CN111334000B - Graphene epoxy resin composite material, preparation method and application - Google Patents
Graphene epoxy resin composite material, preparation method and application Download PDFInfo
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- CN111334000B CN111334000B CN202010273853.8A CN202010273853A CN111334000B CN 111334000 B CN111334000 B CN 111334000B CN 202010273853 A CN202010273853 A CN 202010273853A CN 111334000 B CN111334000 B CN 111334000B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 142
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 122
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 76
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 76
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 112
- 239000000499 gel Substances 0.000 claims abstract description 36
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 33
- PBZROIMXDZTJDF-UHFFFAOYSA-N hepta-1,6-dien-4-one Chemical compound C=CCC(=O)CC=C PBZROIMXDZTJDF-UHFFFAOYSA-N 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000017 hydrogel Substances 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 7
- 238000001723 curing Methods 0.000 claims description 46
- 238000003756 stirring Methods 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 19
- 229910002804 graphite Inorganic materials 0.000 claims description 18
- 239000010439 graphite Substances 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 14
- 238000004821 distillation Methods 0.000 claims description 11
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 6
- 150000008065 acid anhydrides Chemical class 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 4
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004020 conductor Substances 0.000 claims description 2
- 229960003638 dopamine Drugs 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 229940071870 hydroiodic acid Drugs 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 235000009518 sodium iodide Nutrition 0.000 claims description 2
- 150000003573 thiols Chemical class 0.000 claims description 2
- 239000004964 aerogel Substances 0.000 abstract description 29
- 238000006722 reduction reaction Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 16
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 12
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 12
- 229960001124 trientine Drugs 0.000 description 12
- -1 amine compounds Chemical class 0.000 description 7
- 238000004108 freeze drying Methods 0.000 description 7
- 238000001132 ultrasonic dispersion Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 150000008064 anhydrides Chemical class 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 2
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 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
- 230000007547 defect Effects 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229940079101 sodium sulfide Drugs 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 description 1
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- RDNPPYMJRALIIH-UHFFFAOYSA-N 3-methylcyclohex-3-ene-1,1,2,2-tetracarboxylic acid Chemical compound CC1=CCCC(C(O)=O)(C(O)=O)C1(C(O)=O)C(O)=O RDNPPYMJRALIIH-UHFFFAOYSA-N 0.000 description 1
- KOGSPLLRMRSADR-UHFFFAOYSA-N 4-(2-aminopropan-2-yl)-1-methylcyclohexan-1-amine Chemical compound CC(C)(N)C1CCC(C)(N)CC1 KOGSPLLRMRSADR-UHFFFAOYSA-N 0.000 description 1
- JRAFOWMFDBBVPB-UHFFFAOYSA-N 5,6,7,7a-tetrabromo-3ah-2-benzofuran-1,3-dione Chemical compound BrC1=C(Br)C(Br)=CC2C(=O)OC(=O)C21Br JRAFOWMFDBBVPB-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 description 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 1
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 1
- 239000004845 glycidylamine epoxy resin Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229960004337 hydroquinone Drugs 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229940091868 melamine Drugs 0.000 description 1
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 1
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 description 1
- LCXGFVXUJZJODY-UHFFFAOYSA-N n-methylmethanamine;toluene Chemical compound CNC.CC1=CC=CC=C1 LCXGFVXUJZJODY-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 229960001790 sodium citrate Drugs 0.000 description 1
- 229940083599 sodium iodide Drugs 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 238000003815 supercritical carbon dioxide extraction Methods 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
Abstract
The invention belongs to the field of composite materials, particularly relates to the technical field of graphene epoxy resin composite materials, and relates to a graphene epoxy resin composite material, a preparation method and application thereof, wherein graphene oxide is subjected to hydrothermal reduction reaction to obtain graphene hydrogel; the graphene hydrogel is subjected to deionized water and acetone replacement to obtain graphene allyl ketone gel, the graphene allyl ketone gel is added into an epoxy resin acetone solution to be mixed and stirred uniformly, a curing agent is added to be mixed and stirred uniformly, acetone is removed, and the graphene epoxy resin composite material is obtained through curing, so that the toughness, tensile strength, electric conductivity and heat conductivity of the epoxy resin are improved, and the graphene epoxy resin composite material can be applied to the fields of heat conduction materials and electric conduction materials. According to the invention, the graphene gel is not required to be processed into the graphene aerogel, and the graphene gel is directly added into the epoxy resin solution for mixing, so that the purposes of saving equipment and time, improving efficiency and reducing cost are achieved.
Description
Technical Field
The invention relates to the field of composite materials, in particular to the technical field of graphene epoxy resin composite materials, and relates to a graphene epoxy resin composite material, a preparation method and application thereof.
Background
Graphene is a carbon nanomaterial with a two-dimensional structure discovered in 2004, has good mechanical properties, conductivity, heat conductivity and the like, and has important application prospects in the fields of materials science, energy, biomedicine, micro-nano processing and the like. The graphene aerogel is an aerogel newly developed in recent years, and has the unique advantages of low density, high specific surface area, large pore volume, high conductivity, good thermal stability, controllable structure and the like. In 2013, the subject group of Zhejiang polymer professor with high molecular weight was manufactured to have a density as low as 0.16mg/cm 3 Is currently the lightest solid material known in the world.
The graphene aerogel is applied to the epoxy resin, and a plurality of reports are provided for improving the performance of the epoxy resin.
The invention patent of application publication number CN106082202A discloses a preparation method and application of graphene aerogel, wherein a mixture of epoxy resin and a curing agent is poured into a mold containing the graphene aerogel, and the graphene aerogel is fully soaked in the mixture and then is heated and cured to obtain the graphene aerogel/epoxy resin composite material with high conductivity and mechanical property.
The invention patent of application publication number CN108276983A discloses a preparation method of a graphene aerogel epoxy resin composite fracturing propping agent, and the preparation method comprises the steps of mixing epoxy resin and a curing agent, adding the obtained graphene aerogel balls, and carrying out impregnation, degassing and curing on the obtained mixture to obtain the graphene aerogel composite fracturing propping agent.
The research on the modification of graphene oxide aerogel to enhance and toughen epoxy resin (plastics industry 2018, volume 46, stage 6) reports that graphene oxide aerogel is prepared by a sol-gel method, and then a mixture of epoxy resin and a curing agent is poured into the formed graphene oxide aerogel and cured to obtain the graphene oxide aerogel.
The graphene aerogel epoxy resin composite material prepared by the method is prepared by firstly preparing the graphene aerogel and then mixing and curing the graphene aerogel with epoxy resin, and the method has the following defects: the preparation method has the advantages of long time (freeze drying is needed, the freeze drying time is long), high equipment requirement (the freeze drying equipment which can be industrially applied has high requirements on freeze drying, and the freeze drying requirements continuously provide a low-temperature environment), expensive equipment and high cost, so that the graphene aerogel cannot be industrially produced in a large scale. Therefore, the graphene aerogel epoxy resin composite material cannot be produced in a large scale in industry.
In view of this, the inventor finds a simple method for preparing the graphene aerogel epoxy resin composite material through a large number of experiments.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a graphene epoxy resin composite material.
Another object of the present invention is to provide a graphene epoxy resin composite material having good toughness, tensile strength, electrical conductivity and thermal conductivity.
The invention also aims to provide application of the graphene epoxy resin composite material.
The technical scheme of the invention is as follows:
a preparation method of a graphene epoxy resin composite material comprises the following steps,
s1, adding 1 part of graphene oxide and 1-5 parts of reducing agent into 1000 parts of 100-fold deionized water in parts by weight, performing ultrasonic dispersion for 20-30 minutes, sealing and placing in a hydrothermal kettle at 90-120 ℃ and heating for 12-24 hours to obtain graphene hydrogel;
s2, replacing the graphene hydrogel obtained in the step S1 with deionized water for 2-3 times, then replacing with acetone for 3-5 times, and removing redundant acetone to obtain graphene allyl ketone gel;
s3, adding epoxy resin into an acetone solvent for dissolving, adding the graphite allyl ketone gel obtained in the step S2, uniformly stirring and mixing, adding a curing agent, uniformly stirring, carrying out reduced pressure distillation to remove acetone, and curing to obtain the graphene epoxy resin composite material.
Preferably, the graphene oxide in step S1 is selected from graphene oxide by Hummers method or modified graphene oxide by Hummers method.
Preferably, the reducing agent in step S1 is one or more selected from sodium iodide, sodium sulfide, hydroquinone, ascorbic acid, dopamine, melamine, sodium citrate and hydroiodic acid. The reducing agent may also be selected from amine compounds, such as diaminodiphenylmethane, triethylenetetramine, diaminodiphenylsulfone or diethylaminopropylamine. The weight portion of the reducing agent is preferably 1.5 to 3 parts.
The deionized water replacement in the step S2 may be adding deionized water, then ultrasonically treating in an ultrasonic cleaner for 10-15 seconds, and then pouring out the excess water, or vibrating on an oscillator for 3-5 minutes and then pouring out the excess water; the acetone replacement can be to add acetone and then pour out the excess acetone by ultrasonic treatment in an ultrasonic cleaner for 10-15 seconds, or can be to pour out the excess acetone after vibrating on an oscillator for 3-5 minutes.
In step S2, the removal of excess acetone is performed by pouring out excess acetone, and then sucking off acetone that is not bound to the graphite allyl ketone gel with filter paper. The acetone bound on the graphite allyl ketone gel is the acetone required for forming the graphite allyl ketone gel.
Preferably, the weight ratio of the epoxy resin, the acetone solvent, the graphite allyl ketone gel and the curing agent in the step S3 is 100:100-1000:5-200: 3-100.
More preferably, the weight ratio of the epoxy resin, the acetone solvent, the graphite allyl ketone gel and the curing agent is 100:200-600:10-100: 10-80.
The epoxy resin is preferably one or more of glycidyl ether epoxy resin, glycidyl ester epoxy resin and glycidyl amine epoxy resin, and more preferably glycidyl ether epoxy resin, such as bisphenol A epoxy resin. The epoxy value of the epoxy resin is 0.02 to 0.6, preferably 0.2 to 0.52.
Preferably, the curing agent in step S3 is one selected from the group consisting of an amine curing agent, an acid anhydride curing agent, a phenol curing agent, a thiol curing agent, and a boron amine complex curing agent. More preferably, the curing agent is selected from amine curing agents or anhydride curing agents. The amine curing agent can be one selected from aliphatic amine curing agents, alicyclic amine curing agents, aromatic amine curing agents and modified amine curing agents, and specifically can be selected from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, N' -diethylaminopropylamine, N-aminoethyl piperazine, menthane diamine, isophorone diamine, 1, 3-bis (aminomethyl) cyclohexane, m-phenylenediamine, toluene dimethylamine, diaminodiphenyl sulfone, diaminodiphenylmethane or beta-hydroxyethyl ethylenediamine. The acid anhydride curing agent can be selected from one of aromatic acid anhydride, alicyclic acid anhydride, aliphatic acid anhydride or halogen-containing acid anhydride, and specifically can be selected from one of phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, maleic anhydride, elaeostearic anhydride, alkenyl succinic anhydride, tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, glutaric anhydride, terpene-based acid anhydride, hydrogenated methyl nadic anhydride, methylcyclohexene tetracarboxylic dianhydride, polyazelaic anhydride, polysebacic anhydride, poly eicosanedioic anhydride or 1,4,5, 6-tetrabromophthalic anhydride.
The graphene epoxy resin composite material prepared by the preparation method of any one of the above embodiments.
The graphene epoxy resin composite material described in the above embodiment is applied to the field of conductive materials.
The graphene epoxy resin composite material provided by the embodiment is applied to the field of heat conduction materials.
The invention has the beneficial effects that:
(1) the graphene aerogel does not need to be reprocessed into the graphene aerogel. The graphene gel is industrially processed into the graphene aerogel, expensive freeze drying equipment or supercritical carbon dioxide extraction equipment is required, the processing time is long, and the cost is high. According to the invention, the graphene gel is directly added into the epoxy resin solution, and the step of forming the graphene aerogel is omitted, so that the cost is low, the operability is high, and the method is suitable for industrial production.
(2) The obtained graphene epoxy resin composite material has good toughness, high tensile strength, high thermal conductivity and high electrical conductivity. Compared with the composite material obtained by dispersing the graphene sheets into the epoxy resin, the composite material obtained by the invention has better performance when the addition amount of the graphene gel is lower.
Detailed Description
The technical solution of the present invention is further illustrated and described by the following detailed description.
Unless otherwise specified, the parts in the following embodiments are parts by weight.
Detailed description of the preferred embodiments
Preparation of graphite allyl ketone gel
Adding 1 part of Hummers method graphene oxide and 2 parts of sodium citrate into 200 parts of deionized water, performing ultrasonic dispersion for 30 minutes, sealing, and heating at 110 ℃ for 16 hours in a hydrothermal kettle to obtain graphene hydrogel 1; and replacing the graphene hydrogel 1 with deionized water for 2 times, and replacing with acetone which is 5 times of the volume of the graphene hydrogel for 5 times, wherein the replacement condition is that the ultrasonic cleaner performs ultrasonic treatment for 12 seconds at normal temperature, and removing redundant acetone to obtain the graphene allyl ketone gel 1. The graphite allyl ketone gel 1 was baked in an oven at 70 ℃ for 2 hours, and the solid content of the graphite allyl ketone gel 1 was found to be 4.4 wt%.
Adding 1 part of Hummers method graphene oxide and 5 parts of ascorbic acid into 600 parts of deionized water, performing ultrasonic dispersion for 20 minutes, sealing, and heating in a hydrothermal kettle at 100 ℃ for 20 hours to obtain graphene hydrogel 2; and replacing the graphene hydrogel 2 with deionized water for 3 times, and replacing with acetone 7 times the volume of the graphene hydrogel for 5 times under the condition of ultrasonic cleaning for 12 seconds at normal temperature to remove redundant acetone, so as to obtain the graphene allyl ketone gel 2. The graphite allyl ketone gel 2 was baked in an oven at 70 ℃ for 2 hours, and the solid content of the graphite allyl ketone gel 2 was found to be 4.7 wt%.
Adding 1 part of improved Hummers method graphene oxide and 3 parts of sodium sulfide into 900 parts of deionized water, ultrasonically dispersing for 25 minutes, sealing, and heating in a hydrothermal kettle at 120 ℃ for 12 hours to obtain graphene hydrogel 3; and replacing the graphene hydrogel 3 with deionized water for 3 times, and replacing with acetone 10 times the volume of the graphene hydrogel for 4 times under the condition of ultrasonic cleaning for 12 seconds at normal temperature, and removing redundant acetone to obtain the graphene allyl ketone gel 3. The graphite allyl ketone gel 3 was baked in an oven at 70 ℃ for 2 hours, and the solid content of the graphite allyl ketone gel 3 was found to be 4.8 wt%.
Example 1
Adding 100 parts of bisphenol A epoxy resin into 220 parts of acetone solvent for dissolving, adding 5 parts of graphene allyl ketone gel 1, stirring and mixing uniformly, adding 15 parts of triethylene tetramine, stirring uniformly, carrying out reduced pressure distillation to remove acetone, and curing to obtain the graphene epoxy resin composite material 1.
Example 2
Adding 100 parts of bisphenol A epoxy resin into 350 parts of acetone solvent for dissolving, adding 12 parts of graphene allyl ketone gel 1, stirring and mixing uniformly, adding 15 parts of triethylene tetramine, stirring uniformly, carrying out reduced pressure distillation to remove acetone, and curing to obtain the graphene epoxy resin composite material 2.
Example 3
Adding 100 parts of bisphenol A epoxy resin into 450 parts of acetone solvent for dissolving, adding 25 parts of graphene allyl ketone gel 2, stirring and mixing uniformly, adding 15 parts of triethylene tetramine, stirring uniformly, carrying out reduced pressure distillation to remove acetone, and curing to obtain the graphene epoxy resin composite material 3.
Example 4
Adding 100 parts of bisphenol A epoxy resin into 600 parts of acetone solvent for dissolving, adding 50 parts of graphene allyl ketone gel 2, stirring and mixing uniformly, adding 15 parts of triethylene tetramine, stirring uniformly, carrying out reduced pressure distillation to remove acetone, and curing to obtain the graphene epoxy resin composite material 4.
Example 5
Adding 100 parts of bisphenol A epoxy resin into 800 parts of acetone solvent for dissolving, adding 100 parts of graphene allyl ketone gel 2, stirring and mixing uniformly, adding 15 parts of triethylene tetramine, stirring uniformly, carrying out reduced pressure distillation to remove acetone, and curing to obtain the graphene epoxy resin composite material 5.
Example 6
Adding 100 parts of bisphenol A epoxy resin into 500 parts of acetone solvent for dissolving, adding 60 parts of graphite allyl ketone gel 3, stirring and mixing uniformly, adding 80 parts of phthalic anhydride, stirring uniformly, distilling under reduced pressure to remove acetone, and curing to obtain the graphene epoxy resin composite material 6.
Example 7
Adding 100 parts of bisphenol A epoxy resin into 500 parts of acetone solvent for dissolving, adding 150 parts of graphite allyl ketone gel 3, stirring and mixing uniformly, adding 80 parts of phthalic anhydride, stirring uniformly, distilling under reduced pressure to remove acetone, and curing to obtain the graphene epoxy resin composite material 7.
Comparative example 1
And (3) removing the solvent from the graphene allyl ketone gel 1 in a freeze drying device to obtain the graphene aerogel 1.
Adding 0.6 part of graphene aerogel 1 into 20 parts of acetone, performing ultrasonic dispersion, adding the obtained product into a mixed solution of 100 parts of bisphenol A epoxy resin and 350 parts of acetone, uniformly stirring and dispersing, adding 15 parts of triethylene tetramine, uniformly stirring, performing reduced pressure distillation to remove the acetone, and curing to obtain the graphene epoxy resin composite material 8.
Comparative example 2
Adding 2.5 parts of the graphene aerogel 1 in the comparative example 1 into 100 parts of acetone, performing ultrasonic dispersion, adding the obtained mixture into a mixed solution of 100 parts of bisphenol A epoxy resin and 350 parts of acetone, uniformly stirring and dispersing, adding 15 parts of triethylene tetramine, uniformly stirring, performing reduced pressure distillation to remove acetone, and curing to obtain the graphene epoxy resin composite material 9.
Comparative example 3
Graphene oxide by a Hummers method is dispersed in water and then reduced by sodium borohydride to obtain graphene sheets.
Adding 0.6 part of graphene sheet into 20 parts of acetone, performing ultrasonic dispersion, adding the obtained product into a mixed solution of 100 parts of bisphenol A type epoxy resin and 350 parts of acetone, uniformly stirring and dispersing, adding 15 parts of triethylene tetramine, uniformly stirring, performing reduced pressure distillation to remove acetone, and curing to obtain the graphene epoxy resin composite material 10.
Comparative example 4
Adding 2.5 parts of graphene sheets into 100 parts of acetone, performing ultrasonic dispersion, adding the obtained mixture into a mixed solution of 100 parts of bisphenol A epoxy resin and 350 parts of acetone, uniformly stirring and dispersing, adding 15 parts of triethylene tetramine, uniformly stirring, performing reduced pressure distillation to remove the acetone, and curing to obtain the graphene epoxy resin composite material 11.
Comparative example 5
And adding 15 parts of triethylene tetramine into 100 parts of bisphenol A epoxy resin, uniformly stirring, and curing to obtain the epoxy resin.
Performance testing
Toughness: and testing the flexural modulus and flexural strength of the graphene epoxy resin composite material 1-11 and the epoxy resin by using an electronic tensile machine. The results are shown in Table 1.
Tensile strength: and testing the tensile modulus and tensile strength of the graphene epoxy resin composite material 1-11 and the epoxy resin by using an electronic tensile machine. The results are shown in Table 1.
Thermal conductivity: and testing the heat conductivity coefficients of the graphene epoxy resin composite material 1-11 and the epoxy resin by using a heat flow meter heat conductivity coefficient instrument. The results are shown in Table 2.
Conductivity: and testing the conductivities of the graphene-epoxy resin composite material 1-11 and the epoxy resin by using an ultrahigh-resistance micro-current measuring instrument. The results are shown in Table 2.
TABLE 1
| Examples | Flexural modulus/MPa | Flexural Strength/MPa | Tensile modulus/MPa | Tensile strength/MPa |
| Example 1 | 2111 | 73 | 1784 | 43 |
| Example 2 | 2294 | 78 | 1886 | 48 |
| Example 3 | 2597 | 87 | 2024 | 55 |
| Example 4 | 2835 | 94 | 2183 | 59 |
| Example 5 | 3103 | 104 | 2392 | 68 |
| Example 6 | 2917 | 99 | 2245 | 63 |
| Example 7 | 3006 | 101 | 2313 | 65 |
| Comparative example 1 | 2352 | 79 | 1917 | 49 |
| Comparative example 2 | 2891 | 97 | 2229 | 62 |
| Comparative example 3 | 2237 | 75 | 1815 | 46 |
| Comparative example 4 | 2741 | 88 | 2103 | 53 |
| Comparative example 5 | 2055 | 70 | 1722 | 39 |
As can be seen from the data in Table 1, the graphene epoxy resin composite material prepared by the method has better bending strength, bending modulus, tensile strength and tensile modulus, and in a certain addition amount range, the toughness and tensile property are gradually improved along with the increase of the addition amount of the graphene; under the condition of similar addition amount, the toughness and tensile property of the composite material of the invention are slightly poorer than those of the composite material added with the graphene aerogel, but are better than those of the composite material added with the graphene sheet.
TABLE 2
| Examples | Thermal conductivity/W.m -1 K -1 | conductivity/S.m -1 |
| Example 1 | 0.35 | 5.2×10 -6 |
| Example 2 | 0.44 | 1.9×10 -4 |
| Example 3 | 0.51 | 5.7×10 -3 |
| Example 4 | 0.68 | 3.1×10 -2 |
| Example 5 | 1.17 | 6.3×10 -2 |
| Example 6 | 0.83 | 4.9×10 -2 |
| Example 7 | 1.85 | 9.2×10 -2 |
| Comparative example 1 | 0.34 | 2.7×10 -4 |
| Comparative example 2 | 0.68 | 4.5×10 -2 |
| Comparative example 3 | 0.38 | 1.3×10 -10 |
| Comparative example 4 | 0.71 | 1.9×10 -3 |
| Comparative example 5 | 0.19 | 1.1×10 -14 |
As can be seen from the data in table 2, the graphene epoxy resin composite material prepared by the method of the present invention has good thermal conductivity and electrical conductivity, and as the content of graphene increases, the thermal conductivity and the electrical conductivity increase, and at a lower addition amount, the graphene epoxy resin composite material has a certain thermal conductivity and electrical conductivity, especially electrical conductivity, and at a lower addition amount, the graphene epoxy resin composite material has good electrical conductivity, and the graphene sheets with similar content have poor electrical conductivity.
In conclusion, the graphene epoxy resin composite material prepared by the preparation method provided by the invention has good toughness, tensile strength, electrical conductivity and thermal conductivity, and can be applied to the field needing heat conduction materials or electric conduction materials.
The foregoing has shown and described the principles, major features, and advantages of the invention. It should be understood by those skilled in the art that the present invention is not limited by the foregoing embodiments, which are merely preferred embodiments of the present invention, and the scope of the present invention should not be limited thereby, and that equivalent changes and modifications made within the scope of the present invention and the specification should be covered thereby. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. A preparation method of a graphene epoxy resin composite material is characterized by comprising the following steps: comprises the following steps of (a) carrying out,
s1, adding 1 part of graphene oxide and 1-5 parts of reducing agent into 1000 parts of deionized water of 100-;
s2, replacing the graphene hydrogel obtained in the step S1 with deionized water for 2-3 times, then replacing with acetone for 3-5 times, and removing redundant acetone to obtain graphene allyl ketone gel;
s3, adding epoxy resin into an acetone solvent for dissolving, adding the graphite allyl ketone gel obtained in the step S2, uniformly stirring and mixing, adding a curing agent, uniformly stirring, carrying out reduced pressure distillation to remove acetone, and curing to obtain the graphene epoxy resin composite material.
2. The method of claim 1, wherein: the graphene oxide in the step S1 is selected from graphene oxide by a Hummers method or graphene oxide by a modified Hummers method.
3. The method of claim 1, wherein: in step S1, the reducing agent is selected from one or more of sodium iodide, sodium sulfide, hydroquinone, ascorbic acid, dopamine, melamine, sodium citrate, and hydroiodic acid.
4. The method of claim 1, wherein: in the step S3, the weight ratio of the epoxy resin, the acetone solvent, the graphite allyl ketone gel and the curing agent is 100:100-1000:5-200: 3-100.
5. The method of claim 4, wherein: the weight ratio of the epoxy resin, the acetone solvent, the graphite allyl ketone gel and the curing agent is 100:200-600:10-100: 10-80.
6. The method of claim 1, wherein: the curing agent in step S3 is one selected from an amine curing agent, an acid anhydride curing agent, a phenol curing agent, a thiol curing agent, and a boron-amine complex curing agent.
7. A graphene epoxy resin composite material obtained by the preparation method of any one of claims 1 to 6.
8. The graphene epoxy resin composite material according to claim 7 is applied to the field of conductive materials.
9. The graphene epoxy resin composite material according to claim 7 is applied to the field of heat conduction materials.
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| CN103627139A (en) * | 2013-09-25 | 2014-03-12 | 杭州师范大学 | Preparation method of functionalized graphene oxide/epoxy resin nanocomposite |
| CN105271212A (en) * | 2015-11-30 | 2016-01-27 | 航天特种材料及工艺技术研究所 | Graphene aerogel material and preparation method thereof |
| CN108341929A (en) * | 2018-03-19 | 2018-07-31 | 温岭市创嘉信息科技有限公司 | A kind of Graphene epoxy resin composite material and preparation method thereof |
| EP3502054A1 (en) * | 2017-12-21 | 2019-06-26 | Palo Alto Research Center Incorporated | Functionalized graphene oxide curable formulations |
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| CN103627139A (en) * | 2013-09-25 | 2014-03-12 | 杭州师范大学 | Preparation method of functionalized graphene oxide/epoxy resin nanocomposite |
| CN105271212A (en) * | 2015-11-30 | 2016-01-27 | 航天特种材料及工艺技术研究所 | Graphene aerogel material and preparation method thereof |
| EP3502054A1 (en) * | 2017-12-21 | 2019-06-26 | Palo Alto Research Center Incorporated | Functionalized graphene oxide curable formulations |
| CN108341929A (en) * | 2018-03-19 | 2018-07-31 | 温岭市创嘉信息科技有限公司 | A kind of Graphene epoxy resin composite material and preparation method thereof |
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Denomination of invention: A graphene epoxy resin composite material, preparation method and application Granted publication date: 20220909 Pledgee: Agricultural Bank of China Limited Shanghai Yangtze River Delta Integrated Demonstration Zone Sub branch Pledgor: Yingporui Intelligent Technology (Shanghai) Co.,Ltd. Registration number: Y2024310000171 |