CN113277504A - Multifunctional auxiliary agent containing graphene nano material and preparation method thereof - Google Patents
Multifunctional auxiliary agent containing graphene nano material and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 61
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000012752 auxiliary agent Substances 0.000 title claims abstract description 13
- 239000002270 dispersing agent Substances 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 230000009471 action Effects 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 39
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 26
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 22
- 229920001223 polyethylene glycol Polymers 0.000 claims description 21
- 239000002202 Polyethylene glycol Substances 0.000 claims description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 239000013067 intermediate product Substances 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 150000004985 diamines Chemical class 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical group [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 9
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 9
- 101710141544 Allatotropin-related peptide Proteins 0.000 claims description 8
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims description 6
- 238000007710 freezing Methods 0.000 claims description 6
- 230000008014 freezing Effects 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 6
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 claims description 5
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 5
- 229910021590 Copper(II) bromide Inorganic materials 0.000 claims description 5
- 239000008139 complexing agent Substances 0.000 claims description 5
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 5
- 239000012044 organic layer Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- YOCIJWAHRAJQFT-UHFFFAOYSA-N 2-bromo-2-methylpropanoyl bromide Chemical compound CC(C)(Br)C(Br)=O YOCIJWAHRAJQFT-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 3
- 238000005699 Etard reaction Methods 0.000 claims description 3
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 125000003172 aldehyde group Chemical group 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 230000009435 amidation Effects 0.000 claims description 3
- 238000007112 amidation reaction Methods 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- HSDAJNMJOMSNEV-UHFFFAOYSA-N benzyl chloroformate Chemical compound ClC(=O)OCC1=CC=CC=C1 HSDAJNMJOMSNEV-UHFFFAOYSA-N 0.000 claims description 3
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 229910001923 silver oxide Inorganic materials 0.000 claims description 3
- 238000010025 steaming Methods 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- 238000010257 thawing Methods 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 claims description 2
- -1 sodium aminoborohydride Chemical compound 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 17
- 239000011248 coating agent Substances 0.000 abstract description 16
- 238000005260 corrosion Methods 0.000 abstract description 7
- 230000007797 corrosion Effects 0.000 abstract description 5
- 238000004873 anchoring Methods 0.000 abstract description 2
- 239000002612 dispersion medium Substances 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The scheme relates to a multifunctional auxiliary agent containing a graphene nano material and a preparation method thereof. According to the scheme, the dispersing agent with a specific structure is utilized to enhance the dispersibility of the modified graphene in various solvent systems, the multi-arm dispersing agent has rich anchoring groups, can easily enter between graphene sheet layers, can generate hydrogen bond action, adsorption action and the like with active groups on the surface of the graphene, is firmly combined, is not easy to settle in the solvent systems, and has good stability; the dispersion medium can be common organic solvent or water, has wide application range and can effectively improve the corrosion resistance of the coating.
Description
Technical Field
The invention relates to the field of functional nano materials, in particular to a multifunctional auxiliary agent containing a graphene nano material and a preparation method thereof.
Background
The nano material has five effects of unique volume effect, surface effect, quantum size effect, quantum tunneling effect and dielectric confinement effect, and has excellent performance in the aspects of light, electricity, mechanics and the like, so that the nano material is preparedIs well appreciated by researchers. Graphene (Gr) is a structure represented by sp2The hybridized special nano material with the honeycomb crystal structure is a two-dimensional material with the thinnest known thickness in the world at present, and due to the special structure, the graphene has excellent physical and chemical properties and is widely applied to the fields of composite materials, capacitors, sensors, coatings and the like.
Graphene with a two-dimensional layered structure has a certain shielding effect on corrosive substances, and is an ideal performance reinforcing filler for an anticorrosive coating, however, due to the fact that the distance between graphene sheet layers is small, a polymer is difficult to enter between the graphene sheet layers, the graphene sheet layers are easy to agglomerate in the coating and difficult to disperse uniformly, and the graphene is difficult to exert the anticorrosive performance when being directly added into the coating. The graphene is subjected to appropriate chemical modification, so that the dispersion performance of the graphene in a coating system can be effectively improved, the graphene/polymer composite material prepared by an in-situ polymerization method is uniform in dispersion and high in chemical bonding degree, but the defects that the reaction conditions are difficult to control, the conductivity and the corrosion resistance of the graphene are reduced due to the fact that the grafted polymer chain is too long, and the like exist.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to prepare a functional nano graphene material with good dispersibility, which can be applied to a polymer, by using graphene as a starting material and chemically modifying the graphene and combining an auxiliary dispersing agent, and can ensure that the conductivity and the corrosion resistance of the nano graphene material are not influenced.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of a multifunctional auxiliary agent containing a graphene nano material comprises the following steps:
1) dissolving aminotoluene in a mixed solution of ethanol and water, adding sodium bicarbonate, then cooling to 5 ℃, adding a dioxane solution of benzyl chloroformate, and stirring for reaction at 0 ℃ to protect amino;
2) dissolving the protected aminotoluene in carbon disulfide, and oxidizing methyl into aldehyde group according to Etard reaction to obtain an intermediate product 1;
3) adding graphene oxide and a solvent DMF (dimethyl formamide) into a reaction bottle, dispersing the graphene oxide and the solvent DMF uniformly, then dropwise adding DMF (dimethyl formamide) solutions of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide and N-hydroxysuccinimide into the reaction bottle for activation, and then adding polyethylene glycol diamine for reacting at 80-100 ℃ for 24 hours for amidation;
4) adding the obtained amidated product and the intermediate product 1 into a reaction bottle, adding water, performing ultrasonic treatment to uniformly disperse the amidated product and the intermediate product 1, adjusting the pH value to 6.5 to obtain a mixed solution, dropwise adding sodium amino borohydride into the mixed solution, stirring and reacting at room temperature for 12 hours, and filtering and freeze-drying the mixture after the reaction to obtain an intermediate product 2;
5) dispersing the intermediate product 2 in a mixed solvent of methanol and tert-butyl alcohol, adding a catalytic amount of palladium carbon, introducing hydrogen, stirring for reaction for 3 hours, deprotecting amino, filtering, and drying to finally obtain the modified graphene shown in formula 1);
6) and dispersing the modified graphene and the auxiliary dispersing agent in a solvent system to obtain the multifunctional auxiliary agent containing the graphene nano material.
Further, the auxiliary dispersant has a structural formula shown in formula 2):
wherein n is an integer of 5 to 20.
Further, the preparation of the auxiliary dispersant comprises the following steps:
s1: the polyethylene glycol reacts with p-toluenesulfonyl chloride under the action of a silver oxide/potassium iodide catalyst to obtain TsO-PEG-OH, and then reacts with ammonium chloride in ammonia water to obtain NH2-PEG-OH；
S2: obtained NH2dissolving-PEG-OH in deionized water, adding equimolar amount of benzaldehyde-4-sodium sulfonate, adjusting pH to 6.5 to obtain mixed solution, and taking amino hydroborationDropwise adding sodium into the mixed solution, stirring and reacting for 12 hours at room temperature, and dialyzing, freezing and drying the reaction solution to obtain a solid; then carrying out esterification reaction with acrylic acid to obtain a reactive anionic-nonionic monomer;
s3: adding pentaerythritol, triethylamine and anhydrous dioxane into a reaction bottle, introducing nitrogen to replace air in the reaction bottle, placing the reaction bottle in an environment at-18 ℃, dropwise adding a tetrahydrofuran solution of 2-bromoisobutyryl bromide in a nitrogen atmosphere, and after dropwise adding, moving the reaction bottle to room temperature to react for 12 hours under stirring; extracting with dichloromethane, collecting an organic layer, washing, drying, rotary steaming and recrystallizing to obtain an ATRP four-head initiator;
s4: sequentially adding a catalyst, a coordination agent, the ATRP four-head initiator and a reactive anionic-nonionic monomer into a schlenk bottle, adding tetrahydrofuran, stirring to dissolve and mix the tetrahydrofuran uniformly, filling nitrogen into the schlenk bottle through three cycles of freezing, air extraction, thawing and inflation, and reacting for 2-5 hours at 60 ℃; after the reaction is finished, adding tetrahydrofuran for dissolving and diluting, and then precipitating and separating out a polymer in a large amount of n-hexane after passing through neutral alumina, thus obtaining the auxiliary dispersing agent.
Further, the catalyst is cupric bromide, cuprous bromide or a mixture of the cupric bromide and the cuprous bromide; the complexing agent is bipyridine or N, N, N' -pentamethyldiethylenetriamine.
Furthermore, the feeding molar ratio of the catalyst, the complexing agent, the ATRP four-head initiator and the reactive anionic-nonionic monomer is 1:2:1: 50-100.
Furthermore, the multifunctional auxiliary agent is counted by mass of water, the modified graphene accounts for 5-15%, and the auxiliary dispersing agent accounts for 1-10%.
Further, the molecular weight of the polyethylene glycol diamine is preferably between 400-2000 g/mol; the molecular weight of the polyethylene glycol is preferably between 200 and 800 g/mol.
The Graphene Oxide (GO) is prepared by oxidizing graphene (Gr), and the surface of the Graphene Oxide (GO) contains carboxyl, hydroxyl, epoxy and other groups. The existing method for preparing graphene oxide is an improved Hummers method, and is simple to operate, mature in technology and high in oxidation degree. According to the scheme, more active sites are exposed on the surface of graphene by an improved Hummers method, then a PEG chain, imine and aniline groups are introduced to the surface of a graphene structure through molecular design to prepare functional graphene oxide, and an anionic-nonionic dispersing agent with a specific structure is used as an auxiliary material to obtain the multifunctional auxiliary agent containing the graphene nano material.
According to the scheme, firstly, polyethylene glycol diamine with low molecular weight is selected, on one hand, the hydrophilicity of graphene is increased, the dispersibility of the graphene in water is improved, on the other hand, amino groups at two ends of the polyethylene glycol diamine are used as reaction sites, anilino is introduced at the tail end of a graphene molecule as a bridge, the corrosion resistance of the graphene molecule is improved, and meanwhile, the intrinsic anticorrosive material is prepared by continuing to carry out in-situ polymerization with aniline; in addition, the anionic-nonionic dispersant with a specific structure is utilized to enhance the dispersibility of the modified graphene in various solvent systems, the multi-arm dispersant has abundant anchoring groups, can easily enter between graphene sheets, generates hydrogen bond action, adsorption action and the like with active groups on the surface of the graphene, is firmly combined, is not easy to settle in the solvent systems, and has good stability.
The invention has the beneficial effects that: the surface of the graphene oxide is modified, and a specific dispersing agent is combined, so that the dispersibility and stability of the graphene in the coating can be greatly improved; the dispersion medium can be common organic solvent or water, has wide application range and can effectively improve the corrosion resistance of the coating.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In addition, the technical features involved in the different embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The invention provides a preparation method of a multifunctional auxiliary agent containing a graphene nano material, which comprises the following steps:
1) dissolving aminotoluene in a mixed solution of ethanol and water, adding sodium bicarbonate, then cooling to 5 ℃, adding a dioxane solution of benzyl chloroformate, and stirring for reaction at 0 ℃ to protect amino;
2) dissolving the protected aminotoluene in carbon disulfide, and oxidizing methyl into aldehyde group according to Etard reaction to obtain an intermediate product 1;
3) firstly, preparing graphene oxide by using an improved Hummers method, adding the graphene oxide and a solvent DMF (dimethyl formamide) into a reaction bottle to uniformly disperse the graphene oxide and the solvent DMF, then dropwise adding a DMF solution of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide and N-hydroxysuccinimide into the reaction bottle to activate, and then adding polyethylene glycol diamine to react at 80-100 ℃ for 24 hours for amidation;
4) adding the obtained amidated product and the intermediate product 1 into a reaction bottle, adding water, performing ultrasonic treatment to uniformly disperse the amidated product and the intermediate product 1, adjusting the pH value to 6.5 to obtain a mixed solution, dropwise adding sodium amino borohydride into the mixed solution, stirring and reacting at room temperature for 12 hours, and filtering and freeze-drying the mixture after the reaction to obtain an intermediate product 2;
5) dispersing the intermediate product 2 in a mixed solvent of methanol and tert-butyl alcohol, adding a catalytic amount of palladium carbon, introducing hydrogen, stirring for reaction for 3 hours, deprotecting amino, filtering, and drying to finally obtain the modified graphene shown in formula 1);
6) dispersing 5-15% of the modified graphene and 1-10% of an auxiliary dispersant in a solvent system to obtain the multifunctional additive containing the graphene nano material.
Wherein the auxiliary dispersant is prepared by the following steps.
S1: adding polyethylene glycol (PEG-600) and dichloromethane into a reaction bottle, stirring to uniformly mix, adding a catalytic amount of silver oxide/potassium iodide catalyst, adding paratoluensulfonyl chloride with the same molar amount as the polyethylene glycol, stirring and reacting for 2-3 h at room temperature, and filtering and washing to obtain TsO-PEG-OH;
s2: dissolving TsO-PEG-OH in 25% ammonia water, adding equimolar ammonium chloride, stirring at 30 deg.C for 3 days, extracting with dichloromethane, and purifying the collected organic layer by column chromatography to obtain NH2-PEG-OH；
S3: the obtained NH2Dissolving PEG-OH in deionized water, adding equimolar amount of benzaldehyde-4-sodium sulfonate, adjusting pH to 6.5 to obtain a mixed solution, dropwise adding sodium aminoborohydride into the mixed solution, stirring and reacting at room temperature for 12 hours, and dialyzing, freezing and drying the reaction solution to obtain a solid; dissolving the solid in toluene, adding a polymerization inhibitor hydroquinone, a catalyst p-toluenesulfonic acid and monomer acrylic acid, heating to 110-120 ℃, stirring and refluxing for 4 hours, washing with a saturated sodium carbonate solution, separating liquid, performing rotary evaporation on an organic layer to remove the solvent, and recrystallizing to obtain the reactive anionic-nonionic monomer shown in the formula 1);
s4: adding pentaerythritol, triethylamine and anhydrous dioxane into a reaction bottle, introducing nitrogen to replace air in the reaction bottle, placing the reaction bottle in an environment at-18 ℃, dropwise adding a tetrahydrofuran solution of 2-bromoisobutyryl bromide in a nitrogen atmosphere, and after dropwise adding, moving the reaction bottle to room temperature to react for 12 hours under stirring; extracting with dichloromethane, collecting an organic layer, washing, drying, rotary steaming and recrystallizing to obtain an ATRP four-head initiator;
s5: sequentially adding 0.1mmol of catalyst (mixture of cupric bromide and cuprous bromide), 0.2mmol of complexing agent (bipyridyl bby), 0.01mmol of ATRP four-head initiator and 10mmol of reactive anionic-nonionic monomer into a schlenk bottle, adding tetrahydrofuran, stirring to dissolve and mix uniformly, filling nitrogen into the schlenk bottle through three cycles of freezing, air extraction, thawing and inflation, and reacting for 2-5 hours at 60 ℃; after the reaction is finished, adding tetrahydrofuran for dissolving and diluting, and then precipitating and separating out a polymer in a large amount of n-hexane after passing through neutral alumina, thus obtaining the anionic-nonionic dispersing agent.
Example 1: according to the preparation process, the molecular weight of the polyethylene glycol diamine is 400g/mol, the modified graphene and the auxiliary dispersant are prepared, and 15g of the modified graphene and 10g of the auxiliary dispersant are dispersed in 100g of water, so that the multifunctional assistant containing the graphene nano material is obtained.
Example 2: according to the preparation process, the molecular weight of the polyethylene glycol diamine is 1000g/mol, the modified graphene and the auxiliary dispersant are prepared, 10g of the modified graphene and 8g of the auxiliary dispersant are dispersed in 100g of DMF, and the multifunctional assistant containing the graphene nano material is obtained.
Example 3: according to the preparation process, the molecular weight of the polyethylene glycol diamine is 2000g/mol, the modified graphene and the auxiliary dispersant are prepared, 6g of the modified graphene and 5g of the auxiliary dispersant are dispersed in 100g of ethyl acetate, and the multifunctional assistant containing the graphene nano material is obtained.
Comparative example 1: according to the preparation process, the molecular weight of the polyethylene glycol diamine is 800g/mol, the modified graphene is prepared, 10g of the modified graphene and 8g of the auxiliary dispersing agent (OP-10 and sodium dodecyl benzene sulfonate with equal mass) are dispersed in 100g of DMF, and the multifunctional auxiliary agent containing the graphene nano material is obtained.
Comparative example 2: according to the preparation process, the molecular weight of the polyethylene glycol diamine is 800g/mol, the modified graphene is prepared, 10g of the modified graphene is taken and dispersed in 100g of DMF, and the multifunctional auxiliary agent containing the graphene nano material is obtained.
Evaluation of stability of the multifunctional auxiliary prepared in examples 1 to 3 and comparative examples 1 to 2: 10ml of each of the raw materials is taken, kept stand for 24 hours at the temperature of 5 ℃, 40 ℃ and the temperature of 5-40 ℃ under the circulating condition, and whether the layering or agglomeration phenomenon occurs is observed. 10ml of the suspension was centrifuged at 1000rpm/min for 10min, and the sedimentation was observed.
The prepared multifunctional additive is added into a commercially available polyurethane waterproof coating in an amount of 1%, and the mixture is kept stand for one week to observe whether an agglomeration phenomenon occurs. Preparing a standard coating according to GB1727, curing for 7 days, and placing the coating into a salt spray box to test the salt spray resistance of the coating. The test results are reported in table 1.
TABLE 1
As can be seen by combining the table 1, when the modified graphene of the embodiment 1-3 and the comparative example 1-2 are added into the coating, the salt spray resistance reaches over 96 hours, namely, the modified graphene of the embodiment is ensured to have self anti-corrosion performance to a certain extent due to the introduction of short-chain PEG chains and the combination of aniline groups at the chain ends; but also causes the reduction of the dispersion performance, for example, in comparative example 2, the centrifugal stability and the storage stability are poor when no dispersant is added, the dispersion in the coating is unstable, and the agglomeration is easy; however, if only a combination of a conventional anionic dispersant and a nonionic dispersant is used to help disperse the modified graphene as in comparative example 1, there is a certain improvement in the dispersion, but it is still not stable enough. In conclusion, the modified graphene can be well dispersed in the coating under the combined action of the modified graphene and the auxiliary dispersant, so that the anti-corrosion performance of the coating is improved, and the coating has a certain application value.
While embodiments of the invention have been disclosed above, it is not limited to the applications listed in the description and the embodiments, which are fully applicable in all kinds of fields of application of the invention, and further modifications may readily be effected by those skilled in the art, so that the invention is not limited to the specific details without departing from the general concept defined by the claims and the scope of equivalents.
Claims (8)
1. A preparation method of a multifunctional auxiliary agent containing a graphene nano material is characterized by comprising the following steps:
1) dissolving aminotoluene in a mixed solution of ethanol and water, adding sodium bicarbonate, then cooling to 5 ℃, adding a dioxane solution of benzyl chloroformate, and stirring for reaction at 0 ℃ to protect amino;
2) dissolving the protected aminotoluene in carbon disulfide, and oxidizing methyl into aldehyde group according to Etard reaction to obtain an intermediate product 1;
3) adding graphene oxide and a solvent DMF (dimethyl formamide) into a reaction bottle, dispersing the graphene oxide and the solvent DMF uniformly, then dropwise adding DMF (dimethyl formamide) solutions of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide and N-hydroxysuccinimide into the reaction bottle for activation, and then adding polyethylene glycol diamine for reacting at 80-100 ℃ for 24 hours for amidation;
4) adding the obtained amidated product and the intermediate product 1 into a reaction bottle, adding water, performing ultrasonic treatment to uniformly disperse the amidated product and the intermediate product 1, adjusting the pH value to 6.5 to obtain a mixed solution, dropwise adding sodium amino borohydride into the mixed solution, stirring and reacting at room temperature for 12 hours, and filtering and freeze-drying the mixture after the reaction to obtain an intermediate product 2;
5) dispersing the intermediate product 2 in a mixed solvent of methanol and tert-butyl alcohol, adding a catalytic amount of palladium carbon, introducing hydrogen, stirring for reaction for 3 hours, deprotecting amino, filtering, and drying to finally obtain the modified graphene shown in formula 1);
6) and dispersing the modified graphene and the auxiliary dispersing agent in a solvent system to obtain the multifunctional auxiliary agent containing the graphene nano material.
2. The method for preparing the multifunctional assistant containing the graphene nanomaterial according to claim 1, wherein the auxiliary dispersant has a structural formula shown in formula 2):
wherein n is an integer of 5 to 20.
3. The method for preparing the multifunctional additive containing the graphene nano-material according to claim 1, wherein the preparation of the auxiliary dispersant comprises the following steps:
s1: the polyethylene glycol reacts with p-toluenesulfonyl chloride under the action of a silver oxide/potassium iodide catalyst to obtain TsO-PEG-OH, and then reacts with ammonium chloride in ammonia water to obtain NH2-PEG-OH；
S2: obtained NH2Dissolving PEG-OH in deionized water, adding equimolar amount of benzaldehyde-4-sodium sulfonate, adjusting pH to 6.5 to obtain a mixed solution, dropwise adding sodium aminoborohydride into the mixed solution, stirring and reacting at room temperature for 12 hours, and dialyzing, freezing and drying the reaction solution to obtain a solid; then carrying out esterification reaction with acrylic acid to obtain a reactive anionic-nonionic monomer;
s3: adding pentaerythritol, triethylamine and anhydrous dioxane into a reaction bottle, introducing nitrogen to replace air in the reaction bottle, placing the reaction bottle in an environment at-18 ℃, dropwise adding a tetrahydrofuran solution of 2-bromoisobutyryl bromide in a nitrogen atmosphere, and after dropwise adding, moving the reaction bottle to room temperature to react for 12 hours under stirring; extracting with dichloromethane, collecting an organic layer, washing, drying, rotary steaming and recrystallizing to obtain an ATRP four-head initiator;
s4: sequentially adding a catalyst, a coordination agent, the ATRP four-head initiator and a reactive anionic-nonionic monomer into a schlenk bottle, adding tetrahydrofuran, stirring to dissolve and mix the tetrahydrofuran uniformly, filling nitrogen into the schlenk bottle through three cycles of freezing, air extraction, thawing and inflation, and reacting for 2-5 hours at 60 ℃; after the reaction is finished, adding tetrahydrofuran for dissolving and diluting, and then precipitating and separating out a polymer in a large amount of n-hexane after passing through neutral alumina, thus obtaining the auxiliary dispersing agent.
4. The method for preparing the multifunctional additive containing the graphene nano-material according to claim 3, wherein the catalyst is cupric bromide, cuprous bromide or a mixture of the cupric bromide and the cuprous bromide; the complexing agent is bipyridine or N, N, N' -pentamethyldiethylenetriamine.
5. The preparation method of the multifunctional assistant containing the graphene nano-material according to claim 3, wherein the feeding molar ratio of the catalyst, the complexing agent, the ATRP four-head initiator and the reactive anionic-nonionic monomer is 1:2:1: 50-100.
6. The preparation method of the multifunctional additive containing the graphene nano-material as claimed in claim 1, wherein the multifunctional additive is characterized in that the modified graphene accounts for 5-15% and the auxiliary dispersant accounts for 1-10% of the mass fraction of water.
7. The method for preparing the multifunctional assistant containing the graphene nano-material as claimed in claim 3, wherein the molecular weight of the polyethylene glycol diamine is 400-2000 g/mol; the molecular weight of the polyethylene glycol is 200-800 g/mol.
8. The multifunctional additive containing the graphene nano-material prepared by the preparation method of any one of claims 1 to 7.
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