30 in the compound of formula 1, x=40 in the compound of formula 2, y=4, x+y=44 in the compound of formula 3, n=20 in the compound of formula 3, wherein the mass ratio of the compound of formula 1 to the compound of formula 2 to the compound of formula 3 is 70:20:10), 5 parts of the compound of formula 4 as a reaction auxiliary agent (o= 8,p =5, q=2, o+p+q=15, r in the compound of formula 4 1 Is hydrogen, Z is ethylene, x=0, R 2 Methyl), 6.2 parts of hydrogen-containing silicone oil (s=40, t=4, s+t=44 in the compound of formula 5, hydrogen content t/(74s+60t+162) =0.12%, r=20, 74r+134=1614 in the compound of formula 6, hydrogen content 2/(74r+162) =0.12%, wherein the mass ratio of the compound of formula 5 to the compound of formula 6 is 3.2:3), 3.2 parts of the compound of formula 5, 3 parts of the compound of formula 6Gold catalyst (Shanghai He Lishi Karstedt Catalyst, pt-5000 ppm) 5ppm based on platinum, 800 parts of thermally conductive filler, wherein 100 parts of zinc oxide powder (US Zine 205XL, specific surface area 2.7m 2 Per gram, D50 of 0.5 μm), 100 parts of alumina 1 powder (Denka ASFP-40, specific surface area of 6-8 m) 2 Per gram, D50 of 0.3-0.5 μm), 400 parts of alumina 2 powder (Denka DAW-05, specific surface area of 0.5 m) 2 Per gram, D50 of 5 μm), 200 parts of alumina 3 powder (Denka DAW-10, specific surface area of 0.3m 2 Per g, D50 of 10 μm) and 0.01 part of polymerization inhibitor 1-ethynyl cyclohexanol, wherein the ratio SiH/sivi=0.2 of the amounts of substances of total silahydrogen functional groups and total silylhenyl functional groups in all compounds of formulae 1 to 6;
the preparation method of the compound of the formula 1 comprises the following steps: in a four-neck flask containing a stirring, condensing and refluxing water diversion device, adding 37.2g of 1, 3-divinyl-1, 3-tetramethyl disiloxane (0.2 mol, VM-18, orange setting in QC), 444g of octamethyl cyclotetrasiloxane (1.5 mol, D4, hesheng silicon industry) and 2.6g of tetramethyl ammonium hydroxide silicon alkoxide with 2% alkali content, heating to 110 ℃ for ring opening equilibrium reaction for 4 hours, then heating to 160 ℃ for reaction for 2 hours, decomposing the tetramethyl silicon alkoxide catalyst, removing unreacted low molecules under the condition of vacuum degree of less than or equal to-0.085 MPa, and obtaining vinyl polysiloxane at the end of a compound of a formula 1 with volatile content of less than or equal to 1% under the condition of 150 ℃ for 1 hour, wherein m=30;
the preparation method of the compound of the formula 2 comprises the following steps: into a four-necked flask equipped with a stirring, condensing and refluxing water-dividing apparatus, 32.4g of hexamethyldisiloxane (0.2 mol, MM, sichuan chemical), 68.8g of 1,3,5, 7-tetramethyl-1, 3,5, 7-tetravinylcyclotetrasiloxane (0.2 mol, viD4, ind. Orange), 592g of octamethyl cyclotetrasiloxane (2 mol, D4, hexacarrier) and 3.6g of tetramethylammonium hydroxide silicon alkoxide having a base content of 2%, heating to 110 ℃ for ring-opening equilibrium reaction for 4 hours, then heating to 160 ℃ for reaction for 2 hours, decomposing a tetramethyl silicon alkoxide catalyst, and removing unreacted low molecules under the condition that the vacuum degree is less than or equal to-0.085 MPa to obtain side group vinyl polysiloxane of a compound of the formula 2 with the volatile content less than or equal to 1% under the condition that the vacuum degree is less than or equal to 150 ℃ for 1 hour, wherein x=40, y=4 and x+y=44;
the preparation method of the compound of the formula 3 comprises the following steps: in a four-neck flask containing a stirring, condensing and refluxing water diversion device, adding 17.4g of 1, 3-pentamethyl-1-vinyl disiloxane (0.1 mol, gelest), 296g of octamethyl cyclotetrasiloxane (2 mol, D4, hesheng silicon industry) and 2g of tetramethyl ammonium hydroxide silicon alkoxide with 2% alkali content, heating to 110 ℃ for ring-opening equilibrium reaction for 4 hours, heating to 160 ℃ for reaction for 2 hours, decomposing the tetramethyl silicon alkoxide catalyst, and removing unreacted low molecules under the condition of vacuum degree of less than or equal to-0.085 MPa to obtain a compound of formula 3 with volatile component of less than or equal to 1% under the condition of 150 ℃ for 1 hour, wherein n=20;
the preparation method of the compound of the formula 4 comprises the following steps: 240.4g of side hydrogen-containing polysiloxane similar to the structure (C-1) was introduced into a four-necked flask containing stirring, condensing and introducing nitrogen and a constant pressure dropping funnel, wherein s=10 and t=5, and the preparation method was referred to synthesis example 4, which had a theoretical molecular weight of 1174 and a theoretical hydrogen content of 0.6%. Then, karstedt catalyst (He Lishi) with a content of 1.85. 1.85gPt of 5000ppm was added to the above reactant, the temperature was raised to 80 ℃, 59.2g of vinyltrimethoxysilane (A-171, chemie) was added dropwise through a constant pressure dropping funnel, the addition was completed within 30 minutes, and the reaction temperature was controlled to not exceed 110 ℃. Continuing to react for 2 hours in a temperature range of 80-90 ℃ after the dripping is finished until all silicon vinyl bonds disappear, thereby obtaining the compound of the formula 4, wherein o= 8,p =5, q=2, o+p+q=15 and R 1 Is hydrogen, Z is ethylene, x=0, R 2 Is methyl;
the preparation method of the compound of the formula 5 comprises the following steps: in a four-neck flask containing a stirring, condensing and refluxing water diversion device, adding 32.4g of hexamethyldisiloxane (0.2 mol, MM, chuan Xiang chemical), 48g of 1,3,5, 7-tetramethyl cyclotetrasiloxane (0.2 mol, D4H, jiangxi Xin Jia Yi) and 592g of octamethyl cyclotetrasiloxane (2 mol, D4, hesheng silicon industry), then adding 3.5g of trifluoromethanesulfonic acid (analytically pure, michel), adding 35g of sodium bicarbonate (analytically pure, ke Long Shiji) for neutralization after reaction equilibrium for 6 hours at 80 ℃, filtering to remove unreacted low molecules by using a rapid filter paper at a temperature of 120 ℃ and a vacuum degree of less than or equal to-0.085 MPa, and obtaining a compound of the formula 5 with a volatile component of less than or equal to 1% under the conditions of 120 ℃ for 1h, wherein s=40, t=4, s+t=44, and a hydrogen content t/(s 60t+162) =0.12%;
the preparation method of the compound of the formula 6 comprises the following steps: 26.8g of 1, 3-tetramethyl disiloxane (0.2 mol, VM-29, orange building, state) and 296g of octamethyl cyclotetrasiloxane (1 mol, D4, silicon rich) are put into a four-neck flask containing a stirring, condensing and refluxing water diversion device, then 1.6g of trifluoromethanesulfonic acid (analytically pure, michael) is added, after the reaction is balanced for 4 hours at 60 ℃, 16g of sodium bicarbonate (analytically pure, family Long Shiji) is added for neutralization, after the rapid filter paper is used for filtering and desalting, unreacted low molecules are removed under the conditions that the temperature is 120 ℃ and the vacuum degree is less than or equal to-0.085 MPa, and the volatile component is less than or equal to 1% of a compound of a formula 6 under the conditions that the temperature is 120 ℃ and the vacuum degree is less than or equal to 1h, wherein r=20 and the hydrogen content is 2/(74r+162) =0.12%;
the preparation method of the heat conduction interface material comprises the following steps: placing the compounds of the formulas 1, 2, 3, 4, 5 and 6, a polymerization inhibitor and a platinum catalyst into a glass reaction kettle, uniformly mixing, reacting at 500rpm and 150 ℃ for 3 hours until the infrared silicon-hydrogen peak disappears to obtain base oil, then placing the base oil into a kneader, cooling to 60 ℃, adding a heat conducting filler, kneading at 50rpm for 8 hours, and vacuum defoaming at-0.09 MPa for 2 hours to obtain the heat conducting interface material.
Example 2
The amount of the compound of formula 4 in example 1 was replaced by 10 parts, and the other parameters were the same as in example 1, in which the ratio SiH/sivi=0.32 of the amounts of the substances of the silicon hydride and the silicon vinyl group.
Example 3
The amounts of the components in example 1 were replaced with 100 parts of a silicone resin having a silicon vinyl structure (wherein the mass ratio of the compound of formula 1 to the compound of formula 2 to the compound of formula 3 was 80:15:5, and the compound of formula 1 to the compound of formula 2 to the compound of formula 3 was 5), 5 parts of a compound of formula 4 as a reaction auxiliary, and 6.1 parts of a hydrogen-containing silicone oil (wherein the mass ratio of the compound of formula 5 to the compound of formula 6 was 3.1:3), and the other parameters were the same as in example 1, except that the ratio of the amounts of silicon hydride to silicon vinyl was SiH/sivi=0.2.
Comparative example 1
The amounts of the components in example 1 were replaced with 100 parts of a silicone resin having a silicon vinyl structure (wherein the mass ratio of the compound of formula 1 to the compound of formula 2 to the compound of formula 3 was 70:20:10, and the compound of formula 1 to the compound of formula 2 to the compound of formula 3 was 10), 0 part of a compound of formula 4 as a reaction auxiliary, 14.5 parts of a hydrogen-containing silicone oil (wherein the mass ratio of the compound of formula 5 to the compound of formula 6 was 11.5:3, and the compound of formula 5 to the compound of formula 6 was 11.5:3), and the other parameters were the same as in example 1, with the ratio of the amounts of silicon hydride and silicon vinyl materials SiH/sivi=0.2.
Comparative example 2
The amounts of the components in example 1 were replaced with 100 parts of a silicone resin having a silicon vinyl structure (wherein the mass ratio of the compound of formula 1 to the compound of formula 2 to the compound of formula 3 is 100:0:0), 5 parts of the compound of formula 4 to the compound of formula 3, 5.5 parts of a hydrogen-containing silicone oil (wherein the mass ratio of the compound of formula 5 to the compound of formula 6 is 2.5:3), and the other parameters were the same as in example 1, with the ratio of the amounts of silicon hydride to silicon vinyl material SiH/sivi=0.2.
Reliability evaluation method
1) Appearance degradation reliability test: the samples of the different examples and comparative examples were subjected to mechanical stress and aging tests using a vertical flow observation jig having a structure as shown in FIG. 1, each sample having a thickness of 0.5mm and each sample of the examples and comparative examples having a number of 4 sheets, and the samples were observed for slip, chalking and cracking, the test items and methods are shown in tables 1 and 2, and the test results are shown in Table 3.
Table 1 vertical flow observation fixture test items and methods
Table 2 random vibration test conditions
TABLE 3 reliability test results of appearance deterioration
2) Performance degradation reliability test
After the samples of the different examples and comparative examples were subjected to the aging test using a thermal resistance test jig having a thickness of 0.5mm and a number of samples of 4 pieces for each example and comparative example, the samples were tested for the change in thermal conductivity and thermal resistance before and after aging according to the method of ASTM5470 using a thermal conductivity meter TIMLW-9389 (taiwan rayleigh), the test items and methods of which are shown in table 4, and the test results of which are shown in tables 5 and 6.
Table 4 thermal resistance test fixture test items and methods
TABLE 5 results of reliability test of Performance degradation Heat conductivity (lambda)
TABLE 6 thermal resistance test results of performance degradation reliability test
As can be seen from tables 3,5 and 6, the heat conduction interface material provided by the invention has basically consistent heat conduction coefficient and heat resistance under the condition of similar powder filling proportion, does not generate the phenomena of sliding, cracking and pulverization after the reliability test, and has the change rate of the heat resistance and the heat conduction coefficient less than or equal to 20% after the reliability test; the comparative example 1 contains no compound of formula 4, which may cause poor wetting and dispersion state of the heat conducting powder, large initial thermal resistance, slip and cracking after reliability aging, and the change rate of the heat conducting coefficient is larger than that of the embodiment of the invention, and the change rate of the thermal resistance after aging is more than or equal to 20%; the comparative example 2 contains only one kind of vinyl polysiloxane resin formula 1 compound, which may cause uneven distribution of crosslinking points in the heat conduction interface material, and the compound of formula 2 may cause poor wetting contact with the surface of the heat dissipation substrate, and the phenomena of sliding and cracking occur after reliability aging, and the rates of change of thermal resistance and heat conduction coefficient after aging are all more than or equal to 20%.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The heat-conducting interface material is prepared from the following raw materials in parts by weight: 100 parts of polysiloxane resin with a silicon vinyl structure, 1-20 parts of reaction auxiliary agent, 2-40 parts of hydrogen-containing silicone oil, 0.1-1600 ppm of platinum catalyst calculated by platinum, 100-4000 parts of heat conduction filler and 0.001-1.6 parts of polymerization inhibitor;
the polysiloxane resin with the silicon vinyl structure comprises compounds shown in a formula 1, a formula 2 and a formula 3; the mass ratio of the compounds shown in the formula 1, the formula 2 and the formula 3 is (30-90): (10-30): (5-20);
in the formula 1, m is more than or equal to 20 and less than or equal to 150, me is methyl, and Vi is vinyl;
in the formula 2, y is more than or equal to 1 and less than or equal to 5, x+y is more than or equal to 20 and less than or equal to 150, me is methyl, and Vi is vinyl;
in the formula 3, n is more than or equal to 20 and less than or equal to 65, me is methyl, and Vi is vinyl;
the structure of the reaction auxiliary agent is shown as a formula 4:
in the formula 4, R 1 Is hydrogen, ethenyl, propenyl or butenyl, R 2 Is methyl, ethyl or propyl, R 3 Is methyl, ethyl or propyl, Z is methylene, ethylene or propylene, x is an integer of 0-2, p is more than or equal to 3 and less than or equal to 7, q is more than or equal to 1 and less than or equal to 3, and o+p+q is more than or equal to 10 and less than or equal to 20.
2. The thermally conductive interface material of claim 1, wherein the hydrogen-containing silicone oil comprises compounds of formulas 5 and 6;
in the formula 5, s+t is more than or equal to 20 and less than or equal to 100, and t/(74s+60t+162) is more than or equal to 0.05% and less than or equal to 0.5%;
in the formula 6, 1500 is less than or equal to 74r+134 is less than or equal to 4000, and 0.05 percent is less than or equal to 2/(74r+162) is less than or equal to 0.13 percent.
3. The heat-conducting interface material according to claim 2, wherein the hydrogen-containing silicone oil has a mass ratio of the compounds represented by formula 5 and formula 6 of (1 to 20): (1-20).
4. The thermally conductive interface material of claim 1, wherein the thermally conductive filler comprises one or more of aluminum oxide, zinc oxide, silicon dioxide, silicon carbide, silicon nitride, magnesium oxide, aluminum nitride, boron nitride, graphite and derivatives thereof, aluminum powder, silver powder, nickel powder, and iron powder.
5. The thermally conductive interface material of claim 1 or 4, wherein the thermally conductive filler has a particle size of 0.1 to 120 μm.
6. The thermally conductive interface material of claim 1, wherein the polymerization inhibitor comprises one of 1-ethynyl cyclohexanol, 3, 5-dimethyl-1-hexyn-3-ol, 1,3,5, 7-tetramethyl-1, 3,5, 7-tetravinyl cyclotetrasiloxane, and diethyl fumarate.
7. The method for preparing a thermal interface material according to any one of claims 1 to 6, comprising the steps of:
(1) Mixing polysiloxane resin with a silicon vinyl structure, a reaction auxiliary agent, hydrogen-containing silicone oil, a polymerization inhibitor and a platinum catalyst for addition reaction to obtain base oil;
(2) And (3) mixing the base oil obtained in the step (1) with a heat-conducting filler to obtain the heat-conducting interface material.
8. The process according to claim 7, wherein the temperature of the addition reaction in the step (1) is 25 to 150℃and the time of the addition reaction is 0.2 to 24 hours.
9. The method according to claim 7, wherein the mixing time in the step (2) is 0.5 to 24 hours.
10. Use of a thermally conductive interface material according to any one of claims 1 to 6 or a thermally conductive interface material prepared according to the preparation method of any one of claims 7 to 9 in a thermally conductive material.
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