CN116023785B - Heat-conducting gel and preparation method thereof - Google Patents
Heat-conducting gel and preparation method thereof Download PDFInfo
- Publication number
- CN116023785B CN116023785B CN202111251097.XA CN202111251097A CN116023785B CN 116023785 B CN116023785 B CN 116023785B CN 202111251097 A CN202111251097 A CN 202111251097A CN 116023785 B CN116023785 B CN 116023785B
- Authority
- CN
- China
- Prior art keywords
- thermally conductive
- conductive gel
- parts
- normal temperature
- heat
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000001879 gelation Methods 0.000 title description 2
- 229920002545 silicone oil Polymers 0.000 claims abstract description 48
- 239000000843 powder Substances 0.000 claims abstract description 35
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 34
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 24
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000000945 filler Substances 0.000 claims abstract description 12
- 239000003112 inhibitor Substances 0.000 claims abstract description 12
- 239000004970 Chain extender Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000012756 surface treatment agent Substances 0.000 claims abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 66
- 238000003756 stirring Methods 0.000 claims description 41
- 229910052739 hydrogen Inorganic materials 0.000 claims description 27
- 239000001257 hydrogen Substances 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 19
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 13
- IRVZFACCNZRHSJ-UHFFFAOYSA-N 2,4,6,8-tetramethyl-2,4,6,8-tetraphenyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound O1[Si](C)(C=2C=CC=CC=2)O[Si](C)(C=2C=CC=CC=2)O[Si](C)(C=2C=CC=CC=2)O[Si]1(C)C1=CC=CC=C1 IRVZFACCNZRHSJ-UHFFFAOYSA-N 0.000 claims description 12
- KQAHMVLQCSALSX-UHFFFAOYSA-N decyl(trimethoxy)silane Chemical compound CCCCCCCCCC[Si](OC)(OC)OC KQAHMVLQCSALSX-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical group C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 claims description 11
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 11
- 238000007599 discharging Methods 0.000 claims description 11
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 11
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 9
- 239000012043 crude product Substances 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- NRTJGTSOTDBPDE-UHFFFAOYSA-N [dimethyl(methylsilyloxy)silyl]oxy-dimethyl-trimethylsilyloxysilane Chemical group C[SiH2]O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C NRTJGTSOTDBPDE-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- -1 oxime compound Chemical class 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 5
- 230000003472 neutralizing effect Effects 0.000 claims description 5
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 claims description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- VNRWTCZXQWOWIG-UHFFFAOYSA-N tetrakis(trimethylsilyl) silicate Chemical compound C[Si](C)(C)O[Si](O[Si](C)(C)C)(O[Si](C)(C)C)O[Si](C)(C)C VNRWTCZXQWOWIG-UHFFFAOYSA-N 0.000 claims description 4
- 239000012467 final product Substances 0.000 claims description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 2
- XOCOMEGNVMCRMP-UHFFFAOYSA-N 2,2,4,4,6,6,8,8-octaethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound CC[Si]1(CC)O[Si](CC)(CC)O[Si](CC)(CC)O[Si](CC)(CC)O1 XOCOMEGNVMCRMP-UHFFFAOYSA-N 0.000 claims description 2
- QTRQFVAKGZFBRT-UHFFFAOYSA-N 2-(3,3,3-trifluoropropyl)-1,3,5,2,4,6-trioxatrisilinane Chemical compound FC(F)(F)CC[SiH]1O[SiH2]O[SiH2]O1 QTRQFVAKGZFBRT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052580 B4C Inorganic materials 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- SCPWMSBAGXEGPW-UHFFFAOYSA-N dodecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OC)(OC)OC SCPWMSBAGXEGPW-UHFFFAOYSA-N 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 claims description 2
- 239000003456 ion exchange resin Substances 0.000 claims description 2
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 2
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 claims description 2
- 229960003493 octyltriethoxysilane Drugs 0.000 claims description 2
- 150000002903 organophosphorus compounds Chemical class 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 claims description 2
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 239000004971 Cross linker Substances 0.000 claims 1
- 239000002981 blocking agent Substances 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000011231 conductive filler Substances 0.000 claims 1
- 229940008099 dimethicone Drugs 0.000 claims 1
- 239000004205 dimethyl polysiloxane Substances 0.000 claims 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims 1
- DYXYFYSDMOOWRX-UHFFFAOYSA-N tris(dimethylsilyloxy)-methylsilane Chemical group C[SiH](C)O[Si](C)(O[SiH](C)C)O[SiH](C)C DYXYFYSDMOOWRX-UHFFFAOYSA-N 0.000 claims 1
- CQZDNELEZXTFEH-UHFFFAOYSA-N tris(dimethylsilyloxy)-phenylsilane Chemical compound C[SiH](C)O[Si](O[SiH](C)C)(O[SiH](C)C)C1=CC=CC=C1 CQZDNELEZXTFEH-UHFFFAOYSA-N 0.000 claims 1
- 238000010276 construction Methods 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 18
- 239000000463 material Substances 0.000 description 14
- 229910052710 silicon Inorganic materials 0.000 description 12
- 239000010703 silicon Substances 0.000 description 12
- 238000007790 scraping Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 230000032683 aging Effects 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 230000005311 nuclear magnetism Effects 0.000 description 6
- 239000003039 volatile agent Substances 0.000 description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000017525 heat dissipation Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- RXUVTQUYUYZESC-UHFFFAOYSA-N tris(dimethylsilyl)-methylsilane Chemical compound C[SiH](C)[Si](C)([SiH](C)C)[SiH](C)C RXUVTQUYUYZESC-UHFFFAOYSA-N 0.000 description 3
- BGISVIDNIBCUTN-UHFFFAOYSA-N [bis[(dimethyl-$l^{3}-silanyl)oxy]-methylsilyl]oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)(O[Si](C)C)O[Si](C)C BGISVIDNIBCUTN-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 1
- 101150074789 Timd2 gene Proteins 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012782 phase change material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- MQBQQASLEDRXDB-UHFFFAOYSA-N tris(dimethylsilyl)-phenylsilane Chemical compound C[SiH](C)[Si]([SiH](C)C)([SiH](C)C)c1ccccc1 MQBQQASLEDRXDB-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a heat-conducting gel and a preparation method thereof, wherein the heat-conducting gel is prepared from the following raw materials in mass content: 2-20% of vinyl silicone oil, 75-95% of high heat conduction filler, 1-3% of surface treatment agent, 0.3-1.0% of chain extender, 0.02-0.06% of cross-linking agent, 0.1-1.0% of catalyst and 0.05-0.1% of inhibitor. The invention also provides a preparation method of the heat-conducting gel, and the heat-conducting gel silicone oil prepared by the method has better compatibility with a powder system, is lower in viscosity and has better construction property in practical application.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a heat-conducting gel and a preparation method thereof.
Background
In the working process of the electronic component, heat is generated, heat accumulation can cause thermal failure of the electronic component, and according to statistics of failure mechanisms of the electronic component, the thermal failure rate of the electronic component is more than 50% due to the fact that the heat accumulation cannot be effectively outwards diffused, so that the heat dissipation problem of the electronic component becomes an important concern of terminal application, and the thermal interface material plays an important role in the thermal failure mechanism. Because the contact surface of the heating element and the radiator is not completely flat, a certain gap exists between the interfaces, the heat conductivity of the air is only 0.024W/(m.K), the heat transfer efficiency is greatly reduced, the thermal interface material mainly fills the gap between the heating element and the radiator, so that heat is effectively and timely removed, the components are ensured to work at normal temperature, the service life of equipment or devices is prolonged, and particularly, along with the rapid development (such as the generalization of 5G) of the semiconductor field and the communication fields, the integration level of the electronic components is higher and higher, and simultaneously, the higher heat flux density is also accompanied, so that higher requirements are put forward on the thermal interface material.
The thermal interface material comprises heat conduction silicone grease, heat conduction gel, heat conduction phase change material, heat conduction gasket and the like, and compared with the heat conduction silicone grease, the heat conduction gel has no pumping phenomenon, is soft, has high bonding degree with an interface and lower contact thermal resistance compared with the heat conduction gasket, and is characterized by being mainly used as gap filler and TIM2 material in a plurality of thermal interface materials. The gel with high heat conductivity mainly comprises reactive silicone oil, heat conducting filler, surface treating agent, catalyst, inhibitor and the like, and especially the filling amount of powder is more than 90%, which easily leads to higher viscosity of the system, so that a special powder treatment process is required to effectively improve the treatment effect of the surface treating agent on the powder, increase the compatibility of the silicone oil and the powder, and reduce the viscosity of the system. On the other hand, the heat-conducting gel has the great characteristics of lower hardness, certain wettability to heating element devices and higher bonding degree, so that the crosslinking density of the system is required to be controlled at a lower level, and the problem of obvious increase of the hardness in the high-temperature aging process cannot occur, because once the hardness rises in the use process, the bonding degree with the interface of the device becomes poor, the contact thermal resistance is increased, and the heat dissipation effect is greatly reduced.
The existing heat conducting gel in the market has higher heat conductivity coefficient, but has the problem of hardness rise in the high-temperature aging process, so that the contact thermal resistance with an interface is increased in the use process, and the heat transfer effect is greatly reduced. On the other hand, the viscosity of the system is high, and the fluidity is poor, so that the product has poor construction property in the actual use process, and a certain trouble is caused to users.
Disclosure of Invention
The invention aims to provide the high-heat-conductivity gel which has higher heat conductivity and lower heat resistance, and is applied between a radiator and a heating source interface to achieve a good heat dissipation effect. The heat-conducting gel provided by the invention has the advantages that most of crosslinking reactions can be finished by the crosslinking agent with a specific structure, residual silicon and hydrogen are less, the degree of further crosslinking after high-temperature aging is less, the hardness is not obviously increased, gaps are not generated along with the increase of the hardness in the bonding degree of the soft gel and the interface, and therefore, the thermal resistance is not obviously increased.
The invention also provides a preparation method of the heat-conducting gel, and the heat-conducting gel silicone oil prepared by the method has better compatibility with a powder system, is lower in viscosity and has better construction property in practical application.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the heat-conducting gel is prepared from the following raw materials in percentage by mass: 2% -20% of vinyl silicone oil, 75% -95% of high heat conduction filler, 1% -3% of surface treatment agent, 0.3% -1.0% of chain extender, 0.02% -0.06% of cross-linking agent, 0.1% -1.0% of catalyst and 0.05% -0.1% of inhibitor.
Preferably, the vinyl silicone oil is a double-ended vinyl silicone oil, and in order to provide better oil permeation resistance, the viscosity of the vinyl silicone oil is preferably 20 to 3000 mpa.s (at 25 ℃), and more preferably the viscosity of the vinyl silicone oil is 100 to 1000 mp.s
Preferably, the high thermal conductivity filler is one or more of alumina, zinc oxide, aluminum nitride, boron carbide, silicon carbide, graphene, carbon nanotubes, preferably alumina and aluminum nitride.
Preferably, the alumina is spherical and comprises three alumina with different particle sizes, wherein the first spherical alumina has D50 of 0.1-1 μm and maximum particle size of not more than 2 μm. The second spherical alumina has D50 of 2.5-6 μm and maximum particle size of not more than 25 μm. The third spherical alumina D50 is 30-50 μm, and the maximum particle size is not more than 180 μm.
Preferably, the aluminum nitride is spherical, the D50 is 60-100 μm, and the maximum particle size is not more than 250 μm.
Preferably, the surface treating agent is one or two of hexadecyl trimethoxy silane, dodecyl trimethoxy silane, decyl trimethoxy silane, octyl triethoxy silane, propyl trimethoxy silane, vinyl trimethoxy silane and methyl trimethoxy silane.
Preferably, the chain extender is double-end hydrogen dimethyl silicone oil, and in order to consider the viscosity of the system and the mechanical properties of the material, the viscosity of the double-end hydrogen dimethyl silicone oil is preferably 5-100 mpa.s (the temperature is 25 ℃), and more preferably the viscosity of the double-end hydrogen dimethyl silicone oil is 5-50 mp.s.
Preferably, the crosslinking agent has the following structural formula:
structural formula A:
wherein R is 2 Methyl, ethyl, phenyl or trifluoropropyl, preferably phenyl; r is R 3 Is methyl, phenyl or the following structure:
x=5-100, y=0-10, more preferably x=5-30, y=1-5.
The crosslinking agent used as a comparative example is represented by the structural formula B:
wherein R is 1 Is hydrogen or methyl, preferably methyl. m=1-5, n=5-100, preferably m=1-2, n=20-30.
The specific structure in the comparative example is as follows:
structural formula B-1 as comparative example:
structural formula B-2 as comparative example:
after the gel is solidified, the cross-linking agent with a general structure (for example, the structural formula B in the comparative example) can generate the phenomenon of hardness rise after long-term high-temperature aging, because the cross-linking agent with the general structure is compact in arrangement of silicon and hydrogen, when certain silicon and hydrogen in the cross-linking agent are cross-linked, the activity of the adjacent silicon and hydrogen is reduced due to steric hindrance, the adjacent silicon and hydrogen cannot participate in cross-linking, and finally the cross-linking agent remains in a system, and in the high-temperature aging process, the residual silicon and hydrogen can continuously cross-link, so that the hardness rise, and after the hardness rises, the degree of adhesion between the gel and a device interface is reduced, so that the thermal resistance is increased; the cross-linking agent with the special structure is reasonable in arrangement and less affected by steric hindrance (when the silicon and hydrogen are adjacent, after one silicon and hydrogen react, the adjacent silicon and hydrogen are limited due to steric hindrance activity, the branched chain structure can enable the distance between the silicon and hydrogen to be far, the activities of the silicon and hydrogen are not affected, most of the silicon and hydrogen can participate in the cross-linking reaction, the residual is less, and the hardness of the gel cannot be obviously increased even after 1000h of high-temperature aging after cross-linking solidification.
The preparation method of the structure A cross-linking agent comprises the following steps: adding the monomer, the end capping agent and the catalyst into a reaction kettle, heating to 40-60 ℃, and reacting for 3-6h. Then cooling to room temperature, adding a neutralizing agent, reacting for 1-2h, and filtering to obtain a crude product. Then devolatilizing for 1-2 hours at 120-150 ℃ and 0.5-1kPa to obtain the final product.
Preferably, in the synthesis process of the cross-linking agent structure A, octamethyl cyclotetrasiloxane (D4), methyl mixed ring body (DMC), octaethyl cyclotetrasiloxane, tetramethyl tetraphenyl cyclotetrasiloxane and trifluoropropyl cyclotrisiloxane are adopted as monomers, and octamethyl cyclotetrasiloxane (D4) and tetramethyl tetraphenyl cyclotetrasiloxane are further preferred. The molar ratio of the octamethyl cyclotetrasiloxane to the end capping agent ranges from 1 to 90, and the molar ratio of the tetramethyl tetraphenyl cyclotetrasiloxane to the end capping agent ranges from 0.5 to 8.
Preferably, in the synthesis process of the cross-linking agent structure A, the end-capping agent adopts methyltris (dimethylsiloxane) silane, phenyltris (dimethylsiloxane) silane and tetra (trimethylsiloxy) silane.
Preferably, in the synthesis process of the cross-linking agent structure A, acidic substances such as trifluoromethanesulfonic acid, concentrated sulfuric acid, acid clay, ion exchange resin and the like are adopted as the catalyst, and the trifluoromethanesulfonic acid is further preferred; the dosage is 0.05-0.1wt% of the total mass of the monomer and the end capping agent. The neutralizing agent is selected from calcium carbonate, sodium bicarbonate, diatomaceous earth, activated carbon, etc., and preferably calcium carbonate. The dosage is 0.5-1wt% of the total mass of the monomer and the end capping agent
Preferably, the catalyst is one of platinum itself, chloroplatinic acid, a platinum-olefin complex, a platinum-alcohol complex or a platinum coordination compound, and the content is 0.1% -0.5%.
Preferably, the inhibitor acts to inhibit the progress of the hydrosilylation reaction at room temperature, thereby ensuring long shelf life and service life. The inhibitors selected include alkynol compounds, various nitrides, organic phosphorus compounds, oxime compounds, organic chlorides, and the like, with alkynol compounds being preferred. If the amount is less than 0.05% by weight, the storage life and the service life are both short, and if the amount is more than 0.1% by weight, the curing speed is lowered, so that the content is selected to be in the range of 0.05% to 0.1%, more preferably the content of the above inhibitor is 0.03% to 0.07%.
The invention also provides a preparation method of the heat-conducting gel, which has effective preparation conditions and steps, can fully hydrolyze the surface treating agent and improve the compatibility of silicone oil and powder, and comprises the following steps:
(1) Mixing vinyl silicone oil and a surface treating agent in a 2L double planetary mixer at normal temperature, adding high-heat-conductivity filler powder in batches, stirring for 10-30min to obtain uniform paste after each addition, adding powder for the next time until the powder addition is completed completely, and stirring for a certain time to obtain uniform paste;
(2) Heating for 30-60min, preferably 40-50min to 110-180deg.C, preferably 120-150deg.C, vacuum stirring for 60-120min, pressure lower than-0.09 MPa, cooling to below 40deg.C, and breaking vacuum with nitrogen;
(3) Then adding part of chain extender, mixing uniformly, adding cross-linking agent, inhibitor and catalyst, mixing at normal temperature for 10-60min, preferably 20-40min, defoaming for 10-40min, preferably 20-30min, and discharging.
The gel powder prepared by the method has good compatibility with silicone oil, is low in viscosity, and has good workability in practical application.
Preferably, the mixing time at room temperature in step (1) is in the range of 5 to 20 minutes, preferably 5 to 10 minutes.
Preferably, the high thermal conductivity filler in step (1) is alumina or aluminum nitride, which is added in three portions on average, and the time interval is in the range of 10-30min, preferably 10-15min.
Preferably, the temperature rise time in step (2) is in the range of 30 to 60 minutes, preferably 40 to 50 minutes.
Preferably, the elevated temperature in step (2) is in the range of from 110 to 180 ℃, preferably 120 to 150 ℃.
The technical scheme provided by the invention has the following beneficial effects:
the high heat conduction gel provided by the invention has the heat conductivity higher than 4 w/(m.k) and the thermal resistance lower than 0.35 ℃ cm 2 In addition, the system silicone oil has better compatibility with powder, the viscosity is lower than 600 pa.s, and the system silicone oil has good workability.
Detailed Description
The invention is further illustrated by the following examples, but is not limited to the examples set forth.
Raw material information:
methyltri (dimethylsiloxane) silane (CAS number 17082-46-1), 97%; phenyltris (dimethylsiloxane) silane (CAS number: 18027-45-7), 97%; tetra (trimethylsiloxy) silane (CAS number 17082-47-2), 97%, available from Gelest. Octamethyl cyclotetrasiloxane, 99%, commercially available from dow chemical; methyl phenyl cyclosiloxane (CAS number: 77-63-4), 99.3%, commercially available from Beijing Hua Weirui chemical Co., ltd. 98% of trifluoromethanesulfonic acid; calcium carbonate, AR, purchased from Shanghai Ala Biochemical technologies Co., ltd; double-ended vinyl silicone oils (500 mpa.s) available from Runner materials Co.
Nuclear magnetic analysis instrument: bruker model 400M
Example 1
Into a 15L glass reactor, 4.24kg of octamethyltetrasiloxane (14.3 mol), 876g of tetramethyltetraphenylcyclotetrasiloxane (1.6 mol), 268.8g of methyltris (dimethylsilyl) silane (1 mol) and 5.4g of trifluoromethanesulfonic acid (0.1 wt%) were charged, and then the temperature was raised to 50℃for 4 hours. Cooled to room temperature, 53.9g of calcium carbonate was added, reacted for 2 hours, and then filtered to obtain a crude product. Volatiles were then removed at 150℃and 1kPa for 2 hours to give 4.74kg of product in 88% yield.
The structure of the material is identified by nuclear magnetism, and the result is that:
1 H NMR(400MHz,CDCl 3 ):[d,ppm]＝0.07(-SiCH 3 ,302.4H),0.18(-SiCH 3 ,3H),4.71(-Si-H-,3H),7.18(-SiC 6 H 5 ,12.6H),7.27(-SiC 6 H 5 ,12.6H),7.45(-SiC 6 H 5 ,6.3H).
the structure is (A-1):
example 2
Into a 15L glass reactor, 6.75kg of octamethyltetrasiloxane (22.8 mol), 1.63kg of tetramethyltetraphenylcyclotetrasiloxane (3.0 mol), 268.5g of methyltris (dimethylsiloxy) silane (1 mol) and 8.6g of trifluoromethanesulfonic acid (0.1 wt%) were charged, and then the temperature was raised to 40℃for 3 hours. Cooled to room temperature, 86.4g of calcium carbonate was added, reacted for 2 hours, and then filtered to obtain a crude product. Volatiles were then removed at 130℃and 1kPa for 2h to give 7.69kg of product in 89% yield.
The structure of the material is identified by nuclear magnetism, and the result is that:
1 H NMR(400MHz,CDCl 3 ):[d,ppm]＝0.08(-SiCH 3 ,480.6H),0.19(-SiCH 3 ,3H),4.70(-Si-H-,3H),7.17(-SiC 6 H 5 ,23.4H),7.26(-SiC 6 H 5 ,23.4H),7.46(-SiC 6 H 5 ,11.7H).
the structure (A-2) is as follows:
example 3
Into a 15L glass reactor, 4.15kg of octamethyltetrasiloxane (14.0 mol), 583.8g of tetramethyltetraphenylcyclotetrasiloxane (1.1 mol), 330.5g of phenyltris (dimethylsilyl) silane (1 mol) and 5.1g of trifluoromethanesulfonic acid (0.1 wt%) were charged, and then heated to 60℃for 3 hours. Cooled to room temperature, 50.6g of calcium carbonate was added, reacted for 2 hours, and then filtered to obtain a crude product. Volatiles are then removed at 120℃and 0.6kPa for 2 hours to give 4.45kg of product in 88% yield.
The structure of the material is identified by nuclear magnetism, and the result is that:
1 H NMR(400MHz,CDCl 3 ):[d,ppm]＝0.07(-SiCH 3 ,295.2H),4.74(-Si-H-,3H),7.19(-SiC 6 H 5 ,10.4H),7.26(-SiC 6 H 5 ,10.4H),7.45(-SiC 6 H 5 ,5.2H).
the structure (A-3) is as follows:
example 4
Into a 15L glass reactor, 10.04kg of octamethyltetrasiloxane (33.9 mol), 2.67kg of tetramethyltetraphenylcyclotetrasiloxane (4.9 mol), 328.8g of tetrakis (trimethylsiloxy) silane (1 mol) and 13.0g of trifluoromethanesulfonic acid (0.1 wt%) were charged, and then heated to 50℃for reaction for 6 hours. Cooled to room temperature, 130.4g of calcium carbonate was added, reacted for 1.5 hours, and then filtered to obtain a crude product. Volatiles were then removed at 150℃under 1kPa for 2h to give 11.61kg of product in 89% yield.
The structure of the material is identified by nuclear magnetism, and the result is that:
1 H NMR(400MHz,CDCl 3 ):[d,ppm]＝0.08(-SiCH 3 ,715.2H),4.78(-Si-H-,4H),7.18(-SiC 6 H 5 ,38.4H),7.23(-SiC 6 H 5 ,38.4H),7.45(-SiC 6 H 5 ,19.2H).
the structure (A-4) is as follows:
example 5
Into a 5L glass reactor, 1.26kg of octamethyltetrasiloxane (4.3 mol), 417g of tetramethyltetraphenylcyclotetrasiloxane (0.8 mol), 268.8g of methyltris (dimethylsilyl) silane (1 mol) and 1.9g of trifluoromethanesulfonic acid (0.1 wt%) were charged, and then the temperature was raised to 40℃for reaction for 6 hours. Cooled to room temperature, 19.5g of calcium carbonate was added, reacted for 1 hour, and then filtered to obtain a crude product. Volatiles were then removed at 150℃and 1kPa for 2 hours to give 1.70kg of product in 87% yield.
The structure of the material is identified by nuclear magnetism, and the result is that:
1 H NMR(400MHz,CDCl 3 ):[d,ppm]＝0.07(-SiCH 3 ,90H),0.18(-SiCH 3 ,3H),4.71(-Si-H-,3H),7.18(-SiC 6 H 5 ,6H),7.27(-SiC 6 H 5 ,6H),7.45(-SiC 6 H 5 ,3H).
the structure is (A-5):
example 6
Into a 5L glass reactor, 2.53kg of octamethyltetrasiloxane (8.52 mol), 417.1g of tetramethyltetraphenylcyclotetrasiloxane (0.8 mol), 26.9g of methyltri (dimethylsilyl) silane (0.1 mol) and 3.0g of trifluoromethanesulfonic acid (0.1 wt%) were charged, and then heated to 40℃for reaction for 5 hours. Cooled to room temperature, 29.7g of calcium carbonate was added, reacted for 2 hours, and then filtered to obtain a crude product. Volatiles were then removed at 130℃and 1kPa for 2 hours to give 2.59kg of product in 87% yield.
The structure of the material is identified by nuclear magnetism, and the result is that:
1 H NMR(400MHz,CDCl 3 ):[d,ppm]＝0.06(-SiCH 3 ,1800H),0.18(-SiCH 3 ,3H),4.74(-Si-H-,3H),7.18(-SiC 6 H 5 ,60H),7.25(-SiC 6 H 5 ,60H),7.48(-SiC 6 H 5 ,30H).
the structure is (A-6):
example 7
Firstly, 30 parts of 500 mpa.s silicone oil double-end vinyl silicone oil and 23.85 parts of decyl trimethoxy silane are mixed in a 2L double-planetary mixer for 5min at normal temperature, then 57 parts of spherical alumina with the D50 of 0.5 mu m is added, the mixture is stirred for 10min at normal temperature, the rotating speed is 500rpm/min, when the powder is in a fine paste state, the other 57 parts of spherical alumina with the D50 of 0.5 mu m is added, and the mixture is still stirred for 10min at normal temperature, and the rotating speed is 500rpm/min; then 128.25 parts of spherical alumina with the D50 of 3 mu m is added, and the mixture is stirred for 10min at normal temperature, and the rotating speed is 500rpm/min; adding 128.25 parts of spherical aluminum oxide with the D50 of 3 mu m, stirring for 10min at normal temperature, rotating at 500rpm/min, taking out of the kettle after the powder is in a fine paste form; then 399 parts of spherical alumina with D50 of 40 μm are added, stirred at normal temperature for 15min at the speed of 300rpm/min, then another 399 parts of spherical alumina with D50 of 40 μm are added, stirred at normal temperature for 15min at the speed of 300rpm/min; finally adding 256.50 parts of spherical aluminum nitride with the D50 of 70 mu m, stirring at normal temperature for 20min at the rotating speed of 200rpm/min, scraping after finishing, heating for 30min to 110 ℃, vacuumizing at 110 ℃ for 1h, keeping the vacuum degree below-0.09 MPa, cooling to below 40 ℃, and breaking vacuum by using nitrogen; then 0.75 part of ethynyl cyclohexanol, 4.5 parts of double-end hydrogen-containing silicone oil, 0.9 part of A-1 structural cross-linking agent, 15 parts of Kadset catalyst (He Lishi noble metal technology Co., ltd.) are added, mixed for 10 minutes at normal temperature, defoamed for 10 minutes, and discharged. The parts are mass parts.
Example 8
Firstly, 90 parts of 500 mpa.s double-end vinyl silicone oil and 30 parts of decyl trimethoxy silane are taken and mixed in a 2L double-planetary mixer for 10min at normal temperature, then 54.41 parts of spherical alumina with the D50 of 0.5 mu m is added, the mixture is stirred for 10min at normal temperature, the rotating speed is 500rpm/min, when the powder is in a fine paste state, the other 54.41 parts of spherical alumina with the D50 of 0.5 mu m is added, and the mixture is still stirred for 10min at normal temperature, and the rotating speed is 500rpm/min; then 122.42 parts of spherical alumina with the D50 of 3 mu m is added, and the mixture is stirred for 10min at normal temperature, and the rotating speed is 500rpm/min; adding 122.42 parts of spherical aluminum oxide with the D50 of 3 mu m, stirring for 10min at normal temperature, rotating at 500rpm/min, taking out of the kettle after the powder is in a fine paste form; then adding 380.86 parts of spherical alumina with the D50 of 40 mu m, stirring for 15min at normal temperature and the rotating speed of 300rpm/min, and then adding 380.86 parts of spherical alumina with the D50 of 40 mu m, stirring for 15min at normal temperature and the rotating speed of 300rpm/min; finally adding 244.84 parts of spherical aluminum nitride with the D50 of 70 mu m, stirring at normal temperature for 20min at the rotating speed of 200rpm/min, scraping after finishing, heating to 130 ℃ for 40min, vacuumizing at 130 ℃ for 1h, keeping the vacuum degree below-0.09 MPa, cooling to below 40 ℃, and breaking vacuum by using nitrogen; then adding 5 parts of ethynyl cyclohexanol, 12 parts of hydrogen-containing silicone oil at the end, 0.75 part of A-2 structural cross-linking agent, 1.05 parts of Karster catalyst, mixing for 20min at normal temperature, defoaming for 20min, and discharging.
Example 9
Firstly, 165 parts of 500 mpa.s double-end vinyl silicone oil and 15 parts of decyl trimethoxy silane are taken and mixed in a 2L double-planetary mixer for 20min at normal temperature, then 52.06 parts of spherical alumina with the D50 of 0.5 mu m is added, the mixture is stirred for 10min at normal temperature, the rotating speed is 500rpm/min, when the powder is in a fine paste state, the other 52.06 parts of spherical alumina with the D50 of 0.5 mu m is added, the mixture is still stirred for 10min at normal temperature, and the rotating speed is 500rpm/min; then 117.13 parts of spherical alumina with the D50 of 3 mu m is added, and the mixture is stirred for 10min at normal temperature, and the rotating speed is 500rpm/min; adding 117.13 parts of spherical aluminum oxide with the D50 of 3 mu m, stirring for 10min at normal temperature, rotating at 500rpm/min, taking out of the kettle after the powder is in a fine paste form; then adding 364.39 parts of spherical alumina with the D50 of 40 mu m, stirring for 15min at normal temperature and the rotating speed of 300rpm/min, and then adding 364.39 parts of spherical alumina with the D50 of 40 mu m, stirring for 15min at normal temperature and the rotating speed of 300rpm/min; finally adding 234.25 parts of spherical aluminum nitride with the D50 of 70 mu m, stirring for 30min at normal temperature and the rotating speed of 200rpm/min, scraping after finishing, heating for 60min to 150 ℃, vacuumizing and preserving heat for 2h at 150 ℃, reducing the vacuum degree to below-0.09 MPa, and breaking vacuum by using nitrogen; then adding 1.5 parts of ethynyl cyclohexanol, 9 parts of terminal hydrogen-containing silicone oil, 0.6 part of A-3 structural cross-linking agent, 7.5 parts of Karster catalyst, mixing for 60min at normal temperature, defoaming for 40min, and discharging.
Example 10
Firstly, 240 parts of 500 mpa.s double-end vinyl silicone oil and 37.5 parts of decyl trimethoxy silane are mixed in a 2L double-planetary mixer for 10min at normal temperature, then 48.19 parts of spherical alumina with the D50 of 0.5 mu m is added, the mixture is stirred for 10min at normal temperature, the rotating speed is 500rpm/min, when the powder is in a fine paste state, the other 48.19 parts of spherical alumina with the D50 of 0.5 mu m is added, and the mixture is still stirred for 10min at normal temperature, and the rotating speed is 500rpm/min; then 108.42 parts of spherical alumina with the D50 of 3 mu m is added, and the mixture is stirred for 10min at normal temperature, and the rotating speed is 500rpm/min; adding 108.42 parts of spherical aluminum oxide with the D50 of 3 mu m, stirring for 10min at normal temperature, rotating at 500rpm/min, taking out of the kettle after the powder is in a fine paste form; then adding 337.3 parts of spherical alumina with the D50 of 40 mu m, stirring for 15min at normal temperature and the rotating speed of 300rpm/min, and then adding 337.3 parts of spherical alumina with the D50 of 40 mu m, stirring for 15min at normal temperature and the rotating speed of 300rpm/min; finally adding 216.84 parts of spherical aluminum nitride with the D50 of 70 mu m, stirring at normal temperature for 20min at the rotating speed of 200rpm/min, scraping after finishing, heating to 180 ℃ for 40min, vacuumizing at 180 ℃ for 1h, keeping the vacuum degree below-0.09 MPa, cooling to below 40 ℃, and breaking vacuum by using nitrogen; then adding 0.9 part of ethynyl cyclohexanol, 6 parts of terminal hydrogen-containing silicone oil, 0.45 part of A-4 structural cross-linking agent, 10.5 parts of Karster catalyst, mixing for 20min at normal temperature, defoaming for 20min, and discharging.
Example 11
Firstly, 300 parts of 500 mpa.s double-end vinyl silicone oil and 45 parts of decyl trimethoxy silane are mixed in a 2L double-planetary mixer for 10min at normal temperature, 45.48 parts of spherical alumina with the D50 of 0.5 mu m is added, the mixture is stirred for 10min at normal temperature, the rotating speed is 500rpm/min, when the powder is in a fine paste state, the other 45.48 parts of spherical alumina with the D50 of 0.5 mu m is added, and the mixture is still stirred for 10min at normal temperature, and the rotating speed is 500rpm/min; then 102.33 parts of spherical alumina with the D50 of 3 mu m is added, and the mixture is stirred for 10min at normal temperature, and the rotating speed is 500rpm/min; adding 102.33 parts of spherical alumina with the D50 of 3 mu m, stirring for 10min at normal temperature, stirring at 500rpm/min, taking out of the kettle after the powder is in a fine paste form; then adding 318.36 parts of spherical alumina with the D50 of 40 mu m, stirring for 15min at normal temperature and the rotating speed of 300rpm/min, and then adding 318.36 parts of spherical alumina with the D50 of 40 mu m, stirring for 15min at normal temperature and the rotating speed of 300rpm/min; finally adding 204.66 parts of spherical aluminum nitride with the D50 of 70 mu m, stirring at normal temperature for 20min at the rotating speed of 200rpm/min, scraping after finishing, heating to 180 ℃ for 40min, vacuumizing at 180 ℃ for 1h, keeping the vacuum degree below-0.09 MPa, cooling to below 40 ℃, and breaking vacuum by using nitrogen; then adding 1.2 parts of ethynyl cyclohexanol, 15 parts of terminal hydrogen-containing silicone oil, 0.3 part of A-5 structural cross-linking agent and 1.5 parts of Karster catalyst, mixing for 20min at normal temperature, defoaming for 20min, and discharging.
Example 12
Firstly, 300 parts of 500 mpa.s double-end vinyl silicone oil and 45 parts of decyl trimethoxy silane are mixed in a 2L double-planetary mixer for 10min at normal temperature, 45.48 parts of spherical alumina with the D50 of 0.5 mu m is added, the mixture is stirred for 10min at normal temperature, the rotating speed is 500rpm/min, when the powder is in a fine paste state, the other 45.48 parts of spherical alumina with the D50 of 0.5 mu m is added, and the mixture is still stirred for 10min at normal temperature, and the rotating speed is 500rpm/min; then 102.33 parts of spherical alumina with the D50 of 3 mu m is added, and the mixture is stirred for 10min at normal temperature, and the rotating speed is 500rpm/min; adding 102.33 parts of spherical alumina with the D50 of 3 mu m, stirring for 10min at normal temperature, stirring at 500rpm/min, taking out of the kettle after the powder is in a fine paste form; then adding 318.36 parts of spherical alumina with the D50 of 40 mu m, stirring for 15min at normal temperature and the rotating speed of 300rpm/min, and then adding 318.36 parts of spherical alumina with the D50 of 40 mu m, stirring for 15min at normal temperature and the rotating speed of 300rpm/min; finally adding 204.66 parts of spherical aluminum nitride with the D50 of 70 mu m, stirring at normal temperature for 20min at the rotating speed of 200rpm/min, scraping after finishing, heating to 180 ℃ for 40min, vacuumizing at 180 ℃ for 1h, keeping the vacuum degree below-0.09 MPa, cooling to below 40 ℃, and breaking vacuum by using nitrogen; then adding 1.2 parts of ethynyl cyclohexanol, 15 parts of terminal hydrogen-containing silicone oil, 0.3 part of A-6 structural cross-linking agent and 1.5 parts of Karster catalyst, mixing for 20min at normal temperature, defoaming for 20min, and discharging.
Comparative example 1
Firstly, 30 parts of 500 mpa.s silicone oil double-end vinyl silicone oil and 23.85 parts of decyl trimethoxy silane are mixed in a 2L double-planetary mixer for 5min at normal temperature, then 57 parts of spherical alumina with the D50 of 0.5 mu m is added, the mixture is stirred for 10min at normal temperature, the rotating speed is 500rpm/min, when the powder is in a fine paste state, the other 57 parts of spherical alumina with the D50 of 0.5 mu m is added, and the mixture is still stirred for 10min at normal temperature, and the rotating speed is 500rpm/min; then 128.25 parts of spherical alumina with the D50 of 3 mu m is added, and the mixture is stirred for 10min at normal temperature, and the rotating speed is 500rpm/min; adding 128.25 parts of spherical aluminum oxide with the D50 of 3 mu m, stirring for 10min at normal temperature, rotating at 500rpm/min, taking out of the kettle after the powder is in a fine paste form; then 399 parts of spherical alumina with D50 of 40 μm are added, stirred at normal temperature for 15min at the speed of 300rpm/min, then another 399 parts of spherical alumina with D50 of 40 μm are added, stirred at normal temperature for 15min at the speed of 300rpm/min; finally adding 256.50 parts of spherical aluminum nitride with the D50 of 70 mu m, stirring at normal temperature for 20min at the rotating speed of 200rpm/min, scraping after finishing, heating for 30min to 110 ℃, vacuumizing at 110 ℃ for 1h, keeping the vacuum degree below-0.09 MPa, cooling to below 40 ℃, and breaking vacuum by using nitrogen; then adding 0.75 part of ethynyl cyclohexanol, 4.5 parts of double-end hydrogen-containing silicone oil, 0.9 part of B-1 structural cross-linking agent and 15 parts of Kadster catalyst, mixing for 10min at normal temperature, defoaming for 10min, and discharging.
Comparative example 2
Firstly, 90 parts of 500 mpa.s double-end vinyl silicone oil and 30 parts of decyl trimethoxy silane are taken and mixed in a 2L double-planetary mixer for 10min at normal temperature, then 54.41 parts of spherical alumina with the D50 of 0.5 mu m is added, the mixture is stirred for 10min at normal temperature, the rotating speed is 500rpm/min, when the powder is in a fine paste state, the other 54.41 parts of spherical alumina with the D50 of 0.5 mu m is added, and the mixture is still stirred for 10min at normal temperature, and the rotating speed is 500rpm/min; then 122.42 parts of spherical alumina with the D50 of 3 mu m is added, and the mixture is stirred for 10min at normal temperature, and the rotating speed is 500rpm/min; adding 122.42 parts of spherical aluminum oxide with the D50 of 3 mu m, stirring for 10min at normal temperature, rotating at 500rpm/min, taking out of the kettle after the powder is in a fine paste form; then adding 380.86 parts of spherical alumina with the D50 of 40 mu m, stirring for 15min at normal temperature and the rotating speed of 300rpm/min, and then adding 380.86 parts of spherical alumina with the D50 of 40 mu m, stirring for 15min at normal temperature and the rotating speed of 300rpm/min; finally adding 244.84 parts of spherical aluminum nitride with the D50 of 70 mu m, stirring at normal temperature for 20min at the rotating speed of 200rpm/min, scraping after finishing, heating to 130 ℃ for 40min, vacuumizing at 130 ℃ for 1h, keeping the vacuum degree below-0.09 MPa, cooling to below 40 ℃, and breaking vacuum by using nitrogen; then adding 5 parts of ethynyl cyclohexanol, 12 parts of hydrogen-containing silicone oil at the end, 0.75 part of B-2 structural cross-linking agent, 1.05 parts of Karster catalyst, mixing for 20min at normal temperature, defoaming for 20min, and discharging.
Comparative example 3
Firstly, 30 parts of 500 mpa.s silicone oil double-end vinyl silicone oil and 23.85 parts of decyl trimethoxy silane are mixed in a 2L double-planetary mixer for 5min at normal temperature, then 57 parts of spherical alumina with the D50 of 0.5 mu m is added, the mixture is stirred for 10min at normal temperature, the rotating speed is 500rpm/min, when the powder is in a fine paste state, the other 57 parts of spherical alumina with the D50 of 0.5 mu m is added, and the mixture is still stirred for 10min at normal temperature, and the rotating speed is 500rpm/min; then 128.25 parts of spherical alumina with the D50 of 3 mu m is added, and the mixture is stirred for 10min at normal temperature, and the rotating speed is 500rpm/min; adding 128.25 parts of spherical aluminum oxide with the D50 of 3 mu m, stirring for 10min at normal temperature, rotating at 500rpm/min, taking out of the kettle after the powder is in a fine paste form; then 399 parts of spherical alumina with D50 of 40 μm are added, stirred at normal temperature for 15min at the speed of 300rpm/min, then another 399 parts of spherical alumina with D50 of 40 μm are added, stirred at normal temperature for 15min at the speed of 300rpm/min; finally adding 256.50 parts of spherical aluminum nitride with the D50 of 70 mu m, stirring at normal temperature for 20min at the rotating speed of 200rpm/min, scraping after finishing, heating for 30min to 70 ℃, vacuumizing at 70 ℃ for 1h, keeping the temperature for 1h, cooling to below 40 ℃ and breaking vacuum by using nitrogen; then adding 0.75 part of ethynyl cyclohexanol, 4.5 parts of double-end hydrogen-containing silicone oil, 0.9 part of A-1 structural cross-linking agent and 15 parts of Kadster catalyst, mixing for 20min at normal temperature, defoaming for 20min, and discharging.
Comparative example 4
Firstly, 90 parts of 500 mpa.s double-end vinyl silicone oil and 30 parts of decyl trimethoxy silane are taken and mixed in a 2L double-planetary mixer for 10min at normal temperature, then 54.41 parts of spherical alumina with the D50 of 0.5 mu m is added, the mixture is stirred for 10min at normal temperature, the rotating speed is 500rpm/min, when the powder is in a fine paste state, the other 54.41 parts of spherical alumina with the D50 of 0.5 mu m is added, and the mixture is still stirred for 10min at normal temperature, and the rotating speed is 500rpm/min; then 122.42 parts of spherical alumina with the D50 of 3 mu m is added, and the mixture is stirred for 10min at normal temperature, and the rotating speed is 500rpm/min; adding 122.42 parts of spherical aluminum oxide with the D50 of 3 mu m, stirring for 10min at normal temperature, rotating at 500rpm/min, taking out of the kettle after the powder is in a fine paste form; then adding 380.86 parts of spherical alumina with the D50 of 40 mu m, stirring for 15min at normal temperature and the rotating speed of 300rpm/min, and then adding 380.86 parts of spherical alumina with the D50 of 40 mu m, stirring for 15min at normal temperature and the rotating speed of 300rpm/min; finally adding 244.84 parts of spherical aluminum nitride with the D50 of 70 mu m, stirring at normal temperature for 20min at the rotating speed of 200rpm/min, scraping after finishing, heating to the temperature of 40min to 210 ℃, vacuumizing at the temperature of 210 ℃ for heat preservation for 1h, cooling to the temperature of below 40 ℃ and breaking vacuum by using nitrogen, wherein the vacuum degree is lower than-0.09 MPa; then adding 5 parts of ethynyl cyclohexanol, 12 parts of hydrogen-containing silicone oil at the end, 0.75 part of A-2 structural cross-linking agent, 1.05 parts of Karster catalyst, mixing for 20min at normal temperature, defoaming for 20min, and discharging.
The experimental test results are shown in the following table:
/>
Claims (26)
1. the heat-conducting gel is characterized by being prepared from the following raw materials in percentage by mass: 2-20% of vinyl silicone oil, 75-95% of high heat conduction filler, 1-3% of surface treatment agent, 0.3-1.0% of chain extender, 0.02-0.06% of cross-linking agent, 0.1-1.0% of catalyst and 0.05-0.1% of inhibitor;
the cross-linking agent has the following structural formula:
structural formula A
Wherein R is 2 Is methyl, ethyl, phenyl or trifluoropropyl, R 3 Is methyl, phenyl or the following structure:
x＝5-100，y＝1-10。
2. the thermally conductive gel of claim 1, wherein the vinyl silicone oil is a double-ended vinyl silicone oil.
3. The thermally conductive gel of claim 2, wherein the vinyl silicone oil has a viscosity of 20-3000 mpa-s at 25 ℃.
4. A thermally conductive gel according to claim 3, wherein the vinyl silicone oil has a viscosity of 100-1000 mpa-s at 25 ℃.
5. The thermally conductive gel of claim 1, wherein the high thermal conductivity filler is one or more of aluminum oxide, zinc oxide, aluminum nitride, boron carbide, silicon carbide, graphene, carbon nanotubes.
6. The thermally conductive gel of claim 1, wherein the highly thermally conductive filler is aluminum oxide or aluminum nitride.
7. The thermally conductive gel of claim 5 or 6, wherein the alumina is spherical and comprises three types of alumina having different particle sizes, the first spherical alumina having a D50 of 0.1-1 μm and a maximum particle size of no more than 2 μm; the second spherical alumina has D50 of 2.5-6 μm and maximum particle diameter of no more than 25 μm; the third spherical alumina D50 is 30-50 μm, and the maximum particle size is not more than 180 μm.
8. The gel of claim 5 or 6, wherein the aluminum nitride has a spherical shape, a D50 of 60-100 μm, and a maximum particle size of not more than 250 μm.
9. The thermally conductive gel of claim 1, wherein the surface treating agent is one or two of hexadecyltrimethoxysilane, dodecyltrimethoxysilane, decyltrimethoxysilane, octyltriethoxysilane, propyltrimethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane.
10. The thermally conductive gel of claim 1, wherein the chain extender is double-ended hydrogen dimethicone.
11. The thermally conductive gel of claim 10, wherein the double-ended hydrodimethicone has a viscosity of 5-100 mpa-s at 25 ℃.
12. The thermally conductive gel of claim 10 or 11, wherein the double-ended hydrodimethicone has a viscosity of 5-50 mp-s at 25 ℃.
13. The thermally conductive gel of claim 1, wherein R in the cross-linking agent 2 Is phenyl, x=5-30, y=1-5.
14. The thermally conductive gel of claim 1, wherein the method of preparing the structure a cross-linker comprises the steps of: adding a monomer, a blocking agent and a catalyst into a reaction kettle, heating to 40-60 ℃, reacting for 3-6 hours, then cooling to room temperature, adding a neutralizing agent, reacting for 1-2 hours, filtering to obtain a crude product, and devolatilizing to obtain a final product; wherein, the monomer adopts octamethyl cyclotetrasiloxane, octaethyl cyclotetrasiloxane, tetramethyl tetraphenyl cyclotetrasiloxane and trifluoropropyl cyclotrisiloxane.
15. The heat conductive gel of claim 14, wherein the structure a cross-linking agent is prepared by devolatilizing at 120-150 ℃ for 1-2 hours at 0.5-1kPa to obtain the final product.
16. The thermally conductive gel of claim 14, wherein the structure a cross-linking agent is prepared by a process wherein the monomer is octamethyltetrasiloxane, tetramethyl tetraphenyl cyclotetrasiloxane.
17. The thermally conductive gel of claim 14, wherein in the method of preparing the cross-linking agent of structure a, the end-capping agent is methyltri (dimethylsiloxy) silane, phenyltri (dimethylsiloxy) silane, tetra (trimethylsiloxy) silane.
18. The heat-conducting gel according to claim 14, wherein in the preparation method of the cross-linking agent with the structure A, the catalyst is one or more of trifluoromethanesulfonic acid, concentrated sulfuric acid, acid clay and ion exchange resin, and the dosage is 0.05-0.1wt% of the total mass of the monomer and the end-capping agent; the neutralizing agent adopts one or more of calcium carbonate, sodium bicarbonate, diatomite and active carbon, and the dosage is 0.5-1wt% of the total mass of the monomer and the end capping agent.
19. The thermally conductive gel of claim 18, wherein in the method of preparing the cross-linking agent of structure a, the catalyst is trifluoromethanesulfonic acid and the neutralizing agent is calcium carbonate.
20. The thermally conductive gel of claim 1, wherein the catalyst is one of platinum, chloroplatinic acid, a platinum-olefin complex, a platinum-alcohol complex, or a platinum coordination compound in an amount of 0.1% to 0.5%.
21. The thermally conductive gel of claim 1, wherein the inhibitor comprises one or more of an alkynol compound, an organic phosphorous compound, an oxime compound, and an organic chloride, and the inhibitor is present in an amount of 0.03% to 0.07%.
22. The thermally conductive gel of claim 21, wherein said inhibitor is ethynyl cyclohexanol.
23. A method of preparing a thermally conductive gel according to any one of claims 1 to 22, comprising the steps of:
(1) Mixing vinyl silicone oil and a surface treating agent in a double planetary mixer for 5-20min at normal temperature, then adding high-heat-conductivity filler, adding high-heat-conductivity filler powder in batches, stirring for 10-30min to be uniform paste after each addition, and then adding the powder for the next time until the powder addition is completed;
(2) Heating for 30-60min to 110-180deg.C, vacuum stirring for 60-120min, pressure lower than-0.09 MPa, cooling to below 40deg.C, and breaking vacuum with nitrogen;
(3) Then adding a chain extender, uniformly mixing, adding a cross-linking agent, an inhibitor and a catalyst, mixing for 10-60min at normal temperature, defoaming for 10-40min, and discharging.
24. The method of claim 23, wherein the heating time in step (2) is 40-50min.
25. The method of claim 23 or 24, wherein the temperature is raised to 120-150 ℃ in step (2).
26. The process of claim 23, wherein the high thermal conductivity filler in step (1) is alumina or aluminum nitride, and is added in three portions at an average time interval ranging from 10 to 30 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111251097.XA CN116023785B (en) | 2021-10-27 | 2021-10-27 | Heat-conducting gel and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111251097.XA CN116023785B (en) | 2021-10-27 | 2021-10-27 | Heat-conducting gel and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116023785A CN116023785A (en) | 2023-04-28 |
| CN116023785B true CN116023785B (en) | 2024-04-09 |
Family
ID=86069276
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111251097.XA Active CN116023785B (en) | 2021-10-27 | 2021-10-27 | Heat-conducting gel and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116023785B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10189838A (en) * | 1996-12-25 | 1998-07-21 | Siegel:Kk | Heat conductive gel |
| CN111393855A (en) * | 2020-03-18 | 2020-07-10 | 平湖阿莱德实业有限公司 | High-thermal-conductivity gel composition with excellent weather resistance |
| CN112552688A (en) * | 2020-12-16 | 2021-03-26 | 广德祥源新材科技有限公司 | High-thermal-conductivity organic silicon gel sheet and preparation method thereof |
| CN113248931A (en) * | 2021-05-31 | 2021-08-13 | 广东恒大新材料科技有限公司 | Heat-conducting gel with high heat conductivity and high extrusion rate and preparation method thereof |
| CN115678286A (en) * | 2022-11-25 | 2023-02-03 | 四川天邑康和通信股份有限公司 | Easily-filled and easily-repaired heat-conducting gel and preparation method thereof |
-
2021
- 2021-10-27 CN CN202111251097.XA patent/CN116023785B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10189838A (en) * | 1996-12-25 | 1998-07-21 | Siegel:Kk | Heat conductive gel |
| CN111393855A (en) * | 2020-03-18 | 2020-07-10 | 平湖阿莱德实业有限公司 | High-thermal-conductivity gel composition with excellent weather resistance |
| CN112552688A (en) * | 2020-12-16 | 2021-03-26 | 广德祥源新材科技有限公司 | High-thermal-conductivity organic silicon gel sheet and preparation method thereof |
| CN113248931A (en) * | 2021-05-31 | 2021-08-13 | 广东恒大新材料科技有限公司 | Heat-conducting gel with high heat conductivity and high extrusion rate and preparation method thereof |
| CN115678286A (en) * | 2022-11-25 | 2023-02-03 | 四川天邑康和通信股份有限公司 | Easily-filled and easily-repaired heat-conducting gel and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116023785A (en) | 2023-04-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107501953B (en) | Heat-conducting silicone grease containing liquid metal heat-conducting filler | |
| CN112608480B (en) | Asymmetric silicone oil and preparation method and application thereof | |
| CN113248931A (en) | Heat-conducting gel with high heat conductivity and high extrusion rate and preparation method thereof | |
| CN110903656B (en) | Low-volatility temperature-resistant heat-conducting silica gel cement material and preparation method and application thereof | |
| CN103087614A (en) | Insulating heat conduction high-temperature resistant electrical appliance coating and preparation method thereof | |
| WO2022126383A1 (en) | Asymmetric silicone oil, preparation method therefor, and application thereof | |
| CN105802237B (en) | Heat-conducting silica gel composition, heat-conducting silica gel and preparation method thereof | |
| CN110982277B (en) | Single-component temperature-resistant heat-conducting silicon mud composition and preparation method thereof | |
| CN111777996B (en) | Organic silicon cooling liquid containing phase change component and preparation method and application thereof | |
| CN101787256A (en) | Addition type silicone adhesive composition and preparation method thereof | |
| CN109593510A (en) | Alkoxy end-capped organosilicon polymer, preparation method and single-component de-alcoholized organosilicon sealant | |
| CN114437546A (en) | High-thermal-conductivity organic silicon gel and preparation method thereof | |
| CN112961657A (en) | Composite heat conduction material and preparation method thereof, heat conduction gel and preparation method thereof | |
| CN108659225A (en) | A kind of electrostatic-resistant heat conducting silicone oil and its synthetic method | |
| CN116023785B (en) | Heat-conducting gel and preparation method thereof | |
| CN109312216B (en) | High thermal conductivity composite material | |
| CN114907699B (en) | Heat conduction interface material and preparation method and application thereof | |
| CN110862576B (en) | Modified boron nitride particles and preparation method and application thereof | |
| CN116082580A (en) | Powder surface modifier, modified powder and preparation method and application thereof | |
| CN113999647B (en) | Organic silicon pouring sealant and preparation method thereof | |
| CN115074079A (en) | Single-component addition type organic silicon heat-conducting adhesive and preparation method thereof | |
| CN109796600A (en) | A kind of modified chain alkyl polysiloxanes and preparation method thereof | |
| CN114958246A (en) | Multifunctional auxiliary agent and preparation method thereof | |
| CN107236129A (en) | The preparation and application of vinyl benzene organopolysiloxane resin of the side base containing epoxy radicals | |
| CN112646375A (en) | Preparation method of high-temperature-resistant insulating silicone grease for household appliances |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |