CN116355572A - Heat conducting gel composition, heat conducting gel, preparation method of heat conducting gel and heating component - Google Patents

Heat conducting gel composition, heat conducting gel, preparation method of heat conducting gel and heating component Download PDF

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CN116355572A
CN116355572A CN202310333062.3A CN202310333062A CN116355572A CN 116355572 A CN116355572 A CN 116355572A CN 202310333062 A CN202310333062 A CN 202310333062A CN 116355572 A CN116355572 A CN 116355572A
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heat
antioxidant
conducting gel
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韩驰旻
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Guangzhou Yinhan Energy Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • C09J167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

The embodiment of the application provides a heat-conducting gel composition, a heat-conducting gel, a preparation method of the heat-conducting gel composition and a heating component, and relates to the field of functional glue. The heat-conducting gel composition comprises an A component and a B component, wherein the A component contains polyhydric alcohol for providing hydroxyl, the B component contains polybasic acid anhydride for providing acid anhydride groups, and the A component and/or the B component also contains heat-conducting filler; the molar ratio of the hydroxyl groups to the anhydride groups in the component A and the component B is 1:1-1:2. The heat-conducting gel formed by using the heat-conducting gel composition in the embodiment of the application almost does not contain D3-D10 small molecular ring bodies, so that the occurrence of short circuit accidents of a circuit can be reduced, the use temperature range is wider, and the heat-conducting gel composition is not easy to harden and embrittle under the low-temperature condition.

Description

Heat conducting gel composition, heat conducting gel, preparation method of heat conducting gel and heating component
Technical Field
The application relates to the field of functional glue, in particular to a heat-conducting gel composition, a heat-conducting gel, a preparation method of the heat-conducting gel and a heating element.
Background
Electronic circuits such as consumer electronics and new energy automobiles use heat conductive gel as a heat-radiating adhesive for heat-generating components, and heat-radiating components. At present, the mainstream heat-conducting gel is a gel base of the heat-conducting gel, and organic silicon resin has D3-D10 low-mixing small molecular ring bodies (namely methyl cyclosiloxane, wherein D3 is hexamethyl cyclotrisiloxane, D4 is octamethyl cyclotetrasiloxane, D5 is decamethyl cyclopentasiloxane, and so on, D10 is twenty methyl cyclodecasiloxane), and the small molecular ring bodies pollute electronic circuits, so that the abnormal risks such as circuit short circuits and the like are caused.
In order to reduce the content of D3-D10 small molecular ring bodies in the organic silicon resin, the main current method is to use a thin film evaporator to carry out the low-pressure treatment on the silicone oil, but a certain residual exists.
There are some prior arts (for example, described in CN110003438A, CN109181279A, CN102277121A, CN108164992 a) that use polymer polyols such as polyether polyols and hydroxyl-terminated polybutadiene, and isocyanate-cured products instead of silicones to prepare heat-conductive gels, but Tg (Glass Transition Temperature ) of the cured products is about 0-20 ℃, and the cured products become hard and brittle in low-temperature environments, and have poor soft elastic properties compared with silicone resins, which cannot meet the requirements of wide-temperature use scenes such as automobiles.
Disclosure of Invention
The embodiment of the application aims to provide a heat-conducting gel composition, a heat-conducting gel, a preparation method thereof and a heating element, wherein the heat-conducting gel does not contain a D3-D10 small molecule ring body, when the heat-conducting gel is used in the heating element, a circuit is not easy to short, the using temperature range of the heat-conducting gel is wider, and the heat-conducting gel is not easy to harden and embrittle under the low-temperature condition.
In a first aspect, embodiments of the present application provide a thermally conductive gel composition, including an a-component and a B-component, wherein the a-component contains a polyol for providing hydroxyl groups, the B-component contains a polybasic acid anhydride for providing acid anhydride groups, and the a-component and/or the B-component further contains a thermally conductive filler; the molar ratio of hydroxyl groups to anhydride groups in the component A and the component B is 1:1-1:2.
In the technical scheme, when the heat-conducting gel composition is used, hydroxyl groups in polyol and anhydride groups in polybasic acid anhydride can be polymerized to generate polymers, but the heat-conducting filler does not participate in the reaction, but can be dispersed in the polymers generated by the polyol and the polybasic acid anhydride, so that the heat-conducting gel can be generated. The polymer formed by the polyalcohol and the polyanhydride is used as a matrix material (namely a gum base), so that the polymer can play a role of bearing the heat conducting filler, has viscosity, enables the heat conducting gel to be adhered to the surfaces of articles such as heating elements and the like, and reduces the interface thermal resistance of the heating power element and the heat dissipation element; the heat conducting filler can increase the heat conductivity coefficient of the heat conducting gel, so that heat can be rapidly dispersed from the heat conducting gel, the service life of the heat conducting gel is prolonged, and meanwhile, the heat conducting gel can also play a role in protecting articles such as heating elements.
The heat-conducting gel composition in the embodiment of the application does not contain functional groups such as methyl siloxane, so that the heat-conducting gel composition does not generate D3-D10 low-mixing small-molecule ring bodies when in use, and a circuit is not easy to pollute. In addition, in the embodiment of the application, the molar ratio of the hydroxyl groups in the polyol to the anhydride groups in the polybasic acid anhydride is 1:1-1:2, so that the polybasic acid anhydride does not completely react during polymerization, at least half of the acid anhydride is hydrolyzed into carboxylic acid, and the Tg of the formed polymer is usually below-40 ℃, and compared with the polyurethane-based heat-conducting gel, the temperature range of the heat-conducting gel is wider, and the heat-conducting gel is not easy to harden and embrittle under the low-temperature condition.
In one possible implementation, the polyol comprises one or more of a hydroxyl-terminated polybutadiene, a hydrogenated hydroxyl-terminated polybutadiene, a polyether polyol, castor oil, a castor oil modified polyester polyol; and/or the polybasic acid anhydride comprises one or more of maleic anhydride, 3', 4' -benzophenone tetracarboxylic dianhydride and pyromellitic dianhydride.
In one possible implementation, the thermally conductive filler comprises at least one of aluminum oxide, aluminum hydroxide, boron nitride, gold, silver, copper, carbon nanotubes.
In one possible implementation manner, the component A and/or the component B further comprises at least one of plasticizer, antioxidant and anti-hydrolysis agent; optionally, the plasticizer comprises one or more of diisononyl 1, 2-cyclohexanedicarboxylate, diisononyl 2, 4-trimethyl-1, 3-pentanediol diisobutyrate, liquid petroleum resin, and liquid polybutadiene; optionally, the antioxidant is a hindered phenolic material; further optionally, the antioxidants include one or more of antioxidant 245, antioxidant 1010, antioxidant 1035, antioxidant 1076, antioxidant 1098, antioxidant 1135, antioxidant 1330, antioxidant 3114; optionally, the anti-hydrolysis agent comprises one or more of 3-glycidoxypropyl trimethoxysilane and bisphenol A epoxy resin.
In a second aspect, an embodiment of the present application provides a thermally conductive gel, where the composition includes a gum base and a thermally conductive filler uniformly dispersed in the gum base, the gum base is a branched-chain carboxyl-containing ester polymer, and the gum base has a chemical formula:
Figure BDA0004155522030000031
wherein R is 1 Is any one of alkyl, alkenyl, ether bond, aromatic ring, ricinoleic acid, polypropylene oxide, aromatic polyester and aliphatic polyester, R 2 Is any one of alkyl, alkenyl and aromatic ring.
In the technical scheme, the gum base is an ester polymer with carboxyl in a branched chain, so that the gum base does not contain a D3-D10 low-mixing small molecular ring body, and is not easy to pollute a circuit when being used for articles such as electronic elements; in addition, the Tg of the rubber base in the embodiment of the application is below-40 ℃, and compared with the polyurethane-based heat conduction gel, the temperature range of the heat conduction gel in the embodiment of the application is wider, and the heat conduction gel is not easy to harden and crisp under the low-temperature condition.
In one possible implementation, R 1 、R 2 Respectively alkyl and alkenyl.
In one possible implementation, the liquid to powder ratio of the gum base to the thermally conductive filler is 1:1.5 to 1:7.
In the technical scheme, the heat conducting gel meeting the conditions has better heat dissipation capability and viscosity, and is less easy to harden and become brittle under the low-temperature condition.
In a third aspect, embodiments of the present application provide a method for preparing a thermally conductive gel, including the following steps: mixing the component A and the component B, and polymerizing in the presence of a catalyst; the component A contains polyhydric alcohol for providing hydroxyl, the component B contains polybasic acid anhydride for providing acid anhydride groups, and the component A and/or the component B also contains heat-conducting filler; the molar ratio of the hydroxyl groups to the anhydride groups in the component A and the component B is 1:1-1:2.
In one possible implementation mode, the polyanhydride in the A component and the polyanhydride in the B component can be subjected to polymerization reaction under the action of a catalyst, so that a gum base without D3-D10 small molecular ring bodies can be generated after the A component and the B component are mixed, and the temperature range of the generated gum base is wider by controlling the molar ratio of groups to be within the range; the heat conductive filler in the raw material does not react, but is uniformly distributed in the generated gum base, and forms heat conductive gel together with the gum base. The heat-conducting gel formed by the preparation method is not easy to cause short circuit of a circuit when in use, and the Tg temperature of the heat-conducting gel is low, so that the heat-conducting gel is not easy to harden and embrittle under the low-temperature condition.
In one possible implementation, the catalyst is a tertiary amine; optionally, the catalyst comprises at least one of 2,4, 6-tris (dimethylaminomethyl) phenol, benzyl dimethylamine, triethylamine, triethanolamine, o-hydroxybenzyl dimethylamine.
In a fourth aspect, an embodiment of the present application provides a heat-generating component, where the bonding portion is provided with the above-mentioned heat-conducting gel.
The heating component containing the heat conducting gel is not easy to cause short circuit accidents, and meanwhile, the bonding is firm under the low-temperature condition.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions in the embodiments of the present application will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The following describes the heat conductive gel composition, the heat conductive gel and the preparation method thereof in detail.
The heat-conducting gel can be obtained by polymerizing components in a heat-conducting gel composition, wherein the heat-conducting gel composition comprises an A component and a B component, the A component contains a polyol for providing hydroxyl groups, the B component contains polybasic acid anhydride for providing acid anhydride groups, and the A component and/or the B component also contain a heat-conducting filler; in addition, after the component A and the component B are mixed, the mol ratio of hydroxyl groups to anhydride groups is 1:1-1:2.
When the heat-conducting gel composition is used, the polyol in the component A and the polybasic acid anhydride in the component B can be subjected to polymerization reaction to generate a gum base, the heat-conducting filler does not participate in the reaction and can be dispersed in the generated gum base, and as the molar ratio of hydroxyl groups to acid anhydride groups is 1:1-1:2, the acid anhydride groups in the polybasic acid anhydride can not be completely reacted, and the incompletely reacted acid anhydride can be hydrolyzed to generate carboxylic acid to form an ester polymer with branched carboxyl groups, and the polymer is called as the gum base in the heat-conducting gel.
The reaction principle described above can be represented by the following chemical formula:
Figure BDA0004155522030000051
wherein R is 1 Is any one of alkyl, alkenyl, ether bond, aromatic ring, ricinoleic acid, polypropylene oxide, aromatic polyester and aliphatic polyester, R 2 Is any one of alkyl, alkenyl and aromatic ring. For example, R 1 、R 2 Respectively alkyl and alkenyl.
The polymer generated by the reaction is the gum base in the heat-conducting gel, and the heat-conducting filler which does not participate in the reaction is uniformly dispersed in the gum base and forms the heat-conducting gel together with the gum base. The heat conducting filler can increase the heat conductivity coefficient of the heat conducting gel, so that heat can be rapidly dispersed from the heat conducting gel, the service life of the heat conducting gel is prolonged, and meanwhile, the heat conducting filler can also play a role in protecting articles such as heating elements, and the like, therefore, the heat conducting filler is powder with the median particle diameter D50 of 5-50 mu m, and the material is at least one of alumina, aluminum hydroxide, boron nitride, gold, silver, copper and carbon nano tubes.
The gum base does not contain organic silicon resin or D3-D10 small molecule low-mixing small molecule ring bodies, so that a circuit is not easy to pollute when the gum base is used. In addition, the Tg of the above gum base is generally below-40 ℃, and compared with the polyurethane-based heat conductive gel, the heat conductive gel of the embodiments of the present application has a broader temperature range, and is not easy to harden or embrittle under low temperature conditions.
Illustratively, the polyol in the thermally conductive gel composition includes one or more of a hydroxyl-terminated polybutadiene, a hydrogenated hydroxyl-terminated polybutadiene, a polyether polyol, castor oil, a castor oil modified polyester polyol; the polybasic acid anhydride comprises one or more of maleic anhydride, 3', 4' -benzophenone tetracarboxylic dianhydride and pyromellitic dianhydride.
In addition, one or more auxiliary agents such as plasticizer, antioxidant, anti-hydrolysis agent, water scavenger, catalyst and the like can be added into the component A and/or the component B of the heat-conducting gel composition according to specific requirements, wherein the plasticizer comprises one or more of 1, 2-cyclohexane dicarboxylic acid diisononyl ester, 2, 4-trimethyl-1, 3-pentanediol diisobutyrate, liquid petroleum resin and liquid polybutadiene; the antioxidant is a hindered phenol material; further optionally, the antioxidants include one or more of antioxidant 245, antioxidant 1010, antioxidant 1035, antioxidant 1076, antioxidant 1098, antioxidant 1135, antioxidant 1330, antioxidant 3114; the hydrolysis resisting agent comprises one or more of 3-glycidyl ether oxypropyl trimethoxy silane and bisphenol A epoxy resin. The catalyst is typically a tertiary amine; further, the tertiary amine catalyst comprises at least one of 2,4, 6-tris (dimethylaminomethyl) phenol, benzyl dimethylamine, triethylamine, triethanolamine and o-hydroxybenzyl dimethylamine.
When the heat-conducting gel disclosed by the embodiment of the application is used at the bonding position of the heating element, the probability of short-circuit accidents of the heating element can be reduced, and meanwhile, the heating element can be bonded more firmly under the low-temperature condition.
When the above heat conductive gel composition is used to prepare a heat conductive gel, it is general to prepare a component a and a component B separately, and then mix the a component and the B component and polymerize in the presence of a catalyst. Illustratively, in the preparation of the heat-conducting gel, the component A and the component B contain heat-conducting fillers, and the specific steps are generally as follows:
s100, preparing a component A: the step is to heat and stir the polyol, the heat conductive filler and other auxiliary agents uniformly under the condition that the vacuum degree is not more than-90 kPa until no bubble is generated.
More specifically, in this embodiment, the specific components in the component a include, by weight, 10 to 30 parts of polyol, 0 to 20 parts of plasticizer, 70 to 80 parts of thermally conductive filler, 1 to 5 parts of antioxidant, 1 to 5 parts of hydrolysis inhibitor, and 1 to 5 parts of catalyst.
S200, forming a component B: the step is to heat and stir the polybasic acid anhydride, the heat conducting filler and other auxiliary agents uniformly under the condition that the vacuum degree is not more than-90 kPa until no bubble is generated.
More specifically, in this embodiment, the specific components in the component B include, by weight, 10 to 30 parts of polybasic acid anhydride, 0 to 20 parts of plasticizer, 70 to 80 parts of heat conductive filler, and 1 to 10 parts of water scavenger.
Of course, in this step, a small amount of polyol may be added into the component B in advance, and the molar ratio of hydroxyl groups to anhydride groups in the polyol is between 1:4 and 1:6, so that the polybasic acid anhydride in the component B undergoes a monoesterification reaction to form a polybasic acid anhydride curing agent, and then the polybasic acid anhydride curing agent after the monoesterification reaction is used as a reaction component of the component B, which is favorable for increasing the types of subsequently generated gum bases, and meanwhile, the mixing proportion of the component AB is close, so that the component AB can be directly used without distinguishing the component AB during mixing, and the poor curing effect caused by misoperation can be avoided, thereby meeting the different situations in practical use. In the strict sense, when the anhydride in the B component is dibasic anhydride, after a small amount of polyol is added to carry out monoesterification reaction, part or all of dibasic anhydride is no longer polybasic anhydride, but contains an anhydride group and an ester of carboxylic acid. However, for simplicity of reference, the reaction product is still referred to as a polybasic acid anhydride curing agent. And in the subsequent step, when the molar ratio of the hydroxyl group to the acid anhydride group is determined, the hydroxyl group is the amount of hydroxyl group before the reaction, and the acid anhydride group is the amount of acid anhydride before the reaction.
S300, mixing the component A and the component B: in the step, after the component A and the component B are mixed, the polyol in the component A and the polybasic acid anhydride in the component B can be subjected to polymerization reaction under the action of a catalyst, and in the step, the molar ratio of hydroxyl groups in the component A to acid anhydride groups in the component B needs to be controlled within the range of 1:1-1:2.
It should be noted that, in this step, S100 and S200 are not particularly sequential.
The features and capabilities of the present application are described in further detail below in connection with the examples.
Example 1
The embodiment of the application provides a heat-conducting gel, which is prepared by the following steps:
(1) 200g of castor oil, 800g of hydrogenated hydroxyl-terminated polybutadiene having an average molecular weight of 2000g/mol and an average functionality of 1.9, 300g of diisononyl 1, 2-cyclohexanedicarboxylate, 1700g of 20 μm spherical alumina, 1950g of 30 μm aluminum hydroxide and 45g of Pasteur 1010 were charged into a double planetary mixer. Stirring at normal pressure for 7 min at a stirring speed of 40r/min, vacuumizing to a vacuum degree of-90 kPa after the mixture is formed into paste, stirring at a stirring speed of 40r/min and a dispersing speed of 600r/min for 120 min, simultaneously starting circulating hot water, and controlling the temperature of the mixture to 110 ℃. Then cooling to room temperature of 25 ℃, adding 4g of 3-glycidoxypropyl trimethoxysilane, 5g of 2,4, 6-tris (dimethylaminomethyl) phenol, vacuumizing to the vacuum degree of-90 kPa, and stirring for 30 minutes at the stirring rotation speed of 40r/min to obtain the component A.
(2) Putting 1800g of 40 mu m spherical alumina and 1780g of 10 mu m aluminum hydroxide into a vacuum roller powder dryer, opening a heating oil bath when the vacuum degree reaches-90 kPa, enabling the temperature of the filler to be 110 ℃, starting a rolling rotation speed of 4r/min, baking for 120 minutes until the moisture of the heat conducting filler is not more than 500ppm, cooling to the room temperature of 25 ℃, pouring into a double planetary mixer, taking 110g of maleic anhydride with the average molecular weight of 3000g/mol, 20g of 1, 2-cyclohexane diisononyl dicarboxylate, 10g of 3A molecular sieve activated powder, adding into the double planetary mixer, stirring for 7 minutes at the stirring rotation speed of 40r/min under normal pressure, vacuumizing until the powder liquid forms paste, stirring for 60 minutes at the dispersing rotation speed of 600r/min at the stirring rotation speed of 40r/min, and obtaining the component B.
(3) And mixing the component A and the component B according to the mass ratio of 1:1 to prepare the heat-conducting gel.
Example 2
The embodiment of the application provides a heat-conducting gel, which is prepared by the following steps:
(1) 130g of castor oil modified polyester polyol having an average molecular weight of 840g/mol and an average functionality of 3, 870g of hydroxyl-terminated polybutadiene having an average molecular weight of 2800g/mol and an average functionality of 2.4, 80g of liquid polybutadiene having a viscosity of 750cps, 2450g of 20 μm spherical alumina, 150g of 5 μm aluminum hydroxide and 3.5g of antioxidant 245 were charged into a double planetary mixer. Stirring at normal pressure at 40r/min for 7 min, vacuumizing to-90 kPa after the powder liquid forms paste, stirring at 40r/min at 600r/min for 120 min, and simultaneously starting circulating hot water to control the temperature of the material to 110 ℃. Then cooling to room temperature of 25 ℃, adding 3.8g of 3-glycidoxypropyl trimethoxysilane, 4.5g of triethylamine, vacuumizing to the vacuum degree of-90 kPa, and stirring for 30 minutes at the stirring speed of 40r/min to obtain the component A.
(2) Putting 452.2g of 20 mu m spherical alumina and 18.2g of 10 mu m aluminum hydroxide into a vacuum roller powder dryer, opening a heating oil bath when the vacuum degree is-90 kPa, enabling the temperature of the filler to be 110 ℃, starting a rolling rotating speed of 4r/min, baking for 120 minutes until the moisture of the heat conducting filler is not more than 500ppm, and cooling to room temperature of 25 ℃ for later use.
Adding 50.53g of hydroxyl-terminated polybutadiene with average molecular weight of 2000g/mol and average functionality of 2, 117.91g of hydroxyl-terminated polybutadiene with average molecular weight of 3000g/mol and average functionality of 3 into a reaction kettle, vacuumizing to a vacuum degree of-90 kPa, stirring at a stirring rotation speed of 15r/min, opening a heating oil bath to a liquid of 110 ℃, stirring for 120 minutes until the water content of the mixture is not more than 500ppm, adding 27.57g of pyromellitic dianhydride under the protection of nitrogen, cooling to 80 ℃, stirring for 30 minutes at a stirring rotation speed of 15r/min until the pyromellitic dianhydride is completely reacted, and cooling to a room temperature of 25 ℃.
Placing the dehydrated aluminum oxide, aluminum hydroxide and polybasic acid anhydride curing agent into a double planetary mixer, adding 7.5g of 3A molecular sieve activated powder into the double planetary mixer, stirring for 7 minutes at normal pressure at a stirring speed of 40r/min, vacuumizing to a vacuum degree of-90 kPa after powder liquid forms paste, and stirring for 60 minutes at a dispersing speed of 600r/min at a stirring speed of 40r/min to obtain the component B.
(3) Mixing the glue of the component A and the glue of the component B according to the mass ratio of 1:1 to prepare the heat-conducting gel.
Example 3
The embodiment provides a heat conducting gel, which is prepared by the following steps:
(1) 800g of a polyether polyol 330N having an average molecular weight of 4800g/mol and an average functionality of 3, 200g of a hydrogenated hydroxyl-terminated polybutadiene having an average molecular weight of 3000g/mol and an average functionality of 1.9, 500g of diisononyl 1, 2-cyclohexanedicarboxylate, 7500g of 20 μm spherical alumina, 2250g of 5 μm aluminum hydroxide and 6g of an antioxidant 1010 were charged into a double planetary mixer. Stirring at normal pressure at 40r/min for 7 min, vacuumizing to vacuum degree of-90 kPa after the powder liquid forms paste, stirring at 40r/min at 600r/min for 120 min, and simultaneously starting circulating hot water to control the material temperature to 110 ℃. Then cooling to room temperature, adding 6g of 3-glycidoxypropyl trimethoxysilane, 5.8g of triethylamine, vacuumizing to the vacuum degree of-90 kPa, and stirring for 30 minutes at the stirring rotation speed of 40r/min to obtain the component A.
(2) Putting 3405.65g of 40 mu m spherical alumina and 1021.69g of 5 mu m aluminum hydroxide into a vacuum roller powder dryer, opening a heating oil bath when the vacuum degree is-90 kPa, enabling the temperature of the filler to be 110 ℃, starting the rolling rotation speed to bake for 120 minutes until the moisture of the heat-conducting filler is not more than 500ppm, and cooling to the room temperature of 25 ℃ for later use.
Adding 380g of polyether polyol with average molecular weight of 3000g/mol and average functionality of 3, 120g of hydroxyl-terminated polybutadiene with average molecular weight of 2000g/mol and average functionality of 2 into a reaction kettle, vacuumizing to vacuum degree of-90 kPa at stirring rotation speed of 15r/min, opening a heating oil bath to liquid of 100-110 ℃, stirring for 120 min until the water content of the mixture is not more than 500ppm, adding 181.13g of 3,3', 4' -benzophenone tetracarboxylic dianhydride under nitrogen protection, cooling to 80 ℃, stirring at stirring rotation speed of 15r/min for 30 min until the 3,3', 4' -benzophenone tetracarboxylic dianhydride is completely reacted, and cooling to room temperature.
Placing the dehydrated aluminum oxide, aluminum hydroxide and polybasic acid anhydride curing agent into a double planetary mixer, adding 20.43g of 3A molecular sieve activated powder into the double planetary mixer, stirring for 5-10 minutes at normal pressure at a stirring speed of 40r/min, vacuumizing until the vacuum degree is-90 kPa after the powder liquid forms paste, and stirring for 60 minutes at a dispersing speed of 600r/min at a stirring speed of 40r/min to obtain the component B.
(3) Mixing the glue of the component A and the glue of the component B according to the mass ratio of 1:1 to prepare the heat-conducting gel.
Comparative example 1
The comparative example provides an organosilicon heat-conducting gel, which is prepared by the following steps:
(1) Weighing 963.6g of 300cps double-end-capped vinyl polydimethylsiloxane, 366.4g of 500cps double-end-capped vinyl polydimethylsiloxane, 1995g of 10 mu m alumina powder, 4655g of 40 mu m spherical alumina powder, 1995g of 10 mu m aluminum hydroxide and 20g of platinum catalyst, adding into a planetary stirrer, stirring at the normal pressure and the stirring speed of 60r/min for 20 minutes, vacuumizing to the vacuum degree of-90 kPa after the powder liquid forms paste, stirring at the stirring speed of 60r/min and the dispersing speed of 600r/min for 60 minutes, and simultaneously starting cyclic heating, wherein the material temperature is controlled to be not higher than 100 ℃ to prepare the component A.
(2) Weighing 857g of 500cps double-end-capped vinyl polydimethylsiloxane, 175g of 300cps single-end-capped vinyl polydimethylsiloxane, 1995g of 10 mu m alumina powder, 4655g of 40 mu m spherical alumina powder, 1995g of 10 mu m aluminum hydroxide, 77.3g of 0.1% end-side hydrogen-containing silicone oil, 221.7g of 0.18% end-side hydrogen-containing silicone oil, 0.3g of acetylene cyclohexanol inhibitor and 2g of carbon black, adding into a planetary stirrer, stirring at normal pressure at the stirring speed of 60r/min for 20 minutes, vacuumizing to the vacuum degree of-90 kPa after the powder liquid forms paste, stirring at the dispersing speed of 600r/min for 60 minutes, and simultaneously starting cyclic heating, wherein the material temperature is controlled to be not higher than 100 ℃ to obtain the component B.
(3) Mixing the glue of the component A and the glue of the component B according to the mass ratio of 1:1 to prepare the organic silicon heat-conducting gel.
Comparative example 2
The comparative example provides a thermally conductive gel, which is prepared as follows:
(1) 200g of castor oil, 800g of hydrogenated hydroxyl-terminated polybutadiene having an average molecular weight of 2000g/mol and an average functionality of 1.9, 300g of diisononyl 1, 2-cyclohexanedicarboxylate, 1700g of 20 μm spherical alumina, 1950g of 30 μm aluminum hydroxide and 45g of Pasteur 1010 are taken in a double planetary mixer. Stirring at normal pressure at a stirring speed of 40r/min for 5-10 min, vacuumizing to a vacuum degree of-90 kPa, stirring at a stirring speed of 40r/min, dispersing at a stirring speed of 600r/min for 120 min, simultaneously starting circulating hot water, and controlling the material temperature to 100-110 ℃. Then cooling to room temperature of 25 ℃, adding 4g of 3-glycidol ether oxypropyl trimethoxysilane, vacuumizing to the vacuum degree of-90 kPa, and stirring for 30 minutes at the stirring rotating speed of 40r/min to obtain the component A glue.
(2) Mixing the A-component glue with polymeric MDI (4, 4' -diphenylmethane diisocyanate, diphenylmethane diisocyanate) in a mass ratio of 25:1 to prepare the polyurethane heat-conducting gel.
Application example
The products of each example and comparative example were respectively tested for Tg and thermal conductivity using DSC (Differential Scanning Calorimeter ) and thermal conductivity tester, and whether each product had small molecule silane precipitated was observed, and the specific results are shown in the following table:
TABLE 1 product Properties of examples 1-3 and comparative examples 1-3
Figure BDA0004155522030000131
In summary, the thermally conductive gel of the embodiments of the present application has good thermal conductivity and a lower Tg.
The above is only an example of the present application, and is not intended to limit the scope of the present application, and various modifications and variations will be apparent to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application should be included in the protection scope of the present application.

Claims (10)

1. A thermally conductive gel composition, characterized in that it comprises an a-component containing a polyol for providing hydroxyl groups and a B-component containing a polybasic acid anhydride for providing acid anhydride groups, and in that the a-component and/or the B-component further contains a thermally conductive filler; the molar ratio of the hydroxyl groups to the anhydride groups in the component A and the component B is 1:1-1:2.
2. The thermally conductive gel composition of claim 1, wherein the polyol comprises one or more of a hydroxyl-terminated polybutadiene, a hydrogenated hydroxyl-terminated polybutadiene, a polyether polyol, castor oil, a castor oil modified polyester polyol;
and/or the polybasic acid anhydride comprises one or more of maleic anhydride, 3', 4' -benzophenone tetracarboxylic dianhydride and pyromellitic dianhydride.
3. The thermally conductive gel composition of claim 1, wherein the thermally conductive filler comprises at least one of aluminum oxide, aluminum hydroxide, boron nitride, gold, silver, copper, carbon nanotubes.
4. The thermally conductive gel composition of claim 1, wherein the a-component and/or the B-component further comprises at least one of a plasticizer, an antioxidant, and an anti-hydrolysis agent;
optionally, the plasticizer comprises one or more of diisononyl 1, 2-cyclohexanedicarboxylate, diisononyl 2, 4-trimethyl-1, 3-pentanediol diisobutyrate, liquid petroleum resin, liquid polybutadiene;
optionally, the antioxidant is a hindered phenolic material; further optionally, the antioxidant comprises one or more of antioxidant 245, antioxidant 1010, antioxidant 1035, antioxidant 1076, antioxidant 1098, antioxidant 1135, antioxidant 1330, antioxidant 3114;
optionally, the hydrolysis inhibitor comprises one or more of 3-glycidyl ether oxypropyl trimethoxysilane and bisphenol A epoxy resin.
5. The heat-conducting gel is characterized by comprising a rubber base and a heat-conducting filler uniformly dispersed in the rubber base, wherein the rubber base is an ester polymer with branched chains containing carboxyl groups, and the chemical formula of the rubber base is as follows:
Figure FDA0004155522020000021
wherein R is 1 Is any one of alkyl, alkenyl, ether bond, aromatic ring, ricinoleic acid, polypropylene oxide, aromatic polyester and aliphatic polyester, R 2 Is any one of alkyl, alkenyl and aromatic ring.
6. The thermally conductive gel of claim 5, wherein R 1 、R 2 Respectively alkyl and alkenyl.
7. The thermally conductive gel of claim 5, wherein the liquid to powder ratio of the gum base to the thermally conductive filler is 1:1.5 to 1:7.
8. A method of preparing a thermally conductive gel as claimed in claim 5, comprising the steps of:
mixing the component A and the component B, and polymerizing in the presence of a catalyst;
the component A contains polyhydric alcohol for providing hydroxyl, the component B contains polybasic acid anhydride for providing acid anhydride groups, and the component A and/or the component B also contains heat-conducting filler;
the molar ratio of the hydroxyl groups to the anhydride groups in the component A to the component B is 1:1-1: 2.
9. the method of preparing a thermally conductive gel of claim 8, wherein the catalyst is a tertiary amine; optionally, the catalyst comprises at least one of 2,4, 6-tris (dimethylaminomethyl) phenol, benzyl dimethylamine, triethylamine, triethanolamine, o-hydroxybenzyl dimethylamine.
10. A heating element is characterized in that the heat conducting gel as claimed in claim 5 is arranged at the bonding part.
CN202310333062.3A 2023-03-31 2023-03-31 Heat conducting gel composition, heat conducting gel, preparation method of heat conducting gel and heating component Pending CN116355572A (en)

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