CN111748090B - Surface modifier, heat-conducting encapsulating composite material and preparation method thereof - Google Patents

Surface modifier, heat-conducting encapsulating composite material and preparation method thereof Download PDF

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CN111748090B
CN111748090B CN201910253272.5A CN201910253272A CN111748090B CN 111748090 B CN111748090 B CN 111748090B CN 201910253272 A CN201910253272 A CN 201910253272A CN 111748090 B CN111748090 B CN 111748090B
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heat
hydroxyl
surface modifier
silicone oil
conducting
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CN111748090A (en
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周明
黄少华
靳雪
刘建辉
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BYD Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
    • 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
    • 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
    • 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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Abstract

The disclosure relates to a surface modifier and a heat-conducting encapsulating composite material and a preparation method thereof, wherein the surface modifier contains a compound shown as a formula (I):
Figure DDA0002012907270000011
wherein R is1Is alkylene, phenylene or cycloalkylene, R3And R4Each independently is R5OR OR5，R5And R2Each independently is C1-C3 alkyl, R is a group obtained by losing n hydroxyl groups of a polyhydroxy polymer, n is 2 or 3, and the polyhydroxy polymer is at least one of polyether polyol, hydroxyl-terminated polysiloxane and polyether modified hydroxyl-terminated polysiloxane. The surface modifier disclosed by the invention can improve the interface compatibility of the inorganic heat-conducting filler and the silicone oil matrix, and improve the heat-conducting property and the construction convenience of the heat-conducting encapsulating composite material.

Description

Surface modifier, heat-conducting encapsulating composite material and preparation method thereof
Technical Field
The disclosure relates to the field of composite materials, in particular to a surface modifier, a heat-conducting potting composite material and a preparation method thereof.
Background
Along with the development of electronic technology, the integration degree of circuits is higher and higher, so that heat generated by electronic elements is difficult to dissipate in time, and the performance stability and the service life of an electric appliance are influenced. The heat-conducting encapsulating composite material (encapsulating adhesive) not only can well dissipate heat, but also can play a role in moisture prevention, dust prevention and shock prevention, and is more and more widely applied to electronic products.
The existing method for preparing the heat-conducting encapsulating composite material is to directly mix inorganic heat-conducting filler with a silicone oil matrix; or modifying the heat-conducting filler by using a silane coupling agent monomer, and then mixing the modified heat-conducting filler with the silicone oil matrix. In the two technical schemes, a larger gap exists between the inorganic heat-conducting filler and the silicone oil matrix interface, the thermal resistance and the viscosity of the composite material are larger, so that the construction is difficult, and the vulcanized silicone rubber has the defects of poor heat-conducting property, pores and the like. This is because the poor compatibility between the inorganic filler particles and the organic resin matrix interface tends to cause the filler particles to agglomerate in the resin matrix and not to be dispersed efficiently. In addition, because the surface tension difference between the inorganic filler particles and the organic resin is different, the resin is difficult to wet the surfaces of the filler particles, so that gaps exist at the interface of the inorganic filler particles and the organic resin, and the interface thermal resistance of the composite material is increased. The silane coupling agent is used for carrying out surface treatment on the filler particles to improve the interface combination condition of the filler particles and the inorganic filler particles, but the coupling agent and the surfaces of the inorganic filler particles only form single-point connection, so that larger gaps still exist between the modified filler and the organic resin interface.
Disclosure of Invention
An object of the present disclosure is to provide a surface modifier capable of modifying an inorganic heat conductive filler to improve interfacial compatibility of the inorganic heat conductive filler and a silicone oil matrix, a method for preparing the same, and a composition for preparing a heat conductive potting composite.
Another object of the present disclosure is to provide a heat conductive potting composite material having good heat conductive performance and construction convenience, and a method for preparing the same.
To achieve the above object, a first aspect of the present disclosure: provided is a surface modifier containing a compound represented by the formula (I):
Figure BDA0002012907260000021
wherein R is1Is alkylene, phenylene or cycloalkylene, R3And R4Each independently is R5OR OR5，R5And R2Each independently is C1-C3 alkyl, R is a group obtained by losing n hydroxyl groups of a polyhydroxy polymer, n is 2 or 3, and the polyhydroxy polymer is at least one of polyether polyol, hydroxyl-terminated polysiloxane and polyether modified hydroxyl-terminated polysiloxane.
Alternatively, R1Is propylene, R2、R3And R4Each independently is methyl or ethyl; the weight average molecular weight of the polyhydroxy polymer is 1000-2000; the polyether polyol is polyoxypropylene glycol and/or polyoxyethyleneAn alkylene glycol; the hydroxyl-terminated polysiloxane is hydroxyl-terminated polydimethylsiloxane; the polyether modified hydroxyl-terminated polysiloxane is hydroxyl-terminated polyether modified silicone oil.
In a second aspect of the present disclosure: there is provided a method of preparing a surface modifier according to the first aspect of the disclosure, the method comprising: contacting an isocyanate silane coupling agent with a structure shown as a formula (II) with a polyhydroxy polymer under esterification reaction conditions;
Figure BDA0002012907260000022
wherein R is1Is alkylene, phenylene or cycloalkylene, R3And R4Each independently is R5OR OR5，R5And R2Each independently is a C1-C3 alkyl group, and the polyhydroxy polymer is at least one of polyether polyol, hydroxyl-terminated polysiloxane and polyether-modified hydroxyl-terminated polysiloxane.
Alternatively, the molar ratio of the isocyanate silane coupling agent to the polyhydroxy polymer in terms of-NCO is (1-1.05): 1.
alternatively, the esterification reaction conditions comprise: the temperature is 50-70 ℃ and the time is 1-2.5 h.
A third aspect of the disclosure: there is provided a composition for preparing a heat-conducting potting composite, the composition comprising a silicone oil matrix and an inorganic heat-conducting filler, and the inorganic heat-conducting filler being modified with the surface modifier according to the first aspect of the disclosure.
Optionally, the surface modifier is contained in an amount of 0.1 to 0.7 part by weight and the inorganic heat-conducting filler is contained in an amount of 77 to 87 parts by weight, based on 13 to 22 parts by weight of the silicone oil matrix.
Optionally, the inorganic heat conductive filler is aluminum oxide, zinc oxide or aluminum nitride, or a combination of two or three thereof;
the silicone oil matrix is vinyl silicone oil and/or hydrogen-containing silicone oil.
A fourth aspect of the present disclosure: there is provided a method of preparing a heat-conducting potting composite using a composition according to the third aspect of the present disclosure, the method comprising: under the hydrolysis condition, mixing the surface modifier with an inorganic heat-conducting filler, then carrying out heating treatment to obtain powder, and then mixing the powder with a silicone oil matrix.
Optionally, the hydrolysis conditions comprise being carried out in humid air and/or with the addition of water; the conditions of the heat treatment include: the temperature is 80-100 ℃, and the time is 30-60 min.
Optionally, the method further comprises: and mixing the surface modifier with the inorganic heat-conducting filler under the condition of centrifugal stirring, wherein the centrifugal stirring time is 5-15 min.
The fifth aspect of the present disclosure: providing a heat-conducting potting composite prepared by the method of the fourth aspect of the present disclosure.
According to the technical scheme, the surface modifier is prepared by taking an isocyanate silane coupling agent and a polyhydroxy polymer as raw materials and performing esterification condensation reaction, wherein the end group of the surface modifier contains a plurality of hydrolytic groups and can react with hydroxyl on the surface of the inorganic heat-conducting filler to form a coating effect, so that the interface compatibility of the inorganic heat-conducting filler and a silicone oil matrix is improved. The heat-conducting encapsulating composite material prepared from the inorganic heat-conducting filler modified by the surface modifier and the silicone oil matrix has low thermal resistance and viscosity, and shows good heat-conducting performance and construction convenience.
Additional features and advantages of the disclosure will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present disclosure. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.
The first aspect of the disclosure: provided is a surface modifier containing a compound represented by the formula (I):
Figure BDA0002012907260000041
wherein R is1Is alkylene, phenylene or cycloalkylene, R3And R4Each independently is R5OR OR5，R5And R2Each independently is C1-C3 alkyl, R is a group obtained by losing n hydroxyl groups of a polyhydroxy polymer, n is 2 or 3, and the polyhydroxy polymer is at least one of polyether polyol, hydroxyl-terminated polysiloxane and polyether modified hydroxyl-terminated polysiloxane.
The terminal group of the compound of formula (I) contains a plurality of hydrolyzable groups (e.g., -OR)2Or when-R3、-R4Each independently is OR5When is-R3or-R4) The inorganic heat-conducting filler can react with hydroxyl on the surface of the inorganic heat-conducting filler to form a coating effect, so that the interface compatibility of the inorganic heat-conducting filler and a silicone oil matrix is improved.
Further, R1May be propylene, R2、R3And R4May each independently be methyl or ethyl. The steric hindrance of the groups is small, so that the surface modifier with the chain-shaped molecular structure has certain flexibility.
According to the disclosure, the weight average molecular weight of the polyhydroxy polymer is preferably 1000-2000, and the surface modifier prepared from the polyhydroxy polymer in the above range is more favorable for forming a thin coating layer when reacting with hydroxyl on the surface of the inorganic heat-conducting filler, so as to further improve the interface compatibility of the inorganic heat-conducting filler and the silicone oil matrix, and at the same time, not additionally increase the interface thermal resistance between the inorganic heat-conducting filler and the silicone oil matrix. Further, the polyether polyol may be a polyoxypropylene diol and/or a polyoxyethylene diol; the hydroxyl-terminated polysiloxane can be hydroxyl-terminated polydimethylsiloxane; the polyether modified hydroxyl-terminated polysiloxane can be a hydroxyl-terminated polysiloxane with a side chain grafted polyether structure, and further can be double-hydroxyl-terminated polyether modified silicone oil; the group R obtained after the polyhydroxy polymer of the kind loses n hydroxyl groups is similar to the molecular structure of silicone oil, so that the compatibility of the inorganic heat-conducting filler modified by the surface modifier of the structure and a silicone oil matrix is better.
In a second aspect of the present disclosure: there is provided a method of preparing a surface modifier according to the first aspect of the disclosure, the method comprising: contacting an isocyanate silane coupling agent with a structure shown as a formula (II) with a polyhydroxy polymer under esterification reaction conditions;
Figure BDA0002012907260000051
wherein R is1Is alkylene, phenylene or cycloalkylene, R3And R4Each independently is R5OR OR5，R5And R2Each independently is a C1-C3 alkyl group, and the polyhydroxy polymer is at least one of polyether polyol, hydroxyl-terminated polysiloxane and polyether-modified hydroxyl-terminated polysiloxane.
According to the disclosure, the surface modifier of the disclosure can be prepared by performing an esterification reaction on an isocyanate silane coupling agent and a polyhydroxy polymer as raw materials.
Further, R1May be propylene, R2、R3And R4May each independently be methyl or ethyl.
According to the disclosure, the weight average molecular weight of the polyhydroxy polymer is preferably 1000-2000, and the surface modifier prepared from the polyhydroxy polymer in the range is more favorable for forming a thin coating layer when reacting with hydroxyl on the surface of the inorganic heat-conducting filler, so that the interface compatibility of the inorganic heat-conducting filler and a silicone oil matrix is further improved, and the interface thermal resistance between the inorganic heat-conducting filler and the silicone oil matrix is not additionally increased.
According to the present disclosure, the polyether polyol is an oligomer having an ether bond in the main chain and a terminal group or a side group containing more than 2 hydroxyl groups, and may be, for example, polyether polyol DL1000, polyether polyol DL2000, or the like, and in order to further promote the modifying ability of the surface modifier to the inorganic heat conductive filler, the polyether polyol in the present disclosure may be polyoxypropylene glycol and/or polyoxyethylene glycol.
According to the present disclosure, the hydroxyl-terminated polysiloxane may preferably be hydroxyl-terminated polydimethylsiloxane; the polyether modified hydroxyl-terminated polysiloxane can be preferably hydroxyl-terminated polyether modified silicone oil; the polyhydroxy polymer of the kind is similar to the molecular structure of silicone oil, so that the compatibility of the inorganic heat-conducting filler modified by the surface modifier of the structure and a silicone oil matrix is better.
According to the present disclosure, the desired esterification reaction effect can be obtained when the molar amounts of-NCO of the isocyanate silane coupling agent and-OH of the polyhydroxy polymer are relatively close, and preferably, the molar ratio of the isocyanate silane coupling agent to the polyhydroxy polymer in terms of-NCO is (1-1.05): 1.
according to the present disclosure, the esterification reaction conditions may include: the temperature is 50-70 ℃ and the time is 1-2.5 h.
A third aspect of the disclosure: there is provided a composition for preparing a heat-conducting potting composite, the composition comprising a silicone oil matrix and an inorganic heat-conducting filler, and the inorganic heat-conducting filler being modified with the surface modifier according to the first aspect of the disclosure.
The surface modifier disclosed by the invention is adopted to modify the inorganic heat-conducting filler, so that a 'lipophilic layer' can be formed on the surface of the inorganic heat-conducting filler, thereby forming 'seamless connection' with a silicone oil matrix, reducing the thermal resistance and viscosity of a composite material system, and further improving the heat-conducting property and the construction convenience of a product.
According to the disclosure, the surface modifier is preferably contained in an amount of 0.1 to 0.7 parts by weight and the inorganic heat conductive filler is preferably contained in an amount of 77 to 87 parts by weight, based on 13 to 22 parts by weight of the silicone oil matrix. The composition obtained in the proportioning range is beneficial to preparing the heat-conducting encapsulating composite material with lower heat resistance and viscosity.
In accordance with the present disclosure, the inorganic thermally conductive filler may be of a conventional kind in the art, and may be, for example, alumina, zinc oxide, or aluminum nitride, or a combination of two or three thereof.
According to the present disclosure, the type of the silicone oil matrix is also not particularly limited, and may be, for example, vinyl silicone oil and/or hydrogen-containing silicone oil.
A fourth aspect of the present disclosure: there is provided a method of preparing a heat-conducting potting composite using a composition according to the third aspect of the present disclosure, the method comprising: under the hydrolysis condition, mixing the surface modifier with an inorganic heat-conducting filler, then carrying out heating treatment to obtain powder, and then mixing the powder with a silicone oil matrix.
According to the present disclosure, the hydrolysis conditions may include being carried out in humid air and/or with the addition of water. In order to further improve the mixing degree of the surface modifier and the inorganic heat conductive filler, the method may further include: and mixing the surface modifier with the inorganic heat-conducting filler under the condition of centrifugal stirring, wherein the centrifugal stirring time can be 5-15 min.
According to the present disclosure, the conditions of the heat treatment may include: the temperature is 80-100 ℃, and the time is 30-60 min. After the heating treatment, the inorganic heat-conducting filler is modified by the surface modifier, so that the compatibility with the silicone oil matrix is improved, and the subsequent operation of mixing with the silicone oil matrix is more convenient.
The fifth aspect of the present disclosure: providing a heat-conducting potting composite prepared by the method of the fourth aspect of the present disclosure.
The heat-conducting encapsulating composite material disclosed by the invention has lower thermal resistance and viscosity, and shows good heat-conducting property and construction convenience.
The present disclosure is further illustrated by the following examples, which are merely illustrative and explanatory of the present disclosure and are not restrictive thereof.
Examples 1 to 9 are provided to illustrate the surface modifier and the method for producing the same of the present disclosure.
Example 1
3-isocyanatopropyl-methyldimethoxysilane (from macrographic new materials, with the trade designation T-02; CAS number: 26115-72-0) and polyoxypropylene diol (from Doxoda blue, with the trade designation DL-1000; CAS number: 25322-69-4, with a weight average molecular weight of 1000) were reacted as-NCO: OH (molar ratio) is 1, and esterification reaction is carried out at 65 ℃ for 2h to obtain the surface modifier A1 prepared in the example, and the structural formula is as follows:
Figure BDA0002012907260000081
n1 is an integer from 14 to 16. Sealing and storing for later use.
Example 2
3-isocyanatopropylmethyldimethoxysilane (from macrographic new materials, commercial number T-02; CAS number: 26115-72-0) and polyoxyethylene glycol (from Aladdin, commercial number P103719, weight average molecular weight 1000) were reacted as a mixture of-NCO: OH (molar ratio) of 1.05 and esterification reaction at 65 ℃ for 2h to obtain the surface modifier A2 prepared in this example, and its formula is:
Figure BDA0002012907260000082
n2 is an integer from 19 to 21. Sealing and storing for later use.
Example 3
3-isocyanatopropyl-methyldimethoxysilane (from macrographic new materials, commercial number T-02; CAS number: 26115-72-0) and polyoxypropylene diol (from Doxoda Lanzhong, commercial number DL-2000; CAS number: 9003-11-6, weight average molecular weight 2000) were reacted as-NCO: OH (molar ratio) is 1, and esterification reaction is carried out at 65 ℃ for 2h to obtain the surface modifier A3 prepared in the example, and the structural formula is as follows:
Figure BDA0002012907260000083
n3 is an integer from 30 to 33. Sealing and storing for later use.
Example 4
3-isocyanatopropyl methyldimethoxysilane (from macrographic new materials, with the trade name of T-02; CAS number: 26115-72-0) and hydroxyl-terminated polydimethylsiloxane (from Zhongbao silicon materials, with the trade name of hydroxyl silicone oil-1000, with the weight-average molecular weight of 1000) were mixed according to the ratio of-NCO: OH (molar ratio) is 1, and esterification reaction is carried out at 65 ℃ for 2h to obtain the surface modifier A4 prepared in the example, and the structural formula is as follows:
Figure BDA0002012907260000091
n4 is an integer from 11 to 13. Sealing and storing for later use.
Example 5
3-isocyanatopropyl methyldimethoxysilane (from macrographic new materials, with the trade name of T-02; CAS number: 26115-72-0) and hydroxyl-terminated polydimethylsiloxane (from Zhongbao silicon materials, with the trade name of hydroxyl silicone oil-2000, with the weight-average molecular weight of 2000) were reacted according to the following formula of-NCO: OH (molar ratio) of 1.05 and esterification reaction at 65 ℃ for 2h to obtain the surface modifier A5 prepared in this example, and its formula is:
Figure BDA0002012907260000092
n5 is an integer from 24 to 26. Sealing and storing for later use.
Example 6
3-isocyanatopropyl methyldimethoxysilane (from macrographic new materials, with the trade name of T-02; CAS number: 26115-72-0) and double-end hydroxyl polyether modified silicone oil (from Kaijia chemical industry, with the trade name of SF-8427, with the weight-average molecular weight of 2000) are mixed according to the weight ratio of-NCO: OH (molar ratio) is 1, and esterification reaction is carried out at 65 ℃ for 2h to obtain the surface modifier A6 prepared in the example, and the structural formula is as follows:
Figure BDA0002012907260000101
R1is alkylene, R2Is C1-C2 alkyl, x is an integer of 8-9, and n6 is an integer of 18-20. Sealing and storing for later use.
Example 7
Isocyanatopropyltrimethoxysilane (available from Aladdin under the trade designation CAS number: 15396-00-6) and polyoxypropylene diol (available from Dow of Lanxingdong under the trade designation DL-1000; CAS number: 25322-69-4, weight average molecular weight 1000) were reacted in the following order to obtain a mixture of-NCO: OH (molar ratio) is 1, and esterification reaction is carried out at 65 ℃ for 2h to obtain the surface modifier A7 prepared in the example, and the structural formula is as follows:
Figure BDA0002012907260000102
n7 is an integer from 14 to 16. Sealing and storing for later use.
Example 8
3-isocyanatopropyl-methyldimethoxysilane (from macrographic new materials, commercial number T-02; CAS number: 26115-72-0) and polyoxypropylene diol (from Doxoda Lanxingdong, commercial number DL-3000, weight average molecular weight 3000) were reacted as-NCO: OH (molar ratio) is 1, and esterification reaction is carried out at 65 ℃ for 2h to obtain the surface modifier A8 prepared in the example, and the structural formula is as follows:
Figure BDA0002012907260000111
n8 is an integer from 48 to 50. Sealing and storing for later use.
Example 9
3-isocyanatopropyl-methyldimethoxysilane (from macrographic new materials, with the trade designation T-02; CAS number: 26115-72-0) and polyoxypropylene diol (from Doxoda blue, with the trade designation DL-1000; CAS number: 25322-69-4, with a weight average molecular weight of 1000) were reacted as-NCO: OH (molar ratio) of 1.1 and esterification reaction at 65 ℃ for 2h to obtain the surface modifier A9 prepared in this example, and its formula is:
Figure BDA0002012907260000112
n9 is an integer from 14 to 16. Sealing and storing for later use.
Examples 10-18 are presented to illustrate the thermally conductive potting composite of the present disclosure and methods of making the same.
Example 10
86.61 parts by weight of alumina and 0.39 part by weight of a surface modifier A1 were mixed in humid air, centrifugally stirred for 15min, and then subjected to heat treatment at 90 ℃ for 50min to obtain powder, which was mixed with 13 parts by weight of vinyl silicone oil to obtain the heat-conducting potting composite material B1 prepared in this example.
Examples 11 to 18
The heat-conducting potting composite materials B2 to B9 were prepared according to the method of example 10 using the surface modifiers A2 to A9, respectively.
Comparative example 1
86.61 parts by weight of alumina and 0.39 part by weight of hexadecyl trimethoxy silane were mixed in humid air, centrifugally stirred for 15min, and then subjected to heat treatment at 90 ℃ for 50min to obtain powder, and the powder was mixed with 13 parts by weight of vinyl silicone oil to obtain the heat-conducting potting composite material C1 prepared in the present comparative example.
Test examples
The viscosity and the thermal conductivity of the heat-conducting potting composite materials prepared in examples 10 to 18 and comparative example 1 were tested, and the obtained results are listed in table 1.
The viscosity is tested by a DVS + rotational viscometer under the following test conditions: temperature: 25 ℃; a rotor: rotor No. 6 or 7. The thermal conductivity was measured using a DRL-III thermal conductivity tester.
TABLE 1
Viscosity, cP Thermal conductivity, W/(m. K)
Example 10 19000 3.52
Example 11 19400 3.50
Example 12 21000 3.46
Example 13 9600 3.75
Example 14 9860 3.72
Example 15 10500 3.68
Example 16 19500 3.51
Example 17 22300 3.44
Example 18 21000 3.41
Comparative example 1 41800 3.42
Remarking: the heat conduction test sample was liquid silica gel.
As can be seen from table 1, the thermally conductive potting composite of the present disclosure has a lower viscosity and a higher thermal conductivity.
The preferred embodiments of the present disclosure have been described in detail above, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all fall within the protection scope of the present disclosure.
It should be noted that, in the foregoing embodiments, various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various combinations that are possible in the present disclosure are not described again.
In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.

Claims (11)

1. A composition for preparing a heat-conducting potting composite material is characterized by comprising a silicone oil matrix and an inorganic heat-conducting filler, wherein the inorganic heat-conducting filler is modified by a surface modifier;
the surface modifier comprises a compound shown as a formula (I):
Figure FDA0003294217500000011
wherein R is1Is alkylene, phenylene or cycloalkylene, R3And R4Each independently is R5OR OR5，R5And R2Each independently is C1-C3 alkyl, R is a group obtained by losing n hydroxyl groups of a polyhydroxy polymer, n is 2 or 3, and the polyhydroxy polymer is at least one of polyether polyol, hydroxyl-terminated polysiloxane and polyether modified hydroxyl-terminated polysiloxane.
2. The composition of claim 1, wherein R1Is propylene, R2、R3And R4Each independently is methyl or ethyl; the weight average molecular weight of the polyhydroxy polymer is 1000-2000; the polyether polyol is polyoxypropylene glycol and/or polyoxyethylene glycol; the hydroxyl-terminated polysiloxane is hydroxyl-terminated polydimethylsiloxane; the polyether modified hydroxyl-terminated polysiloxane is hydroxyl-terminated polyether modified silicone oil.
3. The composition of claim 1, wherein the surface modifying agent is prepared by a process comprising: contacting an isocyanate silane coupling agent with a structure shown as a formula (II) with a polyhydroxy polymer under esterification reaction conditions;
Figure FDA0003294217500000012
wherein R is1Is alkylene, phenylene or cycloalkylene, R3And R4Each independently is R5OR OR5，R5And R2Each independently is a C1-C3 alkyl group, and the polyhydroxy polymer is at least one of polyether polyol, hydroxyl-terminated polysiloxane and polyether-modified hydroxyl-terminated polysiloxane.
4. The composition of claim 3, wherein the isocyanate silane coupling agent and the polyhydroxy polymer are present in a molar ratio of isocyanate silane coupling agent to polyhydroxy polymer, calculated as-NCO, (1-1.05): 1.
5. the composition of claim 3, wherein the esterification reaction conditions comprise: the temperature is 50-70 ℃ and the time is 1-2.5 h.
6. The composition according to claim 1, wherein the surface modifier is contained in an amount of 0.1 to 0.7 parts by weight and the inorganic heat conductive filler is contained in an amount of 77 to 87 parts by weight, based on 13 to 22 parts by weight of the silicone oil matrix.
7. The composition of claim 1, wherein the inorganic thermally conductive filler is aluminum oxide, zinc oxide, or aluminum nitride, or a combination of two or three thereof;
the silicone oil matrix is vinyl silicone oil and/or hydrogen-containing silicone oil.
8. A method of preparing a heat-conducting potting composite using the composition of any of claims 1-7, the method comprising: under the hydrolysis condition, mixing the surface modifier with an inorganic heat-conducting filler, then carrying out heating treatment to obtain powder, and then mixing the powder with a silicone oil matrix.
9. The process according to claim 8, wherein the hydrolysis conditions comprise carrying out in humid air and/or with the addition of water; the conditions of the heat treatment include: the temperature is 80-100 ℃, and the time is 30-60 min.
10. The method of claim 8, wherein the method further comprises: and mixing the surface modifier with the inorganic heat-conducting filler under the condition of centrifugal stirring, wherein the centrifugal stirring time is 5-15 min.
11. A heat conducting potting composite prepared by the method of any of claims 8 to 10.
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