CN115449288A - Environment-friendly water-based paint and preparation method thereof - Google Patents
Environment-friendly water-based paint and preparation method thereof Download PDFInfo
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- CN115449288A CN115449288A CN202211164453.9A CN202211164453A CN115449288A CN 115449288 A CN115449288 A CN 115449288A CN 202211164453 A CN202211164453 A CN 202211164453A CN 115449288 A CN115449288 A CN 115449288A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000003973 paint Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims description 18
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 35
- 229920002126 Acrylic acid copolymer Polymers 0.000 claims abstract description 28
- 239000008367 deionised water Substances 0.000 claims abstract description 22
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 22
- 229920001046 Nanocellulose Polymers 0.000 claims abstract description 21
- 239000002562 thickening agent Substances 0.000 claims abstract description 17
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 15
- 229920002678 cellulose Polymers 0.000 claims abstract description 14
- 239000001913 cellulose Substances 0.000 claims abstract description 14
- 239000002270 dispersing agent Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- 239000000377 silicon dioxide Substances 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 12
- -1 lauryl alcohol ester Chemical class 0.000 claims description 11
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 229920002635 polyurethane Polymers 0.000 claims description 7
- 239000004814 polyurethane Substances 0.000 claims description 7
- NPFYZDNDJHZQKY-UHFFFAOYSA-N 4-Hydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 NPFYZDNDJHZQKY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- LCPDWSOZIOUXRV-UHFFFAOYSA-N phenoxyacetic acid Chemical compound OC(=O)COC1=CC=CC=C1 LCPDWSOZIOUXRV-UHFFFAOYSA-N 0.000 claims description 6
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 5
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 5
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 5
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 5
- 150000004645 aluminates Chemical class 0.000 claims description 4
- 239000007822 coupling agent Substances 0.000 claims description 4
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 4
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 4
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 4
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 4
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 claims description 3
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 claims description 3
- OXJPSXOFVIBYOQ-UHFFFAOYSA-N 2-methyl-3,4-diphenylphenol Chemical compound C=1C=CC=CC=1C=1C(C)=C(O)C=CC=1C1=CC=CC=C1 OXJPSXOFVIBYOQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003377 acid catalyst Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- PSGAAPLEWMOORI-PEINSRQWSA-N medroxyprogesterone acetate Chemical compound C([C@@]12C)CC(=O)C=C1[C@@H](C)C[C@@H]1[C@@H]2CC[C@]2(C)[C@@](OC(C)=O)(C(C)=O)CC[C@H]21 PSGAAPLEWMOORI-PEINSRQWSA-N 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 229920002050 silicone resin Polymers 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 20
- 238000000746 purification Methods 0.000 abstract description 10
- 230000007613 environmental effect Effects 0.000 abstract description 7
- 239000000839 emulsion Substances 0.000 abstract description 6
- 238000007790 scraping Methods 0.000 abstract description 3
- 239000012752 auxiliary agent Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 21
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 15
- 238000000576 coating method Methods 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 7
- 229920006243 acrylic copolymer Polymers 0.000 description 6
- 239000010410 layer Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 230000002045 lasting effect Effects 0.000 description 3
- 229910021426 porous silicon Inorganic materials 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N ethyl butylhexanol Natural products CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000012434 nucleophilic reagent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical class [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having 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
- 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
-
- 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
- C09D7/65—Additives macromolecular
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to the technical field of water-based paint, and provides environment-friendly water-based paint which comprises, by weight, 40-60 parts of modified polyurethane-acrylic acid copolymer, 20-30 parts of nano titanium dioxide, 20-30 parts of nano cellulose, 10-20 parts of graphene oxide, 40-60 parts of deionized water, 1-10 parts of film-forming auxiliary agent, 0.1-5 parts of defoaming agent, 1-10 parts of thickening agent and 1-10 parts of dispersing agent; the hardness, the wear resistance and the like of the water-based paint are greatly improved, so that the water-based paint is resistant to scraping and difficult to strip after being sprayed, and can exert excellent purification effect, and the environment-friendly effect is better; preparing a pre-emulsion, mixing and interweaving the pre-emulsion with partial graphene oxide and partial nano-cellulose in advance to form a grid structure in advance, and adding the rest nano-cellulose and graphene oxide while adding nano-titanium dioxide; the water-based paint can improve the hardness and the wear resistance of the water-based paint, and keeps the adhesion stability of the nano titanium dioxide, thereby continuously and efficiently exerting the purification effect and having better environmental protection.
Description
Technical Field
The invention relates to the technical field of water-based paint, and particularly relates to environment-friendly water-based paint and a preparation method thereof.
Background
With the implementation of environmental protection policies, the environmental protection consciousness of consumers is continuously improved, and particularly, the VOC emission limit standards are set in provinces and cities across the country, so that the development of environment-friendly coatings such as non-solvent type coatings, water-based paints and the like is encouraged to bring opportunities. Although the traditional coating still occupies a large market share, the water-based paint takes water as a solvent, saves a large amount of resources, eliminates the fire hazard during construction, reduces the air pollution, improves the operation environment conditions, is a green industry, and is the future development direction of paints.
However, the performance of the water-based paint in the aspects of hardness, wear resistance and the like is weaker than that of the paint in the using process, so that the water-based paint is not resistant to scraping and collision after being sprayed, is easy to strip, greatly influences the using effect, does not have the performance of purifying air, is poor in environmental protection performance, and is large in limitation in use.
Disclosure of Invention
Based on the problems, the invention provides an environment-friendly water-based paint which comprises, by weight, 40-60 parts of a modified polyurethane-acrylic acid copolymer, 20-30 parts of nano titanium dioxide, 20-30 parts of nano cellulose, 10-20 parts of graphene oxide, 40-60 parts of deionized water, 1-10 parts of a film-forming assistant, 0.1-5 parts of a defoaming agent, 1-10 parts of a thickening agent and 1-10 parts of a dispersing agent.
Further, the coating comprises, by weight, 40-50 parts of a modified polyurethane-acrylic acid copolymer, 22-29 parts of nano titanium dioxide, 22-28 parts of nano cellulose, 12-18 parts of graphene oxide, 50-60 parts of deionized water, 1-5 parts of a film-forming aid, 0.1-3 parts of a defoaming agent, 1-5 parts of a thickening agent and 1-5 parts of a dispersing agent.
Further, the modified polyurethane-acrylic acid copolymer is obtained by modifying the polyurethane-acrylic acid copolymer by using palladium-silicon dioxide.
Further, the preparation method of the modified polyurethane-acrylic acid copolymer comprises the following steps:
(1) Taking a proper amount of deionized water and isopropanol into a reaction bottle, heating to 30-60 ℃, then dropwise adding a proper amount of silane coupling agent (such as KH-550 and KH-570), aluminate coupling agent (such as distearoyl isopropyl aluminate), acid catalyst, polyurethane and acrylic acid, heating to about 60 ℃ after dropwise adding, then adding DMPA and NMP, uniformly mixing, adding a certain amount of TEA, and carrying out neutralization reaction for a period of time; the inventors used aluminate-based coupling agents such as: distearoyl isopropyl aluminate is put in the system, so that the inorganic part of the distearoyl isopropyl aluminate is fully bonded with the hydroxyl on the surface of the raw material; then adding silane coupling agent (such as KH-550, KH-570) to hydrolyze and dehydrate to form silanol group, reacting with raw material hydroxyl group to form a layer of methacryloxy chemical group with chemical active group on the surface, carbon-carbon double bond with crosslinking activity and organic long chain group containing aluminum ion. In the reaction process, methacryloxy is easily attacked by a nucleophilic reagent, and is crosslinked with itself or double bonds to form a coating layer on the surface of the raw material, so that an aluminate organic group and aluminum ions are inserted in the coating layer, and the hardness and the wear resistance of the finished product are improved. In addition, excessive silane coupling agent can be added, so that when unreacted active groups of the silane coupling agent react with acrylic acid, the unreacted groups can react with methyl methacrylate in the acrylic acid and similar structures, the initial binding power and hardness, the lasting binding capacity and hardness of the system are increased, the water resistance and compatibility of the system are improved, and the quality of products can be further improved.
(2) And cooling the obtained prepolymer to room temperature, adding a water dispersion of palladium acetate and silicon dioxide, and dispersing at a high speed for 1h to obtain the modified polyurethane-acrylic copolymer.
According to the invention, palladium-silicon dioxide is used for modifying polyurethane-acrylic acid copolymer, and then nano cellulose and graphene oxide are added for coating the polyurethane-acrylic acid copolymer; because the added nano-cellulose and the added graphene oxide have the effects of electrostatic repulsion and steric hindrance stabilization, the dispersion stability of the palladium-silicon dioxide is improved, the palladium-silicon dioxide and the waterborne polyurethane raw material are dispersed more uniformly, the agglomeration phenomenon cannot occur, and the coating property is more stable, so that the hardness, the wear resistance and other aspects of the waterborne paint can be greatly improved in the using process, and the scratch resistance, the collision resistance and the paint removal difficulty of the waterborne paint after spraying can be realized. In addition, under the porous structure formed by the nano-cellulose and the graphene oxide, the nano-titanium dioxide is dispersed more uniformly, has a larger specific surface area, and is easy to adsorb gas molecules, so that the excellent purification effect can be exerted, and the environment-friendly effect is better.
More importantly, the inventor utilizes the characteristic of larger specific surface area of the porous silicon, so that the adsorption between the porous silicon and the nano titanium dioxide is more and more stable, but the research of the inventor finds that the porous silicon is unstable, is easy to oxidize and cannot maintain excellent lasting stability in the using process; therefore, the inventor utilizes palladium-silica to modify polyurethane-acrylic acid copolymer, utilizes the cooperation of hollow mesoporous silicon and palladium nanoparticles to inhibit the agglomeration of system substances and promote the effective mass transfer of polyurethane and acrylic acid, and can more uniformly load palladium-silica, nano titanium dioxide and the like, so that the water-based paint has better wear resistance and can exert excellent purification effect.
Further, the film forming auxiliary agent comprises one or more of dipropylene glycol methyl ether, dodecyl alcohol ester, propylene glycol butyl ether and propylene glycol methyl ether acetate.
Further, the defoaming agent is one or more of organic silicon resin, tributyl phosphate and a defoaming agent BYK 088.
Further, the thickening agent is acrylic acid thickening agent and carboxymethyl cellulose,
further, the dispersing agent is one or more of sodium polyacrylate salt, sodium hexametaphosphate, 4-hydroxybenzophenone, diphenylcresol and phenoxyacetic acid.
The invention also provides a preparation method of the environment-friendly water-based paint, which comprises the following steps:
s1: adding the modified polyurethane-acrylic copolymer, partial graphene oxide, partial nano-cellulose, deionized water and a dispersing agent into a reaction kettle, heating to 60-80 ℃, and stirring for 15-20 minutes at the rotating speed of 1200-1600 revolutions per minute;
s2: after the dispersion is uniform, adding the nano titanium dioxide, the rest of the nano cellulose and the rest of the graphene oxide, and stirring for 1 hour at the rotating speed of 800-950 revolutions per minute; then adding a film forming agent, stirring for 8 hours at the rotating speed of 300-450 rpm and the temperature of 100 ℃, and cooling to room temperature;
s3: adding deionized water, stirring at the rotation speed of 500 revolutions per minute and the temperature of 100 ℃ for 2 hours under the protection of nitrogen, and cooling to room temperature; and finally, adding a defoaming agent and a thickening agent, and stirring at the rotating speed of 2000 rpm for 1 hour at room temperature to obtain the environment-friendly water-based paint.
Furthermore, 1/3 weight part of graphene oxide and 1/3 weight part of nanocellulose are added into the S1.
The preparation method comprises the steps of firstly preparing pre-emulsion, mixing and interweaving the pre-emulsion with partial graphene oxide and partial nano-cellulose in advance to form a grid structure in advance, so that subsequently added nano-titanium dioxide can be more uniformly dispersed in a system and can more stably fill gaps of the grid, adding the rest nano-cellulose and the rest graphene oxide while adding the nano-titanium dioxide, thus the interweaving effect between the grid structure and the nano-titanium dioxide is stronger and more stable, the nano-titanium dioxide can be filled and adhered by the double-layer grid structure formed in the front and back, the interweaving effect between the palladium-silicon dioxide and the nano-titanium dioxide in the modified polyurethane-acrylic copolymer is stronger, and the double-layer grid structure enables the system to be more stable, so that better hardness and wear resistance can be kept, the adhesion stability of the nano-titanium dioxide is kept, the purification effect can be continuously and efficiently exerted, and the environmental protection performance is better.
The technical scheme of the embodiment of the invention at least has the following advantages and beneficial effects:
1. according to the environment-friendly water-based paint disclosed by the invention, the polyurethane-acrylic acid copolymer is modified by using the palladium-silicon dioxide, and then the nanocellulose and the graphene oxide are added to coat the copolymer, so that the dispersion stability of the palladium-silicon dioxide is improved due to the electrostatic repulsion and steric hindrance stabilizing effects of the added nanocellulose and graphene oxide, the palladium-silicon dioxide and the water-based polyurethane raw material are more uniformly dispersed, and the coating property is more stable, so that the hardness, the wear resistance and the like of the water-based paint are greatly improved in the using process, and the water-based paint is resistant to scraping and collision after being sprayed and is not easy to strip. In addition, under the porous structure formed by the nano-cellulose and the graphene oxide, the nano-titanium dioxide is dispersed more uniformly, has a larger specific surface area, and is easy to adsorb gas molecules, so that the excellent purification effect can be exerted, and the environment-friendly effect is better.
2. The preparation method comprises the steps of firstly preparing pre-emulsion, mixing and interweaving the pre-emulsion with partial graphene oxide and partial nano-cellulose in advance to form a grid structure in advance, so that subsequently added nano-titanium dioxide can be more uniformly dispersed in a system and can more stably fill gaps of the grid, adding the rest nano-cellulose and the rest graphene oxide while adding the nano-titanium dioxide, thus the interweaving effect between the grid structure and the nano-titanium dioxide is stronger and more stable, the nano-titanium dioxide can be filled and adhered by the double-layer grid structure formed in the front and back, the interweaving effect between the palladium-silicon dioxide and the nano-titanium dioxide in the modified polyurethane-acrylic copolymer is stronger, and the double-layer grid structure enables the system to be more stable, so that better hardness and wear resistance can be kept, the adhesion stability of the nano-titanium dioxide is kept, the purification effect can be continuously and efficiently exerted, and the environmental protection performance is better.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
An environment-friendly water-based paint comprises 500g of palladium-silicon dioxide modified polyurethane-acrylic acid copolymer, 250g of nano titanium dioxide, 260g of nano cellulose, 150g of graphene oxide, 460g of deionized water, 60g of dipropylene glycol methyl ether, 20g of organic silicon resin, 30g of acrylic acid thickener and 50g of polyacrylic acid sodium salt.
The preparation method of the water paint comprises the following steps:
s1: adding the modified polyurethane-acrylic copolymer, 1/3 weight part of graphene oxide, 1/3 weight part of nano-cellulose, deionized water and a dispersing agent into a reaction kettle, heating to 70 ℃, and stirring for 15 minutes at the rotating speed of 1400 revolutions per minute; the preparation method of the modified polyurethane-acrylic acid copolymer comprises the following steps: (1) Putting deionized water and isopropanol into a reaction bottle, heating to 50 ℃, adding a silane coupling agent, an aluminate coupling agent, an acid catalyst, polyurethane and acrylic acid, continuing heating, adding DMPA and NMP, uniformly mixing, adding TEA, and carrying out a neutralization reaction for a period of time; (2) And cooling the obtained prepolymer to room temperature, adding a water dispersion of palladium acetate and silicon dioxide, and dispersing at a high speed to obtain the modified polyurethane-acrylic acid copolymer.
S2: after the dispersion is uniform, adding the nano titanium dioxide and the rest nano cellulose and graphene oxide, and stirring for 1 hour at the rotating speed of 900 revolutions per minute; then adding a film forming agent, stirring for 8 hours at the rotating speed of 400 r/min and the temperature of 100 ℃, and cooling to room temperature;
s3: adding deionized water, stirring at the rotation speed of 500 revolutions per minute and the temperature of 100 ℃ for 2 hours under the protection of nitrogen, and cooling to room temperature; and finally, adding a defoaming agent and a thickening agent, and stirring at the rotating speed of 2000 rpm for 1 hour at room temperature to obtain the environment-friendly water-based paint.
Example 2
The environment-friendly water-based paint comprises, by weight, 600g of modified polyurethane-acrylic acid copolymer, 300g of nano titanium dioxide, 300g of nano cellulose, 200g of graphene oxide, 600g of deionized water, 100g of lauryl alcohol ester, 50g of tributyl phosphate, 100g of carboxymethyl cellulose and 100g of sodium hexametaphosphate.
The preparation method is the same as in example 1.
Example 3
The environment-friendly water-based paint comprises, by weight, 400g of a modified polyurethane-acrylic acid copolymer, 200g of nano titanium dioxide, 200g of nano cellulose, 100g of graphene oxide, 400g of deionized water, 10g of propylene glycol butyl ether, 5g of a BYK088 defoaming agent, 10g of an acrylic acid thickening agent and 10g of 4-hydroxybenzophenone.
The preparation method is the same as in example 1.
Example 4
An environment-friendly water-based paint comprises, by weight, 440g of a modified polyurethane-acrylic acid copolymer, 220g of nano titanium dioxide, 220g of nano cellulose, 120g of graphene oxide, 430g of deionized water, 30g of propylene glycol monomethyl ether acetate, 10g of tributyl phosphate, 20g of carboxymethyl cellulose and 30g of diphenylcresol.
The preparation method is the same as that of example 1.
Example 5
The environment-friendly water-based paint comprises, by weight, 480g of a modified polyurethane-acrylic acid copolymer, 280g of nano titanium dioxide, 280g of nano cellulose, 180g of graphene oxide, 480g of deionized water, 70g of propylene glycol monomethyl ether acetate, 40g of organic silicon resin, 70g of an acrylic acid thickening agent and 60g of phenoxyacetic acid.
The preparation method is the same as that of example 1.
Example 6
An environment-friendly water-based paint comprises, by weight, 520g of a modified polyurethane-acrylic acid copolymer, 290g of nano titanium dioxide, 280g of nano cellulose, 180g of graphene oxide, 570g of deionized water, 50g of dodecyl alcohol ester, 30g of tributyl phosphate, 50g of carboxymethyl cellulose and 50g of sodium hexametaphosphate.
The preparation method is the same as that of example 1.
Comparative example 1
This comparative example differs from example 1 in that: the polyurethane-acrylic copolymer was not modified.
Comparative example 2
This comparative example differs from example 1 in that: and the nano-cellulose and graphene oxide are not contained.
Comparative example 3
This comparative example differs from example 1 in that: does not contain nano titanium dioxide.
Comparative example 4
This comparative example differs from example 1 in that: the composite material comprises 200g of palladium-silicon dioxide modified polyurethane-acrylic acid copolymer, 100g of nano titanium dioxide, 100g of nano cellulose, 50g of graphene oxide, 30g of deionized water, 5g of film-forming additive, 0.1g of defoaming agent, 5g of thickening agent and 5g of dispersing agent.
Comparative example 5
This comparative example differs from example 1 in that: the composite material comprises 800g of palladium-silicon dioxide modified polyurethane-acrylic acid copolymer, 500g of nano titanium dioxide, 400g of nano cellulose, 300g of graphene oxide, 700g of deionized water, 200g of film-forming additive, 100g of defoaming agent, 200g of thickening agent and 150g of dispersing agent.
Comparative example 6
The comparative example differs from example 1 in that: in the preparation process, all raw materials are mixed in the first step.
Examples of the experiments
The water-based paints obtained in the examples 1-6 and the comparative examples 1-6 are subjected to related performance tests according to GB/T23999-2009 Water-based woodware coating for interior decoration; testing the adhesion according to ASTM D3359; testing the formaldehyde absorption rate according to JCT 1074-2008 indoor air purification function coating material purification performance; the performance results are shown in table 1:
TABLE 1 results of performance testing of the aqueous paints obtained in examples and comparative examples
As can be seen from the data in Table 1, the performance parameters of the aqueous paint obtained in the examples of the present invention, such as hardness, scratch resistance, water-resistant adhesion, and formaldehyde absorption, are better than those of the comparative examples.
Specifically, the polyurethane-acrylic acid copolymer in comparative example 1 is not modified, is easily oxidized in the using process, and cannot maintain lasting stability, so that the adsorption amount of nano titanium dioxide is reduced and unstable, the hardness is low, the nano titanium dioxide is easily scratched, and the formaldehyde absorption rate is low;
comparative example 2 does not contain nano-cellulose and graphene oxide, so that palladium-silicon dioxide and the aqueous polyurethane raw material are poor in dispersibility and easy to agglomerate, and nano-titanium dioxide is poor in dispersibility and adhesion, so that the adhesive force is low, the hardness is low, the scratch is easy to occur, and the formaldehyde absorption rate is low;
comparative example 3 does not contain nano titanium dioxide, has no adsorbability on formaldehyde, cannot achieve the purification effect, and is not environment-friendly;
the amounts of the raw materials of comparative example 4 and comparative example 5 are not in the range of the scheme, and all the parameters are poor;
the preparation method of the comparative example 6 mixes all the raw materials, and the obtained water-based paint has poor hardness and adhesion, so that the interweaving effect between the grid structure in the system and the nano titanium dioxide is poor, the good hardness and wear resistance can not be maintained, the adhesion stability of the nano titanium dioxide can not be maintained, the formaldehyde purification effect is poor, and the environmental protection property of the water-based paint is poor.
The present invention has been described in terms of the preferred embodiment, and it is not intended to be limited to the embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The environment-friendly water-based paint is characterized by comprising, by weight, 40-60 parts of modified polyurethane-acrylic acid copolymer, 20-30 parts of nano titanium dioxide, 20-30 parts of nano cellulose, 10-20 parts of graphene oxide, 40-60 parts of deionized water, 1-10 parts of film-forming assistant, 0.1-5 parts of defoaming agent, 1-10 parts of thickening agent and 1-10 parts of dispersing agent.
2. The environment-friendly water-based paint as claimed in claim 1, which comprises, by weight, 40-50 parts of modified polyurethane-acrylic acid copolymer, 22-29 parts of nano titanium dioxide, 22-28 parts of nano cellulose, 12-18 parts of graphene oxide, 50-60 parts of deionized water, 1-5 parts of a film-forming assistant, 0.1-3 parts of a defoaming agent, 1-5 parts of a thickening agent, and 1-5 parts of a dispersing agent.
3. The environment-friendly water-based paint according to any one of claims 1-2, wherein the modified polyurethane-acrylic acid copolymer is obtained by modifying a polyurethane-acrylic acid copolymer with palladium-silica.
4. The environment-friendly water-based paint as claimed in claim 3, wherein the preparation method of the modified polyurethane-acrylic acid copolymer comprises the following steps:
(1) Taking a proper amount of deionized water and isopropanol into a reaction bottle, heating to 30-60 ℃, adding a proper amount of silane coupling agent, aluminate coupling agent, acid catalyst, polyurethane and acrylic acid, continuing heating, then adding DMPA and NMP, uniformly mixing, adding a certain amount of TEA, and carrying out neutralization reaction for a period of time;
(2) And cooling the obtained prepolymer to room temperature, adding aqueous dispersion of palladium acetate and silicon dioxide, and dispersing at high speed to obtain the modified polyurethane-acrylic acid copolymer.
5. The environmentally friendly aqueous paint of any one of claims 1-2, wherein the coalescent includes one or more of dipropylene glycol methyl ether, lauryl alcohol ester, propylene glycol butyl ether, and propylene glycol methyl ether acetate.
6. The environment-friendly water-based paint according to any one of claims 1-2, wherein the defoaming agent is one or more of silicone resin, tributyl phosphate and a defoaming agent BYK 088.
7. The eco-friendly aqueous paint according to any one of claims 1 to 2, wherein the thickener is an acrylic thickener or carboxymethyl cellulose.
8. The environment-friendly water-based paint according to any one of claims 1-2, wherein the dispersant is one or more of polyacrylic acid sodium salt, sodium hexametaphosphate, 4-hydroxybenzophenone, diphenylcresol and phenoxyacetic acid.
9. A method for preparing the environment-friendly water-based paint according to any one of claims 1 to 8, characterized by comprising the steps of:
s1: adding the modified polyurethane-acrylic acid copolymer, part of graphene oxide, part of nano-cellulose, deionized water and a dispersing agent into a reaction kettle, heating to 60-80 ℃, and stirring at a high speed for a period of time;
s2: after the dispersion is uniform, adding the nano titanium dioxide, the rest of the nano cellulose and the rest of the graphene oxide, and stirring for a period of time; then adding a film forming agent, stirring for a period of time, and cooling to room temperature;
s3: adding deionized water, stirring under the protection of nitrogen, and cooling to room temperature; and finally, adding a defoaming agent and a thickening agent, and stirring for a period of time to obtain the environment-friendly water-based paint.
10. The preparation method of the environment-friendly water-based paint as claimed in claim 9, wherein 1/3 weight part of graphene oxide and 1/3 weight part of nanocellulose are added into S1.
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|---|---|---|---|---|
| CN105754470A (en) * | 2016-03-01 | 2016-07-13 | 山东农业大学 | Method for modifying waterborne wood coating by hybridizing one-dimensional nano-cellulose by virtue of two-dimensional graphene oxide |
| CN109354933A (en) * | 2018-10-16 | 2019-02-19 | 绩溪县马道竹木制品有限公司 | A kind of bamboo wood furniture wear-resistant paint and preparation method thereof |
| CN110358437A (en) * | 2019-06-19 | 2019-10-22 | 施雪丽 | A kind of high-performance environment-friendly water paint and preparation method thereof |
| CN114574087A (en) * | 2022-03-29 | 2022-06-03 | 温州环诺新材料科技有限公司 | Environment-friendly water-based paint and preparation method thereof |
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- 2022-09-23 CN CN202211164453.9A patent/CN115449288A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105754470A (en) * | 2016-03-01 | 2016-07-13 | 山东农业大学 | Method for modifying waterborne wood coating by hybridizing one-dimensional nano-cellulose by virtue of two-dimensional graphene oxide |
| CN109354933A (en) * | 2018-10-16 | 2019-02-19 | 绩溪县马道竹木制品有限公司 | A kind of bamboo wood furniture wear-resistant paint and preparation method thereof |
| CN110358437A (en) * | 2019-06-19 | 2019-10-22 | 施雪丽 | A kind of high-performance environment-friendly water paint and preparation method thereof |
| CN114574087A (en) * | 2022-03-29 | 2022-06-03 | 温州环诺新材料科技有限公司 | Environment-friendly water-based paint and preparation method thereof |
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Application publication date: 20221209 |