CN116333549B - Polymer cement anti-corrosion paint based on functional MXene and preparation method thereof - Google Patents
Polymer cement anti-corrosion paint based on functional MXene and preparation method thereof Download PDFInfo
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- CN116333549B CN116333549B CN202310340969.2A CN202310340969A CN116333549B CN 116333549 B CN116333549 B CN 116333549B CN 202310340969 A CN202310340969 A CN 202310340969A CN 116333549 B CN116333549 B CN 116333549B
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- mxene
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- polymer cement
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- 239000011414 polymer cement Substances 0.000 title claims abstract description 66
- 239000003973 paint Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000005260 corrosion Methods 0.000 title abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 58
- 239000000839 emulsion Substances 0.000 claims abstract description 55
- 238000000576 coating method Methods 0.000 claims abstract description 44
- 239000011248 coating agent Substances 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229920000642 polymer Polymers 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 239000004568 cement Substances 0.000 claims abstract description 17
- XEWQXJJJOIKGTP-UHFFFAOYSA-N 2-methylprop-2-enoic acid;octadecanoic acid Chemical compound CC(=C)C(O)=O.CCCCCCCCCCCCCCCCCC(O)=O XEWQXJJJOIKGTP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 14
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 22
- 239000000178 monomer Substances 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 13
- 239000002518 antifoaming agent Substances 0.000 claims description 13
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000011161 development Methods 0.000 claims description 8
- 239000002270 dispersing agent Substances 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- 238000004945 emulsification Methods 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 239000011344 liquid material Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- -1 alcohol ester Chemical class 0.000 claims description 3
- 238000005530 etching Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 claims description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 2
- 239000011398 Portland cement Substances 0.000 claims description 2
- 239000006172 buffering agent Substances 0.000 claims description 2
- 239000003431 cross linking reagent Substances 0.000 claims description 2
- 239000003995 emulsifying agent Substances 0.000 claims description 2
- 238000004108 freeze drying Methods 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 2
- 239000008158 vegetable oil Substances 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- 239000013530 defoamer Substances 0.000 claims 1
- 230000002209 hydrophobic effect Effects 0.000 abstract description 17
- 230000032683 aging Effects 0.000 abstract description 9
- 230000007797 corrosion Effects 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 9
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract description 8
- 230000004048 modification Effects 0.000 abstract description 7
- 238000012986 modification Methods 0.000 abstract description 7
- 230000007774 longterm Effects 0.000 abstract description 6
- 230000004888 barrier function Effects 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 3
- 238000007654 immersion Methods 0.000 abstract description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 abstract 2
- 230000009977 dual effect Effects 0.000 abstract 1
- 238000005457 optimization Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 17
- 230000000694 effects Effects 0.000 description 9
- 239000003607 modifier Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 238000001132 ultrasonic dispersion Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- 230000018109 developmental process Effects 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- 239000013049 sediment Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- HPEUJPJOZXNMSJ-UHFFFAOYSA-N Methyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC HPEUJPJOZXNMSJ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 239000002064 nanoplatelet Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 210000000795 conjunctiva Anatomy 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- CAMHHLOGFDZBBG-UHFFFAOYSA-N epoxidized methyl oleate Natural products CCCCCCCCC1OC1CCCCCCCC(=O)OC CAMHHLOGFDZBBG-UHFFFAOYSA-N 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- GCSJLQSCSDMKTP-UHFFFAOYSA-N ethenyl(trimethyl)silane Chemical compound C[Si](C)(C)C=C GCSJLQSCSDMKTP-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000012025 fluorinating agent Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000003829 resin cement Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000005303 weighing 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/064—Copolymers with monomers not covered by C09D133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- 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
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
- C09D1/06—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances cement
- C09D1/08—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances cement with organic additives
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
Abstract
The invention provides a preparation method of a polymer cement anticorrosive paint based on functionalized MXene, which comprises the following steps: first, for Ti 3 C 2 Performing hydrophobic modification on the MXene powder to obtain functionalized MXene powder; secondly, adding functional MXene powder and methyl acrylic acid stearate in the emulsion polymerization process to prepare modified polymer emulsion; finally, mixing the powder component containing cement with the liquid component containing the modified polymer emulsion to obtain the polymer cement anticorrosive paint based on the functionalized MXene. The polymer cement anticorrosive paint prepared by the invention introduces the functionalized MXene and the methyl acrylic acid stearate, and the functionalized MXene fully plays a role through the optimization of the preparation process. The combined application of the methyl acrylate and the MXene shows the dual effects of chemical combination and physical barrier, improves the hydrophobic property of the coating, has the advantages of high mechanical strength, good corrosion resistance and ageing resistance and the like, is suitable for a long-term water immersion environment, and has wide popularization and application prospects.
Description
Technical Field
The invention belongs to the technical field of anti-corrosion paint, and particularly relates to a polymer cement anti-corrosion paint based on functional MXene and a preparation method thereof.
Background
The polymer cement waterproof paint (JS waterproof paint for short) is a double-component water-based anticorrosive paint which is prepared by taking polymer emulsion such as polyacrylate, ethylene-vinyl acetate and the like and cement as main raw materials, adding filler and other auxiliary agents, and solidifying conjunctiva through water evaporation and cement hydration reaction. Wherein, one component is inorganic powder (cement, quartz sand, various additives, inorganic fillers and the like), the other component is organic liquid (polymer emulsion), and the two components are reasonably proportioned on site during construction, are evenly mixed and stirred into putty, and form a high-strength and tough waterproof film after coating and solidification. In the 80 s of the 20 th century, germany developed polymer cement anticorrosive coatings based on acrylates. The development of JS paint is started in the beginning of the 20 th century of China in the 90 th year. The inorganic-organic composite anticorrosive paint with rigid-flexible combination has better performance than CCCCWC paint, has the advantages of high elasticity and large elongation of the organic material, has the cohesiveness, durability and water resistance of the cement inorganic material, has been rapidly developed since the advent, and has been widely applied to waterproof engineering at home and abroad. However, the polymer cement anticorrosive paint does not have high water resistance, and particularly in a long-term water immersion environment, the long-term water resistance, corrosion resistance and ultraviolet aging resistance of the polymer cement anticorrosive paint are seriously counteracted.
MXene is considered the fastest growing platelet material in the post-graphene era, since MXene is composed of a polymer withStacked sheets of Van der Waals force and hydrogen bonding so they can be exfoliated in colloidal solution into single or few layer nanoplatelets, which MXene nanoplatelets can become Mn 1 X n T x . The hydrophobic modifier is used for chemically modifying the MXene, and the modified MXene is added into the paint, so that the hydrophobic property of the paint can be further improved. For example: the invention discloses a preparation method of a super-hydrophobic conductive anticorrosive paint for a grounding grid, which is disclosed by adding fluorinated modified MXene and fluorinated modified carbon nano tubes into epoxy resin to improve the hydrophobic property of the prepared anticorrosive paint and further realize a long-acting anticorrosive effect.
However, it is difficult for the functionalized MXene to function effectively for the matrix of the polymer cement anticorrosive paint because the polymer cement paint is an organic-inorganic two-component composite material, the viscosity of the emulsion makes it impossible to disperse MXene in the polymer emulsion, and in the process of preparing the coating by mixing the emulsion with cement further, MXene cannot be uniformly dispersed in every part of the coating, so that it is difficult to obtain the expected hydrophobic anticorrosive effect. In addition, although the MXene is applied to a resin or polymer cement coating system, the MXene is equivalent to a layer of physical barrier in the system, and plays a certain role in the mechanical property, corrosion resistance and ageing resistance of the coating, the performance of the polymer cement organic-inorganic composite system material is still far from being improved by only relying on the single role of the barrier.
Based on the method, a brand-new preparation method of the polymer cement anti-corrosion coating based on the functionalized MXene is provided, so that the mechanical strength, long-term water resistance, corrosion resistance and ultraviolet ageing resistance of the polymer cement anti-corrosion coating are improved, the method has important significance for further widening the application field of the polymer cement anti-corrosion coating, and the method is also a technical problem to be solved by researchers.
Disclosure of Invention
The invention aims to provide a preparation method of a polymer cement anticorrosive paint based on functionalized MXene, which has higher mechanical property, long-term water resistance, corrosion resistance and ultraviolet aging resistance.
The second purpose of the invention is to provide the polymer cement anticorrosive paint based on the functionalized MXene, which has higher mechanical property, long-term water resistance, corrosion resistance and ultraviolet aging resistance.
One of the achievement purposes of the invention adopts the technical proposal that: the preparation method of the polymer cement anticorrosive paint based on the functionalized MXene comprises the following steps:
s1, ti is mixed with 3 C 2 Dispersing the MXene powder in a solvent, and regulating the pH value to 3-4 to obtain a mixed solution; according to vinyltrimethoxysilane A-171 and Ti 3 C 2 The mass ratio of the MXene powder is (8-12) 1, A-171 is added into the mixed solution, and the mixture is heated and reacted for a certain time to obtain the functionalized MXene powder;
s2, adding the functionalized MXene powder, an emulsifying agent, a buffering agent, a cross-linking agent and methyl acrylic acid stearate into deionized water, and mixing to obtain a dispersion liquid; adding the dispersion liquid into a monomer, performing pre-emulsification operation, adding an initiator, performing polymerization reaction for a certain time, stopping the reaction, then performing heating development, adjusting the pH of the product to 7-8, and filtering to obtain modified polymer emulsion; the addition amount of the functionalized MXene powder is 0.1-0.3 wt.% of the mass of the monomer, and the addition amount of the methyl acrylic stearate is 1-5 wt.% of the monomer;
s3, mixing cement and a dispersing agent to obtain a powder component, and mixing the modified polymer emulsion with a film forming auxiliary agent, a defoaming agent and water to obtain a liquid component; and adding the powder component into the liquid component, and stirring until the powder component and the liquid component are uniformly mixed to obtain the polymer cement anticorrosive paint based on the functionalized MXene.
The general idea of the invention is as follows: in order to make the functionalized MXene function more effectively in the polymer cement paint system, the preparation method mainly improves the following two aspects:
on the one hand, A-171 (vinyltrimethylsilane) is used for Ti 3 C 2 Hydrophobic modification of the MXene powder, the A-171 molecular structure containing a vinyl function having an unsaturated double bond structure and three hydrolyzable groupsMethoxy group, at H + And under the catalysis of temperature, A-171 is hydrolyzed to generate active silicon hydroxyl which can be subjected to condensation reaction with the hydroxyl on the surface of MXene to form chemical bonding. Further, unlike other hydrophobic modifiers (e.g., KH-570 or fluorinated modifiers), the unsaturated double bond on the vinyl functionality of A-171 undergoes an addition reaction with the newly initiated unsaturated double bond on MXene under the initiation of water to graft onto the MXene surface, and this bi-directional reaction results in a significantly faster hydrolysis rate of A-171 than that of the fluorinating agent and KH-570, while through the bi-directional reaction, A-171 effects coupling and attachment between MXene and the polymer emulsion, thereby improving the bond between the two and improving the dispersibility of MXene.
On the other hand, in order to ensure that the MXene can be fully and uniformly dispersed in the emulsion, the invention abandons the use of the commercial polymer emulsion, adopts the batch method emulsion polymerization to synthesize the acrylic emulsion containing the functionalized MXene powder, ensures the uniform dispersion of the MXene in the emulsion by adding the functionalized MXene in the process of synthesizing the emulsion, and further ensures that the functionalized MXene can be uniformly dispersed at each part of the coating in the process of mixing the polymer emulsion and cement to form the coating, thereby effectively playing a role. In addition, a certain proportion of methyl stearate (stearyl methacrylate, STEA for short) is added in the emulsion polymerization stage, the methyl methacrylate-methyl stearate copolymer is produced through the polymerization reaction of free radicals between the methyl methacrylate and the methyl methacrylate, and the methyl methacrylate-methyl stearate copolymer is matched with the functionalized MXene, so that the comprehensive performances of hydrophobicity, durability and the like of the coating are improved under the combined action of two aspects of chemical combination and physical barrier.
Further, in step S1, pH adjustment is performed using 1mol/L hydrochloric acid. The pH value is adjusted to 3-4, so that the mixed solution is acidic, the homopolymerization of silanol generated by subsequent hydrolysis of A-171 caused by dehydration self-condensation can be prevented, side reaction is avoided, and the full play of the modification effect of A-171 is ensured. Control A-171 and Ti 3 C 2 The mass ratio of the-MXene powder is (8-12): 1, and the chemical modification can be fully completed.
Preferably, in the step S1, ti 3 C 2 The preparation method of the-MXene powder comprises the following steps:dissolving LiF powder in hydrochloric acid, and adding Ti 3 AlC 2 Etching the powder for 48-60 h at 40-45 ℃ and the rotating speed of 350-400 rpm, washing, ultrasonic processing, centrifugal collection, freeze drying and grinding the product in sequence to obtain Ti 3 C 2 -MXene powder.
Preferably, in the step S1, the solvent is selected from the group consisting of deionized water and an absolute ethanol mixed solution, ti 3 C 2 The dosage ratio of the MXene powder to the mixed solution is (1-3): 800g/ml. Preferably, in the mixed solution, the volume ratio of deionized water to absolute ethyl alcohol is 1:9, and Ti is as follows 3 C 2 The ratio of the amount of the MXene powder to the mixed solution was 1.6:800g/ml. The dispersion is ultrasonic dispersion, the temperature of the ultrasonic dispersion is 45 ℃, and the time of the ultrasonic dispersion is 60min.
Preferably, in the step S1, the heating reaction is performed at a temperature of 70 to 80 ℃ for a time of 4 to 6 hours.
Further, in the step S2, monomers are prepared from methacrylic acid (MAA), butyl Acrylate (BA) and Methyl Methacrylate (MMA) according to the following steps (6 to 10): (100-130): (60-70) by mass ratio. Preferably, the mass ratio of methacrylic acid, butyl acrylate and methyl methacrylate is 8:126:66.
In the present invention, it is desirable to control the amount of the functionalized MXene powder added to 0.1 to 0.3wt.% of the monomer. It was found that when the amount of functionalized MXene powder added is higher than 0.3wt.%, excessive MXene particles produce large area agglomeration in the coating, which in turn leads to a decrease in performance; when the amount is less than 0.1%, the effect is not exerted because the amount added is too small. Meanwhile, in emulsion polymerization, the adding amount of the methyl acrylic acid stearate is controlled to be 1-5 wt.% of the monomer, and when the adding amount is less than 1%, the generated MMA-STEA copolymer is too little; when the blending amount is more than 5%, excessive MMA is consumed by the chemical reaction, and the synthetic emulsion process is affected, resulting in a decrease in coating properties.
Preferably, the functionalized MXene powder is added in an amount of 0.2wt.% of the monomer, the amount of stearic methacrylate added is 2.5wt.% of the monomer.
Preferably, in the step S2, the temperature of the pre-emulsification is 40-50 ℃ and the time is 15-30 min; the temperature of the polymerization reaction is 75-80 ℃ and the time is 3-4 h; the temperature of the temperature rise and development is 85-90 ℃ and the time is 30-50 min. In the invention, the pH of the product is adjusted to 7-8, so that the modified polymer emulsion can be prevented from reacting with alkaline components in cement.
Further, in the step S3, the powder component is added into the liquid component by adopting a mode of firstly stirring slowly and then stirring rapidly; the rotating speed of the slow stirring is 100-200 rpm/min, and the time is 1-3 min; the rotating speed of the rapid stirring is 300-500 rpm/min, and the time is 3-5 min.
The second technical scheme adopted for realizing the purpose of the invention is as follows: there is provided a functionalized MXene-based polymer cement anticorrosive paint prepared according to the preparation method of one of the objects of the present invention.
Further, the polymer cement anticorrosive paint consists of a powder component and a liquid component according to the mass ratio of 1:1; the powder comprises the following components in parts by weight: 30-35 parts of cement; 2-3 parts of dispersing agent; the liquid material comprises the following components in parts by weight: 29-33 parts of modified polymer emulsion; 0.5-1 part of defoaming agent; 0.5-1 part of film forming auxiliary agent; 2-3 parts of water.
Preferably, the cement is Portland cement having a strength grade of 42.5 or 52.5.
Preferably, the dispersant is selected from polyethylene glycol or hydroxypropyl methacrylate.
Preferably, the defoaming agent is selected from at least one of vegetable oil type defoaming agents, polyethylene glycol type defoaming agents and silicone type defoaming agents.
Preferably, the film forming aid is selected from the group consisting of a TEXANOL ester alcohol or alcohol ester dodecafilm forming aid.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention provides a preparation method of a polymer cement anti-corrosion coating based on functionalized MXene, which utilizes A-171 to prepare a coating for Ti 3 C 2 -MXene powder for lyophobic purposesThe water modification can accelerate the hydrolysis speed and promote the coupling and connection between the MXene and the polymer emulsion, thereby improving the combination between the MXene and the polymer emulsion and improving the dispersibility of the MXene; the intermittent emulsion polymerization is adopted, and the functionalized MXene is added in the process of synthesizing the emulsion, so that the MXene is ensured to be uniformly dispersed in the coating, the effect can be effectively exerted, and the comprehensive improvement of the mechanical strength, the waterproof performance and the corrosion resistance of the coating is realized.
(2) The polymer cement waterproof paint based on the functional MXene prepared by the invention has stronger mechanical property. The addition of the functionalized MXene powder can form a good physical barrier in the polymer cement organic-inorganic composite coating, and when the coating is acted by external force, the stress can be transferred to the MXene through the polymer film, so that the stress damage of the coating is relieved, and the service life of the coating is prolonged.
(3) In the polymer cement anti-corrosion coating based on the functionalized MXene, the lamellar structure of the functionalized MXene forms a good labyrinth effect in the coating, and plays a key role in enhancing the corrosion resistance of the coating. Furthermore, the functionalized MXene is used as a layered nano material, after the MXene is added into the coating, the viscosity of the coating is increased to prevent oxygen from diffusing into the coating, and on the other hand, the uniform distribution of the MXene in the coating can prevent the transmission of internal oxygen, so that the ageing resistance of the coating is enhanced.
(4) In the invention, functional monomer methyl acrylic acid stearate is added in the process of synthesizing polymer emulsion, and the methyl acrylic acid-methyl acrylic acid stearate copolymer is produced by the polymerization reaction of free radicals between the functional monomer methyl acrylic acid stearate and methyl methacrylate, so that the invention plays a role in improving the hydrophobicity and durability of the coating.
Drawings
FIG. 1 is a schematic flow chart of a method for preparing a polymer cement anticorrosive paint based on functionalized MXene;
FIG. 2 is a photograph showing a comparison of modified polymer emulsion obtained by emulsion polymerization and modified emulsion obtained by ultrasonic dispersion in example 1 of the present invention; wherein, (a) is the modified polymer emulsion prepared by the invention; (b) The modified polymer emulsion is obtained by adopting ultrasonic dispersion;
FIG. 3 is a comparison of a coating of a polymer cement prepared according to example 1 of the present invention using A-171 as the hydrophobic modifier of MXene with a coating of a polymer cement prepared using KH-570 as the hydrophobic modifier of MXene; wherein, (a) is A-171 modification; (b) is KH-570 modified;
FIG. 4 is a schematic illustration of the chemical reaction of methyl methacrylate with stearic acid methacrylate to form a copolymer in an embodiment of the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
The invention will be further illustrated, but is not limited, by the following examples.
The main steps and parameters related to the examples 1 to 7 of the present invention are shown in the following table 1, and the main raw materials and parts by weight thereof related to the preparation of the polymer cement paint of the examples 1 to 7 are shown in the following table 2.
TABLE 1
TABLE 2
Example 1
A preparation method of a polymer cement anticorrosive paint based on functionalized MXene comprises the following steps:
step 1: preparation of Ti 3 C 2 T x MXene powder: a glass pipette was used to take 160ml of 9M HCI in a 250ml covered polytetrafluoroethylene beaker (equipped with a magnetic stirrer), 8.0g of LiF powder was added, and the mixture was magnetically stirred at room temperature for 15min to make it fully dissolved in HCl. Then 8.0g of Ti was slowly added to the solution mixture phase 3 AlC 2 The powder is etched for 48h at 350rpm in a water bath environment at 40-45 ℃. And (3) washing and centrifuging by using 1M HCl and deionized water in sequence after etching is finished until the PH of supernatant fluid after centrifuging is more than or equal to 6.5. The lower precipitate was collected and dispersed with water and placed in an ultrasonic machine at 35 ℃ for 45min to exfoliate. Centrifuging at 5000rpm for 60min with high speed centrifuge, collecting lower layer black sediment, and vacuum filtering (0.22 um water-based filter membrane) to collect Ti dispersed in suspension 3 C 2 T x -MXene powder. Drying the collected black sediment in a vacuum freeze dryer for 24 hours, taking out and grinding to obtain powder which is Ti 3 C 2 T x -MXene。
Step 2: preparation of functionalized MXene powder: 1.6g of Ti 3 C 2 T x the-MXene powder was dispersed in a mixed solution consisting of 80ml DI and 720ml absolute ethanol, stirred at low speed at room temperature to ensure uniform dispersion, and the mixed phase was placed in an ultrasonic cleaner for ultrasonic dispersion at 45 ℃ for 60min. 50ml of 1M HCl was added to adjust the pH of the solution to around 3.5 to prevent subsequent homopolymerization of the modifier. Then 16g A-171 is added into the mixed phase solution, and the mixture is placed in a water bath kettle and magnetically stirred for 5 hours under the constant temperature water bath of 75 ℃. After the reaction, the solution was washed with ethanol and deionized water in this order, and then centrifuged at 4500rpm for 10min in a high-speed centrifuge, and the operation was circulated until the supernatant of the mixed phase after centrifugation was neutral. Collecting black sediment of the layer, drying the sediment for 24 hours at the temperature of 70 ℃ in a constant temperature drying box, grinding the dried black solid to obtain the hydrophobically modified Ti 3 C 2 Tx-MXene powder.
Step 3: preparing a modified polymer emulsion: taking 5g OP-10, 3g SDS, 1g NaHCO 3 、0.75gC 3 H 5 NO, 120g deionized water, 0.2% (based on monomer mass fraction) functionDissolving MXene powder and 2.5 percent (mass fraction of monomer) of methyl acrylic acid stearate in a beaker 1 (matched with a magnetic stirrer), and uniformly stirring and dispersing for later use; 1.5g (NH) 4 ) 2 S 2 O 8 50g of deionized water is uniformly stirred in a beaker 2 for standby; weighing 8g of MAA, 126g of BA and 66g of MMA in a three-neck flask, adding the mixed solution in the beaker 1, heating the mixed solution to 45 ℃ in a water bath for pre-emulsification for 20min, adding the mixed solution in the beaker 2, then adjusting the temperature of the water bath kettle to 80 ℃ for continuous reaction for 4h, and heating to 85 ℃ for development for 45min after the reaction is completed. The emulsion in the three-necked flask was poured out using NH 3 .H 2 And O is used for regulating the pH value to 7-8, and after the mixture is cooled, 100-mesh filter cloth is used for filtering, so that the functionalized MXene modified acrylic emulsion is obtained.
Step 4: preparing a polymer cement coating: according to the parts by weight, 33 parts of cement and 2 parts of dispersing agent are stirred in a stirrer for 30min to obtain a powder component; to 30 parts of the prepared modified acrylic emulsion were added 3 parts of deionized water, 1 part of a film-forming auxiliary agent, and 1 part of a defoaming agent in this order, and stirred again at 2000rmp for 3 minutes to obtain a uniform liquid component. And finally, adding the uniformly mixed powder into the liquid material, slowly stirring (150 rmp/min) for 1 min, and rapidly stirring (300 rmp/min) for 4 min to obtain the uniform functionalized MXene modified polymer cement anticorrosive paint.
FIG. 2 is a photograph showing the comparison of modified polymer emulsion obtained by emulsion polymerization with modified emulsion obtained by ultrasonic dispersion in this example.
FIG. 2 (a) shows the modified polymer emulsion obtained by adding functionalized MXene when the emulsion is synthesized by the batch method in step 3 of this example, and it can be seen that the functionalized MXene is uniformly dispersed in the emulsion; in contrast, fig. 2 (b) is a graph showing the effect of adding functionalized MXene into an emulsion and dispersing by using ultrasound, and it is known that ultrasonic dispersion cannot effectively disperse functionalized MXene in the emulsion, and the effect of improving mechanical properties and preventing corrosion by hydrophobic property is difficult to achieve in the coating obtained by the preparation method.
FIG. 3 is a photograph showing a comparison of a coating of a polymer cement prepared using A-171 as the hydrophobic modifier of MXene and a coating of a polymer cement prepared using KH-570 as the hydrophobic modifier of MXene in this embodiment. As can be seen from FIG. 3, the dispersibility of the MXene modified by A-171 in the acrylic emulsion coating is obviously better than KH-570, which is of great significance in improving the hydrophobic property of polymer cement.
Examples 2 and 3
Based on example 1, the main parameters of each step were adjusted according to tables 1 and 2, and the other steps were unchanged, to prepare functionalized MXene modified polymer cement anticorrosive coatings, respectively.
Example 4
Based on the embodiment 1, 0.1 percent (accounting for the mass fraction of the monomer) of functional MXene is added in the process of synthesizing the acrylic emulsion in the step 3, and other steps and parameters are unchanged, so that the functional MXene modified polymer cement anticorrosive paint is obtained.
Example 5
Based on the embodiment 1, 0.3 percent (accounting for the mass fraction of the monomer) of functionalized MXene is added in the process of synthesizing the acrylic emulsion in the step 3, and other steps and parameters are unchanged, so that the functionalized MXene modified polymer cement anticorrosive paint is obtained.
Example 6
Based on the example 1, 1 percent (monomer mass fraction) of methyl acrylic acid stearate is added during the synthesis of the acrylic emulsion in the step 3, and other steps and parameters are unchanged, so that the functionalized MXene modified polymer cement anticorrosive paint is obtained.
Example 7
Based on the example 1, 5 percent (monomer mass fraction) of methyl acrylic acid stearate is added in the process of synthesizing the acrylic emulsion in the step 3, and other steps and parameters are unchanged, so that the functionalized MXene modified polymer cement anticorrosive paint is obtained.
Comparative example 1
The conventional polymer cement paint is directly prepared.
Step 1: preparing a modified polymer emulsion: taking 5g OP-10, 3g SDS, 1g NaHCO 3 、0.75gC 3 H 5 NO, 120g of deionized water are placed in a beaker 1 (provided with a magnetic stirrer), and are stirred and dispersed uniformly for standby; 1.5g (NH) 4 ) 2 S 2 O 8 50g deionized water was stirred in beaker 2Homogenizing for later use; 8g of MAA, 126g of BA and 66g of MMA are weighed into a three-neck flask, mixed solution in a beaker 1 is added, water bath is heated to 45 ℃ for pre-emulsification for 20min, mixed solution in a beaker 2 is added, the temperature of a water bath kettle is regulated to 80 ℃ for continuous reaction for 4h, and after the reaction is completed, the temperature is raised to 85 ℃ for development for 45min. The emulsion in the three-necked flask was poured out using NH 3 .H 2 And regulating the pH value to 7-8 by O, and filtering by using a filter cloth with 100 meshes after cooling to obtain the acrylic emulsion.
Step 2: preparing a polymer cement coating: according to the parts by weight, 33 parts of cement and 2 parts of dispersing agent are stirred in a stirrer for 30min to obtain a powder component; to 30 parts of the prepared acrylic emulsion were added 3 parts of deionized water, 1 part of a film-forming auxiliary agent, 1 part of a defoaming agent in this order, and stirred again at 2000rmp for 3 minutes to obtain a uniform liquid component. And finally, adding the uniformly mixed powder into the liquid material, slowly stirring (150 rmp/min) for 1 min, and rapidly stirring (300 rmp/min) for 4 min to obtain the polymer cement anticorrosive paint.
Comparative example 2
The functionalized MXene is mixed in an ultrasonically dispersed manner in a polymer emulsion.
Based on the embodiment 1, when the emulsion is synthesized in the step 3, other raw materials are directly subjected to emulsion polymerization without adding functional MXene to obtain polymer emulsion; and then adding 0.2% of functionalized MXene accounting for the mass fraction of the acrylic acid monomer into the polymer emulsion in an ultrasonic mixing mode (the ultrasonic power is 40Hz and the dispersion time is 60 min) to obtain modified polymer emulsion, and then preparing the polymer cement anticorrosive paint according to the step 4.
Comparative example 3
Preparing the KH-570 modified functionalized MXene polymer cement paint.
Based on the embodiment 1, the A-171 modifier in the step 2 is changed into KH-570, and other steps and parameters are unchanged, so that the functional MXene modified polymer cement anticorrosive paint is obtained.
Comparative example 4
Polymer cement coatings of unmodified MXene were prepared.
Based on example 1, the hydrophobic property of step 2 was omittedA modification step, namely directly carrying out the modification on the Ti prepared in the step 1 3 C 2 T x The modified polymer emulsion is prepared by replacing the functionalized MXene in the step 3 with the MXene powder, and the rest steps are unchanged, so that the polymer cement anticorrosive paint is prepared.
Comparative example 5
A polymer cement paint was prepared that was functionalized MXene without the addition of methacrylate stearate.
On the basis of the embodiment 1, the operation of adding the methyl acrylic acid stearate in the step 3 is omitted, and other steps and parameters are unchanged, so that the functionalized MXene modified polymer cement anticorrosive paint is obtained.
Performance testing
Mechanical property test
Examples 1 to 7 and comparative examples 1 to 5 were subjected to sample preparation test for properties such as tensile strength, elongation and adhesive strength according to GBT 23445-2009, and the results of each property test are shown in tables 3 to 1 and 3 to 2. Wherein the acid treatment method is that H with concentration of 2% 2 SO 4 Soaking in the solution for 7d; the alkali treatment method comprises soaking in 0.1% NaOH solution for 7d; the aging treatment method is that the glass is exposed for 7d in an ultraviolet aging box.
Table 3-1:
TABLE 3-2
As can be seen from tables 3-1 and 3-2,
compared with the polymer cement anticorrosive paint prepared in comparative examples 1-5, the polymer cement anticorrosive paint based on the functionalized MXene prepared in examples 1-7 has higher tensile strength, elongation at break and bonding strength, and the mechanical property and weather resistance of the polymer cement anticorrosive paint are improved compared with those of comparative examples 1-5.
Comparing the performance test results of example 1 with those of examples 4 and 5, it is known that the optimum amount of the functionalized MXene is 0.2% of the mass fraction of the monomer, and when the amount is more than 0.2%, excessive MXene particles are agglomerated in the paint, resulting in a decrease in performance.
Comparing the performance test results of example 1 with those of examples 6 and 7, it is found that the optimum blending amount of the stearic acid methacrylate is 2.5%, and when the blending amount is less than 1%, the MMA-STEA copolymer produced is too small to function; when the blending amount is more than 5%, excessive MMA is consumed by the chemical reaction, and the synthetic emulsion process is affected, resulting in a decrease in coating properties.
(II) hydrophobic Property test
The polymer cement paints prepared in examples 1 to 7 and comparative examples 1 to 5 were respectively brushed on a calcium silicate plate according to the standard of GB/T30693-2014 measurement of contact angle of plastic film with water, and subjected to hydrophobicity test, and the results after the test are shown in Table 4:
table 4:
| sample of | Static contact angle measurement (°) | Rolling angle measurement value (°) |
| Example 1 | 142 | 7 |
| Example 2 | 140 | 8 |
| Example 3 | 141 | 8 |
| Example 4 | 123 | 12 |
| Example 5 | 133 | 9 |
| Example 6 | 124 | 11 |
| Example 7 | 121 | 14 |
| Comparative example 1 | 99 | 26 |
| Comparative example 2 | 102 | 24 |
| Comparative example 3 | 116 | 16 |
| Comparative example 4 | 107 | 20 |
| Comparative example 5 | 113 | 18 |
As can be seen from the analysis of Table 4, the contact angles and rolling angles of comparative examples 1-7 and comparative examples 1-5 are measured, the static contact angle of the polymer cement anticorrosive paint added with the functionalized MXene can be more than 120 degrees, the rolling angle is less than 15 degrees, and the polymer cement anticorrosive paint prepared by comparative examples 1-5 has better hydrophobic performance.
The foregoing is merely illustrative of the preferred embodiments of the present invention and is not intended to limit the embodiments and scope of the present invention, and it should be appreciated by those skilled in the art that equivalent substitutions and obvious variations may be made using the teachings of the present invention, which are intended to be included within the scope of the present invention.
Claims (10)
1. A preparation method of a polymer cement anticorrosive paint based on functionalized MXene comprises the following steps:
s1, ti is mixed with 3 C 2 Dispersing the MXene powder in a solvent, and regulating the pH value to 3-4 to obtain a mixed solution; according to vinyltrimethoxysilane A-171 and Ti 3 C 2 The mass ratio of the MXene powder is (8-12) 1, A-171 is added into the mixed solution, and the mixture is heated and reacted for a certain time to obtain the functionalized MXene powder;
s2, adding the functionalized MXene powder, an emulsifying agent, a buffering agent, a cross-linking agent and methyl acrylic acid stearate into deionized water, and mixing to obtain a dispersion liquid; adding the dispersion liquid into a monomer, performing pre-emulsification operation, adding an initiator, performing polymerization reaction for a certain time, stopping the reaction, then performing heating development, adjusting the pH of the product to 7-8, and filtering to obtain modified polymer emulsion; the addition amount of the functionalized MXene powder is 0.1-0.3 wt.% of the mass of the monomer, and the addition amount of the methyl acrylic stearate is 1-5 wt.% of the monomer;
s3, mixing cement and a dispersing agent to obtain a powder component, and mixing the modified polymer emulsion, a film forming auxiliary agent, a defoaming agent and water to obtain a liquid component; and adding the powder component into the liquid component, and stirring until the powder component and the liquid component are uniformly mixed to obtain the polymer cement anticorrosive paint based on the functionalized MXene.
2. The method according to claim 1, wherein in the step S1, ti is 3 C 2 The preparation method of the-MXene powder comprises the following steps: dissolving LiF powder in hydrochloric acid, and adding Ti 3 AlC 2 Etching the powder for 48-60 h at 40-45 ℃ and the rotating speed of 350-400 rpm, washing, ultrasonic processing, centrifugal collection, freeze drying and grinding the product in sequence to obtain Ti 3 C 2 -MXene powder.
3. The method according to claim 2, wherein in the step S1, the solvent is selected from the group consisting of deionized water and absolute ethanol, ti 3 C 2 The dosage ratio of the MXene powder to the mixed solution is (1-3): 800g/ml; the temperature of the heating reaction is 70-80 ℃, and the time of the heating reaction is 4-6 h.
4. The method according to claim 1, wherein in the step S2, the monomers are composed of methacrylic acid, butyl acrylate and methyl methacrylate according to (6 to 10): (100-130): (60-70) by mass ratio.
5. The method according to claim 4, wherein in the step S2, the polymerization reaction is carried out at a temperature of 75 to 80℃for 3 to 4 hours; the temperature of the heating development is 85-90 ℃, and the time of the heating development is 30-50 min.
6. The method according to claim 1, wherein in the step S3, the powder component is added to the liquid component by stirring at a slow speed and then stirring at a fast speed; the rotating speed of the slow stirring is 100-200 rpm, and the time is 1-3 min; the rotating speed of the rapid stirring is 300-500 rpm, and the time is 3-5 min.
7. A functionalized MXene-based polymer cement anti-corrosive coating, characterized in that it is prepared according to the preparation method of any one of claims 1 to 6.
8. The polymer cement anticorrosive paint according to claim 7, wherein the polymer cement anticorrosive paint is composed of a powder component and a liquid component in a mass ratio of 1:1;
the powder comprises the following components in parts by weight: 30-35 parts of cement and 2-3 parts of dispersing agent;
the liquid material comprises the following components in parts by weight: 29 to 33 parts of modified polymer emulsion, 0.5 to 1 part of defoamer, 0.5 to 1 part of film forming auxiliary agent and 2 to 3 parts of deionized water.
9. The polymer cement anticorrosive paint according to claim 8, wherein,
the cement is ordinary Portland cement, and the strength grade of the cement is 42.5 or 52.5;
the dispersing agent is selected from polyethylene glycol or hydroxypropyl methacrylate.
10. The polymer cement anticorrosive paint according to claim 9, wherein,
the defoaming agent is at least one selected from vegetable oil defoaming agents, polyethylene glycol defoaming agents and organic silicon defoaming agents;
the film forming aid is selected from the group consisting of a TEXANOL ester alcohol or alcohol ester dodecafilm forming aid.
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| KR20220066584A (en) * | 2020-11-16 | 2022-05-24 | 광주과학기술원 | Nanofiber composite material, manufacturing method thereof, and ion exchange membrane including the same |
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