CN102352110A - Super flexible high-molecular heat conduction material and preparation method thereof - Google Patents
Super flexible high-molecular heat conduction material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 229920005989 resin Polymers 0.000 claims abstract description 82
- 239000011347 resin Substances 0.000 claims abstract description 82
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 75
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 239000011159 matrix material Substances 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 229920002050 silicone resin Polymers 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 61
- 229910052710 silicon Inorganic materials 0.000 claims description 61
- 239000010703 silicon Substances 0.000 claims description 61
- 239000000945 filler Substances 0.000 claims description 34
- 229910052739 hydrogen Inorganic materials 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 25
- 229910020388 SiO1/2 Inorganic materials 0.000 claims description 17
- 229910020485 SiO4/2 Inorganic materials 0.000 claims description 17
- 229920002545 silicone oil Polymers 0.000 claims description 17
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 8
- 239000011787 zinc oxide Substances 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 7
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 6
- 229910007161 Si(CH3)3 Inorganic materials 0.000 claims description 6
- ARLJCLKHRZGWGL-UHFFFAOYSA-N ethenylsilicon Chemical compound [Si]C=C ARLJCLKHRZGWGL-UHFFFAOYSA-N 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 239000004020 conductor Substances 0.000 claims description 5
- 238000005096 rolling process Methods 0.000 claims description 5
- 229910052582 BN Inorganic materials 0.000 claims description 4
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 2
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 2
- 229920005570 flexible polymer Polymers 0.000 claims 6
- 238000001723 curing Methods 0.000 abstract description 74
- 238000011049 filling Methods 0.000 abstract description 9
- 238000003490 calendering Methods 0.000 abstract description 4
- 238000000465 moulding Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005303 weighing Methods 0.000 description 6
- 230000017525 heat dissipation Effects 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000000805 composite resin Substances 0.000 description 3
- 150000001875 compounds Chemical group 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013006 addition curing Methods 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
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- 238000004377 microelectronic Methods 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a super flexible high-molecular heat conduction material and a preparation method thereof. The super flexible high-molecular heat conduction material consists of matrix resin and heat conduction filling material in a mass ratio of 100:300-100:1100; the matrix resin comprises, by weight, 85-90% of organic silicone resin A, 5-10% of organic silicone resin B, 1-3% of curing agent a, 0-1% of curing agent b and 0.1-1% of catalyst; the heat conduction filling material comprises, by weight, 70-95% of spherical filling material and 5-30% of acicular filling material. The method comprises steps of: adding the organic silicone resin, the curing agents and the catalyst successively according to the proportion into a mixer and mixing to obtain a matrix resin; mixing with the heat conduction filling material according to a ratio of 100:300-100:1100, wherein the heat conduction filling material is prepared by first adding 70-95% of spherical filling material, stirring, adding 5-305 of acicular filling material, stirring and mixing; the carrying out calendaring molding and solidifying.
Description
Technical Field
The invention relates to a heat conduction material, in particular to an ultra-flexible high-polymer heat conduction material and a preparation method thereof, belonging to the field of high polymer materials.
Background
At present, the microelectronic assembly is more and more intensive, and the working environment thereof is rapidly changed to a high temperature. The reliability of the electronic components is reduced by 10% when the temperature of the electronic components rises by 2 ℃, so that the timely heat dissipation becomes an important factor influencing the service life of the electronic components. Along with the miniaturization and function integration of electronic products, the internal structure of an electronic device is more and more complex, the density of components is higher and higher, the heat productivity is higher and higher, and the requirement on heat conduction materials is higher and higher.
The heat conduction material is adhered to the surface of the device or filled in a gap between the two surfaces, air in the gap is removed, the device is protected from being corroded by the outside, movement or deformation stress is absorbed, heat generated by the operation of the internal device is conducted out in time, and the heat conduction material plays roles in heat conduction, sealing, filling, insulation, shock absorption and corrosion prevention and is a functional material with wide application.
The heat conducting paste takes inert resin as a matrix, is not cured and has good wettability, but is easy to deform at high temperature, separate out and even flow, pollute devices, limit the application of the heat conducting paste in wider gaps, and particularly limit a plurality of devices which are not on the same plane and need heat dissipation.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the super-flexible high-molecular heat conduction material and the preparation method thereof, so that the super-flexible high-molecular heat conduction material has the advantages of reduced hardness, reduced stress, improved heat resistance, difficult decomposition at high temperature, reduced cost and wide application.
The technical scheme for solving the technical problems is as follows: the high-molecular heat conduction material comprises two parts, namely 100: 300-100: 1100 of matrix resin and heat conduction filler, wherein the matrix resin comprises the following raw materials, by weight, 85-90% of organic silicon resin A, 5-10% of organic silicon resin B, 1-3% of curing agent a, 0-1% of curing agent B and 0.1-1% of catalyst; the heat filler comprises, by weight, 70-95% of a spherical filler and 5-30% of a needle-shaped filler.
The invention has the beneficial effects that: the super-flexible high-polymer heat-conducting material has the adjustable hardness of 5-15 (Shore E) and the heat-conducting coefficient of 1-6.0W/m·The adjustable K can be used for heat dissipation of high-power electronic products and design and development of a large number of civil electronic products, has lower cost and good dielectric property, and can play a role in insulation and sealing.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, the silicone resin A is a linear or branched vinyl silicon resin, the structural formula of the linear vinyl silicon resin is represented by the following general formula (I), and the branched vinyl silicon resin is represented by the following general formula (II):
CH2=CH-Si(CH3)2O[(CH3)2SiO]e(CH3)2Si－CH=CH2（Ⅰ）；
(CH3)3SiO[(CH3)2SiO]ｍ[(CH2=CH)(CH3)SiO]ｎSi(CH3)3（Ⅱ）；
wherein in the formula (I), e = 50-200;
in the formula (II), m + n = 50-260;
the further scheme has the advantages that the vinyl silicone resin is cured by addition curing, no micromolecules escape in the curing process, no odor and no pollution are generated, the temperature resistance is good, the vinyl silicone resin can be used within the range of-50-260 ℃, no micromolecules migrate out, no odor is generated, and the surface of a corrosion device is not polluted.
Further, the organic silicon resin B contains R1 3SiO1/2Structural unit and SiO4/2A copolymer of structural units wherein R is1 3SiO1/2Structural unit and the SiO4/2The molar ratio of the structural units is 0.5 to 0.9.
The further scheme has the beneficial effects that the content of the organic silicon resin B and the content of the organic silicon resin R are adjusted1 3SiO1/2Structural unit and the SiO4/2The molar ratio of the structural units can adjust the surface viscosity of the cured product, and the cured product is smooth in surface and viscous, so that the method is suitable for different process requirements.
Further, the curing agent a is a hydrogen-containing silicone oil curing agent, and the structural formula of the curing agent a is represented by the following general formula (III):
R-Si(CH3)2-O-[SiHCH3-O]m-[Si-(CH3)2-O]n-Si(CH3)2-R （Ⅲ）
wherein R represents CH3Or H, f + g = 8-98.
Further, the curing agent b is a terminal hydrogen silicone oil curing agent, and the structural formula of the curing agent b is represented by the following general formula (IV):
H-O-[Si-(CH3)2-O]h-R （Ⅳ）
wherein R represents CH3Or H, H is an integer of 50-280;
the beneficial effects of adopting above-mentioned further scheme are that, through the proportion and the quantity of adjusting two kinds of curing agents, can obtain the condensate that hardness is at 5~15 (shore E) according to actual need, guarantee attached compactness, can be used to various irregular surfaces or fill between the device gap, can produce corresponding deformation when it receives certain pressure, reply in time again after the pressure is eliminated, keep the contact of maximum area in the use all the time, the radiating effect is good, satisfy the application demand of different positions.
Further, the catalyst is a platinum complex catalyst.
Further, the platinum complex catalyst is one or a mixture of any more of chloroplatinic acid-isopropanol complex, chloroplatinic acid-divinyltetramethylsiloxane complex and chloroplatinic acid-diethyl phthalate complex.
Further, the spherical filler is one or a mixture of any more of aluminum powder, zinc powder, copper powder, alumina, aluminum nitride, boron nitride, silicon carbide and boron nitride.
Further, the needle-shaped material is one or a mixture of any more of zinc oxide whisker, potassium titanate whisker, silicon nitride whisker and beta-SiC whisker.
The further scheme has the advantages that the use amount of each component can be adjusted according to specific process requirements, the heat conductivity coefficient is adjustable within 1-6W/m.K,
and the heat dissipation requirements of different power devices are met.
Another technical solution of the present invention for solving the above technical problems is as follows: a preparation method of a high-molecular heat-conducting composite material comprises the steps of sequentially adding 85-90 wt% of organic silicon resin A, 5-10 wt% of organic silicon resin B, 1-3 wt% of a curing agent a, 0-1 wt% of a curing agent B and 0.1-1 wt% of a catalyst into a stirrer to be mixed for 30-60 minutes to obtain matrix resin, adding heat-conducting filler consisting of 70-95 wt% of spherical filler and 5-30 wt% of needle-shaped filler into the matrix resin, wherein the weight ratio of the matrix resin to the heat-conducting filler is 100: 300-100: 1100, the spherical filler is firstly added into the heat-conducting filler, the needle-shaped filler is added after stirring for 30-60 minutes, the needle-shaped filler is added into the heat-conducting filler to be stirred for 30-60 minutes, then the matrix resin and the heat-conducting filler are stirred for 30-60 minutes to be mixed under a vacuum, and rolling the mixture into a film with the thickness of 2-10 mm, and curing for 10-30 minutes at the temperature of 60-120 ℃ to obtain the composite material.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
The polymer heat-conducting composite material comprises, by weight, 100: 300-100: 1100 of matrix resin and heat-conducting filler, wherein the matrix resin comprises, by weight, 85-90% of organic silicon resin A, 5-10% of organic silicon resin B, 1-3% of curing agent a, 0-1% of curing agent B and 0.1-1% of catalyst; the heat filler comprises, by weight, 70-95% of a spherical filler and 5-30% of a needle-shaped filler.
Example 1
Accurately weighing 90g of organic silicon resin A, 5g of organic silicon resin B, 3g of curing agent a and 1g of catalyst, adding the components into a double-planetary power mixing stirrer, stirring for 30 minutes, adding 210g of spherical aluminum oxide into the mixture, stirring for 30 minutes, adding 90g of zinc oxide whisker, stirring for 30 minutes under a vacuum condition, calendering the mixture into a sheet with the thickness of 2mm, and curing for 10 minutes at 60 ℃ to obtain the organic silicon resin composite material;
wherein,
the organic silicon resin A is straight-chain organic silicon resin with a structural formula of CH2=CH-Si(CH3)2O[(CH3)2SiO]200(CH3)2Si－CH=CH2；
The organic silicon resin B contains R1 3SiO1/2Structural unit and SiO4/2A copolymer of structural units wherein R is1 3SiO1/2Structural unit and the SiO4/2The molar ratio of the structural units is 0.5;
the curing agent a is a hydrogen-containing silicone oil curing agent, and the structural formula of the curing agent a is shown as the following structural formula (III): R-Si (CH)3)2-O-[SiHCH3-O]f-[Si-(CH3)2-O]g-Si(CH3)2-R (iii), wherein R is? f + g = 8.
Example 2
Accurately weighing the organic silicon resin A87g, the organic silicon resin B7g, the curing agent a2g, the curing agent b0.5g and the catalyst 1g, adding the components into a double-planetary power mixing stirrer, stirring for 30 minutes, adding the spherical alumina 490 into the mixture, stirring for 30 minutes, adding the zinc oxide whisker 210g, stirring for 30 minutes under a vacuum condition, calendering the mixture into a sheet with the thickness of 2mm, and curing for 10 minutes at 60 ℃ to obtain the organic silicon resin composite material.
Wherein,
the organic silicon resin A is straight-chain organic silicon resin with a structural formula of CH2=CH-Si(CH3)2O[(CH3)2SiO]100(CH3)2Si－CH=CH2；
The organic silicon resin B contains R1 3SiO1/2Structural unit and SiO4/2A copolymer of structural units wherein R is1 3SiO1/2Structural unit and the SiO4/2The molar ratio of the structural units is 0.7;
the curing agent a is a hydrogen-containing silicone oil curing agent, and the structure of the curing agent a is shown in a structural formula (III): R-Si (CH)3)2-O-[SiHCH3-O]f-[Si-(CH3)2-O]g-Si(CH3)2-R (iii), wherein R represents? F + g =98;
the curing agent b is a hydrogen-terminated silicone oil curing agent, and the structure of the curing agent b is shown in a structural formula (IV):
H-O-[Si-(CH3)2-O]50-R (IV) wherein R represents CH3Or H.
Example 3
Accurately weighing the organic silicon resin A85g, the organic silicon resin B10g, the curing agent a1g, the curing agent B1g and 0.1g of catalyst, adding the components into a double-planetary power mixing stirrer, stirring for 45 minutes, adding 880g of spherical alumina into the mixture, stirring for 45 minutes, adding 220g of zinc oxide whiskers, stirring for 45 minutes under a vacuum condition, rolling the mixture into a sheet with the thickness of 2mm, and curing for 20 minutes at 90 ℃ to obtain the organic silicon resin.
Wherein,
the organic silicon resin A is straight-chain organic silicon resin with a structural formula of CH2=CH-Si(CH3)2O[(CH3)2SiO]50(CH3)2Si－CH=CH2；
The organic silicon resin B is a compound containing R1 3SiO1/2Structural unit and SiO4/2A copolymer of structural units wherein R is1 3SiO1/2Structural unit and the SiO4/2The molar ratio of the structural units is 0.9;
the curing agent a is a hydrogen-containing silicone oil curing agent, and the structure of the curing agent a is shown in a structural formula (III):
R-Si(CH3)2-O-[SiHCH3-O]f-[Si-(CH3)2-O]g-Si(CH3)2-R (III), wherein R represents CH3Or H, f + g = 40;
the curing agent b is a hydrogen-terminated silicone oil curing agent, and the structure of the curing agent b is shown in a structural formula (IV): H-O- [ Si- (CH)3)2-O]280-R (IV) wherein R represents CH3Or H.
Example 4
Accurately weighing the organic silicon resin A87g, the organic silicon resin B7g, the curing agent a2g, the curing agent b0.5g and the catalyst 0.5g, adding the components into a double-planetary power mixing stirrer, stirring for 30 minutes, adding spherical alumina 285 into the mixture, stirring for 30 minutes, adding zinc oxide whisker 15g, stirring for 30 minutes under a vacuum condition, rolling the mixture into a sheet with the thickness of 5mm, and curing for 10 minutes at 120 ℃ to obtain the organic silicon resin.
Wherein,
the organic silicon resin A is branched organic silicon resin, and the structural formula of the organic silicon resin A is shown in a structural formula (II): (CH)3)3SiO[(CH3)2SiO]ｍ[(CH2=CH)(CH3)SiO]ｎSi(CH3)3（Ⅱ），m+n=260；
The organic silicon resin B is a compound containing R1 3SiO1/2Structural unit and SiO4/2A copolymer of structural units wherein R is1 3SiO1/2Structural unit and the SiO4/2The molar ratio of the structural units is 0.7;
the curing agent a is a hydrogen-containing silicone oil curing agent, and the structure of the curing agent a is shown in a structural formula (III):
R-Si(CH3)2-O-[SiHCH3-O]f-[Si-(CH3)2-O]g-Si(CH3)2-R (III), wherein R represents CH3Or H, f + g =50;
the curing agent b is a hydrogen-terminated silicone oil curing agent, and the structure of the curing agent b is shown in a structural formula (IV):
H-O-[Si-(CH3)2-O]h-R (IV), R represents CH3Or H, H = 200.
Example 5
Accurately weighing the organic silicon resin A87g, the organic silicon resin B5g, the curing agent a3g, the curing agent b0.5g and the catalyst 0.5g, adding the components into a double-planetary power mixing stirrer, stirring for 30 minutes, adding 720g of spherical alumina into the mixture, stirring for 30 minutes, adding 180g of zinc oxide whisker, stirring for 30 minutes under a vacuum condition, rolling the mixture into a sheet with the thickness of 10mm, and curing for 30 minutes at 90 ℃ to obtain the organic silicon resin B5-containing composite material.
Wherein,
the organic silicon resin A is branched organic silicon resin, and the structural formula of the organic silicon resin A is shown in a structural formula (II):
(CH3)3SiO[(CH3)2SiO]ｍ[(CH2=CH)(CH3)SiO]ｎSi(CH3)3（Ⅱ），m+n=150；
the organic silicon resin B is a compound containing R1 3SiO1/2Structural unit and SiO4/2Structural unitWherein R is1 3SiO1/2Structural unit and the SiO4/2The molar ratio of the structural units is 0.9;
the curing agent a is a hydrogen-containing silicone oil curing agent, and the structure of the curing agent a is shown in a structural formula (III):
R-Si(CH3)2-O-[SiHCH3-O]f-[Si-(CH3)2-O]g-Si(CH3)2-R (III), wherein R represents CH3Or H, f + g =98;
the curing agent b is a hydrogen-terminated silicone oil curing agent, and the structure of the curing agent b is shown in a structural formula (IV):
H-O-[Si-(CH3)2-O]h-R (IV) wherein R represents CH3Or H, H = 280.
Example 6
Accurately weighing the organic silicon resin A87g, the organic silicon resin B7g, the curing agent a2g, the curing agent b0.5g and the catalyst 1g, adding the components into a double-planetary power mixing stirrer, stirring for 30 minutes, adding the spherical alumina 490 into the mixture, stirring for 30 minutes, adding the zinc oxide whisker 210g, stirring for 30 minutes under a vacuum condition, calendering the mixture into a sheet with the thickness of 2mm, and curing for 10 minutes at 60 ℃ to obtain the organic silicon resin composite material.
Wherein,
the organic silicon resin A is branched organic silicon resin, and the structural formula of the organic silicon resin A is shown in a structural formula (II): (CH)3)3SiO[(CH3)2SiO]ｍ[(CH2=CH)(CH3)SiO]ｎSi(CH3)3（Ⅱ），m+n=50；
The organic silicon resin B contains R1 3SiO1/2Structural unit and SiO4/2A copolymer of structural units wherein R is1 3SiO1/2Structural unit and the SiO4/2Structural sheetThe molar ratio of the elements is 0.7;
the curing agent a is a hydrogen-containing silicone oil curing agent, and the structure of the curing agent a is shown in a structural formula (III):
R-Si(CH3)2-O-[SiHCH3-O]f-[Si-(CH3)2-O]g-Si(CH3)2-R (III), wherein R represents CH3Or H, f + g =98;
the curing agent b is a hydrogen-terminated silicone oil curing agent, and the structure of the curing agent b is shown in a structural formula (IV):
H-O-[Si-(CH3)2-O]h-R (IV) wherein R represents CH3Or H, H = 50.
Comparative example 1
97g of organic silicon resin, 2.5g of curing agent and 0.5g of catalyst are accurately weighed, the components are added into a double-planetary power mixing stirrer to be stirred for 30 minutes, 1000g of spherical alumina is added into the mixture to be stirred for 60 minutes, the mixture is stirred for 30 minutes under the vacuum condition, the mixture is rolled into a sheet with the thickness of 2mm, and the sheet is cured for 20 minutes at the temperature of 90 ℃ to obtain the high-performance silicon-based organic silicon resin.
Wherein the organic silicon resin is branched chain organic silicon resin, and the structural formula is as follows: (CH)3)3SiO[(CH3)2SiO]50[(CH2=CH)(CH3)SiO]50Si(CH3)3(ii) a The curing agent is hydrogen-containing silicone oil curing agent, and the structural formula is as follows: H-Si (CH)3)2-O-[SiHCH3-O]30-[Si-(CH3)2-O]20-Si(CH3)2-H。
Comparative example 2
97g of organic silicon resin, 2.5g of curing agent and 0.5g of catalyst are accurately weighed, the components are added into a double-planetary power mixing stirrer to be stirred for 30 minutes, 300g of aluminum powder is added into the mixture to be stirred for 60 minutes, the mixture is stirred for 30 minutes under the vacuum condition, the mixture is rolled into a sheet with the thickness of 2mm, and the sheet is cured for 20 minutes at the temperature of 90 ℃ to obtain the high-performance aluminum-silicon composite material.
Wherein the organic silicon resin is a linear organic silicon resin, and the structural formula of the organic silicon resin is as follows: CH (CH)2=CH-Si(CH3)2O[(CH3)2SiO] 200 (CH3)2Si－CH=CH2(I) (ii) a The curing agent is hydrogen-containing silicone oil curing agent, and the structural formula is as follows: H-Si (CH)3)2-O-[SiHCH3-O]20-[Si-(CH3)2-O]30-Si(CH3)2-H。
Test experiment 1 hardness test
Hardness tests were performed on the samples obtained in examples 1 to 6 and comparative examples 1 to 2 using a Shore E durometer in accordance with ASTM D2340.
Test experiment 2 thermal conductivity test
The samples obtained in examples 1 to 6 and comparative examples 1 to 2 were subjected to a thermal conductivity test in accordance with ASTM D5470 using a thermal conductivity tester model TPS 2500S from Hot Disk.
Test experiment 3 thickness test
The samples prepared in examples 1 to 6 and comparative examples 1 to 2 were subjected to thickness measurement according to ASTM D374 using a model HD-10-2 thickness meter of Shanghai chemical machinery four factories.
Test experiment 4 breakdown Voltage test
The samples prepared in examples 1 to 6 and comparative examples 1 to 2 were subjected to breakdown voltage testing according to ASTM D149 using a Gilin Huayang HJC-50KV computer-controlled voltage breakdown tester.
The results of the tests are shown in table 1.
TABLE 1 results of the tests
As can be seen from the data in Table 1, the thermal conductivity of the super-flexible high thermal conductivity polymer material in the embodiment of the invention is 1-6.0W/m·The K range is adjustable, the hardness can be adjusted within the range of Shore E5-15, the thickness can be adjusted within the range of 2-10 mm, and the process requirements of devices with different sizes and different powers are met; the breakdown voltage is more than 6000V, and the insulation requirement of electronic products is met.
As can be seen from the comparison between the examples and the comparative examples, the thermal conductivity coefficient can only reach 3.5W/m by using the simple long-chain silicone resin and the hydrogen-terminated silicone oil as the matrix resin and the spherical alumina as the filler·K, the hardness is Shore E45, and the requirement of low-stress occasions is difficult to meet; aluminum powder with high heat conductivity coefficient is used as heat-conducting filler, the tackifying speed is high, the aluminum powder can only be added to 300 percent, and the heat conductivity coefficient can only reach 4.5W/m·K, the hardness is in Shore E60, and meanwhile, the insulation performance is reduced, so that the requirement of high insulation is difficult to meet.
The low-cost high-heat-conductivity polymer composite material can be used for the aspects of heat dissipation and heat conduction of electronic packaging, large-scale LED light sources, automobiles, aerospace equipment and the like.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. An ultra-flexible high polymer heat conduction material is characterized by comprising a base resin and a heat conduction filler in a weight ratio of 100: 300-100: 1100,
the base resin comprises, by weight, 85-90% of organic silicon resin A, 5-10% of organic silicon resin B, 1-3% of curing agent a, 0-1% of curing agent B and 0.1-1% of catalyst;
the heat filler comprises, by weight, 70-95% of a spherical filler and 5-30% of a needle-shaped filler.
2. The super-flexible high-molecular heat-conducting material according to claim 1, wherein the silicone resin A is a linear or branched vinyl silicon resin, the structural formula of the linear vinyl silicon resin is represented by the following general formula (I), and the branched vinyl silicon resin is represented by the following general formula (II):
CH2=CH-Si(CH3)2O[(CH3)2SiO]e(CH3)2Si－CH=CH2（Ⅰ）；
(CH3)3SiO[(CH3)2SiO]ｍ[(CH2=CH)(CH3)SiO]ｎSi(CH3)3（Ⅱ）；
wherein in the formula (I), e = 50-200;
in the formula (II), m + n = 50-260.
3. The ultra-flexible polymer heat-conducting composite material as claimed in claim 1, wherein the silicone resin B contains R1 3SiO1/2Structural unit and SiO4/2A copolymer of structural units wherein R is1 3SiO1/2Structural unit and the SiO4/2The molar ratio of the structural units is 0.5 to 0.9.
4. The ultra-flexible polymer heat-conducting composite material as claimed in claim 1, wherein the curing agent a and the curing agent b are both hydrogen-containing silicone oil curing agents, the curing agent a is represented by the following general formula (III), and the curing agent b is represented by the following general formula (IV):
R-Si(CH3)2-O-[SiHCH3-O]f-[Si-(CH3)2-O]g-Si(CH3)2-R （Ⅲ）；
H-O-[Si-(CH3)2-O]h-R （Ⅳ）；
wherein, formula (III)) In the formula, R represents CH3Or H, f + g = 8-98;
in the formula (IV), R represents CH3Or H and H are integers between 50 and 280.
5. The ultra-flexible polymeric thermally conductive material of any one of claims 1 to 4, wherein the catalyst is a platinum complex catalyst.
6. The ultra-flexible polymer thermal conductive material according to claim 5, wherein the platinum complex catalyst is one or a mixture of more than one of chloroplatinic acid-isopropanol complex, chloroplatinic acid-divinyltetramethylsiloxane complex and chloroplatinic acid-diethyl phthalate complex.
7. The super-flexible polymer heat conduction material according to any one of claims 1 to 3, wherein the spherical filler is one or a mixture of any several of aluminum powder, zinc powder, copper powder, aluminum oxide, aluminum nitride, boron nitride, silicon carbide and boron nitride.
8. The super-flexible polymer heat conduction material according to any one of claims 1 to 3, wherein the needle-shaped material is one or a mixture of any several of zinc oxide whisker, potassium titanate whisker, silicon nitride whisker and beta-SiC whisker.
9. A method for preparing the ultra-flexible polymer thermal conductive material according to any one of claims 1 to 8, wherein the method comprises:
adding 85-90 wt% of organic silicon resin A, 5-10 wt% of organic silicon resin B, 1-3 wt% of curing agent a, 0-1 wt% of curing agent B and 0.1-1 wt% of catalyst into a stirrer in sequence, mixing for 30-60 minutes to obtain matrix resin, adding heat-conducting filler consisting of 70-95 wt% of spherical filler and 5-30 wt% of needle-shaped filler into the matrix resin, wherein the weight ratio of the matrix resin to the heat-conducting filler is 100: 300-100: 1100, adding the spherical filler into the heat-conducting filler, stirring for 30-60 minutes, adding the needle-shaped filler, stirring for 30-60 minutes, stirring the matrix resin and the heat-conducting filler for 30-60 minutes under a vacuum condition, mixing, rolling into a film with the thickness of 2-10 mm, and curing for 10-30 minutes at 60-120 ℃, and (5) obtaining the product.
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