CN116693776A - Preparation method of water-based organic silicon acrylate composite emulsion and stain-resistant coating - Google Patents
Preparation method of water-based organic silicon acrylate composite emulsion and stain-resistant coating Download PDFInfo
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- CN116693776A CN116693776A CN202310593743.3A CN202310593743A CN116693776A CN 116693776 A CN116693776 A CN 116693776A CN 202310593743 A CN202310593743 A CN 202310593743A CN 116693776 A CN116693776 A CN 116693776A
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- 239000000839 emulsion Substances 0.000 title claims abstract description 114
- 238000000576 coating method Methods 0.000 title claims abstract description 82
- 239000011248 coating agent Substances 0.000 title claims abstract description 72
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 41
- SOGFHWHHBILCSX-UHFFFAOYSA-J prop-2-enoate silicon(4+) Chemical compound [Si+4].[O-]C(=O)C=C.[O-]C(=O)C=C.[O-]C(=O)C=C.[O-]C(=O)C=C SOGFHWHHBILCSX-UHFFFAOYSA-J 0.000 title claims abstract description 5
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 239000002131 composite material Substances 0.000 title abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 65
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 56
- -1 acrylic ester Chemical class 0.000 claims abstract description 25
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 24
- 239000003999 initiator Substances 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 8
- 238000009775 high-speed stirring Methods 0.000 claims abstract description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 55
- 239000012874 anionic emulsifier Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 230000003373 anti-fouling effect Effects 0.000 claims description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000012986 chain transfer agent Substances 0.000 claims description 8
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- ZIWRUEGECALFST-UHFFFAOYSA-M sodium 4-(4-dodecoxysulfonylphenoxy)benzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCOS(=O)(=O)c1ccc(Oc2ccc(cc2)S([O-])(=O)=O)cc1 ZIWRUEGECALFST-UHFFFAOYSA-M 0.000 claims description 7
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- 125000000129 anionic group Chemical group 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000006184 cosolvent Substances 0.000 claims description 5
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 5
- 239000012875 nonionic emulsifier Substances 0.000 claims description 5
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 5
- 239000002562 thickening agent Substances 0.000 claims description 5
- 239000000080 wetting agent Substances 0.000 claims description 5
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 239000013530 defoamer Substances 0.000 claims description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 4
- 239000004744 fabric Substances 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 239000010985 leather Substances 0.000 claims description 4
- 239000006179 pH buffering agent Substances 0.000 claims description 4
- 239000004033 plastic Substances 0.000 claims description 4
- 229920003023 plastic Polymers 0.000 claims description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 3
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005060 rubber Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 3
- 239000002023 wood Substances 0.000 claims description 3
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 claims description 2
- ZHUWXKIPGGZNJW-UHFFFAOYSA-N 6-methylheptyl 3-sulfanylpropanoate Chemical compound CC(C)CCCCCOC(=O)CCS ZHUWXKIPGGZNJW-UHFFFAOYSA-N 0.000 claims description 2
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 2
- 239000002518 antifoaming agent Substances 0.000 claims 1
- 238000011109 contamination Methods 0.000 claims 1
- 238000001308 synthesis method Methods 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 23
- 230000002209 hydrophobic effect Effects 0.000 abstract description 7
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 239000000693 micelle Substances 0.000 abstract description 3
- 239000012752 auxiliary agent Substances 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000010008 shearing Methods 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 15
- 239000003921 oil Substances 0.000 description 11
- 239000004447 silicone coating Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 229920002799 BoPET Polymers 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 5
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 5
- 238000004945 emulsification Methods 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 239000002313 adhesive film Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000003889 chemical engineering Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000006174 pH buffer Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- YOIZTLBZAMFVPK-UHFFFAOYSA-N 2-(3-ethoxy-4-hydroxyphenyl)-2-hydroxyacetic acid Chemical compound CCOC1=CC(C(O)C(O)=O)=CC=C1O YOIZTLBZAMFVPK-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/068—Polysiloxanes
-
- 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
- C09D151/085—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 on to polysiloxanes
-
- 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
- C09D7/20—Diluents or solvents
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)
Abstract
The invention relates to a preparation method of a water-based organic silicon acrylate composite emulsion and a stain-resistant coating, belonging to the fields of polymer material synthesis and coating. The invention disperses the organosilicon monomer, the acrylic ester monomer and the curing agent in water under the action of the emulsifying agent by the shearing force of high-speed stirring, reduces the size of monomer liquid drops in the water phase by using ultrasonic waves to form miniemulsion, wherein the monomer and the curing agent in the small-size liquid drops have uniform composition, and overcomes the defect that hydrophobic monomer is not easy to be incorporated into micelle and is captured by free radicals to initiate polymerization to form long chains in the traditional emulsion polymerization; adding a water-soluble initiator to perform heating polymerization to obtain stable aqueous high-content (70 wt% of the total mass of the monomers) organosilicon copolyacrylate emulsion in which the curing agent is dispersed; and adding various auxiliary agents to compound and coat the surface of the substrate, and curing at high temperature to obtain the coating with low adhesion and anti-graffiti properties.
Description
Technical Field
The invention relates to a preparation method of a water-based organic silicon acrylate composite emulsion and a stain-resistant coating, belonging to the fields of polymer material synthesis and coating.
Background
The water-based acrylic ester has better flexibility, excellent weather resistance, corrosion resistance and the like, and is widely applied to buildings, furniture, plastics, automobile coatings, textile coatings, leather surface treatment and the like. However, the aqueous acrylic acid has relatively poor water resistance and stain resistance due to the hydrophilic group, which limits the application of the aqueous acrylic acid in the field of high-performance coatings. The organic silicon resin has lower surface tension, good hydrophobicity and oleophobicity, can endow the surface of the material with excellent low adhesion and stain resistance, but has poor mechanical strength and adhesion, and the water resistance and the stain resistance of the water-based acrylic ester coating can be effectively improved by compounding the organic silicon with the water-based acrylic ester resin.
The end group modified organosilicon macromer and the acrylic monomer are copolymerized to prepare organosilicon modified acrylic resin, and the common copolymerization method is solution, emulsion and miniemulsion polymerization. The aqueous organosilicon modified acrylic ester is prepared by polymerizing an appropriate solvent to obtain a resin solution, neutralizing, emulsifying, converting into a water phase and removing the solvent by rotary evaporation. For example, application materials and Interfaces (ACS Applied Materials & Interfaces,2017,9,9029-9037) report that organosilicon monomers and acrylate monomers are copolymerized by free radical solutions to prepare organosilicon grafted acrylate resins, and compounded with curing agents to prepare stain resistant coatings; chemical engineering (Chemical Engineering Journal,2018, 351, 210-220) reports that organosilicon monomers and acrylate monomers (containing acrylic acid) are copolymerized by free radical solution to prepare organosilicon grafted acrylate resins, amine compounds are further added for neutralization and emulsification, and finally solvents are removed to prepare organosilicon modified acrylic resin aqueous dispersions and anti-fouling coatings. The organic solvent is used in the synthesis process of the organosilicon modified acrylic resin, and the organic solvent is required to be removed at last, so that the process is complicated. And emulsion polymerization is difficult to form stable emulsion for organosilicon monomers with larger copolymer molecular weight, so that organosilicon modified acrylic emulsion is difficult to synthesize, and in addition, for the introduction of high-content organosilicon monomers, emulsification is difficult, coarse emulsion is easy to delaminate, and the emulsion polymerization process is easy to gel. The unique monomer droplet nucleation mechanism of miniemulsion polymerization can enable various acrylic ester mixed monomers with high content of organosilicon monomers to stably form miniemulsion in the presence of an emulsifier, so that the aqueous organosilicon modified acrylic emulsion can be successfully prepared by a one-step method. For example, european J Polymer (European Polymer Journal,2022, 168, 111107) reports that an aqueous organosilicon modified acrylic emulsion is prepared by miniemulsion polymerization of an organosilicon macromer with a molecular weight of 5861, methyl methacrylate and butyl acrylate, and a water-resistant adhesive film is prepared after compounding with a curing agent and curing at high temperature; however, the organic silicon content is not high, and the curing agent is not uniformly mixed in the system, so that the anti-fouling performance of the adhesive film is not strong. Based on the above, the invention attempts to synthesize high-content organosilicon acrylic ester emulsion (containing curing agent) by optimizing the type of the emulsifying agent, the miniemulsion polymerization process, the introduction mode of the curing agent and the like, and prepares the stain-resistant coating, which has better stain resistance on the surfaces of the base materials such as leather, plastics, rubber, fiber, glass, metal, fabric, wood and the like, and has better application prospect.
Disclosure of Invention
The main purpose of the invention is to provide a preparation method for preparing high-content (70 wt% of the total monomer mass) organosilicon copolyacrylate emulsion containing curing agent by a one-step method. Dispersing an organosilicon monomer, an acrylic ester monomer and a water-based curing agent in water through shearing force of high-speed stirring under the action of an emulsifier, reducing the size of monomer liquid drops in a water phase by using an ultrasonic cell crusher to form miniemulsion, wherein the monomer in the small-size liquid drops and the water-based curing agent are uniform in composition, and the defect that hydrophobic monomers are not easy to be incorporated into micelles and are captured by free radicals to initiate polymerization to form long chains in the traditional emulsion polymerization is overcome; adding a water-soluble initiator to perform heating polymerization to obtain stable aqueous organosilicon copolyacrylate emulsion dispersed with a curing agent; and adding various auxiliary agents to compound and coat the surface of the substrate, and curing at high temperature to obtain the coating with the characteristics of stain resistance and graffiti resistance.
In one embodiment of the invention, a method for preparing a high-content aqueous organosilicon copolyacrylate emulsion comprises the following steps: uniformly mixing a metered organosilicon monomer, various acrylic ester monomers, a chain transfer agent and a water-based curing agent, dripping the mixture into an aqueous solution added with a metered emulsifying agent and a pH buffering agent, stirring and dispersing the mixture in water at a high speed to form a coarse emulsion, and performing ultrasonic treatment by an ultrasonic cell grinder to obtain a fine emulsion; and (3) filling 1/10-1/4 of the obtained miniemulsion and part of the aqueous solution of the initiator into a four-neck flask for reaction for 1-2h at 60-80 ℃, and after blue light appears at the bottom of the flask, dropwise adding the rest miniemulsion and the aqueous solution of the initiator, and after dropwise adding and preserving heat for 5-12h, obtaining the required organosilicon copolyacrylate emulsion with the curing agent dispersed therein, wherein the solid content of the organosilicon copolyacrylate emulsion is 25-45wt%.
In one embodiment of the invention, the high-content organosilicon acrylic ester copolymerization emulsion component comprises the following components in percentage by mass:
the mass fractions of the components in the mixed monomer are as follows: 45-70wt% of organic silicon monomer, 1-3wt% of hydroxyl-containing acrylic ester monomer and 20-50wt% of other acrylic ester monomer;
other small amounts of initiator, chain transfer agent and pH buffer are not included, wherein the amount of the initiator is 0.5-3wt% of the mass of the mixed monomer, the amount of the chain transfer agent is 0.3-1.5 wt% of the mass of the mixed monomer, and the amount of the pH buffer is 1-4wt% of the mass of the mixed monomer.
In one embodiment of the present invention, the silicone monomer is selected from one of methacrylate-end-capped modified polydimethylsiloxane (PDMS-MA) or acrylate-end-capped modified polydimethylsiloxane (PDMS-AE) having a functionality of 1 and a molecular weight of 4500-6500.
In one embodiment of the invention, the hydroxyl-containing acrylic monomer is selected from one of hydroxyethyl acrylate (HEA), hydroxyethyl methacrylate (HEMA) and hydroxypropyl acrylate (HPA);
in one embodiment of the present invention, the other acrylic monomer is selected from one of Methyl Methacrylate (MMA), methyl Acrylate (MA), ethyl Acrylate (EA), butyl Methacrylate (BMA), butyl Acrylate (BA), isooctyl methacrylate (EHMA) and isooctyl acrylate (2-EHA).
In one embodiment of the present invention, the emulsifier is two or more of a nonionic emulsifier and an anionic emulsifier. Preferably one of the following types, namely an anionic emulsifier and an anionic emulsifier, wherein the mass ratio of the two components is 2:1; the anionic, anionic and nonionic emulsifiers are compounded, and the mass ratio of the three components is 2:1:1; the nonionic emulsifier is preferably one of alkylphenol ethoxylates, fatty alcohol ethoxylates and polyether type polysiloxane emulsifier; the anionic emulsifier is preferably one of sodium dodecyl diphenyl ether disulfonate (2A-1), sodium Dodecyl Benzene Sulfonate (SDBS), sodium Dodecyl Sulfate (SDS) and sodium stearate;
in one embodiment of the invention, the aqueous curing agent is a closed isocyanate curing agent, preferably one of Shiquanxing F-70D, jiubang chemical JB-696C, bayer BL3370MPA, xudi chemical WS20-70D and Guanzhu new material BL-8127;
in one embodiment of the invention, the initiator is one of potassium persulfate, ammonium persulfate, azodiisobutylamidine hydrochloride, azodiiso Ding Mi hydrochloride, azodiiso Ding Mi, azodicyanovaleric acid.
In one embodiment of the invention, the chain transfer agent is one of dodecyl mercaptan, mercaptoethanol, mercaptoacetic acid and isooctyl 3-mercaptopropionate IOMP;
the invention relates to an aqueous high-content organosilicon copolyacrylate emulsion with a dispersed curing agent, which is prepared by the method.
The aqueous high-content organosilicon copolyacrylate emulsion is applied to the field of anti-fouling functional coatings on the surfaces of substrates such as leather, plastics, rubber, fibers, glass, metal, fabrics, wood and the like.
In one embodiment of the invention, the method for preparing the stain-resistant coating comprises the following steps: weighing the high-content organosilicon copolyacrylate emulsion dispersed with the curing agent, adding cosolvent, defoamer, wetting agent and thickener (the addition proportion is 0.6 wt%,0.1 wt% and 0.1 wt%) and uniformly mixing to obtain the water-based anti-fouling paint; the surface of the base material is coated by a coating rod (pretreated by aqueous acrylic emulsion or aqueous polyurethane), and the high-temperature curing is carried out to prepare the stain-resistant coating with the thickness of 4-20 mu m.
In one embodiment of the invention, the specific preparation method of the stain-resistant coating comprises the following steps:
(1) 0.015g of cosolvent, 0.008g of defoamer, 0.375g of wetting agent and 0.025g of thickener are weighed into 10g of 70% silicone emulsion prepared by A-example 1 and stirred at room temperature for 20min. And after being uniformly stirred, the mixture is placed in a vacuum drying oven at 25 ℃, and the vacuum is pumped for 1h to eliminate bubbles generated by stirring, so that the influence of bubbles on the stain resistance of a coating in the coating process is avoided.
(2) The surface of the PET film subjected to the prime coating treatment is coated by a coating rod (the PET film is pretreated by aqueous acrylic emulsion or aqueous polyurethane), and the PET film is cured at high temperature (120 ℃,2min;150 ℃ for 3 min) to ensure that the aqueous curing agent is unblocked to generate curing reaction, so that an anti-fouling coating with excellent performance is formed, and the anti-fouling coating is named as a 70% organosilicon coating.
Advantageous effects
1. The solvent used in the aqueous high-content organosilicon copolyacrylate emulsion is water, and no organic solvent is used in the synthesis process, so that no VOC is discharged, and the aqueous high-content organosilicon copolyacrylate emulsion is safe and environment-friendly.
2. The invention utilizes the advantages of miniemulsion polymerization, namely, the defect that hydrophobic monomers are not easy to be incorporated into micelles in the traditional emulsion polymerization and form long chains by free radical capture initiation polymerization can be overcome, and the high-content organosilicon copolyacrylate emulsion dispersed with the curing agent is successfully prepared by a one-step method.
3. The high-content organosilicon copolyacrylate emulsion is prepared by optimizing the composition and the proportion of the emulsifier, and the coating has the characteristics of hydrophobicity, low adhesion and excellent anti-fouling property, and stains of the oil pen can be easily wiped clean by paper towels.
Drawings
FIG. 1 is a digital photograph of an emulsion, a being the emulsion of A-example 1 (70% silicone) (with curing agent); b is a-example 2 (50% silicone) emulsion (containing curative); c is a-example 2 (30% silicone) emulsion (containing curative); d is the A-control 1 (B-70% silicone) emulsion and e is the A-control 2 (C-70% silicone).
FIG. 2 shows the particle size distribution curves and particle sizes (hydraulic diameters) and polydispersity index (PDI) of the emulsion of A-example 1 (70% silicone) (with curing agent), A-example 2 (50% silicone and 30% silicone) (with curing agent), and A-comparative example 2 (B-70% silicone), respectively.
FIG. 3 is a digital photograph of a coating, a being B-example 2 (30% silicone coating); b is B-example 2 (50% silicone coating); c is B-example 1 (70% silicone) coating, c1 is 70% silicone coating before oil pen-contaminated wipe, c2 is a digital photograph after 70% silicone coating is wiped.
FIG. 4 is a bar graph of water contact angle and digital photograph of contact angle for B-example 1 (70% silicone) coating, B-example 2 (50% silicone and 30% silicone) coating, and B-comparative example 2 (C-70% silicone) coating.
Detailed Description
Specific embodiments of the present invention will be further described in more detail and in complete detail with reference to the following specific examples, but the embodiments of the present invention are not limited thereto.
A. Preparation method of organosilicon copolyacrylate emulsion
Example 1 preparation of 70wt% Silicone copolyacrylate (curing agent-containing) emulsion
(1) 17.5g PDMS-MA, 6.75g MMA, 0.75g HEMA and 0.3g aqueous curing agent (Bayer BL3370 MPA) are weighed into a beaker, and 0.25g dodecyl mercaptan is added into the beaker and stirred uniformly;
(2) Into a four-necked flask, 0.4g of an anionic emulsifier A (sodium dodecyl diphenyl ether disulfonate), 0.2g of an anionic emulsifier B (sodium dodecyl sulfate) and 0.2g of NaH were added 2 PO 4 、0.5g NaHCO 3 Stirring with 50g of water at high speed (1000 rpm) for 15min, continuing to stir at high speed, dropwise adding the monomer in the process, stirring at low speed and aging for 20min to obtain coarse emulsion, and performing ultrasonic treatment with an ultrasonic cell pulverizer for 60min to obtain fine emulsion;
(3) 0.4g of APS was weighed and dissolved in 1g of water and designated as initiator solution 1, and 1.2g of APS was weighed and dissolved in 20g of water and designated as initiator solution 2, and the solution was completely dissolved by sonication; 15g of miniemulsion and initiator solution 1 are taken and added into a four-neck flask; reacting for 20min at 70 ℃, and starting to dropwise add the residual monomer and the initiator solution 2 when blue light appears in the emulsion at the bottom of the bottle; controlling the dropping speed, and finishing dropping at the same time for about 2.5 hours; keeping the temperature at 70 ℃ for 6 hours, heating to 90 ℃ for reaction for 2 hours until the emulsion has no monomer taste, cooling to room temperature, stopping the reaction, and filtering the emulsion by using nylon filter cloth with 200 meshes to obtain the residual liquid which is 70wt% of organosilicon copolyacrylate emulsion (containing curing agent), and marking as 70% of organosilicon; the solid content was found to be 25% by weight.
Example 2 30wt% and 50wt% organosilicon copolyacrylate (containing curing agent) emulsion preparation method
Referring to example 1, the mass of each monomer in step (1) was changed as shown in Table 1, and the remaining conditions were unchanged, to prepare 30wt% and 50wt% silicone copolyacrylate (containing a curing agent) emulsions, which were designated as 30wt% silicone and 50wt% silicone.
Table 1 example 2 monomer composition comparison table
Comparative example 1 preparation of 70wt% organosilicon copolyacrylate (curing agent-containing) emulsion (changing emulsifier ratio)
Referring to example 1, the compound emulsifier in step (2) was changed to the emulsifier ratio as described below, and the remaining conditions were unchanged.
a. Changing the composite emulsifier into 0.6g sodium dodecyl benzene sulfonate (an anionic emulsifier), gradually layering the coarse emulsion in the process of preparing the coarse emulsion in a low-speed ageing process after the monomer is dripped, separating the mixed monomer dissolved with the curing agent from the water phase in the oil phase, performing emulsification failure, continuing to perform ultrasonic treatment and then polymerizing to prepare 70wt% of organosilicon copolyacrylate (containing the curing agent) emulsion of the emulsion changing system, and marking as B-70% of organosilicon;
b. the composite emulsifier is replaced by 0.6g of sodium dodecyl sulfate (an anionic emulsifier), after the miniemulsion subjected to ultrasonic treatment is dripped for 1h in the polymerization process, the residual miniemulsion in the dripping funnel is gradually layered, a large amount of oil phase appears on the upper layer, the emulsion stability is poor, the emulsion prepared by continuously dripping is relatively turbid, unreacted oil phase organosilicon macromer exists, the oil phase exists on the surface of a coating after the surface of a substrate is dried, and the coating dryness is poor. It is described that the emulsion is prepared by using only sodium dodecyl sulfate as an anionic emulsifier, which is difficult to emulsify the mixed monomer of high-content organosilicon copolyacrylate to form stable miniemulsion, and the monomer conversion rate of the emulsion is low;
c. after the composite emulsifier is changed into 0.6g of sodium dodecyl diphenyl ether disulfonate (an anionic emulsifier), the miniemulsion added dropwise in the polymerization process is relatively stable, oil phase separation does not occur, the high-content organosilicon copolyacrylate emulsion is coated on the surface of a substrate after the polymerization is finished, the surface of the coating is relatively oily after the surface of the substrate is dried, the dryness is poor, and the oil phase is unreacted organosilicon macromer. The high-content organosilicon copolyacrylate emulsion is prepared by only using sodium dodecyl diphenyl ether disulfonate as an anionic emulsifier, so that the organosilicon grafting rate is low;
d. after the composite emulsifier is changed into 0.4g of sodium dodecyl diphenyl ether disulfonate and 0.2g of alkylphenol ethoxylates (OP-10) (compounded by anionic and nonionic emulsifiers), the polymerization stability is poor, a large amount of white slag appears in the system after the double-dripping of the miniemulsion and the initiator is finished and the heat preservation is carried out for 2 hours, and the polymerization fails. The method shows that the anionic emulsifier with better emulsification effect such as sodium dodecyl diphenyl ether disulfonate and the OP-10 nonionic emulsifier (the anionic emulsifier and the nonionic emulsifier are compounded) can not be used for successfully preparing the high-content organosilicon copolyacrylate emulsion.
Comparative example 2 preparation method of 70wt% organosilicon copolyacrylate emulsion
Referring to example 1, the aqueous curing agent in step (1) was removed, and the remaining conditions were unchanged, to prepare a 70wt% silicone copolyacrylate emulsion designated as C-70% silicone.
Comparative example 3 preparation of 70wt% organosilicon copolyacrylate (curing agent-containing) emulsion (changing APS initiator to AIBN)
Referring to example 1, the aqueous initiator APS in step (3) was changed to the oil-soluble initiator AIBN, and the APS was dissolved in water to the same content of AIBN and added to the mixed monomer for ultrasonic dissolution; only the coarse emulsion containing AIBN initiator is dripped in the polymerization process, and the rest conditions are unchanged. In the preparation process of the emulsion after the oil-soluble initiator is changed, a large amount of slag appears in the reaction liquid after the crude emulsion is dripped in half, and then the crude emulsion is continuously dripped, so that more slag in the system is increased, the reaction liquid does not show the state of emulsion any more, and the polymerization fails. The reason is probably that the oily initiator dissolved in the monomer is dispersed in the coarse emulsion latex particles along with the coarse emulsification of the monomer, after the polymerization dripping is started, enough monomers are initiated to polymerize after the initiator dispersed in the latex particles is decomposed, the molecular chain in the latex particles grows too fast and is subjected to polymerization, macroscopic appearance is that the slag in the reaction liquid is more and more, and the polymerization fails, so that AIBN is not suitable for being used for the miniemulsion polymerization of the organosilicon copolyacrylate.
B. Preparation method of organosilicon copolyacrylate coating
Application example 1 preparation method of 70wt% organosilicon copolyacrylate coating
(1) 0.015g of cosolvent, 0.008g of defoamer, 0.375g of wetting agent and 0.025g of thickener are weighed into 10g of 70% silicone emulsion prepared by A-example 1 and stirred at room temperature for 20min. And after being uniformly stirred, the mixture is placed in a vacuum drying oven at 25 ℃, and the vacuum is pumped for 1h to eliminate bubbles generated by stirring, so that the influence of bubbles on the stain resistance of a coating in the coating process is avoided.
(2) The surface of the PET film subjected to the prime coating treatment is coated by a coating rod (the PET film is pretreated by aqueous acrylic emulsion or aqueous polyurethane), and the PET film is dried for 1h at room temperature and then cured at high temperature (120 ℃ C., 2min;150 ℃ C., 3 min), so that the aqueous curing agent is ensured to be deblocked and undergo curing reaction, and an anti-fouling coating with excellent performance is formed, and the anti-fouling coating is named as a 70% organic silicon coating.
Application example 2 30wt% and 50wt% organosilicon copolyacrylate coating preparation method
Referring to application example 1, the 70% silicone emulsion prepared from A-example 1 in step (1) was changed to 30% silicone emulsion and 50% silicone emulsion prepared from A-example 2, and the other conditions were unchanged, to prepare 30wt% and 50wt% silicone copolyacrylate coatings, which were denoted as 30% silicone coating and 50% silicone coating.
Comparative example 4 preparation of 70wt% organosilicon copolyacrylate (post-Water-based curing agent) coating
Referring to application example 1, 70% silicone emulsion prepared from A-example 1 in step (1) was changed to C-70% silicone prepared from A-comparative example 2, and 0.03g of an aqueous curing agent (Bayer BL3370 MPA) was added thereto, with the other conditions unchanged, to prepare a 70% by weight silicone copolyacrylate (post-curing agent) coating, designated as C-70% silicone coating.
Table 2 comparison of different sample properties
FIG. 1 is a digital photograph of an A-example 1 (70% silicone) emulsion (containing a curing agent), an A-example 2 (50% silicone and 30% silicone) emulsion (containing a curing agent), an A-control 1 (B-70% silicone) emulsion, and an A-control 2 (C-70% silicone) emulsion. Wherein a is 30% silicone; b is 50% organosilicon; c is 70% organosilicon; d is B-70% of organic silicon; e is C-70% organosilicon. It is obvious that the organosilicon emulsion with B-70% is uneven, and obvious oil drops float on the upper layer of the emulsion, because only one anionic emulsifier is selected, a large amount of hydrophobic organosilicon monomer is not sufficiently stabilized, and the organosilicon monomer is not completely reacted after polymerization, so that the emulsion preparation fails. The other four emulsions have obvious blue light and transparent emulsion, which indicates that the improved composite emulsifier can stabilize hydrophobic organosilicon monomers and curing agents, and the high-content organosilicon copolyacrylate emulsion containing the curing agents is successfully prepared.
FIG. 2 and Table 2 show the particle size distribution curves and particle sizes (hydraulic diameters) and polydispersity index (PDI) of the A-example 1 (70% silicone) emulsion (containing a curing agent), the A-example 2 (50% silicone and 30% silicone) emulsion (containing a curing agent), and the A-comparative example 2 (C-70% silicone) emulsion, respectively. The particle size and the dispersion index of the 70% organosilicon emulsion are 176.3nm and 0.174 respectively, and the particle size and the dispersion index of the C-70% organosilicon emulsion are 173.2nm and 0.155 respectively, and the particle size of the 70% organosilicon emulsion containing the curing agent is slightly larger than that of the emulsion without the curing agent. The particle size and the dispersion index of 30% of organic silicon and 50% of organic silicon emulsion are respectively 146.6nm and 0.117;160.6,0.015. The results show that the emulsion particles of the emulsion are larger in particle size along with the increase of the content of the hydrophobic organosilicon monomer, and the particle size distribution curves are all unimodal, which indicates that the three monomers are successfully copolymerized and the curing agent is uniformly present in the emulsion particles, the emulsion has more emulsion particles with one size, and the particle sizes are concentrated, so that the organosilicon copolyacrylate emulsion particles containing the curing agent are stably present in the water phase.
FIG. 3 is a digital photograph of a B-application example 1 (70% silicone) coating, a B-application example 2 (50% silicone, 30% silicone) coating, respectively. Wherein a is a 30% silicone coating; b is a 50% silicone coating; c is 70% of the organic silicon coating, c1 is 70% of the organic silicon coating, and c2 is 70% of the organic silicon coating after wiping before the pollution of the oil pen is wiped. A-example 2 the corresponding emulsion (30% silicone and 50% silicone) had a relatively high MMA content, so that the coating had some cracking after curing, but the 70% silicone emulsion had an increased silicone monomer content and a reduced MMA content, making the high silicone content coating intact. By observing the digital photographs before and after wiping in comparison with fig. c1 and c2, the stains of the oil pen on the surface of the coating are easy to wipe, and it is obvious that the high-content organosilicon copolyacrylate can endow the coating with an exceptionally excellent decontamination effect.
FIG. 4 is a bar graph of water contact angle and digital photograph of contact angle for B-application example 1 (70% silicone) coating, B-application example 2 (50% silicone and 30% silicone) coating, and B-control example 4 (C-70% silicone) coating. The result shows that as the organosilicon ratio of the organosilicon copolyacrylate emulsion is increased from 30-70wt%, the water contact angle of the corresponding coating before curing is increased from 58 degrees to 92 degrees, the water contact angle of the coating after curing is increased from 78 degrees to 105 degrees, the water contact angles of the organosilicon copolyacrylate anti-fouling coating before and after curing are both increased along with the increase of the organosilicon ratio, and the water contact angle of the coating after curing is higher than that before curing, which further shows that the increase of the water contact angle and the influence of the crosslinking curing on the surface water contact angle of the coating are larger. And the contact angle of the coating of the comparative application example 1 and the coating of the comparative example 2 after curing shows that the contact angle of the coating of the example 1 after curing is slightly higher than that of the coating of the comparative example 2, which shows that the problem of dispersing the curing agent can be effectively solved by introducing the curing agent in the polymerization process, and the coating with uniformly dispersed curing agent has stronger hydrophobicity after curing. Shows the hydrophobic property of the 70 percent (high content) organosilicon copolyacrylate anti-fouling coating containing the curing agent.
Claims (5)
1. The aqueous high-content organosilicon acrylic ester copolymer emulsion is characterized in that the synthesis method of the high-content organosilicon acrylic ester copolymer emulsion is as follows:
(1) Uniformly mixing organosilicon and acrylic ester mixed monomers, a chain transfer agent and a water-based curing agent, then dripping the mixture into an aqueous solution added with an emulsifying agent and a pH buffering agent, and dispersing the mixture into water by high-speed stirring to form coarse emulsion;
(2) Ultrasonic treating the coarse emulsion in ice bath with ultrasonic cell breaker to obtain fine emulsion;
(3) Filling 1/10-1/4 of the miniemulsion and part of the initiator aqueous solution into a four-neck flask for reacting for 0.2-1h at 60-80 ℃, and after blue light appears at the bottom of the flask, dropwise adding the rest miniemulsion and the initiator aqueous solution, and after dropwise adding and preserving heat for 5-12h, obtaining the required organic silicon acrylate emulsion dispersed with the curing agent, wherein the solid content of the emulsion is 25-45wt%;
the high-content organosilicon acrylic ester copolymer emulsion comprises the following components in percentage by mass:
the mass fractions of the components in the mixed monomer are as follows: 45-70wt% of organic silicon monomer, 1-3wt% of hydroxyl-containing acrylic ester monomer and 20-50wt% of other acrylic ester monomer; in addition, a small amount of initiator, chain transfer agent and pH buffering agent are added, wherein the amount of the initiator accounts for 0.5-3wt% of the total monomer mass, the amount of the chain transfer agent accounts for 0.3-1.5 wt% of the total monomer mass, and the amount of the pH buffering agent accounts for 1-4wt% of the total monomer mass.
2. The method of claim 1, wherein the silicone monomer is selected from one of methacrylate-end-capped modified polydimethylsiloxane or acrylate-end-capped modified polydimethylsiloxane having a functionality of 1 and a molecular weight of 4500-6500;
the hydroxyl-containing acrylic ester monomer is one of hydroxyethyl acrylate, hydroxyethyl methacrylate and hydroxypropyl acrylate;
the other acrylic ester monomers are selected from one of methyl methacrylate, methyl acrylate, ethyl acrylate, butyl methacrylate, butyl acrylate, isooctyl methacrylate and isooctyl acrylate;
the emulsifying agent is two or more of nonionic emulsifying agent and anionic emulsifying agent. Preferably one of the following types, namely an anionic emulsifier and an anionic emulsifier, wherein the mass ratio of the two components is 2:1; the anionic, anionic and nonionic emulsifiers are compounded, and the mass ratio of the three components is 2:1:1; the nonionic emulsifier is preferably one of alkylphenol ethoxylates, fatty alcohol ethoxylates and polyether type polysiloxane emulsifier; the anionic emulsifier is preferably one of sodium dodecyl diphenyl ether disulfonate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and sodium stearate;
the water-based curing agent is a closed isocyanate curing agent and is one of Shiquanxing F-70D, jiubang chemical JB-696C, bayer BL3370MPA, xudi chemical WS20-70D and Guanzhu new material BL-8127;
the initiator is one of potassium persulfate, ammonium persulfate, azodiisobutylamidine hydrochloride, azodiiso Ding Mi hydrochloride, azodiiso Ding Mi, and azodicyanovaleric acid;
the chain transfer agent is one of dodecyl mercaptan, mercaptoethanol, thioglycollic acid and isooctyl 3-mercaptopropionate IOMP.
3. The stain-resistant coating is characterized in that a cosolvent, a defoaming agent, a wetting agent and a thickening agent are added into the high-content organosilicon copolyacrylate emulsion with the curing agent dispersed in the claims 1-2, and the mixture is stirred uniformly to obtain the water-based stain-resistant coating;
in the stain-resistant coating, the addition proportion of the cosolvent is 0.6 weight percent of the mass of the water-based organosilicon copolyacrylate emulsion; the adding proportion of the defoamer is 0.1 wt% of the mass of the aqueous organosilicon copolyacrylate emulsion; the addition proportion of the wetting agent is 0.1 weight percent of the mass of the aqueous organosilicon copolyacrylate emulsion; the addition proportion of the thickener is 0.1 wt% of the mass of the water-based organosilicon copolyacrylate emulsion; and coating the prepared anti-fouling coating on the surface of a substrate by using a coating rod, and curing at high temperature to prepare the anti-fouling coating, wherein the thickness of the coating is 4-20 mu m.
4. A stain resistant coating according to claim 3, wherein the high temperature cure is at 130 to 150 ℃ for 1 to 5 minutes.
5. The aqueous high-content organosilicon copolyacrylate emulsion prepared by the method of any one of claims 1 to 4 can be applied to the field of surface contamination-resistant functional coatings of leather, plastics, rubber, fibers, glass, metal, fabrics, wood and other substrates.
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