CN109666259A - A kind of preparation method of modified graphene oxide, modified graphene and modified graphene epoxy resin dispersion liquid - Google Patents
A kind of preparation method of modified graphene oxide, modified graphene and modified graphene epoxy resin dispersion liquid Download PDFInfo
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- CN109666259A CN109666259A CN201710958014.8A CN201710958014A CN109666259A CN 109666259 A CN109666259 A CN 109666259A CN 201710958014 A CN201710958014 A CN 201710958014A CN 109666259 A CN109666259 A CN 109666259A
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- graphene
- modified graphene
- epoxy resin
- graphene oxide
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 277
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 99
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 99
- 239000006185 dispersion Substances 0.000 title claims abstract description 73
- 239000007788 liquid Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 137
- 150000001875 compounds Chemical class 0.000 claims abstract description 41
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000000243 solution Substances 0.000 claims description 35
- 239000003960 organic solvent Substances 0.000 claims description 28
- 230000004048 modification Effects 0.000 claims description 27
- 238000012986 modification Methods 0.000 claims description 27
- 239000000843 powder Substances 0.000 claims description 27
- -1 phenol compound Chemical class 0.000 claims description 26
- 239000012744 reinforcing agent Substances 0.000 claims description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 18
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 claims description 16
- 229920002873 Polyethylenimine Polymers 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 14
- 239000003638 chemical reducing agent Substances 0.000 claims description 13
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 12
- 150000001448 anilines Chemical class 0.000 claims description 12
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- 150000001336 alkenes Chemical class 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 9
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical class NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 claims description 9
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 8
- IOHPVZBSOKLVMN-UHFFFAOYSA-N 2-(2-phenylethyl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1CCC1=CC=CC=C1 IOHPVZBSOKLVMN-UHFFFAOYSA-N 0.000 claims description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 8
- 239000004575 stone Substances 0.000 claims description 8
- 238000010790 dilution Methods 0.000 claims description 6
- 239000012895 dilution Substances 0.000 claims description 6
- 229940113088 dimethylacetamide Drugs 0.000 claims description 6
- 229960003511 macrogol Drugs 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 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 5
- 235000019441 ethanol Nutrition 0.000 claims description 5
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 5
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 4
- 238000012805 post-processing Methods 0.000 claims description 4
- 235000010265 sodium sulphite Nutrition 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 claims description 3
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 150000001412 amines Chemical class 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 23
- 239000011347 resin Substances 0.000 abstract description 23
- 239000003973 paint Substances 0.000 abstract description 18
- 238000007385 chemical modification Methods 0.000 abstract description 15
- 238000000576 coating method Methods 0.000 abstract description 14
- 238000010521 absorption reaction Methods 0.000 abstract description 13
- 229910002804 graphite Inorganic materials 0.000 abstract description 13
- 239000010439 graphite Substances 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 11
- 239000011248 coating agent Substances 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 9
- 239000004593 Epoxy Substances 0.000 abstract description 8
- 238000005411 Van der Waals force Methods 0.000 abstract description 3
- 125000003636 chemical group Chemical group 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 14
- 238000003756 stirring Methods 0.000 description 12
- 238000003908 quality control method Methods 0.000 description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 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 8
- 238000006722 reduction reaction Methods 0.000 description 8
- 239000008096 xylene Substances 0.000 description 8
- 238000013386 optimize process Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- WQPDQJCBHQPNCZ-UHFFFAOYSA-N cyclohexa-2,4-dien-1-one Chemical compound O=C1CC=CC=C1 WQPDQJCBHQPNCZ-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000005213 imbibition Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 150000001559 benzoic acids Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- OSNIIMCBVLBNGS-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-2-(dimethylamino)propan-1-one Chemical compound CN(C)C(C)C(=O)C1=CC=C2OCOC2=C1 OSNIIMCBVLBNGS-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 1
- ZYUVGYBAPZYKSA-UHFFFAOYSA-N 5-(3-hydroxybutan-2-yl)-4-methylbenzene-1,3-diol Chemical compound CC(O)C(C)C1=CC(O)=CC(O)=C1C ZYUVGYBAPZYKSA-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 238000001530 Raman microscopy Methods 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- AOGYCOYQMAVAFD-UHFFFAOYSA-N chlorocarbonic acid Chemical compound OC(Cl)=O AOGYCOYQMAVAFD-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- NHADDZMCASKINP-HTRCEHHLSA-N decarboxydihydrocitrinin Natural products C1=C(O)C(C)=C2[C@H](C)[C@@H](C)OCC2=C1O NHADDZMCASKINP-HTRCEHHLSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical group [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
- C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
- C08J3/092—Hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/02—Polyamines
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Paints Or Removers (AREA)
Abstract
The present invention provides a kind of preparation methods of modified graphene epoxy resin dispersion liquid, compound containing phenyl ring and graphene oxide are modified by chemical reaction, grafting has benzene class rigidity chemical group on the surface of graphene, the Van der Waals force between graphene macromolecular is greatly reduced using its biggish steric hindrance, in addition, there is stronger chemical compatibility between remaining compound and epoxy resin containing phenyl ring, graphene can be made to merge with resin, be conducive to graphite olefine resin in the extensive use in the fields such as coating.The method that the present invention uses chemical modification, graphene epoxy resin dispersion liquid is prepared for by more easy mode, Compound Degree of the graphene in resin is high, the water absorption rate for the anticorrosive paint for being successfully realized graphene in the epoxy evenly dispersed, and being prepared by the graphite olefine resin declines to a great extent.
Description
Technical field
The invention belongs to modified graphene technical field, it is related to a kind of modified graphene oxide, modified graphene and modification
The preparation method of graphene epoxy resin dispersion liquid more particularly to a kind of modified graphene oxide for anticorrosive paint, modification
The preparation method of graphene and chemical modification graphene epoxy resin dispersion liquid.
Background technique
Graphene (Graphene) is a kind of new material of individual layer laminated structure being made of carbon atom.It is one kind by carbon
Atom forms the flat film that hexangle type is in honeycomb lattice, the two-dimensional material of only one carbon atom thickness with sp2 hybridized orbit.
As a kind of two dimensional crystal of only one layer of atomic thickness being made of carbon atom, it is at present into most thin in application field
Material and most tough material；Graphene has huge theoretical specific surface area simultaneously, and physicochemical properties are stablized, can be in senior engineer
Make to keep good structural stability under voltage and high current fast charging and discharging；Graphene also has excellent electric conductivity, can be with
Internal resistance is reduced, the cyclical stability of supercapacitor is improved；In addition, graphene be almost it is fully transparent, only absorb 2.3%
Light.And it is very fine and close, even the smallest gas atom (helium atom) can not also penetrate.These features are very suitable to it
As the raw material of transparent electron product, such as transparent touch display screen, luminescent screen and solar panel.Just because of graphene
With above-mentioned many excellent physical chemical property, in energy storage material, environmental project, sensing sensitive aspect is widely used,
Referred to as " dark fund " or " king of new material ", and potential application prospect is vast, and it is burnt to have become global concern at present
Point and research hotspot.
The whole world at present, all material because of the weight of corrosion loss about 1%, corrode bring economic loss and account for about country every year
The 4% of economic total volume, anti-corrosion road are shouldered heavy responsibilities.In anticorrosive paint industry, most important several anticorrosive paints are mainly epoxy
Class, polyurethane kind and zinc rich primer class coating.And it is domestic, the industries such as ocean engineering, shipbuilding and green marine wind energy are swift and violent
Development, under new international situation and national policy, marine corrosion protects economic benefit huge, then greatly develops under this background new
Type anticorrosive paint is imperative.
For anticorrosive paint, water absorption rate is a critically important standard, and water absorption rate directly affects many performances of coating,
Paint film water resistance after can result in film forming is bad, so that paint film softens, hardness decline, intensity is deteriorated, the higher paint of water absorption rate
Film-strength loss is bigger, so that antiseptic property be caused to decline.
In recent years, the coating products containing graphite alkenes material gradually have relevant report, however in practical applications, stone
There is also many problems and restraining factors, such as graphene easily to reunite for black alkene.Due to graphene and its derivative specific surface
Product is larger, there is stronger model ylid bloom action power each other, reunites and wrapping phenomena is obvious, prevents it from stable dispersion, dispersion
It also is easy to reunite again afterwards to be difficult to open together.Although there is numerous studies by adding different types of dispersing agent or modification
Mode improve the dispersion effect of graphene, but effect is poor in practical application, and can also additionally introduce other impurities, right
Follow-up study adversely affects, and graphene is as a kind of flexible material, with other materials in coating, it is easier to occur
Reunion situation directly affects the effect that graphite alkenes material plays in coating.
Therefore, how to find a kind of mode may be uniformly dispersed in graphene in coating, successfully realize that graphene exists
It is evenly dispersed in epoxy resin, preferably improve the performance of coating, it has also become many forward position scientific research personnel urgently solve in field
One of certainly the problem of.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing a kind of modified graphene oxide, modified graphene
With the preparation method of modified graphene epoxy resin dispersion liquid, especially a kind of modified graphene oxide for anticorrosive paint,
The preparation method of modified graphene and modified graphene epoxy resin dispersion liquid, the present invention by the way of chemical modification so that
Graphene can be evenly dispersed in a polymer matrix, preferably merges with resin, is successfully realized graphene in epoxy resin
In it is evenly dispersed, and the water absorption rate of anticorrosive paint prepared by the graphite olefine resin declines to a great extent.
The present invention provides a kind of preparation methods of modified graphene epoxy resin dispersion liquid, comprising the following steps:
A after) being reacted graphene oxide, the compound containing phenyl ring and reinforcing agent, modified graphite oxide is obtained
Alkene dispersion liquid；
The compound containing phenyl ring includes amino benzenes compounds, phenol compound, benzoic acid derivative and benzene
One of pyridyl ethers compound is a variety of；
B after) graphene oxide dispersion for the modification for obtaining above-mentioned steps and reducing agent carry out electronation, changed
The graphene dispersing solution of property；
C) graphene dispersing solution for the modification for obtaining above-mentioned steps after post treatment, obtains modified graphene powder；
D after) being mixed modified graphene powder, epoxy resin and organic solvent that above-mentioned steps obtain, changed
Property graphene epoxy resin dispersion liquid.
Preferably, the compound containing phenyl ring includes p-phenylenediamine, para-aminophenol, P aminobenzoates, N-N
One of dimethylaniline and 2,4,6- tri- (dimethylamino methyl) phenol are a variety of；
The reinforcing agent includes one of polyvinylpyrrolidone, polyethyleneimine and Macrogol 600 or a variety of；
The graphene oxide includes graphene oxide powder or graphene oxide water solution；
The reducing agent includes one of sodium sulfite, glucose and hydrazine hydrate or a variety of；
The organic solvent includes DMAC N,N' dimethyl acetamide, dimethylbenzene, N,N-dimethylformamide, N- crassitude
Ketone, 2-Pyrrolidone, dimethyl sulfoxide, ethyl alcohol, ethylene glycol, isopropanol, n-butanol, acetone, butanone, propene carbonate, the third two
One of alcohol methyl ether and butyl acetate are a variety of.
Preferably, the mass ratio of the graphene oxide and the compound containing phenyl ring is 1:(1~20)；
The mass ratio of the reinforcing agent and the compound containing phenyl ring is 1:(1~100)；
The mass ratio of the reducing agent and the graphene oxide is (0.1~10): 1；
The mass ratio of the modified graphene powder and the epoxy resin is (0.2~2): 100.
Preferably, the temperature of the reaction is 50~100 DEG C；
The time of the reaction is 2~8h；
The temperature of the electronation is 50~100 DEG C；
The time of the electronation is 6~48h；
The post-processing includes centrifuge separation and/or drying.
Preferably, the time of the centrifuge separation is 20~60min；
The revolving speed of the centrifuge separation is 2000~5000r/min；
The time of the drying be 8~for 24 hours；
The temperature of the drying is 40~70 DEG C.
Preferably, the step D) specifically:
D1 after the modified graphene powder for) obtaining above-mentioned steps and the mixing of the first organic solvent, modified graphene is obtained
Slurry；
D2) the modified graphene slurry for obtaining the dilution and above-mentioned steps of epoxy resin and the second organic solvent is again
After mixing, modified graphene epoxy resin dispersion liquid is obtained.
Preferably, the mass ratio of the modified graphene powder and first organic solvent is 1:(5~100)；
Mass fraction of the epoxy resin in the dilution is 50%~80%；
The mixed time is 20~60min；The mixed revolving speed is 2000~5000r/min；
The time mixed again is 30~90min；The revolving speed mixed again is 2000~5000r/min.
The present invention provides a kind of modified graphene oxide, the compound by graphene oxide and containing phenyl ring is after preparing
It obtains；
The compound containing phenyl ring includes amino benzenes compounds, phenol compound, benzoic acid derivative and benzene
One of pyridyl ethers compound is a variety of.
It preferably, further include reinforcing agent；
The reinforcing agent includes one of polyvinylpyrrolidone, polyethyleneimine and Macrogol 600 or a variety of；
The compound containing phenyl ring includes p-phenylenediamine, para-aminophenol, P aminobenzoates, N-N dimethyl
One of aniline and 2,4,6- tri- (dimethylamino methyl) phenol are a variety of；
The mass ratio of the graphene oxide and the compound containing phenyl ring is 1:(1~20)；
The mass ratio of the reinforcing agent and the compound containing phenyl ring is 1:(1~100).
The present invention also provides a kind of modified graphene, the oxidation stone of the modification as described in above-mentioned technical proposal any one
Black alkene obtains after carrying out reduction.
The present invention provides a kind of preparation methods of modified graphene epoxy resin dispersion liquid, include the following steps, first
After graphene oxide, the compound containing phenyl ring and reinforcing agent are reacted, modified graphene oxide dispersion is obtained；Institute
Stating the compound containing phenyl ring includes amino benzenes compounds, phenol compound, benzoic acid derivative and phenyl ethers chemical combination
One of object is a variety of；Then the graphene oxide dispersion and reducing agent of modification above-mentioned steps obtained carry out chemistry also
After original, modified graphene dispersing solution is obtained；The graphene dispersing solution for the modification that above-mentioned steps are obtained again after post treatment, obtains
To modified graphene powder；Finally modified graphene powder, epoxy resin and organic solvent that above-mentioned steps obtain are mixed
After conjunction, modified graphene epoxy resin dispersion liquid is obtained.Compared with prior art, the present invention is for bad present on physical modification
Gesture, selection use chemical modification graphene, and due to the preparation of existing chemical modification graphene composite epoxy resin material
It is most of using by graphene surface carboxyl chloride, then the mode reacted with aminated compounds in method, also have graphene
The acidified modified mode reacted again with benzoxazine of surface carboxyl groups chloroethene.Therefore it needs to carry out multiple chemical to graphene to react
To the graphene of chemical modification, there is a problem of complex process and very big to environmental hazard.Still lack at present simultaneously efficient
The preparation method of chemical modification graphene composite epoxy resin material, and graphene sheet layer in the prior art and resin-bound
Difference, stability are bad, it is difficult to have the defect of practical application in fields such as anticorrosive paints.
The present invention is based on pi-pi bond strong between the high-specific surface area of graphene and lamella effects, so that graphene is difficult to
It is evenly dispersed in a polymer matrix, it is believed that can graphene evenly dispersed in a polymer matrix, and with polymeric matrix it
Between to generate strong interfacial effect be to influence the key factor of composite material, provide a kind of for graphene anticorrosive paint field
Chemical modification graphene resin dispersion liquid preparation method, by phenyl amines, phenol, benzoic acids and phenyl ether compound
Deng the compound containing phenyl ring and graphene oxide by chemical reaction modification, grafting has benzene class rigidization on the surface of graphene
Group is learned, the Van der Waals force between graphene macromolecular is greatly reduced using its biggish steric hindrance, in addition, remaining aniline
There is stronger chemical compatibility between class, benzoic acids, phenylate substance and epoxy resin, graphene can be made to melt with resin
It closes, is conducive to graphite olefine resin in the extensive use in the fields such as coating.The method that the present invention uses chemical modification, by more simple
Easy mode is prepared for graphene epoxy resin dispersion liquid, and Compound Degree of the graphene in resin is high, is successfully realized graphite
Alkene in the epoxy evenly dispersed, and the water absorption rate of anticorrosive paint prepared by the graphite olefine resin declines to a great extent.
The experimental results showed that the present invention uses the modified graphene epoxy resin dispersion liquid of modified graphene preparation, graphite
Alkene in the epoxy evenly dispersed, the water absorption rate of graphene epoxy resin declines to a great extent, the water suction after 48h impregnates after solidification
Minimum rate is only 0.5%.
Detailed description of the invention
Fig. 1 is the process flow diagram that the present invention prepares modified graphene epoxy resin dispersion liquid；
Fig. 2 is the Raman mapping map of modified graphene epoxy resin dispersion liquid prepared by the embodiment of the present invention 1；
Fig. 3 is the scanning electron microscope (SEM) photograph of graphene epoxy resin dispersion liquid prepared by the embodiment of the present invention 1.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still
It should be appreciated that these descriptions are intended merely to further illustrate the features and advantages of the present invention, rather than to invention claim
Limitation.
All raw materials of the present invention, are not particularly limited its source, buying on the market or according to those skilled in the art
The preparation of conventional method known to member.
All raw materials of the present invention, are not particularly limited its purity, and present invention preferably employs analyze the preparation of pure or graphene
The purity requirement of field routine.
All raw materials of the present invention, the trade mark and abbreviation belong to this field routine trade mark and abbreviation, each trade mark and abbreviation
In the field of its associated uses be it is explicit, those skilled in the art according to the trade mark, abbreviation and corresponding purposes,
It can be commercially available from city's mid-sales or conventional method is prepared.
The present invention provides a kind of preparation methods of modified graphene epoxy resin dispersion liquid, comprising the following steps:
A after) being reacted graphene oxide, the compound containing phenyl ring and reinforcing agent, modified graphite oxide is obtained
Alkene dispersion liquid；
The compound containing phenyl ring includes amino benzenes compounds, phenol compound, benzoic acid derivative and benzene
One of pyridyl ethers compound is a variety of；
B after) graphene oxide dispersion for the modification for obtaining above-mentioned steps and reducing agent carry out electronation, changed
The graphene dispersing solution of property；
C) graphene dispersing solution for the modification for obtaining above-mentioned steps after post treatment, obtains modified graphene powder；
D after) being mixed modified graphene powder, epoxy resin and organic solvent that above-mentioned steps obtain, changed
Property graphene epoxy resin dispersion liquid.
After the present invention first reacts graphene oxide, the compound containing phenyl ring and reinforcing agent, modification is obtained
Graphene oxide dispersion.
The definition of the graphene oxide is not particularly limited in the present invention, with oxidation stone well known to those skilled in the art
The concept of black alkene, those skilled in the art can select according to practical situations, product requirement and quality requirement
It selects and adjusts, graphene oxide of the present invention is preferably the graphene oxide of broad sense, preferably includes graphene oxide, part also
Former graphene oxide etc., more preferably single-layer graphene oxide, multilayer graphene oxide lamp, the in the present invention oxidation
Graphene is particularly preferred as the high-quality graphene oxide (patent No.: CN 106115669A) and oxidation stone of the production of Ou Bo company
One of black alkene (CN 106430175A) is a variety of.
The compound containing phenyl ring is not particularly limited in the present invention, is contained with routine well known to those skilled in the art
There is the compound of phenyl ring, those skilled in the art can control according to practical raw applicable cases, modified requirement and quality
It is selected and is adjusted, the compound of the present invention containing phenyl ring preferably includes amino benzenes compounds, phenol compound, benzene
One of formic acid compound and phenyl ether compound are a variety of, more preferably amino benzenes compounds, phenol compound,
Benzoic acid derivative or phenyl ether compound, be specifically as follows p-phenylenediamine, para-aminophenol, P aminobenzoates,
N-N dimethylaniline and 2, one of 4,6- tri- (dimethylamino methyl) phenol or a variety of, or be p-phenylenediamine, to amino
Phenol, P aminobenzoates, N-N dimethylaniline or 2,4,6- tri- (dimethylamino methyl) phenol.
The additional amount of the compound containing phenyl ring is not particularly limited in the present invention, known to those skilled in the art
The modified additional amount of regular oxidation graphene, those skilled in the art can according to practical condition, it is modified require with
And quality control is selected and is adjusted, the mass ratio of graphene oxide of the present invention and the compound containing phenyl ring is excellent
It is selected as 1:(1~20), more preferably 1:(3~18), more preferably 1:(5~15) and, most preferably 1:(7~12).
The reinforcing agent is not particularly limited in the present invention, with conventional reinforcing agent well known to those skilled in the art,
Those skilled in the art can select and adjust, this hair according to practical raw applicable cases, modified requirement and quality control
The bright reinforcing agent preferably includes one of polyvinylpyrrolidone, polyethyleneimine and Macrogol 600 or a variety of, more excellent
It is selected as polyvinylpyrrolidone, polyethyleneimine or Macrogol 600.
The additional amount of the reinforcing agent is not particularly limited in the present invention, with regular oxidation well known to those skilled in the art
Graphene is modified additional amount, and those skilled in the art can control according to practical condition, modified requirement and quality
Selected and adjusted, the mass ratio of reinforcing agent of the present invention and the compound containing phenyl ring be preferably 1:(1~
100), more preferably 1:(10~90), more preferably 1:(20~80), more preferably 1:(40~60).
The time of the reaction is not particularly limited in the present invention, with similar reaction well known to those skilled in the art when
Between, those skilled in the art can select and adjust according to practical condition, modified requirement and quality control,
The time of reaction of the present invention is preferably 2~8h, more preferably 3~7h, more preferably 4~6h.
The temperature of the reaction is not particularly limited in the present invention, with the temperature of similar reaction well known to those skilled in the art
Degree, those skilled in the art can select and adjust according to practical condition, modified requirement and quality control,
The temperature of reaction of the present invention is preferably 50~100 DEG C, more preferably 60~90 DEG C, more preferably 70~80 DEG C.
The mode of the reaction is not particularly limited in the present invention, in a manner of popular response well known to those skilled in the art
, those skilled in the art can require according to practical condition, modification and quality control be selected and be adjusted, this
The preferred back flow reaction of mode temperature of the reaction is invented, more preferably return stirring reacts.
The graphene oxide dispersion and reducing agent of then modification that the present invention obtains above-mentioned steps carry out electronation
Afterwards, modified graphene dispersing solution is obtained；
The reducing agent is not particularly limited in the present invention, with conventional reduction agent well known to those skilled in the art,
Those skilled in the art can select and adjust, this hair according to practical raw applicable cases, modified requirement and quality control
The bright reducing agent preferably includes one of sodium sulfite, glucose and hydrazine hydrate or a variety of, more preferably sodium sulfite, Portugal
Grape sugar or hydrazine hydrate.
The additional amount of the reducing agent is not particularly limited in the present invention, with regular oxidation well known to those skilled in the art
Graphene restores additional amount, and those skilled in the art can control according to practical condition, modified requirement and quality
It is selected and is adjusted, the mass ratio of reducing agent of the present invention and the graphene oxide is preferably (0.1~10): 1, it is more excellent
It is selected as (0.5~8): 1, more preferably (1~6): 1, more preferably (2~4): 1.
The time of the electronation is not particularly limited in the present invention, with similar chemistry well known to those skilled in the art
The time of reduction, those skilled in the art can select according to practical condition, modified requirement and quality control
It selects and adjusts, the time of electronation of the present invention is preferably 6~48h, more preferably 16~38h, more preferably 20~
30h。
The temperature of the electronation is not particularly limited in the present invention, with similar chemistry well known to those skilled in the art
The temperature of reduction reaction, those skilled in the art can according to practical condition, it is modified require and quality control into
Row selection and adjustment, the temperature of electronation of the present invention is preferably 50~100 DEG C, and more preferably 60~90 DEG C, more preferably
It is 70~80 DEG C.
The graphene dispersing solution for the modification that the present invention again obtains above-mentioned steps after post treatment, obtains modified graphene powder
Body.
The specific steps of the post-processing are not particularly limited in the present invention, after routine well known to those skilled in the art
Processing step, those skilled in the art can require according to practical condition, activation and quality control selects
And adjustment, post-processing step of the present invention preferably includes to separate and/or drying, more preferably separation and drying are specifically as follows
Centrifuge separation and vacuum drying.
The actual conditions of the drying are not particularly limited in the present invention, and those skilled in the art can be according to actual production
Situation, activation require and quality control is selected and adjusted, and the temperature of drying of the present invention is preferably 40~70 DEG C, more
Preferably 45~65 DEG C, more preferably 50~60 DEG C, are specifically as follows 55~60 DEG C.The time of drying of the present invention is preferably
8~for 24 hours, more preferably 10~22h, more preferably 12~20h are specifically as follows 14~18h.
The present invention finally mixes modified graphene powder, epoxy resin and organic solvent that above-mentioned steps obtain
Afterwards, modified graphene epoxy resin dispersion liquid is obtained.
The epoxy resin is not particularly limited in the present invention, with epoxy resin well known to those skilled in the art,
Those skilled in the art can control according to practical condition, product requirement and quality and select and adjust, the present invention
The epoxy resin preferably includes bisphenol A type epoxy resin, is more specifically preferably E-51 bisphenol A type epoxy resin and/or 601 pairs
Phenol A type epoxy resin, most preferably E-51 bisphenol A type epoxy resin or 601 bisphenol A type epoxy resins.
The other parameters of the epoxy resin are not particularly limited in the present invention, with routine well known to those skilled in the art
The parameter of epoxy resin, those skilled in the art can according to practical situations, product requirement and quality requirement into
Row selection and adjustment.
The additional amount of the epoxy resin is not particularly limited in the present invention, is added with routine well known to those skilled in the art
Enter amount, those skilled in the art can select and adjust according to practical situations, product requirement and quality requirement
Whole, the mass ratio of modified graphene powder of the present invention and the epoxy resin is (0.2~2): 100, more preferably (0.5
~1.8): 100, more preferably (0.8~1.6): 100, more preferably (1.0~1.5): 100.
The selection of the organic solvent is not particularly limited in the present invention, organic with routine well known to those skilled in the art
Solvent, those skilled in the art can select and adjust according to practical situations, product requirement and quality requirement
Whole, organic solvent of the present invention preferably includes n,N-dimethylacetamide, dimethylbenzene, n,N-Dimethylformamide, N- methyl
Pyrrolidones, 2-Pyrrolidone, dimethyl sulfoxide, ethyl alcohol, ethylene glycol, isopropanol, n-butanol, acetone, butanone, propylene carbonate
One of ester, propylene glycol monomethyl ether and butyl acetate are a variety of, more preferably n,N-dimethylacetamide, dimethylbenzene, N, N- bis-
Methylformamide, N-Methyl pyrrolidone, 2-Pyrrolidone, dimethyl sulfoxide, ethyl alcohol, ethylene glycol, isopropanol, n-butanol, third
Ketone, butanone, propene carbonate, propylene glycol monomethyl ether or butyl acetate are specifically as follows n,N-dimethylacetamide, dimethylbenzene, N,
Dinethylformamide, N-Methyl pyrrolidone or 2-Pyrrolidone.
The additional amount of the organic solvent is not particularly limited in the present invention, has with routine well known to those skilled in the art
The additional amount of solvent, those skilled in the art can according to practical situations, product requirement and quality requirement into
Row selection and adjustment.
The present invention is to further increase the property of product, optimization and complete reaction route, the step D) it is particularly preferred as:
D1 after the modified graphene powder for) obtaining above-mentioned steps and the mixing of the first organic solvent, modified graphene is obtained
Slurry；
D2) the modified graphene slurry for obtaining the dilution and above-mentioned steps of epoxy resin and the second organic solvent is again
After mixing, modified graphene epoxy resin dispersion liquid is obtained.
The specific choice of first organic solvent and the second organic solvent is not particularly limited in the present invention, with this field
Conventional organic solvent known to technical staff, those skilled in the art can according to practical situations, product requirement with
And quality requirement is selected and is adjusted, the first organic solvent of the present invention and the second organic solvent is independent preferably is selected from
In aforementioned organic solvents, range of choice is identical with optimum principle, and this is no longer going to repeat them.
The additional amount of first organic solvent is not particularly limited in the present invention, with well known to those skilled in the art normal
The additional amount of organic solvent is advised, those skilled in the art can want according to practical situations, product requirement and quality
It asks and is selected and adjusted, the mass ratio of modified graphene powder of the present invention and first organic solvent is preferably 1:(5
~100), more preferably 1:(10~80), more preferably 1:(15~60), it is specifically as follows 1:15.
The additional amount of second organic solvent is not particularly limited in the present invention, with well known to those skilled in the art normal
The additional amount of organic solvent is advised, those skilled in the art can want according to practical situations, product requirement and quality
It asks and is selected and adjusted, mass fraction of the epoxy resin of the present invention in the dilution is preferably 50%~80%,
More preferably 55%~75%, more preferably 60%~70%, it is specifically as follows 75%.
The mixed concrete mode is not particularly limited in the present invention, is stirred with well known to those skilled in the art
Mode, those skilled in the art can control according to practical condition, product requirement and quality and select and adjust
Whole, the present invention is to further increase the uniformity and performance of dispersion liquid and post-coatings product, optimized process flow, the mixing
Magnetic agitation and/or mechanical stirring, more preferably magnetic agitation or mechanical stirring are preferably included, it is mixed to be specifically as follows high-speed stirred
It closes.
The mixed time is not particularly limited in the present invention, with it is well known to those skilled in the art be stirred when
Between, those skilled in the art can control according to practical condition, product requirement and quality and select and adjust,
The present invention is to further increase the uniformity and performance of dispersion liquid, optimized process flow, the mixed time is preferably 20~
60min, more preferably 25~55min, more preferably 30~50min, more preferably 35~45min.
The mixed speed is not particularly limited in the present invention, is with mixed speed well known to those skilled in the art
Can, those skilled in the art can control according to practical condition, product requirement and quality and select and adjust, this hair
Bright is the uniformity and performance for further increasing dispersion liquid and post-coatings product, optimized process flow, the mixed revolving speed
Preferably 2000~5000r/min, more preferably 2500~4500r/min, more preferably 3000~4000r/min.
The concrete mode mixed again is not particularly limited in the present invention, with stirring well known to those skilled in the art
Hybrid mode, those skilled in the art can control according to practical condition, product requirement and quality and select
And adjustment, the present invention are to further increase the uniformity and performance of dispersion liquid and post-coatings product, optimized process flow is described
Mixing preferably includes magnetic agitation and/or mechanical stirring, more preferably magnetic agitation or mechanical stirring again, is specifically as follows height
Speed is stirred.
The time mixed again is not particularly limited in the present invention, is stirred with well known to those skilled in the art
Time, those skilled in the art can according to practical condition, product requirement and quality control select and
Adjustment, the present invention is to further increase the uniformity and performance of dispersion liquid, optimized process flow, and the time mixed again is excellent
It is selected as 30~90min, more preferably 40~80min, more preferably 50~70min.
The speed mixed again is not particularly limited in the present invention, with mixed speed well known to those skilled in the art
Degree, those skilled in the art can control according to practical condition, product requirement and quality and select and adjust,
The present invention is to further increase the uniformity and performance of dispersion liquid and post-coatings product, and optimized process flow is described to mix again
The revolving speed of conjunction is preferably 2000~5000r/min, more preferably 2500~4500r/min, more preferably 3000~4000r/
min。
The present invention provides a kind of modified graphene oxide, the compound by graphene oxide and containing phenyl ring is after preparing
It obtains；
The compound containing phenyl ring includes amino benzenes compounds, phenol compound, benzoic acid derivative and benzene
One of pyridyl ethers compound is a variety of.
The present invention is to further increase the property of product, optimization and complete product route, in the modified graphene oxide
It further include reinforcing agent, i.e., the described modified graphene oxide is preferably passed through by graphene oxide, the compound containing phenyl ring and reinforcing agent
It is obtained after preparation.
The present invention to the selection of the raw material in the modified graphene oxide and composition and corresponding optimum principle, with
The selection of corresponding raw material and composition in the preparation method of aforementioned modified graphene oxide epoxy resin dispersion liquid, and it is corresponding
Optimum principle can be corresponded to, and this is no longer going to repeat them.
The present invention also provides a kind of modified graphene, the oxidation stone of the modification as described in above-mentioned technical proposal any one
Black alkene obtains after carrying out reduction.
The mode and step of the reduction is not particularly limited in the present invention, with conventional oxygen well known to those skilled in the art
Graphite alkene reduction mode and step, those skilled in the art can according to practical condition, product requirement and
Quality requirement is selected and is adjusted, and reduction mode of the present invention is preferably electronation.
Above-mentioned steps of the present invention provide a kind of modified graphene oxide, modified graphene and modified graphene epoxy resin
The preparation method of dispersion liquid.The present invention provides a kind of chemical modification graphene complex loops for graphene anticorrosive paint field
The preparation method of oxygen resin dispersion liquid can be unfavorable for composite property with reunion etc. of the effective solution graphene in resin
The phenomenon that raising.Using the method for the chemical modification graphene oxide once chemically reacted, by the substances such as phenyl amines and oxidation stone
Black alkene is modified by chemical reaction, is had benzene class rigidity chemical group in surface of graphene oxide grafting, is utilized its biggish sky
Between steric hindrance the Van der Waals force between graphene macromolecular is greatly reduced, avoid graphene reunite, sedimentation the problems such as.In addition, this
The prepared modified graphene epoxy resin dispersion liquid of invention, phenyl amines etc. have stronger chemistry between substances and epoxy resin
Compatibility can promote modified graphene preferably to merge with resin, be conducive to graphite olefine resin answering extensively in fields such as coating
With.
The present invention is more easily prepared for modified graphene oxide, modified graphene and modified graphene composite epoxy tree
Rouge dispersion liquid simplifies preparation process, reduces the risk in preparation process, also uses the environmentally friendly material of less harmful,
Reduce the pollution to environment, it is easy to industrialized production.The composite material dispersion liquid that this method obtains, graphene and resin compounded journey
It spends very high, successfully realizes graphene in the epoxy evenly dispersed, so that the anticorrosive paint of graphite olefine resin preparation
Water absorption rate declines to a great extent, and has a good application prospect in fields such as anticorrosive paints.
The experimental results showed that the present invention uses the modified graphene epoxy resin dispersion liquid of modified graphene preparation, graphite
Alkene in the epoxy evenly dispersed, the water absorption rate of graphene epoxy resin declines to a great extent, the water suction after 48h impregnates after solidification
Minimum rate is only 0.5%.
In order to further illustrate the present invention, with reference to embodiments to a kind of modified graphene oxide provided by the invention,
The preparation method of modified graphene and modified graphene epoxy resin dispersion liquid is described in detail, but it is to be understood that these
Embodiment is to be implemented under the premise of the technical scheme of the present invention, gives detailed embodiment and specifically operated
Journey is only further explanation the features and advantages of the present invention, rather than limiting to the claimed invention, guarantor of the invention
Shield range is also not necessarily limited to following embodiments.
Embodiment 1
Chemical modification graphene composite epoxy resin dispersion liquid:
One, the mixed solution of a certain proportion of p-phenylenediamine and polyethyleneimine is added into graphene oxide water solution,
Return stirring 4h at 80 DEG C, obtains modified graphene oxide dispersion；(mass ratio of p-phenylenediamine and polyethyleneimine is
The mass ratio of 80:1, graphene oxide and p-phenylenediamine is 1:6)；
Two, the graphene oxide dispersion by the modification that step 1 obtains heats, a certain amount of hydrazine hydrate is added,
Reaction a period of time obtains modified graphene dispersing solution.80 DEG C of heating temperature, the mass ratio of hydrazine hydrate and graphene oxide is
2:1, reaction time are for 24 hours；
Three, the graphene dispersing solution that will be modified obtained in step 2,5000r/min are centrifuged 60 DEG C of 10min, vacuum dryings
12h obtains modified graphene powder；
Four, a certain amount of dimethyl acetamide, and 3000r/ are added into modified graphene powder obtained in step 3
Min high-speed stirred 40min obtains modified graphene slurry, and the mass ratio of modified graphene and dimethyl acetamide is 1:15；
Five, configured epoxy resin xylene solution is added in modified graphene slurry obtained in step 4, and high
Modified graphene composite epoxy resin dispersion liquid is obtained after speed stirring.Wherein mass fraction of the epoxy resin in xylene solution
It is 75%, the ratio of modified graphene and epoxy resin is 1.2%.
Referring to Fig. 1, Fig. 1 is the process flow diagram that the present invention prepares modified graphene epoxy resin dispersion liquid.
Raman spectrum imaging is carried out to modified graphene epoxy resin dispersion liquid prepared by the embodiment of the present invention 1.
Referring to fig. 2, Fig. 2 be the embodiment of the present invention 1 prepare modified graphene epoxy resin dispersion liquid Raman it is micro- at
As map.Wherein, left side is the Raman image figure of composite material dispersion liquid, and right side is the matching peak of the most two kinds of substances of ingredient,
Red area and blue region are the mixing peak of graphene and epoxy resin, (all have the graphene characteristic peak i.e. peak D and G
Peak).
As shown in Figure 2, graphene composite epoxy resin material, and graphene and epoxy has successfully been prepared in the present embodiment
Resin mutually blends, and graphene is well dispersed in resin.
The modified graphene epoxy resin dispersion liquid prepared to the embodiment of the present invention 1 is seen using scanning electron microscope
It examines.
It is the scanning electron microscope (SEM) photograph of graphene epoxy resin dispersion liquid prepared by the embodiment of the present invention 1 referring to Fig. 3, Fig. 3.By scheming
3 it is found that graphene composite epoxy resin compact structure.
After the modified graphene epoxy resin cure of preparation of the embodiment of the present invention, water imbibition test is carried out.
Referring to table 1, table 1 is the water absorption rate data after the modified graphene epoxy resin cure of preparation of the embodiment of the present invention.
Table 1
As shown in Table 1, the graphene epoxy resin that embodiment 1 obtains after hardening, impregnates the water suction of 48h in deionized water
Rate is 0.5%.
Embodiment 2
The present embodiment prepares chemical modification graphene composite epoxy resin by following steps:
One, the mixing that a certain proportion of para-aminophenol and polyethyleneimine are added into graphene oxide water solution is molten
Liquid, return stirring 6h at 60 DEG C, obtains modified graphene oxide dispersion；The mass ratio of para-aminophenol and polyethyleneimine
Example is 20:1, and the mass ratio of graphene oxide and para-aminophenol is 1:4.
Two, the graphene oxide dispersion by the modification that step 1 obtains heats, and a certain amount of hydrazine hydrate is added, instead
Modified graphene dispersing solution should be obtained for a period of time.80 DEG C of heating temperature, the mass ratio of hydrazine hydrate and graphene oxide is 2:
1, the reaction time is for 24 hours；
Three, the graphene dispersing solution that will be modified obtained in step 2,5000r/min are centrifuged 60 DEG C of 10min, vacuum dryings
8h obtains modified graphene powder；
Four, a certain amount of dimethyl acetamide, and 3000r/ are added into modified graphene powder obtained in step 3
Min high-speed stirred 40min obtains modified graphene slurry, and the mass ratio of modified graphene and dimethyl acetamide is 1:35；
Five, configured epoxy resin xylene solution is added in modified graphene slurry obtained in step 4, and high
Modified graphene compound resin dispersion liquid is obtained after speed stirring, wherein mass fraction of the epoxy resin in xylene solution is
70%, the ratio of modified graphene and epoxy resin is 0.4%.
Water imbibition test is carried out to the modified graphene epoxy resin of preparation of the embodiment of the present invention.
As shown in Table 1, the modified graphene epoxy resin that the present embodiment 2 obtains after hardening, impregnates 48h in deionized water
Water absorption rate be 1.8%.
Embodiment 3
The present embodiment prepares chemical modification graphene composite epoxy resin by following steps:
One, the mixing of a certain proportion of P aminobenzoates and polyethyleneimine is added into graphene oxide water solution
Solution, return stirring 6h at 60 DEG C, obtains modified graphene oxide dispersion；P aminobenzoates and polyethyleneimine
Mass ratio is 5:1, and the mass ratio of graphene oxide and P aminobenzoates is 1:3.
Two, the graphene oxide dispersion by the modification that step 1 obtains heats, and a certain amount of hydrazine hydrate is added, instead
Modified graphene dispersing solution should be obtained for a period of time.80 DEG C of heating temperature, the mass ratio of hydrazine hydrate and graphene oxide is 2:
1, the reaction time is for 24 hours；
Three, the graphene dispersing solution that will be modified obtained in step 2,5000r/min are centrifuged 60 DEG C of 10min, vacuum dryings
12h obtains modified graphene powder；
Four, a certain amount of propylene oxide, and 3000r/min high are added into modified graphene powder obtained in step 3
Speed stirring 40min obtains modified graphene slurry, and the mass ratio of modified graphene and propylene oxide is 1:15；
Five, configured epoxy resin xylene solution is added in modified graphene slurry obtained in step 4, and high
Modified graphene compound resin dispersion liquid is obtained after speed stirring, wherein mass fraction of the epoxy resin in xylene solution is
60%, the ratio of modified graphene and epoxy resin is 0.5%.
Water imbibition test is carried out to the modified graphene epoxy resin of preparation of the embodiment of the present invention.
As shown in Table 1, the modified graphene epoxy resin that the present embodiment 3 obtains after hardening, impregnates 48h in deionized water
Water absorption rate be 1.3%.
Embodiment 4
The present embodiment prepares chemical modification graphene composite epoxy resin by following steps:
One, the mixing of a certain proportion of N-N dimethylaniline and polyethyleneimine is added into graphene oxide water solution
Solution, return stirring 6h at 60 DEG C, obtains modified graphene oxide dispersion；N-N dimethylaniline and polyethyleneimine
Mass ratio is 10:1, and the mass ratio of graphene oxide and N-N dimethylaniline is 1:3.5.
Two, the graphene oxide dispersion by the modification that step 1 obtains heats, and a certain amount of hydrazine hydrate is added, instead
Modified graphene dispersing solution should be obtained for a period of time.80 DEG C of heating temperature, the mass ratio of hydrazine hydrate and graphene oxide is 2:
1, the reaction time is for 24 hours；
Three, the graphene dispersing solution that will be modified obtained in step 2,5000r/min are centrifuged 60 DEG C of 10min, vacuum dryings
12h obtains modified graphene powder；
Four, a certain amount of propylene oxide, and 3000r/min high are added into modified graphene powder obtained in step 3
Speed stirring 40min obtains modified graphene slurry, and the mass ratio of modified graphene and propylene oxide is 1:15；
Five, configured epoxy resin xylene solution is added in modified graphene slurry obtained in step 4, and high
Modified graphene compound resin dispersion liquid is obtained after speed stirring, wherein mass fraction of the epoxy resin in xylene solution is
60%, the ratio of modified graphene and epoxy resin is 2%.
Water imbibition test is carried out to the modified graphene epoxy resin of preparation of the embodiment of the present invention.
As shown in Table 1, the modified graphene epoxy resin that the present embodiment 4 obtains after hardening, impregnates 48h in deionized water
Water absorption rate be 1.6%.
Above to provided by the invention a kind of for the modified graphene oxide of anticorrosive paint, modified graphene and modified stone
The preparation method of black alkene epoxy resin dispersion liquid is described in detail, and specific case used herein is to original of the invention
Reason and embodiment are expounded, and the above embodiments are only used to help understand, and method and its core of the invention is thought
Think, including best mode, and but also any person skilled in the art can practice the present invention, including manufacture and use
Any device or system, and implement the method for any combination.It should be pointed out that coming for those skilled in the art
It says, without departing from the principle of the present invention, can be with several improvements and modifications are made to the present invention, these improvement and modification
It also falls within the protection scope of the claims of the present invention.The range of the invention patent protection is defined by the claims, and can
Including those skilled in the art it is conceivable that other embodiments.It is not different from right if these other embodiments have and wants
The structural element of character express is sought, or if they include the equivalent structure with the character express of claim without essence difference
Element, then these other embodiments should also be included in the scope of the claims.
Claims (10)
1. a kind of preparation method of modified graphene epoxy resin dispersion liquid, which comprises the following steps:
A after) being reacted graphene oxide, the compound containing phenyl ring and reinforcing agent, modified graphene oxide point is obtained
Dispersion liquid；
The compound containing phenyl ring includes amino benzenes compounds, phenol compound, benzoic acid derivative and phenyl ether
One of class compound is a variety of；
B after) graphene oxide dispersion for the modification for obtaining above-mentioned steps and reducing agent carry out electronation, modification is obtained
Graphene dispersing solution；
C) graphene dispersing solution for the modification for obtaining above-mentioned steps after post treatment, obtains modified graphene powder；
D after) being mixed modified graphene powder, epoxy resin and organic solvent that above-mentioned steps obtain, modified stone is obtained
Black alkene epoxy resin dispersion liquid.
2. preparation method according to claim 1, which is characterized in that the compound containing phenyl ring includes to benzene two
One in amine, para-aminophenol, P aminobenzoates, N-N dimethylaniline and 2,4,6- tri- (dimethylamino methyl) phenol
Kind is a variety of；
The reinforcing agent includes one of polyvinylpyrrolidone, polyethyleneimine and Macrogol 600 or a variety of；
The graphene oxide includes graphene oxide powder or graphene oxide water solution；
The reducing agent includes one of sodium sulfite, glucose and hydrazine hydrate or a variety of；
The organic solvent include DMAC N,N' dimethyl acetamide, dimethylbenzene, N,N-dimethylformamide, N-Methyl pyrrolidone,
2-Pyrrolidone, dimethyl sulfoxide, ethyl alcohol, ethylene glycol, isopropanol, n-butanol, acetone, butanone, propene carbonate, propylene glycol first
One of ether and butyl acetate are a variety of.
3. preparation method according to claim 1, which is characterized in that the graphene oxide and the change containing phenyl ring
The mass ratio for closing object is 1:(1~20)；
The mass ratio of the reinforcing agent and the compound containing phenyl ring is 1:(1~100)；
The mass ratio of the reducing agent and the graphene oxide is (0.1~10): 1；
The mass ratio of the modified graphene powder and the epoxy resin is (0.2~2): 100.
4. preparation method according to claim 1, which is characterized in that the temperature of the reaction is 50~100 DEG C；
The time of the reaction is 2~8h；
The temperature of the electronation is 50~100 DEG C；
The time of the electronation is 6~48h；
The post-processing includes centrifuge separation and/or drying.
5. the preparation method according to claim 4, which is characterized in that the time of the centrifuge separation is 20~60min；
The revolving speed of the centrifuge separation is 2000~5000r/min；
The time of the drying be 8~for 24 hours；
The temperature of the drying is 40~70 DEG C.
6. preparation method according to claim 1, which is characterized in that the step D) specifically:
D1 after the modified graphene powder for) obtaining above-mentioned steps and the mixing of the first organic solvent, modified graphene slurry is obtained；
D2) the modified graphene slurry that the dilution and above-mentioned steps of epoxy resin and the second organic solvent obtain is mixed again
Afterwards, modified graphene epoxy resin dispersion liquid is obtained.
7. preparation method according to claim 6, which is characterized in that the modified graphene powder and described first organic
The mass ratio of solvent is 1:(5~100)；
Mass fraction of the epoxy resin in the dilution is 50%~80%；
The mixed time is 20~60min；The mixed revolving speed is 2000~5000r/min；
The time mixed again is 30~90min；The revolving speed mixed again is 2000~5000r/min.
8. a kind of modified graphene oxide, which is characterized in that the compound by graphene oxide and containing phenyl ring obtains after preparing
It arrives；
The compound containing phenyl ring includes amino benzenes compounds, phenol compound, benzoic acid derivative and phenyl ether
One of class compound is a variety of.
9. modified graphene oxide according to claim 8, which is characterized in that further include reinforcing agent；
The reinforcing agent includes one of polyvinylpyrrolidone, polyethyleneimine and Macrogol 600 or a variety of；
The compound containing phenyl ring includes p-phenylenediamine, para-aminophenol, P aminobenzoates, N-N dimethylaniline
With one of 2,4,6- tri- (dimethylamino methyl) phenol or a variety of；
The mass ratio of the graphene oxide and the compound containing phenyl ring is 1:(1~20)；
The mass ratio of the reinforcing agent and the compound containing phenyl ring is 1:(1~100).
10. a kind of modified graphene, which is characterized in that the graphene oxide of the modification as described in claim 8 or 9 is after carrying out reduction
It obtains.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111454641A (en) * | 2020-05-29 | 2020-07-28 | 南京长江涂料有限公司 | Aqueous single-component conductive coating for insulator and preparation method thereof |
| CN113292739A (en) * | 2021-06-18 | 2021-08-24 | 广东航迈新材料科技有限公司 | Production method of high-graphene-concentration latex |
| CN113913048A (en) * | 2021-03-26 | 2022-01-11 | 杭州安誉科技有限公司 | High-thermal-conductivity PCR reaction tube and preparation process thereof |
| CN114032674A (en) * | 2021-12-17 | 2022-02-11 | 南通强生石墨烯科技有限公司 | Graphene chemical-resistant fiber and preparation method thereof |
| CN115206689A (en) * | 2022-07-07 | 2022-10-18 | 浙江理工大学 | Graphene modified material and preparation method thereof |
| CN115746704A (en) * | 2022-10-17 | 2023-03-07 | 保利长大工程有限公司 | Steel bridge deck composite structure with excellent corrosion resistance |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104211053A (en) * | 2014-09-04 | 2014-12-17 | 济宁利特纳米技术有限责任公司 | Preparation method of modified graphene aqueous dispersion |
| CN104231547A (en) * | 2014-09-04 | 2014-12-24 | 济宁利特纳米技术有限责任公司 | Method for preparing aqueous graphene/epoxy resin nanocomposite material |
| CN105385310A (en) * | 2016-01-04 | 2016-03-09 | 沈阳顺风实业集团有限公司 | Steel structure fireproof anticorrosion function integrated coating and preparing method thereof |
| CN106744834A (en) * | 2016-11-28 | 2017-05-31 | 江南大学 | A kind of preparation method of aqueous-dispersible conductive Graphene |
-
2017
- 2017-10-16 CN CN201710958014.8A patent/CN109666259B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104211053A (en) * | 2014-09-04 | 2014-12-17 | 济宁利特纳米技术有限责任公司 | Preparation method of modified graphene aqueous dispersion |
| CN104231547A (en) * | 2014-09-04 | 2014-12-24 | 济宁利特纳米技术有限责任公司 | Method for preparing aqueous graphene/epoxy resin nanocomposite material |
| CN105385310A (en) * | 2016-01-04 | 2016-03-09 | 沈阳顺风实业集团有限公司 | Steel structure fireproof anticorrosion function integrated coating and preparing method thereof |
| CN106744834A (en) * | 2016-11-28 | 2017-05-31 | 江南大学 | A kind of preparation method of aqueous-dispersible conductive Graphene |
Non-Patent Citations (3)
| Title |
|---|
| B. RAMEZANZADEH ET AL: "Enhancement of barrier and corrosion protection performance of an epoxy coating through wet transfer of amino functionalized graphene oxide", 《CORROSION SCIENCE》 * |
| 徐思亭等: "《塑料材料与助剂》", 31 July 2007, 天津大学出版社 * |
| 方志刚等: "《舰艇结构腐蚀防护》", 31 May 2017, 北京：国防工业出版社 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111454641A (en) * | 2020-05-29 | 2020-07-28 | 南京长江涂料有限公司 | Aqueous single-component conductive coating for insulator and preparation method thereof |
| CN113913048A (en) * | 2021-03-26 | 2022-01-11 | 杭州安誉科技有限公司 | High-thermal-conductivity PCR reaction tube and preparation process thereof |
| CN113292739A (en) * | 2021-06-18 | 2021-08-24 | 广东航迈新材料科技有限公司 | Production method of high-graphene-concentration latex |
| CN114032674A (en) * | 2021-12-17 | 2022-02-11 | 南通强生石墨烯科技有限公司 | Graphene chemical-resistant fiber and preparation method thereof |
| CN115206689A (en) * | 2022-07-07 | 2022-10-18 | 浙江理工大学 | Graphene modified material and preparation method thereof |
| CN115206689B (en) * | 2022-07-07 | 2024-02-09 | 浙江理工大学 | Graphene modified material and preparation method thereof |
| CN115746704A (en) * | 2022-10-17 | 2023-03-07 | 保利长大工程有限公司 | Steel bridge deck composite structure with excellent corrosion resistance |
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