CN117343634A - Polyurethane wear-resistant floor paint and preparation method thereof - Google Patents
Polyurethane wear-resistant floor paint and preparation method thereof Download PDFInfo
- Publication number
- CN117343634A CN117343634A CN202311522214.0A CN202311522214A CN117343634A CN 117343634 A CN117343634 A CN 117343634A CN 202311522214 A CN202311522214 A CN 202311522214A CN 117343634 A CN117343634 A CN 117343634A
- Authority
- CN
- China
- Prior art keywords
- polyurethane
- floor paint
- component
- resistant floor
- wear
- 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
- 239000003973 paint Substances 0.000 title claims abstract description 80
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 64
- 239000004814 polyurethane Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000010455 vermiculite Substances 0.000 claims abstract description 41
- 229910052902 vermiculite Inorganic materials 0.000 claims abstract description 41
- 235000019354 vermiculite Nutrition 0.000 claims abstract description 41
- 239000002135 nanosheet Substances 0.000 claims abstract description 40
- 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 33
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002070 nanowire Substances 0.000 claims abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 15
- 239000011787 zinc oxide Substances 0.000 claims abstract description 15
- 239000000945 filler Substances 0.000 claims abstract description 10
- 239000000049 pigment Substances 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 239000003085 diluting agent Substances 0.000 claims abstract description 8
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 8
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 8
- 239000002270 dispersing agent Substances 0.000 claims abstract description 7
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims abstract description 4
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims abstract description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims abstract description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 43
- 239000008367 deionised water Substances 0.000 claims description 34
- 229910021641 deionized water Inorganic materials 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 238000005406 washing Methods 0.000 claims description 27
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 150000002009 diols Chemical class 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000004793 Polystyrene Substances 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 9
- 239000002105 nanoparticle Substances 0.000 claims description 9
- 229920002223 polystyrene Polymers 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 8
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 8
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 claims description 7
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 7
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 7
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 7
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- KTGAFVGVECOGCK-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propanedioic acid Chemical compound OCC(CO)(C(O)=O)C(O)=O KTGAFVGVECOGCK-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000004806 packaging method and process Methods 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 claims description 4
- 229920005614 potassium polyacrylate Polymers 0.000 claims description 4
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 claims description 3
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 3
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical group [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 3
- PPVBGPLECSKJDX-UHFFFAOYSA-N 2-(hydroxymethyl)propanedioic acid Chemical compound OCC(C(O)=O)C(O)=O PPVBGPLECSKJDX-UHFFFAOYSA-N 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims 2
- 238000001704 evaporation Methods 0.000 claims 1
- 238000009830 intercalation Methods 0.000 abstract description 8
- 230000002687 intercalation Effects 0.000 abstract description 8
- 238000004132 cross linking Methods 0.000 abstract description 2
- 238000011049 filling Methods 0.000 abstract description 2
- 230000005484 gravity Effects 0.000 abstract description 2
- 238000003892 spreading Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 8
- 239000012065 filter cake Substances 0.000 description 8
- 230000007935 neutral effect Effects 0.000 description 8
- 238000000967 suction filtration Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- 239000013530 defoamer Substances 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000013008 moisture curing Methods 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- IEDVJHCEMCRBQM-UHFFFAOYSA-N trimethoprim Chemical compound COC1=C(OC)C(OC)=CC(CC=2C(=NC(N)=NC=2)N)=C1 IEDVJHCEMCRBQM-UHFFFAOYSA-N 0.000 description 1
- 229960001082 trimethoprim Drugs 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
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
- 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
- C09D7/60—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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses polyurethane wear-resistant floor paint and a preparation method thereof, which belong to the technical field of polyurethane floor paint and comprise the following components in percentage by mass of 7.5-8: the component A and the component B of the composition 1 are respectively prepared from an aqueous polyurethane prepolymer, graphene nanowires, intercalated modified vermiculite nano sheets, tetrapod-like zinc oxide whiskers, nano silicon dioxide, a dispersing agent, a defoaming agent, a leveling agent, a polyurethane reactive diluent and pigment and filler; the component B is any one of toluene diisocyanate, dicyclohexylmethane diisocyanate and hexamethylene diisocyanate; the intercalation modified vermiculite nano sheets play a role in filling, the tetrapod-like zinc oxide whiskers play a role in supporting, and the graphene nano wires and the tetrapod-like zinc oxide whiskers are dispersed between the intercalation modified vermiculite nano sheets to form a stable space structure, so that the viscosity of the polyurethane wear-resistant floor paint is increased, the excessive spreading of the polyurethane wear-resistant floor paint due to gravity is reduced, the crosslinking density is increased, and the wear resistance of the polyurethane wear-resistant floor paint is improved.
Description
Technical Field
The invention belongs to the technical field of polyurethane floor paint, and particularly relates to polyurethane wear-resistant floor paint and a preparation method thereof.
Background
Floor paint is a special paint applied to the surface of the ground, and the main purpose of the floor paint is to improve the performance, appearance and durability of the ground. The floor paint generally comprises epoxy floor paint, polyurethane floor paint and acrylic floor paint according to material classification, wherein the polyurethane floor paint not only has better wear resistance and corrosion resistance, but also has better weather resistance, so that the floor paint can be used indoors and outdoors and is commonly used in industrial plants, warehouses, production workshops, laboratories and the like.
The polyurethane floor paint comprises water-based polyurethane floor paint and solvent-based polyurethane floor paint according to component classification, the solvent-based polyurethane floor paint is generally in a moisture curing mode, and is cured through the reaction of higher-activity isocyanate groups and moisture in the air, wherein organic solvents are volatilized in a large amount and have great environmental pollution, the water-based polyurethane floor paint takes water as a diluent, has low volatile organic compound content and has small influence on the environment, but the hardness of the water-based polyurethane floor paint is smaller than that of the solvent-based polyurethane floor paint, and the water-based polyurethane floor paint has defects in high-hardness application scenes such as parking lots. Chinese patent publication No. CN108795126B discloses a graphene water-based super wear-resistant floor paint and a preparation method thereof, and the wear resistance and mechanical properties of a paint film are enhanced. However, the solvent of the waterborne polyurethane floor paint is water, the volatilization speed is slower than that of an organic solvent, longer drying time is needed, the viscosity of the waterborne polyurethane floor paint is generally smaller, the waterborne polyurethane floor paint can be slowly spread after ground construction, the coating is too thin, thicker coating can be obtained after multiple layers of construction are needed, and the cost is increased.
Disclosure of Invention
The invention aims at providing a polyurethane wear-resistant floor paint, solving the problem that the existing waterborne polyurethane floor paint is easy to thin after construction, and the second aim is to provide a preparation method of the polyurethane wear-resistant floor paint.
The aim of the invention can be achieved by the following technical scheme:
the polyurethane wear-resistant floor paint comprises a component A and a component B, wherein the mass ratio of the dosage of the component A to the dosage of the component B is 7.5-8:1.
the component A comprises the following components in parts by mass:
80-85 parts of aqueous polyurethane prepolymer, 8-10.5 parts of graphene nanowires, 12-14 parts of intercalated modified vermiculite nano sheets, 7.5-10 parts of tetrapod-like zinc oxide whiskers, 2-5 parts of nano silicon dioxide, 0.8-1 part of dispersing agent, 0.4-0.6 part of defoaming agent, 1.2-1.4 parts of flatting agent, 4-5 parts of polyurethane reactive diluent and 35-50 parts of pigment and filler.
The component B is any one of toluene diisocyanate, dicyclohexylmethane diisocyanate and hexamethylene diisocyanate.
Further, the dispersing agent is sodium polyacrylate or potassium polyacrylate.
Further, the polyurethane reactive diluent is any one of 1, 6-hexanediol diacrylate, diethylene glycol diacrylate and triethylene glycol diacrylate.
The preparation method of the polyurethane wear-resistant floor paint comprises the following steps:
step one: adding isophorone diisocyanate, hydroxyl-terminated polybutadiene diol, polytetrahydrofuran diol and acetone into a reaction kettle, carrying out reflux reaction for 50-60min at 80-85 ℃ and 500-800r/min, then dissolving 2, 2-bis (hydroxymethyl) malonic acid with N-methylpyrrolidone, adding into the reaction kettle, continuing to react for 120-130min under the same conditions to obtain an intermediate prepolymer blocked by isocyanate groups, cooling to 60 ℃, adding trimethoyl alcohol and stannous octoate into the reaction kettle, continuing to react for 90-100min, cooling to 40 ℃ and then adding triethylamine, reacting for 40-45min, finally adding deionized water at 0-5 ℃ and 1800-2000r/min, carrying out heat preservation and stirring for 30-40min, carrying out rotary evaporation to remove acetone, and standing for defoaming to obtain an aqueous polyurethane prepolymer;
step two: stirring and mixing graphene oxide, polystyrene nano particles and deionized water, then performing ultrasonic dispersion for 1.5-2h, then adding 56% ferric chloride solution by mass fraction, stirring for 40-60min under the condition of 200-500r/min, and performing vacuum drying to obtain composite powder;
step three: placing the composite powder into a crucible, transferring the crucible into a tubular vacuum furnace, heating to 180-200 ℃ at the speed of 3-5 ℃/min, preserving heat for 60-80min, heating to 750-780 ℃ at the speed of 3-5 ℃/min, preserving heat for 120-150min, cooling to 180-200 ℃ at the speed of 5-10 ℃/min, naturally cooling, soaking in 36% hydrochloric acid solution for 30-40min, washing with deionized water until the pH value of the last washing solution is neutral, vacuum drying at 50-60 ℃, and crushing to obtain graphene nanowires;
step four: adding vermiculite nano sheets and hydrochloric acid with the mass fraction of 10% and the weight of 2-3 times of the vermiculite nano sheets into a reaction kettle, stirring for 120-150min at 70-75 ℃ and 300-500r/min, washing a filter cake with deionized water until the last washing liquid is neutral after suction filtration, and drying at 70-80 ℃ to obtain acidified vermiculite nano sheets; adding acidified vermiculite nano sheets, hexadecyl trimethyl ammonium bromide and deionized water into a stirring kettle, stirring for 120-150min at 60-65 ℃ and 300-500r/min, washing a filter cake with deionized water after suction filtration until no bromide ions are detected in the final washing liquid, and drying at 70-80 ℃ to obtain intercalated modified vermiculite nano sheets;
step five: adding the aqueous polyurethane prepolymer, the graphene nanowire, the intercalated modified vermiculite nano sheet, the tetrapod-like zinc oxide whisker, the nano silicon dioxide, the dispersing agent, the defoaming agent, the flatting agent, the polyurethane reactive diluent and the pigment filler into a grinding machine, stirring for 1-2h under the condition of 1500-2000r/min, and carrying out vacuum defoaming to obtain a component A; and packaging the component A and the component B respectively to obtain the polyurethane wear-resistant floor paint.
Further, in the first step, isophorone diisocyanate, hydroxyl-terminated polybutadiene diol, polytetrahydrofuran diol, acetone, 2-bis (hydroxymethyl) malonic acid, N-methylpyrrolidone, trimethoyl alcohol, stannous octoate and deionized water are used in an amount ratio of 45-48g:60-70g:30-35g:300-350mL:8.8-9g:16-18g:26.5-28g:1.25-1.3g:820-850mL.
Further, the dosage ratio of graphene oxide, polystyrene nanoparticles, deionized water and ferric chloride solution in the second step is 10mg:50mg:6mL:3-3.5mL.
Further, in the fourth step, the dosage ratio of the acidified vermiculite nano sheet, the hexadecyl trimethyl ammonium bromide and the deionized water is 5-7g:0.3-0.4g:50-60mL.
The invention has the beneficial effects that:
the polyurethane wear-resistant floor paint disclosed by the invention is a double-component waterborne polyurethane floor paint, and is more environment-friendly compared with a solvent-type polyurethane floor paint. The aqueous polyurethane prepolymer in the component A is prepared by reacting isophorone diisocyanate with various hydroxyl compounds to obtain an intermediate prepolymer containing isocyanate groups, then carrying out chain extension of trimethoprim and neutralization of triethylamine, and then dispersing with deionized water, thus being beneficial to improving the flexibility of a cured paint film; the graphene oxide takes the polystyrene nano particles as a template, and in the high-temperature heating process, the polystyrene nano particles are decomposed into small molecular carbon chains, and the small molecular carbon chains and the graphene oxide are reassembled into the three-dimensional crosslinked graphene nano wires, so that the abrasion resistance of the floor paint is improved.
The intercalation modified vermiculite nano sheets play a role in filling, the tetrapod-like zinc oxide whiskers play a role in supporting, the graphene nano wires are carded and dispersed, and the graphene nano wires and the tetrapod-like zinc oxide whiskers are dispersed between the intercalation modified vermiculite nano sheets to form a stable space structure, so that the viscosity of the polyurethane wear-resistant floor paint is increased, the excessive spreading and thinning of the polyurethane wear-resistant floor paint due to gravity are reduced, the crosslinking density of the polyurethane wear-resistant floor paint is increased, and the wear resistance of the polyurethane wear-resistant floor paint is further improved.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment provides polyurethane wear-resistant floor paint, which comprises a component A and a component B, wherein the component B is toluene diisocyanate; packaging the component A and the component B respectively to obtain the polyurethane wear-resistant floor paint, wherein the mass ratio of the dosage of the component A to the dosage of the component B is 7.5:1.
the component A is prepared by the following steps:
step one: 45kg of isophorone diisocyanate, 60kg of hydroxyl-terminated polybutadiene diol, 30kg of polytetrahydrofuran diol and 300L of acetone are added into a reaction kettle, reflux reaction is carried out for 50min at 80 ℃ and 500r/min, then 8.8kg of 2, 2-bis (hydroxymethyl) malonic acid is dissolved by 16kg of N-methylpyrrolidone and then is added into the reaction kettle, the reaction is continued for 120min under the same conditions, an isocyanate-terminated intermediate prepolymer is obtained, the temperature is reduced to 60 ℃, 26.5kg of trimethoyl alcohol and stannous octoate are added into the reaction kettle and are further reacted for 90min, the temperature is reduced to 40 ℃ after chain extension is completed, 1.25kg of triethylamine is added into the reaction kettle and is neutralized for 40min, finally deionized water is added at 0 ℃ and 1800r/min, the acetone is removed by rotary evaporation after heat preservation and stirring for 30min, and the water-based polyurethane prepolymer is obtained after standing and defoaming.
Step two: mixing 10kg of graphene oxide, 50kg of polystyrene nano particles and 6000L of deionized water under stirring, then performing ultrasonic dispersion for 1.5h, adding 3000L of 56% ferric chloride solution, stirring for 40min under the condition of 200r/min, and performing vacuum drying to obtain composite powder; and (3) loading the composite powder into a crucible, transferring the crucible into a tubular vacuum furnace, heating to 180 ℃ at the speed of 3 ℃/min, preserving heat for 60min, heating to 750 ℃ at the speed of 3 ℃/min, preserving heat for 120min, cooling to 180 ℃ at the speed of 5 ℃/min, naturally cooling, soaking for 30min by using a hydrochloric acid solution with the mass fraction of 36%, washing with deionized water until the pH value of the last washing solution is neutral, drying in vacuum at the temperature of 50 ℃, and crushing to obtain the graphene nanowire.
Step three: adding vermiculite nano sheets and hydrochloric acid with the mass fraction of 10% and the weight of 2 times of the vermiculite nano sheets into a reaction kettle, stirring for 120min at 70 ℃ and 300r/min, washing a filter cake with deionized water until the final washing liquid is neutral after suction filtration, and drying at 70 ℃ to obtain acidified vermiculite nano sheets; adding 5kg of acidified vermiculite nano sheets, 0.3kg of hexadecyl trimethyl ammonium bromide and 50L of deionized water into a stirring kettle, stirring for 120min at 60 ℃ and 300r/min, washing a filter cake with deionized water after suction filtration until no bromide ions are detected in the final washing liquid, and drying at 70 ℃ to obtain the intercalated modified vermiculite nano sheets.
Step four: 8kg of aqueous polyurethane prepolymer, 0.8kg of graphene nanowire, 1.2kg of intercalation modified vermiculite nano sheet, 0.75kg of tetrapod-like zinc oxide whisker, 0.2kg of nano silicon dioxide, 0.08kg of sodium polyacrylate, 0.04kg of defoamer, 0.12kg of flatting agent, 0.4kg of 1, 6-hexanediol diacrylate and 3.5kg of pigment and filler are added into a grinder, stirred for 1h under the condition of 1500r/min, and vacuum defoamed to obtain a component A.
Example 2
The embodiment provides polyurethane wear-resistant floor paint, which comprises a component A and a component B, wherein the component B is dicyclohexylmethane diisocyanate; packaging the component A and the component B respectively to obtain the polyurethane wear-resistant floor paint, wherein the mass ratio of the dosage of the component A to the dosage of the component B is 7.8:1.
the component A is prepared by the following steps:
step one: adding 46kg of isophorone diisocyanate, 65kg of hydroxyl-terminated polybutadiene diol, 32.5kg of polytetrahydrofuran diol and 325L of acetone into a reaction kettle, carrying out reflux reaction for 55min at the temperature of 82 ℃ and the speed of 650r/min, then adding 8.9kg of 2, 2-bis (hydroxymethyl) malonic acid into the reaction kettle after dissolving 17kg of N-methylpyrrolidone, continuously reacting for 125min under the same conditions to obtain an isocyanate-terminated intermediate prepolymer, cooling to 60 ℃, adding 27.2kg of trimethoyl alcohol and stannous octoate into the reaction kettle, continuously reacting for 95min, cooling to 40 ℃ after chain extension, adding 1.28kg of triethylamine into the reaction kettle, neutralizing for 42min, finally adding deionized water at the temperature of 4 ℃ and the speed of 1900r/min, carrying out rotary evaporation to remove acetone after preserving heat and stirring for 35min, and standing for defoaming to obtain the aqueous polyurethane prepolymer.
Step two: mixing 10kg of graphene oxide, 50kg of polystyrene nano particles and 6000L of deionized water under stirring, then performing ultrasonic dispersion for 1.8 hours, then adding 3250L of 56% ferric chloride solution, stirring for 50min under the condition of 350r/min, and performing vacuum drying to obtain composite powder; and (3) loading the composite powder into a crucible, transferring the crucible into a tubular vacuum furnace, heating to 190 ℃ at the speed of 4 ℃/min, preserving heat for 70min, heating to 765 ℃ at the speed of 4 ℃/min, preserving heat for 135min, cooling to 190 ℃ at the speed of 8 ℃/min, naturally cooling, soaking for 35min by using a hydrochloric acid solution with the mass fraction of 36%, washing with deionized water until the pH value of the last washing solution is neutral, drying in vacuum at 55 ℃, and crushing to obtain the graphene nanowire.
Step three: adding vermiculite nano sheets and hydrochloric acid with the mass fraction of 10% which is 2.5 times of the weight of the vermiculite nano sheets into a reaction kettle, stirring for 135min at 72 ℃ and 400r/min, washing a filter cake with deionized water until the final washing liquid is neutral after suction filtration, and drying at 75 ℃ to obtain acidified vermiculite nano sheets; adding 6kg of acidified vermiculite nano sheets, 0.35kg of hexadecyl trimethyl ammonium bromide and 55L of deionized water into a stirring kettle, stirring for 135min at 62 ℃ and 400r/min, washing a filter cake with deionized water after suction filtration until no bromide ions are detected in the final washing liquid, and drying at 75 ℃ to obtain the intercalated modified vermiculite nano sheets.
Step four: 8.2kg of aqueous polyurethane prepolymer, 0.9kg of graphene nanowire, 1.3kg of intercalation modified vermiculite nano sheet, 0.9kg of tetrapod-like zinc oxide whisker, 0.35kg of nano silicon dioxide, 0.09kg of potassium polyacrylate, 0.05kg of defoamer, 0.13kg of flatting agent, 0.45kg of diglycol diacrylate and 4.2kg of pigment and filler are added into a grinder, stirred for 1.5h under the condition of 1800r/min, and vacuum defoamed to obtain a component A.
Example 3
The embodiment provides polyurethane wear-resistant floor paint, which comprises a component A and a component B, wherein the component B is any one of hexamethylene diisocyanate; packaging the component A and the component B respectively to obtain the polyurethane wear-resistant floor paint, wherein the mass ratio of the dosage of the component A to the dosage of the component B is 8:1.
the component A is prepared by the following steps:
step one: 48kg of isophorone diisocyanate, 70kg of hydroxyl-terminated polybutadiene diol, 35kg of polytetrahydrofuran diol and 350L of acetone are added into a reaction kettle, reflux reaction is carried out for 60min at the temperature of 85 ℃ and the speed of 800r/min, then 9kg of 2, 2-bis (hydroxymethyl) malonic acid is dissolved by 18kg of N-methylpyrrolidone and then is added into the reaction kettle, the reaction is continued for 130min under the same conditions, an intermediate prepolymer blocked by isocyanate groups is obtained, the temperature is reduced to 60 ℃, 28kg of trimethoyl alcohol and stannous octoate are added into the reaction kettle and are continued to react for 100min, the temperature is reduced to 40 ℃ after chain extension is completed, 1.3kg of triethylamine is added into the reaction kettle and is neutralized for 45min, finally deionized water is added at the temperature of 5 ℃ and the speed of 2000r/min, the acetone is removed by rotary evaporation after the heat preservation and stirring for 40min, and the water-based polyurethane prepolymer is obtained after standing and defoaming.
Step two: mixing 10kg of graphene oxide, 50kg of polystyrene nano particles and 6000L of deionized water under stirring, then performing ultrasonic dispersion for 2 hours, adding 3500L of 56% ferric chloride solution, stirring for 60 minutes under the condition of 500r/min, and performing vacuum drying to obtain composite powder; and (3) loading the composite powder into a crucible, transferring the crucible into a tubular vacuum furnace, heating to 200 ℃ at a speed of 5 ℃/min, preserving heat for 80min, heating to 780 ℃ at a speed of 5 ℃/min, preserving heat for 150min, cooling to 200 ℃ at a speed of 10 ℃/min, naturally cooling, soaking for 40min by using a hydrochloric acid solution with a mass fraction of 36%, washing with deionized water until the pH value of the last washing solution is neutral, drying in vacuum at 60 ℃, and crushing to obtain the graphene nanowire.
Step three: adding 3 times of vermiculite nano sheets and hydrochloric acid with the mass fraction of 10% into a reaction kettle, stirring for 150min at 75 ℃ and 500r/min, washing a filter cake with deionized water until the final washing solution is neutral after suction filtration, and drying at 80 ℃ to obtain acidified vermiculite nano sheets; adding 7kg of acidified vermiculite nano sheets, 0.4kg of hexadecyl trimethyl ammonium bromide and 60L of deionized water into a stirring kettle, stirring for 150min at 65 ℃ and 500r/min, washing a filter cake with deionized water after suction filtration until no bromide ions are detected in the final washing liquid, and drying at 80 ℃ to obtain the intercalated modified vermiculite nano sheets.
Step four: 8.5kg of waterborne polyurethane prepolymer, 1.05kg of graphene nanowire, 1.4kg of intercalation modified vermiculite nano sheet, 1kg of tetrapod-like zinc oxide whisker, 0.5kg of nano silicon dioxide, 0.1kg of potassium polyacrylate, 0.06kg of defoamer, 0.14kg of flatting agent, 0.5kg of triethylene glycol diacrylate and 5kg of pigment filler are added into a grinder, stirred for 2 hours under the condition of 2000r/min, and subjected to vacuum deaeration to obtain a component A.
Comparative example 1: the graphene nanowires are not added to the foundation of the embodiment 3, and the rest steps are kept unchanged, so that the polyurethane wear-resistant floor paint is prepared.
Comparative example 2: on the basis of example 3, graphene nanowires are replaced by commercially available graphene oxide, and the rest steps remain unchanged, so that the polyurethane wear-resistant floor paint is prepared.
Comparative example 3: the polyurethane wear-resistant floor paint is prepared on the basis of the embodiment 3 without adding intercalation modified vermiculite nano sheets and keeping the rest steps unchanged.
Comparative example 4: on the basis of the example 3, four needle-shaped zinc oxide whiskers are not added, and the rest steps are kept unchanged, so that the polyurethane wear-resistant floor paint is prepared.
In the examples and the comparative examples, the defoamer was Pick BYK-A500, the leveling agent was Santuo STA-3184A, and the pigment filler was a commercial pigment filler.
The polyurethane abrasion-resistant floor paints in examples 1 to 3 and comparative examples 1 to 4 were mixed and constructed according to the amount ratio, respectively, floor paints 1mm thick were roll-coated on an aluminum plate by using a roller, the aluminum plate was left with an unencreased area for the floor paint to flow, the paint film thickness was again detected after curing, the paint film thickness retention after curing (paint film thickness retention= (thickness after curing/thickness before curing) ×100%) was calculated, the adhesion of the paint films was detected according to GB/T1720-2020, the hardness of the different paint films was detected according to GB/T6739-2022 (pencil method), and the abrasion resistance of the different paint films was detected according to GB/T1768-2006. The results are shown in Table 1:
TABLE 1
As can be seen from table 1, the paint films in examples 1 to 3 have extremely high paint film thickness retention rates, and comparative examples 1 and 4 show that the graphene nanowires and the tetrapod-like zinc oxide whiskers have a large influence on the hardness of the paint films, and comparative examples show that the graphene nanowires, the intercalated modified vermiculite nanoplatelets and the tetrapod-like zinc oxide whiskers all contribute to improving the wear resistance of the paint films.
It should be noted that in this document, terms such as "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The polyurethane wear-resistant floor paint is characterized by comprising a component A and a component B, wherein the mass ratio of the dosage of the component A to the dosage of the component B is 7.5-8:1, a step of;
the component A comprises the following components in parts by mass:
80-85 parts of aqueous polyurethane prepolymer, 8-10.5 parts of graphene nanowires, 12-14 parts of intercalated modified vermiculite nano sheets, 7.5-10 parts of tetrapod-like zinc oxide whiskers, 2-5 parts of nano silicon dioxide, 0.8-1 part of dispersing agent, 0.4-0.6 part of defoaming agent, 1.2-1.4 parts of flatting agent, 4-5 parts of polyurethane reactive diluent and 35-50 parts of pigment and filler;
the component B is any one of toluene diisocyanate, dicyclohexylmethane diisocyanate and hexamethylene diisocyanate.
2. The polyurethane wear-resistant floor paint of claim 1, wherein the dispersing agent is sodium polyacrylate or potassium polyacrylate.
3. The polyurethane wear-resistant floor paint according to claim 1, wherein the polyurethane reactive diluent is any one of 1, 6-hexanediol diacrylate, diethylene glycol diacrylate and triethylene glycol diacrylate.
4. The polyurethane wear-resistant floor paint as claimed in claim 1, wherein the aqueous polyurethane prepolymer is prepared by the steps of:
adding isophorone diisocyanate, hydroxyl-terminated polybutadiene diol, polytetrahydrofuran diol and acetone into a reaction kettle, carrying out reflux reaction for 50-60min at 80-85 ℃ and 500-800r/min, dissolving 2, 2-bis (hydroxymethyl) malonic acid with N-methylpyrrolidone, adding into the reaction kettle, reacting for 120-130min, cooling to 60 ℃, adding trimethoyl alcohol and stannous octoate, reacting for 90-100min, cooling to 40 ℃, adding triethylamine, reacting for 40-45min, adding deionized water at 0-5 ℃ and 1800-2000r/min, stirring for 30-40min, rotationally evaporating to remove acetone, standing, defoaming, and obtaining the aqueous polyurethane prepolymer.
5. The polyurethane wear-resistant floor paint according to claim 4, wherein the dosage ratio of isophorone diisocyanate, hydroxyl-terminated polybutadiene diol, polytetrahydrofuran diol, acetone, 2-bis (hydroxymethyl) malonic acid, N-methylpyrrolidone, trimethoyl alcohol, stannous octoate and deionized water is 45-48g:60-70g:30-35g:300-350mL:8.8-9g:16-18g:26.5-28g:1.25-1.3g:820-850mL.
6. The polyurethane wear-resistant floor paint of claim 1, wherein the graphene nanowires are prepared by the following steps:
stirring and mixing graphene oxide, polystyrene nano particles and deionized water, then performing ultrasonic dispersion for 1.5-2h, adding 56wt% ferric chloride solution, stirring for 40-60min at 200-500r/min, vacuum drying to obtain composite powder, transferring into a tubular vacuum furnace, heating to 180-200 ℃ at 3-5 ℃/min, preserving heat for 60-80min, heating to 750-780 ℃ at 3-5 ℃/min, preserving heat for 120-150min, cooling to 180-200 ℃ at 5-10 ℃/min, naturally cooling, soaking for 30-40min with hydrochloric acid solution, washing, drying, and crushing to obtain the graphene nano wires.
7. The polyurethane wear-resistant floor paint according to claim 6, wherein the dosage ratio of graphene oxide, polystyrene nanoparticles, deionized water and ferric chloride solution is 10mg:50mg:6mL:3-3.5mL.
8. The polyurethane wear-resistant floor paint of claim 1, wherein the intercalated modified vermiculite nano sheets are prepared by the following steps:
adding vermiculite nano sheets and 10% wt hydrochloric acid which is 2-3 times of the weight of the vermiculite nano sheets into a reaction kettle, stirring for 120-150min at 70-75 ℃ and 300-500r/min, filtering, washing and drying to obtain acidified vermiculite nano sheets; adding the acidified vermiculite nano sheet, hexadecyl trimethyl ammonium bromide and deionized water into a stirring kettle, stirring for 120-150min at 60-65 ℃ and 300-500r/min, filtering, washing and drying to obtain the intercalated modified vermiculite nano sheet.
9. The polyurethane wear-resistant floor paint of claim 8, wherein the dosage ratio of the acidified vermiculite nano sheets, the cetyltrimethylammonium bromide and the deionized water is 5-7g:0.3-0.4g:50-60mL.
10. The method for preparing the polyurethane wear-resistant floor paint as claimed in claim 1, comprising the following steps:
adding the aqueous polyurethane prepolymer, the graphene nanowire, the intercalated modified vermiculite nano sheet, the tetrapod-like zinc oxide whisker, the nano silicon dioxide, the dispersing agent, the defoaming agent, the flatting agent, the polyurethane reactive diluent and the pigment filler into a grinding machine, stirring for 1-2h under the condition of 1500-2000r/min, and carrying out vacuum defoaming to obtain a component A; and packaging the component A and the component B respectively to obtain the polyurethane wear-resistant floor paint.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311522214.0A CN117343634B (en) | 2023-11-15 | 2023-11-15 | Polyurethane wear-resistant floor paint and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311522214.0A CN117343634B (en) | 2023-11-15 | 2023-11-15 | Polyurethane wear-resistant floor paint and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117343634A true CN117343634A (en) | 2024-01-05 |
| CN117343634B CN117343634B (en) | 2024-04-16 |
Family
ID=89363339
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311522214.0A Active CN117343634B (en) | 2023-11-15 | 2023-11-15 | Polyurethane wear-resistant floor paint and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117343634B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101850983A (en) * | 2010-03-12 | 2010-10-06 | 中国科学院新疆理化技术研究所 | Ball milling method for preparing organic vermiculite with large layer distance |
| CN105255345A (en) * | 2015-10-09 | 2016-01-20 | 滁州环球聚氨酯科技有限公司 | Heat-resisting scratch-resisting car paint with modified waterborne polyurethane dispersoid |
| CN108795126A (en) * | 2018-01-27 | 2018-11-13 | 厦门中凯新材石墨烯科技有限公司 | A kind of aqueous super abrasive floor paint of graphene and preparation method thereof |
-
2023
- 2023-11-15 CN CN202311522214.0A patent/CN117343634B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101850983A (en) * | 2010-03-12 | 2010-10-06 | 中国科学院新疆理化技术研究所 | Ball milling method for preparing organic vermiculite with large layer distance |
| CN105255345A (en) * | 2015-10-09 | 2016-01-20 | 滁州环球聚氨酯科技有限公司 | Heat-resisting scratch-resisting car paint with modified waterborne polyurethane dispersoid |
| CN108795126A (en) * | 2018-01-27 | 2018-11-13 | 厦门中凯新材石墨烯科技有限公司 | A kind of aqueous super abrasive floor paint of graphene and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117343634B (en) | 2024-04-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101638464B (en) | Method for preparing polyurethane-polyacrylic ester microemulsion | |
| DE10038941C2 (en) | Polyurethane (polymer hybrid) dispersion with reduced hydrophilicity, process for its preparation and its use | |
| CN103555192B (en) | A kind of organic-silicon-modified waterborne UV coating and preparation method thereof | |
| DE19812751C2 (en) | Solvent-free polyurethane dispersion | |
| CN111019504B (en) | Waterborne polyurethane coating composition and application thereof | |
| CN103087286B (en) | Waterborne polyurethane elastic dispersion and preparation method thereof | |
| CN110483728B (en) | Preparation method of strippable waterborne polyurethane resin and application of strippable waterborne polyurethane resin in coating | |
| CN105131807A (en) | Hydrophobic water-based fluorescent polyurethane paint and preparation method thereof | |
| CN103467693B (en) | A kind of preparation method of the aqueous polyurethane with good freeze/thaw stability | |
| CN105062341A (en) | Polyaldehyde modified aqueous polyurethane with film formation assisting function, and preparation method and application thereof | |
| CN117343634B (en) | Polyurethane wear-resistant floor paint and preparation method thereof | |
| CN103194124A (en) | Three-component all-environment-friendly aqueous carpentry paint | |
| CN104341572A (en) | Preparation method of solvent-free water-based polyurethane resin | |
| CN111925642A (en) | Preparation method of self-repairing carbon nanotube-cation waterborne polyurethane electromagnetic shielding composite material | |
| CN110358047B (en) | Waterborne polyurethane coating for environment-friendly temperature-resistant transfer coating and preparation method thereof | |
| CN110669201A (en) | Preparation method and application of waterborne polyurethane emulsion | |
| CN109355924B (en) | Preparation method of polyurethane coating containing nano filler and coptis chinensis extract for textile | |
| CN115058184A (en) | Water-based environment-friendly coating and preparation method thereof | |
| KR101109571B1 (en) | Preparing method for water dispersable polyurethane resin containing inorganic compounds and aqueous coating composition containing said water dispersable polyurethane resin | |
| CN114349896A (en) | Hydroxyl polyacrylate dispersoid and preparation method thereof, high-performance water-based bi-component polyurethane coating and preparation method thereof | |
| CN108484864B (en) | Organic sepiolite modified bi-component waterborne polyurethane and preparation method thereof | |
| CN109337567A (en) | A kind of polyether-ether-ketone modified polyurethane water-repellent preservation wear-resistant paint | |
| CN112500548A (en) | Waterborne polyurethane-polyurea and preparation method thereof | |
| CN115851101B (en) | Coating composition, preparation method thereof, coating and application thereof | |
| CN112266459B (en) | High-solid-content aqueous polyurethane emulsion and preparation method 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 |