CN117050651A - Self-healing high-viscosity water polyurethane waterproof paint and preparation method thereof - Google Patents
Self-healing high-viscosity water polyurethane waterproof paint and preparation method thereof Download PDFInfo
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- CN117050651A CN117050651A CN202310931086.9A CN202310931086A CN117050651A CN 117050651 A CN117050651 A CN 117050651A CN 202310931086 A CN202310931086 A CN 202310931086A CN 117050651 A CN117050651 A CN 117050651A
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 75
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 75
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000003973 paint Substances 0.000 title claims description 20
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 54
- 238000000576 coating method Methods 0.000 claims abstract description 39
- 239000011248 coating agent Substances 0.000 claims abstract description 37
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 27
- 229920000570 polyether Polymers 0.000 claims abstract description 27
- 229920005862 polyol Polymers 0.000 claims abstract description 25
- 150000003077 polyols Chemical class 0.000 claims abstract description 25
- 229920002545 silicone oil Polymers 0.000 claims abstract description 25
- 239000004970 Chain extender Substances 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 239000007822 coupling agent Substances 0.000 claims abstract description 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- 239000004014 plasticizer Substances 0.000 claims abstract description 20
- 239000000945 filler Substances 0.000 claims abstract description 19
- 239000000049 pigment Substances 0.000 claims abstract description 19
- JGUQDUKBUKFFRO-CIIODKQPSA-N dimethylglyoxime Chemical compound O/N=C(/C)\C(\C)=N\O JGUQDUKBUKFFRO-CIIODKQPSA-N 0.000 claims abstract description 18
- 239000004593 Epoxy Substances 0.000 claims abstract description 16
- 239000006260 foam Substances 0.000 claims abstract description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000005058 Isophorone diisocyanate Substances 0.000 claims abstract description 15
- 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 abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 21
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 9
- -1 fatty acid ester Chemical class 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 239000004034 viscosity adjusting agent Substances 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 6
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 6
- 229920001451 polypropylene glycol Polymers 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 3
- 238000004078 waterproofing Methods 0.000 claims description 3
- CBOCVOKPQGJKKJ-UHFFFAOYSA-L Calcium formate Chemical compound [Ca+2].[O-]C=O.[O-]C=O CBOCVOKPQGJKKJ-UHFFFAOYSA-L 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 229940044172 calcium formate Drugs 0.000 claims description 2
- 235000019255 calcium formate Nutrition 0.000 claims description 2
- 239000004281 calcium formate Substances 0.000 claims description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 abstract description 8
- 239000000463 material Substances 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 230000008439 repair process Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- FKOKUHFZNIUSLW-UHFFFAOYSA-N 2-Hydroxypropyl stearate Chemical group CCCCCCCCCCCCCCCCCC(=O)OCC(C)O FKOKUHFZNIUSLW-UHFFFAOYSA-N 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical group NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 3
- 239000011527 polyurethane coating Substances 0.000 description 3
- 229940093625 propylene glycol monostearate Drugs 0.000 description 3
- 239000012779 reinforcing material Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 125000000879 imine group Chemical group 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920006264 polyurethane film Polymers 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- KYNFOMQIXZUKRK-UHFFFAOYSA-N 2,2'-dithiodiethanol Chemical compound OCCSSCCO KYNFOMQIXZUKRK-UHFFFAOYSA-N 0.000 description 1
- 239000004954 Polyphthalamide Substances 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical class O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 238000007344 nucleophilic reaction Methods 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical class [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000005498 phthalate group Chemical group 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920006375 polyphtalamide Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000012970 tertiary amine catalyst 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
- C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- 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
- C09D175/08—Polyurethanes from polyethers
-
- 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
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 provides a self-healing high-viscosity water-based polyurethane waterproof coating and a preparation method thereof, wherein the self-healing high-viscosity water-based polyurethane waterproof coating comprises the following raw materials in parts by weight: 20-40 parts of isophorone diisocyanate, 10-20 parts of polyether polyol, 30-50 parts of acrylic acid modified waterborne polyurethane compound, 30-50 parts of epoxy modified waterborne polyurethane, 10-20 parts of dimethylglyoxime, 4-8 parts of plasticizer, 4-8 parts of viscosity regulator, 8-15 parts of chain extender, 5-10 parts of curing agent, 2-4 parts of early strength agent, 4-8 parts of low-hydrogen silicone oil, 6-10 parts of coupling agent, 1-4 parts of foam homogenizing agent, 1-2 parts of catalyst and 2-6 parts of pigment and filler. The water-based polyurethane waterproof coating has the characteristics of good waterproof property, high strength, high toughness, high adhesion degree with a matrix and capability of self-repairing tiny cracks.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to a self-healing high-viscosity water polyurethane waterproof coating and a preparation method thereof.
Background
The aqueous polyurethane (WPU) coating has the advantages of good adhesiveness, low cost, good flexibility, good wear resistance and the like, and compared with the traditional polyurethane coating, the WPU coating has low or zero emission of Volatile Organic Compounds (VOCs) and is widely used in the fields of clothing, construction, transportation, aerospace, medical supplies and the like. However, in the use process, the materials inevitably generate microcracks and damages, so that the performance of the materials is reduced, and meanwhile, the cohesiveness of the aqueous polyurethane coating and the matrix is mainly from the absorption and solidification of capillary force to the matrix to form a film, so that the mechanical embedded adhesive force is formed, the mechanical embedded adhesive force is easy to fall off, the service time of the mechanical embedded adhesive force is influenced, and the application range of the mechanical embedded adhesive force in the waterproof field of the building is reduced.
The Chinese patent with publication number of CN105482065B provides a self-healing polyurethane resin containing disulfide bonds, which comprises the following raw materials in parts by weight: 10-30 parts of polyether or polyester polyol, 3-20 parts of polyisocyanate, 1-10 parts of chain extender containing disulfide bonds, 0.001-1 part of organotin or tertiary amine catalyst and 50-80 parts of organic solvent. The above polyurethane resin has a self-healing ability, but has limitations in terms of adhesion to a substrate, tensile strength, and water resistance.
Therefore, the prior art has a large room for improvement.
Disclosure of Invention
The invention aims to make up the defects of the prior art, and provides a self-healing high-viscosity water polyurethane waterproof coating and a preparation method thereof, which increase the self-healing property of the coating, improve the waterproof property and the mechanical property, and enable the obtained water polyurethane waterproof coating to have the characteristics of high strength, high toughness, high bonding degree with a matrix and capability of self-repairing tiny cracks.
In order to achieve the above purpose, the present invention is realized by the following technical scheme:
the self-healing high-viscosity water polyurethane waterproof paint comprises the following raw materials in parts by weight:
20-40 parts of isophorone diisocyanate, 10-20 parts of polyether polyol, 30-50 parts of acrylic acid modified waterborne polyurethane compound, 30-50 parts of epoxy modified waterborne polyurethane, 10-20 parts of dimethylglyoxime, 4-8 parts of plasticizer, 4-8 parts of viscosity regulator, 8-15 parts of chain extender, 5-10 parts of curing agent, 2-4 parts of early strength agent, 4-8 parts of low-hydrogen silicone oil, 6-10 parts of coupling agent, 1-4 parts of foam homogenizing agent, 1-2 parts of catalyst and 2-6 parts of pigment and filler.
According to the above scheme, the polyether polyol is at least one of polyethylene glycol, polypropylene glycol, polytetrahydrofuran glycol and polyoxypropylene glycol.
According to the above scheme, the plasticizer is at least one of phthalate, epoxy hydrocarbon and fatty acid ester.
According to the scheme, the viscosity regulator is acetone.
According to the above scheme, the chain extender is at least one of Triethylamine (TEA), trimethylolpropane (TMP), and dimethylolbutyric acid (DMBA).
According to the above scheme, the curing agent is at least one of aliphatic amine, alicyclic and polyamide.
According to the scheme, the early strength agent is at least one of nitrite, chromate, triethanolamine, calcium formate and urea.
According to the scheme, the pigment and filler is at least one of talcum powder, nano modified silicon dioxide and nano modified zirconium oxide.
According to the above scheme, the coupling agent is hydroxyl-terminated polydimethylsiloxane (HTPDMS).
According to the scheme, the foam homogenizing agent is at least one of CGY-A, CGY-FDA and B-8462.
According to the scheme, the catalyst is dibutyl tin dilaurate.
By adding the acrylic acid modified waterborne polyurethane compound, the coating has the advantages of both the waterborne acrylic acid coating and the waterborne polyurethane coating; the epoxy modified waterborne polyurethane is added, so that the coating film has strong adhesive force and good chemical resistance. The plasticizer increases the fluidity of the paint and improves the interaction between the paint and the concrete; the curing agent has the effects of increasing the curing amount of the coating and improving the performance of the coating; the foam homogenizing agent enables the raw materials to be uniformly mixed in the foaming process, and the modification of the silicone oil on polyurethane is promoted by virtue of the emulsifying property and low surface tension of the foam homogenizing agent; the viscosity regulator regulates the viscosity of the emulsion and provides a reaction environment for polyurethane chain extension; the catalyst promotes the reaction of the chain extender and isocyanate; the early strength agent can shorten the formation time of the waterproof layer, enhance the early strength and is beneficial to the rapid waterproof effect of the coating; the pigment and filler reduces crack sensitivity of the coating, improves the overall performance and weather resistance of the coating, and can also improve the combination property of the coating and a collective; the coupling agent can react with certain groups on the surface of the reinforcing material and can react with matrix resin to form an interface layer between the reinforcing material and the resin matrix, so that the bonding strength between the reinforcing material and the resin is enhanced, and the performance of the waterproof coating is improved.
The strength of the coating can be improved by adding low-hydrogen silicone oil, and researches show that the internal rotation capacity of Si-O-S i is better than that of C-O-C, and the Young's modulus of polyurethane is gradually reduced and the tensile strength and the elongation at break are gradually increased along with the increase of the amount of the silicone oil. Meanwhile, when the polyurethane waterproof coating is applied to the surface of a concrete matrix, the organosilicon can form a silicon-oxygen-carbon bond (S i-O-C) with hydroxyl groups on the silicate surface of the concrete, so that the organic groups are connected with silicate materials. The chemical bond has stronger chemical stability and mechanical property, and the bonding between the organosilicon and the silicate material can enhance the hydrolytic resistance and heat resistance of the material. The added dimethylglyoxime is a difunctional imine monomer, hydroxyl groups at two ends of the dimethylglyoxime can react with isophorone diisocyanate in a nucleophilic way to obtain an oxime-carbamate structure unit with a reversible bond forming effect, and under the heating conditions of microwaves, illumination and the like, oxime-carbamate bonds are dissociated, bonded after cooling, and have reversibility, and simultaneously, polyurethane chain segments with imine groups start to flow, and dynamic imine bonds are exchanged to repair damaged parts, so that the self-repair of the material is realized.
The invention also provides a preparation method of the self-healing high-viscosity water polyurethane waterproof paint, which comprises the following steps:
1) Vacuum drying and dewatering polyether polyol, pouring the dehydrated polyether polyol into a reaction kettle, adding a catalyst, slowly adding isophorone diisocyanate while stirring, heating to 75-90 ℃, and preserving heat for 2-3 h;
2) Adding an acrylic acid modified waterborne polyurethane compound, epoxy modified waterborne polyurethane, dimethylglyoxime and low-hydrogen silicone oil into the solution obtained in the step 1), and preserving heat for 2 hours at 80 ℃;
3) Adding a chain extender and a coupling agent into the solution obtained in the step 2), cooling to 60 ℃, then adding a viscosity regulator, a plasticizer, an early strength agent, a curing agent and a foam homogenizing agent, heating to 60 ℃, and preserving heat for 2 hours;
4) Heating to 80 ℃, then adding pigment and filler in the step 3), and continuing stirring for 1-2 h to obtain the self-healing high-viscosity water polyurethane waterproof coating.
The hydroxyl groups at two ends of the dimethylglyoxime and isophorone diisocyanate undergo nucleophilic reaction to obtain an oxime-carbamate reversible bonding unit with a reversible bonding effect; in addition, the compact and symmetrical rigid structure of the dimethylglyoxime can be used as a rigid component in polyurethane construction, and an internal imine group is combined to form a hydrogen bond between molecular chains, so that the mechanical strength of the system is enhanced.
The invention has the beneficial effects that:
the raw material formula of the water-based polyurethane waterproof coating is reasonably arranged, so that the self-healing property of the coating is improved, and the waterproof property and the mechanical property are improved, so that the water-based polyurethane waterproof coating has the characteristics of high strength, high toughness, high adhesion with a matrix and capability of self-repairing tiny cracks, and can be applied to waterproofing of indoor places such as roofs, basements, toilets and the like.
Detailed Description
For a better understanding of the present invention, the following examples are set forth to illustrate the invention further, but are not to be construed as limiting the invention.
Example 1
The self-healing high-viscosity water polyurethane waterproof paint comprises the following raw materials in parts by weight:
20 parts of isophorone diisocyanate, 10 parts of polyether polyol, 40 parts of acrylic modified waterborne polyurethane compound, 40 parts of epoxy modified waterborne polyurethane, 12 parts of dimethylglyoxime, 4 parts of plasticizer, 5 parts of viscosity modifier, 8 parts of chain extender, 5 parts of curing agent, 2 parts of early strength agent, 4 parts of low-hydrogen silicone oil, 8 parts of coupling agent, 2 parts of B-8462 foam homogenizing agent, 1 part of catalyst and 3 parts of pigment and filler.
The polyether polyol is polyethylene glycol, the plasticizer is propylene glycol monostearate, the viscosity modifier is acetone, the curing agent is polyphthalamide, the early strength agent is triethanolamine, the low-hydrogen silicone oil is polyether modified silicone oil, the coupling agent is hydroxyl-terminated polydimethylsiloxane, the catalyst is dibutyl tin dilaurate, and the pigment and filler is talcum powder. The chain extender comprises 4 parts by weight of dimethylolbutyric acid (DMBA) and 4 parts by weight of Triethylamine (TEA).
The preparation method of the self-healing high-viscosity water polyurethane waterproof paint comprises the following steps:
1) Vacuum drying and dewatering polyether polyol, pouring the dehydrated polyether polyol into a reaction kettle, adding a catalyst, slowly adding isophorone diisocyanate while stirring, heating to 75 ℃, and preserving heat for 2 hours;
2) Adding an acrylic acid modified waterborne polyurethane compound, epoxy modified waterborne polyurethane, dimethylglyoxime and low-hydrogen silicone oil into the solution obtained in the step 1), and preserving heat for 2 hours at 80 ℃;
3) Adding a chain extender and a coupling agent into the solution obtained in the step 2), cooling to 60 ℃, then adding a viscosity regulator, a plasticizer, an early strength agent, a curing agent and a foam homogenizing agent, heating to 60 ℃, and preserving heat for 2 hours;
4) Heating to 80 ℃, then adding pigment and filler in the step 3), and continuing stirring for 1h to obtain the self-healing high-viscosity water polyurethane waterproof coating.
Example 2
The self-healing high-viscosity water polyurethane waterproof paint comprises the following raw materials in parts by weight:
24 parts of isophorone diisocyanate, 12 parts of polyether polyol, 30 parts of an acrylic modified waterborne polyurethane compound, 50 parts of epoxy modified waterborne polyurethane, 10 parts of dimethylglyoxime, 6 parts of a plasticizer, 4 parts of a viscosity regulator, 14 parts of a chain extender, 6 parts of a curing agent, 3 parts of an early strength agent, 5 parts of low-hydrogen silicone oil, 6 parts of a coupling agent, 1 part of a B-8462 foam homogenizing agent, 1 part of a catalyst and 2 parts of a pigment and filler.
The polyether polyol is polypropylene glycol, the plasticizer is propylene glycol monostearate, the viscosity modifier is acetone, the curing agent is m-xylylenediamine, the early strength agent is urea, the low-hydrogen silicone oil is alkyl modified silicone oil, the coupling agent is hydroxyl end-capped polydimethylsiloxane, the catalyst is dibutyl tin dilaurate, and the pigment and filler is modified nano silicon dioxide. The chain extender comprises 4 parts by weight of dimethylolbutyric acid (DMBA), 4 parts by weight of Triethylamine (TEA), 3 parts by weight of Trimethylolpropane (TMP) and 3 parts by weight of dimethylolbutyric acid (DMBA).
The preparation method of the self-healing high-viscosity water polyurethane waterproof paint comprises the following steps:
1) Vacuum drying and dewatering polyether polyol, pouring the dehydrated polyether polyol into a reaction kettle, adding a catalyst, slowly adding isophorone diisocyanate while stirring, heating to 80 ℃, and preserving heat for 2 hours;
2) Sequentially adding an acrylic acid modified waterborne polyurethane compound, epoxy modified waterborne polyurethane, dimethylglyoxime and low-hydrogen silicone oil into the solution obtained in the step 1), and preserving heat for 2 hours at 80 ℃;
3) Adding a chain extender and a coupling agent into the solution obtained in the step 2), cooling to 60 ℃, then sequentially adding a viscosity regulator, a plasticizer, an early strength agent, a curing agent and a foam homogenizing agent, heating to 60 ℃, and preserving heat for 2 hours;
4) Heating to 80 ℃, then adding pigment and filler in the step 3), and continuing stirring for 1h to obtain the self-healing high-viscosity water polyurethane waterproof coating.
Example 3
The self-healing high-viscosity water polyurethane waterproof paint comprises the following raw materials in parts by weight:
26 parts of isophorone diisocyanate, 13 parts of polyether polyol, 50 parts of acrylic modified waterborne polyurethane compound, 30 parts of epoxy modified waterborne polyurethane, 12 parts of dimethylglyoxime, 4 parts of plasticizer, 5 parts of viscosity modifier, 10 parts of chain extender, 5 parts of curing agent, 2 parts of early strength agent, 5 parts of low-hydrogen silicone oil, 8 parts of coupling agent, 2 parts of CGY-FDA foam stabilizer, 1 part of catalyst and 3 parts of pigment and filler.
The polyether polyol is polytetrahydrofuran glycol, the plasticizer is propylene glycol monostearate, the viscosity modifier is acetone, the curing agent is m-xylylenediamine, the early strength agent is urea, the low-hydrogen silicone oil is alkyl modified silicone oil, the coupling agent is hydroxyl end-capped polydimethylsiloxane, the catalyst is dibutyl tin dilaurate, and the pigment and filler is talcum powder. The chain extender comprises 3 parts by weight of Triethylamine (TEA), 4 parts by weight of Trimethylolpropane (TMP), 3 parts by weight of dimethylolbutyric acid (DMBA).
The preparation method of the self-healing high-viscosity water polyurethane waterproof paint comprises the following steps:
1) Vacuum drying and dewatering polyether polyol, pouring the dehydrated polyether polyol into a reaction kettle, adding a catalyst, slowly adding isophorone diisocyanate while stirring, heating to 80 ℃, and preserving heat for 2.5 hours;
2) Adding an acrylic acid modified waterborne polyurethane compound, epoxy modified waterborne polyurethane, dimethylglyoxime and low-hydrogen silicone oil into the solution obtained in the step 1), and preserving heat for 2 hours at 85 ℃;
3) Adding a chain extender and a coupling agent into the solution obtained in the step 2), cooling to 60 ℃, then adding a viscosity regulator, a plasticizer, an early strength agent, a curing agent and a foam homogenizing agent, heating to 60 ℃, and preserving heat for 2 hours;
4) Heating to 80 ℃, then adding pigment and filler in the step 3), and continuing stirring for 1.5h to obtain the self-healing high-viscosity water polyurethane waterproof coating.
Example 4
The self-healing water-based polyurethane waterproof coating comprises the following raw materials in parts by weight:
40 parts of isophorone diisocyanate, 20 parts of polyether polyol, 35 parts of acrylic modified waterborne polyurethane compound, 35 parts of epoxy modified waterborne polyurethane, 20 parts of dimethyl glyoxime, 8 parts of plasticizer, 8 parts of viscosity modifier, 15 parts of chain extender, 10 parts of curing agent, 4 parts of early strength agent, 8 parts of low-hydrogen silicone oil, 10 parts of coupling agent, 4 parts of CGY-A foam stabilizer, 2 parts of catalyst and 6 parts of pigment and filler.
The polyether polyol is polyoxypropylene glycol, the plasticizer is phthalate, the viscosity regulator is acetone, the curing agent is m-xylylenediamine, the early strength agent is triethanolamine, the low-hydrogen silicone oil is alkyl modified silicone oil, the coupling agent is hydroxyl end-capped polydimethylsiloxane, the catalyst is dibutyl tin dilaurate, and the pigment and filler is nano modified zirconia. The chain extender comprises 5 parts by weight of Triethylamine (TEA), 5 parts by weight of Trimethylolpropane (TMP), 5 parts by weight of dimethylolbutyric acid (DMBA).
The preparation method of the self-healing high-viscosity water polyurethane waterproof paint comprises the following steps:
1) Vacuum drying and dewatering polyether polyol, pouring the dehydrated polyether polyol into a reaction kettle, adding a catalyst, slowly adding isophorone diisocyanate while stirring, heating to 90 ℃, and preserving heat for 3 hours;
2) Adding an acrylic acid modified waterborne polyurethane compound, epoxy modified waterborne polyurethane, dimethylglyoxime and low-hydrogen silicone oil into the solution obtained in the step 1), and preserving heat for 2 hours at 80 ℃;
3) Adding a chain extender and a coupling agent into the solution obtained in the step 2), cooling to 60 ℃, then adding a viscosity regulator, a plasticizer, an early strength agent, a curing agent and a foam homogenizing agent, heating to 60 ℃, and preserving heat for 2 hours;
4) Heating to 80 ℃, then adding pigment and filler in the step 3), and continuing stirring for 2 hours to obtain the self-healing high-viscosity water polyurethane waterproof coating.
Comparative example 1
A self-healing water-based polyurethane waterproof paint is prepared from the same raw materials and preparation method as in example 4, except that low-hydrogen silicone oil is not added.
Comparative example 2
The preparation raw materials and the preparation method of the self-healing high-viscosity water-based polyurethane waterproof paint are basically the same as those of the example 4, except that: no dimethylglyoxime is added; 30 parts of a chain extender, 2-hydroxyethyl disulfide, was added.
The aqueous polyurethane waterproof coatings obtained in examples 1 to 4 and comparative examples 1 to 2 were subjected to performance test, and the test results are shown in table 1 below:
TABLE 1
The method for calculating the repair rate comprises the following steps: transferring a polyurethane film with the thickness of 1mm multiplied by 0.5mm between two stainless steel plates, heating at 160 ℃ for 30min, and stretching until the polyurethane film fails; recombining the failed steel plates, heating at 160 ℃ for 30min, and stretching again until the steel plates fail; stretching speed is 20mm/min, maximum displacement is 220mm, each film is measured for 3 times, and average value is obtained; the average values of the tensile strength before and after repair are recorded as D1 and D2, respectively, and the repair rate (η) of the repaired material is calculated according to the formula: η= (D2-D1)/d1×100% calculated. The remaining test items were tested according to the GBT19250-2013 standard except for repair rate.
From the above table 1, it can be seen that the water-based polyurethane waterproof paint of the present invention has the characteristics of good waterproof property, high strength, high toughness, high adhesion to a substrate, and capability of self-repairing fine cracks.
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the structures, features and principles of the invention are therefore intended to be embraced therein.
Claims (10)
1. The self-healing high-viscosity water polyurethane waterproof paint is characterized by comprising the following raw materials in parts by weight:
20-40 parts of isophorone diisocyanate, 10-20 parts of polyether polyol, 30-50 parts of acrylic acid modified waterborne polyurethane compound, 30-50 parts of epoxy modified waterborne polyurethane, 10-20 parts of dimethylglyoxime, 4-8 parts of plasticizer, 4-8 parts of viscosity regulator, 8-15 parts of chain extender, 5-10 parts of curing agent, 2-4 parts of early strength agent, 4-8 parts of low-hydrogen silicone oil, 6-10 parts of coupling agent, 1-4 parts of foam homogenizing agent, 1-2 parts of catalyst and 2-6 parts of pigment and filler.
2. The self-healing high viscosity aqueous polyurethane waterproof coating according to claim 1, wherein the polyether polyol is at least one of polyethylene glycol, polypropylene glycol, polytetrahydrofuran glycol and polyoxypropylene glycol.
3. The self-healing high viscosity aqueous polyurethane waterproof coating according to claim 1, wherein the plasticizer is at least one of phthalate, epoxy hydrocarbon and fatty acid ester.
4. The self-healing high viscosity aqueous polyurethane waterproof coating according to claim 1, wherein the viscosity modifier is acetone.
5. The self-healing high viscosity water-based polyurethane waterproof coating according to claim 1, wherein the chain extender is at least one of triethylamine, trimethylol propane and dimethylol butyric acid.
6. The self-healing high viscosity aqueous polyurethane waterproof coating according to claim 1, wherein the curing agent is at least one of aliphatic amine, alicyclic and polyamide.
7. The self-healing high viscosity water-based polyurethane waterproof coating according to claim 1, wherein the early strength agent is at least one of nitrite, chromate, triethanolamine, calcium formate and urea.
8. The self-healing, high viscosity aqueous polyurethane waterproofing paint according to claim 1, wherein the coupling agent is a hydroxyl terminated polydimethylsiloxane.
9. The self-healing, high viscosity water resistant polyurethane waterproofing paint according to claim 1, wherein the catalyst is dibutyl tin dilaurate.
10. A method for preparing the self-healing high-viscosity water-based polyurethane waterproof paint according to any one of claims 1 to 9, comprising the following steps:
1) Vacuum drying and dewatering polyether polyol, pouring the dehydrated polyether polyol into a reaction kettle, adding a catalyst, slowly adding isophorone diisocyanate while stirring, heating to 75-90 ℃, and preserving heat for 2-3 h;
2) Adding an acrylic acid modified waterborne polyurethane compound, epoxy modified waterborne polyurethane, dimethylglyoxime and low-hydrogen silicone oil into the solution obtained in the step 1), and preserving heat for 2 hours at 80 ℃;
3) Adding a chain extender and a coupling agent into the solution obtained in the step 2), cooling to 60 ℃, then adding a viscosity regulator, a plasticizer, an early strength agent, a curing agent and a foam homogenizing agent, heating to 60 ℃, and preserving heat for 2 hours;
4) Heating to 80 ℃, then adding pigment and filler in the step 3), and continuing stirring for 1-2 h to obtain the self-healing high-viscosity water polyurethane waterproof coating.
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