CN114292520A - Flame-retardant heat-conducting silicone gel and preparation method and application thereof - Google Patents
Flame-retardant heat-conducting silicone gel and preparation method and application thereof Download PDFInfo
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- CN114292520A CN114292520A CN202111676818.1A CN202111676818A CN114292520A CN 114292520 A CN114292520 A CN 114292520A CN 202111676818 A CN202111676818 A CN 202111676818A CN 114292520 A CN114292520 A CN 114292520A
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000003063 flame retardant Substances 0.000 title claims abstract description 71
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 238000001879 gelation Methods 0.000 title description 2
- 239000000945 filler Substances 0.000 claims abstract description 57
- 239000000499 gel Substances 0.000 claims abstract description 41
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 23
- 239000002318 adhesion promoter Substances 0.000 claims abstract description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000741 silica gel Substances 0.000 claims abstract description 18
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 15
- 239000010703 silicon Substances 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims description 155
- 229920002545 silicone oil Polymers 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 42
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 23
- 239000001257 hydrogen Substances 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 23
- 239000000843 powder Substances 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 21
- 230000007062 hydrolysis Effects 0.000 claims description 18
- 238000006460 hydrolysis reaction Methods 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 18
- 239000000347 magnesium hydroxide Substances 0.000 claims description 17
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 17
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 15
- 238000001291 vacuum drying Methods 0.000 claims description 14
- 238000005303 weighing Methods 0.000 claims description 12
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 4
- 239000011231 conductive filler Substances 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229910003460 diamond Inorganic materials 0.000 claims description 2
- 239000010432 diamond Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 125000003700 epoxy group Chemical group 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 150000004767 nitrides Chemical class 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 125000005529 alkyleneoxy group Chemical group 0.000 claims 1
- 125000005395 methacrylic acid group Chemical group 0.000 claims 1
- -1 methoxy, ethoxy Chemical group 0.000 claims 1
- 230000017525 heat dissipation Effects 0.000 abstract description 9
- 238000010438 heat treatment Methods 0.000 abstract description 6
- 239000003377 acid catalyst Substances 0.000 description 16
- 235000011837 pasties Nutrition 0.000 description 8
- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-UHFFFAOYSA-N 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- FDGQPSKFXQJTLG-UHFFFAOYSA-N O(C)C(=C(C(=O)O)C)OCC Chemical group O(C)C(=C(C(=O)O)C)OCC FDGQPSKFXQJTLG-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003302 alkenyloxy group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
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- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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Abstract
A flame-retardant heat-conducting silicone gel and a preparation method and application thereof belong to the technical field of heat-conducting gel. The flame-retardant heat-conducting silicone gel comprises the following raw materials: adding organosilicon, heat-conducting filler, silane coupling agent, adhesion promoter and catalyst; the addition type organic silicon accounts for 7-30% of the total mass of the raw materials, the silane coupling agent accounts for 0.3-3% of the mass of the heat-conducting filler, the adhesion promoter accounts for 0.1-1% of the mass of the addition type organic silicon, and the catalyst accounts for 0.1-0.5% of the mass of the addition type organic silicon. The invention also provides a preparation method and application of the flame-retardant heat-conducting silica gel. The flame-retardant heat-conducting silica gel prepared by the invention is suitable for being applied to heat dissipation systems of power batteries and electronic devices, and has the characteristics of simple operation, high-efficiency heat conduction, high-efficiency flame retardance and good adhesion with heating components and heat dissipation components.
Description
Technical Field
The invention belongs to the technical field of heat-conducting gel, and particularly relates to flame-retardant heat-conducting silicone gel and a preparation method and application thereof.
Background
With the vigorous development of the new energy automobile industry, the safety performance of the power battery gradually becomes the focus of attention. In addition to the battery's own performance, the battery's thermal management issues have a significant impact on the safety and useful life of the battery. Firstly, the temperature of the battery directly affects the energy and power performance in use, and defects in the production and manufacturing process or improper operation in the use process can cause local overheating of the battery, further cause chain exothermic reaction, finally cause serious accidents of smoking, fire and even explosion, and threaten the life safety of vehicle drivers and passengers. Secondly, the service life of the battery is indirectly influenced by the working and storage temperature of the battery, the service life of the battery is accelerated by overhigh temperature, and the generally suitable temperature is about 10-30 ℃. The large-scale power battery relatively reduces the ratio of the surface area to the volume of the battery, so that the internal heat of the battery is not easy to dissipate, the problems of uneven internal temperature and local temperature rise can occur, and the aging of the battery is accelerated. Therefore, when the thermal management system of the power battery is designed, not only effective heat dissipation needs to be carried out when the temperature of the battery is high, and thermal runaway accidents are prevented, but also the battery at a high temperature is prevented from being attenuated too fast, so that the service life of the whole battery pack is ensured.
In order to effectively discharge the heat in the power battery, the reasonable and effective utilization of the heat management material is particularly important. The battery module has a poor heat dissipation effect due to the high thermal resistance when in direct contact with the heat dissipation aluminum case. Therefore, a certain amount of thermal interface material needs to be filled between the two to achieve the effects of improving heat conduction, filling gaps and cushioning. In consideration of the working environment of the battery, the thermal interface material used is required to have not only good thermal conductivity but also excellent flame retardancy as well as compressibility and resilience.
The thermal interface material is a composite material which takes a flexible high polymer material as a matrix and is combined with a heat conduction filler, and can effectively fill up gaps between solid interfaces and increase effective contact area, thereby improving heat dissipation efficiency. The key to influence the thermal conductivity and flame retardant ability of the thermal interface material is the type and nature of the thermally conductive filler.
The invention patent with publication number CN108164992B discloses a heat-conducting rubber sheet material containing heat-conducting filler and flame retardant, which adopts the mixing way of an internal mixer to realize the uniform mixing of materials such as polyurethane, heat-conducting filler and flame retardant, and adopts the hot-pressing way to obtain the heat-conducting rubber sheet material. However, the heat-conducting filler selected by the method has high proportion and poor flame retardance, so that the flame retardant capability of the whole material is poor; in addition, the heat-conducting rubber sheet material has high hardness, has poor adhesion with the battery module and the heat dissipation device, and is easy to fall off in the using process; moreover, a large amount of air bubbles are inevitably introduced into the mixture in the production process, so that the intrinsic thermal resistance of the material is seriously increased. The invention patent with publication number CN108034255A discloses a flame-retardant heat-conducting gasket material with organic silicon as a matrix and containing a brominated flame retardant. However, although the addition of the halogen flame retardant can improve the flame retardant capability of the material, the halogen flame retardant can generate harmful gas while resisting flame, and has great pollution to the environment; in addition, the heat conducting gasket still has the problem of poor adhesion of the material invented in patent CN108164992B in the using process, and has a great potential safety hazard. The invention patent with publication number CN111518392A discloses a flame-retardant heat-conducting silicone gel containing heat-conducting filler and flame retardant, which can better avoid the problem of poor adhesion presented in the above patents CN108164992B and CN 108034255A. However, the components of the gel are mainly alpha-alumina and hexagonal boron nitride heat-conducting fillers with poor flame retardance, and the content of the flame retardant is low, so that the overall flame retardance of the gel is poor; furthermore, because of the poor compatibility of the heat-conducting filler and the organic silicon matrix, the thermal conductivity of the finally prepared gel is low.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to design and provide a flame-retardant heat-conducting silicone gel, and a preparation method and application thereof. The gel solves the problems of poor sealing property and poor heat conduction performance between the flame-retardant heat conducting strip and a heating body and a heat radiating body when the flame-retardant heat conducting strip is used, and solves the problem that the existing gel is difficult to simultaneously meet the characteristics of high heat conduction and high flame retardance. The gel material provided by the invention takes the heat-conducting filler with high flame retardance as a main component, not only realizes good adhesion between the gel material and a heating body and a heat radiation body and ensures high coverage rate filling between the heating body and the heat radiation body, but also has the characteristics of high heat conduction and high flame retardance, and effectively avoids safety accidents while realizing high-efficiency heat radiation.
In order to achieve the purpose, the invention adopts the following technical scheme:
the flame-retardant heat-conducting silicone gel is characterized by comprising the following raw material components: adding organosilicon, heat-conducting filler, silane coupling agent, adhesion promoter and catalyst;
the addition type organic silicon accounts for 7-30% of the total mass of the raw materials, the silane coupling agent accounts for 0.3-3% of the mass of the heat-conducting filler, the adhesion promoter accounts for 0.1-1% of the mass of the addition type organic silicon, and the catalyst accounts for 0.1-0.5% of the mass of the addition type organic silicon. The crosslinking degree of the cured matrix is adjusted by adjusting the proportion of different types of silicone oil, so that the mechanical property of the silicone gel is regulated and controlled.
The flame-retardant heat-conducting silica gel is characterized in that the heat-conducting filler accounts for 10-18% of the total mass of the raw materials, and the silane coupling agent accounts for 0.5-2% of the mass of the heat-conducting filler.
The flame-retardant heat-conducting silicone gel is characterized in that the addition type organic silicone comprises vinyl terminated silicone oil, side chain hydrogen-containing silicone oil and hydrogen terminated silicone oil or comprises vinyl terminated silicone oil and side chain hydrogen-containing silicone oil, and the normal-temperature viscosity of the addition type organic silicone is 50-3000 cps. When the viscosity of the silicone oil is lower than 50cps, the heat-conducting filler is easy to settle in the using process; when the viscosity is higher than 3000cps, it is difficult to uniformly disperse the heat conductive filler in the silicone oil.
The flame-retardant heat-conducting silicone gel is characterized in that the heat-conducting filler comprises the following components in percentage by volume: 70-100% of flame-retardant heat-conducting filler and 0-30% of conventional heat-conducting filler, preferably, the flame-retardant heat-conducting filler comprises one or more of aluminum hydroxide and magnesium hydroxide, the conventional heat-conducting filler comprises one or more of metal powder, metal oxide, metal nitride, metal carbide and diamond, the average particle size of the aluminum hydroxide and the average particle size of the magnesium hydroxide are both 1-50 microns, preferably 2-30 microns, and the average particle size of the conventional heat-conducting filler is 1-50 microns, preferably 2-20 microns. The aluminum hydroxide and the magnesium hydroxide not only have good flame retardant effect, but also do not contain halogen elements such as bromine, chlorine and the like, and can inhibit smoke and prevent pollution. The conventional heat-conducting powder is beneficial to reducing the internal thermal resistance of the silica gel, thereby improving the heat-conducting efficiency.
The flame-retardant heat-conducting silica gel is characterized in that the silane coupling agent has one or more of vinyl, methoxy, ethoxy, methacrylic acid group and epoxy group. The purpose is to improve the compatibility between the heat-conducting filler and the matrix silicone oil. The adhesion promoter is a polymer comprising at least one group of alkoxy, alkenyloxy, epoxy, aliphatic group and hydrosilyl, and aims to improve the adhesion strength between the solidified gel and the heating body and the heat radiator. The catalyst comprises one or more of platinum chloride, chloroplatinic acid and a compound of the chloroplatinic acid and olefin, and aims to induce a crosslinking reaction between vinyl silicone oil and hydrogen-containing silicone oil.
The preparation method of the flame-retardant heat-conducting silicone gel is characterized by comprising the following steps:
(1) weighing heat-conducting filler, pre-stirring, weighing silane coupling agent, adding the silane coupling agent into water, hydrolyzing, stirring and mixing with the pre-stirred heat-conducting filler uniformly, and drying in vacuum to obtain surface-modified heat-conducting filler;
(2) taking addition type organic silicon and an adhesion promoter, stirring and mixing the addition type organic silicon and the adhesion promoter with the surface modified heat-conducting filler obtained in the step (1) uniformly to form a paste, and cooling to room temperature to obtain a mixture;
(3) and (3) dropwise adding a catalyst into the mixture obtained in the step (2), and continuously stirring and uniformly mixing to obtain the flame-retardant heat-conducting silica gel.
The preparation method is characterized in that the mass of water in the step (1) is 20-100% of the mass of the silane coupling agent, and the hydrolysis conditions are as follows: the hydrolysis time is 0.5-3 h, the hydrolysis temperature is 20-65 ℃, the stirring mode comprises a planetary stirrer, and the stirring conditions are as follows: stirring speed is 50-120 r/min, stirring time is 1-4 h, stirring temperature is 20-150 ℃, and the vacuum drying conditions are as follows: the temperature is 100-150 ℃, and the vacuum degree is less than or equal to-0.1 MPa.
The preparation method is characterized in that the stirring mode in the step (2) comprises a planetary stirrer, and the stirring conditions are as follows: the stirring speed is 50-120 r/min, the stirring time is 0.5-2 h, the stirring temperature is 60-100 ℃, and the vacuum degree is less than or equal to-0.1 MPa. The purpose of high-temperature stirring is to reduce the viscosity of the silicone oil, and the full dispersion of the heat-conducting filler is easier to realize by matching with a vacuum state.
The preparation method is characterized in that the stirring conditions in the step (3) are as follows: the stirring speed is 50-80 r/min, the stirring time is 20-60 min, the stirring temperature is 20-25 ℃, and the vacuum degree is less than or equal to-0.1 MPa. The purpose of using a lower stirring speed is to prevent heat generation by friction during stirring, which leads to premature crosslinking of the silica gel.
The flame-retardant heat-conducting silica gel is applied to high heat-conducting and high flame-retardant thermal interface materials.
Compared with the prior art, the invention has the following beneficial effects:
the flame-retardant heat-conducting silica gel prepared by the invention is suitable for being applied to heat dissipation systems of power batteries and electronic devices, and has the characteristics of simple operation, high-efficiency heat conduction, high-efficiency flame retardance and good adhesion with heating components and heat dissipation components. By adjusting the formula of the vinyl silicone oil and the hydrogen-containing silicone oil and the proportion of the raw materials such as the heat-conducting filler, the silane coupling agent, the adhesion promoter and the like, the flame retardant capability, the heat-conducting capability and the mechanical property of the silicone gel can be continuously optimized and adjusted, so that the silicone gel can meet different performance requirements of systems such as power batteries, electronic devices and the like in practical application.
Drawings
FIG. 1 shows the morphology of a flame-retardant thermally conductive filler-magnesium hydroxide;
FIG. 2 shows the fracture morphology of the cured gel.
Detailed Description
The invention will be further explained with reference to the drawings and examples.
Example 1:
the preparation method of the flame-retardant heat-conducting silicone gel comprises the following steps:
(1) 400g of flame-retardant heat-conducting filler 5 mu m magnesium hydroxide, 700g of 20 mu m magnesium hydroxide and 180g of heat-conducting filler 15 mu m spherical alumina are weighed and placed in a planetary stirrer in advance for pre-stirring for 10min, the rotating speed of the stirrer is 100r/min, and the temperature is raised to 90 ℃ in the stirring process. Then, a modifying solution containing 6.4g of gamma-glycidoxypropyltrimethoxysilane and 1.6g of water (the hydrolysis temperature of the silane coupling agent is 50 ℃ and the hydrolysis time is 1 hour) which is hydrolyzed in advance is added into the pre-stirred powder, and the stirring is continued for 1 hour at the rotation speed of 100 r/min. All the above stirring processes were carried out under normal pressure. After stirring, placing the modified powder in a vacuum drying oven at 150 ℃ for vacuum drying for 3h, wherein the vacuum degree is less than or equal to-0.1 MPa.
(2) 690g of the modified powder is weighed into a stirrer, and then 98.5g, 20.5g, 8.7g and 2g of 1000cps viscosity vinyl-terminated silicone oil, 200cps viscosity side hydrogen-containing silicone oil, 50cps viscosity end hydrogen-containing silicone oil and allyl trimethoxy silane adhesion promoter are added. The stirring speed is set to be 100r/min, the stirring time is 30min, the stirring temperature is 70 ℃, and the vacuum degree is kept to be less than or equal to-0.1 MPa in the stirring process. After the stirring was completed, the obtained pasty mixture was cooled to 20 ℃.
(3) And (3) weighing 0.3g of chloroplatinic acid catalyst, adding the chloroplatinic acid catalyst into the mixture in the step (2), continuously stirring for 20min at the stirring speed of 50r/min and the stirring temperature of 20 ℃, and keeping the vacuum degree to be less than or equal to-0.1 MPa in the stirring process. And obtaining the flame-retardant heat-conducting silica gel after stirring.
Wherein, the morphology of the flame-retardant heat-conducting filler-magnesium hydroxide is shown in figure 1, and the fracture morphology of the cured gel is shown in figure 2.
Example 2:
the preparation method of the flame-retardant heat-conducting silicone gel comprises the following steps:
(1) 400g of flame-retardant heat-conducting filler 5 mu m magnesium hydroxide, 700g of 20 mu m magnesium hydroxide and 180g of heat-conducting filler 15 mu m spherical alumina are weighed and placed in a planetary stirrer in advance for pre-stirring for 10min, the rotating speed of the stirrer is 100r/min, and the temperature is raised to 90 ℃ in the stirring process. Then, a modifying solution containing 6.4g of gamma-glycidoxypropyltrimethoxysilane and 1.6g of water (the hydrolysis temperature of the silane coupling agent is 50 ℃ and the hydrolysis time is 1 hour) which is hydrolyzed in advance is added into the pre-stirred powder, and the stirring is continued for 1 hour at the rotation speed of 100 r/min. All the above stirring processes were carried out under normal pressure. After stirring, placing the modified powder in a vacuum drying oven at 150 ℃ for vacuum drying for 3h, wherein the vacuum degree is less than or equal to-0.1 MPa.
(2) 730g of the modified powder is weighed into a stirrer, and then 98.5g, 20.5g, 8.7g and 2g of 1000cps viscosity vinyl-terminated silicone oil, 200cps viscosity side hydrogen-containing silicone oil, 50cps viscosity end hydrogen-containing silicone oil and allyl trimethoxy silane adhesion promoter are added. The stirring speed is set to be 100r/min, the stirring time is 30min, the stirring temperature is 70 ℃, and the vacuum degree is kept to be less than or equal to-0.1 MPa in the stirring process. After the stirring was completed, the obtained pasty mixture was cooled to 20 ℃.
(3) And (3) weighing 0.3g of chloroplatinic acid catalyst, adding the chloroplatinic acid catalyst into the mixture in the step (2), continuously stirring for 20min at the stirring speed of 50r/min and the stirring temperature of 20 ℃, and keeping the vacuum degree to be less than or equal to-0.1 MPa in the stirring process. And obtaining the flame-retardant heat-conducting silica gel after stirring.
Example 3:
the preparation method of the flame-retardant heat-conducting silicone gel comprises the following steps:
(1) 200g of flame-retardant heat-conducting filler 5 mu m magnesium hydroxide, 900g of 20 mu m magnesium hydroxide and 180g of heat-conducting filler 15 mu m spherical alumina are weighed and placed in a planetary stirrer in advance for pre-stirring for 10min, the rotating speed of the stirrer is 100r/min, and the temperature is raised to 90 ℃ in the stirring process. Then, a modifying solution containing 6.4g of gamma-glycidoxypropyltrimethoxysilane and 1.6g of water (the hydrolysis temperature of the silane coupling agent is 50 ℃ and the hydrolysis time is 1 hour) which is hydrolyzed in advance is added into the pre-stirred powder, and the stirring is continued for 1 hour at the rotation speed of 100 r/min. All the above stirring processes were carried out under normal pressure. After stirring, placing the modified powder in a vacuum drying oven at 150 ℃ for vacuum drying for 3h, wherein the vacuum degree is less than or equal to-0.1 MPa.
(2) 730g of the modified powder is weighed into a stirrer, and then 98.5g, 20.5g, 8.7g and 2g of 1000cps viscosity vinyl-terminated silicone oil, 200cps viscosity side hydrogen-containing silicone oil, 50cps viscosity end hydrogen-containing silicone oil and allyl trimethoxy silane adhesion promoter are added. The stirring speed is set to be 100r/min, the stirring time is 30min, the stirring temperature is 70 ℃, and the vacuum degree is kept to be less than or equal to-0.1 MPa in the stirring process. After the stirring was completed, the obtained pasty mixture was cooled to 20 ℃.
(3) And (3) weighing 0.3g of chloroplatinic acid catalyst, adding the chloroplatinic acid catalyst into the mixture in the step (2), continuously stirring for 20min at the stirring speed of 50r/min and the stirring temperature of 20 ℃, and keeping the vacuum degree to be less than or equal to-0.1 MPa in the stirring process. And obtaining the flame-retardant heat-conducting silica gel after stirring.
Example 4:
(1) 400g of flame-retardant heat-conducting filler 5 mu m magnesium hydroxide, 700g of 20 mu m magnesium hydroxide and 180g of heat-conducting filler 15 mu m spherical alumina are weighed and placed in a planetary stirrer in advance for pre-stirring for 10min, the rotating speed of the stirrer is 100r/min, and the temperature is raised to 90 ℃ in the stirring process. Then, a modifying solution containing 12.8g of gamma-glycidoxypropyltrimethoxysilane and 3.2g of water (the hydrolysis temperature of the silane coupling agent is 50 ℃ and the hydrolysis time is 1 hour) which is hydrolyzed in advance is added into the pre-stirred powder, and the stirring is continued for 1 hour at the rotation speed of 100 r/min. All the above stirring processes were carried out under normal pressure. After stirring, placing the modified powder in a vacuum drying oven at 150 ℃ for vacuum drying for 3h, wherein the vacuum degree is less than or equal to-0.1 MPa.
(2) 730g of the modified powder is weighed into a stirrer, and then 98.5g, 20.5g, 8.7g and 2g of 1000cps viscosity vinyl-terminated silicone oil, 200cps viscosity side hydrogen-containing silicone oil, 50cps viscosity end hydrogen-containing silicone oil and allyl trimethoxy silane adhesion promoter are added. The stirring speed is set to be 100r/min, the stirring time is 30min, the stirring temperature is 70 ℃, and the vacuum degree is kept to be less than or equal to-0.1 MPa in the stirring process. After the stirring was completed, the obtained pasty mixture was cooled to 20 ℃.
(3) And (3) weighing 0.3g of chloroplatinic acid catalyst, adding the chloroplatinic acid catalyst into the mixture in the step (2), continuously stirring for 20min at the stirring speed of 50r/min and the stirring temperature of 20 ℃, and keeping the vacuum degree to be less than or equal to-0.1 MPa in the stirring process. And obtaining the flame-retardant heat-conducting silica gel after stirring.
Example 5:
(1) 400g of flame-retardant heat-conducting filler 5 mu m aluminum hydroxide, 700g of 20 mu m aluminum hydroxide and 180g of heat-conducting filler 15 mu m spherical aluminum oxide are weighed and placed in a planetary stirrer in advance for pre-stirring for 10min, the rotating speed of the stirrer is 100r/min, and the temperature is raised to 90 ℃ in the stirring process. Then, a modifying solution containing 6.4g of gamma-glycidoxypropyltrimethoxysilane and 1.6g of water (the hydrolysis temperature of the silane coupling agent is 50 ℃ and the hydrolysis time is 1 hour) which is hydrolyzed in advance is added into the pre-stirred powder, and the stirring is continued for 1 hour at the rotation speed of 100 r/min. All the above stirring processes were carried out under normal pressure. After stirring, placing the modified powder in a vacuum drying oven at 150 ℃ for vacuum drying for 3h, wherein the vacuum degree is less than or equal to-0.1 MPa.
(2) 730g of the modified powder is weighed into a stirrer, and then 98.5g, 20.5g, 8.7g and 2g of 1000cps viscosity vinyl-terminated silicone oil, 200cps viscosity side hydrogen-containing silicone oil, 50cps viscosity end hydrogen-containing silicone oil and allyl trimethoxy silane adhesion promoter are added. The stirring speed is set to be 100r/min, the stirring time is 30min, the stirring temperature is 70 ℃, and the vacuum degree is kept to be less than or equal to-0.1 MPa in the stirring process. After the stirring was completed, the obtained pasty mixture was cooled to 20 ℃.
(3) And (3) weighing 0.3g of chloroplatinic acid catalyst, adding the chloroplatinic acid catalyst into the mixture in the step (2), continuously stirring for 20min at the stirring speed of 50r/min and the stirring temperature of 20 ℃, and keeping the vacuum degree to be less than or equal to-0.1 MPa in the stirring process. And obtaining the flame-retardant heat-conducting silica gel after stirring.
Example 6:
(1) 400g of flame-retardant heat-conducting filler 5 mu m aluminum hydroxide, 700g of 20 mu m aluminum hydroxide and 180g of heat-conducting filler 15 mu m spherical aluminum oxide are weighed and placed in a planetary stirrer in advance for pre-stirring for 10min, the rotating speed of the stirrer is 100r/min, and the temperature is raised to 90 ℃ in the stirring process. Then, a modifying solution containing 12.8g of gamma-glycidoxypropyltrimethoxysilane and 3.2g of water (the hydrolysis temperature of the silane coupling agent is 50 ℃ and the hydrolysis time is 1 hour) which is hydrolyzed in advance is added into the pre-stirred powder, and the stirring is continued for 1 hour at the rotation speed of 100 r/min. All the above stirring processes were carried out under normal pressure. After stirring, placing the modified powder in a vacuum drying oven at 150 ℃ for vacuum drying for 3h, wherein the vacuum degree is less than or equal to-0.1 MPa.
(2) 730g of the modified powder is weighed into a stirrer, and then 98.5g, 20.5g, 8.7g and 2g of 1000cps viscosity vinyl-terminated silicone oil, 200cps viscosity side hydrogen-containing silicone oil, 50cps viscosity end hydrogen-containing silicone oil and allyl trimethoxy silane adhesion promoter are added. The stirring speed is set to be 100r/min, the stirring time is 30min, the stirring temperature is 70 ℃, and the vacuum degree is kept to be less than or equal to-0.1 MPa in the stirring process. After the stirring was completed, the obtained pasty mixture was cooled to 20 ℃.
(3) And (3) weighing 0.3g of chloroplatinic acid catalyst, adding the chloroplatinic acid catalyst into the mixture in the step (2), continuously stirring for 20min at the stirring speed of 50r/min and the stirring temperature of 20 ℃, and keeping the vacuum degree to be less than or equal to-0.1 MPa in the stirring process. And obtaining the flame-retardant heat-conducting silica gel after stirring.
Comparative example 1:
(1) 400g of flame-retardant heat-conducting filler 5 mu m magnesium hydroxide, 700g of 20 mu m magnesium hydroxide and 180g of heat-conducting filler 15 mu m spherical alumina are weighed and placed in a planetary stirrer in advance for pre-stirring for 10min, the rotating speed of the stirrer is 100r/min, and the temperature is raised to 90 ℃ in the stirring process. All the above stirring processes were carried out under normal pressure.
(2) 730g of the modified powder is weighed into a stirrer, and then 98.5g, 20.5g, 8.7g and 2g of 1000cps viscosity vinyl-terminated silicone oil, 200cps viscosity side hydrogen-containing silicone oil, 50cps viscosity end hydrogen-containing silicone oil and allyl trimethoxy silane adhesion promoter are added. The stirring speed is set to be 100r/min, the stirring time is 30min, the stirring temperature is 70 ℃, and the vacuum degree is kept to be less than or equal to-0.1 MPa in the stirring process. After the stirring was completed, the obtained pasty mixture was cooled to 20 ℃.
(3) And (3) weighing 0.3g of chloroplatinic acid catalyst, adding the chloroplatinic acid catalyst into the mixture in the step (2), continuously stirring for 20min at the stirring speed of 50r/min and the stirring temperature of 20 ℃, and keeping the vacuum degree to be less than or equal to-0.1 MPa in the stirring process. And obtaining the flame-retardant heat-conducting silica gel after stirring.
Comparative example 2:
(1) 400g of flame-retardant heat-conducting filler 5 mu m aluminum hydroxide, 700g of 20 mu m aluminum hydroxide and 180g of heat-conducting filler 15 mu m spherical aluminum oxide are weighed and placed in a planetary stirrer in advance for pre-stirring for 10min, the rotating speed of the stirrer is 100r/min, and the temperature is raised to 90 ℃ in the stirring process. All the above stirring processes were carried out under normal pressure.
(2) 730g of the modified powder is weighed into a stirrer, and then 98.5g, 20.5g, 8.7g and 2g of 1000cps viscosity vinyl-terminated silicone oil, 200cps viscosity side hydrogen-containing silicone oil, 50cps viscosity end hydrogen-containing silicone oil and allyl trimethoxy silane adhesion promoter are added. The stirring speed is set to be 100r/min, the stirring time is 30min, the stirring temperature is 70 ℃, and the vacuum degree is kept to be less than or equal to-0.1 MPa in the stirring process. After the stirring was completed, the obtained pasty mixture was cooled to 20 ℃.
(3) And (3) weighing 0.3g of chloroplatinic acid catalyst, adding the chloroplatinic acid catalyst into the mixture in the step (2), continuously stirring for 20min at the stirring speed of 50r/min and the stirring temperature of 20 ℃, and keeping the vacuum degree to be less than or equal to-0.1 MPa in the stirring process. And obtaining the flame-retardant heat-conducting silica gel after stirring.
The performance parameters of the flame-retardant heat-conducting silicone gels prepared in examples 1 to 6 and comparative examples 1 to 2 were tested, and the test results of the gels are shown in table 1. The curing temperature for all gel samples was 100 ℃ and the curing time was 3 h.
TABLE 1 TABLE of Performance parameters of the flame-retardant thermally conductive silicone gels obtained in examples 1 to 6 and comparative examples 1 to 2
As shown in Table 1, the flame-retardant heat-conducting silicone gel prepared by the method and the formula of the invention has the advantages of high flame retardance, high heat conductivity, soft texture and excellent resilience. The flame-retardant heat-conducting silicone gel prepared in example 4 has the best performance. Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, and although the best embodiments are described in detail, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The flame-retardant heat-conducting silicone gel is characterized by comprising the following raw material components: adding organosilicon, heat-conducting filler, silane coupling agent, adhesion promoter and catalyst;
the addition type organic silicon accounts for 7-30% of the total mass of the raw materials, the silane coupling agent accounts for 0.3-3% of the mass of the heat-conducting filler, the adhesion promoter accounts for 0.1-1% of the mass of the addition type organic silicon, and the catalyst accounts for 0.1-0.5% of the mass of the addition type organic silicon.
2. The flame-retardant heat-conducting silicone gel according to claim 1, wherein the heat-conducting filler accounts for 10-18% of the total mass of the raw materials, and the silane coupling agent accounts for 0.5-2% of the mass of the heat-conducting filler.
3. The flame-retardant heat-conducting silicone gel according to claim 1, wherein the addition silicone comprises a vinyl-terminated silicone oil, a side chain hydrogen-containing silicone oil and a hydrogen-terminated silicone oil or comprises a vinyl-terminated silicone oil and a side chain hydrogen-containing silicone oil, and the addition silicone has a room-temperature viscosity of 50 to 3000 cps.
4. The flame-retardant heat-conductive silicone gel according to claim 1, wherein the heat-conductive filler comprises the following components in percentage by volume: 70-100% of flame-retardant heat-conducting filler and 0-30% of conventional heat-conducting filler, preferably, the flame-retardant heat-conducting filler comprises one or more of aluminum hydroxide and magnesium hydroxide, the conventional heat-conducting filler comprises one or more of metal powder, metal oxide, metal nitride, metal carbide and diamond, the average particle size of the aluminum hydroxide and the average particle size of the magnesium hydroxide are both 1-50 microns, preferably 2-30 microns, and the average particle size of the conventional heat-conducting filler is 1-50 microns, preferably 2-20 microns.
5. The flame-retardant, thermally conductive silicone gel according to claim 1, wherein said silane coupling agent has a group comprising one or more of vinyl, methoxy, ethoxy, methacrylic, and epoxy groups, said adhesion promoter is a polymer comprising at least one of alkoxy, alkyleneoxy, epoxy, aliphatic, and hydrosilyl groups, and said catalyst comprises one or more of platinum chloride, chloroplatinic acid, and a complex of chloroplatinic acid and an olefin.
6. The method for preparing the flame-retardant heat-conducting silicone gel according to claim 1, comprising the steps of:
(1) weighing heat-conducting filler, pre-stirring, weighing silane coupling agent, adding the silane coupling agent into water, hydrolyzing, stirring and mixing with the pre-stirred heat-conducting filler uniformly, and drying in vacuum to obtain surface-modified heat-conducting filler;
(2) taking addition type organic silicon and an adhesion promoter, stirring and mixing the addition type organic silicon and the adhesion promoter with the surface modified heat-conducting filler obtained in the step (1) uniformly to form a paste, and cooling to room temperature to obtain a mixture;
(3) and (3) dropwise adding a catalyst into the mixture obtained in the step (2), and continuously stirring and uniformly mixing to obtain the flame-retardant heat-conducting silica gel.
7. The method according to claim 6, wherein the water in the step (1) accounts for 20 to 100% by mass of the silane coupling agent, and the hydrolysis conditions are as follows: the hydrolysis time is 0.5-3 h, the hydrolysis temperature is 20-65 ℃, the stirring mode comprises a planetary stirrer, and the stirring conditions are as follows: stirring speed is 50-120 r/min, stirring time is 1-4 h, stirring temperature is 20-150 ℃, and the vacuum drying conditions are as follows: the temperature is 100-150 ℃, and the vacuum degree is less than or equal to-0.1 MPa.
8. The method according to claim 6, wherein the stirring in the step (2) comprises a planetary stirrer, and the stirring is performed under the following conditions: the stirring speed is 50-120 r/min, the stirring time is 0.5-2 h, the stirring temperature is 60-100 ℃, and the vacuum degree is less than or equal to-0.1 MPa.
9. The method according to claim 9, wherein the stirring conditions in the step (3) are: the stirring speed is 50-80 r/min, the stirring time is 20-60 min, the stirring temperature is 20-25 ℃, and the vacuum degree is less than or equal to-0.1 MPa.
10. The flame-retardant, thermally conductive silicone gel according to any one of claims 1 to 5, which is used as a high-thermal-conductivity and high-flame-retardant thermal interface material.
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| CN102942895A (en) * | 2012-11-15 | 2013-02-27 | 烟台德邦科技有限公司 | Heat-conduction electronic potting adhesive and preparation method thereof |
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