CN114231115A - Graphene single-component aqueous epoxy resin emulsion and preparation method thereof - Google Patents
Graphene single-component aqueous epoxy resin emulsion and preparation method thereof Download PDFInfo
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- CN114231115A CN114231115A CN202111589511.8A CN202111589511A CN114231115A CN 114231115 A CN114231115 A CN 114231115A CN 202111589511 A CN202111589511 A CN 202111589511A CN 114231115 A CN114231115 A CN 114231115A
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 69
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 69
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 36
- 239000000839 emulsion Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000004945 emulsification Methods 0.000 title description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000000178 monomer Substances 0.000 claims abstract description 35
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 30
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 20
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims abstract description 14
- -1 acrylic ester Chemical class 0.000 claims abstract description 12
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 12
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 239000003999 initiator Substances 0.000 claims abstract description 9
- BDLXTDLGTWNUFM-UHFFFAOYSA-N 2-[(2-methylpropan-2-yl)oxy]ethanol Chemical compound CC(C)(C)OCCO BDLXTDLGTWNUFM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000021281 monounsaturated fatty acids Nutrition 0.000 claims abstract description 6
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims abstract description 5
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 11
- 239000004593 Epoxy Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 229920001046 Nanocellulose Polymers 0.000 claims description 8
- 229920001213 Polysorbate 20 Polymers 0.000 claims description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 8
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 claims description 8
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 239000003085 diluting agent Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000005543 nano-size silicon particle Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000006386 neutralization reaction Methods 0.000 claims description 4
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 4
- CUXYLFPMQMFGPL-UHFFFAOYSA-N (9Z,11E,13E)-9,11,13-Octadecatrienoic acid Natural products CCCCC=CC=CC=CCCCCCCCC(O)=O CUXYLFPMQMFGPL-UHFFFAOYSA-N 0.000 claims description 3
- CUXYLFPMQMFGPL-SUTYWZMXSA-N all-trans-octadeca-9,11,13-trienoic acid Chemical compound CCCC\C=C\C=C\C=C\CCCCCCCC(O)=O CUXYLFPMQMFGPL-SUTYWZMXSA-N 0.000 claims description 3
- IFPMZBBHBZQTOV-UHFFFAOYSA-N 1,3,5-trinitro-2-(2,4,6-trinitrophenyl)-4-[2,4,6-trinitro-3-(2,4,6-trinitrophenyl)phenyl]benzene Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C(C=2C(=C(C=3C(=CC(=CC=3[N+]([O-])=O)[N+]([O-])=O)[N+]([O-])=O)C(=CC=2[N+]([O-])=O)[N+]([O-])=O)[N+]([O-])=O)=C1[N+]([O-])=O IFPMZBBHBZQTOV-UHFFFAOYSA-N 0.000 claims description 2
- 229910015900 BF3 Inorganic materials 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Substances FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Natural products CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 239000005642 Oleic acid Substances 0.000 claims 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 claims 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 claims 1
- 229960004488 linolenic acid Drugs 0.000 claims 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 claims 1
- 229920001296 polysiloxane Polymers 0.000 claims 1
- 238000007142 ring opening reaction Methods 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000032050 esterification Effects 0.000 abstract description 3
- 238000005886 esterification reaction Methods 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 6
- 238000000053 physical method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229920006334 epoxy coating Polymers 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
Classifications
-
- 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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
-
- 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
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
Abstract
The invention discloses a graphene single-component aqueous epoxy resin emulsion and a preparation method thereof, and the emulsion comprises, by mass, epoxy resin modified by acrylate monomers, 5-10% of monounsaturated fatty acid, 1-2% of a catalyst, 5-10% of styrene, 5-10% of maleic anhydride, 1-2% of AMP-95, 0.5-2% of modified graphene and 10-20% of water, wherein the epoxy resin modified by the acrylate monomers is prepared from 20-35% of bisphenol F type epoxy resin, 5-15% of ethylene glycol tert-butyl ether, 1.5-2% of an initiator and 20-35% of acrylate monomers. According to the invention, the acrylic ester monomer is used for grafting and modifying the epoxy resin, the unsaturated fatty acid is used for ring opening and esterification to modify the epoxy resin, and then the styrene and the maleic anhydride are added to react with the hydroxyl formed by ring opening to introduce the hydrophilic group, so that the epoxy resin has hydrophilicity, and the preparation method of the epoxy resin emulsion has the advantages of simple process, environmental protection, low cost and good performance.
Description
Technical Field
The invention relates to the technical field of aqueous epoxy emulsion, in particular to graphene single-component aqueous epoxy resin emulsion and a preparation method thereof.
Background
Epoxy resin has excellent characteristics and the like and is widely applied to various fields of coatings, adhesives, composite materials and the like, most of the traditional epoxy resin coatings are solvent type, most of organic volatile matters in the coatings belong to toxic substances, and are directly discharged into the atmosphere to seriously pollute the environment, in recent years, laws and regulations related to environmental pollution limitation are successively issued, a system with zero VOC or low V0C and HAP of the coatings becomes the research direction of novel materials, and the waterborne epoxy coating has low VOC content, small smell and safe use, can be cleaned by water, meets the requirements of environmental protection and energy conservation, and quickly becomes an important development direction of modern coatings.
The existing epoxy resin aqueous method is usually a self-emulsifying method, which mainly comprises the steps of introducing hydrophilic groups into epoxy resin, neutralizing to form salt, adding water and dispersing, so that the epoxy resin has water solubility, wherein the particle size is nano-scale.
Disclosure of Invention
In order to solve the technical problems mentioned in the background art, the graphene single-component aqueous epoxy resin emulsion and the preparation method thereof are provided.
In order to achieve the purpose, the invention adopts the following technical scheme:
a graphene single-component aqueous epoxy resin emulsion comprises, by mass, an acrylic monomer modified epoxy resin, 5-10% of monobasic unsaturated fatty acid, 1-2% of a catalyst, 5-10% of styrene, 5-10% of maleic anhydride, 1-2% of AMP-95, 0.5-2% of modified graphene, 3-3.5% of nanocellulose and 10-20% of water, wherein the acrylic monomer modified epoxy resin is prepared from 20-35% of bisphenol F type epoxy resin, 5-15% of a film forming aid, 1.5-2% of an initiator, 20-35% of an acrylic monomer, 2-3% of nano modified organosilicon and 5-8% of an epoxy diluent, the film forming aid is one of ethylene glycol tert-butyl ether, alcohol ether dodeca, an acetone alcohol compound or a diacid ester compound, the bisphenol F type epoxy resin, the film-forming assistant and the epoxy diluent are added into a reactor to be heated to form a homogeneous phase, the temperature is controlled to be 70-80 ℃, the acrylic monomer dissolved with the initiator is firstly dripped, and then the nano modified organic silicon is dripped to obtain the acrylic monomer modified epoxy resin.
As a further description of the above technical solution:
the catalyst is one of triphenylphosphine, tribenzylmethylammonium chloride and boron trifluoride amine complex.
As a further description of the above technical solution:
the initiator is tert-butyl peroxybenzoate or benzoyl peroxide.
As a further description of the above technical solution:
the acrylate monomer is one or more of methyl methacrylate, di-isooctyl acrylate, butyl acrylate and styrene.
As a further description of the above technical solution:
the acrylate monomer is one or more of methyl methacrylate, di-isooctyl acrylate, butyl acrylate and styrene.
As a further description of the above technical solution:
the modified graphene is prepared from 0.75-1% of polyoxyethylene sorbitan monolaurate, 0.75-1% of sodium dodecyl sulfate, 0.5-1% of physical method graphene powder and 97-98.5% of water, wherein 0.75-1% of polyoxyethylene sorbitan monolaurate, 0.75-1% of sodium dodecyl sulfate and 97-98.5% of water are added into a reaction kettle to be uniformly mixed, then 0.5-1% of physical method graphene powder is added into the solution to be stirred and dispersed by 900-1200 rpmtl until the average particle size D50 is smaller than 10 mu m, and then the modified graphene is kept stand for later use, so that the modified graphene is obtained.
As a further description of the above technical solution:
the nano modified organic silicon comprises 3-7% of silane coupling agent, 8-14% of methyl triethoxysilane, 16-22% of absolute ethyl alcohol, 1-2% of alumina and 10-12%, the silane coupling agent, the methyl triethoxysilane, the absolute ethyl alcohol and the alumina are added into a reaction kettle, the temperature is heated to 60-80 ℃, the mixed solution of the absolute ethyl alcohol and deionized water is dripped within 3 hours, and the temperature is kept for 5 hours, so that the nano silicon dioxide solution is obtained.
As a further description of the above technical solution:
a preparation method of a graphene single-component water-based epoxy resin emulsion comprises the following steps:
s1, preparing acrylic ester monomer modified epoxy resin;
s2, preparing the graphene single-component water-based epoxy resin emulsion: heating the epoxy resin modified by the acrylate monomer to 120-150 ℃, adding the monounsaturated fatty acid and the catalyst, adding styrene and maleic anhydride, reacting for 2.0-3.0 h, adding the modified graphene, reacting for 1.0-2.0 h, cooling to 50-60 ℃, adding AMP-95 for neutralization for 0.5-1.0 h, and dispersing water for 0.5-1.0 h to obtain the graphene single-component aqueous epoxy resin solution.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that: according to the invention, the acrylic ester monomer is used for grafting and modifying the epoxy resin, the unsaturated fatty acid is used for ring opening and esterification to modify the epoxy resin, and then the styrene and the maleic anhydride are added to react with the hydroxyl formed by ring opening to introduce the hydrophilic group, so that the epoxy resin has hydrophilicity.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. 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.
Example one
The invention provides a technical scheme that: the graphene single-component aqueous epoxy resin emulsion comprises, by mass, 30% of bisphenol F epoxy resin, 10% of ethylene glycol tert-butyl ether, 1.5% of tert-butyl peroxybenzoate, 20% of an acrylate monomer, 2% of nano modified organic silicon, 5% of an epoxy diluent, 8% of eleostearic acid, 1.5% of triphenylphosphine, 8% of styrene, 7% of maleic anhydride, 1% of AMP-95, 1% of modified graphene, 3% of nanocellulose and 12% of water.
Specifically, the bisphenol F epoxy resin is bisphenol F epoxy resin JER 807F 170, and the 20% acrylate monomer is 10% methyl methacrylate, 5% di-iso-octyl acrylate and 5% butyl acrylate.
Specifically, the modified graphene is prepared from 0.75-1% of polyoxyethylene sorbitan monolaurate, 0.75-1% of sodium dodecyl sulfate, 0.5-1% of physical method graphene powder and 97-98.5% of water, wherein 0.75-1% of polyoxyethylene sorbitan monolaurate, 0.75-1% of sodium dodecyl sulfate and 97-98.5% of water are added into a reaction kettle to be uniformly mixed, then 0.5-1% of physical method graphene powder is added into the solution to be stirred and dispersed by 900-1200 rpmtl until the average particle size D50 is smaller than 10 mu m, and then the modified graphene is kept stand for later use to obtain the modified graphene.
Specifically, the nano modified organosilicon comprises 3-7% of silane coupling agent, 8-14% of methyltriethoxysilane, 16-22% of absolute ethyl alcohol, 1-2% of alumina and 10-12%, the silane coupling agent, the methyltriethoxysilane, the absolute ethyl alcohol and the alumina are added into a reaction kettle, the temperature is increased to 60-80 ℃, the mixed solution of the absolute ethyl alcohol and the deionized water is dripped within 3 hours, and the temperature is maintained for 5 hours, so that the nano silicon dioxide solution is obtained.
A preparation method of a graphene single-component water-based epoxy resin emulsion comprises the following steps:
s1, preparing the epoxy resin modified by the acrylate monomer: adding bisphenol F type epoxy resin and ethylene glycol tert-butyl ether into a reactor, heating to form a homogeneous phase, controlling the temperature to be 70-80 ℃, dropwise adding an acrylate monomer dissolved with an initiator, and dropwise adding nano modified organic silicon to obtain acrylate monomer modified epoxy resin;
s2, preparing the graphene single-component water-based epoxy resin emulsion: heating the epoxy resin modified by the acrylate monomer to 120-150 ℃, adding the monounsaturated fatty acid and the catalyst, adding styrene and maleic anhydride, reacting for 2.0-3.0 h, adding the modified graphene and the nanocellulose, reacting for 1.0-2.0 h, cooling to 50-60 ℃, adding AMP-95 for neutralization for 0.5-1.0 h, and then dispersing water for 0.5-1.0 h to obtain the graphene single-component aqueous epoxy resin solution.
Example two
The invention provides a technical scheme that: the graphene single-component aqueous epoxy resin emulsion comprises, by mass, 30% of bisphenol F epoxy resin, 10% of ethylene glycol tert-butyl ether, 1.5% of tert-butyl peroxybenzoate, 20% of an acrylate monomer, 2% of nano modified organic silicon, 5% of an epoxy diluent, 5% of eleostearic acid, 1.5% of triphenylphosphine, 8% of styrene, 10% of maleic anhydride, 1% of AMP-95, 1% of modified graphene, 3% of nanocellulose and 12% of water.
Specifically, the bisphenol F epoxy resin is bisphenol F epoxy resin JER 807F 170, and the 20% acrylic monomer is 15% methyl methacrylate, 2.5% di-iso-octyl acrylate, and 2.5% butyl acrylate.
Specifically, the modified graphene is prepared from 0.75-1% of polyoxyethylene sorbitan monolaurate, 0.75-1% of sodium dodecyl sulfate, 0.5-1% of physical method graphene powder and 97-98.5% of water, wherein 0.75-1% of polyoxyethylene sorbitan monolaurate, 0.75-1% of sodium dodecyl sulfate and 97-98.5% of water are added into a reaction kettle to be uniformly mixed, then 0.5-1% of physical method graphene powder is added into the solution to be stirred and dispersed by 900-1200 rpmtl until the average particle size D50 is smaller than 10 mu m, and then the modified graphene is kept stand for later use to obtain the modified graphene.
Specifically, the nano modified organosilicon comprises 3-7% of silane coupling agent, 8-14% of methyltriethoxysilane, 16-22% of absolute ethyl alcohol, 1-2% of alumina and 10-12%, the silane coupling agent, the methyltriethoxysilane, the absolute ethyl alcohol and the alumina are added into a reaction kettle, the temperature is increased to 60-80 ℃, the mixed solution of the absolute ethyl alcohol and the deionized water is dripped within 3 hours, and the temperature is maintained for 5 hours, so that the nano silicon dioxide solution is obtained.
A preparation method of a graphene single-component water-based epoxy resin emulsion comprises the following steps:
s1, preparing the epoxy resin modified by the acrylate monomer: adding bisphenol F type epoxy resin and ethylene glycol tert-butyl ether into a reactor, heating to form a homogeneous phase, controlling the temperature to be 70-80 ℃, dropwise adding an acrylate monomer dissolved with an initiator, and dropwise adding nano modified organic silicon to obtain acrylate monomer modified epoxy resin;
s2, preparing the graphene single-component water-based epoxy resin emulsion: heating the epoxy resin modified by the acrylate monomer to 120-150 ℃, adding the monounsaturated fatty acid and the catalyst, adding styrene and maleic anhydride, reacting for 2.0-3.0 h, adding the modified graphene and the nanocellulose, reacting for 1.0-2.0 h, cooling to 50-60 ℃, adding AMP-95 for neutralization for 0.5-1.0 h, and then dispersing water for 0.5-1.0 h to obtain the graphene single-component aqueous epoxy resin solution.
Firstly, the invention grafts and modifies the epoxy resin by acrylate monomer, then uses the epoxy resin modified by unsaturated fatty acid ring-opening esterification, then adds styrene and maleic anhydride to react with hydroxyl formed by ring-opening to introduce hydrophilic group, thus leading the epoxy resin to have hydrophilicity, secondly, the preparation method of the epoxy resin emulsion of the invention has simple process, environmental protection, low cost and good performance, wherein, the nano silicon dioxide can improve the corrosion resistance of the coating prepared by the emulsion, in the film forming process, the nano silicon dioxide particles can effectively improve the interface bonding tension between the emulsion and the filler, thus achieving the function of strengthening and repairing the defect, thereby effectively improving the mechanical performance of the coating after film forming, wherein, the nano high specific surface and the belt emulsification property of the nano cellulose can be used for well loading, emulsifying, dispersing and modifying the graphene, the modified graphene is prevented from agglomerating, is uniformly dispersed in the initial stage before the epoxy emulsion is subjected to water-based treatment at high speed, and is subjected to water-based treatment to prepare the water-based epoxy emulsion containing the modified graphene and the nano-cellulose.
The following table 1 is a comparison between the film performance indexes of the water-based primer anti-corrosion paints prepared from the emulsions of the embodiments 1 and 2 and the performances of the comparative examples, wherein the comparative examples are water-based primer anti-corrosion paints prepared from two-component water-based epoxy resin:
TABLE 1
| Detecting items | Comparative example | Example 1 | Example 2 | Detection method |
| Appearance of the product | Is flat and smooth | Is flat and smooth | Is flat and smooth | Visual inspection of |
| Adhesion/grade | 0 | 0 | 0 | GB/T1720-79 |
| Hardness of | H | 2H | 4H | GB/T1730-79 |
| Flexibility/mm | 1 | 1 | 1 | GB/T1731-93 |
| Impact resistance/cm | 50 | 50 | 50 | GB/T1732-93 |
| Water resistance/h | 120 | 600 | 600 | GB/T1733-93 |
| Alkali resistance/h | ≥24 | ≥120 | ≥120 | GB/T1763-79 |
| Neutral salt fog resistance per hour | ≥360 | ≥1440 | ≥1440 | GB/T1771-91 |
As can be seen from Table 1, compared with the coating film performance of the comparative example, the waterborne primer anti-corrosion paint prepared by the invention has the advantages that the comprehensive performance is obviously improved, and the water resistance and the salt spray resistance are improved by orders of magnitude.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (8)
1. The graphene single-component aqueous epoxy resin emulsion is characterized by comprising, by mass, an acrylic monomer modified epoxy resin, 5-10% of monobasic unsaturated fatty acid, 1-2% of a catalyst, 5-10% of styrene, 5-10% of maleic anhydride, 1-2% of AMP-95, 0.5-2% of modified graphene, 3-3.5% of nanocellulose and 10-20% of water, wherein the acrylic monomer modified epoxy resin is prepared from 20-35% of bisphenol F type epoxy resin, 5-15% of a film forming aid, 1.5-2% of an initiator, 20-35% of an acrylic monomer, 2-3% of nano modified organosilicon and 5-8% of an epoxy diluent, the film forming aid is one of ethylene glycol tert-butyl ether, alcohol ether dodeca, an acetone alcohol compound or a diacid ester compound, the bisphenol F type epoxy resin, the film-forming assistant and the epoxy diluent are added into a reactor to be heated to form a homogeneous phase, the temperature is controlled to be 70-80 ℃, the acrylic monomer dissolved with the initiator is firstly dripped, and then the nano modified organic silicon is dripped to obtain the acrylic monomer modified epoxy resin.
2. The graphene one-component aqueous epoxy resin emulsion according to claim 1, wherein the catalyst is one of triphenylphosphine, tribenzylmethylammonium chloride and boron trifluoride amine complex.
3. The graphene one-component aqueous epoxy resin emulsion according to claim 1, wherein the initiator is one of tert-butyl peroxybenzoate or benzoyl peroxide.
4. The graphene mono-component aqueous epoxy resin emulsion according to claim 1, wherein the monounsaturated fatty acid is one of eleostearic acid, linolenic acid or soya-oleic acid.
5. The graphene mono-component water-based epoxy resin emulsion as claimed in claim 1, wherein the acrylate monomer is one or more of methyl methacrylate, di-iso-octyl acrylate, butyl acrylate and styrene.
6. The graphene one-component aqueous epoxy resin emulsion according to claim 1, wherein the modified graphene is prepared from 0.75-1% of polyoxyethylene sorbitan monolaurate, 0.75-1% of sodium dodecyl sulfate, 0.5-1% of physical graphene powder and 97-98.5% of water, the 0.75-1% of polyoxyethylene sorbitan monolaurate, 0.75-1% of sodium dodecyl sulfate and 97-98.5% of water are added into a reaction kettle to be uniformly mixed, then 0.5-1% of physical graphene powder is added into the solution to be stirred and dispersed at 900-1200 mtrpl, and the solution is left to stand for standby after the average particle size D50 is smaller than 10 μm, so as to obtain the modified graphene.
7. The graphene single-component water-based epoxy resin emulsion according to claim 1, wherein the nano modified silicone comprises 3% -7% of a silane coupling agent, 8% -14% of methyltriethoxysilane, 16% -22% of absolute ethyl alcohol, 1% -2% of alumina and 10% -12%, the silane coupling agent, the methyltriethoxysilane, the absolute ethyl alcohol and the alumina are added into a reaction kettle, the reaction kettle is heated to 60-80 ℃, a mixed solution of the absolute ethyl alcohol and deionized water is dripped within 3 hours, and the temperature is kept for 5 hours to obtain a nano silicon dioxide solution.
8. The preparation method of the graphene single-component aqueous epoxy resin emulsion according to claim 1, characterized by comprising the following steps:
s1, preparing acrylic ester monomer modified epoxy resin;
s2, preparing the graphene single-component water-based epoxy resin emulsion: heating the epoxy resin modified by the acrylate monomer to 120-150 ℃, adding the monounsaturated fatty acid and the catalyst, adding styrene and maleic anhydride, reacting for 2.0-3.0 h, adding the modified graphene and the nanocellulose, reacting for 1.0-2.0 h, cooling to 50-60 ℃, adding AMP-95 for neutralization for 0.5-1.0 h, and then dispersing water for 0.5-1.0 h to obtain the graphene single-component aqueous epoxy resin solution.
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