CN114015117B - Heat-conducting filler and ageing-resistant organic silicon heat-conducting gel prepared from heat-conducting filler - Google Patents
Heat-conducting filler and ageing-resistant 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 120
- 229910052710 silicon Inorganic materials 0.000 title abstract description 16
- 230000032683 aging Effects 0.000 title abstract description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title abstract description 8
- 239000010703 silicon Substances 0.000 title abstract description 8
- 229920002545 silicone oil Polymers 0.000 claims abstract description 53
- 239000003607 modifier Substances 0.000 claims abstract description 49
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 44
- 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 239000003112 inhibitor Substances 0.000 claims abstract description 23
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 23
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 12
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 61
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 27
- 238000005507 spraying Methods 0.000 claims description 24
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 17
- 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
- 239000000843 powder Substances 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- -1 methyltrimethoxysilane 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
- 238000004321 preservation 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
- 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
- 238000004519 manufacturing process Methods 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 14
- 229920001971 elastomer Polymers 0.000 abstract description 9
- 230000009194 climbing Effects 0.000 abstract description 3
- 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 19
- 239000003921 oil Substances 0.000 description 10
- 230000000694 effects 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
- 150000002431 hydrogen Chemical class 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 230000004913 activation Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000013329 compounding Methods 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
- 238000001556 precipitation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000005540 biological transmission 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
- 238000001914 filtration Methods 0.000 description 1
- 238000000227 grinding 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
- 235000011837 pasties Nutrition 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method 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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- 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
- 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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- 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
- 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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- C—CHEMISTRY; METALLURGY
- 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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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- 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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- 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
- 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
Abstract
The invention discloses a heat-conducting filler and ageing-resistant 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 modifier is dissolved in the organic solvent to prepare the modifier solution, so that the aluminum oxide and the graphene oxide are connected together through silane, the two ends of the silane modifier are hydroxyl, the branched chains are methyl and vinyl, the vinyl unit in the silane can be crosslinked with hydrogen-containing silicone oil through hydrosilylation reaction, the base rubber and the filler form a whole, the compatibility between the heat-conducting filler and the silicone rubber is improved, the hardness climbing at high temperature is reduced, the heat conducting performance of the heat conducting gel is remarkably improved, and the problems of limited single use addition amount, high cost and the like of the graphene are also overcome.
Description
Technical Field
The patent relates to the technical field of thermal interface materials, in particular to a heat-conducting filler and ageing-resistant organic silicon heat-conducting gel prepared by the heat-conducting filler.
Background
The heat generated by the semiconductor must be dissipated to the surrounding environment to maintain the temperature of the semiconductor element junction within a safe operating range. Typically, such heat dissipation processes require the diffusion of heat by means of heat sinks; if the heat sink is fixed to the surface of the semiconductor package, the two surfaces need to be brought into close contact. When the two surfaces are connected together, only the high point position is contacted, the low point position is formed with an air gap, and generally, more than 90% of the air gap exists in the contact area, so that the thermal resistance is greatly increased.
In order to eliminate the air gaps on the contact interface, a thermal interface material with a heat conductivity coefficient far greater 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 transmission efficiency is improved, and the element junction temperature is reduced. The conventional heat-conducting gel has the problems of rising hardness, precipitating silicone oil, reducing flexibility and the like in the high-temperature aging process, so that the heat conduction and heat dissipation performances of the gel can be seriously influenced, and the application requirements of the precise electronic element can not be met.
Therefore, the preparation of the heat-conducting filler and the ageing-resistant organic silicon heat-conducting gel prepared by the heat-conducting filler have important significance.
Disclosure of Invention
The invention aims to provide a heat-conducting filler and an aging-resistant organic silicon heat-conducting gel prepared by the heat-conducting filler, so as to solve the problems in the prior art.
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.
More preferably, the silane modifier is a silane molecule, and the structural formula of the silane modifier is as follows:
wherein m=1, 2,3,4; r1 is alkoxy or hydroxy; r2 is one of ethenyl, propenyl or butenyl.
More optimally, the aluminum oxide is one or more compound powder of spherical, spheroidal or angular type, the median particle diameter is 5-30 mu m, the graphene oxide is flake, the size of the microchip is 1-5 mu m, and the thickness is 0.8-1.2 nm.
More optimally, the heat conducting filler is formed by compounding aluminum oxide and graphene oxide according to the proportion of 6-8:4-2.
A method for preparing a thermally conductive filler, comprising the steps of:
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 at 50-70 g/min;
step 3: stirring, reacting for 1-2 h at a constant temperature, adding methyltrimethoxysilane toluene solution, reacting completely, cooling to room temperature, and baking at 120 ℃ for 2-3 h.
More preferably, in step 1, the organic solvent is one or a mixture of several 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-terminated 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 preservation.
More 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.
More 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%.
More preferably, the inhibitor is an alkynol inhibitor; the catalyst is a platinum catalyst.
The technical scheme is as follows:
(1) The heat conducting filler adopts the technical scheme that aluminum oxide and graphene oxide are compounded, the aluminum oxide is of a spherical structure, the graphene oxide is of a sheet structure, the heat conducting effect can be improved after reasonable compounding, and the generation of 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 are connected together through silane, two ends of the silane modifier are hydroxyl groups, branched chains are methyl groups and vinyl groups, vinyl units in the silane can be crosslinked with hydrogen-containing silicone oil through hydrosilylation reaction, base rubber and filler form a whole, separation of the filler and the base rubber is not easy to occur in a high-temperature aging process, agglomeration among the fillers can be reduced, and the high-temperature aging resistance of the rubber is improved. After the heat-conducting gel prepared by the method is solidified, the hardness is low in climbing in the high-temperature aging process, the oil precipitation is obviously reduced, and the heat-conducting performance is not obviously reduced after aging for 1000 hours.
(3) In the process of spraying the silane modifier solution to the filler under the stirring condition, controlling the spraying rate at 50-70 g/min; the method can ensure that the aluminum oxide and graphene oxide filler particles are far larger than the modifier solution, so that active groups at two ends of the modifier can fully react with hydroxyl groups on the particles, and the crosslinking of the aluminum oxide and the graphene oxide is realized.
(4) The reaction principle is as follows:
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1:
step 1: dissolving a silane modifier DA30 (An Biya special silicon Co., ltd., hydroxyl groups at two ends and methyl and vinyl groups at branched chains) in acetone to prepare a 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 stirring, and controlling the spraying rate at 70g/min.
Step 3: and (3) carrying out heat preservation reaction for 1h under the stirring condition, adding 30% methyltrimethoxysilane toluene solution, completely reacting, cooling to room temperature, and placing the filler into a baking oven at 120 ℃ for baking for 2h to obtain the heat-conducting filler.
Example 2: a thermally conductive filler prepared using KH560 silane modifier.
Step 1: KH560 (gamma-glycidoxypropyl trimethoxysilane) is dissolved in acetone to prepare 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 stirring, and controlling the spraying rate at 70g/min.
Step 3: and (3) carrying out heat preservation reaction for 1h under the stirring condition, adding 30% methyltrimethoxysilane toluene solution, completely reacting, cooling to room temperature, and placing the filler into a baking oven at 120 ℃ for baking for 2h to obtain the heat-conducting filler.
Example 3: the aluminum oxide and the graphene oxide are compounded according to the proportion of 5:5 to obtain the heat-conducting filler.
Step 1: DA20 (An Biya special silicon Co., ltd., alkoxy at both ends, methyl and vinyl at branched chain) is dissolved in acetone to prepare modifier solution; the proportion 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 stirring, and controlling the spraying rate at 70g/min.
Step 3: and (3) carrying out heat preservation reaction for 1h under the stirring condition, adding 30% methyltrimethoxysilane toluene solution, completely reacting, cooling to room temperature, and placing the filler into a baking oven at 120 ℃ for baking for 2h to obtain the heat-conducting filler.
Example 4: the modification treatment is not carried out.
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% methyltrimethoxysilane toluene solution, reacting completely, cooling to room temperature, and placing the filler into a 120 ℃ oven for baking for 2 hours to obtain the heat-conducting filler.
Experiment 1:
after the surface coupling agent modifies the compound filler powder, the surface property of the compound filler powder changes, and the modification effect is evaluated by the following samples of examples 1-3, specifically by the activation index and oil absorption value, and the determination method of the activation index and the oil absorption value is as follows:
method for measuring activation index: adding a proper amount of weighed modified compound filler powder into a container containing 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 sediment from the mass of the total modified compound filler to obtain the mass of the floating material, wherein the divisor of the mass of the floating material 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 samples, placing the samples on a glass plate, dropwise adding dibutyl phthalate, continuously grinding the samples by using a glass rod until the samples are 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 for the modified compound filler tests prepared in examples 1 to 4 are shown in the following table:
table 1 comparison of modification effects
| Project | Example 1 | Example 2 | Example 3 | Example 4 |
| Modifying agent | DA30 | KH560 | DA20 | Without any means for |
| Appearance phenomenon | Floating in water | Part of the water floats in the water | Part of the water floats in the water | All settle to the bottom |
| Activation index | 0.861 | 0.625 | 0.736 | 0 |
| Oil absorption value | 25 | 28 | 26 | 37 |
Conclusion: from the experimental results of the above table, the modified compound filler prepared in example 1 has a more excellent activation index than the samples of examples 2 and 3, indicating that the modified compound filler prepared in example 1 has a more excellent surface hydrophobicity.
In the embodiment 3, the compound filler contains 50% graphene oxide powder, and as the graphene oxide is of a lamellar structure, the increase of the proportion can cause poor dispersion effect of aluminum oxide and graphene oxide, thereby influencing the modification effect of the filler;
compared with the unmodified compound filler, the modified compound filler in examples 1-3 has different degrees of reduction in oil absorption value, because the modified compound filler has reduced agglomeration, improved dispersibility, further reduced inter-particle gaps due to chemical coating on the surface of the modifier, changed the surface of the compound filler from polar to nonpolar, reduced inter-particle friction, better lubricating performance, increased bulk density and reduced oil absorption value.
Example 5:
the methyl side hydrogen silicone oil with the viscosity of 500cps, the vinyl content of 0.4-0.6%, the viscosity of 100-200 cps and the hydrogen content of 0.01-0.05% is selected, and the components are 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 (An Biya special silicon Co., ltd., hydroxyl groups at two ends and methyl and vinyl groups at branched chains) in toluene to prepare a modifier solution; the proportion 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 stirring, and controlling the spraying rate at 50g/min.
Step 3: and (3) carrying out heat preservation reaction for 1h under the stirring condition, adding 30% methyltrimethoxysilane toluene solution, completely reacting, cooling to room temperature, and placing the filler in a baking oven at 120 ℃ for 2h to obtain the heat-conducting filler.
Step 4: proportioning according to the weight portions of the components, adding vinyl-terminated silicone oil, hydrogen-containing silicone oil and heat conducting filler into a planetary stirring kettle, and stirring for 30min for the first time; 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 completion of the mixing, and refrigerating and preserving to obtain the high-temperature-resistant organosilicon heat-conducting gel.
Example 6:
the methyl side hydrogen silicone oil with the viscosity of 1000cps, the vinyl content of 0.3-0.4%, the viscosity of 50-100 cps and the hydrogen content of 0.04-0.10% is selected, and the components are 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 DA30 (An Biya special silicon Co., ltd., hydroxyl groups at two ends and methyl and vinyl groups at branched chains) in ethyl ester to prepare a modifier solution; the proportion 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 stirring, and controlling the spraying rate at 60g/min.
Step 3: and (3) carrying out heat preservation reaction for 1h under the stirring condition, adding 30% methyltrimethoxysilane toluene solution, completely reacting, cooling to room temperature, and placing the filler in a baking oven at 120 ℃ for 2h to obtain the heat-conducting filler.
Step 4: proportioning according to the weight portions of the components, adding vinyl-terminated silicone oil, hydrogen-containing silicone oil and heat conducting filler into a planetary stirring kettle, and stirring for 30min for the first time; 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 completion of the mixing, and refrigerating and preserving to obtain the high-temperature-resistant organosilicon heat-conducting gel.
Example 7:
the methyl side hydrogen silicone oil with the viscosity of 2000cps, the vinyl content of 0.2-0.3%, the viscosity of 20-50 cps and the hydrogen content of 0.1-0.15% is selected, and the components are 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 a silane modifier DA30 (An Biya special silicon Co., ltd., hydroxyl groups at two ends and methyl and vinyl groups at branched chains) in acetone to prepare a 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 stirring, and controlling the spraying rate at 70g/min.
Step 3: and (3) carrying out heat preservation reaction for 1h under the stirring condition, adding 30% methyltrimethoxysilane toluene solution, completely reacting, cooling to room temperature, and placing the filler into a baking oven at 120 ℃ for baking for 2h to obtain the heat-conducting filler.
Step 4: proportioning according to the weight portions of the components, adding vinyl-terminated silicone oil, hydrogen-containing silicone oil and heat conducting filler into a planetary stirring kettle, and stirring for 30min for the first time; 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 completion of the mixing, and refrigerating and preserving to obtain the high-temperature-resistant organosilicon heat-conducting gel.
Example 8:
the methyl side hydrogen silicone oil with the viscosity of 1000cps, the vinyl content of 0.3-0.4%, the viscosity of 20-50 cps and the hydrogen content of 0.04-0.10% is selected, and the components are 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 (An Biya special silicon Co., ltd., alkoxy is arranged at two ends, and methyl and vinyl are arranged at a branched chain) 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 stirring, and controlling the spraying rate at 60g/min.
Step 3: and (3) carrying out heat preservation reaction for 1h under the stirring condition, adding 30% methyltrimethoxysilane toluene solution, completely reacting, cooling to room temperature, and placing the filler in a baking oven at 120 ℃ for 2h to obtain the heat-conducting filler.
Step 4: proportioning according to the weight portions of the components, adding vinyl-terminated silicone oil, hydrogen-containing silicone oil and heat conducting filler into a planetary stirring kettle, and stirring for 30min for the first time; 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 completion of the mixing, and refrigerating and preserving to obtain the high-temperature-resistant organosilicon heat-conducting gel.
Comparative example 1: the injection rate was set at 80g/min against the injection rate effect.
The methyl side hydrogen silicone oil with the viscosity of 500cps, the vinyl content of 0.4-0.6%, the viscosity of 100-200 cps and the hydrogen content of 0.01-0.05% is selected, and the components are 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 (An Biya special silicon Co., ltd., hydroxyl groups at two ends and methyl and vinyl groups at branched chains) in toluene to prepare a modifier solution; the proportion 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 stirring, and controlling the spraying rate at 80g/min.
Step 3: and (3) carrying out heat preservation reaction for 1h under the stirring condition, adding 30% methyltrimethoxysilane toluene solution, completely reacting, cooling to room temperature, and baking in a baking oven at 120 ℃ for 2h to obtain the heat-conducting filler.
Step 4: proportioning according to the weight portions of the components, adding vinyl-terminated silicone oil, hydrogen-containing silicone oil and heat conducting filler into a planetary stirring kettle, and stirring for 30min for the first time; 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 completion of the mixing, and refrigerating and preserving to obtain the high-temperature-resistant organosilicon heat-conducting gel.
Comparative example 2: the injection rate was set at 150g/min against the injection rate effect.
The methyl side hydrogen silicone oil with the viscosity of 1000cps, the vinyl content of 0.3-0.4%, the viscosity of 50-100 cps and the hydrogen content of 0.04-0.1% is selected, and the components are 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 DA30 (An Biya special silicon Co., ltd., hydroxyl groups at two ends and methyl and vinyl groups at branched chains) in ethyl ester to prepare a modifier solution; the proportion 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 stirring, and controlling the spraying rate at 150g/min.
Step 3: and (3) carrying out heat preservation reaction for 1h under the stirring condition, adding 30% methyltrimethoxysilane toluene solution, completely reacting, cooling to room temperature, and baking in a baking oven at 120 ℃ for 2h to obtain the heat-conducting filler.
Step 4: proportioning according to the weight portions of the components, adding vinyl-terminated silicone oil, hydrogen-containing silicone oil and heat conducting filler into a planetary stirring kettle, and stirring for 30min for the first time; 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 completion of the mixing, and refrigerating and preserving to obtain the high-temperature-resistant organosilicon heat-conducting gel.
Comparative example 3: and comparing the non-modified compound filler.
The methyl side hydrogen silicone oil with the viscosity of 500cps, the vinyl content of 0.4-0.6%, the viscosity of 50-100 cps and the hydrogen content of 0.01-0.05% is selected, and the components are 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.
Wherein, the proportion of alumina to graphene oxide in the heat conduction filler is 8:2, the median particle diameter of the alumina powder is 20-25 mu m, the size of the micro-plate of the graphene oxide is 2-3 mu m, and the thickness is 1.0-1.2 nm.
Proportioning according to the weight portions of the components, adding vinyl-terminated silicone oil, hydrogen-containing silicone oil and heat conducting filler into a planetary stirring kettle, and stirring for 30min for the first time; 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 completion of the mixing, and refrigerating and preserving to obtain the high-temperature-resistant organosilicon 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 remainder was the same as in example 2.
According to the preparation method of the organic silicon heat-conducting gel, after the heat-conducting filler is added, the compatibility between the filler and the base rubber is poor, and after stirring and dispersing, a continuous pasty material cannot be formed, so that subsequent sample preparation and performance test cannot be performed.
Experiment 2:
after the six groups of organosilicon heat-conducting gel samples prepared above are cured completely at 100 ℃/30min, the heat-conducting property 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 testing method comprises the following steps: the completely solidified sample was placed in an oven at 150 c, taken out every 200h, cooled to room temperature, and tested for hardness, tensile strength, elongation at break and heat conductivity according to the above criteria.
The six groups of samples were tested and the data obtained are shown in Table 2.
Table 2 results of thermally conductive gel sample testing
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 rubber sheet has higher heat conductivity coefficient, lower hardness and better flexibility, and the hardness climb is smaller after high-temperature aging, so that the long-time use requirement of the electronic equipment can be met.
2. As can be seen from the data of example 6 and comparative examples 1 or 2, increasing the injection rate of the modifier resulted in insufficient modification of the filler, which resulted in rapid onset of hardness of the cured film, and failure to meet the equipment requirements.
3. The data of example 6 and example 8 show that the filler modified by hydroxyl and alkoxy has better modification effect, has good compatibility with the base rubber, and can reduce the hardness climbing of the rubber during the high-temperature aging process.
4. Compared with the embodiment 5 or 6, the embodiment 7 adopts the vinyl-terminated silicone oil of 2000cps, can well reduce the hardness of the heat-conducting gel after solidification, improve the flexibility and can meet the equipment use requirement under severe conditions.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A thermally conductive filler characterized by: the heat-conducting filler is modified by a silane modifier, and is a mixture of aluminum oxide and graphene oxide;
the silane modifier is a silane molecule, and the structural formula of the silane modifier is shown as follows:
wherein m=1, 2,3,4; r1 is alkoxy or hydroxy; r2 is one of ethenyl, propenyl or butenyl;
the aluminum oxide is one or more compound powder of spherical, spheroidal or angular type, the median particle diameter is 5-30 mu m, the graphene oxide is flaky, the size of the microchip is 1-5 mu m, and the thickness is 0.8-1.2 nm;
the heat conduction filler is aluminum oxide and graphene oxide according to the proportion of 6-8: 4~2.
2. A method for producing the heat conductive filler according to claim 1, characterized in that: 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, namely spraying the silane modifier solution into the filler, and controlling the spraying rate at 50-70 g/min;
step 3: stirring, reacting for 1-2 h at a constant temperature, adding methyltrimethoxysilane toluene solution, reacting completely, cooling to room temperature, and baking at 120 ℃ for 2-3 h.
3. The method for preparing a heat conductive filler according to claim 2, wherein: in the step 1, the organic solvent is one or a mixture of more of toluene, ethanol, ethyl acetate, acetone or methyl ethyl ketone.
4. A method of preparing a thermally conductive gel from the thermally conductive filler of claim 1, wherein: the method comprises the following steps: adding vinyl-terminated 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 preservation.
5. The method according to claim 4, 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.
6. The method according to claim 4, 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%.
7. The method according to claim 5, wherein: the inhibitor is an alkynol inhibitor; the catalyst is a platinum catalyst.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104530708A (en) * | 2014-12-16 | 2015-04-22 | 惠州力王佐信科技有限公司 | High-performance heat conduction material |
| CN105754350A (en) * | 2016-04-06 | 2016-07-13 | 深圳市欧普特工业材料有限公司 | High-heat-conductivity gel sheet and preparation method thereof |
| CN106634863A (en) * | 2016-12-30 | 2017-05-10 | 深圳市大族元亨光电股份有限公司 | Graphene based silica gel heat-conductive gasket and preparation method thereof |
| CN113444487A (en) * | 2020-09-14 | 2021-09-28 | 浙江大学山东工业技术研究院 | Bi-component addition type heat-conducting silica gel for heat dissipation of LED lighting chip |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104530708A (en) * | 2014-12-16 | 2015-04-22 | 惠州力王佐信科技有限公司 | High-performance heat conduction material |
| CN105754350A (en) * | 2016-04-06 | 2016-07-13 | 深圳市欧普特工业材料有限公司 | High-heat-conductivity gel sheet and preparation method thereof |
| CN106634863A (en) * | 2016-12-30 | 2017-05-10 | 深圳市大族元亨光电股份有限公司 | Graphene based silica gel heat-conductive gasket and preparation method thereof |
| CN113444487A (en) * | 2020-09-14 | 2021-09-28 | 浙江大学山东工业技术研究院 | Bi-component addition type heat-conducting silica gel for heat dissipation of LED lighting chip |
Non-Patent Citations (1)
| Title |
|---|
| 刘洋 等.石墨烯硅橡胶复合材料的性能研究.材料科学与工艺.2020,第28卷(第28期),72-79. * |
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