CN116675815A - POSS composite polyacrylate aqueous dispersion and preparation method thereof - Google Patents
POSS composite polyacrylate aqueous dispersion and preparation method thereof Download PDFInfo
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- CN116675815A CN116675815A CN202310652337.XA CN202310652337A CN116675815A CN 116675815 A CN116675815 A CN 116675815A CN 202310652337 A CN202310652337 A CN 202310652337A CN 116675815 A CN116675815 A CN 116675815A
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- 239000006185 dispersion Substances 0.000 title claims abstract description 47
- 229920000058 polyacrylate Polymers 0.000 title claims abstract description 40
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000000576 coating method Methods 0.000 claims abstract description 24
- 239000011248 coating agent Substances 0.000 claims abstract description 20
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 7
- 239000000178 monomer Substances 0.000 claims description 40
- 239000008367 deionised water Substances 0.000 claims description 34
- 229910021641 deionized water Inorganic materials 0.000 claims description 34
- 239000003995 emulsifying agent Substances 0.000 claims description 34
- 239000000839 emulsion Substances 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 23
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000003999 initiator Substances 0.000 claims description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-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 12
- 239000011521 glass Substances 0.000 claims description 11
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000003431 cross linking reagent Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 6
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 5
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical group CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 229960002887 deanol Drugs 0.000 claims description 5
- 239000012972 dimethylethanolamine Substances 0.000 claims description 5
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 5
- UCWBKJOCRGQBNW-UHFFFAOYSA-M sodium;hydroxymethanesulfinate;dihydrate Chemical compound O.O.[Na+].OCS([O-])=O UCWBKJOCRGQBNW-UHFFFAOYSA-M 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- 229920000734 polysilsesquioxane polymer Polymers 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims 2
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 claims 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical group [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims 1
- 239000002612 dispersion medium Substances 0.000 claims 1
- 229910052500 inorganic mineral Inorganic materials 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 239000011707 mineral Substances 0.000 claims 1
- 235000010755 mineral Nutrition 0.000 claims 1
- 238000010979 pH adjustment Methods 0.000 claims 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims 1
- 239000004033 plastic Substances 0.000 claims 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims 1
- 239000004289 sodium hydrogen sulphite Substances 0.000 claims 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims 1
- 239000000758 substrate Substances 0.000 claims 1
- 239000002023 wood Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 20
- 239000002245 particle Substances 0.000 abstract description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 5
- 239000004971 Cross linker Substances 0.000 abstract 1
- 239000004815 dispersion polymer Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 56
- 238000012360 testing method Methods 0.000 description 32
- 239000003973 paint Substances 0.000 description 29
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- -1 acrylic ester Chemical class 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 229920002554 vinyl polymer Polymers 0.000 description 7
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 239000004816 latex Substances 0.000 description 5
- 229920000126 latex Polymers 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- 230000008961 swelling Effects 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 238000002845 discoloration Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- 239000012085 test solution Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000004108 freeze drying Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical group CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000007373 indentation Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003094 microcapsule Substances 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005494 tarnishing Methods 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- 238000005303 weighing Methods 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
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000012633 leachable Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229920003169 water-soluble polymer Polymers 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
-
- 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
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention designs and synthesizes a novel POSS composite polyacrylate aqueous dispersion. The dispersion is prepared under emulsion polymerization conditions with POSS having acrylic groups as a crosslinker. The aqueous polymer dispersion had a significantly greater molecular weight and average particle size than the control group without the addition of POSS. The coating prepared based on the POSS composite polyacrylate water dispersion has remarkably more excellent hardness and chemical resistance compared with a control group.
Description
Technical Field
The invention belongs to the field of POSS composite material water dispersion, and relates to a POSS composite polyacrylate water dispersion and a preparation method thereof.
Background
The aqueous polyacrylate dispersions are generally prepared by emulsion polymerization using acrylates or methacrylates as main monomers. The paint prepared by using the water-soluble polymer as a main film forming substance has no toxicity environmental protection and good weather resistance. However, the existing paint which uses polyacrylate water dispersion as main film forming substance has the problems of easy swelling of paint film, poor scratch resistance, poor chemical resistance and the like.
One of the reasons for insufficient chemical resistance of common polyacrylate water dispersion coatings is that non-reactive emulsifiers used in the emulsion polymerization process remain in the coating and paint film and are easily dissolved out when contacting chemicals, causing swelling or breakage of the paint film. The use of reactive emulsifiers allows for a significant reduction in the residual emulsifier content of the finished emulsion, which in turn increases the chemical resistance.
The addition of inorganic nonmetallic atoms such as silicon to polyacrylate water dispersion is a common technology in the prior art, but the modification of organosilicon compounds is not remarkable for improving the performance of the coating, and the problem can not be fundamentally solved. For example, patent CN103059313B discloses a method for preparing an organosilicon modified polyacrylate aqueous dispersion, the hardness and acid and alkali resistance of the obtained paint film are not obviously improved compared with those of a control group, and the paint film of a part of the formula still swells when contacted with an organic solvent to generate lacquer diseases. POSS, which is known as polyhedral oligomeric silsesquioxane (polyhedral oligomeric silsesquioxanes), is a type of polyhedral organic-inorganic hybrid material. The structure of the POSS compound comprises a silica octahedral framework, and each vertex on the framework is provided with an organic group which can be designed and changed according to the needs, so that various applications of the POSS compound in the fields of materials and chemistry are realized. POSS polymer composites refer to new materials formed by the combination of POSS molecules with polymers. Due to the structural characteristics of POSS molecules, the POSS polymer composite material has higher performances such as thermal stability, mechanical strength, wear resistance and the like compared with the traditional silicon hybrid polymer composite material. Meanwhile, the structure of the POSS can be designed and changed, so that the regulation and optimization of the performance of the composite material are realized. Wherein the POSS with reactive functional groups can be linked to the polymer via covalent bonds to achieve more excellent properties. For example, patent CN104592473a discloses a preparation method of POSS modified polyurethane resin, and attempts to add several POSS into polyurethane resin respectively, and as a result, softening temperature, mechanical property and hydrophobic property of the resin are all improved.
Although POSS polyacrylate resin composite materials have been reported, the main research only involves the use of vinyl-containing POSS and acrylic acid to form microcapsules by emulsion polymerization, and then mixing the microcapsules with epoxy resin, filler and the like to prepare an anticorrosive paint (CN 111205745B); or the vinyl POSS and methyl methacrylate are subjected to solution polymerization to prepare thermosetting plastic (CN 113881048A). CN109535350a discloses a technique for using aqueous dispersion of fluorine-containing polyacrylate compounded with vinyl POSS for coating, and found that vinyl POSS can only be grafted on the surface of latex particles, and can not form cross-links; zhang Jianqiao reports (paint industry, 2007, 37, 10-18) on a synthetic method of acrylic ester emulsion with participation of vinyl POSS and characterizes the curve of particle size and emulsion gel rate increasing with POSS addition; however, at an increase in the POSS addition to 5%, the particle size increase of the emulsion was still not significant (about 12%). In summary, vinyl POSS has limited improvement in emulsion performance.
The reactivity ratio of ethylene to acrylate may be one of the reasons for the limitation of vinyl POSS applications described above. The reactivity ratio is the ratio of the chain growth rate constants of the homopolymer and the copolymer at the time of copolymerization of the monomers, and the higher the reactivity ratio of the monomers, the stronger the tendency to self-polymerize, the less likely the copolymerization system is formed (Dan Jianbing, polymer report, 2021,1, 61-65). The reactivity ratios of ethylene and methyl methacrylate, which are common monomers, were 0.20 (ethylene) and 17.00 (methyl methacrylate), respectively, when copolymerized (polymer emulsion synthesis principle performance and application, cao Tongyu). Whereas acrylic groups are structurally similar to methyl methacrylate, taking methyl acrylate as an example, reactivity ratios of 0.34 (methyl acrylate) and 1.69 (methyl methacrylate), respectively, when copolymerized with methyl methacrylate, indicate that POSS with acrylic groups in the polymerization reaction is more prone to form copolymers with acrylate/methacrylate monomers than POSS with vinyl groups.
The addition of POSS having acrylic groups in emulsion polymerization has been reported in several patents. For example, the number of the cells to be processed,
patent CN103923248B discloses a method for preparing an acrylic ester emulsion by using methacryloxypropyl POSS of T8, T10 and T12 as reactive emulsifiers, methyl methacrylate, butyl acrylate and styrene, wherein the emulsification effect is poor when the addition amount of the POSS emulsifier is low, and a large amount of condensation is generated after the reaction when the addition amount is too high. In order to achieve a better emulsification effect, the POSS addition amount reaches 10-30% of the monomer mass;
patent CN106947030a discloses a preparation method of an emulsion with oleic acid amide propyl POSS as an emulsifier and methacryloxypropyl POSS added, wherein the added amount of the used POSS emulsifier reaches 3.6% of the total monomer amount, and the added amount of the methacryloxypropyl POSS reaches 3.9%, so that the emulsion with better physicochemical properties is obtained. However, the synthesis period of the oleamide propyl POSS is long, and the purification process involves a large amount of organic solvents, which is unfavorable for the application in industrial production.
The invention takes methacrylate, acrylic ester, styrene and the like as monomers, adds cage polysilsesquioxane OA-POSS or OMA-POSS as a POSS cross-linking agent, and synthesizes the POSS composite polyacrylate aqueous dispersion in a seed emulsion polymerization mode. In the case of a very small amount of POSS added (0.12% of the emulsion mass), the latex particle size of the aqueous dispersion increased significantly by 33% and the weight average molecular mass increased significantly by 80%. Meanwhile, the reactive emulsifier changes the hydrophilic capacity of the latex particles, so that the aqueous dispersion has higher stability.
The cold liquid resistance and physical properties of the prepared paint film are obviously improved, the quality loss of the paint film after the treatment of the organic solvent ethyl acetate is only 0.7%, which shows that the soluble matters in the paint film are very few, namely the POSS composite polyacrylate water dispersion has excellent water resistance, organic solvent resistance and scratch resistance after the film is formed.
Disclosure of Invention
The invention provides a POSS composite polyacrylate aqueous dispersion and a preparation method thereof.
The preparation method of the POSS composite polyacrylate water dispersion comprises the following steps:
1. preparing a solution:
1.1, adding an emulsifying agent into water, sequentially adding a hard monomer, a soft monomer and a POSS cross-linking agent, and stirring at a high speed for 30-60 minutes to prepare a stable monomer pre-emulsion A;
the hard monomer is one or two of methyl methacrylate and styrene; the soft monomer is one or two of butyl acrylate and isooctyl acrylate; the hard monomer and the soft monomer are all chemical pure products purchased in the company of Hindex reagent;
the POSS cross-linking agent is cage-shaped polysilsesquioxane OA-POSS or OMA-POSS shown in the formula (I);
the emulsifier is a non-reactive emulsifier or a compound of the non-reactive emulsifier and the reactive emulsifier; preferably, the compound of the reactive emulsifier and the non-reactive emulsifier is adopted.
The non-reactive emulsifier is selected from: sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, is a chemically pure product purchased from the company of haynes reagent; the products NOVELUTION 390, NOVELUTION 3203N, NOVELUTION 3208K, NOVELUTION 3400K, NOVELUTION AG35N, NOVELUTION ZS27N, NOVELUTION ZS37A, NOVELUTION LE73N or NOVELUTION S03N purchased from Sasol corporation; the product RHODAAL DS-4AP purchased from Solvay company; preferably, the non-reactive emulsifier is sodium dodecyl benzene sulfonate or RHODACALDS-4AP;
the adopted reactive emulsifier is a compound shown in a formula (II);
in the formula (II), R represents an ethylene oxide group, and n represents the number of R groups; preferably, n=6-10; more preferably, n=9;
the compounds of formula (II) may be abbreviated as OE-n, respectively, depending on the value of n; for example, the reactive emulsifier of n=9 is abbreviated as OE-9 in the examples below.
1.2, preparing a part of initiator into a solution B with the mass concentration of 3% -5% by using deionized water;
the initiator is ammonium persulfate or potassium persulfate, and is a chemical pure product purchased in the company of Hien reagent;
1.3 preparing sodium bicarbonate and part of emulsifier into solution C by deionized water;
the sodium bicarbonate is a chemical pure product purchased from the company of Hien's reagent;
1.4, preparing a part of initiator into a solution D with the mass concentration of 2% -3% by using deionized water;
the initiator is ammonium persulfate or potassium persulfate, and is a chemical pure product purchased in the company of Hien reagent;
1.5, preparing oxidant into solution E with the mass concentration of 4% -6% by using deionized water;
the oxidant is hydrogen peroxide or tert-butyl hydroperoxide, which are all aqueous solutions purchased from the company of Henry reagent.
1.6, preparing a reducing agent into a solution F with the mass concentration of 4% -6% by using deionized water;
the reducing agent is BRUGGOLITE FF6M, which is inA product purchased from Chemical company;
1.7 deionized water is used for the pH regulator according to the mass ratio of regulator to water of 1:1 diluted solution G.
The pH regulator is dimethylethanolamine or 28% ammonia water, and is a chemical pure product purchased from the company of Hien reagent.
2. Polymerization process
Solution C was added to a 1L jacketed glass reactor equipped with a condenser, thermometer and stirrer, the temperature of the reactor was raised to 80-85 ℃ after nitrogen substitution, and stirring was started (stirrer diameter d=60 mm, rotational speed 200-300 RPM). Taking 5% of monomer pre-emulsion A by mass as seeds, adding the seeds into a reaction kettle, stirring for 3-5min, and then adding a solution B; stirring is continued for 20-30min. Then, simultaneously dripping the monomer pre-emulsion A and the solution D, and uniformly adding the residual monomer pre-emulsion A within 3 hours; solution D was added at constant rate over 3h 15 min. After the dripping, the kettle temperature is reduced to 60 ℃, and the solution E and the solution F are simultaneously dripped, and the dripping is completed within 30min. After the dripping is finished, the kettle temperature is reduced to 40 ℃, solution G is added at one time, after stirring is carried out for 5-10min, the pH value is adjusted to 8-9, and the mixture is discharged through a 200-mesh filter screen, thus obtaining the POSS composite polyacrylate aqueous dispersion.
3. Preparation of the coating
The invention further aims to provide an application of the POSS composite polyacrylate aqueous dispersion in a coating, wherein the POSS composite polyacrylate aqueous dispersion is used as a film forming substance, and a leveling agent and a film forming auxiliary agent are compounded to prepare the aqueous coating, so that a coated paint film has higher hardness, better chemical resistance and lower quality loss rate of an organic solvent.
Compared with the prior art, the invention has the following beneficial effects:
the present invention uses acryloxypropyl POSS (OA-POSS) or methacryloxypropyl POSS (OMA-POSS) with eight reactive functional groups to prepare POSS composite polyacrylate aqueous dispersions with higher degree of crosslinking, larger particle size and higher weight average molecular weight. In the case of a very small amount of POSS added (0.12% of the emulsion mass), the latex particle size of the aqueous dispersion increased significantly by 33% and the weight average molecular mass increased significantly by 80%. Meanwhile, the reactive emulsifier changes the hydrophilic capacity of the latex particles, so that the aqueous dispersion has higher stability.
By using the coating prepared by the POSS composite polyacrylate water dispersion, a paint film with excellent physical and chemical properties can be formed, and particularly, the coating has extremely low mass loss rate when being treated by an organic solvent. The quality loss of a paint film after the treatment of the organic solvent ethyl acetate is only 0.7%, and the quality loss is obviously reduced by 40.9% compared with a control group without the POSS. This result demonstrates that the very few leachables in the paint film, i.e., the POSS composite polyacrylate aqueous dispersion, after film formation, has excellent water resistance, organic solvent resistance, and scratch resistance.
Compared with the prior art, the POSS composite polyacrylate water dispersion prepared by the invention meets the requirement of the coating prepared by the water dispersion on chemical resistance, and simultaneously adopts cheaper and easily obtained raw materials and a simple synthesis method, so that the cost is controllable and the industrial production is easy.
Detailed Description
The following describes the embodiments of the present invention in further detail with reference to examples. The examples are intended to describe the invention in detail and should not be construed as limiting the invention.
Example 1: preparation and characterization of POSS composite polyacrylate aqueous dispersion
2.67g of RHODACALDS-4AP and 1.50g of OE-9 are added into 175.50g of deionized water, 210.00g of methyl methacrylate, 30.00g of styrene, 60.00g of isooctyl acrylate and 0.90g of OA-POSS are sequentially added, and the mixture is stirred at a high speed for 60 minutes to prepare a stable monomer pre-emulsion A;
preparing a solution B from 0.60g of initiator ammonium persulfate and 15.00g of deionized water;
solution C was prepared from 0.60g sodium bicarbonate and 4.00g RHODACAL DS-4AP with 180.00g deionized water;
preparing 0.96g of initiator ammonium persulfate into solution D by using 36.00g of deionized water;
solution E was prepared from 0.42g of 70% aqueous t-butyl hydroperoxide with 6.00g of deionized water;
0.36g BRUGGOLITE FF6M was prepared as solution F with 6.00g deionized water;
solution G was prepared from 3.00G of the pH regulator dimethylethanolamine with 3.00G of deionized water.
Solution C was added to a 1L jacketed glass reactor equipped with a condenser, thermometer and stirrer, the temperature of the reactor was raised to 80-85 ℃ after nitrogen substitution, and stirring was started (stirrer diameter d=60 mm, rotational speed 200-300 RPM). Taking 5% of monomer pre-emulsion A by mass as seeds, adding the seeds into a reaction kettle, stirring for 3-5min, and then adding a solution B; stirring is continued for 20-30min. Then, simultaneously dripping the monomer pre-emulsion A and the solution D, and uniformly adding the residual monomer pre-emulsion A within 3 hours; solution D was added at constant rate over 3h 15 min. After the dripping, the kettle temperature is reduced to 60 ℃, and the solution E and the solution F are simultaneously dripped, and the dripping is completed within 30min. After the dripping is finished, the kettle temperature is reduced to 40 ℃, solution G is added at one time, after stirring is carried out for 5-10min, the pH value is adjusted to 8-9, and the mixture is discharged through a 200-mesh filter screen, thus obtaining the POSS composite polyacrylate water dispersion A-1.
The particle size distribution test is carried out on diluted polyacrylate water dispersion A-1 (the concentration after dilution is 4.0g/L and the experimental temperature is 25 ℃) by using a Zetasizer nano SZ type laser particle sizer, the average value of the three test results is 178.83nm, and the average PdI=0.247;
the A-1 was subjected to freeze-drying treatment, and the obtained solid had a weight average molecular weight of 50942g/mol as measured by Gel Permeation Chromatography (GPC).
Example 2: preparation and characterization of POSS composite polyacrylate aqueous dispersion
To 175.50g deionized water was added 0.60g sodium dodecyl benzene sulfonate and 1.50g OE-9, followed by 210.00g methyl methacrylate, 30.00g styrene, 60.00g isooctyl acrylate and 0.93g OMA-POSS, and stirred at high speed for 60 minutes to prepare a stable monomer pre-emulsion A;
preparing a solution B from 0.60g of initiator ammonium persulfate and 15.00g of deionized water;
solution C was prepared from 0.60g sodium bicarbonate and 0.90g sodium dodecyl benzene sulfonate with 180.00g deionized water;
solution D was prepared from 0.96g of initiator potassium persulfate with 36.00g of deionized water;
solution E was prepared from 0.15g of 70% aqueous t-butyl hydroperoxide with 6.00g of deionized water;
0.36g BRUGGOLITE FF6M was prepared as solution F with 6.00g deionized water;
solution G was prepared from 3.00G of the pH regulator dimethylethanolamine with 3.00G of deionized water.
Solution C was added to a 1L jacketed glass reactor equipped with a condenser, thermometer and stirrer, the temperature of the reactor was raised to 80-85 ℃ after nitrogen substitution, and stirring was started (stirrer diameter d=60 mm, rotational speed 200-300 RPM). Taking 5% of monomer pre-emulsion A by mass as seeds, adding the seeds into a reaction kettle, stirring for 3-5min, and then adding a solution B; stirring is continued for 20-30min. Then, simultaneously dripping the monomer pre-emulsion A and the solution D, and uniformly adding the residual monomer pre-emulsion A within 3 hours; solution D was added at constant rate over 3h 15 min. After the dripping, the kettle temperature is reduced to 60 ℃, and the solution E and the solution F are simultaneously dripped, and the dripping is completed within 30min. After the dripping is finished, the kettle temperature is reduced to 40 ℃, solution G is added at one time, after stirring is carried out for 5-10min, the pH value is adjusted to 8-9, and the mixture is discharged through a 200-mesh filter screen, thus obtaining the POSS composite polyacrylate water dispersion A-2.
The particle size distribution test is carried out on diluted polyacrylate aqueous dispersion A-2 (the concentration after dilution is 4.0g/L and the experimental temperature is 25 ℃) by using a Zetasizer Nano SZ type laser particle sizer, the average value of the three test results is 180.16nm, and the average PdI=0.251;
the A-2 was subjected to freeze-drying treatment, and the obtained solid had a weight average molecular weight of 50877g/mol as measured by Gel Permeation Chromatography (GPC).
Example 3: control experiment
2.67g of RHODACALDS-4AP and 1.50g of OE-9 are added into 175.50g of deionized water, 210.00g of methyl methacrylate, 30.00g of styrene and 60.00g of isooctyl acrylate are sequentially added, and the mixture is stirred at a high speed for 60 minutes to prepare a stable monomer pre-emulsion A;
preparing a solution B from 0.60g of initiator ammonium persulfate and 15.00g of deionized water;
solution C was prepared from 0.60g sodium bicarbonate and 4.00g RHODACAL DS-4AP with 180.00g deionized water;
preparing 0.96g of initiator ammonium persulfate into solution D by using 36.00g of deionized water;
solution E was prepared from 0.42g of 70% aqueous t-butyl hydroperoxide with 6.00g of deionized water;
0.36g BRUGGOLITE FF6M was prepared as solution F with 6.00g deionized water;
solution G was prepared from 3.00G of the pH regulator dimethylethanolamine with 3.00G of deionized water.
Solution C was added to a 1L jacketed glass reactor equipped with a condenser, thermometer and stirrer, the temperature of the reactor was raised to 80-85 ℃ after nitrogen substitution, and stirring was started (stirrer diameter d=60 mm, rotational speed 200-300 RPM). Taking 5% of monomer pre-emulsion A by mass as seeds, adding the seeds into a reaction kettle, stirring for 3-5min, and then adding a solution B; stirring is continued for 20-30min. Then, simultaneously dripping the monomer pre-emulsion A and the solution D, and uniformly adding the residual monomer pre-emulsion A within 3 hours; solution D was added at constant rate over 3h 15 min. After the dripping, the kettle temperature is reduced to 60 ℃, and the solution E and the solution F are simultaneously dripped, and the dripping is completed within 30min. After the dripping is finished, the kettle temperature is reduced to 40 ℃, the solution G is added at one time, after stirring for 5-10min, the pH value is adjusted to 8-9, and the polyacrylate water dispersion A-0 is obtained after discharging through a 200-mesh filter screen.
The particle size distribution test is carried out on diluted polyacrylate water dispersion A-0 (the concentration after dilution is 4.0g/L and the experimental temperature is 25 ℃) by using a Zetasizer nano SZ type laser particle sizer, the average value of the three test results is 115.33nm, and the average PdI=0.041;
the A-1 was subjected to freeze-drying treatment, and the obtained solid had a weight average molecular weight of 28251g/mol as measured by Gel Permeation Chromatography (GPC).
Example 4: preparation of coatings and coating tests Using the products obtained in examples 1 and 3 as raw materials
1. Coating formulation table:
wherein, the coating 1 is prepared by taking polyacrylate water dispersion A-0 (blank control) obtained by a control test as a raw material; coating 2 is a polyacrylate aqueous dispersion A-0 and a coating (experimental control) prepared by taking 0.12% of OA-POSS added after polymerization reaction as a raw material, and note that in the experimental control group, the reactive functional group is not connected with the polymer through a covalent bond because the OA-POSS is added in the coating preparation stage and is physically mixed; coating 3 is a coating (experimental group) prepared from the POSS composite polyacrylate aqueous dispersion A-1 obtained in example 1.
In the three paint formulas, the film forming auxiliary agent is 1, 2-propylene glycol and dipropylene glycol methyl ether with the mass ratio of 1:1, and the leveling agent is BYK-333.
2. The preparation method of the paint comprises the following steps:
in the preparation process of the coating, firstly, the ingredients are accurately weighed into a 50mL centrifuge tube, vortexed for 5min to be fully and uniformly mixed, and the ultrasonic treatment is carried out for 1min to remove foam, a 100-mu m uniform liquid film of the mixed solution is scraped on a clean glass plate by a BGD 206 universal four-side preparation device, and the mixed solution is dried in an oven at 85 ℃ for 24h to determine the resistance and hardness of the mixed solution.
3. Paint film performance detection method
Water resistance: the test solution is distilled water, the middle part of each plate is taken in the test area, water absorbing paper is put on the test area, and a glass cover is added for sealing, so that the filter paper is kept wet in the test process.
Alkali resistance: the test solution is 10% Na 2 CO 3 The solution, the middle part of each plate is taken in the test area, the water absorbing paper is put on the test area, and the test area is sealed by a glass cover, so that the filter paper is kept wet in the test process.
Alcohol resistance: the test solution is 50% (volume fraction) ethanol solution, the middle part of each plate is taken in the test area, water absorbing paper is placed on the test area, and a glass cover is added for sealing, so that the filter paper is kept wet in the test process.
Acid resistance: the test solution is 10% acetic acid solution, the middle part of each plate is taken in the test area, water absorbing paper is placed on the test area, and a glass cover is added for sealing, so that the filter paper is kept wet in the test process.
Rating criteria reference GB/T4893.1-2021 section 1 of physicochemical Properties test of household surface paint film: cold resistance fluid assay: no change in level 1.
The test area is indistinguishable from the adjacent areas.
Grade 2 was slightly changed.
The test area is distinguishable from adjacent areas, such as fade, gloss and color change, only when the light source is projected onto the test surface and reflected into the observer's eye.
The test surface structure was unchanged, such as swelling, fiber protrusion, cracking, and bubbling.
Grade 3 medium change.
The test area is distinguishable from adjacent areas, such as fading, tarnishing, and discoloration, as seen in several directions.
The test surface structure was unchanged, such as swelling, fiber protrusion, cracking, and bubbling.
Level 4 varies significantly.
The test area is clearly distinguishable from adjacent areas, such as discoloration, tarnishing and discoloration, in all visible directions.
And/or slight variations in the structure of the test surface, such as swelling, fiber protrusion, cracking, bubbling.
Grade 5 varies severely.
The test surface structure was significantly changed.
And/or fade, tarnish and discoloration.
And/or the surface material is removed in whole or in part.
And/or the filter paper sticks to the surface.
Pencil hardness: the measurement was carried out with reference to GBT 6739-2006, paint film hardness measured by the color paint and varnish pencil method.
Indentation hardness; the measurement was carried out with reference to GB/T9275-2008 "paint and varnish Barkholtz indentation test".
4. Results of the performance test of the paint film
The measurement results are shown in the following table:
as shown by experimental results, compared with blank control and experimental control, the experimental group has obvious advantages in physical and chemical properties such as hardness, scratch resistance, chemical resistance and the like.
5. Determination of the loss rate of paint film quality
Accurately weighing 0.50-1.00 g of the dry paint film formed by the paint 1 and the paint 3 on a filter paper sheet and marking the dry paint film as m 0 After extraction in a Soxhlet extractor for 24 hours with 100.00g of ethyl acetate as extraction solvent, the residue state was recorded. Drying in an oven at 80deg.C for 1 hr, weighing the residue mass and recording as m 1 The mass loss rate was calculated according to the following formula:
| coating numbering | Experimental grouping | Mass loss rate | Residual state |
| 1 | Blank control | 41.6％ | Most of it dissolves |
| 3 | Experimental group | 0.7％ | Continuous film |
From the results of example 4, it can be seen that the coatings prepared based on the POSS composite polyacrylate aqueous dispersion of larger particle size, higher molecular weight, higher degree of crosslinking have more excellent hardness and chemical resistance properties and significantly less mass loss rate than the control group.
Claims (4)
1. A POSS composite polyacrylate aqueous dispersion characterized by: taking water as a dispersion medium; one or two of methyl methacrylate and styrene are used as hard monomers; one or more of butyl acrylate, butyl methacrylate, isooctyl acrylate and isooctyl methacrylate are used as soft monomers; taking cage-shaped polysilsesquioxane OA-POSS or OMA-POSS as POSS cross-linking agent; one or two of non-reactive emulsifier and reactive emulsifier are used as emulsifier, persulfate is used as initiator, and the POSS composite polyacrylate water dispersion is polymerized by adopting emulsion polymerization process, wherein the polymerization process comprises post-treatment and pH adjustment process;
the method is characterized in that:
the preparation method comprises the following raw materials in percentage by mass: 5 to 10 percent of soft monomer, 30 to 40 percent of hard monomer, 0.1 to 0.5 percent of POSS cross-linking agent, 0.2 to 1.0 percent of initiator, 0.3 to 1.0 percent of emulsifier, 0 to 0.1 percent of sodium bicarbonate, 0 to 0.1 percent of post-treatment agent, 0.3 to 1.0 percent of pH regulator and 50 to 60 percent of deionized water;
the initiator is ammonium persulfate or potassium persulfate;
the adopted emulsifying agent is a non-reactive emulsifying agent or a reactive emulsifying agent or the combination of the non-reactive emulsifying agent and the reactive emulsifying agent;
the adopted non-reactive emulsifier is one or more of sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate, NOVELUTION 390, NOVELUTION 3203N, NOVELUTION 3208K, NOVELUTION 3400K, NOVELUTION AG35N, NOVELUTION ZS27N, NOVELUTION ZS37A, NOVELUTION LE73N, NOVELUTION S03N and RHODACAL DS-4AP, and the adopted reactive emulsifier is a compound shown in formula (II);
in the formula (II), R represents an ethylene oxide group, and n represents the number of R groups;
the adopted aftertreatment agent comprises an oxidant and a reducing agent, wherein the oxidant is hydrogen peroxide or tert-butyl hydroperoxide, and the reducing agent is sodium bisulphite or BRUGGOLITE FF6M;
the adopted pH regulator is dimethylethanolamine or ammonia water with the mass concentration of 28 percent.
2. The method for preparing the POSS composite polyacrylate water dispersion according to claim 1, which comprises the following steps:
preparing a solution: adding part of emulsifier into water, sequentially adding hard monomer, soft monomer and POSS cross-linking agent, and stirring at high speed for 30-60 min to obtain stable monomer pre-emulsion A;
preparing a part of initiator into a solution B with the mass concentration of 3% -5% by using deionized water;
preparing solution C of sodium bicarbonate and partial emulsifier with deionized water;
preparing a part of initiator into a solution D with the mass concentration of 2% -3% by using deionized water;
preparing oxidant into solution E with mass concentration of 4% -6% by using deionized water;
preparing a solution F with the mass concentration of 4% -6% by using deionized water as a reducing agent;
deionized water for the pH regulator is used according to the mass ratio of the regulator to water of 1:1 diluted solution G.
Adding a solution C into a 1L jacketed glass reaction kettle provided with a condensing tube, a thermometer and a stirring paddle, after nitrogen replacement, raising the kettle temperature to 80-85 ℃, and starting stirring; taking 5% of monomer pre-emulsion A by mass as seeds, adding the seeds into a reaction kettle, stirring for 3-5min, and then adding a solution B; continuously stirring for 20-30min; then, simultaneously dripping the monomer pre-emulsion A and the solution D, and uniformly adding the residual monomer pre-emulsion A within 3 hours; solution D was added at constant rate over 3h 15 min. After the dripping, the kettle temperature is reduced to 60 ℃, and the solution E and the solution F are simultaneously dripped, and the dripping is completed within 30min. After the dripping is finished, the kettle temperature is reduced to 40 ℃, solution G is added at one time, after stirring is carried out for 5-10min, the pH value is adjusted to 8-9, and the mixture is discharged through a 200-mesh filter screen, thus obtaining the POSS composite polyacrylate aqueous dispersion.
3. Use of the aqueous POSS composite polyacrylate dispersion according to claim 1 for producing coatings suitable substrates including wood, metal, plastic, glass and minerals.
4. A coating comprising the POSS composite polyacrylate aqueous dispersion of claim 1.
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