CN115947904A - POSS composite polyacrylate water dispersion and preparation method thereof - Google Patents
POSS composite polyacrylate water dispersion and preparation method thereof Download PDFInfo
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- CN115947904A CN115947904A CN202310229066.7A CN202310229066A CN115947904A CN 115947904 A CN115947904 A CN 115947904A CN 202310229066 A CN202310229066 A CN 202310229066A CN 115947904 A CN115947904 A CN 115947904A
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- deionized water
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- 239000006185 dispersion Substances 0.000 title claims abstract description 39
- 229920000058 polyacrylate Polymers 0.000 title claims abstract description 37
- 239000002131 composite material Substances 0.000 title claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 59
- 238000002360 preparation method Methods 0.000 title description 12
- 238000000576 coating method Methods 0.000 claims abstract description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 7
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 4
- 239000000178 monomer Substances 0.000 claims description 38
- 239000008367 deionised water Substances 0.000 claims description 34
- 229910021641 deionized water Inorganic materials 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 32
- 239000000839 emulsion Substances 0.000 claims description 26
- 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
- 239000003995 emulsifying agent Substances 0.000 claims description 15
- 239000003999 initiator Substances 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 14
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 12
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 9
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 229920000734 polysilsesquioxane polymer Polymers 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 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
- 238000001816 cooling Methods 0.000 claims description 5
- 229960002887 deanol Drugs 0.000 claims description 5
- 239000012972 dimethylethanolamine Substances 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000007800 oxidant agent Substances 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
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 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
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims 2
- 238000004519 manufacturing process Methods 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
- 238000010438 heat treatment Methods 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
- 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
- 230000029219 regulation of pH Effects 0.000 claims 1
- 235000010267 sodium hydrogen sulphite Nutrition 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 15
- 239000002245 particle Substances 0.000 abstract description 14
- 239000004815 dispersion polymer Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 55
- 238000012360 testing method Methods 0.000 description 33
- 239000003973 paint Substances 0.000 description 19
- 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
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 230000009257 reactivity Effects 0.000 description 5
- 230000008961 swelling Effects 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 239000002250 absorbent Substances 0.000 description 4
- 230000002745 absorbent Effects 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000002474 experimental method 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
- 239000007787 solid Substances 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- 239000012085 test solution Substances 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 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
- 150000001875 compounds Chemical class 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000005562 fading Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000004108 freeze drying Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000007373 indentation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003094 microcapsule Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 238000010186 staining Methods 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 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
- 238000003556 assay Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- VQLYBLABXAHUDN-UHFFFAOYSA-N bis(4-fluorophenyl)-methyl-(1,2,4-triazol-1-ylmethyl)silane;methyl n-(1h-benzimidazol-2-yl)carbamate Chemical compound C1=CC=C2NC(NC(=O)OC)=NC2=C1.C=1C=C(F)C=CC=1[Si](C=1C=CC(F)=CC=1)(C)CN1C=NC=N1 VQLYBLABXAHUDN-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007334 copolymerization reaction 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
- 230000000694 effects Effects 0.000 description 1
- 238000010556 emulsion polymerization method 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
- 239000000945 filler Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000001105 regulatory effect 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
- 125000005373 siloxane group Chemical group [SiH2](O*)* 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
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001187 thermosetting 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)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (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 the crosslinking agent. The aqueous polymer dispersion had a significantly greater molecular weight and average particle size than the control without POSS added. Coatings formulated based on the above-described POSS composite polyacrylate aqueous dispersions have significantly superior hardness and chemical resistance properties compared to the control.
Description
Technical Field
The invention belongs to the field of POSS composite material aqueous dispersion, and relates to a POSS composite polyacrylate aqueous dispersion and a preparation method thereof.
Background
Aqueous polyacrylate dispersions are usually prepared by emulsion polymerization using acrylates or methacrylates as the main monomers. The paint prepared by using the compound as a main film forming substance has the advantages of no toxicity, environmental protection and good weather resistance. However, the existing coating taking polyacrylate water dispersion as a main film forming substance generally has the problems of low crosslinking density, easy swelling of a paint film and the like, so that the scratch resistance and the chemical resistance of the product are insufficient.
In the preparation method of the polyacrylate aqueous dispersion with high solid content and low viscosity disclosed in patent CN108864359B, the used hydrophilic monomer acrylic acid accounts for 7-12% of the mass ratio, and ideal water resistance and alcohol resistance are difficult to obtain; the patent CN103059313B discloses a preparation method of an organosilicon modified polyacrylate water 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 paint diseases are generated by swelling of part of the paint film of the formula when the paint film is contacted with an organic solvent.
POSS, collectively known as polyhedral oligomeric silsesquioxanes (polysilsesquioxanes), is a class of cage-like polyhedral organic-inorganic hybrid materials. The structure of the POSS compound comprises a silica octahedral framework, each vertex on the framework is provided with an organic group, and the organic groups can be designed and changed according to needs, so that the POSS compound can be applied to various fields of materials and chemistry. POSS polymer composites refer to new materials formed by the combination of POSS molecules with polymers. Because the POSS molecules contain siloxane groups, the POSS polymer composite material has higher thermal stability, mechanical strength, wear resistance and other properties. Meanwhile, the structure of the POSS can be designed and changed, so that the performance of the composite material can be regulated, controlled and optimized. Among them, POSS having a reactive functional group can be linked to a polymer through a covalent bond to obtain more excellent properties. For example, in a preparation method of a POSS modified polyurethane resin disclosed in patent CN104592473A, several POSS are tried to be added into the polyurethane resin respectively, and as a result, the softening temperature, the mechanical property and the hydrophobic property of the resin are all improved.
Although the POSS polyacrylate resin composite material has been reported, the main research only relates to that POSS containing vinyl and acrylic acid are subjected to emulsion polymerization to form microcapsules, and then the microcapsules are mixed with epoxy resin, filler and the like to prepare an anticorrosive coating (CN 111205745B); or vinyl POSS and methyl methacrylate are subjected to solution polymerization to prepare the thermosetting plastic (CN 113881048A). CN109535350A discloses a technology of using vinyl POSS compounded fluorine-containing polyacrylate water dispersion for coating, and finds that the vinyl POSS can only be grafted on the surface of latex particles and can not form cross-linking; zhang Cambridge reports (coating industry, 2007, 37, 10-18) a synthesis method of an acrylate emulsion with vinyl POSS and characterizes curves of particle size and emulsion gel fraction increasing with POSS addition amount; however, the particle size increase of the emulsion was still not significant (about 12%) when the POSS addition was increased to 5%. In summary, vinyl POSS has limited effect on improving emulsion properties.
Reactivity ratios of ethylene with acrylates may be one of the reasons for the limitations of the use of the above-described vinyl POSS. The reactivity ratio is the ratio of the chain growth rate constants of the homopolymer and the copolymer in the copolymerization of the monomers, and the larger the reactivity ratio of the monomers, the stronger the tendency to self-polymerize, and the less easily the copolymer system is formed (Ministry of civil engineering, macromolecules, 2021,1, 61-65). The reactivity ratios of ethylene and methyl methacrylate are 0.20 (ethylene) and 17.00 (methyl methacrylate) respectively (the performance and application of polymer emulsion synthesis principle, cao Tongye). While the acrylic group is similar in structure to methyl methacrylate, taking methyl acrylate as an example, the reactivity ratios of the acrylic group to methyl methacrylate are 0.34 (methyl acrylate) and 1.69 (methyl methacrylate), respectively, indicating that POSS having an acrylic group is more likely to form a copolymer with an acrylate/methacrylate monomer than POSS having a vinyl group in the polymerization reaction.
The method for preparing the POSS composite polyacrylate aqueous dispersion by adding POSS with acrylic group and the application thereof have not been reported. According to the invention, the POSS composite polyacrylate aqueous dispersion is synthesized by using methacrylate, acrylate, styrene and the like as monomers and acrylic-based polyhedral oligomeric silsesquioxane as a POSS cross-linking agent through an emulsion polymerization method. Under the condition that the adding amount of POSS is less than 0.5 percent, the particle size of the emulsion particles is increased by 33 percent compared with the condition that POSS is not added, the weight-average molecular weight is increased by 80 percent, the mass loss of a paint film after the treatment of organic solvent ethyl acetate is only 0.7 percent, and the mass loss is remarkably reduced by 40.9 percent compared with a control group which is not added with POSS. After being prepared into a coating, the POSS composite polyacrylate water dispersion has the advantages of low viscosity, easy construction, scratch resistance of a paint film and good chemical resistance.
Disclosure of Invention
The invention provides a POSS composite polyacrylate aqueous dispersion and a preparation method thereof.
A preparation method of POSS composite polyacrylate water dispersion comprises the following steps:
1.1 Adding an emulsifier 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 chemical pure products purchased from Schenss reagent company;
the POSS cross-linking agent is acrylic group-cage polysilsesquioxane, the CAS number is 1620202-27-28, and the purity is 90%;
the emulsifier is one or two of a non-reactive emulsifier and a reactive emulsifier, and the non-reactive emulsifier is selected from: sodium dodecyl sulfate and sodium dodecyl benzene sulfonate are chemically pure products purchased from Schench reagent company; novelusion 390, novelusion 3203N, novelusion 3208K, novelusion 3400K, novelusion AG35N, novelusion ZS27N, novelusion ZS37A, novelusion PA89N, novelusion LE73N, or novelusion S03N, products available from Sasol corporation; the product RHODACAL DS-4AP purchased from Solvay corporation. The reactive emulsifier is selected from: the products ADEKA REASOAP SE-10N, ADEKA REASOAP SR-10, ADEKA REASOAP SR-1025, ADEKA REASOAP ER-10, ADEKA REASOAP ER-20, ADEKA REASOAP ER-30 or ADEKA REASOAP PP-70 purchased from ADEKA corporation;
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 from Henshi reagent company;
1.3 Preparing sodium bicarbonate and part of emulsifier into solution C by using deionized water;
the sodium bicarbonate is a chemical pure product purchased from Schensz reagent company;
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 which are chemical pure products purchased from the Schensts reagent company;
1.5 Preparing an oxidant into a 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 Schensz reagent company.
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 a product purchased from Br 7803ggemann Chemical company;
1.7 And (2) adding deionized water into the pH regulator according to the mass ratio of the regulator to water of 1:1 diluted solution G.
The pH regulator is dimethyl ethanolamine or 28% ammonia water, and is a chemical pure product purchased from Schench reagent company.
2. Polymerisation process
Solution C was added to a 1L jacketed glass reactor equipped with a condenser, thermometer and stirring paddle, the temperature of the kettle was raised to 80-85 ℃ after nitrogen substitution, and stirring was turned on (stirring paddle diameter D =60 mm, rotation speed 200-300 RPM). Taking 5% by mass of the monomer pre-emulsion A as a seed, adding the seed into a reaction kettle, stirring for 3-5 min, and then adding the solution B; stirring for 20-30 min. Then, simultaneously dripping the monomer pre-emulsion A and the solution D, and adding the residual monomer pre-emulsion A at a constant speed within 3 h; solution D was added at constant rate over 3h 15 min. After the dripping is finished, the temperature of the kettle is reduced to 60 ℃, and the solution E and the solution F are dripped simultaneously and are dripped within 30 min. And after dripping, cooling the kettle to 40 ℃, adding the solution G at one time, stirring for 5-10 min, adjusting the pH value to 8-9, and discharging through a 200-mesh filter screen to obtain the POSS composite polyacrylate water dispersion.
According to the invention, the preparation of the POSS composite polyacrylate aqueous dispersion is realized by using POSS with acrylic acid groups for the first time, and the POSS composite polyacrylate aqueous dispersion is successfully applied to a coating formula. The above-described POSS composite polyacrylate aqueous dispersions have significantly higher crosslink density, larger particle size, and higher weight average molecular weight than the control without POSS added. The coating prepared by using the POSS composite polyacrylate water dispersion can form a paint film which is remarkably excellent, particularly has better chemical resistance and hardness, and has more advantages compared with a control group without POSS.
Description of the preferred embodiment
The following examples are given to further illustrate embodiments of the present invention. The examples are intended to describe the invention in detail and should not be construed as limiting the invention.
2.67 g of RHODACAL DS-4AP and 1.50 g of ADEKA REASOAP SR-10 are added into 175.50 g of deionized water, 210.00 g of methyl methacrylate, 30.00 g of styrene, 60.00 g of isooctyl acrylate and 0.90 g of acrylic acid-cage polysilsesquioxane are sequentially added, and the mixture is stirred at high speed for 60 minutes to prepare stable monomer pre-emulsion A;
preparing 0.60 g of initiator ammonium persulfate into a solution B by using 15.00 g of deionized water;
preparing solution C from 0.60 g of sodium bicarbonate and 4.00 g of RHODACAL DS-4AP with 180.00 g of deionized water;
preparing 0.96 g of initiator ammonium persulfate into a solution D by using 36.00 g of deionized water;
preparing solution E from 0.42 g of 70% tert-butyl hydroperoxide aqueous solution and 6.00 g of deionized water;
preparing solution F from 0.36 g of BRUGGOLITE FF6M and 6.00 g of deionized water;
3.00G of pH regulator dimethylethanolamine was mixed with 3.00G of deionized water to prepare a solution G.
The solution C was added to a 1L jacketed glass reaction kettle equipped with a condenser, thermometer and stirring paddle, the kettle temperature was raised to 80-85 ℃ after nitrogen substitution, and stirring was turned on (stirring paddle diameter D =60 mm, rotation speed 200-300 RPM). Taking 5% by mass of the monomer pre-emulsion A as a seed, adding the seed into a reaction kettle, stirring for 3-5 min, and then adding the solution B; stirring for 20-30 min. Then, simultaneously dripping the monomer pre-emulsion A and the solution D, and adding the rest monomer pre-emulsion A at a constant speed within 3 h; solution D was added at constant rate over 3h 15 min. After the dripping is finished, the temperature of the kettle is reduced to 60 ℃, and the solution E and the solution F are dripped simultaneously and are dripped within 30 min. And after dripping, cooling the kettle to 40 ℃, adding the solution G at one time, stirring for 5-10 min, adjusting the pH value to 8-9, and discharging through a 200-mesh filter screen to obtain the POSS composite polyacrylate aqueous dispersion A-1.
A Zetasizer Nano SZ type laser particle size analyzer is used for carrying out particle size distribution test on the diluted polyacrylate water dispersion A-1 (the concentration after dilution is 4.0g/L, the experiment temperature is 25 ℃), the average value of the three test results is 178.83 nm, and the average PdI =0.247;
a-1 was subjected to freeze-drying, and the obtained solid had a weight-average molecular mass of 50942 g/mol as measured by Gel Permeation Chromatography (GPC).
Adding 0.60 g of sodium dodecyl benzene sulfonate and 1.50 g of ADEKA REASOAP SR-10 into 175.50 g of deionized water, sequentially adding 210.00 g of methyl methacrylate, 30.00 g of styrene, 60.00 g of isooctyl acrylate and 0.90 g of acrylic acid group-cage polysilsesquioxane, and stirring at a high speed for 60 minutes to prepare a stable monomer pre-emulsion A;
preparing 0.60 g of initiator ammonium persulfate into a solution B by using 15.00 g of deionized water;
preparing solution C from 0.60 g of sodium bicarbonate and 0.90 g of sodium dodecyl benzene sulfonate by using 180.00 g of deionized water;
preparing solution D from 0.96 g of initiator potassium persulfate and 36.00 g of deionized water;
preparing 0.15 g of 70% tert-butyl hydroperoxide aqueous solution into a solution E by using 6.00 g of deionized water;
preparing solution F from 0.36 g of BRUGGOLITE FF6M and 6.00 g of deionized water;
3.00G of pH regulator dimethylethanolamine was mixed with 3.00G of deionized water to prepare a solution G.
The solution C was added to a 1L jacketed glass reaction kettle equipped with a condenser, thermometer and stirring paddle, the kettle temperature was raised to 80-85 ℃ after nitrogen substitution, and stirring was turned on (stirring paddle diameter D =60 mm, rotation speed 200-300 RPM). Taking 5% by mass of the monomer pre-emulsion A as a seed, adding the seed into a reaction kettle, stirring for 3-5 min, and then adding the solution B; stirring for 20-30 min. Then, simultaneously dripping the monomer pre-emulsion A and the solution D, and adding the residual monomer pre-emulsion A at a constant speed within 3 h; add solution D at constant speed over 3h 15 min. After the dripping is finished, the temperature of the kettle is reduced to 60 ℃, and the solution E and the solution F are dripped simultaneously and are dripped within 30 min. And after dripping, cooling the kettle to 40 ℃, adding the solution G at one time, stirring for 5-10 min, adjusting the pH value to 8-9, and discharging through a 200-mesh filter screen to obtain the POSS composite polyacrylate aqueous dispersion A-2.
A Zetasizer Nano SZ type laser particle sizer is used for carrying out particle size distribution test on the diluted polyacrylate water dispersion A-2 (the concentration after dilution is 4.0g/L, the experiment temperature is 25 ℃), the average value of the three test results is 180.16 nm, and the average PdI =0.251;
a-2 was subjected to freeze-drying treatment, and the obtained solid had a weight-average molecular mass of 50877 g/mol as measured by Gel Permeation Chromatography (GPC).
2.67 g of RHODACAL DS-4AP and 1.50 g of ADEKA REASOAP SR-10 are added into 175.50 g of deionized water, 210.00 g of methyl methacrylate, 30.00 g of styrene and 60.00 g of isooctyl acrylate are sequentially added, and the mixture is stirred at high speed for 60 minutes to prepare a stable monomer pre-emulsion A;
preparing 0.60 g of initiator ammonium persulfate into a solution B by using 15.00 g of deionized water;
preparing solution C from 0.60 g of sodium bicarbonate and 4.00 g of RHODACAL DS-4AP with 180.00 g of deionized water;
preparing 0.96 g of initiator ammonium persulfate into a solution D by using 36.00 g of deionized water;
preparing solution E from 0.42 g of 70% tert-butyl hydroperoxide aqueous solution and 6.00 g of deionized water;
preparing solution F from 0.36 g of BRUGGOLITE FF6M and 6.00 g of deionized water;
3.00G of pH regulator dimethylethanolamine was mixed with 3.00G of deionized water to prepare a solution G.
The solution C was added to a 1L jacketed glass reaction kettle equipped with a condenser, thermometer and stirring paddle, the kettle temperature was raised to 80-85 ℃ after nitrogen substitution, and stirring was turned on (stirring paddle diameter D =60 mm, rotation speed 200-300 RPM). Taking 5% by mass of the monomer pre-emulsion A as a seed, adding the seed into a reaction kettle, stirring for 3-5 min, and then adding the solution B; stirring for 20-30 min. Then, simultaneously dripping the monomer pre-emulsion A and the solution D, and adding the residual monomer pre-emulsion A at a constant speed within 3 h; solution D was added at constant rate over 3h 15 min. After the dripping is finished, the temperature of the kettle is reduced to 60 ℃, and the solution E and the solution F are dripped simultaneously and are dripped within 30 min. After dripping, cooling the kettle to 40 ℃, adding the solution G at one time, stirring for 5-10 min, adjusting the pH value to 8-9, and discharging through a 200-mesh filter screen to obtain the polyacrylate water dispersion A-0.
A Zetasizer Nano SZ type laser particle sizer is used for carrying out particle size distribution test on the diluted polyacrylate water dispersion A-0 (the concentration after dilution is 4.0g/L, the experimental temperature is 25 ℃), the average value of the three test results is 115.33 nm, and the average PdI =0.041;
a-1 was subjected to freeze-drying treatment, and the obtained solid had a weight-average molecular mass of 28251 g/mol as measured by Gel Permeation Chromatography (GPC).
Wherein, the coating 1 is prepared by taking polyacrylate water dispersion A-0 (blank control) obtained by a control test as a raw material; the coating 2 is a coating (experimental control) prepared by taking polyacrylate aqueous dispersion A-0 and 0.12% of acrylic group-cage polysilsesquioxane additionally added after polymerization as raw materials, and in the experimental control group, the acrylic group-cage polysilsesquioxane is added in the coating preparation stage and is physically mixed, and is not connected with a polymer through a covalent bond; the paint 3 was a paint (experimental group) prepared from the POSS complex polyacrylate aqueous dispersion A-1 obtained in example 1.
In the three coating formulas, the mass ratio of the film-forming assistant to the dipropylene glycol methyl ether is 1:1, and the leveling agent is BYK-333.
In the preparation process of the coating, the ingredients are accurately weighed into a 50 mL centrifuge tube, vortexed for 5 min and fully mixed, ultrasonically treated for 1min for defoaming, a 100-micron uniform liquid film is scraped on a clean glass plate by a BGD206 universal four-side preparation device, and the clean glass plate is dried in an oven at 85 ℃ for 24 h and then the resistance and the hardness of the coating are measured.
Water resistance: the test solution is distilled water, the middle part of each plate is taken in the test area, absorbent paper is placed on the test area, a glass cover is added for sealing, and the filter paper is kept wet in the test process. The experimental time is 24 h, and the test is carried out after the test is placed for 24 h.
Alkali resistance: the test solution is 10% of Na 2 CO 3 Solution, test area the middle part of each plate was taken, absorbent paper was placed on the test area and sealed with a glass cover, and the filter paper was kept wet during the experiment. The experimental time is 24 h, and the test is observed after the test is placed for 1 h.
Alcohol resistance: the test solution is 50% (volume fraction) ethanol solution, the middle part of each plate is taken as a test area, absorbent paper is placed on the test area, a glass cover is added for sealing, and the filter paper is kept wet in the test process. The experimental time is 24 h, and the test is observed after the test is placed for 1 h.
Acid resistance: the test solution is 10% acetic acid solution, the middle part of each plate is taken as a test area, absorbent paper is placed on the test area, a glass cover is added for sealing, and the filter paper is kept wet in the test process. The experimental time is 24 h, and the observation is carried out after the experiment is placed for 24 h.
The rating standard refers to the part 1 of GB/T4893.1-2021 home surface paint film physical and chemical property test: cold liquid resistance assay method ":
grade 1 with no change.
The test area is indistinguishable from the adjacent area.
Slight change in level 2.
The test area is distinguishable from adjacent areas, such as fading, staining and discoloration, only when the light source is projected onto the test surface and reflected into the eye of the observer.
The surface structure was tested without changes such as swelling, fiber protrusions, cracks, blisters.
Grade 3 moderate change.
The test area is distinguishable from adjacent areas, visible in several directions, such as fading, staining and discoloration.
The surface structure was tested without changes such as swelling, fiber protrusions, cracks, blisters.
Grade 4 obvious change.
Visible in all visible directions, the test area is clearly distinguishable from adjacent areas, such as fading, lustre and discolouration.
And/or slight changes in the test surface structure such as swelling, fiber protrusions, cracks, blisters.
Severe grade 5 change.
The test surface structure changed significantly.
And/or fade, shine and discoloration.
And/or the surface material is removed in whole or in part.
And/or filter paper stuck to the surface.
Pencil hardness: the determination is carried out by referring to GBT 6739-2006 paint film hardness determination by a colored paint and varnish pencil method.
Indentation hardness; the determination is carried out by referring to GB/T9275-2008 Bake Holtz color paint and varnish indentation test.
The results of the measurements are given in the following table:
the experimental results show that compared with the blank control and the experimental control, the experimental group has obvious advantages in the physicochemical properties of the coating, such as hardness, scratch resistance, chemical resistance and the like.
Accurately weighing 0.50-1.00 g of a dry paint film formed by the paint 1 and the paint 3 on a filter paper sheet, and recording the dry paint film as m 0 After extraction in a Soxhlet extractor for 24 h with 100.00 g of ethyl acetate as extraction solvent, the residue state was recorded. Drying in an oven at 80 deg.C for 1h, weighing the residue and recording as m 1 Calculating the mass loss rate according to the following formula:
from the results of example 4, it can be seen that coatings prepared based on POSS complex polyacrylate aqueous dispersions of larger particle size, higher molecular weight, higher degree of crosslinking have superior hardness and chemical resistance and significantly less mass loss rate than the control.
Claims (5)
1. An aqueous POSS complex polyacrylate dispersion, characterized by: water is used 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; acrylic group-cage polysilsesquioxane with CAS number of 1620202-27-28 is used as a POSS crosslinking agent; the POSS composite polyacrylate aqueous dispersion is obtained by taking one or two of non-reactive emulsifier and reactive emulsifier as emulsifier and persulfate as initiator and adopting emulsion polymerization process, wherein the polymerization process comprises post-treatment and pH regulation process.
2. The POSS complex polyacrylate water dispersion of claim 1 wherein:
the raw materials are adopted by the following mass percentage: 5-10% of soft monomer, 30-40% of hard monomer, 0.1-0.5% of POSS cross-linking agent, 0.2-1.0% of initiator, 0.3-1.0% of emulsifier, 0-0.1% of sodium bicarbonate, 0-0.1% of post-treating agent, 0.3-1.0% of pH regulator and 50-60% of deionized water;
the initiator is ammonium persulfate or potassium persulfate;
the adopted non-reactive emulsifier is one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, NOVELUTION 390, NOVELUTION 3203N, NOVELUTION 3208K, NOVELUTION 3400K, NOVELUTION AG35N, NOVELUTION ZS27N, NOVELUTION ZS37A, NOVELUTION PA89N, NOVELUTION LE73N, NOVELUTION S03N and RHODACAL DS-4AP, and the adopted reactive emulsifier is one or more of ADEKA REASE-10N, ADEKA REASOAP SR-10, ADEKA REASOAP SR-1025, ADEKA REAER-10, ADEKA SOAP-20, ADEKA SOAP-30 and ADEKA SOAP-70;
the adopted post-treatment agent comprises an oxidizing agent and a reducing agent, wherein the oxidizing agent is hydrogen peroxide or tert-butyl hydrogen peroxide, and the reducing agent is sodium bisulfite or BRUGGOLITE FF6M;
the pH regulator is dimethylethanolamine or ammonia water with the mass concentration of 28 percent.
3. A method of making the POSS composite polyacrylate aqueous dispersion of claim 1 comprising the steps of:
preparing a solution: adding a part of emulsifier into water, sequentially adding hard monomer, soft monomer and POSS cross-linking agent, and stirring at high speed for 30-60 minutes 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 from sodium bicarbonate and part of emulsifier by using deionized water;
preparing a part of initiator into a solution D with the mass concentration of 2-3% by using deionized water;
preparing an oxidant into a solution E with the mass concentration of 4-6% by using deionized water;
preparing a reducing agent into a solution F with the mass concentration of 4-6% by using deionized water;
and (2) adding deionized water into the pH regulator according to the mass ratio of the regulator to the water of 1:1 diluted solution G;
adding the solution C into a 1L jacketed glass reaction kettle provided with a condensing tube, a thermometer and a stirring paddle, replacing with nitrogen, heating the kettle to 80-85 ℃, and starting stirring; taking 5% by mass of the monomer pre-emulsion A as a seed, adding the seed into a reaction kettle, stirring for 3-5 min, and then adding the solution B; continuously stirring for 20-30 min; then, simultaneously dripping the monomer pre-emulsion A and the solution D, and adding the residual monomer pre-emulsion A at a constant speed within 3 h; adding the solution D at a constant speed within 3h 15 min; after dripping, reducing the temperature of the kettle to 60 ℃, and dripping the solution E and the solution F within 30 min; and after dripping, cooling the kettle to 40 ℃, adding the solution G at one time, stirring for 5-10 min, adjusting the pH value to 8-9, and discharging through a 200-mesh filter screen to obtain the POSS composite polyacrylate water dispersion.
4. Use of the aqueous POSS complex polyacrylate dispersion of claim 1 for the production of coatings suitable for substrates including wood, metal, plastic, glass and minerals.
5. A coating comprising the POSS complex polyacrylate water dispersion of claim 1.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106947030A (en) * | 2017-03-27 | 2017-07-14 | 广东千色花化工有限公司 | POSS base hydridization polyacrylate dispersions and preparation method and application |
| CN111410712A (en) * | 2020-04-21 | 2020-07-14 | 陕西科技大学 | POSS (polyhedral oligomeric silsesquioxane) modified polyacrylate fluorine-free waterproof agent and preparation method thereof |
| CN112300334A (en) * | 2020-12-02 | 2021-02-02 | 陕西科技大学 | POSS/organosilicon modified polyacrylate fluorine-free waterproof agent and preparation method thereof |
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- 2023-03-10 CN CN202310229066.7A patent/CN115947904A/en not_active Withdrawn
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106947030A (en) * | 2017-03-27 | 2017-07-14 | 广东千色花化工有限公司 | POSS base hydridization polyacrylate dispersions and preparation method and application |
| CN111410712A (en) * | 2020-04-21 | 2020-07-14 | 陕西科技大学 | POSS (polyhedral oligomeric silsesquioxane) modified polyacrylate fluorine-free waterproof agent and preparation method thereof |
| CN112300334A (en) * | 2020-12-02 | 2021-02-02 | 陕西科技大学 | POSS/organosilicon modified polyacrylate fluorine-free waterproof agent and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 张媛媛;张雪芳;张彩云;高俊刚;: "MAP-POSS改性丙烯酸酯/苯乙烯乳胶的合成与表征", 涂料工业 * |
| 李新武;邹其超;周娟;张世玲;武利民;: "聚苯乙烯-丙烯酸丁酯/八异辛基倍半硅氧烷复合乳液的制备及稳定性研究", 胶体与聚合物 * |
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