CN114015117A - Heat-conducting filler and anti-aging organic silicon heat-conducting gel prepared from heat-conducting filler - Google Patents
Heat-conducting filler and anti-aging organic silicon heat-conducting gel prepared from heat-conducting filler Download PDFInfo
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- 239000000945 filler Substances 0.000 title claims abstract description 124
- 229910052710 silicon Inorganic materials 0.000 title abstract description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title abstract description 16
- 239000010703 silicon Substances 0.000 title abstract description 16
- 230000003712 anti-aging effect Effects 0.000 title abstract description 5
- 229920002545 silicone oil Polymers 0.000 claims abstract description 60
- 239000003607 modifier Substances 0.000 claims abstract description 49
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 46
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000001257 hydrogen Substances 0.000 claims abstract description 39
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 39
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910000077 silane Inorganic materials 0.000 claims abstract description 38
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 35
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 31
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 239000003112 inhibitor Substances 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 61
- 238000005507 spraying Methods 0.000 claims description 24
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 13
- -1 methyl trimethoxy silane toluene Chemical compound 0.000 claims description 12
- 239000004576 sand Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000007599 discharging Methods 0.000 claims description 9
- 239000003292 glue Substances 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 9
- 239000011231 conductive filler Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000013329 compounding Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 claims description 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 claims description 2
- 238000003860 storage Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 21
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 17
- 229920001971 elastomer Polymers 0.000 abstract description 6
- 230000009194 climbing Effects 0.000 abstract description 4
- 238000006459 hydrosilylation reaction Methods 0.000 abstract description 2
- 229920002379 silicone rubber Polymers 0.000 abstract 1
- 239000004945 silicone rubber Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 35
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 239000003921 oil Substances 0.000 description 10
- 230000032683 aging Effects 0.000 description 9
- 230000004048 modification Effects 0.000 description 9
- 238000012986 modification Methods 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 230000004913 activation Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 125000004494 ethyl ester group Chemical group 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000017525 heat dissipation Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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Abstract
The invention discloses a heat-conducting filler and an anti-aging organic silicon heat-conducting gel prepared from the heat-conducting filler, and belongs to the field of thermal interface materials. The organic silicon heat-conducting gel comprises the following components: 100 parts of vinyl-terminated silicone oil, 5-10 parts of hydrogen-containing silicone oil, 1000-1600 parts of heat-conducting filler, 0.02-0.05 part of inhibitor and 0.1-0.3 part of catalyst. According to the invention, the silane-modified aluminum oxide and graphene oxide compound heat-conducting filler is prepared, the silane modifier is dissolved in an organic solvent to prepare a modifier solution, the aluminum oxide and the graphene oxide can be connected together through silane, two ends of the silane modifier are provided with hydroxyl groups, branched chains are methyl and vinyl, and vinyl units in the silane can be crosslinked with hydrogen-containing silicone oil through hydrosilylation reaction, and the base rubber and the filler form a whole, so that the compatibility between the heat-conducting filler and the silicone rubber is improved, the hardness climbing at high temperature is reduced, the heat-conducting property of the heat-conducting gel is obviously improved, and the problems of limited addition amount and high cost of the single use of the graphene are also solved.
Description
Technical Field
The patent relates to the technical field of thermal interface materials, in particular to a heat-conducting filler and an anti-aging organic silicon heat-conducting gel prepared from the heat-conducting filler.
Background
The heat generated by the semiconductor must be dissipated to the ambient environment to maintain the temperature of the semiconductor element junction within safe operating ranges. Generally, this heat dissipation process requires the diffusion of heat by means of heat sinks; if the heat sink is attached to the surface of the semiconductor package, it is necessary to bring the two surfaces into close contact. When two of the above surfaces are joined together, contact will occur only at the high points and air gaps will be formed at the low points, typically over 90% of the air gap in the contact area, resulting in a large increase in thermal resistance.
In order to eliminate the air gaps on the contact interface, a thermal interface material with a thermal conductivity coefficient far higher than that of air, such as heat-conducting gel, needs to be introduced, so that two rough and uneven matching surfaces are tightly connected together, the interface thermal resistance is obviously reduced, the heat flow transfer efficiency is improved, and the temperature of the component is reduced. The conventional heat-conducting gel has the problems of climbing hardness, separating out silicone oil, reducing flexibility and the like in the high-temperature aging process, can seriously affect the heat conduction and heat dissipation performance of the conventional heat-conducting gel, and can not meet the application requirements of precise electronic elements.
Therefore, the preparation of the heat-conducting filler and the aging-resistant organic silicon heat-conducting gel prepared from the heat-conducting filler have important significance in solving the problems.
Disclosure of Invention
The invention aims to provide a heat-conducting filler and an anti-aging organic silicon heat-conducting gel prepared from the heat-conducting filler, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
the heat-conducting filler is modified by a silane modifier and is a mixture of aluminum oxide and graphene oxide.
Preferably, the silane modifier is a silane molecule, and the structural formula of the silane modifier is represented as follows:
wherein m is 1, 2, 3, 4; r1 is alkoxy or hydroxy; r2 is one of ethenyl, propenyl or butenyl.
Preferably, the alumina is a compound powder of one or more of spherical, spheroidal or angular, the median particle size is 5-30 μm, the graphene oxide is flaky, the size of the microchip is 1-5 μm, and the thickness is 0.8-1.2 nm.
Preferably, the heat conducting filler is formed by compounding aluminum oxide and graphene oxide according to the ratio of 6-8: 4-2.
A preparation method of a heat-conducting filler comprises the following steps:
step 1: dissolving a silane modifier in an organic solvent to prepare a modifier solution; adding alumina and graphene oxide filler into a sand mill for dispersion;
step 2: stirring the uniformly dispersed mixed filler, heating to 80-100 ℃, and preheating for 10-30 min; stirring, spraying the silane modifier solution into the filler, and controlling the spraying rate to be 50-70 g/min;
and step 3: stirring, reacting for 1-2 h while keeping the temperature, adding methyl trimethoxy silane toluene solution, reacting completely, cooling to room temperature, and baking for 2-3 h at 120 ℃.
Preferably, in step 1, the organic solvent is one or a mixture of toluene, ethanol, ethyl acetate, acetone or methyl ethyl ketone.
A method for preparing a thermally conductive gel from a thermally conductive filler, comprising the steps of: adding vinyl silicone oil, hydrogen-containing silicone oil and heat-conducting filler, and stirring; after the powder is uniformly dispersed, adding an inhibitor and a catalyst, stirring, vacuumizing, discharging glue, and refrigerating for storage.
Preferably, the heat-conducting gel is prepared from the following components in parts by weight: 100 parts of vinyl-terminated silicone oil, 5-10 parts of hydrogen-containing silicone oil, 1000-1600 parts of heat-conducting filler, 0.02-0.05 part of inhibitor and 0.1-0.3 part of catalyst.
Optimally, the viscosity of the vinyl-terminated silicone oil is 200-5000 cps, and the vinyl content is 0.2-0.8%; the viscosity of the hydrogen-containing silicone oil is 20-200 cps, and the active hydrogen content is 0.01-0.15%.
Preferably, the inhibitor is an alkynol inhibitor; the catalyst is a platinum catalyst.
In the technical scheme:
(1) the technical scheme that the aluminum oxide and the graphene oxide are compounded is adopted for the heat-conducting filler, the aluminum oxide is of a spherical structure, the graphene oxide is of a flaky structure, the heat-conducting effect can be improved after reasonable compounding, and the oil precipitation is reduced.
(2) The silane modifier is dissolved in an organic solvent to prepare a modifier solution, so that aluminum oxide and graphene oxide can be connected together through silane, two ends of the silane modifier are provided with hydroxyl groups, a branched chain is provided with methyl and vinyl, a vinyl unit in the silane can be crosslinked with hydrogen-containing silicone oil through hydrosilylation, the base adhesive and the filler form a whole, the filler and the base adhesive are not easy to separate in a high-temperature aging process, the agglomeration generation between the fillers can be reduced, and the high-temperature aging resistance of the rubber material is improved. After the heat-conducting gel prepared by the invention is cured, the hardness climbing is low in the high-temperature aging process, the oil bleeding is obviously reduced, and the heat-conducting property is not obviously reduced after the aging is carried out for 1000 hours.
(3) Controlling the spraying rate to be 50-70 g/min in the process of spraying the silane modifier solution to the filler under the stirring condition; the method can ensure that the amount of the alumina and graphene oxide filler particles is far larger than that of a modifier solution, so that active groups at two ends of the modifier can fully react with hydroxyl on the particles, and the crosslinking of the alumina and the graphene oxide is realized.
(4) Relating to the reaction principle:
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
step 1: dissolving silane modifier DA30 (Anbia special silicon Co., Ltd., both ends are hydroxyl, and branched chains are methyl and vinyl) in acetone to prepare modifier solution; the ratio of the alumina to the graphene oxide is 6: 4, and the alumina and the graphene oxide filler are weighed and added into a sand mill for dispersion.
Step 2: transferring the uniformly dispersed mixed filler into a reaction kettle, heating to 90 ℃ under stirring, preheating for 20min, spraying the silane modifier solution into the filler under the stirring condition, and controlling the spraying rate to be 70 g/min.
And step 3: keeping the temperature and reacting for 1h under the stirring condition, adding 30% methyl trimethoxy silane toluene solution, reacting completely, cooling to room temperature, and baking the filler in an oven at 120 ℃ for 2h to obtain the heat-conducting filler.
Example 2: a thermally conductive filler prepared using a KH560 silane modifier.
Step 1: dissolving KH560 (gamma-glycidoxypropyltrimethoxysilane) in acetone to obtain modifier solution; the ratio of alumina to graphene oxide is 6: and 4, weighing the alumina and the graphene oxide filler, and adding the alumina and the graphene oxide filler into a sand mill for dispersion.
Step 2: transferring the uniformly dispersed mixed filler into a reaction kettle, heating to 90 ℃ under stirring, preheating for 20min, spraying the silane modifier solution into the filler under the stirring condition, and controlling the spraying rate to be 70 g/min.
And step 3: keeping the temperature and reacting for 1h under the stirring condition, adding 30% methyl trimethoxy silane toluene solution, reacting completely, cooling to room temperature, and baking the filler in an oven at 120 ℃ for 2h to obtain the heat-conducting filler.
Example 3: the heat conducting filler is obtained by compounding the aluminum oxide and the graphene oxide according to the proportion of 5: 5.
Step 1: dissolving DA20 (Anbia Special silicon Co., Ltd., both ends are alkoxy groups, and branched chains are methyl and vinyl) in acetone to prepare a modifier solution; the ratio of the alumina to the graphene oxide is 5: 5, and the alumina and the graphene oxide filler are weighed and added into a sand mill for dispersion.
Step 2: transferring the uniformly dispersed mixed filler into a reaction kettle, heating to 90 ℃ under stirring, preheating for 20min, spraying the silane modifier solution into the filler under the stirring condition, and controlling the spraying rate to be 70 g/min.
And step 3: keeping the temperature and reacting for 1h under the stirring condition, adding 30% methyl trimethoxy silane toluene solution, reacting completely, cooling to room temperature, and baking the filler in an oven at 120 ℃ for 2h to obtain the heat-conducting filler.
Example 4: without modification.
Step 1: the ratio of the alumina to the graphene oxide is 6: 4, and the alumina and the graphene oxide filler are weighed and added into a sand mill for dispersion.
Step 2: adding 30% methyl trimethoxy silane toluene solution, reacting completely, cooling to room temperature, and baking the filler in an oven at 120 deg.C for 2h to obtain the heat-conducting filler.
Experiment 1:
after the surface coupling agent modifies the compound filler powder, the surface properties of the compound filler powder can change, and the following method is used for evaluating the modification effect of the samples in the embodiments 1 to 3, specifically, the modification effect is evaluated through the activation index and the oil absorption value, and the methods for measuring the activation index and the oil absorption value are as follows:
method for determining activation index: adding a proper amount of weighed modified compound filler powder into a container filled with a certain amount of water, fully stirring, standing for more than 1h, filtering, drying and weighing the materials at the bottom of the container, subtracting the mass of the sediment from the mass of the total modified compound filler to obtain the mass of the floater, wherein the divisor of the mass of the floater and the total mass is the activation index of the compound modified filler;
the oil absorption value test method comprises the following steps: weighing a certain amount of sample, placing the sample on a glass plate, dropwise adding dibutyl phthalate, using a glass rod to continuously grind and press the sample to enable the sample to be just agglomerated to be not loose, and measuring an oil absorption value, wherein the oil absorption value is calculated by the following formula:
the modification effect data of the tests on the modified compounded fillers prepared in examples 1 to 4 are shown in the following table:
TABLE 1 comparison of the modification effects
| Item | Example 1 | Example 2 | Example 3 | Example 4 |
| Modifying agent | DA30 | KH560 | DA20 | Is free of |
| Apparent phenomenon | Float in water | Partially float in water | Partially float in water | All settled at the bottom |
| Index of activation | 0.861 | 0.625 | 0.736 | 0 |
| Oil absorption number | 25 | 28 | 26 | 37 |
And (4) conclusion: from the experimental results in the table, it can be seen that the modified compound filler prepared in example 1 has a more excellent activation index than the samples of examples 2 and 3, which indicates that the modified compound filler prepared in example 1 has more excellent surface hydrophobicity.
In the embodiment 3, the compound filler contains 50% of graphene oxide powder, and the graphene oxide is in a flaky structure, so that the dispersion effect of aluminum oxide and graphene oxide is poor due to the increase of the proportion, and the modification effect of the filler is influenced;
compared with unmodified compound fillers, the modified compound fillers in the embodiments 1 to 3 have different degrees of reduced oil absorption values, because the modified compound fillers are reduced in agglomeration and improved in dispersibility, and the surface chemical coating of the modifier further reduces the gaps among particles, so that the surface of the compound fillers is changed from polarity to non-polarity, the friction among the particles is reduced, the lubricating property is better, the stacking density is increased, and the oil absorption value is reduced.
Example 5:
selecting terminal vinyl silicone oil with the viscosity of 500cps and the vinyl content of 0.4-0.6%, methyl side hydrogen-containing silicone oil with the viscosity of 100-200 cps and the hydrogen content of 0.01-0.05%, wherein the components are in proportion as follows: 100 parts of vinyl-terminated silicone oil, 5 parts of hydrogen-containing silicone oil, 1600 parts of heat-conducting filler, 0.02 part of inhibitor and 0.2 part of platinum catalyst.
Step 1: dissolving a silane modifier DA30 (Anbia special silicon Co., Ltd., both ends are hydroxyl, and branched chains are methyl and vinyl) in toluene to prepare a modifier solution; the ratio of the alumina to the graphene oxide is 8: 2, and the alumina and the graphene oxide filler are weighed and added into a sand mill for dispersion.
Step 2: transferring the uniformly dispersed mixed filler into a reaction kettle, heating to 80 ℃ under stirring, preheating for 30min, spraying the silane modifier solution into the filler under the stirring condition, and controlling the spraying rate at 50 g/min.
And step 3: keeping the temperature and reacting for 1h under the stirring condition, adding 30% methyl trimethoxy silane toluene solution, reacting completely, cooling to room temperature, and baking the filler in an oven at 120 ℃ for 2h to obtain the heat-conducting filler.
And 4, step 4: mixing the components in parts by weight, adding vinyl silicone oil, hydrogen-containing silicone oil and heat-conducting filler into a planetary stirring kettle, and stirring for the first time for 30 min; and after the powder is uniformly dispersed, adding an inhibitor and a catalyst, stirring for the second time, vacuumizing to ensure that the materials are uniformly mixed without bubbles, discharging the glue into a specific package after the materials are completely mixed, and refrigerating and storing to obtain the high-temperature-resistant organic silicon heat-conducting gel.
Example 6:
vinyl-terminated silicone oil with the viscosity of 1000cps and the vinyl content of 0.3-0.4%, methyl side hydrogen-containing silicone oil with the viscosity of 50-100 cps and the hydrogen content of 0.04-0.10% are selected, and the components are in proportion as follows: 100 parts of vinyl-terminated silicone oil, 3 parts of hydrogen-containing silicone oil, 1400 parts of heat-conducting filler, 0.03 part of inhibitor and 0.3 part of platinum catalyst.
Step 1: dissolving silane modifier DA30 (Anbia special silicon Co., Ltd., both ends are hydroxyl, and branched chains are methyl and vinyl) in ethyl ester to prepare modifier solution; the ratio of the alumina to the graphene oxide is 7: 3, and the alumina and the graphene oxide filler are weighed and added into a sand mill for dispersion.
Step 2: transferring the uniformly dispersed mixed filler into a reaction kettle, heating to 100 ℃ under stirring, preheating for 10min, spraying the silane modifier solution into the filler under the stirring condition, and controlling the spraying rate to be 60 g/min.
And step 3: keeping the temperature and reacting for 1h under the stirring condition, adding 30% methyl trimethoxy silane toluene solution, reacting completely, cooling to room temperature, and baking the filler in an oven at 120 ℃ for 2h to obtain the heat-conducting filler.
And 4, step 4: mixing the components in parts by weight, adding vinyl silicone oil, hydrogen-containing silicone oil and heat-conducting filler into a planetary stirring kettle, and stirring for the first time for 30 min; and after the powder is uniformly dispersed, adding an inhibitor and a catalyst, stirring for the second time, vacuumizing to ensure that the materials are uniformly mixed without bubbles, discharging the glue into a specific package after the materials are completely mixed, and refrigerating and storing to obtain the high-temperature-resistant organic silicon heat-conducting gel.
Example 7:
selecting vinyl-terminated silicone oil with the viscosity of 2000cps and the vinyl content of 0.2-0.3%, methyl side hydrogen-containing silicone oil with the viscosity of 20-50 cps and the hydrogen content of 0.1-0.15%, wherein the ratio of the components is as follows: 100 parts of vinyl-terminated silicone oil, 2 parts of hydrogen-containing silicone oil, 1200 parts of heat-conducting filler, 0.02 part of inhibitor and 0.2 part of platinum catalyst.
Step 1: dissolving silane modifier DA30 (Anbia special silicon Co., Ltd., both ends are hydroxyl, and branched chains are methyl and vinyl) in acetone to prepare modifier solution; the ratio of the alumina to the graphene oxide is 6: 4, and the alumina and the graphene oxide filler are weighed and added into a sand mill for dispersion.
Step 2: transferring the uniformly dispersed mixed filler into a reaction kettle, heating to 90 ℃ under stirring, preheating for 20min, spraying the silane modifier solution into the filler under the stirring condition, and controlling the spraying rate to be 70 g/min.
And step 3: keeping the temperature and reacting for 1h under the stirring condition, adding 30% methyl trimethoxy silane toluene solution, reacting completely, cooling to room temperature, and baking the filler in an oven at 120 ℃ for 2h to obtain the heat-conducting filler.
And 4, step 4: mixing the components in parts by weight, adding vinyl silicone oil, hydrogen-containing silicone oil and heat-conducting filler into a planetary stirring kettle, and stirring for the first time for 30 min; and after the powder is uniformly dispersed, adding an inhibitor and a catalyst, stirring for the second time, vacuumizing to ensure that the materials are uniformly mixed without bubbles, discharging the glue into a specific package after the materials are completely mixed, and refrigerating and storing to obtain the high-temperature-resistant organic silicon heat-conducting gel.
Example 8:
vinyl-terminated silicone oil with the viscosity of 1000cps and the vinyl content of 0.3-0.4%, methyl side hydrogen-containing silicone oil with the viscosity of 20-50 cps and the hydrogen content of 0.04-0.10% are selected, and the components are in proportion as follows: 100 parts of vinyl-terminated silicone oil, 3 parts of hydrogen-containing silicone oil, 1400 parts of heat-conducting filler, 0.03 part of inhibitor and 0.3 part of platinum catalyst.
Step 1: dissolving a silane modifier DA20 (Anbia special silicon Co., Ltd., both ends are alkoxy groups, and branched chains are methyl and vinyl) in toluene to prepare a modifier solution; the ratio of alumina to graphene oxide is 7: and 3, weighing the alumina and the graphene oxide filler, and adding the alumina and the graphene oxide filler into a sand mill for dispersion.
Step 2: transferring the uniformly dispersed mixed filler into a reaction kettle, heating to 100 ℃ under stirring, preheating for 10min, spraying the silane modifier solution into the filler under the stirring condition, and controlling the spraying rate to be 60 g/min.
And step 3: keeping the temperature and reacting for 1h under the stirring condition, adding 30% methyl trimethoxy silane toluene solution, reacting completely, cooling to room temperature, and baking the filler in an oven at 120 ℃ for 2h to obtain the heat-conducting filler.
And 4, step 4: mixing the components in parts by weight, adding vinyl silicone oil, hydrogen-containing silicone oil and heat-conducting filler into a planetary stirring kettle, and stirring for the first time for 30 min; and after the powder is uniformly dispersed, adding an inhibitor and a catalyst, stirring for the second time, vacuumizing to ensure that the materials are uniformly mixed without bubbles, discharging the glue into a specific package after the materials are completely mixed, and refrigerating and storing to obtain the high-temperature-resistant organic silicon heat-conducting gel.
Comparative example 1: the injection rate was set to 80g/min, compared to the injection rate effect.
Selecting terminal vinyl silicone oil with the viscosity of 500cps and the vinyl content of 0.4-0.6%, methyl side hydrogen-containing silicone oil with the viscosity of 100-200 cps and the hydrogen content of 0.01-0.05%, wherein the components are in proportion as follows: 100 parts of vinyl-terminated silicone oil, 5 parts of hydrogen-containing silicone oil, 1600 parts of heat-conducting filler, 0.02 part of inhibitor and 0.2 part of platinum catalyst.
Step 1: dissolving a silane modifier DA30 (Anbia special silicon Co., Ltd., both ends are hydroxyl, and branched chains are methyl and vinyl) in toluene to prepare a modifier solution; the ratio of the alumina to the graphene oxide is 8: 2, and the alumina and the graphene oxide filler are weighed and added into a vertical sand mill for dispersion.
Step 2: transferring the uniformly dispersed mixed filler into a reaction kettle, heating to 80 ℃ under stirring, preheating for 30min, spraying the silane modifier solution into the filler under the stirring condition, and controlling the spraying rate to be 80 g/min.
And step 3: keeping the temperature and reacting for 1h under the stirring condition, adding 30% methyl trimethoxy silane toluene solution, reacting completely, cooling to room temperature, and baking for 2h in an oven at 120 ℃ to obtain the heat-conducting filler.
And 4, step 4: mixing the components in parts by weight, adding vinyl silicone oil, hydrogen-containing silicone oil and heat-conducting filler into a planetary stirring kettle, and stirring for the first time for 30 min; and after the powder is uniformly dispersed, adding an inhibitor and a catalyst, stirring for the second time, vacuumizing to ensure that the materials are uniformly mixed without bubbles, discharging the glue into a specific package after the materials are completely mixed, and refrigerating and storing to obtain the high-temperature-resistant organic silicon heat-conducting gel.
Comparative example 2: the injection rate was set to 150g/min, compared to the injection rate effect.
Vinyl-terminated silicone oil with the viscosity of 1000cps and the vinyl content of 0.3-0.4%, methyl side hydrogen-containing silicone oil with the viscosity of 50-100 cps and the hydrogen content of 0.04-0.1% are selected, and the components are in proportion as follows: 100 parts of vinyl-terminated silicone oil, 3 parts of hydrogen-containing silicone oil, 1400 parts of heat-conducting filler, 0.03 part of inhibitor and 0.3 part of platinum catalyst.
Step 1: dissolving silane modifier DA30 (Anbia special silicon Co., Ltd., both ends are hydroxyl, and branched chains are methyl and vinyl) in ethyl ester to prepare modifier solution; the ratio of the alumina to the graphene oxide is 7: 3, and the alumina and the graphene oxide filler are weighed and added into a sand mill for dispersion.
Step 2: transferring the uniformly dispersed mixed filler into a reaction kettle, heating to 80 ℃ under stirring, preheating for 30min, spraying the silane modifier solution into the filler under the stirring condition, and controlling the spraying rate to be 150 g/min.
And step 3: keeping the temperature and reacting for 1h under the stirring condition, adding 30% methyl trimethoxy silane toluene solution, reacting completely, cooling to room temperature, and baking for 2h in an oven at 120 ℃ to obtain the heat-conducting filler.
And 4, step 4: mixing the components in parts by weight, adding vinyl silicone oil, hydrogen-containing silicone oil and heat-conducting filler into a planetary stirring kettle, and stirring for the first time for 30 min; and after the powder is uniformly dispersed, adding an inhibitor and a catalyst, stirring for the second time, vacuumizing to ensure that the materials are uniformly mixed without bubbles, discharging the glue into a specific package after the materials are completely mixed, and refrigerating and storing to obtain the high-temperature-resistant organic silicon heat-conducting gel.
Comparative example 3: and (4) comparing the modified compound filler.
Selecting terminal vinyl silicone oil with the viscosity of 500cps and the vinyl content of 0.4-0.6%, methyl side hydrogen-containing silicone oil with the viscosity of 50-100 cps and the hydrogen content of 0.01-0.05%, wherein the components are in proportion as follows: 100 parts of vinyl-terminated silicone oil, 3 parts of hydrogen-containing silicone oil, 1600 parts of heat-conducting filler, 0.03 part of inhibitor and 0.3 part of platinum catalyst.
The ratio of the alumina to the graphene oxide in the heat-conducting filler is 8: 2, the aluminum oxide powder is not modified, the median particle size of the aluminum oxide powder is 20-25 mu m, the microchip size of the graphene oxide is 2-3 mu m, and the thickness of the graphene oxide is 1.0-1.2 nm.
Mixing the components in parts by weight, adding vinyl silicone oil, hydrogen-containing silicone oil and heat-conducting filler into a planetary stirring kettle, and stirring for the first time for 30 min; and after the powder is uniformly dispersed, adding an inhibitor and a catalyst, stirring for the second time, vacuumizing to ensure that the materials are uniformly mixed without bubbles, discharging the glue into a specific package after the materials are completely mixed, and refrigerating and storing to obtain the high-temperature-resistant organic silicon heat-conducting gel.
Comparative example 4: the amount of graphene oxide in the filler was increased, the ratio of alumina to graphene oxide was 5: 5, and the rest was the same as in example 2.
According to the preparation method of the organic silicon heat-conducting gel, the filler and the base rubber are poor in compatibility after the heat-conducting filler is added, and a continuous paste material cannot be formed after stirring and dispersing, so that subsequent sample preparation and performance test cannot be carried out.
Experiment 2:
after the six groups of prepared organic silicon heat-conducting gel samples are completely cured at 100 ℃/30min, the heat-conducting performance is tested according to ASTM-D5470, the hardness is tested according to ASTM-D2240, and the tensile strength and the elongation at break are tested according to GB/T1040.4-2006. The high-temperature aging resistance test method comprises the following steps: and (3) putting the completely cured sample into an oven at 150 ℃, taking out the sample every 200 hours, cooling to room temperature, and testing the hardness, tensile strength, elongation at break and heat conductivity according to the above standards.
The results of the data obtained by testing the six groups of samples are shown in table 2.
Table 2 thermally conductive gel sample test results
And (4) conclusion: 1. the data of example 5 and comparative example 3 show that the modified compound filler has better compatibility with the base rubber, the cured film has higher thermal conductivity, lower hardness and better flexibility, and after high-temperature aging, the hardness climbs less, thus meeting the long-time use requirement of electronic equipment.
2. It can be seen from the data of example 6 and comparative examples 1 and 2 that increasing the injection rate of the modifier results in insufficient filler modification, which results in a cured film with a fast rise in hardness and failure to meet equipment requirements.
3. The data of example 6 and example 8 show that the filler modified by hydroxyl and alkoxy has better modification effect and good compatibility with the base rubber, and the hardness climbing of the rubber material in the high-temperature aging process can be reduced.
4. Compared with the embodiment 5 or 6, the embodiment 7 adopts the 2000cps vinyl-terminated silicone oil, can well reduce the hardness of the heat-conducting gel after curing, improves the flexibility, and can meet the use requirements of equipment under severe conditions.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A thermally conductive filler, characterized in that: the heat-conducting filler is modified by a silane modifier, and is a mixture of aluminum oxide and graphene oxide.
2. A thermally conductive filler as set forth in claim 1, wherein: the silane modifier is a silane molecule, and the structural formula of the silane modifier is represented as follows:
wherein m is 1, 2, 3, 4; r1 is alkoxy or hydroxy; r2 is one of ethenyl, propenyl or butenyl.
3. A thermally conductive filler as set forth in claim 1, wherein: the aluminum oxide is one or more of spherical, spheroidal or angular compound powder, the median particle size is 5-30 mu m, the graphene oxide is flaky, the size of a microchip is 1-5 mu m, and the thickness is 0.8-1.2 m.
4. A thermally conductive filler as set forth in claim 1, wherein: the heat conducting filler is formed by compounding aluminum oxide and graphene oxide according to the ratio of 6-8: 4-2.
5. A preparation method of a heat-conducting filler is characterized by comprising the following steps: the method comprises the following steps:
step 1: dissolving a silane modifier in an organic solvent to prepare a modifier solution; adding alumina and graphene oxide filler into a sand mill for dispersion;
step 2: stirring the uniformly dispersed mixed filler, heating to 80-100 ℃, and preheating for 10-30 min; stirring, spraying the silane modifier solution into the filler, and controlling the spraying rate to be 50-70 g/min;
and step 3: stirring, reacting for 1-2 h while keeping the temperature, adding methyl trimethoxy silane toluene solution, reacting completely, cooling to room temperature, and baking for 2-3 h at 120 ℃.
6. The method for preparing a thermally conductive filler according to claim 5, wherein: in the step 1, the organic solvent is one or a mixture of toluene, ethanol, ethyl acetate, acetone or methyl ethyl ketone.
7. A method for preparing a heat-conducting gel by using the heat-conducting filler as claimed in any one of claims 1 to 6, wherein the method comprises the following steps: the method comprises the following steps: adding vinyl silicone oil, hydrogen-containing silicone oil and heat-conducting filler, and stirring; after the powder is uniformly dispersed, adding an inhibitor and a catalyst, stirring, vacuumizing, discharging glue, and refrigerating for storage.
8. The method of claim 7, wherein: the heat-conducting gel is prepared from the following components in parts by weight: 100 parts of vinyl-terminated silicone oil, 5-10 parts of hydrogen-containing silicone oil, 1000-1600 parts of heat-conducting filler, 0.02-0.05 part of inhibitor and 0.1-0.3 part of catalyst.
9. The method of claim 7, wherein: the viscosity of the vinyl-terminated silicone oil is 200-5000 cps, and the vinyl content is 0.2-0.8%; the viscosity of the hydrogen-containing silicone oil is 20-200 cps, and the active hydrogen content is 0.01-0.15%.
10. The method of claim 7, wherein: the inhibitor is an alkynol inhibitor; the catalyst is a platinum catalyst.
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