CN117903600A - Preparation method of high-heat-conductivity organic silicon rubber composite material - Google Patents
Preparation method of high-heat-conductivity organic silicon rubber composite material Download PDFInfo
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- 229920002379 silicone rubber Polymers 0.000 title claims abstract description 78
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000004945 silicone rubber Substances 0.000 claims abstract description 49
- 229920001577 copolymer Polymers 0.000 claims abstract description 46
- 239000000945 filler Substances 0.000 claims abstract description 29
- 230000005684 electric field Effects 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 19
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical compound C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- 239000010703 silicon Substances 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 27
- 239000000835 fiber Substances 0.000 claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 239000003607 modifier Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
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- 239000002041 carbon nanotube Substances 0.000 claims description 8
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 8
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 8
- GXBYFVGCMPJVJX-UHFFFAOYSA-N Epoxybutene Chemical compound C=CC1CO1 GXBYFVGCMPJVJX-UHFFFAOYSA-N 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 5
- 238000012650 click reaction Methods 0.000 claims description 5
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 5
- 239000004246 zinc acetate Substances 0.000 claims description 5
- WTCSRYZMCHRXLM-UHFFFAOYSA-N 1-bromooct-1-ene Chemical compound CCCCCCC=CBr WTCSRYZMCHRXLM-UHFFFAOYSA-N 0.000 claims description 4
- 239000004020 conductor Substances 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
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- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 229920001296 polysiloxane Polymers 0.000 description 5
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- 238000004073 vulcanization Methods 0.000 description 3
- OXBLVCZKDOZZOJ-UHFFFAOYSA-N 2,3-Dihydrothiophene Chemical compound C1CC=CS1 OXBLVCZKDOZZOJ-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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- 239000000741 silica gel Substances 0.000 description 1
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- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a preparation method of a high-heat-conductivity organic silicon rubber composite material. The method comprises the following steps: step 1: sequentially adding methyl vinyl silicone rubber, an organic silicon copolymer, a heat conducting filler, a vulcanizing agent and a photoinitiator into a mixing roll in a light-shading manner, and uniformly mixing to obtain a silicone rubber prepolymer; step 2: and (3) pre-solidifying the silicone rubber prepolymer in an electric field environment by ultraviolet light, and vulcanizing the silicone rubber prepolymer at high temperature on a flat vulcanizing machine to obtain the organic silicone rubber composite material. The beneficial effects are that: the organosilicon copolymer and the linear organosilicon rubber form a crosslinked network, so that the toughness is improved, the crosslinking degree is ensured, and the mechanical property is effectively improved. By reasonably preparing the heat conducting filler, the interface effect between the heat conducting filler and the matrix polymer is improved while the dispersion uniformity is improved, so that the heat conducting property is effectively improved. The heat conducting filler and the organosilicon copolymer synergistically improve the high-temperature solvent resistance.
Description
Technical Field
The invention relates to the technical field of silicone rubber, in particular to a preparation method of a high-heat-conductivity type organic silicone rubber composite material.
Background
The development of the modern electronic industry promotes the development of novel polymer materials; silicone rubber is one of the polymers widely used in microelectronic devices. The heat dissipation of electronic devices is one of the problems to be solved in electronic products, and this also makes the heat dissipation and high temperature stability of silicone rubber products a major research project.
The heat-conducting organic silicon rubber is silica gel formed by mixing high molecular organic silicon and a heat-conducting material, is widely used in the industries of electronics, electric appliances, instruments and the like, has high elasticity and high temperature stability, and needs to rapidly transfer heat in the instruments so as to relieve the problem of concentrated overheating of products. In the prior art, the heat-conducting property is required to be improved, so that the content of the introduced filler is high, the problems of dispersibility and uniformity exist, and the rigidity is too high, the brittleness is too high, and the mechanical properties such as tear resistance and the like are poor; and thirdly, the interface effect between the filler and the polymer is weak, and the thermal resistance is high. On the other hand, fluorine is generally introduced to increase solvent resistance, but the introduction of fluorine increases the difficulty of vulcanization, increases the production cost, decreases the mechanical strength, and is disadvantageous for use in a severe environment due to poor solvent resistance at high temperature.
In conclusion, the preparation of the high-heat-conductivity organic silicon rubber composite filler has important significance in solving the problems.
Disclosure of Invention
The invention aims to provide a preparation method of a high-heat-conductivity organic silicon rubber composite material, which aims to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
a preparation method of a high-heat-conductivity organic silicon rubber composite material comprises the following steps:
step 1: sequentially adding methyl vinyl silicone rubber, an organic silicon copolymer, a heat conducting filler, a vulcanizing agent and a photoinitiator into a mixing roll in a light-shading manner, and uniformly mixing to obtain a silicone rubber prepolymer;
step 2: and (3) pre-solidifying the silicone rubber prepolymer in an electric field environment by ultraviolet light, and vulcanizing the silicone rubber prepolymer at high temperature on a flat vulcanizing machine to obtain the organic silicone rubber composite material.
More preferably, the raw materials of the silicone rubber prepolymer comprise the following components: 45-55 parts of methyl vinyl silicone rubber, 12-15 parts of organic silicon copolymer, 32-40 parts of heat conducting filler, 1.5-2 parts of vulcanizing agent and 0.5-1 part of photoinitiator.
More optimally, the preparation method of the organosilicon copolymer comprises the following steps: dispersing (mercapto) propyl methyl siloxane-dimethyl siloxane copolymer in n-hexane under inert gas, adding 3, 4-epoxy-1-butene and a photoinitiator, uniformly stirring, performing ultraviolet light click reaction, and evaporating n-hexane to obtain an organosilicon copolymer A; dispersing the organosilicon copolymer A in toluene under inert gas, adding dimer acid and zinc acetate, reacting for 3-4 hours at 100-105 ℃, and evaporating the toluene to obtain the organosilicon copolymer.
More preferably, the mass ratio of (mercapto) propyl methyl siloxane-dimethyl siloxane, 3, 4-epoxy-1-butene and dimer acid is 10 (0.05-0.08) to 0.2-0.3.
More optimally, the preparation method of the heat conduction filler comprises the following steps: (1) Sequentially dispersing cyano diphenol and potassium carbonate in DMF (dimethyl formamide), setting the temperature at 110-120 ℃, adding 1-bromooctene, reacting for 1-2 days, pouring the materials into an ice-water bath for precipitation, recrystallizing and drying to obtain a modifier; (2) Dispersing the carbon nano tube into ethanol, adding mercaptopropyl trimethoxy silane, stirring for 12 hours, adding ammonium fluoride, stirring for 24 hours, washing and drying to obtain a modified carbon nano tube; dispersing silicon carbide fibers in ethanol, adding vinyl trimethoxy silane, stirring for 12 hours, adding ammonium fluoride, stirring for 24 hours, washing and drying to obtain modified silicon carbide fibers; (3) And sequentially dispersing the modified carbon nano tube, the modified silicon carbide fiber, the modifier and the photoinitiator in n-hexane, performing ultraviolet light click reaction, washing and drying to obtain the heat conducting material.
More optimally, the mass ratio of the modified carbon nano tube to the modified silicon carbide fiber to the modifier is 5:1:2.
More optimally, in the modified carbon nano tube, the mass ratio of the carbon nano tube to the mercaptopropyl trimethoxy silane is 1 (1-1.2); in the modified silicon carbide fiber, the mass ratio of the silicon carbide fiber to the vinyl trimethoxy silane is 1 (1.2-1.4).
More optimally, in the ultraviolet light pre-curing process, the ultraviolet light is cured for 3 to 5 minutes under the condition that the electric field environment is an alternating electric field of 10 to 15Hz and 50 to 100V and the ultraviolet light intensity is 200 to 220mW/cm 2; in the high temperature vulcanizing process, the primary vulcanizing is carried out for 10 minutes under the temperature of 160-170 ℃ and the pressure of 5-10 MPa, and the secondary vulcanizing is carried out for 2-4 hours under the temperature of 180-200 ℃.
More optimally, the organic silicon rubber composite material is prepared by the preparation method of the organic silicon rubber composite material with high heat conductivity.
In the technical scheme, the organosilicon copolymer and the linear organosilicon rubber form a crosslinked network, so that the toughness is improved, the crosslinking degree is ensured, and the mechanical property is effectively improved. By reasonably preparing the heat conducting filler, the interface effect between the heat conducting filler and the matrix polymer is improved while the dispersion uniformity is improved, so that the heat conducting property is effectively improved. The heat conducting filler and the organosilicon copolymer synergistically improve the high-temperature solvent resistance.
(1) In the scheme, 3, 4-epoxy-1-butene is grafted and modified by a (mercapto) propyl methyl siloxane-dimethyl siloxane copolymer through a clicking reaction of mercaptan-alkene to obtain an organosilicon copolymer A containing epoxy groups; then the epoxy group reacts with carboxyl to react with dimer acid to form organosilicon copolymer with good thermoplasticity. The copolymer can generate transesterification reaction, polymer chain slippage and rearrangement in the subsequent preparation process of the organic rubber composite material, and has good high-temperature viscoelasticity. Meanwhile, the dimer acid is cross-chain, so that the network crosslinking of the organic silicon rubber composite material is effectively improved, and the water resistance of the organic silicon rubber composite material is effectively improved by long-chain alkyl. The presence of a dynamic transesterification process also gives it good heat and solvent resistance.
(2) In the scheme, the thiol-ene click reaction is also utilized to react and graft the carbon nano tube modified by the sulfhydryl silane coupling agent, the vinyl modified silicon carbide fiber and the modifier containing carbon-carbon double bonds, thereby sequentially obtaining the heat conduction filler.
Wherein, the two silane coupling agents have similar compatibility with two main substances in the organic silicon rubber material, so that the dispersibility of the filler can be effectively improved; meanwhile, the heat-conducting material can be crosslinked in the composite material through photo-curing reaction, so that the interface thermal resistance is reduced, and the heat-conducting property is improved. The carbon nano tube and the silicon carbide fiber are grafted in advance to form a heat conduction network connected by a tube and a line, so that the heat conduction performance is improved. In addition, the heat conducting network formed by the two materials effectively improves the mechanical property, inhibits the swelling of the solvent and improves the high-temperature solvent resistance in cooperation with the organosilicon copolymer.
The modifier is prepared by substitution reaction of liquid crystal monomer cyano diphenol and 1-bromooctene, and is grafted in the heat conducting filler through thiol-ene reaction, so that the heat conducting filler contains cyano diphenol, and the cyano diphenol is induced to be arranged along the direction of an electric field under the action of the electric field and is orderly dispersed in a polymer matrix, thereby obviously improving the heat conducting property.
(3) The heat conducting filler is pre-cured by ultraviolet light and is uniformly interwoven in the network in advance, and the curing stress and brittleness are reduced by primary vulcanization and secondary vulcanization processes. Because the hardness of the high-filler silicone rubber composite material is high, the generated thermal stress has the problem of microcrack generation, and the heat transfer channel of the silicone rubber material and the connecting material is not beneficial to the development.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. 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.
In the following examples, the carbon nanotube source is Allatin, product number C1212152, diameter 11nm; silicon carbide fiber is from Sianziyue biotechnology Co., ltd, the length-diameter ratio is 20-150, (mercapto) propyl methyl siloxane-dimethyl siloxane copolymer is from Michael, and the product number is GEL-SMS-042; the source of methyl vinyl silicone rubber is Wuhan Kano technology Co., ltd., the product number is 8598479, the source of dimer acid is Shanghai Kagaku Biotechnology Co., ltd., the product number is XY31120.
The preparation method of the modifier comprises the following steps: 5g of cyano diphenol and 8g of potassium carbonate are dispersed in 150mL of DMF in sequence, the temperature is set to 120 ℃, 7g of 1-bromooctene is added for reaction for 2 days, the mixture is poured into an ice-water bath for precipitation, the ethanol solvent is used for recrystallization, and the modifier is obtained after drying. Can be amplified in equal proportion.
The preparation method of the modified carbon nano tube comprises the following steps: 10g of carbon nano tube is dispersed in 800mL of ethanol, 11g of mercaptopropyl trimethoxy silane is added, stirring is carried out for 12 hours, 3g of ammonium fluoride is added, stirring is carried out for 24 hours, washing and drying are carried out, and the modified carbon nano tube is obtained. Can be amplified in equal proportion.
The preparation method of the modified silicon carbide fiber comprises the following steps: 10g of silicon carbide fiber is dispersed in 800mL of ethanol, 1.2g of vinyltrimethoxysilane is added, stirring is carried out for 12 hours, ammonium fluoride is added, stirring is carried out for 24 hours, washing and drying are carried out, and the modified silicon carbide fiber is obtained. Can be amplified in equal proportion.
Example 1:
Material preparation: (1) Dispersing 100g of (mercapto) propyl methyl siloxane-dimethyl siloxane copolymer in 200mL of n-hexane under nitrogen atmosphere, adding 0.5g of 3, 4-epoxy-1-butene and 0.1g of photoinitiator 1173, uniformly stirring, and carrying out light-beating for 30 minutes under the ultraviolet light of 365nm and setting the intensity to 80mW/cm 2, and steaming to remove the n-hexane to obtain an organosilicon copolymer A; the obtained organosilicon copolymer A was dispersed in 200mL of toluene under nitrogen atmosphere, 2g of dimer acid and 0.1g of zinc acetate were added, and the mixture was reacted at 105℃for 4 hours, and toluene was distilled off to obtain an organosilicon copolymer, which was amplified in equal proportions. (2) 10g of modified carbon nano tube, 2g of modified silicon carbide fiber, 4g of modifier and photoinitiator are dispersed in 60mL of normal hexane in sequence, light is struck for 30 minutes under ultraviolet light with the intensity of 80mW/cm 2, and the heat conduction material is obtained after washing and drying, and can be amplified in equal proportion.
Step 1: according to parts by weight, adding 45 parts of methyl vinyl silicone rubber, 15 parts of organic silicon copolymer, 40 parts of heat conducting filler, 2 parts of 2, 4-dichloro benzoyl peroxide and 0.5 part of photoinitiator 1173 into a mixing mill in sequence in a light-shading manner, and uniformly mixing to obtain a silicone rubber prepolymer;
Step 2: setting the intensity of the silicone rubber prepolymer to 220mW/cm 2 under 365nm ultraviolet light for 3 minutes under an alternating electric field with the electric field environment of 15Hz and 100V; and (3) vulcanizing the mixture for 10 minutes at the temperature of 170 ℃ and the pressure of 5MPa in a flat vulcanizing machine, and vulcanizing the mixture for 4 hours at 180 ℃ to obtain the organic silicon rubber composite material.
Example 2:
Material preparation: (1) Dispersing 100g of (mercapto) propyl methyl siloxane-dimethyl siloxane copolymer in 200mL of n-hexane under nitrogen atmosphere, adding 0.6g of 3, 4-epoxy-1-butene and 0.1g of photoinitiator 1173, uniformly stirring, and carrying out light-beating for 30 minutes under the ultraviolet light of 365nm and setting the intensity to 80mW/cm 2, and steaming to remove the n-hexane to obtain an organosilicon copolymer A; the obtained organosilicon copolymer A was dispersed in 200mL of toluene under nitrogen atmosphere, 2.5g of dimer acid and 0.1g of zinc acetate were added, and reacted at 105℃for 4 hours, toluene was distilled off, and the organosilicon copolymer was obtained, which was amplified in equal proportions. (2) 10g of modified carbon nano tube, 2g of modified silicon carbide fiber, 4g of modifier and photoinitiator are dispersed in 60mL of normal hexane in sequence, light is struck for 30 minutes under ultraviolet light with the intensity of 80mW/cm 2, and the heat conduction material is obtained after washing and drying, and can be amplified in equal proportion.
Step 1: according to parts by weight, adding 52 parts of methyl vinyl silicone rubber, 14 parts of organic silicon copolymer, 34 parts of heat conducting filler, 1.6 parts of 2, 4-dichloro benzoyl peroxide and 0.8 part of photoinitiator 1173 into a mixing mill in sequence in a light-shading manner, and uniformly mixing to obtain a silicone rubber prepolymer;
Step 2: setting the intensity of the silicone rubber prepolymer to 215mW/cm 2 under the ultraviolet light at 365nm under the alternating electric field with the electric field environment of 12Hz and 80V for 3 minutes; and (3) vulcanizing the mixture for 10 minutes at the temperature of 165 ℃ and the pressure of 6MPa on a flat vulcanizing machine, and vulcanizing the mixture for 3 hours at the temperature of 200 ℃ to obtain the organic silicon rubber composite material.
Example 3:
Material preparation: (1) Dispersing 100g of (mercapto) propyl methyl siloxane-dimethyl siloxane copolymer in 200mL of n-hexane under nitrogen atmosphere, adding 0.8g of 3, 4-epoxy-1-butene and 0.1g of photoinitiator 1173, uniformly stirring, and carrying out light-beating for 30 minutes under the ultraviolet light of 365nm and setting the intensity to 80mW/cm 2, and steaming to remove the n-hexane to obtain an organosilicon copolymer A; the obtained organosilicon copolymer A was dispersed in 200mL of toluene under nitrogen atmosphere, 3g of dimer acid and 0.1g of zinc acetate were added, and the mixture was reacted at 105℃for 4 hours, and toluene was distilled off to obtain an organosilicon copolymer, which was amplified in equal proportions. (2) 10g of modified carbon nano tube, 2g of modified silicon carbide fiber, 4g of modifier and photoinitiator are dispersed in 60mL of normal hexane in sequence, light is struck for 30 minutes under ultraviolet light with the intensity of 80mW/cm 2, and the heat conduction material is obtained after washing and drying, and can be amplified in equal proportion.
Step 1: according to parts by weight, adding 55 parts of methyl vinyl silicone rubber, 13 parts of organic silicon copolymer, 32 parts of heat conducting filler, 2 parts of 2, 4-dichloro benzoyl peroxide and 0.5 part of photoinitiator 1173 into a mixing mill in sequence in a light-shading manner, and uniformly mixing to obtain a silicone rubber prepolymer;
step 2: setting the intensity of the silicone rubber prepolymer to 200mW/cm 2 under 365nm ultraviolet light for 5 minutes under an alternating electric field with the electric field environment of 10Hz and 50V; and (3) vulcanizing the mixture for 10 minutes at the temperature of 170 ℃ and the pressure of 10MPa on a flat vulcanizing machine, and vulcanizing the mixture for 3 hours at the temperature of 200 ℃ to obtain the organic silicon rubber composite material.
Comparative example 1: (mercapto) propylmethylsiloxane-dimethylsiloxane copolymer was used instead of the silicone copolymer, the remainder being the same as in example 2.
Specifically: step 1: according to parts by weight, adding 52 parts of methyl vinyl silicone rubber, 14 parts of (mercapto) propyl methyl siloxane-dimethyl siloxane copolymer, 34 parts of heat conducting filler, 1.6 parts of 2, 4-dichloro benzoyl peroxide and 0.8 part of photoinitiator 1173 into a mixing mill in sequence in a light-shading manner, and uniformly mixing to obtain a silicone rubber prepolymer;
Step 2: setting the intensity of the silicone rubber prepolymer to 215mW/cm 2 under 365nm of ultraviolet light for 3 minutes under an alternating electric field with the electric field environment of 12Hz and 80V; and (3) vulcanizing the mixture for 10 minutes at the temperature of 165 ℃ and the pressure of 6MPa on a flat vulcanizing machine, and vulcanizing the mixture for 3 hours at the temperature of 200 ℃ to obtain the organic silicon rubber composite material.
Comparative example 2: no silicone copolymer was introduced, and the rest was the same as in example 2;
Specifically: step 1: according to parts by weight, adding 66 parts of methyl vinyl silicone rubber, 34 parts of heat conducting filler, 1.6 parts of 2, 4-dichloro benzoyl peroxide and 0.8 part of photoinitiator 1173 into a mixing mill in sequence in a light-shading manner, and uniformly mixing to obtain a silicone rubber prepolymer;
Step 2: setting the intensity of the silicone rubber prepolymer to 215mW/cm 2 under 365nm of ultraviolet light for 3 minutes under an alternating electric field with the electric field environment of 12Hz and 80V; and (3) vulcanizing the mixture for 10 minutes at the temperature of 165 ℃ and the pressure of 6MPa on a flat vulcanizing machine, and vulcanizing the mixture for 3 hours at the temperature of 200 ℃ to obtain the organic silicon rubber composite material.
Comparative example 3: the amount of the organosilicon copolymer introduced was increased to 25 parts, and the remainder was the same as in example 2;
Specifically: step 1: according to parts by weight, adding 41 parts of methyl vinyl silicone rubber, 25 parts of organic silicon copolymer, 34 parts of heat conducting filler, 1.6 parts of 2, 4-dichloro benzoyl peroxide and 0.8 part of photoinitiator 1173 into a mixing mill in sequence in a light-shading manner, and uniformly mixing to obtain a silicone rubber prepolymer;
Step 2: setting the intensity of the silicone rubber prepolymer to 215mW/cm 2 under 365nm of ultraviolet light for 3 minutes under an alternating electric field with the electric field environment of 12Hz and 80V; and (3) vulcanizing the mixture for 10 minutes at the temperature of 165 ℃ and the pressure of 6MPa on a flat vulcanizing machine, and vulcanizing the mixture for 3 hours at the temperature of 200 ℃ to obtain the organic silicon rubber composite material.
Comparative example 4: the mass ratio of the modified carbon nano tube, the modified silicon carbide fiber and the modifier is changed to 3:3:2, and the rest is the same as in the example 2.
Comparative example 5: the alternating electric field was not provided, and the rest was the same as in example 2.
Step 1: according to parts by weight, adding 52 parts of methyl vinyl silicone rubber, 14 parts of organic silicon copolymer, 34 parts of heat conducting filler, 1.6 parts of 2, 4-dichloro benzoyl peroxide and 0.8 part of photoinitiator 1173 into a mixing mill in sequence in a light-shading manner, and uniformly mixing to obtain a silicone rubber prepolymer;
Step 2: setting the intensity of the silicone rubber prepolymer to 215mW/cm 2 under 365nm ultraviolet light, and photo-curing for 3 minutes; and (3) vulcanizing the mixture for 10 minutes at the temperature of 165 ℃ and the pressure of 6MPa on a flat vulcanizing machine, and vulcanizing the mixture for 3 hours at the temperature of 200 ℃ to obtain the organic silicon rubber composite material.
Experiment: carrying out relevant characterization on the high-heat-conductivity organic silicon rubber composite materials prepared in the examples 1-3 and the comparative examples 1-5, wherein the high-temperature solvent resistance is obtained by taking diphenyl ether as a solvent, and soaking for 6 hours at the temperature of 140 ℃; the expanded sample was dried in vacuo and tested for expansion. The results obtained are shown in the following table:
| Examples | Tear strength KN/m | Thermal conductivity W/m . k | Expansion ratio% |
| Example 1 | 19.8 | 2.54 | 3.18 |
| Example 2 | 20.3 | 2.58 | 3.24 |
| Example 3 | 19.5 | 2.53 | 3.17 |
| Comparative example 1 | 18.0 | 2.42 | 5.21 |
| Comparative example 2 | 17.3 | 2.30 | 7.68 |
| Comparative example 3 | 18.6 | 2.48 | 3.15 |
| Comparative example 4 | 19.3 | 2.31 | 3.06 |
| Comparative example 5 | 20.5 | 2.18 | 3.08 |
Conclusion: from the data in the above table, it can be seen that: the organic silicon rubber composite material has excellent mechanical property, heat conducting property and high-temperature solvent resistance. Comparing the data of comparative examples 1 to 5 with example 2, it can be found that: in comparative example 1, since the silicone copolymer was replaced with the (mercapto) propylmethylsiloxane-dimethylsiloxane copolymer, the mechanical properties and the high temperature solvent resistance were lowered; in comparative example 2, since the silicone copolymer was not incorporated, all properties were significantly degraded. In comparative example 3, the mechanical properties were lowered due to the excessive amount of the silicone copolymer introduced. In comparative example 4, the silicon carbide fiber is increased due to the change of the proportion of the heat conductive filler raw material, and the heat conductivity and the expansion rate are obviously reduced; in comparative example 5, since no electric field was provided, the decrease in thermal conductivity was remarkable.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A preparation method of a high-heat-conductivity organic silicon rubber composite material is characterized by comprising the following steps: the method comprises the following steps:
step 1: sequentially adding methyl vinyl silicone rubber, an organic silicon copolymer, a heat conducting filler, a vulcanizing agent and a photoinitiator into a mixing roll in a light-shading manner, and uniformly mixing to obtain a silicone rubber prepolymer;
step 2: and (3) pre-solidifying the silicone rubber prepolymer in an electric field environment by ultraviolet light, and vulcanizing the silicone rubber prepolymer at high temperature on a flat vulcanizing machine to obtain the organic silicone rubber composite material.
2. The method for preparing the high-heat-conductivity organic silicon rubber composite material according to claim 1, which is characterized in that: the raw materials of the silicone rubber prepolymer comprise the following components: 45-55 parts of methyl vinyl silicone rubber, 13-15 parts of organic silicon copolymer, 32-40 parts of heat conducting filler, 1.5-2 parts of vulcanizing agent and 0.5-1 part of photoinitiator.
3. The method for preparing the high-heat-conductivity organic silicon rubber composite material according to claim 1, which is characterized in that: the preparation method of the organosilicon copolymer comprises the following steps: dispersing (mercapto) propyl methyl siloxane-dimethyl siloxane copolymer in n-hexane under inert gas, adding 3, 4-epoxy-1-butene and a photoinitiator, uniformly stirring, performing ultraviolet light click reaction, and evaporating n-hexane to obtain an organosilicon copolymer A; dispersing the organosilicon copolymer A in toluene under inert gas, adding dimer acid and zinc acetate, reacting for 3-4 hours at 100-105 ℃, and evaporating the toluene to obtain the organosilicon copolymer.
4. The method for preparing the high-heat-conductivity organic silicon rubber composite material according to claim 3, wherein the method comprises the following steps: the mass ratio of (mercapto) propylmethylsiloxane-dimethylsiloxane, 3, 4-epoxy-1-butene and dimer acid was 10:
(0.05～0.08):(0.2～0.3)。
5. The method for preparing the high-heat-conductivity organic silicon rubber composite material according to claim 1, which is characterized in that: the preparation method of the heat conduction filler comprises the following steps: (1) Sequentially dispersing cyano diphenol and potassium carbonate in DMF (dimethyl formamide), setting the temperature at 110-120 ℃, adding 1-bromooctene, reacting for 1-2 days, pouring the materials into an ice-water bath for precipitation, recrystallizing and drying to obtain a modifier; (2) Dispersing the carbon nano tube into ethanol, adding mercaptopropyl trimethoxy silane, stirring for 12 hours, adding ammonium fluoride, stirring for 24 hours, washing and drying to obtain a modified carbon nano tube; dispersing silicon carbide fibers in ethanol, adding vinyl trimethoxy silane, stirring for 12 hours, adding ammonium fluoride, stirring for 24 hours, washing and drying to obtain modified silicon carbide fibers; (3) And sequentially dispersing the modified carbon nano tube, the modified silicon carbide fiber, the modifier and the photoinitiator in n-hexane, performing ultraviolet light click reaction, washing and drying to obtain the heat conducting material.
6. The method for preparing the high-heat-conductivity organic silicon rubber composite material according to claim 5, which is characterized in that: the mass ratio of the modified carbon nano tube to the modified silicon carbide fiber to the modifier is 5:1:2.
7. The method for preparing the high-heat-conductivity organic silicon rubber composite material according to claim 5, which is characterized in that: in the modified carbon nano tube, the mass ratio of the carbon nano tube to the mercaptopropyl trimethoxy silane is 1 (1-1.2); in the modified silicon carbide fiber, the mass ratio of the silicon carbide fiber to the vinyl trimethoxy silane is 1 (1.2-1.4).
8. The method for preparing the high-heat-conductivity organic silicon rubber composite material according to claim 1, which is characterized in that: in the ultraviolet light pre-curing process, the ultraviolet light is photo-cured for 3 to 5 minutes under the condition that the electric field environment is 10 to 15Hz and the alternating electric field of 50 to 100V and the ultraviolet light intensity is 200 to 220mW/cm 2; in the high temperature vulcanizing process, the primary vulcanizing is carried out for 10 minutes under the temperature of 160-170 ℃ and the pressure of 5-10 MPa, and the secondary vulcanizing is carried out for 2-4 hours under the temperature of 180-200 ℃.
9. The silicone rubber composite material according to any one of claims 1 to 8, which is prepared by a preparation method of the silicone rubber composite material.
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