CN112552771A - Silicon dioxide composite acrylic acid/epoxy water-based resin and preparation method thereof - Google Patents
Silicon dioxide composite acrylic acid/epoxy water-based resin and preparation method thereof Download PDFInfo
- Publication number
- CN112552771A CN112552771A CN202011432109.4A CN202011432109A CN112552771A CN 112552771 A CN112552771 A CN 112552771A CN 202011432109 A CN202011432109 A CN 202011432109A CN 112552771 A CN112552771 A CN 112552771A
- Authority
- CN
- China
- Prior art keywords
- silicon dioxide
- mass
- acrylic acid
- epoxy
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 250
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 120
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 100
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 89
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000004593 Epoxy Substances 0.000 title claims abstract description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 229920005989 resin Polymers 0.000 title claims abstract description 33
- 239000011347 resin Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 67
- 239000003822 epoxy resin Substances 0.000 claims abstract description 38
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 38
- 239000006185 dispersion Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 26
- 239000000178 monomer Substances 0.000 claims abstract description 25
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims description 47
- 239000012188 paraffin wax Substances 0.000 claims description 31
- 239000003999 initiator Substances 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 25
- 238000001816 cooling Methods 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- 229920000178 Acrylic resin Polymers 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 230000003472 neutralizing effect Effects 0.000 claims description 8
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical group CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000006228 supernatant Substances 0.000 claims description 4
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 5
- 230000032683 aging Effects 0.000 abstract description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 4
- 239000002105 nanoparticle Substances 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 9
- 239000003973 paint Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 7
- 239000004342 Benzoyl peroxide Substances 0.000 description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 description 6
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000005338 heat storage Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000010556 emulsion polymerization method Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 229920006313 waterborne resin Polymers 0.000 description 3
- 239000013035 waterborne resin Substances 0.000 description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention relates to a silicon dioxide composite acrylic acid/epoxy water-based resin and a preparation method thereof. The preparation method of the silicon dioxide composite acrylic acid/epoxy water-based resin comprises the following steps: hybridizing an epoxy resin and a monomer to form an acrylic acid/epoxy hybrid; preparing an aqueous dispersion of Janus type silica particles; adding the prepared Janus type silicon dioxide particle aqueous dispersion into an acrylic acid/epoxy hybrid to form the silicon dioxide composite acrylic acid/epoxy resin. The method has the advantages that the dosage of the functional monomer acrylic acid or methacrylic acid is less, the residual carboxyl is relatively less, the prepared water-based resin is more stable, the storage stability is greatly improved, a raspberry-like structure is formed, and the corrosion resistance, the weather resistance and the aging resistance of the resin are further improved.
Description
Technical Field
The invention relates to the field of coatings, and particularly relates to a silicon dioxide composite acrylic acid/epoxy water-based resin and a preparation method thereof.
Background
Acrylic resins are excellent in stain resistance, weather resistance and toughness, and epoxy resins are good in adhesion, adhesion and corrosion resistance, so that acrylic/epoxy hybrid aqueous resins have been studied by many people, and common methods include a cold-blending method, a solution polymerization method and an emulsion polymerization method. In the cold-blending method, due to the compatibility problem, the layering phenomenon always occurs, and the prepared paint film has poor performance and cannot meet the requirements; in the solution polymerization method, since the epoxy group cannot be completely eliminated, the storage stability thereof tends to be insufficient for industrial requirements; in the emulsion polymerization method for preparing the acrylic acid/epoxy hybrid water-based resin, because the grafting reaction initiated by the active points generated by the hydrogen abstraction of the initiator free radicals is not easy to occur in the emulsion environment, the grafting density is low, the using amount of the emulsifier is large, and the product meeting the requirements is difficult to obtain.
It is also reported in literature that acrylic acid or epoxy and hybrid thereof are subjected to inorganic modification, but inorganic nanoparticles are generally introduced into an organic system, so that the performance of the composite material is improved on the premise of not damaging the characteristics of an organic matrix. At present, cold splicing is commonly used for inorganic modification, namely, inorganic substances with functions are doped in selected polymers, especially inorganic nanoparticles such as silicon dioxide, zinc oxide, titanium dioxide and the like. In consideration of the surface energy difference between inorganic matters and organic matters, the composite emulsion/dispersion prepared by the cold splicing method has poor stability, and the characteristic of poor stability can be improved by modifying inorganic nanoparticles, but the stability problem cannot be thoroughly solved.
Disadvantage 1: the water-based acrylic acid/epoxy system prepared by the cold-splicing method is easy to layer due to the compatibility problem, and the performance of a paint film is poor;
the disadvantage 2 is that the solution polymerization for preparing the water-based acrylic acid/epoxy hybrid has poor storage stability due to the existence of unreacted carboxyl and epoxy, thus being difficult to meet the industrial requirement;
the disadvantage 3 is that the acrylic acid/epoxy hybrid water-based resin prepared by the emulsion polymerization method has low grafting density and large emulsifier dosage because the grafting reaction initiated by the active site generated by the hydrogen abstraction of the initiator free radical in the emulsion environment is not easy to occur, and the product meeting the requirement is difficult to obtain.
Disclosure of Invention
The invention provides a silicon dioxide composite acrylic acid/epoxy water-based resin and a preparation method thereof, the preparation method of the silicon dioxide composite acrylic acid/epoxy water-based resin is simple and feasible, and the acrylic acid/epoxy hybrid paint film has the advantages of good performance, good storage stability, high hardness after film formation, excellent corrosion resistance, good weather resistance and excellent comprehensive performance.
The preparation method of the silicon dioxide composite acrylic acid/epoxy resin comprises the following steps:
(1) hybridizing an epoxy resin and a monomer to form an acrylic acid/epoxy hybrid;
(2) preparing Janus type silicon dioxide particles with one side containing alkyl and the other side not modified, and then dispersing the Janus type silicon dioxide particles in deionized water to form Janus type silicon dioxide particle water dispersion liquid;
(3) and (3) adding the Janus type silicon dioxide particle aqueous dispersion prepared in the step (2) into the acrylic acid/epoxy hybrid prepared in the step (1) to form the silicon dioxide composite acrylic acid/epoxy resin.
Preferably, step (1) comprises the steps of:
adding 50-70 parts by mass of epoxy resin into a container, heating to 110 ℃ of temperature, then adding 20-40 parts by mass of solvent at the rotation speed of 150-300rpm, then increasing the rotation speed to 600rpm of 400-400 and connecting nitrogen, then dropping a mixed solution consisting of 3-9 parts by mass of methacrylic acid and 1-2 parts by mass of initiator for 1-3h, then heating to 140 ℃ of temperature and keeping the temperature for 0.5-2h, then adding 0.1-0.5 part by mass of initiator, and continuing keeping the temperature for 2-4h to obtain an acrylic acid/epoxy intermediate;
adding 20-40 parts by mass of solvent into a second container, increasing the rotating speed to 400-600rpm, raising the temperature to 120 ℃ for 100-120 ℃, then dripping a mixture consisting of 40-60 parts by mass of monomer, 1-2 parts by mass of initiator and 10-20 parts by mass of acrylic acid/epoxy intermediate prepared in the step (1) for 1-3h, then preserving heat for 20-60min, then adding 0.1-0.5 part by mass of initiator, and continuing preserving heat for 1-3 h; then cooling to room temperature to obtain the acrylic acid/epoxy hybrid.
Preferably, the step (2) comprises the steps of:
adding 50-150 parts by mass of alkaline silica sol into a third container, heating to 65-85 ℃, adding 15-45 parts by mass of paraffin wax under the stirring at the stirring speed of 250-3000 rpm, continuing to stir for 20-60min, and then increasing the rotating speed to 1500-3000rpm and continuing to stir for 10-30 min; then cooling to room temperature and filtering to obtain paraffin particles containing the silica;
dispersing the obtained paraffin particles containing silicon dioxide in 50-150 parts by mass of ethanol at room temperature, then adding 5-20 parts by mass of deionized water and 2-10 parts by mass of alkaline neutralizing agent, then adding 2-10g parts by mass of silane coupling agent, then stirring for 2-4h at the stirring speed of 100-500rpm, then heating to 85-95 ℃, continuing stirring for 1-3h, then cooling to room temperature, and finally centrifuging to remove the supernatant to obtain the paraffin particles containing Janus type silicon dioxide particles;
finally, the paraffin particles of the obtained silicon dioxide are centrifugally extracted by chloroform to remove the paraffin, so that Janus type silicon dioxide particles are obtained.
Preferably, the content of the Janus type silicon dioxide particles in the Janus type silicon dioxide particle water dispersion liquid in the step (2) is between 5 and 15 percent by mass.
Preferably, the step (3) comprises the steps of:
heating the acrylic acid/epoxy hybrid resin obtained in the step (1) to 50-70 ℃, then increasing the rotating speed to 1500-3000rpm, then adding 5-15 parts by mass of an alkaline neutralizing agent, then dropping 40-65 parts by mass of the Janus type silicon dioxide particle aqueous dispersion prepared in the step (2), wherein the dropping time is 60-120min, then controlling the stirring speed to 2500-3500rpm, then adding 20-40 parts by mass of the Janus type silicon dioxide particle aqueous dispersion prepared in the step (2), then controlling the stirring speed to 1000-3000rpm, and continuing stirring for 20-60min to obtain the silicon dioxide composite acrylic acid/epoxy resin.
The alkaline neutralizing agent is ammonia water or N, N-dimethylethanolamine water solution with the mass fraction of 50%.
Preferably, the initiator is a thermal decomposition type initiator;
the monomer is one of acrylate monomer, methacrylate monomer and styrene monomer or is formed by mixing the acrylate monomer, the methacrylate monomer and the styrene monomer according to any proportion.
Preferably, the particle size of the alkaline silica sol is between 22 and 25 nm; the solid content is 40 percent; the pH is between 9 and 10;
the silane coupling agent is 3- (2, 3-epoxypropoxy) propyl trimethoxy silane.
The silicon dioxide composite acrylic acid/epoxy resin is prepared by the method.
The principle is as follows: the main technical scheme of the invention is to prepare the silicon dioxide composite acrylic acid/epoxy water-based resin, firstly, preparing acrylic acid/epoxy hybrid, then preparing silicon dioxide nano particles, wherein the silicon dioxide nano particles are Janus nano particles, one surface of the silicon dioxide nano particles is modified by containing alkyl, the other surface of the silicon dioxide nano particles is unmodified, and the silicon dioxide nano particles are added with water in the preparation process of the acrylic acid/epoxy water-based resin, so that the silicon dioxide nano particles can be uniformly dispersed around the acrylic acid/epoxy water-based resin dispersion and can stabilize the acrylic acid/epoxy hybrid water-based resin.
In the step (1), carboxyl and epoxy group are used for reaction, and epoxy resin is grafted to an acrylate polymer chain to form acrylic acid/epoxy hybrid resin; when the silicon dioxide is modified in the step (2), the raw materials adopted are paraffin and partial solvent, and the finally used paraffin and solvent can be recycled; in the method for preparing the silicon dioxide-containing acrylic acid/epoxy waterborne resin, modified silicon dioxide and acrylic acid/epoxy resin are mutually fused to form a raspberry-shaped structure.
The water-based acrylic resin and the water-based epoxy resin mentioned in the background are cold spliced, have the problem of miscibility and are easy to separate; the solution polymerization method is easy to fail in thermal storage stability; the emulsion polymerization method easily causes that the grafting rate is low and cannot meet the requirement; the organic-inorganic hybridization also adopts physical blending, which is easy to cause agglomeration. The invention adopts a solution polymerization method combined with Janus silicon dioxide technology to prepare the silicon dioxide composite acrylic acid/epoxy water-based resin. The silicon dioxide can stabilize acrylic acid/epoxy hybrid, and can stabilize polymer under the condition of relatively hydrophobic property, so that the dosage of functional monomer acrylic acid or methacrylic acid can be reduced, and the polymer has relatively good hydrophobic property and relatively good heat storage stability. The solution polymerization is adopted to solve the problem of low grafting rate of emulsion polymerization.
Compared with the prior art, the invention has the following beneficial effects: compared with the conventional acrylic acid/epoxy hybrid water-based resin, the method has the advantages that the consumption of functional monomers of acrylic acid or methacrylic acid is less, the residual carboxyl is relatively less, the prepared water-based resin is more stable, the storage stability is greatly improved, meanwhile, inorganic silica nano particles are introduced, and a raspberry-like structure is formed by utilizing the difference of hydrophilicity and hydrophobicity, so that the corrosion resistance, the weather resistance and the aging resistance of the resin are further improved. The resin integrates the performances of acrylic acid, epoxy and inorganic nano particles, and can improve the comprehensive performances of the hardness, weather resistance, corrosion resistance, mechanical property and the like of a paint film when being applied to paint.
A special silicon dioxide doping process, namely adding silicon dioxide dispersion liquid in the phase inversion process of preparing the aqueous resin, wherein the silicon dioxide is embedded in the polymer;
the active ingredient of the prepared silicon dioxide dispersion liquid is Janus silicon dioxide nano-particles, namely one end of the silicon dioxide dispersion liquid is modified, and the other end of the silicon dioxide dispersion liquid is unmodified, so that the stability of a polymer dispersed in water can be improved, the agglomeration of inorganic nano-particles is prevented, and the stability of the whole system, particularly the heat storage stability, is improved;
the method is simple, the prepared composite dispersoid is not influenced in gloss, the hardness is greatly increased, and the salt spray resistance is improved.
The dispersion prepared by the method is stable, and has no layering and obvious viscosity change; the heat storage at 50 ℃ for 30 days has no abnormality, and meets the requirement of industrial application; when the coating is applied to a coating, the hardness of a paint film can reach more than 2H, and the artificial accelerated aging resistant time exceeds 1000H; meanwhile, the introduction of the inorganic nano particle silicon dioxide does not influence the performances of fullness, luster and the like of a paint film.
Drawings
FIG. 1 is a flow chart of the preparation method of the present invention.
Detailed Description
The invention will be further illustrated with reference to the following specific examples
Example 1
The preparation method of the silicon dioxide composite acrylic acid/epoxy resin comprises the following steps:
(1) hybridizing an epoxy resin and a monomer to form an acrylic acid/epoxy hybrid;
(2) preparing Janus type silicon dioxide particles with one side containing alkyl and the other side not modified, and then dispersing the Janus type silicon dioxide particles in deionized water to form Janus type silicon dioxide particle water dispersion liquid;
(3) and (3) adding the Janus type silicon dioxide particle aqueous dispersion prepared in the step (2) into the acrylic acid/epoxy hybrid prepared in the step (1) to form the silicon dioxide composite acrylic acid/epoxy resin.
The step (1) comprises the following steps:
adding 50g of epoxy resin into a container, heating to 100 ℃, then adding 20g of solvent at 200rpm, then increasing the rotating speed to 400rpm and connecting nitrogen, then dripping a mixed solution consisting of 3g of methacrylic acid and 1g of initiator for 1h, heating to 110 ℃, keeping the temperature for 0.5h, then adding 0.1g of initiator, and continuing to keep the temperature for 2h to obtain an acrylic acid/epoxy intermediate;
adding 20g of solvent into a second container, increasing the rotating speed to 400rpm, raising the temperature to 100 ℃, then dripping a mixture consisting of 40g of acrylate, 1g of initiator and 10g of acrylic acid/epoxy intermediate prepared in the step (1) for 1 hour, then preserving heat for 20min, then adding 0.1g of initiator, and continuing preserving heat for 1 hour; then cooling to room temperature to obtain the acrylic acid/epoxy hybrid.
The step (2) comprises the following steps:
adding 50g of alkaline silica sol into a third container, heating to 65 ℃, adding 15g of paraffin wax under the stirring of 250rpm, continuing to stir for 20min, and then increasing the rotating speed to 1500rpm and continuing to stir for 10 min; then the temperature is cooled to room temperature and filtered to obtain paraffin particles containing the silica;
dispersing the obtained paraffin particles containing silicon dioxide in 50g of ethanol at room temperature, then adding 5g of deionized water and 2g of ammonia water, then adding 2g of silane coupling agent, stirring at the stirring speed of 100rpm for 2h, then heating to 85 ℃, continuing stirring for 1 hour, then cooling to room temperature, and finally centrifuging to remove the supernatant to obtain the paraffin particles containing Janus type silicon dioxide particles;
finally, the paraffin particles of the obtained silicon dioxide are centrifugally extracted by chloroform to remove the paraffin, so that Janus type silicon dioxide particles are obtained.
Finally, ultrasonically dispersing the obtained Janus silicon dioxide nano particles in water to form Janus silicon dioxide nano particle water dispersion liquid;
the mass percentage of the Janus type silicon dioxide particles in the Janus type silicon dioxide particle water dispersion liquid in the step (2) is 5%.
The step (3) comprises the following steps:
heating the acrylic acid/epoxy hybrid resin obtained in the step (1) to 50 ℃, then increasing the rotating speed to 1500rpm, then adding 5g of 50% N, N-dimethylethanolamine aqueous solution, then dropping 40g of Janus type silicon dioxide particle aqueous dispersion prepared in the step (2), wherein the dropping time is between 60min, then controlling the stirring speed to be 2500rpm, then adding 20-40g of Janus type silicon dioxide particle aqueous dispersion prepared in the step (2), then controlling the stirring speed to be 1000rpm, and continuing stirring for 20min to obtain the silicon dioxide composite acrylic acid/epoxy resin.
The alkaline neutralizing agent is a 50% N, N-dimethylethanolamine aqueous solution.
Preferably, the initiator is a thermal decomposition type initiator (benzoyl peroxide);
the monomer is methacrylate monomer.
Preferably, the particle size of the alkaline silica sol is between 22 and 25 nm; the solid content is 40 percent; the pH is 10;
the silane coupling agent is 3- (2, 3-epoxypropoxy) propyl trimethoxy silane.
Example 2
The preparation method of the silicon dioxide composite acrylic acid/epoxy resin comprises the following steps:
(1) hybridizing epoxy resin and acrylate to form an acrylic acid/epoxy hybrid;
(2) preparing Janus type silicon dioxide particles with one side containing alkyl and the other side not modified, and then dispersing the Janus type silicon dioxide particles in deionized water to form Janus type silicon dioxide particle water dispersion liquid;
(3) and (3) adding the Janus type silicon dioxide particle aqueous dispersion prepared in the step (2) into the acrylic acid/epoxy hybrid prepared in the step (1) to form the silicon dioxide composite acrylic acid/epoxy resin.
The step (1) comprises the following steps:
adding 70g of epoxy resin E44 into a container, heating to 110 ℃, then adding 40g of solvent at 150rpm, then increasing the rotation speed to 600rpm, switching on nitrogen, then dripping a mixed solution consisting of 9g of methacrylic acid and 2g of initiator for 3 hours, then heating to 140 ℃, keeping the temperature for 2 hours, then adding 0.5g of initiator, and continuing to keep the temperature for 4 hours to obtain an acrylic acid/epoxy intermediate;
adding 40g of solvent into a second container, increasing the rotating speed to 600rpm, raising the temperature to 120 ℃, then dripping a mixture consisting of 60g of acrylate monomer, 2g of initiator and 20g of acrylic acid/epoxy intermediate prepared in the step (1) for 3 hours, then preserving heat for 60 minutes, then adding 0.5g of initiator, and continuing preserving heat for 3 hours; then cooling to room temperature to obtain the acrylic acid/epoxy hybrid.
The step (2) comprises the following steps:
adding 150g of alkaline silica sol into a third container, heating to 85 ℃, adding 45g of paraffin wax under the stirring of 250rpm, continuing to stir for 60min, and then increasing the rotating speed to 3000rpm and continuing to stir for 30 min; then cooling to room temperature and filtering to obtain paraffin particles containing the silica;
dispersing the obtained paraffin particles containing silicon dioxide in 150g of ethanol at room temperature, then adding 20g of deionized water and 10g of ammonia water, then adding 10gg of silane coupling agent, stirring at the stirring speed of 500rpm for 4h, then heating to 95 ℃, continuing stirring for 3 hours, then cooling to room temperature, and finally centrifuging to remove the supernatant to obtain the paraffin particles containing Janus type silicon dioxide particles;
finally, the paraffin particles of the obtained silicon dioxide are centrifugally extracted by chloroform to remove the paraffin, so that Janus type silicon dioxide particles are obtained.
Finally, ultrasonically dispersing the obtained Janus silicon dioxide nano particles in water to form Janus silicon dioxide nano particle water dispersion liquid;
the mass percentage of the Janus type silicon dioxide particles in the Janus type silicon dioxide particle water dispersion liquid in the step (2) is 15%.
The step (3) comprises the following steps:
heating the acrylic acid/epoxy hybrid resin obtained in the step (1) to 70 ℃, then increasing the rotating speed to 3000rpm, then adding 15g of 50% N, N-dimethylethanolamine aqueous solution, then dropping 65g of the Janus type silicon dioxide particle aqueous dispersion prepared in the step (2), wherein the dropping time is 120min, then controlling the stirring speed to be 3500rpm, then adding 40g of the Janus type silicon dioxide particle aqueous dispersion prepared in the step (2), then controlling the stirring speed to be 3000rpm, and continuing stirring for 60min to obtain the silicon dioxide composite acrylic acid/epoxy resin.
The alkaline neutralizing agent is ammonia water.
Preferably, the initiator is a thermal decomposition type initiator (benzoyl peroxide);
the monomer is acrylate monomer.
Preferably, the particle size of the alkaline silica sol is between 22 and 25 nm; the solid content is 40 percent; the pH is 9;
the silane coupling agent is 3- (2, 3-epoxypropoxy) propyl trimethoxy silane.
Example 3
A preparation method of silicon dioxide composite acrylic acid/epoxy water-based resin comprises the following steps:
(1) hybridizing an epoxy resin and a monomer to form an acrylic/epoxy hybrid:
adding 60g of epoxy resin E44 into a second container, heating to 110 ℃, adding 11g of ethylene glycol butyl ether and 21.2g of n-butanol, introducing nitrogen, dripping a mixed solution of 6g of methacrylic acid and 1.5g of benzoyl peroxide at the rotation speed of 500rpm, controlling the dripping time to be 2 hours, heating to 120 ℃, preserving heat for 1 hour, then adding 0.3g of benzoyl peroxide, and preserving heat for 3 hours at 120 ℃ to obtain an acrylic acid/epoxy intermediate;
adding 10g of ethylene glycol butyl ether and 20g of n-butanol into a third container while stirring at the temperature of 110 ℃, then dripping a mixture of 4.8g of methacrylic acid, 35g of butyl acrylate, 13.6g of methyl methacrylate, 15g of the acrylic acid/epoxy intermediate prepared in the step (2) and 1.3g of an initiator (benzoyl peroxide) at the rotation speed of 500rpm for 2 hours, then keeping the temperature for 30 minutes, then adding 0.3g of the initiator benzoyl peroxide, and keeping the temperature for 2 hours; then cooling to room temperature to obtain an acrylic acid epoxy hybrid;
(2) preparation of aqueous Janus silica nanoparticle dispersion
Adding 100g of alkaline silica sol into a first container, heating to 75 ℃, adding 30g of paraffin under the stirring of 250rpm, continuously stirring for 30min, increasing the rotating speed to 2000rpm, continuously stirring for 20min, cooling to room temperature, and filtering by 400-mesh filter paper to obtain paraffin particles containing silicon dioxide;
then dispersing the obtained paraffin particles containing the silicon dioxide in a second container filled with 100g of ethanol at room temperature and at a stirring speed of 250rpm, then adding 10g of water, 5g of ammonia water and 5g of 3- (2, 3-epoxypropoxy) propyltrimethoxysilane (A187), continuing stirring for 3 hours, then heating to 90 ℃ and preserving the temperature for 1 hour, then cooling to room temperature, and then centrifuging to obtain the paraffin particles containing the modified silicon dioxide;
dispersing the obtained modified silica-containing paraffin particles in 200g of chloroform at room temperature and at a stirring speed of 250rpm, stirring for 1h, centrifuging to remove the chloroform to obtain Janus silica nanoparticles, and finally ultrasonically dispersing the obtained Janus silica nanoparticles in 400g of water to form Janus silica nanoparticle aqueous dispersion;
(3) preparation of silicon dioxide composite acrylic acid/epoxy water-based resin
Heating the acrylic acid epoxy hybrid prepared in the step (2) to 60 ℃, increasing the rotating speed to 2000rpm, beginning to dropwise add 10g of N, N-dimethylethanolamine aqueous solution (the mass fraction of the N, N-dimethylethanolamine aqueous solution is between 50%), then dropwise add 55g of Janus silicon dioxide aqueous dispersion prepared in the step (1), wherein the dropwise add time is 90min, and then increasing the rotating speed to 3000 rpm; and (2) continuing to drop 30g of Janus silicon dioxide aqueous dispersion prepared in the step (1), then reducing the rotating speed to 2000rpm, and continuing to stir for 30min to obtain the silicon dioxide composite acrylic acid/epoxy waterborne resin.
The synthesis schematic diagrams of the steps (1), (2) and (3) are shown in figure 1.
The resins prepared in examples 1-3 were prepared into silica-containing composite acrylic/epoxy waterborne resin coatings.
Example 4
The main difference between example 4 and example 3 is that the aqueous dispersion of Janus-type silica particles in step (2) has a Janus-type silica particle content of 20% by mass; the others are unchanged.
Comparative example 1
The main difference between comparative example 1 and example 3 is the elimination of step (1) — the acrylic/epoxy intermediate in step (1) — is replaced by 5g of styrene +5g of butyl acrylate +0.5g of methacrylic acid +4.5g of propylene glycol butyl ether, the other steps remaining unchanged.
Comparative example 2
Comparative example 2 differs from example 3 in that in step (3) no Janus-containing silica dispersion is used, but water is used directly instead of the aqueous Janus-type silica particle dispersion.
The above examples 1-4 and comparative examples 1 and 2 were formulated into coatings according to the following composition:
the silicon dioxide-containing composite acrylic acid/epoxy water-based resin coating is prepared from the following components in percentage by mass:
60 parts of the resin of examples 1 to 4 or comparative example 1 or 2
The prepared coating is sprayed on a cold-rolled steel plate, the thickness of the wet film is controlled to be 200 mu m, the cold-rolled steel plate is baked at 80 ℃ for 30min to be cured and used for performance test, and the results are shown in Table 1.
As can be seen from Table 1, the paint films of examples 1-4 are superior in appearance, hardness, gloss, adhesion, flexibility, water resistance, resistance to artificial aging, salt spray resistance and heat storage stability, comparative example 2 is NG in heat storage stability, and comparative example 1 is significantly inferior to example 3 in gloss, water resistance and salt spray resistance.
The properties of the paint plaques prepared from the resins of examples 1 to 4 and comparative examples 1-2 are shown in the following table:
Claims (10)
1. the preparation method of the silicon dioxide composite acrylic acid/epoxy resin is characterized by comprising the following steps: the method comprises the following steps:
(1) hybridizing an epoxy resin and a monomer to form an acrylic acid/epoxy hybrid;
(2) preparing Janus type silicon dioxide particles with one side containing alkyl and the other side not modified, and then dispersing the Janus type silicon dioxide particles in deionized water to form an aqueous dispersion of the Janus type silicon dioxide particles;
(3) and (3) adding the Janus type silicon dioxide particle aqueous dispersion prepared in the step (2) into the acrylic acid/epoxy hybrid prepared in the step (1) to form the silicon dioxide composite acrylic acid/epoxy resin.
2. The method for preparing silica composite acrylic/epoxy resin according to claim 1, wherein: the step (1) comprises the following steps:
adding 50-70 parts by mass of epoxy resin into a container, heating to 110 ℃ of temperature, then adding 20-40 parts by mass of solvent at the rotation speed of 150-300rpm, then increasing the rotation speed to 600rpm of 400-400 and connecting nitrogen, then dropping a mixed solution consisting of 3-9 parts by mass of methacrylic acid and 1-2 parts by mass of initiator for 1-3h, then heating to 140 ℃ of temperature and keeping the temperature for 0.5-2h, then adding 0.1-0.5 part by mass of initiator, and continuing keeping the temperature for 2-4h to obtain an acrylic acid/epoxy intermediate;
adding 20-40 parts by mass of solvent into a second container, increasing the rotating speed to 400-600rpm, raising the temperature to 120 ℃ for 100-120 ℃, then dripping a mixture consisting of 40-60 parts by mass of monomer, 1-2 parts by mass of initiator and 10-20 parts by mass of acrylic acid/epoxy intermediate prepared in the step (1) for 1-3h, then preserving heat for 20-60min, then adding 0.1-0.5 part by mass of initiator, and continuing preserving heat for 1-3 h; then cooling to room temperature to obtain the acrylic acid/epoxy hybrid.
3. The method for preparing silica composite acrylic/epoxy resin according to claim 1, wherein: the step (2) comprises the following steps:
adding 50-150 parts by mass of alkaline silica sol into a third container, heating to 65-85 ℃, adding 15-45 parts by mass of paraffin wax under the stirring at the stirring speed of 250-3000 rpm, continuing to stir for 20-60min, and then increasing the rotating speed to 1500-3000rpm and continuing to stir for 10-30 min; then cooling to room temperature and filtering to obtain paraffin particles containing the silica;
dispersing the obtained paraffin particles containing silicon dioxide in 50-250 parts by mass of ethanol at room temperature, then adding 5-20 parts by mass of deionized water and 2-10 parts by mass of alkaline neutralizing agent, then adding 2-10g parts by mass of silane coupling agent, then stirring for 2-4h at the stirring speed of 100-500rpm, then heating to 85-95 ℃, continuing stirring for 1-3h, then cooling to room temperature, and finally centrifuging to remove the supernatant to obtain the paraffin particles containing Janus type silicon dioxide particles;
finally, the paraffin particles of the obtained silicon dioxide are centrifugally extracted by chloroform to remove the paraffin, so that Janus type silicon dioxide particles are obtained.
4. The method for preparing silica composite acrylic/epoxy resin according to claim 1, wherein: in the step (2), the mass percentage of the Janus type silicon dioxide particles in the Janus type silicon dioxide particle water dispersion liquid is between 5 and 20 percent.
5. The method for preparing silica composite acrylic/epoxy resin according to claim 1, wherein: the step (3) comprises the following steps:
heating the acrylic acid/epoxy hybrid resin obtained in the step (1) to 50-70 ℃, then increasing the rotating speed to 1500-3000rpm, then adding 5-15 parts by mass of an alkaline neutralizing agent, then dropping 40-65 parts by mass of the Janus type silicon dioxide particle aqueous dispersion prepared in the step (2), wherein the dropping time is 60-120min, then controlling the stirring speed to 2500-3500rpm, then adding 20-40 parts by mass of the Janus type silicon dioxide particle aqueous dispersion prepared in the step (2), then controlling the stirring speed to 1000-3000rpm, and continuing stirring for 20-60min to obtain the silicon dioxide composite acrylic acid/epoxy resin.
6. The method for preparing silica composite acrylic/epoxy resin according to claim 2, wherein: the initiator is a thermal decomposition type initiator.
7. The method for preparing silica composite acrylic/epoxy resin according to claim 2, wherein: the monomer is one of acrylate monomer, methacrylate monomer and styrene monomer or is formed by mixing the acrylate monomer, the methacrylate monomer and the styrene monomer in any proportion.
8. The method for preparing a silica composite acrylic/epoxy resin according to claim 3 or 5, characterized in that: the alkaline neutralizing agent is ammonia water or N, N-dimethylethanolamine water solution with the mass fraction of 50%.
9. The method for preparing silica composite acrylic/epoxy resin according to claim 3, wherein:
the particle size of the alkaline silica sol is between 22 and 25 nm; the solid content is 40 percent; the pH is between 9 and 10;
the silane coupling agent is 3- (2, 3-epoxypropoxy) propyl trimethoxy silane.
10. The silicon dioxide composite acrylic acid/epoxy resin is characterized in that: prepared by the method of any one of claims 1-9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011432109.4A CN112552771B (en) | 2020-12-07 | 2020-12-07 | Silicon dioxide composite acrylic acid/epoxy water-based resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011432109.4A CN112552771B (en) | 2020-12-07 | 2020-12-07 | Silicon dioxide composite acrylic acid/epoxy water-based resin and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112552771A true CN112552771A (en) | 2021-03-26 |
| CN112552771B CN112552771B (en) | 2022-07-05 |
Family
ID=75060067
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011432109.4A Active CN112552771B (en) | 2020-12-07 | 2020-12-07 | Silicon dioxide composite acrylic acid/epoxy water-based resin and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112552771B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114574054A (en) * | 2022-03-14 | 2022-06-03 | 浙江优尼科新材料有限公司 | Water-based antifouling treatment agent |
| CN116948498A (en) * | 2023-08-24 | 2023-10-27 | 湖南鑫铃住房设备有限公司 | Waterproof nano coating material for SMC wallboard |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110213066A1 (en) * | 2009-04-03 | 2011-09-01 | Xiaorong Wang | Hairy Polymeric Nanoparticles With First And Second Shell Block Polymer Arms |
| CN111995708A (en) * | 2020-08-31 | 2020-11-27 | 陕西科技大学 | Based on amphiphilic Janus SiO2Nano particle fluorine-containing polyacrylate finishing agent and preparation method thereof |
-
2020
- 2020-12-07 CN CN202011432109.4A patent/CN112552771B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110213066A1 (en) * | 2009-04-03 | 2011-09-01 | Xiaorong Wang | Hairy Polymeric Nanoparticles With First And Second Shell Block Polymer Arms |
| CN111995708A (en) * | 2020-08-31 | 2020-11-27 | 陕西科技大学 | Based on amphiphilic Janus SiO2Nano particle fluorine-containing polyacrylate finishing agent and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| HONG L等: "Ｓｉｍｐｌｅ Ｍｅｔｈｏｄ ｔｏ Ｐｒｏｄｕｃｅ Ｊａｎｕｓ Ｃｏｌｌｏｉｄａｌ Ｐａｒｔｉｃｌｅｓ ｉｎ Ｌａｒｇｅ Ｑｕａｎｔｉｔｙ", 《ＬＡＮＧＭＵＩＲ》 * |
| 刘旭等: "水性油墨用环氧改性水性丙烯酸树脂的合成", 《包装工程》 * |
| 双少敏等: "双面粒子的制备及应用研究新进展", 《山西大学学报(自然科学版)》 * |
| 陈细芳等: "水性环氧-丙烯酸酯复合乳液制备研究进展", 《涂料工业》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114574054A (en) * | 2022-03-14 | 2022-06-03 | 浙江优尼科新材料有限公司 | Water-based antifouling treatment agent |
| CN116948498A (en) * | 2023-08-24 | 2023-10-27 | 湖南鑫铃住房设备有限公司 | Waterproof nano coating material for SMC wallboard |
| CN116948498B (en) * | 2023-08-24 | 2024-03-12 | 湖南鑫铃住房设备有限公司 | Waterproof nano coating material for SMC wallboard |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112552771B (en) | 2022-07-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102924646B (en) | Preparation method of waterproof and whiting-resistant silicon-acrylic composite emulsion for interior wall latex coatings | |
| CN112552771B (en) | Silicon dioxide composite acrylic acid/epoxy water-based resin and preparation method thereof | |
| CN101429267B (en) | Preparation and uses of epoxy/acrylic acid hybridisation emulsion | |
| CN109868026B (en) | Organic silicon modified acrylate resin, preparation method thereof and hydrophobic weather-resistant slow-release modified acrylic resin coating | |
| CN102786644B (en) | Preparation method of acrylic resin finishing agent modified by nano silicon dioxide (SiO2)-coated multi-walled carbon nanotubes | |
| DE60109965T2 (en) | Composite particles, composite particle dispersion composition and process for producing a composite particle dispersion composition | |
| CN100509890C (en) | Organosilicon epoxide acrylate water dispersion, preparation method and application thereof | |
| CN104744639B (en) | A kind of preparation method of organic-silicon-modified normal-temperature multiple self-cross-linking epoxy resin emulsion | |
| CN101372527B (en) | Nano-zinc oxide/acrylic ester grafting composite emulsion and preparation thereof | |
| CN105777980A (en) | Epoxy/carboxyl-containing acrylate copolymer core-shell emulsion and preparation method and application thereof | |
| CN112280043B (en) | Silicon dioxide/polyacrylate/polysiloxane composite emulsion, preparation method and application thereof | |
| CN105273557A (en) | Waterborne wood paint and preparation method thereof | |
| CN103602193A (en) | Priming paint for water-borne heavy anti-corrosion coating and preparation method thereof | |
| EP2675850A1 (en) | Modified composite particles | |
| CN114752279B (en) | High-solid-content water-based graphene anticorrosive paint, and preparation method and application thereof | |
| CN105622831A (en) | Preparation method of acrylic acid organic silicon soap-free copolymerization emulsion | |
| CN103627286A (en) | Water-based finishing coat for heavy-duty coating and preparation method of water-based finishing coat | |
| CN114181607A (en) | Waterborne polyurethane waterproof coating and cold preparation process thereof | |
| CN109369861A (en) | A kind of hydrophilic organic silicon microballoon and preparation method thereof | |
| JP2024504563A (en) | Method for preparing graphene oxide modified styrene-acrylic Pickering emulsion and composite emulsion, and method for preventing corrosion of cementitious materials | |
| CN102675518B (en) | Preparation method for organic-inorganic hybrid fluorine-silicon modified nano waterborne resin | |
| CN110467855A (en) | A kind of graphene modified water-soluble damping paint and preparation method thereof | |
| JPS6363756A (en) | Dispersed paint resin composition | |
| CN113045940A (en) | Emulsion paint for external wall and preparation method thereof | |
| CN112175200B (en) | Silicon dioxide-containing composite hydroxyl acrylic acid dispersion and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240320 Address after: 239400 No.1, Jingsi Road, Mingguang chemical industry concentration area, Chuzhou City, Anhui Province Patentee after: Anhui sanjeshu coating Co.,Ltd. Country or region after: Zhong Guo Address before: 201108 1st and 2nd floors, building 10, 389 Jinglian Road, Minhang District, Shanghai Patentee before: Sankeshu (Shanghai) new material research Co.,Ltd. Country or region before: Zhong Guo |
|
| TR01 | Transfer of patent right |