CN113583535A - Modified acrylic acid anticorrosive emulsion and preparation method thereof - Google Patents
Modified acrylic acid anticorrosive emulsion and preparation method thereof Download PDFInfo
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- CN113583535A CN113583535A CN202110897984.8A CN202110897984A CN113583535A CN 113583535 A CN113583535 A CN 113583535A CN 202110897984 A CN202110897984 A CN 202110897984A CN 113583535 A CN113583535 A CN 113583535A
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- 239000000839 emulsion Substances 0.000 title claims abstract description 53
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000004945 emulsification Methods 0.000 title claims description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 22
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 20
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 19
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 17
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 17
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 17
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000005642 Oleic acid Substances 0.000 claims abstract description 17
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 17
- -1 pH regulator Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003822 epoxy resin Substances 0.000 claims abstract description 15
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 13
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003999 initiator Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 235000013311 vegetables Nutrition 0.000 claims abstract description 9
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 8
- 239000000654 additive Substances 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 5
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims abstract description 5
- 230000000996 additive effect Effects 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 28
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 7
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical group CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 claims description 6
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 6
- 239000002518 antifoaming agent Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 230000003449 preventive effect Effects 0.000 claims description 6
- 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 5
- 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 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000004806 packaging method and process Methods 0.000 claims description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 4
- 230000001502 supplementing effect Effects 0.000 claims description 4
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 claims description 3
- 235000020778 linoleic acid Nutrition 0.000 claims description 3
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 claims description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000002421 anti-septic effect Effects 0.000 claims 2
- 239000003755 preservative agent Substances 0.000 claims 1
- 230000002335 preservative effect Effects 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 29
- 239000011248 coating agent Substances 0.000 abstract description 26
- 239000004593 Epoxy Substances 0.000 abstract description 10
- 229910019142 PO4 Inorganic materials 0.000 abstract description 8
- 239000010452 phosphate Substances 0.000 abstract description 8
- 238000005260 corrosion Methods 0.000 abstract description 6
- 230000007797 corrosion Effects 0.000 abstract description 6
- 239000000178 monomer Substances 0.000 abstract description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 6
- 238000004132 cross linking Methods 0.000 abstract description 4
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 238000005886 esterification reaction Methods 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- WTXXSZUATXIAJO-OWBHPGMISA-N (Z)-14-methylpentadec-2-enoic acid Chemical compound CC(CCCCCCCCCC\C=C/C(=O)O)C WTXXSZUATXIAJO-OWBHPGMISA-N 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000758 substrate Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000012855 volatile organic compound Substances 0.000 description 3
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000013530 defoamer Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 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 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 239000001809 ammonium phosphatide Substances 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- DMSMPAJRVJJAGA-UHFFFAOYSA-N benzo[d]isothiazol-3-one Chemical compound C1=CC=C2C(=O)NSC2=C1 DMSMPAJRVJJAGA-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000002087 whitening effect Effects 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention relates to a modified acrylic acid anticorrosive emulsion and a preparation method thereof, wherein the emulsion comprises the following raw materials: styrene, acrylic compounds, C12-containing carbon olefine acid, inorganic acid, epoxy resin, ether organic solvent, reactive emulsifier, sodium bicarbonate, initiator, pH regulator, additive and the balance of water; the vegetable oleic acid group and epoxy phosphate group modified acrylic acid anticorrosive emulsion is prepared by emulsion polymerization, the addition of oleic acid and epoxy phosphate further generate esterification reaction, the oleic acid can better participate in the polymerization of acrylic monomers after the double bond of the oleic acid is introduced, the oxidation crosslinking degree of the coating is improved after the coating is dried, the hardness, the adhesive force and the compactness of the coating are further improved to a certain extent, and the corrosion resistance is further improved.
Description
Technical Field
The invention relates to the technical field of coatings, and particularly relates to a modified acrylic acid anticorrosive emulsion and a preparation method thereof.
Background
In order to solve the increasingly serious problem of air pollution and deal with the exhaustion of petroleum resources in recent years, green development and sustainable development ideas are put forward in the coating industry, and the traditional solvent-based coating is changed from oil to water. How to more thoroughly control the discharge of the VOCs in the coating becomes the research focus of many colleges and universities, professional institutions and coating practitioners.
The acrylic emulsion is obtained by copolymerizing vinyl alkoxy silane monomer serving as a modifier with monomers such as acrylic esters and alkenyl aromatic compounds in an emulsion polymerization mode. The product has good stability, can be placed for more than one year, can improve the hardness, tensile strength, water resistance and the like of a coating film, and is widely used for exterior wall coatings, waterproof coatings and the like. Because the acrylic emulsion has ultralow VOCs content, a plurality of paint workers use the acrylic emulsion to prepare the industrial anticorrosive paint with low VOCs content, but because of the drying mode of micelle accumulation film forming of the acrylic emulsion, the prepared paint has poor adhesion to a substrate, gaps exist among coating molecules, the atmosphere and moisture have higher passing rate, and the protection performance to the substrate is poor. It is difficult to achieve the ideal substrate protection.
Disclosure of Invention
In order to solve the technical problem that the protective property of the acrylic emulsion to the substrate is poor, the modified acrylic acid anticorrosive emulsion and the preparation method thereof are provided. The modified acrylic acid anticorrosive emulsion can greatly improve the corrosion resistance of the coating and prolong the protection time of the coating on the base material.
In order to achieve the purpose, the invention is realized by the following technical scheme:
the modified acrylic acid anticorrosive emulsion comprises the following raw materials in parts by weight:
10-20% of styrene, 12-36% of acrylic compound, 2-3% of C12-containing carbon olefine acid, 0.5-1% of inorganic acid, 1.5-2.5% of epoxy resin, 0.7-0.9% of ether organic solvent, 1-2% of reactive emulsifier, 0.08-0.15% of sodium bicarbonate, 0.1-0.35% of initiator, 0.1-0.15% of pH regulator, 0.1-0.3% of additive and the balance of water.
Further, the acrylic compound is a mixture of acrylic acid or methacrylic acid and an acrylate compound; the acrylate compound is one or more of methyl methacrylate, butyl acrylate and butyl methacrylate.
Further, the ether organic solvent is dipropylene glycol dimethyl ether; the epoxy resin is epoxy resin E44; the inorganic acid is phosphoric acid with the mass concentration of 85%; the pH regulator is an organic amine, such as AMP-95, N, N dimethylethanolamine.
Further, the reactive emulsifier is one of ER-10, ER-20, ER-30, ER-40, SR-10, SR-20 and SR-1025; the C12-containing olefine acid is dry vegetable oleic acid.
Preferably, the dry vegetable oil acid is eleostearic acid and/or linoleic acid.
Further, the initiator is prepared by matching ammonium persulfate and tert-butyl hydroperoxide according to the mass ratio of (1-3) to (0.3-0.5); the additive comprises a defoaming agent and a mildew preventive. For example, the defoaming agent may be a silicone defoaming agent such as TECH-321W, and the antifungal agent may be ACTICIDE BW20 from Toll, UK.
The invention also provides a preparation method of the modified acrylic acid anticorrosive emulsion, which comprises the following steps:
(1) preparing the raw materials according to a formula, heating the epoxy resin to be below 100 ℃, and adding inorganic acid to react for 3-5 hours under a stirring state; then adding C12-containing carbon olefine acid, continuously heating to above 200 ℃ for reaction, cooling after reaching the acid value, adding an ether organic solvent for dilution to obtain a prepolymer;
(2) heating part of water in the formula, part of reactive emulsifier and part of sodium bicarbonate to 70-80 ℃, and preserving heat to obtain a system to be reacted;
(3) stirring and mixing the residual amount of the water and the residual amount of the reactive emulsifier in the formula, and adding styrene, an acrylic compound, the prepolymer in the step (1) and a part of initiator to perform pre-emulsification reaction to obtain a pre-emulsion;
(4) dropwise adding the pre-emulsion obtained in the step (3) into the system to be reacted obtained in the step (2) at a constant speed for emulsion polymerization reaction, cooling to 60-65 ℃ after the emulsion polymerization reaction is finished, supplementing the rest of the initiator, then carrying out heat preservation reaction, adding a pH regulator to regulate the pH to 6.5-8 after the heat preservation reaction is finished, then adding the additives in the rest formula, stirring uniformly, filtering and packaging to obtain the modified acrylic acid anticorrosive emulsion.
Further, the temperature for the first heating in the step (1) is 60-90 ℃; the temperature of the second temperature rise is 200-220 ℃, and the reaction time is 4-5 h; the temperature for reducing the temperature is 160 ℃; the time of the pre-emulsification reaction in the step (3) is at least 20 min.
Further, the dropping time of the pre-emulsion in the step (4) is controlled to be 3-4h, and after the pre-emulsion is dropped, the emulsion polymerization reaction is maintained for 1 h; the time of the heat preservation reaction is 0.5-1 h.
The beneficial technical effects are as follows:
the modified acrylic acid anticorrosive emulsion is prepared by the steps of reacting epoxy resin with inorganic acid phosphoric acid to obtain epoxy phosphate, introducing epoxy phosphate ester into dry vegetable oleic acid to obtain a prepolymer, and carrying out emulsion polymerization reaction on the prepolymer and raw materials such as styrene, an acrylic acid compound functional monomer, an emulsifier and the like under the action of an initiator. The invention adopts dry vegetable oleic acid to increase the oxidative crosslinking property of the coating after film forming, epoxy phosphate to increase the adhesive force of the coating to a base material, and adopts a simpler synthesis process to prepare the modified acrylic acid anticorrosive emulsion containing vegetable oleic acid groups and epoxy phosphate. The modified acrylic acid anticorrosive emulsion has excellent adhesive force and strong coating sealing property, can greatly increase the corrosion resistance of the coating, and prolongs the protection time of the coating on a base material.
The introduction of epoxy phosphate ester in the invention greatly increases the adhesion of the coating to the substrate, especially the metal substrate; the dry vegetable oleic acid can be subjected to esterification reaction with epoxy phosphate, double bonds of the oleic acid are introduced, so that the oleic acid can better participate in copolymerization of acrylic monomers, the oxidation crosslinking degree is improved after the coating is dried, the compactness of the coating and the adhesion to a base material are further improved to a certain extent, and the excellent adhesion of the coating increases the protection performance to the base material, so that the corrosion resistance is improved.
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. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. 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.
Unless specifically stated otherwise, the numerical values set forth in these examples do not limit the scope of the invention. Techniques, methods known to those of ordinary skill in the relevant art may not be discussed in detail, but are intended to be part of the specification where appropriate. In all examples shown and discussed herein, any particular value should be construed as merely illustrative, and not limiting. Thus, other examples of the exemplary embodiments may have different values.
The experimental methods of the following examples, which are not specified under specific conditions, are generally determined according to national standards; if no corresponding national standard exists, the method is carried out according to the universal international standard or the standard requirement proposed by related enterprises. Unless otherwise indicated, all parts are parts by weight and all percentages are percentages by weight.
Reactive emulsifiers are produced from the ER/SR series of reactive emulsifiers from the company ADEKA REASOAP.
Example 1
The modified acrylic acid anticorrosive emulsion comprises the following raw materials in parts by weight:
10% of styrene, 15% of methyl methacrylate, 20% of butyl acrylate, 0.5% of acrylic acid, 2% of linoleic acid, 1% of phosphoric acid with the concentration of 85 wt%, epoxy resin E442%, 0.8% of dipropylene glycol dimethyl ether, SR-101.5% of reactive emulsifier, 0.8% of sodium bicarbonate, 0.2% of ammonium persulfate, 0.04% of tert-butyl hydroperoxide, 0.12% of pH regulator AMP-950.13%, 0.12% of defoamer TECH-321W, 0.32% of mildew preventive BW 200.12% and the balance of water.
The preparation method of the modified acrylic acid anticorrosive emulsion comprises the following steps:
(1) preparing the raw materials according to a formula, putting epoxy resin E44 into a reaction kettle, heating to 80 ℃, adding phosphoric acid with the concentration of 85 wt% to react for 4 hours under the stirring state; then adding linoleic acid, continuously heating to 200 ℃ for reaction for 5h to reach an acid value (less than 5mgKOH/g), cooling to 160 ℃, adding dipropylene glycol dimethyl ether for olefin conversion to obtain a prepolymer;
(2) putting 60% of water, 40% of reactive emulsifier and sodium bicarbonate in the formula into a reaction kettle, heating to 80 ℃, and preserving heat to obtain a system to be reacted;
(3) adding the residual amount of water and the residual amount of reactive emulsifier in the formula into a dripping tank of a reaction kettle, stirring and mixing, adding styrene, methyl methacrylate, butyl acrylate, acrylic acid, the prepolymer in the step (1) and ammonium persulfate, stirring for 30min, and carrying out pre-emulsification reaction to obtain a pre-emulsion;
(4) dropwise adding the pre-emulsified substance obtained in the step (3) into the system to be reacted in the step (2) at a constant speed within 3-4h for emulsion polymerization reaction, keeping the reaction for 1h after dropwise adding, then cooling to 65 ℃, supplementing tert-butyl hydroperoxide, then adding a pH regulator to adjust the pH to 7 after keeping the temperature for reaction for 45min, then adding a defoaming agent and a mildew preventive, stirring uniformly, filtering and packaging to obtain the modified acrylic acid anticorrosive emulsion.
Example 2
The modified acrylic acid anticorrosive emulsion comprises the following raw materials in parts by weight:
20% of styrene, 10% of methyl methacrylate, 15% of butyl methacrylate, 0.3% of methacrylic acid, 3% of eleostearic acid, 0.6% of 85 wt% phosphoric acid, 442.5% of epoxy resin, 0.9% of dipropylene glycol dimethyl ether, SR-101.8% of reactive emulsifier, 0.1% of sodium bicarbonate, 0.3% of ammonium persulfate, 0.05% of tert-butyl hydroperoxide, AMP-950.12% of pH regulator, 0.1% of defoamer TECH-321W, 200.1% of mildew preventive BW, and the balance of water.
The preparation method of the modified acrylic acid anticorrosive emulsion comprises the following steps:
(1) preparing the raw materials according to a formula, putting epoxy resin E44 into a reaction kettle, heating to 90 ℃, adding phosphoric acid with the concentration of 85 wt% to react for 3 hours under the stirring state; then eleostearic acid is added, the temperature is continuously raised to 220 ℃ for reaction for 3h, the temperature is reduced to 160 ℃ after the acid value is reached (less than 5mgKOH/g), and dipropylene glycol dimethyl ether is added for olefin conversion to obtain a prepolymer;
(2) putting 70% of water in the formula, 30% of reactive emulsifier and sodium bicarbonate into a reaction kettle, heating to 70 ℃, and preserving heat to obtain a system to be reacted;
(3) adding the residual amount of water and the residual amount of reactive emulsifier in the formula into a dripping tank of a reaction kettle, stirring and mixing, adding styrene, methyl methacrylate, butyl acrylate, acrylic acid, the prepolymer in the step (1) and ammonium persulfate, stirring for 30min, and carrying out pre-emulsification reaction to obtain a pre-emulsion;
(4) dropwise adding the pre-emulsified substance obtained in the step (3) into the system to be reacted in the step (2) at a constant speed within 3-4h for emulsion polymerization reaction, keeping the reaction for 1h after dropwise adding, then cooling to 60 ℃, supplementing tert-butyl hydroperoxide, then adding a pH regulator to adjust the pH to 7 after heat preservation reaction for 50min, then adding a defoaming agent and a mildew preventive, stirring uniformly, filtering and packaging to obtain the modified acrylic acid anticorrosive emulsion.
Comparative example 1
This comparative example is identical to the emulsion composition and preparation of example 1, except that linoleic acid was not added.
The particle size of the emulsions of the above examples and comparative examples was measured using a laser particle sizer, and the data is shown in table 1.
TABLE 1 parameters of emulsions prepared in the examples and comparative examples
| Emulsion solid content (%) | Emulsion particle size (nm) | Emulsion stable storage time (Tian) | |
| Example 1 | 49.5 | 55～65 | 180 |
| Example 2 | 49.3 | 45～60 | 180 |
| Comparative example 1 | 50.1 | 55～70 | 180 |
As can be seen from Table 1, the presence or absence of oleic acid had little effect on the particle size and stability of the emulsion.
The emulsions prepared in the above examples and comparative examples were coated on the surface of a polished carbon steel plate to prepare a coating, which was naturally dried, and the obtained coating was tested for adhesion, corrosion resistance and basic mechanical properties. The results are shown in Table 2.
TABLE 2 coating Properties
Note: the condition of the water resistance test is that no whitening and no foaming are considered to pass at the temperature of 40 ℃ for 240 h; the test solution for acid resistance was a 5 wt% hydrochloric acid solution; the test solution for alkali resistance was a 5 wt% sodium hydroxide solution. The adhesion, pencil hardness and impact strength were all measured after natural drying for 2 days.
As can be seen from table 2, in the present invention, dry vegetable oleic acid (eleostearic acid, linolenic acid), epoxy resin E44, 85% phosphoric acid, methyl methacrylate, styrene, butyl (meth) acrylate, hydroxy (meth) acrylate, and (meth) acrylic acid are selected, ammonium persulfate is used as an initiator, a reactive emulsifier is used to perform emulsion polymerization to prepare an acrylic acid anticorrosion emulsion modified by oleic acid groups and epoxy phosphate groups, oleic acid is added to further perform esterification with epoxy phosphate, and double bonds of oleic acid are introduced to enable the oleic acid to better participate in polymerization of acrylic monomers, so that after the coating is dried, the oxidative crosslinking degree of the coating is improved, and the hardness, adhesion and compactness of the coating are further improved to a certain extent, thereby increasing the corrosion resistance. The emulsion obtained in comparative example 1 without the addition of oleic acid had poor adhesion, hardness, etc. properties.
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 (9)
1. The modified acrylic acid anticorrosive emulsion is characterized by comprising the following raw materials in parts by weight:
10-20% of styrene, 12-36% of acrylic compound, 2-3% of C12-containing carbon olefine acid, 0.5-1% of inorganic acid, 1.5-2.5% of epoxy resin, 0.7-0.9% of ether organic solvent, 1-2% of reactive emulsifier, 0.08-0.15% of sodium bicarbonate, 0.1-0.35% of initiator, 0.1-0.15% of pH regulator, 0.1-0.3% of additive and the balance of water.
2. The modified acrylic anticorrosive emulsion according to claim 1, wherein the acrylic compound is a mixture of acrylic acid or methacrylic acid and an acrylate compound; the acrylate compound is one or more of methyl methacrylate, butyl acrylate and butyl methacrylate.
3. The modified acrylic anticorrosive emulsion according to claim 1, wherein the ether-based organic solvent is dipropylene glycol dimethyl ether; the epoxy resin is epoxy resin E44; the inorganic acid is phosphoric acid with the mass concentration of 85%; the pH regulator is an organic amine, such as AMP-95, N, N dimethylethanolamine.
4. The modified acrylic acid antiseptic emulsion of claim 1, wherein the reactive emulsifier is one of ER-10, ER-20, ER-30, ER-40, SR-10, SR-20, SR-1025; the C12-containing olefine acid is dry vegetable oleic acid.
5. The modified acrylic preservative emulsion according to claim 4, wherein the dry vegetable oleic acid is eleostearic acid and/or linoleic acid.
6. The modified acrylic acid antiseptic emulsion of claim 1, wherein the initiator is a mixture of ammonium persulfate and tert-butyl hydroperoxide in a mass ratio of (1-3) to (0.3-0.5); the additive comprises a defoaming agent and a mildew preventive.
7. The method for preparing the modified acrylic anticorrosive emulsion according to any one of claims 1 to 6, characterized by comprising the following steps:
(1) preparing the raw materials according to a formula, heating the epoxy resin to be below 100 ℃, and adding inorganic acid to react for 3-5 hours under a stirring state; then adding C12-containing carbon olefine acid, continuously heating to above 200 ℃ for reaction, cooling after reaching the acid value, adding an ether organic solvent for dilution to obtain a prepolymer;
(2) heating part of water in the formula, part of reactive emulsifier and part of sodium bicarbonate to 70-80 ℃, and preserving heat to obtain a system to be reacted;
(3) stirring and mixing the residual amount of the water and the residual amount of the reactive emulsifier in the formula, and adding styrene, an acrylic compound, the prepolymer in the step (1) and a part of initiator to perform pre-emulsification reaction to obtain a pre-emulsion;
(4) dropwise adding the pre-emulsion obtained in the step (3) into the system to be reacted obtained in the step (2) at a constant speed for emulsion polymerization reaction, cooling to 60-65 ℃ after the emulsion polymerization reaction is finished, supplementing the rest of the initiator, then carrying out heat preservation reaction, adding a pH regulator to regulate the pH to 6.5-8 after the heat preservation reaction is finished, then adding the additives in the rest formula, stirring uniformly, filtering and packaging to obtain the modified acrylic acid anticorrosive emulsion.
8. The method according to claim 7, wherein the temperature of the first temperature rise in the step (1) is 60 to 90 ℃; the temperature of the second temperature rise is 200-220 ℃, and the reaction time is 4-5 h; the temperature for reducing the temperature is 160 ℃; the time of the pre-emulsification reaction in the step (3) is at least 20 min.
9. The preparation method according to claim 7, wherein the dropping time of the pre-emulsion in the step (4) is controlled to be 3-4h, and the emulsion polymerization is maintained for 1h after the dropping of the pre-emulsion; the time of the heat preservation reaction is 0.5-1 h.
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