CN117209962A - Epoxy resin composite material and preparation method thereof - Google Patents
Epoxy resin composite material and preparation method thereof Download PDFInfo
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- CN117209962A CN117209962A CN202311289094.4A CN202311289094A CN117209962A CN 117209962 A CN117209962 A CN 117209962A CN 202311289094 A CN202311289094 A CN 202311289094A CN 117209962 A CN117209962 A CN 117209962A
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 95
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 95
- 239000002131 composite material Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title abstract description 10
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 107
- 229910052582 BN Inorganic materials 0.000 claims abstract description 94
- 125000002091 cationic group Chemical group 0.000 claims abstract description 22
- 239000001913 cellulose Substances 0.000 claims abstract description 22
- 229920002678 cellulose Polymers 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 26
- 239000004005 microsphere Substances 0.000 claims description 17
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 11
- 239000003995 emulsifying agent Substances 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 238000004108 freeze drying Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 8
- 238000007731 hot pressing Methods 0.000 claims description 8
- 230000033444 hydroxylation Effects 0.000 claims description 8
- 238000005805 hydroxylation reaction Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 4
- 230000001070 adhesive effect Effects 0.000 claims description 4
- 230000000640 hydroxylating effect Effects 0.000 claims description 4
- -1 k54 Chemical compound 0.000 claims description 4
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical group C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 4
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 3
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000009477 glass transition Effects 0.000 abstract description 12
- 238000005457 optimization Methods 0.000 abstract description 6
- 238000013461 design Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 19
- 239000000243 solution Substances 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000000945 filler Substances 0.000 description 10
- 238000012546 transfer Methods 0.000 description 7
- 239000011859 microparticle Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Abstract
The application discloses an epoxy resin composite material and a preparation method thereof, wherein the epoxy resin composite material comprises a functionalized boron nitride micro-sheet, cationic nano fibrillated cellulose, epoxy resin, a curing agent and an accelerator; the functionalized boron nitride micro-sheet comprises a functionalized boron nitride micro-sheet I and a functionalized boron nitride micro-sheet II which are different in size, and the average diameter ratio of the functionalized boron nitride micro-sheet I to the functionalized boron nitride micro-sheet II is 1:10-15. According to the application, by adopting the functionalized boron nitride micro-sheets with two sizes and combining the cationic nanofibrillated cellulose, the epoxy resin composite material disclosed by the application can realize lower dielectric loss, higher through plane thermal conductivity and glass transition temperature, realize the cooperative optimization of heat conduction performance, dielectric performance and mechanical performance, and provide technical support for the structural design and performance optimization of a high-performance composite dielectric medium.
Description
Technical Field
The application relates to the technical field of epoxy resin composite materials, in particular to an epoxy resin composite material and a preparation method thereof.
Background
As a high-performance thermosetting resin, the epoxy resin has excellent insulating property, mechanical property, thermal stability, strong adhesive force, corrosion resistance and easy processability due to compact internal molecular structure, and is widely applied to packaging materials of printed circuit boards and electronic devices. With the development of miniaturization and high power of electronic devices, motors and the like, higher requirements are put forward on high thermal conductivity and low dielectric loss of insulating packaging materials, more heat generated by power consumption of the electronic devices cannot be dissipated in time, the service performance and safe and stable operation of the devices are greatly affected, however, the thermal conductivity of the traditional epoxy resin is only 0.2W/(m.K), the thermal management capability is limited, and the requirements of practical application cannot be met.
Therefore, in order to ensure the working efficiency and the service life of the device, the improvement of the heat conduction performance of the epoxy resin through an effective and practical modification means has important research significance. The simplest and effective method for improving the heat conduction performance of the epoxy resin is to add a high heat conduction filler, and the traditional high heat conduction filler such as boron nitride, graphene, carbon nano tubes, zinc oxide whiskers, magnesium oxide, silicon nitride, silicon carbide, aluminum oxide and the like is an effective filler for improving the heat conduction performance of the epoxy resin. However, in order to meet the requirement of high heat conduction, the addition amount of the heat conducting filler in the epoxy resin matrix is often large, so that the mechanical property of the composite material is poor, and the processing complexity and the cost are both increased; and the traditional method for improving the heat conductivity coefficient of the insulating material by the high heat conductivity filler is generally accompanied by a great increase of dielectric loss, and finally leads to thermal breakdown. In general, in order to effectively manage heat generated in various electronic devices, it is important to enhance the heat transfer capability of the thermal interface composite material in the in-plane and in-plane directions. Therefore, how to improve the through plane thermal conductivity of the composite material and also give consideration to excellent dielectric property and mechanical property is an important problem for preparing the high-thermal-conductivity composite material.
Disclosure of Invention
The application aims to provide an epoxy resin composite material and a preparation method thereof.
The technical scheme of the application is as follows:
in one aspect, an epoxy resin composite is provided, comprising a functionalized boron nitride micro-sheet, cationic nanofibrillated cellulose, an epoxy resin, a curing agent and an accelerator; the functionalized boron nitride micro-sheet comprises a functionalized boron nitride micro-sheet I and a functionalized boron nitride micro-sheet II which are different in size, and the average diameter ratio of the functionalized boron nitride micro-sheet I to the functionalized boron nitride micro-sheet II is 1:10-15.
Preferably, the composite material comprises 8-12 parts by mass of functionalized boron nitride micro-sheet one, 20-40 parts by mass of functionalized boron nitride micro-sheet two, 1.2-2 parts by mass of cationic nano fibrillated cellulose, 30-36 parts by mass of epoxy resin, 25-29 parts by mass of curing agent and 0.5-1 part by mass of accelerator.
Preferably, the functionalized boron nitride micro-sheet is prepared by the following steps: hydroxylating the boron nitride micro-sheet to obtain a hydroxylated boron nitride micro-sheet; and modifying the hydroxylated boron nitride micro-sheet by adopting a silane coupling agent to obtain the functionalized boron nitride micro-sheet.
Preferably, sodium hydroxide is adopted to carry out hydroxylation treatment on the boron nitride micro-sheet; the silane coupling agent is 3-aminopropyl triethoxysilane.
Preferably, the curing agent is methyl hexahydrophthalic anhydride and/or methyl tetrahydrophthalic anhydride.
Preferably, the accelerator is one or more of DMP-30, k54, triethylamine and 2-ethyl 4-methylimidazole.
On the other hand, the preparation method of the epoxy resin composite material according to any one of the above is also provided, and comprises the following steps:
s1: adding epoxy resin into deionized water, adding an emulsifier, stirring, adding a curing agent and an accelerator, continuously stirring after stirring uniformly, adding the functionalized boron nitride micron sheet I after stirring uniformly again, heating, stirring, centrifuging, settling, rinsing, and freeze-drying to obtain epoxy resin microspheres with the surface attached with the functionalized boron nitride micron sheet I;
s2: uniformly dispersing the epoxy resin microspheres and the functionalized boron nitride micro-sheets II in a cationic nanofibrillated cellulose solution, stirring, freeze-drying, adding epoxy resin as a gap adhesive, heating, hot-pressing and naturally cooling to obtain the epoxy resin composite material.
Preferably, in step S1, the emulsifier is one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and phosphate.
Preferably, in the step S1, the stirring temperature of heating and stirring is 100-120 ℃, and the stirring time is 2-3h.
Preferably, in step S2, the hot pressing temperature is 100-140 ℃ and the pressure is 20-30MPa.
The beneficial effects of the application are as follows:
according to the application, by adopting the functionalized boron nitride micro-sheets with two sizes and combining the cationic nanofibrillated cellulose, the epoxy resin composite material disclosed by the application can realize lower dielectric loss, higher through plane thermal conductivity and glass transition temperature, realize the cooperative optimization of heat conduction performance, dielectric performance and mechanical performance, and provide technical support for the structural design and performance optimization of a high-performance composite dielectric medium.
Drawings
In order to more clearly illustrate the embodiments of the application or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the application, and that other drawings can be obtained according to these drawings without inventive faculty for a person skilled in the art.
FIG. 1 is a schematic flow chart of a method for preparing an epoxy resin composite material of the present application;
FIG. 2 is a schematic view of the microstructure of the epoxy resin composite of the present application;
FIG. 3 is a graph showing the results of testing the thermal conductivity of each epoxy resin composite material at different BN contents;
FIG. 4 is a graph showing the dielectric properties of the epoxy resin composite of example 1;
FIG. 5 is a graph showing the results of the glass transition temperature test of the epoxy resin composite of example 1;
FIG. 6 is a graph showing the results of comparing through plane thermal conductivity to dielectric loss for each example and each comparative example;
FIG. 7 is a graphical representation of the results of the glass transition temperature comparison test for each example and each comparative example.
Detailed Description
The application will be further described with reference to the drawings and examples. It should be noted that, without conflict, the embodiments of the present application and the technical features of the embodiments may be combined with each other. It is noted that all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs unless otherwise indicated. The use of the terms "comprising" or "includes" and the like in this disclosure is intended to cover a member or article listed after that term and equivalents thereof without precluding other members or articles.
In one aspect, the application provides an epoxy resin composite material comprising functionalized boron nitride micro-sheets, cationic nanofibrillated cellulose, epoxy resin, curing agent and accelerator; the functionalized boron nitride micro-sheet comprises a functionalized boron nitride micro-sheet I and a functionalized boron nitride micro-sheet II which are different in size, and the average diameter ratio of the functionalized boron nitride micro-sheet I to the functionalized boron nitride micro-sheet II is 1:10-15.
In the embodiment, through arranging the functionalized boron nitride micro-sheets with two sizes, the effective arrangement and distribution of the functionalized boron nitride micro-sheets with small sizes in the epoxy resin matrix are utilized to prevent the aggregation and in-plane orientation of the boron nitride micro-sheets, reduce the contact thermal resistance among the boron nitride micro-sheets and form a more continuous and effective heat transfer passage; the large-size functionalized boron nitride micron sheets are utilized to form an efficient phonon transmission channel, so that the heat transfer path is shortened, the interface thermal resistance and phonon scattering are reduced, the through plane thermal conductivity of the epoxy resin composite material is remarkably improved, and the dielectric loss is kept low.
By adding the cationic nanofibrillated cellulose, the characteristics of high chemical stability, excellent thermal stability, high strength, high modulus, environmental friendliness, degradability, a large number of hydroxyl groups and carboxyl groups on the surface, easiness in carrying out various surface modifications, polarity change and the like can be utilized, the cationic nanofibrillated cellulose is crosslinked with epoxy resin, and hydrogen bonds are formed with the functionalized boron nitride micro-sheet, so that the movement of polymer chains is limited, the low dielectric loss is ensured, and the rigidity and the glass transition temperature of the composite material are improved.
In conclusion, the epoxy resin composite material provided by the application realizes lower dielectric loss, higher through plane thermal conductivity and glass transition temperature, and realizes the synergistic optimization of heat conduction performance, dielectric performance and mechanical performance.
In a specific embodiment, the epoxy resin composite material comprises, by mass, 8-12 parts of functionalized boron nitride micro-sheets, 20-40 parts of functionalized boron nitride micro-sheets, 1.2-2 parts of cationic nanofibrillated cellulose, 30-36 parts of epoxy resin, 25-29 parts of curing agent and 0.5-1 part of accelerator.
In a specific embodiment, the functionalized boron nitride micro-sheet is prepared by the following steps: hydroxylating the boron nitride micro-sheet to obtain a hydroxylated boron nitride micro-sheet; and modifying the hydroxylated boron nitride micro-sheet by adopting a silane coupling agent to obtain the functionalized boron nitride micro-sheet.
Optionally, hydroxylating the boron nitride micro-sheet by adopting sodium hydroxide; the silane coupling agent is 3-aminopropyl triethoxysilane. In this example, by using 3-aminopropyl triethoxysilane as the silane coupling agent, it is possible to graft amino groups on the boron nitride micro-plate, causing it to form hydrogen bonds with the cationic nanofibrillated cellulose, limiting the movement of the polymer chains.
The hydroxylation treatment of the boron nitride micro-sheet with sodium hydroxide is only one preferred method of hydroxylation treatment of the boron nitride micro-sheet of the present application, and the purpose of the hydroxylation treatment is to hydroxylate the boron nitride micro-sheet, and other methods capable of achieving the purpose in the prior art are also applicable to the present application.
In a specific embodiment, when the hydroxylation treatment is carried out on the boron nitride micro-sheet by adopting sodium hydroxide, the boron nitride micro-sheet is ultrasonically dispersed in a sodium hydroxide solution, the ultrasonic power is 100-150W, the ultrasonic time is 30-60min, then the mixture is stirred for 24-30h at 70-90 ℃, and finally the mixture is dried for 12-16h, thus obtaining the hydroxylated boron nitride micro-sheet.
In a specific embodiment, when the hydroxylated boron nitride micro-sheet is modified by adopting a silane coupling agent, the silane coupling agent is added into an ethanol solution, the mass ratio of the silane coupling agent to the ethanol solution is 15-20:1, then the hydroxylated boron nitride micro-sheet is added for ultrasonic dispersion, and the functionalized boron nitride micro-sheet can be obtained after freeze drying. Optionally, the time of ultrasonic dispersion is 15-30min, and the time of freeze drying is 20-30h.
In a specific embodiment, the epoxy resin is bisphenol a epoxy resin and/or cycloaliphatic epoxy resin, the curing agent is methyl hexahydrophthalic anhydride and/or methyl tetrahydrophthalic anhydride, and the accelerator is one or more of DMP-30, k54, triethylamine and 2-ethyl 4-methylimidazole.
The specific types of the epoxy resin, the curing agent and the accelerator are only preferred types of the present application, and other types of the epoxy resin composite materials used in the prior art are also applicable to the present application.
On the other hand, as shown in fig. 1, the application also provides a preparation method of the epoxy resin composite material, which comprises the following steps:
s1: adding epoxy resin into deionized water, adding an emulsifier, stirring, adding a curing agent and an accelerator, continuously stirring after stirring uniformly, adding the functionalized boron nitride micron sheet I after stirring uniformly again, heating, stirring, centrifuging, settling, rinsing, and freeze-drying to obtain epoxy resin microspheres with the surface attached with the functionalized boron nitride micron sheet I;
s2: uniformly dispersing the epoxy resin microspheres and the functionalized boron nitride micro-sheets II in a cationic nanofibrillated cellulose solution, stirring, freeze-drying, adding epoxy resin as a gap adhesive, heating, hot-pressing and naturally cooling to obtain the epoxy resin composite material.
In the embodiment, the epoxy resin microsphere of the surface self-assembled functionalized boron nitride micro-sheet is prepared by an emulsion polymerization method, and then is mixed with the functionalized boron nitride micro-sheet with larger size, so that the functionalized boron nitride micro-sheet with larger size is forced to be oriented vertically, the effective construction of a through plane heat conduction channel is realized, and the heat conductivity in the through plane direction is greatly improved; and secondly, introducing cationic nanofibrillated cellulose, wherein the surface of the cationic nanofibrillated cellulose is provided with a large number of hydroxyl groups and carboxyl groups, so that the cationic nanofibrillated cellulose can be crosslinked with epoxy groups and can also form hydrogen bonds with amino groups on the functionalized boron nitride micron sheet, the movement of polymer chains is limited, the low dielectric loss is ensured, and the rigidity and the glass transition temperature of the composite material are improved.
In a specific embodiment, the emulsifier is one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, and phosphate.
In a specific embodiment, in step S1, the stirring temperature of heating and stirring is 100-120 ℃, and the stirring time is 2-3 hours; in the step S2, the hot pressing temperature is 100-140 ℃ and the hot pressing pressure is 20-30MPa.
In a specific embodiment, in step S1, the mass ratio of epoxy resin to deionized water is 1:10-15, wherein the mass of the emulsifier is 0.05% of the mass of the epoxy resin, the stirring speed is 400-600rpm when the emulsifier is added for stirring, and the stirring time is 20-30h; the centrifugal speed is 7000-1000rpm during centrifugation, and the centrifugal time is 8-14min; the temperature is 5-10deg.C and the time is 4-8h during freezing; the temperature is 45-60 ℃ and the time is 24-30h during drying.
Example 1
An epoxy resin composite material is prepared by the following steps:
(1) Preparing hydroxylated boron nitride: first, 3g of small-sized boron nitride microparticles (average diameter of 1 μm) were dispersed in 250mL of sodium hydroxide solution (1 mol/L) and sonicated for 30min. The mixture was then transferred to a magnetic stirrer at a constant temperature of 80 ℃ for stirring for 24 hours. The dispersion obtained was then filtered in a funnel and then washed three times alternately with ethanol and deionized water. Finally, the filtered solid was dried at 100℃for 12 hours to obtain hydroxylated BN (designated BN-OH). This is also true for hydroxylation of 9g of large-size boron nitride microparticles (average diameter 15 μm).
(2) Preparing functionalized boron nitride: BN-OH was modified with 3-aminopropyl triethoxysilane (APTES) by sol-gel method. First, 3mL APTES was added at 191 was added to 200mL of ethanol aqueous solution. The dried BN-OH particles were dispersed into the solution by sonication for 15min. The dispersion was then refluxed to 80 ℃ in a magnetic stirrer for 12h. Subsequently, the BN dispersion was filtered and repeatedly washed with deionized water to prepare APTES functionalized BN (abbreviated BN-APTES).
(3) Preparing epoxy resin microspheres: distilled water is used as a solvent, and the self-assembled core-shell epoxy resin microsphere is prepared through environment-friendly emulsion polymerization. Bisphenol A type epoxy resin (8 g) was charged into a stirred reactor containing 100mL of DI water at 80℃and then 5mg of Sodium Dodecyl Sulfate (SDS) as an emulsifier was added to the mixture, followed by mechanical stirring at 500rpm for 24 hours.
The curing agent methyl hexahydrophthalic anhydride (8 g) and accelerator DMP-30 (0.16 g) were added to the mixture in proportion and mechanically stirred, followed by small-sized BN flakes (3 g) added to the emulsion solution. The surface of the epoxy microsphere is covered due to self-assembly of BN flakes. After stirring the mixed solution at 120℃for 2 hours, the solidified microspheres were precipitated at the bottom of the reactor, followed by centrifugation at 8000rpm for 10min. The rinsing step was repeated three times to remove any remaining emulsifier. After centrifugation and freeze-drying, the epoxy resin microsphere (e-BN microsphere) with the epoxy resin as a core and the h-BN flake as a shell was successfully prepared.
(4) Preparing an epoxy resin composite material: the e-BN microspheres and 9g of large-sized BN flakes are mixed and dispersed in a cationic nanofibrillated cellulose (C-CNF) solution to prepare an e-BN/BN/CNF/epoxy resin composite material, which is mechanically stirred and freeze-dried, followed by adding 2g of epoxy resin as a binder and hot-pressing the mixture at 120 ℃ under 20MPa for 2 hours. Subsequently, they were cooled under a pressure (20 MPa) for 12 hours to obtain an e-BN/BN/CNF/EP epoxy resin composite material in which the total mass of the filler is 40wt% with a thickness of 1mm, in which the small-size boron nitride microplates are 10wt% and the large-size boron nitride microplates are 30wt%, and the microstructure is shown in FIG. 2.
Example 2
Unlike example 1, this example uses the following step (1) to prepare hydroxylated boron nitride:
(1) Preparing hydroxylated boron nitride: 3g of small-sized boron nitride microparticles (average diameter of 1 μm) were dispersed in 200mL of NaOH solution (5 mol/L) by ultrasonic treatment and stirring for 3 hours, and then subjected to hydrothermal treatment again in a stainless steel autoclave of a polytetrafluoroethylene substrate at 180℃for 24 hours to hydroxylate the boron nitride microparticles. The resulting suspension was then filtered and thoroughly washed with water to remove excess lye and ions until the pH of the filtrate was 7. The resulting hydroxylated boron nitride microparticles were collected and dried in a vacuum oven at 60 ℃ for 48h to obtain hydroxylated BN (designated BN-OH). This is also true for hydroxylation of 9g of large-size boron nitride microparticles (average diameter 15 μm).
Example 3
Unlike example 1, the average diameter ratio of the functionalized boron nitride micro-plate one to the functionalized boron nitride micro-plate two of this example was 1:10, i.e., the small size boron nitride micro-plate was 1 μm and the large size boron nitride micro-plate was 10 μm.
Example 4
Unlike example 1, the doping amount of BN in step (4) of this example was 20wt%.
Example 5
Unlike example 1, the doping amount of BN in step (4) of this example was 40wt%.
Comparative example 1
Unlike example 1, the silane coupling agent used in the preparation of the functionalized boron nitride in step (2) of this comparative example was gamma-glycidoxypropyl trimethoxysilane (KH 560), and the functionalized BN obtained by the preparation was abbreviated as BN-KH560.
Comparative example 2
Unlike example 1, the BN flakes employed in step (4) of this comparative example were still small-sized BN flakes (average diameter of 1 μm), and an epoxy resin composite material having a thickness of 1mm and a total mass of 40wt% of the filler was obtained (wherein the small-sized boron nitride micro-flakes were 40wt% and the large-sized boron nitride micro-flakes were 0 wt%).
Comparative example 3
Unlike example 1, the BN flakes employed in step (3) of this comparative example were large-sized BN flakes (average diameter: 15 μm), the BN flakes employed in step (4) were small-sized BN flakes (average diameter: 1 μm), and an epoxy resin composite material having a thickness of 1mm and a total mass of 40wt% was obtained (wherein the small-sized boron nitride micro-flakes were 10wt% and the large-sized boron nitride micro-flakes were 30 wt%).
Comparative example 4
Unlike example 1, this comparative example no longer added large-sized BN flakes in step (4), an epoxy resin composite material having a thickness of 1mm and a total mass of 10wt% of the filler was obtained (wherein the small-sized boron nitride micro-flakes were 10wt% and the large-sized boron nitride micro-flakes were 0 wt%).
Comparative example 5
Unlike example 1, this comparative example no cationic nanofibrillated cellulose was added in step (4), i.e., the cationic nanofibrillated cellulose (C-CNF) solution in step (4) was replaced with an ethanol solution, resulting in an epoxy resin composite with a thickness of 1mm of 40wt% of the total mass of the filler (where the small-sized boron nitride micro-flakes were 10wt% and the large-sized boron nitride micro-flakes were 30 wt%).
Comparative example 6
Unlike example 1, this comparative example, in which small-sized BN flakes were not added in the preparation of the epoxy resin microspheres in step (3), an epoxy resin composite material having a thickness of 1mm and a total mass of 30wt% of the filler was obtained (wherein small-sized boron nitride microplates were 0wt% and large-sized boron nitride microplates were 30 wt%).
The epoxy resin composites prepared in each example and each comparative example were subjected to heat conduction, dielectric loss, and glass transition temperature tests, and the results are shown in fig. 3 to 7.
As can be seen from FIG. 3, with the increase of the BN flake content, the through-plane thermal conductivity of the epoxy resin composite material is remarkably improved due to the anisotropy and the two-dimensional hexagonal layered structure, and at 30% of BN content, the through-plane thermal conductivity of the epoxy resin composite material is 3 times that of pure epoxy resin, and the epoxy microspheres with the surface covered with the BN flake promote the heat transfer inside the epoxy resin composite material along the through-plane direction, so that an interconnected three-dimensional heat transfer network is effectively formed.
As can be seen from fig. 4, the dielectric loss of the epoxy resin composite material of the present application is significantly reduced from 0.007 to 0.00597 by 14.71%.
As can be seen from FIG. 5, the glass transition temperature of the epoxy resin composite material of the application reaches 144.5 ℃, which is improved by 34.17% compared with the temperature of 107.7 ℃ of the pure epoxy resin material.
As can be seen from fig. 6-7, the thermal conductivity in the through plane of comparative examples 3, 4, and 6 is significantly reduced compared to the examples, the heat transfer path is poorly constructed, and the contact thermal resistance is increased; the dielectric losses of comparative examples 1, 2, 3, 5 increase dramatically, approaching 0.01 at 40 KHz; and the glass transition temperatures of comparative examples 1, 2, 3, 5 and 6 were also greatly reduced. Compared with each comparative example, the epoxy resin composite material prepared by the application integrates excellent through plane heat transfer and high glass transition temperature performance, and the dielectric loss of the epoxy resin composite material can be maintained at about 0.005 at 40 kHz.
In conclusion, the method starts from the epoxy resin microsphere (e-BN) with the surface coated with the BN sheet, introduces BN and cationic nanofibrillated cellulose to remarkably improve the through plane thermal conductivity of the material, maintains the high glass transition temperature and low dielectric loss characteristics of the epoxy resin composite material, not only can provide a new thought for structural design and performance optimization of high-performance composite dielectrics, but also has important significance for enriching related basic theories between microstructure-mesostructure-macroscopic performance of the composite dielectrics. Compared with the prior art, the application has obvious progress.
The present application is not limited to the above-mentioned embodiments, but is intended to be limited to the following embodiments, and any modifications, equivalents and modifications can be made to the above-mentioned embodiments without departing from the scope of the application.
Claims (10)
1. An epoxy resin composite material is characterized by comprising a functionalized boron nitride micro-sheet, cationic nanofibrillated cellulose, epoxy resin, a curing agent and an accelerator; the functionalized boron nitride micro-sheet comprises a functionalized boron nitride micro-sheet I and a functionalized boron nitride micro-sheet II which are different in size, and the average diameter ratio of the functionalized boron nitride micro-sheet I to the functionalized boron nitride micro-sheet II is 1:10-15.
2. The epoxy resin composite material according to claim 1, which is characterized by comprising, in parts by mass, 8-12 parts of functionalized boron nitride micro-sheet one, 20-40 parts of functionalized boron nitride micro-sheet two, 1.2-2 parts of cationic nanofibrillated cellulose, 30-36 parts of epoxy resin, 25-29 parts of curing agent and 0.5-1 part of accelerator.
3. The epoxy resin composite material according to claim 1 or 2, wherein the functionalized boron nitride micro-sheet is prepared by the steps of: hydroxylating the boron nitride micro-sheet to obtain a hydroxylated boron nitride micro-sheet; and modifying the hydroxylated boron nitride micro-sheet by adopting a silane coupling agent to obtain the functionalized boron nitride micro-sheet.
4. An epoxy resin composite material according to claim 3, wherein the boron nitride micro-sheet is subjected to hydroxylation treatment with sodium hydroxide; the silane coupling agent is 3-aminopropyl triethoxysilane.
5. The epoxy resin composite of any one of claims 1-4, wherein the curing agent is methyl hexahydrophthalic anhydride and/or methyl tetrahydrophthalic anhydride.
6. An epoxy resin composite according to any one of claims 1 to 4 wherein the accelerator is one or more of DMP-30, k54, triethylamine, 2-ethyl 4-methylimidazole.
7. A method of preparing an epoxy resin composite according to any one of claims 1 to 6, comprising the steps of:
s1: adding epoxy resin into deionized water, adding an emulsifier, stirring, adding a curing agent and an accelerator, continuously stirring after stirring uniformly, adding the functionalized boron nitride micron sheet I after stirring uniformly again, heating, stirring, centrifuging, settling, rinsing, and freeze-drying to obtain epoxy resin microspheres with the surface attached with the functionalized boron nitride micron sheet I;
s2: uniformly dispersing the epoxy resin microspheres and the functionalized boron nitride micro-sheets II in a cationic nanofibrillated cellulose solution, stirring, freeze-drying, adding epoxy resin as a gap adhesive, heating, hot-pressing and naturally cooling to obtain the epoxy resin composite material.
8. The method of preparing an epoxy resin composite according to claim 7, wherein in step S1, the emulsifier is one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, and phosphate.
9. The method for producing an epoxy resin composite according to claim 7, wherein in step S1, the stirring temperature of the heating and stirring is 100 to 120 ℃ and the stirring time is 2 to 3 hours.
10. The method of producing an epoxy resin composite according to claim 7, wherein in step S2, the hot pressing is performed at a temperature of 100 to 140 ℃ and a pressure of 20 to 30MPa.
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