CN117866514B - Preparation method of waterproof unsaturated polyester coating for stone - Google Patents
Preparation method of waterproof unsaturated polyester coating for stone Download PDFInfo
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- CN117866514B CN117866514B CN202410252081.8A CN202410252081A CN117866514B CN 117866514 B CN117866514 B CN 117866514B CN 202410252081 A CN202410252081 A CN 202410252081A CN 117866514 B CN117866514 B CN 117866514B
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- 238000000576 coating method Methods 0.000 title claims abstract description 71
- 239000011248 coating agent Substances 0.000 title claims abstract description 69
- 239000004575 stone Substances 0.000 title claims abstract description 42
- 229920006305 unsaturated polyester Polymers 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000004005 microsphere Substances 0.000 claims abstract description 35
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- -1 phosphate compound Chemical class 0.000 claims abstract description 27
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 19
- 229920005989 resin Polymers 0.000 claims abstract description 19
- 239000011347 resin Substances 0.000 claims abstract description 19
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 16
- 239000010452 phosphate Substances 0.000 claims abstract description 16
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 14
- DCXZWVLJCYXHDV-UHFFFAOYSA-N (4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluoro-2-hydroxyundecyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)CC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F DCXZWVLJCYXHDV-UHFFFAOYSA-N 0.000 claims abstract description 11
- YIWBKTYVIOLLRI-UHFFFAOYSA-N tert-butyl-dimethyl-(1-phenylethenoxy)silane Chemical compound CC(C)(C)[Si](C)(C)OC(=C)C1=CC=CC=C1 YIWBKTYVIOLLRI-UHFFFAOYSA-N 0.000 claims abstract description 11
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 7
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000008367 deionised water Substances 0.000 claims description 41
- 229910021641 deionized water Inorganic materials 0.000 claims description 41
- 238000001816 cooling Methods 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 26
- 239000004579 marble Substances 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 22
- 150000007524 organic acids Chemical class 0.000 claims description 21
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 20
- 229910052731 fluorine Inorganic materials 0.000 claims description 20
- 239000011737 fluorine Substances 0.000 claims description 20
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 14
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- VEUUMBGHMNQHGO-UHFFFAOYSA-N ethyl chloroacetate Chemical compound CCOC(=O)CCl VEUUMBGHMNQHGO-UHFFFAOYSA-N 0.000 claims description 12
- 239000007921 spray Substances 0.000 claims description 12
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 12
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 238000007654 immersion Methods 0.000 claims description 11
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 8
- 150000002191 fatty alcohols Chemical class 0.000 claims description 8
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 8
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 6
- 244000137852 Petrea volubilis Species 0.000 claims description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 239000000428 dust Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- QEWYKACRFQMRMB-UHFFFAOYSA-N fluoroacetic acid Chemical compound OC(=O)CF QEWYKACRFQMRMB-UHFFFAOYSA-N 0.000 claims description 6
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 238000005498 polishing Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- RXMRGBVLCSYIBO-UHFFFAOYSA-M tetramethylazanium;iodide Chemical compound [I-].C[N+](C)(C)C RXMRGBVLCSYIBO-UHFFFAOYSA-M 0.000 claims description 6
- 229920006337 unsaturated polyester resin Polymers 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical group CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000003431 cross linking reagent Substances 0.000 claims description 5
- PBWZKZYHONABLN-UHFFFAOYSA-N difluoroacetic acid Chemical compound OC(=O)C(F)F PBWZKZYHONABLN-UHFFFAOYSA-N 0.000 claims description 5
- 230000003301 hydrolyzing effect Effects 0.000 claims description 5
- MHJHGMSWCVGANA-NSCUHMNNSA-N (e)-4,5-dihydroxyhex-2-enoic acid Chemical compound CC(O)C(O)\C=C\C(O)=O MHJHGMSWCVGANA-NSCUHMNNSA-N 0.000 claims description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 230000003078 antioxidant effect Effects 0.000 claims description 4
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical class [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 claims description 4
- 239000003112 inhibitor Substances 0.000 claims description 4
- 239000003973 paint Substances 0.000 claims description 3
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 238000003847 radiation curing Methods 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 9
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 8
- 241000894006 Bacteria Species 0.000 abstract description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 239000001361 adipic acid Substances 0.000 abstract description 2
- 235000011037 adipic acid Nutrition 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 14
- 229920001558 organosilicon polymer Polymers 0.000 description 14
- 239000000203 mixture Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 238000001723 curing Methods 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- MHJHGMSWCVGANA-UHFFFAOYSA-N 4,5-dihydroxyhex-2-enoic acid Chemical compound CC(O)C(O)C=CC(O)=O MHJHGMSWCVGANA-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- OFJYXXWNRKJMJU-UHFFFAOYSA-N [F].FC(C(=O)O)F Chemical compound [F].FC(C(=O)O)F OFJYXXWNRKJMJU-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- OMRZUNKNTXPTRJ-UHFFFAOYSA-N oxygen(2-) titanium(4+) hydrofluoride Chemical compound F.[O-2].[O-2].[Ti+4] OMRZUNKNTXPTRJ-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- PKDCQJMRWCHQOH-UHFFFAOYSA-N triethoxysilicon Chemical compound CCO[Si](OCC)OCC PKDCQJMRWCHQOH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a preparation method of a waterproof unsaturated polyester coating for stone, and relates to the technical field of coatings. The invention is prepared by polymerizing micron quaternized modified organosilicon polymeric microspheres with tert-butyl dimethyl ((1-phenylvinyl) oxy) silane and 3-perfluorooctyl-2-hydroxypropyl methacrylate to form modified fluorosilicone resin, and adding nano fluoridized titanium dioxide in the polymerization process to achieve micro-nano coarse structure, thereby effectively improving hydrophobicity and simultaneously realizing synergistic antibacterial effect of quaternary ammonium salt and titanium dioxide; the N- (hydroxyethyl) -N, N-bis (trimethoxysilylpropyl) amine reacts with phosphorus pentoxide to generate a phosphate compound, so that the hydrophobicity and the adhesive force of the coating are improved, and meanwhile, the unsaturated polyester prepared from adipic acid and propylene glycol is compatible with the fluorosilicone resin, so that the stability of the coating is improved. The coating prepared by the invention has the effects of water resistance, bacteria resistance and falling resistance.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to a preparation method of a waterproof unsaturated polyester coating for stone.
Background
Stone is commonly used in daily life, and various hotels, guesthouses, offices and most of households can use various stone to lay walls, floors, windowsills, kitchens, cooking surfaces and the like. The surface of the stone material has no waterproof and antifouling functions, and the problems of water seepage, dirt seepage, dark luster and the like are easy to occur; in such a case, professional cleaning companies are usually required to renew the stone surface, which brings additional use cost to users.
In daily life, stone decoration is commonly used in places with more water, such as toilets, kitchens and the like. In particular, in the south, the air humidity is high for a long time in a specific season, so that the service life of the stone is suddenly reduced. The stone material is corroded by water for a long time, and bacteria are easy to breed when the stone material is polluted, so that research and development are carried out on the stone material coating. The stone waterproof paint is one of stone protection technologies and has wide application in the modern stone industry. However, when the traditional stone protective coating is applied to stone floor tiles, stone furniture, table tops and the like, the coating is often insufficient in waterproof performance or antibacterial performance, so that the coating has a large influence on the living environment of households, is easy to fall off, and cannot meet the requirements of users for long-term protection life. The invention innovates a preparation method of waterproof unsaturated polyester coating for stone material to solve the problems.
Disclosure of Invention
The invention aims to provide a preparation method of a waterproof unsaturated polyester coating for stone materials, which aims to solve the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme: the preparation method of the waterproof unsaturated polyester coating for the stone comprises the following steps:
(1) Mixing N1- [ (4-vinylphenyl methyl ] -N2-3- (triethoxysilyl) propyl ] -1, 2-ethylenediamine with deionized water according to a proportion, adding hydrochloric acid until the pH value of the solution is 4-6, reacting at 25 ℃ for 5 hours, adding ammonia water until the pH value of the solution is 6-11, heating to 30 ℃, continuing to react for 3 hours, respectively washing 3 times with deionized water and ethanol, filtering, taking solid, drying at 150 ℃ for 10 hours to obtain organosilicon polymer microspheres with the particle size of 1-15 mu m, dissolving 2-4 parts of ethyl chloroacetate in 15-20 parts of isopropanol, adding 10-14 parts of organosilicon polymer microspheres, reacting at 75 ℃ for 4-6 hours under the protection of nitrogen, adding 5-7 parts of ethyl chloroacetate, continuing to react for 2 hours, and distilling under reduced pressure until no liquid exists to obtain quaternized modified organosilicon polymer microspheres;
(2) 1-2 parts of fluorine-containing organic acid is dissolved in 10 parts of deionized water to obtain a fluorine-containing organic acid aqueous solution, then titanium dioxide powder with the grain diameter of 200-300nm is immersed in the fluorine-containing organic acid aqueous solution according to the feed liquid ratio of 1:10 for 0.5-48h at the temperature of 0-50 ℃, and after drying, heat treatment is carried out for 20-30min at the temperature of 80-160 ℃, and finally cooling is carried out to 25 ℃ to obtain nano-fluorinated titanium dioxide; adding 8-10 parts of methyl methacrylate and 12-14 parts of tert-butyldimethyl ((1-phenylvinyl) oxy) silane after 30 parts of deionized water, 0.6-1 part of fatty alcohol polyoxyethylene ether and 0.1-0.5 part of sodium dodecyl sulfate are stirred and dissolved, reacting for 30min at 50 ℃, adding 0.1-0.3 part of initiator, adding 6-10 parts of quaternized modified organosilicon polymeric microspheres, heating to 80 ℃ for reacting for 2h, then adding 8-10 parts of methyl methacrylate, 6-8 parts of 3-perfluorooctyl-2-hydroxypropyl methacrylate and 0.1-0.3 part of initiator, reacting for 2h at 80 ℃, adding 4-6 parts of nano fluorinated titanium dioxide, stirring for 20min at 500rpm, and cooling to room temperature to obtain modified fluorosilicon resin;
(3) Mixing 8-10 parts of N- (hydroxyethyl) -N, N-bis (trimethoxysilylpropyl) amine and 3-4 parts of phosphorus pentoxide, heating to 70-90 ℃, reacting for 4-6 hours at a temperature of 60-80 ℃, adding 1-2 parts of deionized water, hydrolyzing for 2 hours, and adding potassium hydroxide until the pH value of the solution reaches 7.5-8 to obtain a phosphate compound; under the protection of nitrogen, mixing 10-15 parts of 4, 5-dihydroxy-2-hexenoic acid, 18-20 parts of propylene glycol, 25-30 parts of 2-hexene-1, 6-diacid and 0.3-0.5 part of antioxidant, heating to 180 ℃ for 3 hours, preserving heat for 2 hours, maintaining at a vacuum degree of 0.040MPa for 0.5-1 hour, cooling to 150 ℃, adding 0.3-0.5 part of polymerization inhibitor, continuously cooling to 95 ℃, adding 12-14 parts of glycidyl methacrylate and 0.3-0.5 part of tetramethyl ammonium iodide, continuously reacting for 30min, cooling to 65 ℃, adding 8-10 parts of N, N-dimethylethanolamine, stirring for 15min at 800r/min, adding 12-16 parts of phosphate compound and 130-140 parts of water, and stirring for 30min at 2000-3000r/min to obtain unsaturated polyester;
(4) Mixing 54-59 parts of unsaturated polyester, 28-33 parts of cross-linking agent and 7-13 parts of retarder, stirring for 2 hours at 500-600r/min, adding 24-28 parts of modified fluorosilicone resin and 50-60 parts of deionized water, and stirring for 3 hours at 200-300r/min to obtain waterproof unsaturated polyester resin paint; uniformly polishing the surface of the marble Dan Gongjian once by using 300-mesh sand paper, and cleaning dust on the surface and edges of the marble by using high-pressure air; and uniformly spraying a layer of coating on the surface of the marble workpiece by using a spray gun, and carrying out radiation curing on the sprayed marble substrate under the irradiation of 1000W ultraviolet light for 20-60s to obtain the waterproof unsaturated polyester coating for the stone.
Further, the proportion of the step (1) is 4-6 parts of N1- [ (4-vinylphenylmethyl ] -N2-3- (triethoxysilyl) propyl ] -1, 2-ethylenediamine and 10 parts of deionized water.
Further, the reduced pressure distillation conditions in the step (1) are as follows: the temperature is 145-150 ℃ and the vacuum degree is 0.01MPa.
Further, the drying condition in the step (2) is that the powder is dried for 3 hours at 25 ℃ after the impregnation is completed.
Further, the fluorine-containing organic acid in the step (2) is one of trifluoroacetic acid, difluoroacetic acid and monofluoroacetic acid.
Further, the initiator in the step (2) is potassium persulfate.
Further, in the step (3), the antioxidant is triphenyl phosphite.
Further, in the step (3), the polymerization inhibitor is hydroquinone.
Further, the cross-linking agent in the step (4) is styrene or methyl methacrylate; the retarder is methyl styrene or 3-phenylpropene; a spray gun with a nozzle diameter of 1.0mm and an air pressure of 2-4kg/cm was used.
Further, the thickness of the coating in the step (4) is 120-300 μm.
Compared with the prior art, the invention has the following beneficial effects:
The invention utilizes the mixture of the modified fluorine silicon resin, the phosphate ester active agent, the unsaturated polyester and the like to form the composite coating so as to realize the effects of water resistance, bacteria resistance and falling resistance.
Firstly, N1- [ (4-vinylphenyl methyl ] -N2-3- (triethoxy silicon) propyl ] -1, 2-ethylenediamine is subjected to hydrolytic condensation to polymerize into micron-level organosilicon polymeric microspheres, amino groups on the surfaces of the microspheres are quaternized through ethyl chloroacetate, the quaternized organosilicon polymeric microspheres can reduce the surface energy, improve the hydrophobicity of the coating, adsorb negatively charged bacteria and endow the coating with antibacterial effect, and then the coating is polymerized with tert-butyldimethyl ((1-phenylvinyl) oxy) silane and 3-perfluorooctyl-2-hydroxypropyl methacrylate by means of double bonds of the organosilicon polymeric microspheres to form fluorosilicon resin, so that the waterproof effect of the coating is further enhanced, fluorinated nano titanium dioxide is added in the polymerization process, the fluorinated nano titanium dioxide and the organosilicon polymeric microspheres form a micro-nano coarse structure, the hydrophobic effect of the coating is enhanced, and the titanium dioxide is excited by light to be activated to act cooperatively with the quaternized organosilicon polymeric microspheres, so that the antibacterial effect of the coating is effectively improved.
Secondly, the invention utilizes the phosphate compound generated by the reaction of N- (hydroxyethyl) -N, N-bis (trimethoxy-silylpropyl) amine and phosphorus pentoxide, the molecular structure of the phosphate compound has long-chain hydrophobic groups and hydrophilic groups, and has high surface activity and interface performance, so that the coating has excellent hydrophobicity, and the silicon-oxygen bond on the organosilicon group in the phosphate compound can be adsorbed and reacted with the free active group on the surface of the calcium carbonate of the base stone, thereby enhancing the adhesive force of the coating and the stone and achieving the anti-falling effect; in addition, the phosphate compound is respectively bonded with unsaturated polyester and fluorosilicone resin hydrogen bond prepared by mixing the mixture of the polybasic acid and the adipic acid and the mixture of the polyhydric alcohol and the propylene glycol, so that compatibility of the unsaturated polyester and the fluorosilicone resin hydrogen bond is promoted, long chains are mutually entangled, the stability of the coating is improved, and the adhesive force of the coating is further improved while a super-hydrophobic coating is formed.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In order to more clearly illustrate the method provided by the invention, the following examples are used for describing in detail the method for testing each index of the waterproof unsaturated polyester coating for stone material, which is prepared in the following examples, as follows:
antibacterial properties: the same size examples and comparative examples were tested for antimicrobial efficacy according to ISO 20743.
Hydrophobicity: the contact angle of the liquid drop is measured by a surface contact angle measuring instrument based on a sitting drop method test technology.
Resistance to falling off: referring to GB/T9286, the coated surface is cut using a grippa knife to form a grid pattern that is perpendicular to each other, with a scratch width of 2 mm. And tightly adhering the 3M adhesive tape on the surface of the cross-cut pattern, and peeling at 180 degrees to observe the shedding condition of the coating grid.
Example 1; (1) Mixing 4 parts of N1- [ (4-vinylphenyl methyl ] -N2-3- (triethoxysilyl) propyl ] -1, 2-ethylenediamine with 10 parts of deionized water, adding hydrochloric acid until the pH value of the solution is 4, reacting at 25 ℃ for 5 hours, adding ammonia water until the pH value of the solution is 6, heating to 30 ℃, continuously reacting for 3 hours, respectively washing 3 times with deionized water and ethanol, filtering, taking solid, drying at 150 ℃ for 10 hours to obtain organosilicon polymer microspheres with the particle size of 1 mu m, dissolving 2 parts of ethyl chloroacetate in 15 parts of isopropanol, adding 10 parts of organosilicon polymer microspheres, reacting at 75 ℃ for 4 hours under the protection of nitrogen, adding 5 parts of ethyl chloroacetate, continuously reacting for 2 hours, distilling at 145 ℃ under the vacuum degree of 0.01MPa until no liquid exists, and obtaining quaternized modified organosilicon polymer microspheres;
(2) 1 part of trifluoroacetic acid is dissolved in 10 parts of deionized water to obtain a fluorine-containing organic acid aqueous solution, then titanium dioxide powder with the particle size of 200nm is immersed in the fluorine-containing organic acid aqueous solution according to the feed liquid ratio of 1:10, the immersion time is 0.5h, the temperature is 0 ℃, the powder is dried for 3h at 25 ℃ after the immersion is finished, then the heat treatment is carried out for 20min, the temperature is 80 ℃, and finally the cooling is carried out to 25 ℃ to obtain the nano fluorinated titanium dioxide; 30 parts of deionized water, 0.6 part of fatty alcohol polyoxyethylene ether and 0.1 part of sodium dodecyl sulfate are stirred and dissolved, then 8 parts of methyl methacrylate and 12 parts of tert-butyl dimethyl ((1-phenylvinyl) oxy) silane are added for reaction at 50 ℃ for 30min, then 0.1 part of potassium persulfate and 6 parts of quaternized modified organosilicon polymer microspheres are added, the temperature is raised to 80 ℃ for reaction for 2h, then 8 parts of methyl methacrylate, 6 parts of 3-perfluorooctyl-2-hydroxypropyl methacrylate and 0.1 part of potassium persulfate are added for reaction for 2h at 80 ℃, then 4 parts of nano fluorinated titanium dioxide are added for stirring at 500rpm for 20min, and the modified fluorosilicone resin is obtained after cooling to room temperature;
(3) Mixing 8 parts of N- (hydroxyethyl) -N, N-bis (trimethoxysilylpropyl) amine and 3 parts of phosphorus pentoxide, heating to 70 ℃, preserving heat for 4 hours, cooling to 60 ℃, adding 1 part of deionized water, hydrolyzing for 2 hours, and adding potassium hydroxide until the pH value of the solution reaches 7.5 to obtain a phosphate compound; under the protection of nitrogen, mixing 10 parts of 4, 5-dihydroxyl-2-hexenoic acid, 18 parts of propylene glycol, 25 parts of 2-hexene-1, 6-diacid and 0.3 part of triphenyl phosphite, heating to 180 ℃ for 3 hours, preserving heat for 2 hours, maintaining at a vacuum degree of 0.040MPa for 0.5 hours, cooling to 150 ℃, adding 0.3 part of hydroquinone, continuously cooling to 95 ℃, adding 12 parts of glycidyl methacrylate and 0.3 part of tetramethyl ammonium iodide, continuously reacting for 30 minutes, cooling to 65 ℃, adding 8 parts of N, N-dimethylethanolamine, stirring for 15 minutes at 800r/min, adding 12 parts of phosphate compound and 130 parts of water, and stirring for 30 minutes at 2000r/min to obtain unsaturated polyester;
(4) Mixing 54 parts of unsaturated polyester, 28 parts of styrene and 7 parts of methyl styrene, stirring for 2 hours at 500r/min, adding 24 parts of modified fluorosilicone resin and 50 parts of deionized water, and stirring for 3 hours at 200r/min to obtain a waterproof unsaturated polyester resin coating; uniformly polishing the surface of the marble Dan Gongjian once by using 300-mesh sand paper, and cleaning dust on the surface and edges of the marble by using high-pressure air; a spray gun with the diameter of a nozzle of 1.0mm and the air pressure of 2kg/cm is selected to uniformly spray a layer of coating on the surface of a marble workpiece, the thickness of the coating is 120 mu m, and the sprayed marble substrate is irradiated for curing for 20s under the irradiation of 1000W ultraviolet light to obtain the waterproof unsaturated polyester coating for the stone.
Example 2; (1) Mixing 5 parts of N1- [ (4-vinylphenyl methyl ] -N2-3- (triethoxysilyl) propyl ] -1, 2-ethylenediamine with 10 parts of deionized water, adding hydrochloric acid until the pH value of the solution is 5, reacting at 25 ℃ for 5 hours, adding ammonia water until the pH value of the solution is 8.5, heating to 30 ℃, continuing to react for 3 hours, respectively washing 3 times with deionized water and ethanol, filtering, taking a solid, drying at 150 ℃ for 10 hours to obtain organosilicon polymer microspheres with the particle size of 8 mu m, dissolving 3 parts of ethyl chloroacetate in 17.5 parts of isopropanol, adding 12 parts of organosilicon polymer microspheres, reacting at 75 ℃ for 5 hours under the protection of nitrogen, adding 6 parts of ethyl chloroacetate, continuing to react for 2 hours, and distilling at 147.5 ℃ under the vacuum degree of 0.01MPa until no liquid exists, thereby obtaining quaternized modified organosilicon polymer microspheres;
(2) 1.5 parts of difluoroacetic acid is dissolved in 10 parts of deionized water to obtain a fluorine-containing organic acid aqueous solution, then titanium dioxide powder with the particle size of 250nm is immersed in the fluorine-containing organic acid aqueous solution according to the feed liquid ratio of 1:10, the immersion time is 24.25h, the temperature is 25 ℃, the powder is dried for 3h at 25 ℃ after the immersion is finished, then the heat treatment is carried out for 25min, the temperature is 120 ℃, and finally the cooling is carried out to 25 ℃ to obtain the nano fluoridized titanium dioxide; 30 parts of deionized water, 0.8 part of fatty alcohol polyoxyethylene ether and 0.3 part of sodium dodecyl sulfate are stirred and dissolved, 9 parts of methyl methacrylate and 13 parts of tert-butyl dimethyl ((1-phenylvinyl) oxy) silane are added to react for 30min at 50 ℃, 0.2 part of potassium persulfate and 8 parts of quaternized modified organosilicon polymer microspheres are added to react for 2h at 80 ℃, then 9 parts of methyl methacrylate, 7 parts of 3-perfluorooctyl-2-hydroxypropyl methacrylate and 0.2 part of potassium persulfate are added to react for 2h at 80 ℃,5 parts of nano fluorinated titanium dioxide is added to react for 20min at 500rpm, and the modified fluorosilicone resin is obtained after cooling to room temperature;
(3) 9 parts of N- (hydroxyethyl) -N, N-bis (trimethoxysilylpropyl) amine and 3.5 parts of phosphorus pentoxide are mixed and heated to 80 ℃, the temperature is kept for reaction for 5 hours, the temperature is reduced to 70 ℃, 1.5 parts of deionized water is added for hydrolysis for 2 hours, and potassium hydroxide is added until the pH value of the solution reaches 7.75, so that the phosphate compound is obtained; under the protection of nitrogen, mixing 12.5 parts of 4, 5-dihydroxy-2-hexenoic acid, 19 parts of propylene glycol, 27.5 parts of 2-hexene-1, 6-diacid and 0.4 part of triphenyl phosphite, heating to 180 ℃ for 3 hours, preserving heat for 2 hours, maintaining at a vacuum degree of 0.040MPa for 1.25 hours, cooling to 150 ℃, adding 0.4 part of hydroquinone, continuously cooling to 95 ℃, adding 13 parts of glycidyl methacrylate and 0.4 part of tetramethyl ammonium iodide, continuously reacting for 30 minutes, cooling to 65 ℃, adding 9 parts of N, N-dimethylethanolamine, stirring for 15 minutes at 800r/min, adding 14 parts of phosphate compound and 135 parts of water, stirring for 30 minutes at 2500r/min to obtain unsaturated polyester;
(4) Mixing 56.5 parts of unsaturated polyester, 30.5 parts of styrene and 10 parts of methyl styrene, stirring for 2 hours at 550r/min, adding 26 parts of modified fluorosilicone resin and 55 parts of deionized water, and stirring for 3 hours at 250r/min to obtain a waterproof unsaturated polyester resin coating; uniformly polishing the surface of the marble Dan Gongjian once by using 300-mesh sand paper, and cleaning dust on the surface and edges of the marble by using high-pressure air; a spray gun with the diameter of a nozzle of 1.0mm and the air pressure of 3kg/cm is selected to uniformly spray a layer of coating on the surface of a marble workpiece, the thickness of the coating is 210 mu m, and the sprayed marble substrate is irradiated for curing for 40s under the irradiation of 1000W ultraviolet light to obtain the waterproof unsaturated polyester coating for the stone.
Example 3; (1) Mixing 6 parts of N1- [ (4-vinylphenyl methyl ] -N2-3- (triethoxysilyl) propyl ] -1, 2-ethylenediamine with 10 parts of deionized water, adding hydrochloric acid until the pH value of the solution is 6, reacting at 25 ℃ for 5 hours, adding ammonia water until the pH value of the solution is 11, heating to 30 ℃, continuously reacting for 3 hours, respectively washing 3 times with deionized water and ethanol, filtering, taking solid, drying at 150 ℃ for 10 hours to obtain organosilicon polymer microspheres with the particle size of 15 mu m, dissolving 4 parts of ethyl chloroacetate in 20 parts of isopropanol, adding 14 parts of organosilicon polymer microspheres, reacting at 75 ℃ for 6 hours under the protection of nitrogen, adding 7 parts of ethyl chloroacetate, continuously reacting for 2 hours, repeatedly adding 7 parts of ethyl chloroacetate, reacting at 150 ℃ and distilling at 0.01MPa under reduced pressure until no liquid exists, and obtaining quaternized modified organosilicon polymer microspheres;
(2) 2 parts of monofluoroacetic acid is dissolved in 10 parts of deionized water to obtain a fluorine-containing organic acid aqueous solution, then titanium dioxide powder with the particle size of 300nm is immersed in the fluorine-containing organic acid aqueous solution according to the feed liquid ratio of 1:10, the immersion time is 48 hours, the temperature is 50 ℃, the powder is dried for 3 hours at 25 ℃ after the immersion is completed, then the heat treatment is carried out for 30 minutes, the temperature is 160 ℃, and finally the cooling is carried out to 25 ℃, so that the nano fluorinated titanium dioxide is obtained; 30 parts of deionized water, 1 part of fatty alcohol polyoxyethylene ether and 0.5 part of sodium dodecyl sulfate are stirred and dissolved, 10 parts of methyl methacrylate and 14 parts of tert-butyl dimethyl ((1-phenylvinyl) oxy) silane are added to react for 30min at 50 ℃, 0.3 part of potassium persulfate and 10 parts of quaternized modified organosilicon polymeric microspheres are added to react for 2h at 80 ℃, then 10 parts of methyl methacrylate, 8 parts of 3-perfluorooctyl-2-hydroxypropyl methacrylate and 0.3 part of potassium persulfate are added to react for 2h at 80 ℃,6 parts of nano fluorinated titanium dioxide is added to react for 20min at 500rpm, and the modified fluorosilicone resin is obtained after cooling to room temperature;
(3) Mixing 10 parts of N- (hydroxyethyl) -N, N-bis (trimethoxysilylpropyl) amine and 4 parts of phosphorus pentoxide, heating to 90 ℃, preserving heat for reaction for 6 hours, cooling to 80 ℃, adding 2 parts of deionized water, hydrolyzing for 2 hours, and adding potassium hydroxide until the pH value of the solution reaches 8 to obtain a phosphate compound; under the protection of nitrogen, mixing 15 parts of 4, 5-dihydroxyl-2-hexenoic acid, 20 parts of propylene glycol, 30 parts of 2-hexene-1, 6-diacid and 0.5 part of triphenyl phosphite, heating to 180 ℃ for 3 hours, preserving heat for 2 hours, maintaining at a vacuum degree of 0.040MPa for 1 hour, cooling to 150 ℃, adding 0.5 part of hydroquinone, continuously cooling to 95 ℃, adding 14 parts of glycidyl methacrylate and 0.5 part of tetramethyl ammonium iodide, continuously reacting for 30 minutes, cooling to 65 ℃, adding 10 parts of N, N-dimethylethanolamine, stirring for 15 minutes at 800r/min, adding 16 parts of phosphate compound and 140 parts of water, and stirring for 30 minutes at 3000r/min to obtain unsaturated polyester;
(4) 59 parts of unsaturated polyester, 33 parts of methyl methacrylate and 13 parts of 3-phenylpropene are mixed, after 600r/min stirring is carried out for 2 hours, 28 parts of modified fluorosilicone resin and 60 parts of deionized water are added, and 300r/min stirring is carried out for 3 hours, thus obtaining the waterproof unsaturated polyester resin coating; uniformly polishing the surface of the marble Dan Gongjian once by using 300-mesh sand paper, and cleaning dust on the surface and edges of the marble by using high-pressure air; a spray gun with the diameter of a nozzle of 1.0mm and the air pressure of 4kg/cm is selected to uniformly spray a layer of coating on the surface of a marble workpiece, the thickness of the coating is 300 mu m, and the sprayed marble substrate is irradiated by 1000W ultraviolet light for curing for 60 seconds to obtain the waterproof unsaturated polyester coating for the stone.
Comparative example 1; comparative example 1 differs from example 2 in that steps (1) and (2) are different, and steps (1) and (2) are changed to: (1) Mixing 5 parts of N1- [ (4-vinylphenyl methyl ] -N2-3- (triethoxysilyl) propyl ] -1, 2-ethylenediamine with 10 parts of deionized water, adding hydrochloric acid until the pH value is 5, reacting at 25 ℃ for 5 hours, adding ammonia water until the pH value of the solution is 8.5, heating to 30 ℃, continuing to react for 3 hours, respectively washing 3 times with deionized water and ethanol, filtering, taking a solid, and drying at 150 ℃ for 10 hours to obtain the organosilicon polymeric microspheres with the particle size of 8 mu m;
(2) 1.5 parts of difluoroacetic acid is dissolved in 10 parts of deionized water to obtain a fluorine-containing organic acid aqueous solution, then titanium dioxide powder with the particle size of 250nm is immersed in the fluorine-containing organic acid aqueous solution according to the feed liquid ratio of 1:10, the immersion time is 24.25h, the temperature is 25 ℃, the powder is dried for 3h at 25 ℃ after the immersion is finished, then the heat treatment is carried out for 25min, the temperature is 120 ℃, and finally the cooling is carried out to 25 ℃ to obtain the nano fluoridized titanium dioxide; 30 parts of deionized water, 0.8 part of fatty alcohol polyoxyethylene ether and 0.3 part of sodium dodecyl sulfate are stirred and dissolved, 9 parts of methyl methacrylate and 13 parts of tert-butyl dimethyl ((1-phenylvinyl) oxy) silane are added to react for 30min at 50 ℃, 0.2 part of potassium persulfate and 8 parts of organosilicon polymeric microspheres are added to react for 2h at 80 ℃,9 parts of methyl methacrylate, 7 parts of 3-perfluorooctyl-2-hydroxypropyl methacrylate and 0.2 part of potassium persulfate are added to react for 2h at 80 ℃,5 parts of nano fluorinated titanium dioxide are added to react for 20min at 500rpm, and the mixture is cooled to room temperature to obtain modified fluorosilicone resin; the rest of the procedure is the same as in example 2.
Comparative example 2; comparative example 2 differs from example 2 in that step (1) was not present, and step (2) was changed to: 1.5 parts of difluoroacetic acid is dissolved in 10 parts of deionized water to obtain a fluorine-containing organic acid aqueous solution, then titanium dioxide powder with the particle size of 250nm is immersed in the fluorine-containing organic acid aqueous solution according to the feed liquid ratio of 1:10, the immersion time is 24.25h, the temperature is 25 ℃, the powder is dried for 3h at 25 ℃ after the immersion is finished, then the heat treatment is carried out for 25min, the temperature is 120 ℃, and finally the cooling is carried out to 25 ℃ to obtain the nano fluoridized titanium dioxide; 30 parts of deionized water, 0.8 part of fatty alcohol polyoxyethylene ether and 0.3 part of sodium dodecyl sulfate are stirred and dissolved, 9 parts of methyl methacrylate and 13 parts of tert-butyl dimethyl ((1-phenylvinyl) oxy) silane are added, the mixture is reacted for 30min at 50 ℃, then 0.2 part of potassium persulfate, 9 parts of methyl methacrylate, 7 parts of 3-perfluorooctyl-2-hydroxypropyl methacrylate and 0.2 part of potassium persulfate are added, the mixture is reacted for 2h at 80 ℃, then 5 parts of nano fluorinated titanium dioxide is added, the mixture is stirred for 20min at 500rpm, and the mixture is cooled to room temperature, thus obtaining the modified fluorosilicone resin; the rest of the procedure is the same as in example 2.
Comparative example 3; comparative example 3 differs from example 2 in that steps (2) (4) are different, and steps (2) (4) are changed to: (2) Dissolving 1.5 parts of difluoro acetic acid fluorine-containing organic acid in 10 parts of deionized water to obtain a fluorine-containing organic acid aqueous solution, then soaking titanium dioxide powder with the particle size of 250nm in the fluorine-containing organic acid aqueous solution according to a feed liquid ratio of 1:2 for 24.25 hours at the temperature of 25 ℃, airing the powder at the temperature of 25 ℃ for 3 hours after the soaking is completed, drying, performing heat treatment for 25 minutes again at the temperature of 390 ℃, and finally cooling to the temperature of 25 ℃ to obtain nano fluoride titanium dioxide;
(4) Mixing 56.5 parts of unsaturated polyester, 30.5 parts of styrene cross-linking agent and 10 parts of methyl styrene retarder, stirring for 2 hours at 550r/min, adding 5 parts of fluorinated titanium dioxide, 8 parts of quaternized modified organosilicon microspheres and 55 parts of deionized water, heating to 80 ℃ for reacting for 2 hours, and stirring for 3 hours at 250r/min to obtain a waterproof unsaturated polyester resin coating; uniformly polishing the surface of the marble Dan Gongjian once by using 300-mesh sand paper, and cleaning dust on the surface and edges of the marble by using high-pressure air; a spray gun with the diameter of a nozzle of 1.0mm and the air pressure of 2-4kg/cm is selected to uniformly spray a layer of coating on the surface of a marble workpiece, the thickness of the coating is 210 mu m, and the sprayed marble substrate is irradiated for curing for 40s under the irradiation of 1000W ultraviolet light to obtain the waterproof unsaturated polyester coating for the stone.
Comparative example 4; comparative example 4 differs from example 2 in that step (2) was changed to: 30 parts of deionized water, 0.8 part of fatty alcohol polyoxyethylene ether and 0.3 part of sodium dodecyl sulfate are stirred and dissolved, 9 parts of methyl methacrylate and 13 parts of tert-butyl dimethyl ((1-phenylvinyl) oxy) silane are added to react for 30min at 50 ℃, 0.2 part of potassium persulfate and 8 parts of quaternized modified organosilicon polymeric microspheres are added to react for 2h at 80 ℃, then 9 parts of methyl methacrylate, 7 parts of 3-perfluorooctyl-2-hydroxypropyl methacrylate and 0.2 part of potassium persulfate are added to react for 2h at 80 ℃, and the mixture is cooled to room temperature to obtain modified fluorine silicone resin; the rest of the procedure is the same as in example 2.
Comparative example 5; comparative example 5 differs from example 2 in that step (3) was changed to: under the protection of nitrogen, mixing 12.5 parts of 4, 5-dihydroxy-2-hexenoic acid, 19 parts of propylene glycol, 27.5 parts of 2-hexene-1, 6-diacid and 0.4 part of triphenyl phosphite, heating to 180 ℃ for 3 hours, preserving heat for 2 hours, maintaining at the vacuum degree of 0.040MPa for 1.25 hours, cooling to 150 ℃, adding 0.4 part of hydroquinone, continuously cooling to 95 ℃, adding 13 parts of glycidyl methacrylate and 0.4 part of tetramethyl ammonium iodide, continuously reacting for 30 minutes, cooling to 65 ℃, adding 9 parts of N, N-dimethylethanolamine, and stirring for 800r/min for 15 minutes to obtain unsaturated polyester; the rest of the procedure is the same as in example 2.
Effect example
The results of the performance analysis of the waterproof unsaturated polyester coating for stone materials using examples 1 to 3 of the present invention and comparative examples 1 to 5 are given in table 1 below.
TABLE 1
As can be seen from the comparison of the experimental data of hydrophobicity of the examples and the comparative examples, the invention utilizes N1- [ (4-vinylphenyl methyl ] -N2-3- (triethoxysilyl) propyl ] -1, 2-ethylenediamine to polymerize into the hydrophobic micron-sized organosilicon polymeric microspheres, improves the hydrophobicity of the coating, then polymerizes with tert-butyldimethyl ((1-phenylvinyl) oxy) silane and 3-perfluorooctyl-2-hydroxypropyl methacrylate to form the fluorosilicone resin, further enhances the waterproof effect of the coating, and in the polymerization process, fluorinated nano titanium dioxide is added to form a micro-nano coarse structure with the organosilicon polymeric microspheres, and gains the hydrophobic effect of the coating, in addition, the invention utilizes phosphate compounds generated by the reaction of N- (hydroxyethyl) -N, N-bis (trimethoxy-silicone propyl) amine and phosphorus pentoxide to simultaneously have high surface activity and interface performance, so that the coating obtains excellent hydrophobicity, and can be found from the comparison of the experimental data of the antibacterial property of the examples and the comparative examples, the invention carries out ammonium treatment on the organosilicon polymeric microspheres, and the synergistic effect of the anti-release performance of the organic silicon polymeric microspheres and the antibacterial property of the coating can be improved, and the anti-release performance of the anti-bacterial polyester can be improved, and the anti-release performance of the anti-calcium carbonate can be better than the anti-release polyester can be obtained, and the anti-release polyester can be better than the anti-abrasive coating, and the anti-release effect of the anti-abrasive coating can be obtained, and the anti-release polyester can be compared with the anti-abrasive coating, indirectly improves the shedding resistance of the coating.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (10)
1. The preparation method of the waterproof unsaturated polyester coating for the stone is characterized by comprising the following steps of:
(1) Mixing N1- [ (4-vinylphenyl methyl) -N2-3- (triethoxysilyl) propyl ] -1, 2-ethylenediamine with deionized water in proportion, adding hydrochloric acid until the pH value of the solution is 4-6, reacting at 25 ℃ for 5 hours, adding ammonia water until the pH value of the solution is 6-11, heating to 30 ℃, continuing to react for 3 hours, respectively washing with deionized water and ethanol for 3 times, filtering, taking a solid, and drying at 150 ℃ for 10 hours to obtain the organosilicon polymeric microspheres with the particle size of 1-15 mu m; dissolving 2-4 parts of ethyl chloroacetate in 15-20 parts of isopropanol, adding 10-14 parts of organosilicon polymeric microspheres, reacting for 4-6 hours at 75 ℃ under the protection of nitrogen, adding 5-7 parts of ethyl chloroacetate, continuously reacting for 2 hours, and distilling under reduced pressure until no liquid exists, thus obtaining quaternized modified organosilicon polymeric microspheres;
(2) 1-2 parts of fluorine-containing organic acid is dissolved in 10 parts of deionized water to obtain a fluorine-containing organic acid aqueous solution, then titanium dioxide powder with the particle size of 200-300nm is immersed in the fluorine-containing organic acid aqueous solution according to the feed liquid ratio of 1:10, the immersion time is 0.5-48h, the temperature is 0-50 ℃, after drying, the heat treatment is carried out for 20-30min, the temperature is 80-160 ℃, and finally the temperature is cooled to 25 ℃, so that nano fluorinated titanium dioxide is obtained; adding 8-10 parts of methyl methacrylate and 12-14 parts of tert-butyldimethyl ((1-phenylvinyl) oxy) silane after 30 parts of deionized water, 0.6-1 part of fatty alcohol polyoxyethylene ether and 0.1-0.5 part of sodium dodecyl sulfate are stirred and dissolved, reacting for 30min at 50 ℃, adding 0.1-0.3 part of initiator, adding 6-10 parts of quaternized modified organosilicon polymeric microspheres, heating to 80 ℃ for reacting for 2h, then adding 8-10 parts of methyl methacrylate, 6-8 parts of 3-perfluorooctyl-2-hydroxypropyl methacrylate and 0.1-0.3 part of initiator, reacting for 2h at 80 ℃, adding 4-6 parts of nano fluorinated titanium dioxide, stirring for 20min at 500rpm, and cooling to room temperature to obtain modified fluorosilicon resin;
(3) Mixing 8-10 parts of N- (hydroxyethyl) -N, N-bis (trimethoxysilylpropyl) amine and 3-4 parts of phosphorus pentoxide, heating to 70-90 ℃, reacting for 4-6 hours at a temperature of 60-80 ℃, adding 1-2 parts of deionized water, hydrolyzing for 2 hours, and adding potassium hydroxide until the pH value of the solution reaches 7.5-8 to obtain a phosphate compound; under the protection of nitrogen, mixing 10-15 parts of 4, 5-dihydroxy-2-hexenoic acid, 18-20 parts of propylene glycol, 25-30 parts of 2-hexene-1, 6-diacid and 0.3-0.5 part of antioxidant, heating to 180 ℃ for 3 hours, preserving heat for 2 hours, maintaining at a vacuum degree of 0.040MPa for 0.5-1 hour, cooling to 150 ℃, adding 0.3-0.5 part of polymerization inhibitor, continuously cooling to 95 ℃, adding 12-14 parts of glycidyl methacrylate and 0.3-0.5 part of tetramethyl ammonium iodide, continuously reacting for 30min, cooling to 65 ℃, adding 8-10 parts of N, N-dimethylethanolamine, stirring for 15min at 800r/min, adding 12-16 parts of phosphate compound and 130-140 parts of water, and stirring for 30min at 2000-3000r/min to obtain unsaturated polyester;
(4) Mixing 54-59 parts of unsaturated polyester, 28-33 parts of cross-linking agent and 7-13 parts of retarder, stirring for 2 hours at 500-600r/min, adding 24-28 parts of modified fluorosilicone resin and 50-60 parts of deionized water, and stirring for 3 hours at 200-300r/min to obtain waterproof unsaturated polyester resin paint; uniformly polishing the surface of the marble Dan Gongjian once by using 300-mesh sand paper, and cleaning dust on the surface and edges of the marble by using high-pressure air; and uniformly spraying a layer of coating on the surface of the marble workpiece by using a spray gun, and carrying out radiation curing on the sprayed marble substrate under the irradiation of 1000W ultraviolet light for 20-60s to obtain the waterproof unsaturated polyester coating for the stone.
2. The method for preparing a waterproof unsaturated polyester coating for stone materials according to claim 1, wherein the proportion of the step (1) is 4-6 parts of N1- [ (4-vinylphenylmethyl) -N2-3- (triethoxysilyl) propyl ] -1, 2-ethylenediamine and 10 parts of deionized water.
3. The method for preparing a waterproof unsaturated polyester coating for stone material according to claim 1, wherein the reduced pressure distillation conditions in the step (1) are: the temperature is 145-150 ℃ and the vacuum degree is 0.01MPa.
4. The method for preparing a waterproof unsaturated polyester coating for stone material according to claim 1, wherein the drying conditions in the step (2) are as follows: after impregnation, the powder was dried at 25℃for 3h.
5. The method for preparing a waterproof unsaturated polyester coating for stone material according to claim 1, wherein the fluorine-containing organic acid in the step (2) is one of trifluoroacetic acid, difluoroacetic acid and monofluoroacetic acid.
6. The method for preparing a waterproof unsaturated polyester coating for stone material according to claim 1, wherein the initiator in the step (2) is potassium persulfate.
7. The method for preparing a waterproof unsaturated polyester coating for stone materials according to claim 1, wherein the antioxidant in the step (3) is triphenyl phosphite.
8. The method for preparing a waterproof unsaturated polyester coating for stone material according to claim 1, wherein the polymerization inhibitor in the step (3) is hydroquinone.
9. The method for preparing a waterproof unsaturated polyester coating for stone material according to claim 1, wherein the cross-linking agent in the step (4) is styrene or methyl methacrylate; the retarder is methyl styrene or 3-phenylpropene; a spray gun with a nozzle diameter of 1.0mm and an air pressure of 2-4kg/cm was used.
10. The method for preparing a waterproof unsaturated polyester coating for stone material according to claim 1, wherein the thickness of the coating in the step (4) is 120-300 μm.
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