CN118027724A - Water-based latex self-layering coating based on amphiphilic asymmetric organic-inorganic hybrid nano particles and preparation method thereof - Google Patents
Water-based latex self-layering coating based on amphiphilic asymmetric organic-inorganic hybrid nano particles and preparation method thereof Download PDFInfo
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- 239000002105 nanoparticle Substances 0.000 title claims abstract description 81
- 238000000576 coating method Methods 0.000 title claims abstract description 67
- 239000011248 coating agent Substances 0.000 title claims abstract description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000004816 latex Substances 0.000 title claims abstract description 36
- 229920000126 latex Polymers 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 51
- 239000006185 dispersion Substances 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 27
- 239000003085 diluting agent Substances 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 239000004005 microsphere Substances 0.000 claims abstract description 20
- 239000000839 emulsion Substances 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 12
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 12
- 229910000077 silane Inorganic materials 0.000 claims abstract description 12
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- 239000010703 silicon Substances 0.000 claims abstract description 12
- 239000012298 atmosphere Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 9
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims abstract description 8
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 claims abstract description 8
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 7
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 8
- 238000004945 emulsification Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- GBQYMXVQHATSCC-UHFFFAOYSA-N 3-triethoxysilylpropanenitrile Chemical group CCO[Si](OCC)(OCC)CCC#N GBQYMXVQHATSCC-UHFFFAOYSA-N 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 6
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- WEERVPDNCOGWJF-UHFFFAOYSA-N 1,4-bis(ethenyl)benzene Chemical compound C=CC1=CC=C(C=C)C=C1 WEERVPDNCOGWJF-UHFFFAOYSA-N 0.000 claims description 5
- KVUMYOWDFZAGPN-UHFFFAOYSA-N 3-trimethoxysilylpropanenitrile Chemical compound CO[Si](OC)(OC)CCC#N KVUMYOWDFZAGPN-UHFFFAOYSA-N 0.000 claims description 5
- SCPWMSBAGXEGPW-UHFFFAOYSA-N dodecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OC)(OC)OC SCPWMSBAGXEGPW-UHFFFAOYSA-N 0.000 claims description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- VBGGLSWSRVDWHB-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-henicosafluorodecyl-tris(trifluoromethoxy)silane Chemical compound FC(F)(F)O[Si](OC(F)(F)F)(OC(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F VBGGLSWSRVDWHB-UHFFFAOYSA-N 0.000 claims description 3
- VBHXIMACZBQHPX-UHFFFAOYSA-N 2,2,2-trifluoroethyl prop-2-enoate Chemical compound FC(F)(F)COC(=O)C=C VBHXIMACZBQHPX-UHFFFAOYSA-N 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 2
- DEQJNIVTRAWAMD-UHFFFAOYSA-N 1,1,2,4,4,4-hexafluorobutyl prop-2-enoate Chemical compound FC(F)(F)CC(F)C(F)(F)OC(=O)C=C DEQJNIVTRAWAMD-UHFFFAOYSA-N 0.000 claims description 2
- SYENRPHLJLKTED-UHFFFAOYSA-N 1,3,5-tris(ethenyl)benzene Chemical compound C=CC1=CC(C=C)=CC(C=C)=C1 SYENRPHLJLKTED-UHFFFAOYSA-N 0.000 claims description 2
- PRJNEUBECVAVAG-UHFFFAOYSA-N 1,3-bis(ethenyl)benzene Chemical group C=CC1=CC=CC(C=C)=C1 PRJNEUBECVAVAG-UHFFFAOYSA-N 0.000 claims description 2
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 0.000 claims description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- BAAAEEDPKUHLID-UHFFFAOYSA-N decyl(triethoxy)silane Chemical compound CCCCCCCCCC[Si](OCC)(OCC)OCC BAAAEEDPKUHLID-UHFFFAOYSA-N 0.000 claims description 2
- 230000001804 emulsifying effect Effects 0.000 claims description 2
- SLYCYWCVSGPDFR-UHFFFAOYSA-N octadecyltrimethoxysilane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OC)(OC)OC SLYCYWCVSGPDFR-UHFFFAOYSA-N 0.000 claims description 2
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 claims description 2
- 229960003493 octyltriethoxysilane Drugs 0.000 claims description 2
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 claims description 2
- FZMJEGJVKFTGMU-UHFFFAOYSA-N triethoxy(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OCC)(OCC)OCC FZMJEGJVKFTGMU-UHFFFAOYSA-N 0.000 claims description 2
- WKEXHTMMGBYMTA-UHFFFAOYSA-N trimethyl propyl silicate Chemical compound CCCO[Si](OC)(OC)OC WKEXHTMMGBYMTA-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims 2
- 230000001105 regulatory effect Effects 0.000 claims 1
- 239000002987 primer (paints) Substances 0.000 description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 239000002245 particle Substances 0.000 description 14
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- 229910021642 ultra pure water Inorganic materials 0.000 description 9
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
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- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
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- Paints Or Removers (AREA)
Abstract
The invention relates to a self-layering coating of aqueous latex based on amphiphilic asymmetric organic-inorganic hybrid nano particles and a preparation method thereof, comprising the following preparation steps: s1, dissolving sodium styrene sulfonate and potassium persulfate in methanol water, adding an organic polymerization monomer and a cross-linking agent, and heating under an inert atmosphere to obtain organic microspheres; s2, mixing a silane acrylate monomer, a silane coupling agent monomer, an initiator and water to obtain a monomer emulsion, mixing an organic microsphere dispersion liquid with the monomer emulsion, stirring under an inert atmosphere, adjusting the pH to be alkaline, and heating to obtain amphiphilic asymmetric organic-inorganic hybrid nano particles; s3, dispersing the amphiphilic asymmetric organic-inorganic hybrid nano particles in water, mixing with the water-based latex primer diluent, dripping the mixture on a silicon wafer, and drying to obtain the water-based latex self-layering coating based on the amphiphilic asymmetric organic-inorganic hybrid nano particles. The self-layering coating prepared by the invention has mechanical firmness and low adhesiveness.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a self-layering coating of aqueous latex based on amphiphilic asymmetric organic-inorganic hybrid nano particles and a preparation method thereof.
Background
The coating is ubiquitous in daily life of human beings, and is not enumerated in various aspects ranging from the most common building coating of inner and outer walls to food packaging, kitchen and household appliances, electronic products, sports equipment, entertainment facilities, vehicles and the like. The coating plays a role in color effect and surface protection effect. The traditional coating preparation method is multilayer preparation, and a layer of primer is coated first to increase the adhesion capability with the substrate. The second layer is an intermediate coating layer, which is sometimes coated with a substance having a specific function as required. The outermost layer, also called the topcoat, not only imparts an aesthetic appearance (i.e., smoothness, gloss) to the coating, but also provides stain resistance, scratch resistance, chemical and weather resistance. Although multilayer coating systems can combine the individual properties of each layer, each layer still requires complex formulations, lengthy handling and curing procedures, which severely limit its industrial application due to the large manpower and processing time requirements, excessive energy consumption, and the generation of environmental waste. Therefore, in order to overcome these drawbacks of the conventional multilayer coating, a concept of constructing a self-layering coating having a continuous multilayer structure by a one-step method, the formulation of the self-layering coating is composed of two or more components having different surface energies, phase separation occurs spontaneously during the curing of the coating, and a multilayer or gradient coating is further formed. The self-layering coating prepared by the one-step method is time-saving and labor-saving, reduces energy consumption, and can eliminate interface faults to a great extent, so that the functions of each layer are maintained.
Aqueous self-layering coatings include three main types: binary soft polymers, binary hard colloidal particles, and mixtures of soft polymers and hard colloidal particles. Among them, the binary soft polymer self-layering coating has low mechanical strength, hardness and wear resistance. Binary hard colloid particles exhibit poor film forming properties from layered coatings. The mixture of soft polymer and hard colloidal particles is such that the layered structure of polymer and particles can be achieved by adjusting nanoparticle/polymer interactions such as hydrodynamic interactions, radius of gyration of the polymer, polymer molecular weight, evaporation rate, and sedimentation of aggregated particles or flotation of light particles. However, implementation of these strategies places high demands on polymer-to-particle matching, processing conditions, and nanoparticle characteristics, indicating that a simple method of constructing hard gum-soft polymer composite self-layering coatings with both mechanical robustness and film forming properties is highly desirable before a wide range of industrial applications for high performance aqueous composite self-layering coatings are achieved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an organic-inorganic hybrid amphiphilic asymmetric nanometer self-layering coating and a preparation method thereof.
The aim of the invention can be achieved by the following technical scheme:
One of the technical schemes of the invention is to provide a preparation method of an aqueous latex self-layering coating based on amphiphilic asymmetric organic-inorganic hybrid nano particles, which comprises the following steps:
S1, dissolving sodium styrene sulfonate and potassium persulfate in a mixed solution of methanol and water, adding an organic polymerization monomer and a cross-linking agent, mixing and emulsifying to obtain Pickering emulsion, and heating and reacting in an inert atmosphere to obtain organic microspheres;
S2, dispersing the organic microspheres obtained in the step S1 in water to obtain an organic microsphere dispersion liquid, mixing a silane acrylate monomer, a silane coupling agent monomer, an initiator and water to obtain a monomer emulsion, mixing the organic microsphere dispersion liquid and the monomer emulsion, stirring for a period of time in an inert atmosphere after emulsification, adjusting pH to be alkaline, and heating to react to obtain amphiphilic asymmetric organic-inorganic hybrid nano particles;
S3, dispersing the amphiphilic asymmetric organic-inorganic hybrid nano particles obtained in the step S2 in water to obtain a nano particle dispersion liquid, mixing the water-based latex primer with water to obtain a water-based latex primer diluent, mixing the nano particle dispersion liquid with the water-based latex primer diluent, dripping the mixture on a silicon wafer, and drying to obtain the water-based latex self-layering coating based on the amphiphilic asymmetric organic-inorganic hybrid nano particles.
In some embodiments, in step S1, the organic polymeric monomer is selected from the group consisting of methyl acrylate, butyl acrylate, methyl methacrylate, styrene, p-methylstyrene;
The cross-linking agent is selected from m-divinylbenzene, p-divinylbenzene, 1,3, 5-trivinylbenzene, 1, 3-pentadiene and isoprene.
Preferably, the organic polymeric monomer is selected from methyl methacrylate, butyl acrylate or styrene;
Preferably, the cross-linking agent is selected from the group consisting of p-divinylbenzene, isoprene.
In some embodiments, in step S1, the ratio of the sodium styrenesulfonate, potassium persulfate, aqueous methanol mixed solution, organic polymerization monomer, and crosslinking agent is (80-85) mg: (140-160) mg:200mL:27mL: (0.27-2.7) mL;
the volume ratio of methanol to water in the methanol-water mixed solution is 90:10-50:50.
Preferably, the proportion of the sodium styrenesulfonate, the potassium persulfate, the methanolic water, the organic polymeric monomer and the crosslinking agent is (80-85) mg: (140-160) mg:200mL:27mL: (0.81-2.7) mL;
Preferably, the volume ratio of methanol to water in the methanol-water mixed solution is 90:10-70:30;
In some embodiments, in step S1, the process parameters of the heating reaction under an inert atmosphere are: the inert atmosphere is nitrogen, the temperature of the heating reaction is 70 ℃, and the time of the heating reaction is at least 24 hours.
In some embodiments, in step S1, a fluorine-containing or long carbon chain vinyl monomer is further added in the mixed emulsification reaction to perform hydrophobic surface modification on the organic microsphere, so that the hydrophobicity of the organic-inorganic hybrid amphiphilic asymmetric nanoparticle is increased.
In some embodiments, in step S1, the fluorine-containing or long carbon chain vinyl monomer is selected from trifluoroethyl acrylate, hexafluorobutyl acrylate, trifluoroethyl methacrylate, decyltriethoxysilane, dodecyltrimethoxysilane, octadecyltriethoxysilane;
the addition amount of the fluorine-containing or long carbon chain vinyl monomer is 10-20% of the addition amount of the organic polymerization monomer.
In some embodiments, in step S2, the silane acrylate monomer is selected from the group consisting of propyl 3- (trimethoxysilyl) methacrylate, propyl 3- (trimethoxysilyl) acrylate, butyl 3- (trimethoxysilyl) acrylate, propyl 3- (triethoxysilyl) methacrylate;
The silane coupling agent monomer is selected from 2-cyanoethyl triethoxysilane, 2-cyanoethyl trimethoxysilane, 3-glycidol propoxy trimethoxysilane, 3-amino propyl trimethoxysilane, dodecyl trimethoxysilane, octadecyl trimethoxysilane, triethoxy octyl silane, perfluoro decyl trimethoxysilane and 3-amino propyl triethoxy silane;
the initiator is azobisisobutyronitrile.
Preferably, the silane acrylate monomer is selected from the group consisting of propyl 3- (trimethoxysilyl) methacrylate or propyl 3- (triethoxysilyl) methacrylate;
Preferably, the silane coupling agent monomer is selected from 2-cyanoethyltriethoxysilane, 2-cyanoethyltrimethoxysilane, dodecyltrimethoxysilane, perfluorodecyltrimethoxysilane or 3-aminopropyl triethoxysilane.
In some embodiments, in step S2, the volume ratio of the silane acrylate monomer to the silane coupling agent monomer in the emulsion is 50:50-90:10;
The addition mass of the initiator is 5 times of the sum value of the volumes of the silane acrylate monomer and the silane coupling agent monomer.
Preferably, the volume ratio of the silane acrylate monomer to the silane coupling agent monomer is 70:30-90:10.
Preferably, the proportion of the organic microsphere, the silane acrylate monomer and the silane coupling agent monomer is 6g:9mL:3mL.
In some embodiments, in step S2, the inert atmosphere is nitrogen, the pH of the solution is adjusted to 9.0, the temperature of the heating reaction is 70 ℃, and the time of the heating reaction is at least 36 hours.
In some specific embodiments, when the silane coupling agent monomer in the step S2 is selected from 2-cyanoethyltriethoxysilane and 2-cyanoethyltrimethoxysilane, in the step S3, concentrated sulfuric acid is slowly added into the nanoparticle aqueous solution, and after heating reaction is performed for a period of time, a surface carboxylated organic-inorganic hybrid amphiphilic asymmetric nanoparticle dispersion is obtained, so that the hydrophilicity of the organic-inorganic hybrid amphiphilic asymmetric nanoparticle is increased.
In some embodiments, the concentrated sulfuric acid is slowly added to enable the pH of an acidic environment in the reaction system to be 1.8-2.5, the temperature of the heating reaction is 90 ℃, and the heating reaction time is 12-24 hours.
In some embodiments, in step S3, the nanoparticle dispersion has a nanoparticle concentration of 0.01-0.5g/mL; the concentration of the aqueous emulsion primer in the aqueous emulsion primer diluent is 40% -95% of the original concentration; the pH of the aqueous latex primer diluent is 5.01-12.05; the volume ratio of the aqueous latex primer diluent to the nanoparticle dispersion is 95:5-50:50.
Preferably, the nanoparticle concentration in the nanoparticle dispersion is 0.05-0.2g/mL; the concentration of the aqueous emulsion primer in the aqueous emulsion primer diluent is 55% -90% of the original concentration; the pH of the aqueous latex primer diluent is 7.51-11.21; the volume ratio of the aqueous latex primer diluent to the nanoparticle dispersion is 95:5-70:30.
In some embodiments, in step S3, the thickness of the mixture of the aqueous latex primer diluent and the nanoparticle dispersion that is added dropwise onto the silicon wafer is 100-3000 μm.
Preferably, the thickness of the mixture of the aqueous latex primer diluent and the nanoparticle dispersion liquid which are dripped on the silicon wafer is 300-2000 mu m.
The second technical scheme of the invention is to provide an amphiphilic asymmetric organic-inorganic hybrid nano self-layering coating, which is prepared by the preparation method based on one of the technical schemes.
Compared with the prior art, the invention has the following beneficial effects:
(1) The amphiphilic asymmetric organic-inorganic hybrid nano particles prepared by the method can migrate to a water-air interface to form a self-layering structure and are fixed in the drying process, so that the self-layering coating film forming performance of the water-based latex based on the amphiphilic asymmetric organic-inorganic hybrid nano particles, which is obtained by mixing the self-layering coating film forming material with the primer and then coating the self-layering coating film on a silicon wafer and drying, is excellent in hardness and elastic modulus compared with the primer, and has mechanical firmness and low adhesiveness.
(2) The preparation method of the water-based latex based on the amphiphilic asymmetric organic-inorganic hybrid nano particles is simple, saves time and labor, reduces energy consumption, is environment-friendly, and is suitable for large-scale production.
Drawings
Fig. 1 is a schematic diagram of a modified synthesis route and a self-layering coating for preparing amphiphilic asymmetric organic-inorganic hybrid nano in some examples.
Fig. 2 is a TEM image (left) and SEM image (right) of the cyanated amphiphilic asymmetric organic-inorganic hybrid nanoparticle prepared in example 1.
Fig. 3 is an SEM image of amphiphilicity of the asymmetric organic-inorganic hybrid nanoparticle for verification of cyanation in example 1, wherein the left image is a partial enlarged image of the right image.
Fig. 4 is an SEM image of a self-layering coating based on carboxylated amphiphilic asymmetric organic-inorganic hybrid nanoparticles prepared in example 2 (left) and an SEM image of a control commercial primer coating (right).
Fig. 5 is a graph of micromechanics property test of the amphiphilic asymmetric organic-inorganic hybrid nanoparticle-based self-layering coating prepared in examples 1-4 and a control commercial primer coating.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples. The present embodiment is implemented on the premise of the technical scheme of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following examples.
In the following examples, unless otherwise indicated, the starting materials or processing techniques are all those conventionally commercially available in the art.
Among them, commercial primers are derived from the Peel Stop model primer of Zinsser (fluid color) company.
Example 1:
The embodiment 1 provides a preparation method of a self-layering coating based on cyano amphiphilic asymmetric organic-inorganic hybrid nano, which comprises the following steps:
(1) 85mg of sodium styrenesulfonate and 160mg of potassium persulfate are dissolved in 200mL of methanol water (the volume ratio of methanol to water is 8:2), 27mL of styrene and 0.81mL of p-divinylbenzene are added, the mixture is subjected to ultrasonic emulsification for 10min to form milky Pickering emulsion, nitrogen is blown for 30min, and then the temperature is raised to 70 ℃ for reaction for 24h. And after the reaction is finished, washing the mixture with ethanol and water repeatedly for more than three times in sequence to obtain the polystyrene microsphere.
(2) 6G of the polystyrene microspheres obtained in the step (1) are ultrasonically dispersed in 270mL of ultrapure water, 9mL of 3- (triethoxysilyl) propyl methacrylate and 3mL of 2-cyanoethyltriethoxysilane are added, and then 60mg of azobisisobutyronitrile and 90mL of ultrapure water solution are added for ultrasonic emulsification for 10min. Stirring for 4 hours at room temperature at a rotation speed of 500rpm under the condition of nitrogen to obtain a polystyrene microsphere reaction system with swollen monomers. The pH of the reaction system was adjusted to about 9.0 with ammonia, the temperature was raised to 70℃and the reaction was carried out for 36 hours. After the reaction is finished, ethanol and ultrapure water are respectively used for washing and centrifuging in sequence, and the cyanated amphiphilic asymmetric organic-inorganic hybrid nano particles, which are called JCN for short, are obtained after drying, and are Janus materials.
(3) And (3) dispersing the cyanated amphiphilic asymmetric organic-inorganic hybrid nano particles obtained in the step (2) in water to prepare nano particle dispersion liquid with the concentration of 0.1g/mL, and mixing the commercial primer with water to obtain primer diluent with the commercial primer concentration of 85% of the original concentration. The nanoparticle dispersion liquid and the primer diluent are mixed according to the volume ratio of 1.5:8.5, 120 mu L of the mixed liquid is coated on a silicon wafer with the thickness of 1cm multiplied by 1cm (about 1200 mu m), and then the silicon wafer is dried in a ventilation environment, so that the self-layering coating based on the cyano amphiphilic asymmetric organic-inorganic hybrid nanoparticle is finally obtained.
And (3) carrying out amphipathic verification on the prepared JCN:
Water-paraffin system: firstly, 4mL of ultrapure water and 15mg of JCN are placed in a10 mL glass bottle, and the ultrasonic treatment is carried out for 2min to uniformly disperse particles, so that milky particle aqueous dispersion is obtained. 200mg of paraffin wax having a melting point of 55-60 ℃ was then weighed and added to the above particle dispersion. The temperature was raised to 85℃and the mixture was rapidly stirred at a stirring rate of 1000rpm for 10min to form a water-paraffin emulsion. The paraffin is then rapidly cooled down with liquid nitrogen, and the molten paraffin also fixes the morphology during the liquid nitrogen cooling process. Then evaporating the water in the drying process, and observing the surface structure of the paraffin sample containing the asymmetric particles under a scanning electron microscope. The results are shown in fig. 3, which is an SEM image of the amphiphilic verification of JCN, wherein the left image is a partial enlarged image of the right image, from which it can be seen that JCN is observed on the surface of paraffin microsphere, with hydrophilic end facing outside and hydrophobic end facing inside the paraffin, indicating that JCN has amphiphilic property.
As shown in the schematic structural diagram of the self-layering coating in fig. 1B, a part of JCN will settle to the substrate due to gravity, and another part will migrate to the water-air interface due to the amphipathy of the particles, and fix the morphology during drying.
As shown in FIG. 2, for TEM (left) and SEM (right) images of the JCN prepared, the diameter of the organic portion (polystyrene) of the nanoparticle was about 360nm, and the diameter of the inorganic portion (silica) was about 290nm.
Example 2:
the embodiment 2 provides a preparation method of a self-layering coating based on carboxylated amphiphilic asymmetric organic-inorganic hybrid nano, which comprises the following steps:
(1) 5g of the cyanated amphiphilic asymmetric organic-inorganic hybrid nano particles obtained in the example 1 are taken and dispersed in 400mL of ultrapure water, 100mL of concentrated sulfuric acid is slowly added into the system under the stirring condition, the pH of the system is 2.1, the temperature is raised to 90 ℃, the stirring reaction is carried out for 12 hours, the mixture is respectively centrifugally dispersed by absolute ethyl alcohol and deionized water, the process is repeated for 4-6 times, and the surface carboxylated amphiphilic asymmetric organic-inorganic hybrid nano particles, which are called JCOOH for short, are Janus materials, and are shown in a modification schematic diagram in the figure 1A.
(2) JCOOH obtained in the step (1) is dispersed in water to prepare nano particle dispersion liquid with the concentration of 0.15g/mL, and the commercial primer is mixed with water to obtain primer diluent with the commercial primer concentration of 85% of the original concentration. Mixing the nanoparticle dispersion liquid and the primer diluent according to the volume ratio of 1.5:8.5, taking 120 mu L of the mixed liquid to coat on a silicon wafer with the thickness of 1cm multiplied by 1cm (about 1200 mu m), and then drying in a ventilation environment to finally obtain the self-layering coating based on carboxylated amphiphilic asymmetric organic-inorganic hybrid nanoparticles.
As shown in fig. 4, JCOOH is from SEM images of layered coating (left) and SEM images of commercial primer coating of control group (right), it can be seen from the figures that the surface of the coating formed by the primer is smooth, the contact angle of the coating is lower, which indicates that the coating has stronger hydrophilicity; while hybridized particles were observed on the surface of the self-layering coating after mixing of primer and JCOOH, and the contact angle of the coating was large, indicating that the addition of JCOOH increased the hydrophobicity of the coating.
Example 3:
the embodiment 3 provides a preparation method of a self-layering coating based on fluorinated cyanation amphiphilic asymmetric organic-inorganic hybrid nano, which comprises the following steps:
(1) 85mg of sodium styrenesulfonate and 160mg of potassium persulfate are dissolved in 200mL of methanol water (the volume ratio of methanol to water is 9:1), 27mL of styrene, 3mL of trifluoroethyl acrylate and 0.9mL of p-divinylbenzene are added, ultrasonic emulsification is carried out for 10min, a milky Pickering emulsion is formed, nitrogen is blown for 30min, and then the temperature is raised to 70 ℃ for reaction for 24h. And after the reaction is finished, respectively and repeatedly washing the mixture for more than three times by using ethanol and water in turn to obtain the polystyrene microsphere.
(2) 6G of the polystyrene microspheres obtained in the step (1) are ultrasonically dispersed in 250mL of ultrapure water, 9mL of 3- (triethoxysilyl) propyl methacrylate and 3mL of 2-cyanoethyltriethoxysilane are added, and then 60mg of azobisisobutyronitrile and 90mL of ultrapure water solution are added for ultrasonic emulsification for 10min. Stirring for 4 hours at room temperature at a rotation speed of 500rpm under the condition of nitrogen to obtain a polystyrene microsphere reaction system with swollen monomers. The pH of the reaction system was adjusted to about 9.0 with ammonia, the temperature was raised to 70℃and the reaction was carried out for 24 hours. After the reaction is finished, ethanol and ultrapure water are respectively used for washing and centrifuging in sequence, and the dicyano-fluorinated amphiphilic asymmetric organic-inorganic hybrid nano particles, FJCN for short, which are Janus materials are obtained after drying, and are shown in a modification schematic diagram in figure 1A.
(3) Dispersing the dicyano-fluorinated amphiphilic asymmetric organic-inorganic hybrid nano particles obtained in the step (2) in water to prepare nano particle dispersion liquid with the concentration of 0.1g/mL, and mixing the commercial primer with water to obtain primer diluent with the commercial primer concentration of 85 percent. Mixing the nanoparticle dispersion liquid and the primer diluent liquid according to the volume ratio of 1.5:8.5, taking 100 mu L of the mixed liquid to coat on a silicon wafer with the thickness of 1cm multiplied by 1cm (about 1000 mu m), and then drying in a ventilation environment to finally obtain the self-layering coating based on the fluorinated cyano amphiphilic asymmetric organic-inorganic hybrid nanoparticles.
Example 4:
The embodiment 4 provides a preparation method of a self-layering coating based on fluorinated carboxylated amphiphilic asymmetric organic-inorganic hybrid nanoparticles, which comprises the following steps:
(1) 5g of the fluorinated and cyanated amphiphilic asymmetric organic-inorganic hybrid nano particles obtained in the example 3 are dispersed in 400mL of ultrapure water, 100mL of concentrated sulfuric acid is slowly added into the system under the stirring condition, the pH of the system is 2.1, the temperature is raised to 90 ℃, the stirring reaction is carried out for 12 hours, the mixture is respectively centrifugally dispersed by absolute ethyl alcohol and deionized water, the process is repeated for 4-6 times, and the fluorinated and carboxylated amphiphilic asymmetric organic-inorganic hybrid nano particles, which are called FJCOOH for short, are Janus materials, and are shown in a modification schematic diagram in the figure 1A.
(2) Dispersing the fluorinated carboxylated amphiphilic asymmetric organic-inorganic hybrid nano particles obtained in the step (1) in water to prepare nano particle dispersion liquid with the concentration of 0.1g/mL, and mixing the commercial primer with water to obtain primer diluent with the commercial primer concentration of 85 percent. Mixing the nanoparticle dispersion liquid and the primer diluent according to the volume ratio of 1.5:8.5, taking 100 mu L of the mixed liquid to coat on a silicon wafer with the thickness of 1cm multiplied by 1cm (about 1000 mu m), and then drying in a ventilation environment to finally obtain the self-layering coating based on the fluorinated carboxylated amphiphilic asymmetric organic-inorganic hybrid nanoparticles.
Fig. 5 is a chart of micromechanics property tests of the amphiphilic asymmetric organic-inorganic hybrid nanoparticle-based self-layering coating and the control commercial primer coating obtained in examples 1-4, using a nanoindentation tester (Nano Indentation Tester): manufactured by swiss CSM company under the model number UNHT/NST03050702, is used for characterizing the mechanical properties of the coating material. JCN, JCOOH, FJCN and FJCOOH correspond to the self-differentiating coatings based on amphiphilic asymmetric organic-inorganic hybrid nanoparticles obtained in examples 1-4, respectively, prime corresponding to the commercial primer coating of the control group. As can be seen from the graph, compared with the commercial primer coating of the control group, the hardness HIT and the elastic modulus EIT of the self-layering coating are greatly improved, which indicates that the migration of the amphiphilic asymmetric organic-inorganic hybrid nano particles to the surface of the coating can increase the micromechanics performance of the coating.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (10)
1. The preparation method of the aqueous latex self-layering coating based on the amphiphilic asymmetric organic-inorganic hybrid nano particles is characterized by comprising the following steps of:
S1, dissolving sodium styrene sulfonate and potassium persulfate in a mixed solution of methanol and water, adding an organic polymerization monomer and a cross-linking agent, mixing and emulsifying to obtain Pickering emulsion, and heating and reacting in an inert atmosphere to obtain organic microspheres;
S2, dispersing the organic microspheres obtained in the step S1 in water to obtain an organic microsphere dispersion liquid, mixing a silane acrylate monomer, a silane coupling agent monomer, an initiator and water to obtain a monomer emulsion, mixing the organic microsphere dispersion liquid and the monomer emulsion, stirring for a period of time in an inert atmosphere after emulsification, adjusting pH to be alkaline, and heating to react to obtain amphiphilic asymmetric organic-inorganic hybrid nano particles;
S3, dispersing the amphiphilic asymmetric organic-inorganic hybrid nano particles obtained in the step S2 in water to obtain a nano particle dispersion liquid, mixing the water-based latex primer with water to obtain a water-based latex primer diluent, mixing the nano particle dispersion liquid with the water-based latex primer diluent, dripping the mixture on a silicon wafer, and drying to obtain the water-based latex self-layering coating based on the amphiphilic asymmetric organic-inorganic hybrid nano particles.
2. The method for preparing an aqueous latex self-layering coating based on amphiphilic asymmetric organic-inorganic hybrid nanoparticles according to claim 1, wherein in step S1, the organic polymeric monomer is selected from methyl acrylate, butyl acrylate, methyl methacrylate, styrene, p-methylstyrene;
The cross-linking agent is selected from m-divinylbenzene, p-divinylbenzene, 1,3, 5-trivinylbenzene, 1, 3-pentadiene and isoprene.
3. The method for preparing the aqueous latex self-layering coating based on the amphiphilic asymmetric organic-inorganic hybrid nano particles, according to claim 1, wherein in the step S1, the ratio of the sodium styrenesulfonate, the potassium persulfate, the aqueous methanol mixed solution, the organic polymerization monomer and the cross-linking agent is (80-85) mg: (140-160) mg:200mL:27mL: (0.27-2.7) mL;
the volume ratio of methanol to water in the methanol-water mixed solution is 90:10-50:50.
4. The method for preparing an aqueous latex self-layering coating based on amphiphilic asymmetric organic-inorganic hybrid nanoparticles according to claim 1, wherein in step S1, a vinyl monomer containing fluorine or long carbon chain is further added in the mixed emulsification reaction to carry out hydrophobization surface modification on the organic microspheres;
The vinyl monomer containing fluorine or long carbon chain is selected from trifluoroethyl acrylate, hexafluorobutyl acrylate, trifluoroethyl methacrylate, decyl triethoxysilane, dodecyl trimethoxysilane and octadecyl triethoxysilane;
the addition amount of the fluorine-containing or long carbon chain vinyl monomer is 10-20% of the addition amount of the organic polymerization monomer.
5. The method for preparing an aqueous latex self-layering coating based on amphiphilic asymmetric organic-inorganic hybrid nanoparticles according to claim 1, wherein in step S2, the silane acrylate monomer is selected from the group consisting of propyl 3- (trimethoxysilyl) methacrylate, propyl 3- (trimethoxysilyl) acrylate, butyl 3- (trimethoxysilyl) acrylate, propyl 3- (triethoxysilyl) methacrylate;
The silane coupling agent monomer is selected from 2-cyanoethyl triethoxysilane, 2-cyanoethyl trimethoxysilane, 3-glycidol propoxy trimethoxysilane, 3-amino propyl trimethoxysilane, dodecyl trimethoxysilane, octadecyl trimethoxysilane, triethoxy octyl silane, perfluoro decyl trimethoxysilane and 3-amino propyl triethoxy silane;
the initiator is azobisisobutyronitrile.
6. The method for preparing an aqueous latex self-layering coating based on amphiphilic asymmetric organic-inorganic hybrid nanoparticles according to claim 1, wherein in step S2, the volume ratio of silane acrylate monomer to silane coupling agent monomer in the emulsion is 50:50-90:10;
The addition mass of the initiator is 5 times of the sum value of the volumes of the silane acrylate monomer and the silane coupling agent monomer.
7. The method for preparing an aqueous latex self-layering coating based on amphiphilic asymmetric organic-inorganic hybrid nanoparticles according to claim 1, wherein in the steps S1 and S2, the inert atmosphere is nitrogen, the pH of the solution is regulated to 9.0, the heating reaction temperature is 70 ℃, and the heating reaction time is at least 24 hours.
8. The method for preparing an aqueous latex self-layering coating based on amphiphilic asymmetric organic-inorganic hybrid nanoparticles according to claim 1, wherein when the silane coupling agent monomer in the step S2 is selected from 2-cyanoethyltriethoxysilane and 2-cyanoethyltrimethoxysilane, slowly adding concentrated sulfuric acid into the aqueous solution of the nanoparticles in the step S3, and heating and reacting for a period of time to obtain an organic-inorganic hybrid asymmetric nanoparticle dispersion with carboxylated surfaces;
slowly adding concentrated sulfuric acid to enable the pH value of an acidic environment in a reaction system to be 1.8-2.5, heating the reaction temperature to be 90 ℃, and heating the reaction time to be 12-24h.
9. The method for preparing an aqueous latex self-layering coating based on amphiphilic asymmetric organic-inorganic hybrid nanoparticles according to claim 1, wherein in step S3, the concentration of nanoparticles in the nanoparticle dispersion is 0.01-0.5g/mL; the concentration of the aqueous emulsion primer in the aqueous emulsion primer diluent is 40% -95% of the original concentration; the pH of the aqueous latex primer diluent is 5.01-12.05; the volume ratio of the water-based latex primer diluent to the nanoparticle dispersion liquid is 95:5-50:50;
the thickness of the mixed solution of the water-based latex primer diluent and the nanoparticle dispersion liquid which are dripped on the silicon wafer is 100-3000 mu m.
10. An aqueous latex self-layering coating based on amphiphilic asymmetric organic-inorganic hybrid nanoparticles, which is characterized by being prepared based on the preparation method of any one of claims 1-9.
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