CN115926607B - Bio-based stain-resistant exposed water-based polyurethane waterproof coating and preparation method thereof - Google Patents
Bio-based stain-resistant exposed water-based polyurethane waterproof coating and preparation method thereof Download PDFInfo
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- CN115926607B CN115926607B CN202211716345.8A CN202211716345A CN115926607B CN 115926607 B CN115926607 B CN 115926607B CN 202211716345 A CN202211716345 A CN 202211716345A CN 115926607 B CN115926607 B CN 115926607B
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 46
- 239000004814 polyurethane Substances 0.000 title claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000000576 coating method Methods 0.000 title claims abstract description 43
- 239000011248 coating agent Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 30
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 20
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000008367 deionised water Substances 0.000 claims abstract description 20
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 20
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000004970 Chain extender Substances 0.000 claims abstract description 14
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 14
- 239000003513 alkali Substances 0.000 claims abstract description 13
- 239000006254 rheological additive Substances 0.000 claims abstract description 13
- 230000008961 swelling Effects 0.000 claims abstract description 13
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 229920000570 polyether Polymers 0.000 claims abstract description 12
- 229920005862 polyol Polymers 0.000 claims abstract description 12
- 150000003077 polyols Chemical class 0.000 claims abstract description 12
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000945 filler Substances 0.000 claims abstract description 11
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims abstract description 10
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000654 additive Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 230000000996 additive effect Effects 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 28
- -1 polydimethylsiloxane Polymers 0.000 claims description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 14
- 229920001451 polypropylene glycol Polymers 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 claims description 9
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical group CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 9
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 7
- 239000002270 dispersing agent Substances 0.000 claims description 7
- JPMIIZHYYWMHDT-UHFFFAOYSA-N octhilinone Chemical compound CCCCCCCCN1SC=CC1=O JPMIIZHYYWMHDT-UHFFFAOYSA-N 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- 239000003755 preservative agent Substances 0.000 claims description 7
- 230000002335 preservative effect Effects 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- RBNPOMFGQQGHHO-UHFFFAOYSA-N glyceric acid Chemical compound OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229920000058 polyacrylate Polymers 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000013530 defoamer Substances 0.000 claims description 4
- 230000001804 emulsifying effect Effects 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 238000010025 steaming Methods 0.000 claims description 4
- BHFLSZOGGDDWQM-UHFFFAOYSA-N 1h-benzimidazole;carbamic acid Chemical compound NC(O)=O.C1=CC=C2NC=NC2=C1 BHFLSZOGGDDWQM-UHFFFAOYSA-N 0.000 claims description 3
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- NURURQTUPZLLIW-UHFFFAOYSA-N C=C.NC(S)=S.NC(S)=S.N Chemical compound C=C.NC(S)=S.NC(S)=S.N NURURQTUPZLLIW-UHFFFAOYSA-N 0.000 claims description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 3
- 229920000388 Polyphosphate Polymers 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000002518 antifoaming agent Substances 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 229960002887 deanol Drugs 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 3
- 239000012972 dimethylethanolamine Substances 0.000 claims description 3
- 125000003916 ethylene diamine group Chemical group 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 229930195729 fatty acid Natural products 0.000 claims description 3
- 150000004665 fatty acids Chemical class 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 3
- 239000001205 polyphosphate Substances 0.000 claims description 3
- 235000011176 polyphosphates Nutrition 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 229960004418 trolamine Drugs 0.000 claims description 3
- 229910052882 wollastonite Inorganic materials 0.000 claims description 3
- 239000010456 wollastonite Substances 0.000 claims description 3
- 238000004078 waterproofing Methods 0.000 claims 2
- 229920001522 polyglycol ester Polymers 0.000 claims 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims 1
- 239000000839 emulsion Substances 0.000 abstract description 8
- 230000009477 glass transition Effects 0.000 abstract description 2
- 239000003973 paint Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005336 cracking Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 4
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 4
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical group [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004971 Cross linker Substances 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 description 1
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 230000001050 lubricating effect Effects 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
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
The invention relates to a bio-based stain-resistant exposed water-based polyurethane waterproof coating and a preparation method thereof, wherein the coating comprises the following components in parts by mass: 50-150 parts of polyether polyol, 10-35 parts of 4,4' -dicyclohexylmethane diisocyanate, 1-10 parts of cross-linking agent, 5-10 parts of 2, 2-dimethylolpropionic acid, 1-10 parts of 1, 4-butanediol, 2-10 parts of chain extender, 2-10 parts of trimethylolpropane, 2-10 parts of triethylamine, 30-40 parts of acetone, 80-200 parts of deionized water, 1-10 parts of dustproof agent, 10-40 parts of rutile titanium dioxide, 200-500 parts of filler, 10-100 parts of biological-based film forming additive, 0.1-5 parts of polyurethane rheological additive, 1-5 parts of alkali swelling rheological additive, 60-110 parts of deionized water and 6.5-31 parts of other additives; the bio-based film forming aid is acetylated monoglyceride. According to the invention, polyether polyol and 4,4' -dicyclohexylmethane diisocyanate are used as main reactions to synthesize polyurethane emulsion, and an acetylated monoglyceride bio-based film forming auxiliary agent is adopted, so that the glass transition temperature of the emulsion is effectively reduced, the stain resistance and low temperature resistance of the coating are improved, and meanwhile, the elongation of the coating is increased and the VOC content is low.
Description
Technical Field
The invention relates to the technical field of waterproof coatings, in particular to a bio-based stain-resistant exposed water-based polyurethane waterproof coating and a preparation method thereof.
Background
With the enhancement of environmental protection awareness in the whole society, the waterproof coating is developing to the solvent-free water-based direction, and the polyurethane waterproof coating is being in an important transformation stage of 'oil-to-water' as an important part of the waterproof coating market. The water-based polyurethane waterproof paint has natural advantages in the aspect of environmental protection, and is one of the development directions. Because the coating film of the water-based polyurethane waterproof coating at the present stage is hard, film forming aids such as alcohol ester twelve, dipropylene glycol methyl ether and dipropylene glycol butyl ether are required to be added in the production process, but the film forming aids volatilize in the film forming process and the adding amount is not academic to cause the cracking phenomenon of the coating film.
Although the water-based polyurethane waterproof paint is greatly advanced in recent years, along with the continuous development and improvement of the living standard of the current substances, the requirements of people on the waterproof paint are more and more diversified, so that higher requirements on the high performance and multifunction of the current water-based polyurethane waterproof paint are provided, and particularly, the standards of the exposed water-based polyurethane waterproof paint are more severe.
Chinese patent CN114736592A discloses a single-component anti-cracking water-based polyurethane waterproof coating, which improves the cracking problem of a paint film by introducing a silane coupling agent and a crosslinking agent, has the advantages of high and low temperature denaturation resistance, stronger water impermeability and good mechanical property, but does not mention the problems of stain resistance, weather resistance and the like; chinese patent CN103254752A discloses a water-based polyurethane weather-resistant elastic waterproof coating which solves the problems of complex use process, low elasticity, poor crack resistance and poor ultraviolet radiation resistance of the coating in the prior art, but volatile substances such as ethylene glycol, propylene glycol and the like still exist in the system, and the VOC content is influenced.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: the invention provides a bio-based stain-resistant exposed water-based polyurethane waterproof coating and a preparation method thereof, which aim to achieve the high stain resistance, weather resistance, cracking resistance and mechanical properties required by the exposed polyurethane waterproof coating and are environment-friendly and long-acting.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention provides a bio-based stain-resistant exposed water-based polyurethane waterproof coating, which comprises the following components in parts by mass:
50-150 parts of polyether polyol, 10-35 parts of 4,4' -dicyclohexylmethane diisocyanate, 1-10 parts of cross-linking agent, 5-10 parts of 2, 2-dimethylolpropionic acid, 1-10 parts of 1, 4-butanediol, 2-10 parts of chain extender, 2-10 parts of trimethylolpropane, 2-10 parts of triethylamine, 30-40 parts of acetone, 80-200 parts of deionized water, 1-10 parts of dustproof agent, 10-40 parts of rutile titanium dioxide, 200-500 parts of filler, 10-100 parts of biological-based film forming additive, 0.1-5 parts of polyurethane rheological additive, 1-5 parts of alkali swelling rheological additive, 60-110 parts of deionized water and 6.5-31 parts of other additives;
The bio-based film forming aid is acetylated monoglyceride.
The invention takes polyether polyol and 4,4' -dicyclohexylmethane diisocyanate as main reactions to synthesize polyurethane emulsion, adopts acetylated monoglyceride bio-based film forming auxiliary agent, effectively reduces the glass transition temperature of the emulsion, improves the stain resistance and low temperature resistance of the coating, increases the elongation and toughness of the coating and has low VOC content, in addition, can improve the processability during mixing and the adhesiveness between coating films, overcomes the problem of coating film cracking caused by improper addition of conventional alcohol ester and alcohol ether film forming auxiliary agent, and optimizes the multi-aspect performance of the coating.
Optionally, the crosslinker is a trifunctional aziridine crosslinker.
From the above description, it is known that the addition of the trifunctional aziridine crosslinking agent enables the polymer molecules to form a three-dimensional network structure, thereby improving the strength of the emulsion and enabling the emulsion to form a strong anti-fouling coating film, and improving the cracking resistance, the water washing resistance and the adhesion of the coating film to some extent.
Optionally, the dust-proofing agent is oleamide.
From the above description, the introduction of oleamide can improve the antistatic and lubricating properties of the paint by reducing the surface resistance of the paint, and can also improve the moisture-proof properties, obviously reduce the friction and bonding resistance, and ensure that the surface finish of the paint film is good; can also prevent dust from adhering to the surface of the glass, and improve the stain resistance of the glass.
Optionally, the other auxiliary agents comprise the following components in parts by weight: 1-10 parts of dispersing agent, 4-10 parts of defoamer, 0.5-1 part of pH regulator and 1-10 parts of preservative.
Optionally, the polyether polyol is polypropylene glycol;
The chain extender is ethylenediamine or diethylenetriamine;
The filler is one or more selected from quartz powder, wollastonite powder, calcium carbonate, titanium dioxide, barium sulfate and metakaolin;
the polyurethane rheological aid is polyurethane association polymer;
the alkali swelling rheological additive is a crosslinking emulsion rheological agent formed by copolymerization of high molecular polyacrylate and methacrylic acid.
From the above description, it is known that the complex use of the alkali swelling rheological aid and the polyurethane rheological aid can cause rheological molecules, latex molecules and pigments to form a network structure through interaction, thereby achieving the effects of increasing rheology and resisting cracking.
Optionally, the dispersing agent is selected from one or more of polyacrylate, polyphosphate, cellulose derivative, fatty acid polyethylene glycol ester and sodium dodecyl sulfate;
the defoaming agent is one or more selected from polydimethylsiloxane, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene alcohol amine ether and polyoxypropylene polyoxyethylene glycerol ether;
The pH regulator is one or more selected from ammonia water, dimethylethanolamine, 2-amino-2-methyl-1-propanol and triethanolamine;
The preservative is selected from one or more of octyl-isothiazolinone, bisbenzamide, benzimidazole carbamate and ethylene bis-dithiocarbamic acid ammonium.
The invention also provides a preparation method of the bio-based stain-resistant exposed water-based polyurethane waterproof coating, which comprises the following steps:
s1, reacting polyether polyol, 4' -dicyclohexylmethane diisocyanate and a cross-linking agent for 0.8-1.2h under the protection of nitrogen, wherein the reaction temperature is 55-65 ℃;
s2, continuously adding 2, 2-dimethylolpropionic acid, heating to 68-72 ℃, and reacting for 0.8-1.2h;
S3, cooling to 48-50 ℃, continuously adding acetone and a bio-based film forming auxiliary agent, and stirring at 500-1000rpm for at least 0.5h;
s4, heating to 68-72 ℃, continuously adding 1, 4-butanediol and trimethylolpropane, condensing and refluxing, and reacting for 1.5-2.5h;
s5, cooling to 23-27 ℃, regulating the stirring speed to 550-650rpm, continuously adding triethylamine, and stirring for at least 0.5h;
S6, dripping the chain extender into part of deionized water, uniformly mixing to prepare an aqueous solution, then increasing the stirring rotation speed to 1400-1600rpm, adding the prepared aqueous solution of the chain extender into the product obtained in the step S5, and emulsifying and dispersing for at least 0.5h;
s7, spin-steaming the product obtained in the step S6 at 35-45 ℃ for 3.5-4.5 hours, and removing the organic solvent;
S8, cooling to below 30 ℃, adding the rest deionized water, and stirring at 500rpm;
s9, slowly adding a dustproof agent and other auxiliary agents, then increasing the stirring speed to 1200rpm, and slowly adding rutile titanium dioxide and filler;
S10, reducing the rotating speed to 600rpm, sequentially adding the polyurethane rheological aid and the alkali swelling rheological aid, and uniformly stirring.
Wherein the technical effects corresponding to the preparation method of the bio-based stain-resistant and dew-resistant polyurethane waterproof coating provided in the second aspect are described with reference to the related description of the bio-based stain-resistant and dew-resistant polyurethane waterproof coating provided in the first aspect.
Detailed Description
In order to better understand the above technical solution, the present invention will now be described in detail with reference to specific embodiments. While the preferred embodiments of the present invention are described below, it should be understood that the present invention may be embodied in various forms and should not be limited to the examples set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
The embodiment of the invention provides a bio-based stain-resistant exposed water polyurethane waterproof coating, which comprises the following components in parts by mass:
50-150 parts of polyether polyol, 10-35 parts of 4,4' -dicyclohexylmethane diisocyanate, 1-10 parts of cross-linking agent, 5-10 parts of 2, 2-dimethylolpropionic acid, 1-10 parts of 1, 4-butanediol, 2-10 parts of chain extender, 2-10 parts of trimethylolpropane, 2-10 parts of triethylamine, 30-40 parts of acetone, 80-200 parts of deionized water, 1-10 parts of dustproof agent, 10-40 parts of rutile titanium dioxide, 200-500 parts of filler, 10-100 parts of biological-based film forming additive, 0.1-5 parts of polyurethane rheological additive, 1-5 parts of alkali swelling rheological additive, 60-110 parts of deionized water and 6.5-31 parts of other additives;
The bio-based film forming aid is acetylated monoglyceride.
The cross-linking agent is a trifunctional aziridine cross-linking agent.
The dustproof agent is oleamide.
The other auxiliary agents comprise the following components in parts by weight: 1-10 parts of dispersing agent, 4-10 parts of defoamer, 0.5-1 part of pH regulator and 1-10 parts of preservative.
The polyether polyol is polypropylene glycol.
The chain extender is ethylenediamine or diethylenetriamine.
Preferably, the chain extender is diethylenetriamine.
The filler is one or more selected from quartz powder, wollastonite powder, calcium carbonate, titanium dioxide, barium sulfate and metakaolin.
Preferably, the filler is barium sulfate.
The polyurethane rheological aid is a polyurethane associative polymer.
The alkali swelling rheological additive is a crosslinking emulsion rheological agent formed by copolymerization of high molecular polyacrylate and methacrylic acid.
The dispersing agent is one or more selected from polyacrylate, polyphosphate, cellulose derivative, fatty acid polyethylene glycol ester and sodium dodecyl sulfate.
Preferably, the dispersant is sodium polyacrylate.
The defoaming agent is one or more selected from polydimethylsiloxane, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene alcohol amine ether and polyoxypropylene polyoxyethylene glycerol ether;
preferably, the defoamer is polyoxypropylene polyoxyethylene glyceryl ether.
The pH regulator is one or more selected from ammonia water, dimethylethanolamine, 2-amino-2-methyl-1-propanol and triethanolamine.
Preferably, the pH adjuster is triethanolamine.
The preservative is selected from one or more of octyl-isothiazolinone, bisbenzamide, benzimidazole carbamate and ethylene bis-dithiocarbamic acid ammonium.
Preferably, the preservative is octyl-isothiazolinone.
It is prepared by the following method:
s1, reacting polyether polyol, 4' -dicyclohexylmethane diisocyanate and a cross-linking agent for 0.8-1.2h under the protection of nitrogen, wherein the reaction temperature is 55-65 ℃;
s2, continuously adding 2, 2-dimethylolpropionic acid, heating to 68-72 ℃, and reacting for 0.8-1.2h;
S3, cooling to 48-50 ℃, continuously adding acetone and a bio-based film forming auxiliary agent, and stirring at 500-1000rpm for at least 0.5h;
s4, heating to 68-72 ℃, continuously adding 1, 4-butanediol and trimethylolpropane, condensing and refluxing, and reacting for 1.5-2.5h;
s5, cooling to 23-27 ℃, regulating the stirring speed to 550-650rpm, continuously adding triethylamine, and stirring for at least 0.5h;
S6, dripping the chain extender into part of deionized water, uniformly mixing to prepare an aqueous solution, then increasing the stirring rotation speed to 1400-1600rpm, adding the prepared aqueous solution of the chain extender into the product obtained in the step S5, and emulsifying and dispersing for at least 0.5h;
s7, spin-steaming the product obtained in the step S6 at 35-45 ℃ for 3.5-4.5 hours, and removing the organic solvent;
S8, cooling to below 30 ℃, adding the rest deionized water, and stirring at 500rpm;
s9, slowly adding a dustproof agent and other auxiliary agents, then increasing the stirring speed to 1200rpm, and slowly adding rutile titanium dioxide and filler;
S10, reducing the rotating speed to 600rpm, sequentially adding the polyurethane rheological aid and the alkali swelling rheological aid, and uniformly stirring.
Example 1
A biobased stain-resistant exposed water-based polyurethane waterproof coating comprises the following components in parts by mass:
125 parts of polypropylene glycol, 30 parts of 4,4' -dicyclohexylmethane diisocyanate, 5 parts of trifunctional aziridine crosslinking agent, 10 parts of 2, 2-dimethylolpropionic acid, 5 parts of 1, 4-butanediol, 5 parts of diethylenetriamine, 5 parts of trimethylolpropane, 5 parts of triethylamine, 40 parts of acetone, 200 parts of deionized water, 2 parts of oleamide, 30 parts of rutile titanium dioxide, 400 parts of barium sulfate, 20 parts of acetylated monoglyceride, 2 parts of polyurethane associative polymer, 2 parts of alkali swelling rheological additive, 102 parts of deionized water and 12 parts of other additives; wherein, other auxiliary agents comprise 5 parts of sodium polyacrylate, 5 parts of polyoxypropylene polyoxyethylene glycerol ether, 1 part of triethanolamine and 1 part of octyl-isothiazolinone.
It is prepared by the following method:
S1, polypropylene glycol, 4' -dicyclohexylmethane diisocyanate and a trifunctional aziridine crosslinking agent are reacted for 0.8-1.2h under the protection of nitrogen, and the reaction temperature is 55-65 ℃;
s2, continuously adding 2, 2-dimethylolpropionic acid, heating to 68-72 ℃, and reacting for 0.8-1.2h;
S3, cooling to 48-50 ℃, continuously adding acetone and acetylated monoglyceride, and stirring at 500-1000rpm for at least 0.5h;
s4, heating to 68-72 ℃, continuously adding 1, 4-butanediol and trimethylolpropane, condensing and refluxing, and reacting for 1.5-2.5h;
s5, cooling to 23-27 ℃, regulating the stirring speed to 550-650rpm, continuously adding triethylamine, and stirring for at least 0.5h;
S6, dripping diethylenetriamine into part of deionized water, uniformly mixing to prepare an aqueous solution, then increasing the stirring rotation speed to 1400-1600rpm, adding the prepared diethylenetriamine aqueous solution into the product obtained in the step S5, and emulsifying and dispersing for at least 0.5h;
s7, spin-steaming the product obtained in the step S6 at 35-45 ℃ for 3.5-4.5 hours, and removing the organic solvent;
S8, cooling to below 30 ℃, adding the rest deionized water, and stirring at 500rpm;
S9, slowly adding oleamide, sodium polyacrylate, polyoxypropylene polyoxyethylene glyceryl ether, triethanolamine and octyl-isothiazolinone, then increasing the stirring speed to 1200rpm, and slowly adding rutile titanium dioxide and barium sulfate;
S10, reducing the rotating speed to 600rpm, sequentially adding the polyurethane associative polymer and the alkali swelling rheological additive, and uniformly stirring.
Example 2
This example differs from example 1 in the amount of each component added.
A biobased stain-resistant exposed water-based polyurethane waterproof coating comprises the following components in parts by mass:
125 parts of polypropylene glycol, 30 parts of 4,4' -dicyclohexylmethane diisocyanate, 10 parts of trifunctional aziridine crosslinking agent, 10 parts of 2, 2-dimethylolpropionic acid, 5 parts of 1, 4-butanediol, 5 parts of diethylenetriamine, 5 parts of trimethylolpropane, 5 parts of triethylamine, 40 parts of acetone, 200 parts of deionized water, 6 parts of oleamide, 30 parts of rutile titanium dioxide, 400 parts of barium sulfate, 50 parts of acetylated monoglyceride, 2 parts of polyurethane associative polymer, 2 parts of alkali swelling rheological additive, 63 parts of deionized water and 12 parts of other additives; wherein, other auxiliary agents comprise 5 parts of sodium polyacrylate, 5 parts of polyoxypropylene polyoxyethylene glycerol ether, 1 part of triethanolamine and 1 part of octyl-isothiazolinone.
Comparative example 1
This comparative example differs from example 1 in that it does not contain a trifunctional aziridine crosslinking agent.
Comparative example 2
This comparative example differs from example 1 in that no oleamide was contained.
Comparative example 3
This comparative example differs from example 1 in that it does not contain acetylated monoglyceride.
The waterproof coatings prepared in examples 1-2 and comparative examples 1-3 were subjected to various performance tests according to standard test methods, and the results are shown in tables 1 and 2 below.
TABLE 1 mechanical Property test results of waterproof coating
As can be seen from Table 1, the bio-based stain-resistant and dew-resistant polyurethane waterproof coating materials prepared in examples 1 and 2 are excellent in weather resistance, crack resistance, adhesive strength, tensile property and other properties, and particularly in stain resistance. Compared with the examples, the waterproof coatings prepared in the comparative examples 1-3 have the stain resistance which does not reach the standard value under the condition that the trifunctional aziridine crosslinking agent, the oleamide and the acetylated monoglyceride are not added respectively.
TABLE 2 test results of harmful substance content of waterproof coating
As can be seen from Table 2, the bio-based stain-resistant and dew-resistant polyurethane waterproof coating prepared according to the invention has low VOC content, can meet the A-class standard requirement, and is environment-friendly and long-acting.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (3)
1. A biobased stain-resistant exposed water-based polyurethane waterproof coating comprises the following components in parts by mass:
50-150 parts of polyether polyol, 10-35 parts of 4,4' -dicyclohexylmethane diisocyanate, 1-10 parts of cross-linking agent, 5-10 parts of 2, 2-dimethylolpropionic acid, 1-10 parts of 1, 4-butanediol, 2-10 parts of chain extender, 2-10 parts of trimethylolpropane, 2-10 parts of triethylamine, 30-40 parts of acetone, 80-200 parts of deionized water, 1-10 parts of dustproof agent, 10-40 parts of rutile titanium dioxide, 200-500 parts of filler, 10-100 parts of biological-based film forming additive, 0.1-5 parts of polyurethane rheological additive, 1-5 parts of alkali swelling rheological additive, 60-110 parts of deionized water and 6.5-31 parts of other additives;
The bio-based film forming aid is acetylated monoglyceride;
the other auxiliary agents comprise the following components in parts by weight: 1-10 parts of dispersing agent, 4-10 parts of defoamer, 0.5-1 part of pH regulator and 1-10 parts of preservative;
the cross-linking agent is a trifunctional aziridine cross-linking agent;
the dustproof agent is oleamide;
the preparation method of the bio-based stain-resistant exposed water-based polyurethane waterproof coating comprises the following steps:
s1, reacting polyether polyol, 4' -dicyclohexylmethane diisocyanate and a cross-linking agent for 0.8-1.2h under the protection of nitrogen, wherein the reaction temperature is 55-65 ℃;
s2, continuously adding 2, 2-dimethylolpropionic acid, heating to 68-72 ℃, and reacting for 0.8-1.2h;
S3, cooling to 48-50 ℃, continuously adding acetone and a bio-based film forming auxiliary agent, and stirring for at least 0.5h under 500-1000 rpm;
s4, heating to 68-72 ℃, continuously adding 1, 4-butanediol and trimethylolpropane, condensing and refluxing, and reacting for 1.5-2.5h;
s5, cooling to 23-27 ℃, regulating the stirring speed to 550-650rpm, continuously adding triethylamine, and stirring for at least 0.5h;
S6, dripping the chain extender into part of deionized water, uniformly mixing to prepare an aqueous solution, then increasing the stirring rotation speed to 1400-1600rpm, adding the prepared aqueous solution of the chain extender into the product obtained in the step S5, and emulsifying and dispersing for at least 0.5h;
s7, spin-steaming the product obtained in the step S6 at 35-45 ℃ for 3.5-4.5 hours, and removing the organic solvent;
S8, cooling to below 30 ℃, adding the rest deionized water, and stirring at 500rpm;
s9, slowly adding a dustproof agent and other auxiliary agents, then increasing the stirring speed to 1200rpm, and slowly adding rutile titanium dioxide and filler;
S10, reducing the rotating speed to 600rpm, sequentially adding the polyurethane rheological aid and the alkali swelling rheological aid, and uniformly stirring.
2. The biobased stain resistant, exposed water resistant polyurethane waterproofing coating of claim 1 wherein said polyether polyol is polypropylene glycol;
The chain extender is ethylenediamine or diethylenetriamine;
The filler is one or more selected from quartz powder, wollastonite powder, calcium carbonate, titanium dioxide, barium sulfate and metakaolin;
The polyurethane rheological aid is a polyurethane associative polymer.
3. The biobased stain resistant exposed water resistant polyurethane waterproofing coating of claim 1 wherein said dispersant is selected from one or more of the group consisting of polyacrylates, polyphosphates, cellulose derivatives, fatty acid polyglycol esters, sodium lauryl sulfate;
the defoaming agent is one or more selected from polydimethylsiloxane, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene alcohol amine ether and polyoxypropylene polyoxyethylene glycerol ether;
The pH regulator is one or more selected from ammonia water, dimethylethanolamine, 2-amino-2-methyl-1-propanol and triethanolamine;
The preservative is selected from one or more of octyl-isothiazolinone, bisbenzamide, benzimidazole carbamate and ethylene bis-dithiocarbamic acid ammonium.
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CN113105814A (en) * | 2020-01-13 | 2021-07-13 | 万华化学集团股份有限公司 | Single-component waterborne polyurethane waterproof coating and preparation method thereof |
CN113249020A (en) * | 2021-05-19 | 2021-08-13 | 上海三棵树防水技术有限公司 | High-stain-resistance sewage-water-resistant polyurethane waterproof coating and preparation method thereof |
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CN102102005A (en) * | 2010-12-13 | 2011-06-22 | 嘉兴禾欣化学工业有限公司 | Preparation method of environmentally-friendly aqueous polyurethane adhesive |
CN113105814A (en) * | 2020-01-13 | 2021-07-13 | 万华化学集团股份有限公司 | Single-component waterborne polyurethane waterproof coating and preparation method thereof |
CN111909610A (en) * | 2020-08-14 | 2020-11-10 | 上海三棵树防水技术有限公司 | Polyurethane waterproof coating and preparation method thereof |
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