CN116042069A - Single-component polyurea waterproof coating with refrigeration function and preparation method thereof - Google Patents
Single-component polyurea waterproof coating with refrigeration function and preparation method thereof Download PDFInfo
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- CN116042069A CN116042069A CN202211368567.5A CN202211368567A CN116042069A CN 116042069 A CN116042069 A CN 116042069A CN 202211368567 A CN202211368567 A CN 202211368567A CN 116042069 A CN116042069 A CN 116042069A
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- Prior art keywords
- refrigerant
- fluorescent
- waterproof coating
- mixed solution
- solution
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- 238000000576 coating method Methods 0.000 title claims abstract description 83
- 239000011248 coating agent Substances 0.000 title claims abstract description 73
- 229920002396 Polyurea Polymers 0.000 title claims abstract description 53
- 238000005057 refrigeration Methods 0.000 title claims description 6
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000003507 refrigerant Substances 0.000 claims abstract description 130
- 230000005855 radiation Effects 0.000 claims abstract description 63
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 40
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 36
- 229920000570 polyether Polymers 0.000 claims abstract description 36
- 229920005862 polyol Polymers 0.000 claims abstract description 28
- 150000003077 polyols Chemical class 0.000 claims abstract description 28
- 238000001816 cooling Methods 0.000 claims abstract description 23
- 229920001690 polydopamine Polymers 0.000 claims abstract description 20
- 239000013530 defoamer Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 82
- 239000011259 mixed solution Substances 0.000 claims description 63
- 239000000243 solution Substances 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 238000002156 mixing Methods 0.000 claims description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 29
- 235000019441 ethanol Nutrition 0.000 claims description 24
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 16
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000002518 antifoaming agent Substances 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 239000000872 buffer Substances 0.000 claims description 10
- 239000007853 buffer solution Substances 0.000 claims description 10
- 239000004202 carbamide Substances 0.000 claims description 10
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 7
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 7
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 7
- 239000001099 ammonium carbonate Substances 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 229920006217 cellulose acetate butyrate Polymers 0.000 claims description 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical group O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 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 description 5
- 238000005406 washing Methods 0.000 claims description 5
- WYNCHZVNFNFDNH-UHFFFAOYSA-N Oxazolidine Chemical compound C1COCN1 WYNCHZVNFNFDNH-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 3
- DMTRWFMFBIMXBX-UHFFFAOYSA-L lead(2+);6-methylheptanoate Chemical compound [Pb+2].CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O DMTRWFMFBIMXBX-UHFFFAOYSA-L 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 125000000879 imine group Chemical group 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 2
- 239000012970 tertiary amine catalyst Substances 0.000 claims description 2
- 238000004078 waterproofing Methods 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 8
- 239000004566 building material Substances 0.000 abstract description 2
- 238000012986 modification Methods 0.000 description 16
- 230000004048 modification Effects 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 239000000463 material Substances 0.000 description 15
- 239000003570 air Substances 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 5
- 238000010276 construction Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 150000002466 imines Chemical class 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002310 reflectometry Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical group N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 229960003638 dopamine Drugs 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 235000012736 patent blue V Nutrition 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000009736 wetting Methods 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
- C09D175/02—Polyureas
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/004—Reflecting paints; Signal paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/22—Luminous paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/47—Levelling agents
-
- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to a single-component polyurea waterproof coating with a refrigerating function and a preparation method thereof, belonging to the technical field of building materials. The waterproof coating comprises the following raw materials in parts by weight: 20-30 parts of diisocyanate, 25-40 parts of polyether polyol, 0.3-1 part of catalyst, 25-40 parts of refrigerant, 2-8 parts of latent curing agent, 0.5-2 parts of defoamer and 1-2 parts of flatting agent; the refrigerant consists of fluorescent refrigerant and radiation refrigerant; preferably, the fluorescent refrigerant is an ethyl orthosilicate modified fluorescent refrigerant, and the radiation refrigerant is a polydopamine modified radiation refrigerant. The preparation method comprises the steps of adding all raw material components into a closed reaction kettle, controlling the conditions of temperature, pressure, moisture and the like, and reacting to obtain the waterproof coating. The waterproof coating not only has excellent bonding and weather resistance, but also has cooling and decorating effects, can greatly reduce indoor temperature in hot summer, reduces air conditioner use, and is energy-saving and environment-friendly.
Description
Technical Field
The invention relates to a single-component polyurea waterproof coating with a refrigerating function and a preparation method thereof, belonging to the technical field of building materials.
Background
The one-component polyurea coating is a one-package liquid mixture composed of a prepolymer containing polyisocyanate (-NCO) functional groups or a prepolymer with chemically blocked polyisocyanate functional groups, a blocked amino latent curing agent, an auxiliary agent and the like; the high molecular polymer elastomer is exposed to air after the barrel is opened, the latent curing agent hydrolyzes to release amino groups, and all cross-linking points of the amino groups and the isocyanic acid form the high molecular polymer elastomer with all ureido groups. The curing and crosslinking process does not generate carbon dioxide, and chemical bubbles are completely eradicated from the source. Compared with the double-component polyurea, the single-component manual polyurea does not need special high-pressure airless spraying equipment, can be manually scraped and brushed, has simple construction, and therefore, has more and more application fields.
However, the single-component polyurea in the current market has the problems of weak interface bonding strength, poor weather resistance and the like, and in order to improve the interface bonding strength with a base layer, an interface agent needs to be coated, so that the construction cost is increased, and the construction period is prolonged; the conditions of film cracking and peeling easily occur after the film is directly exposed to the open air for two or three years, and the actual effective service life is very short.
Disclosure of Invention
The invention aims to solve the problems of weak interfacial bonding strength, poor weather resistance and the like of single-component polyurea in the prior art, and provides a single-component polyurea waterproof coating with a refrigerating function and a preparation method thereof. The waterproof coating not only has excellent bonding performance and weather resistance, but also has cooling effect and decorative effect, can greatly reduce indoor temperature in hot summer, is favorable for reducing air conditioner use, and is energy-saving and environment-friendly.
In order to achieve the purpose of the invention, the following technical scheme is provided.
A single-component polyurea waterproof coating with a refrigerating function comprises the following raw material components in parts by weight:
the diisocyanate is Hexamethylene Diisocyanate (HDI), diphenylmethane diisocyanate (MDI) or Toluene Diisocyanate (TDI).
The polyether polyol is more than one of polyether glycol and polyether triol. Preferably the polyether polyol has a functionality of 2 to 4; the polyether diol preferably has a number average molecular weight of 400 to 4000, and the polyether triol preferably has a number average molecular weight of 2000 to 5000. More preferably, the polyether polyol is one or more of polyether polyol EP-330N of Shandong blue Star Dong Co., ltd, polyether polyol MN1000 of Shandong blue Star Dong Co., ltd, polyether polyol DL-2000D of Shandong blue Star Dong Co., ltd, polyethylene glycol and polytetrahydrofuran glycol.
The catalyst is more than one of an organic metal catalyst and a tertiary amine catalyst. The preferred catalyst is one or more of dibutyltin dilaurate, lead isooctanoate and bismuth isooctanoate.
The refrigerant is composed of fluorescent refrigerant and radiation refrigerant. Preferably, the mass ratio of the fluorescent refrigerant to the radiation refrigerant is 2-3:3-4.
The fluorescent refrigerant is long afterglow fluorescent powder. Preferably, the particle size of the fluorescent refrigerant is 300-1000 meshes, and the light-emitting time is more than 8 hours.
More preferably, the fluorescent refrigerant is an ethyl orthosilicate modified fluorescent refrigerant; the fluorescent refrigerant modified by the tetraethoxysilane is preferably prepared by the following method:
(1) Tetraethoxysilane (TEOS) (chemical formula C 8 H 20 O 4 Si) is fully dissolved in ethanol water solution to obtain mixed solution A;
(2) Adding nitric acid into the mixed solution A prepared in the step (1), uniformly mixing, and adjusting the pH value of the mixed solution A to 1-2; then adding ammonium bicarbonate, uniformly mixing, and adjusting the pH value of the mixed solution A to 7-8 to obtain the mixed solution A with the pH value adjusted;
(3) Adding urea and fluorescent refrigerant into the mixed solution A with the pH value adjusted, which is prepared in the step (2), and uniformly mixing to obtain a mixed solution B;
(4) And (3) heating the mixed solution B prepared in the step (3) at 90-100 ℃ to react for 1.5-2.5 hours, cooling to room temperature, standing for more than 1 hour, washing with ethanol aqueous solution, and finally drying to prepare the ethyl orthosilicate modified fluorescent refrigerant.
In step (1):
preferably, the volume ratio of the tetraethoxysilane to the ethanol water solution is 1:1; preferably, the purity of the ethyl orthosilicate is analytically pure.
In the step (2):
preferably the purity of nitric acid is analytically pure; preferably stirring for 10-20 min and uniformly mixing.
In the step (3):
preferably, the mass ratio of the fluorescent refrigerant to TEOS is 1:2-3;
preferably, the molar ratio of urea to silicon element in TEOS is 10:1;
preferably, a magnetic stirrer is used for uniform mixing.
In the step (4):
the heating reaction is preferably carried out by heating in a water bath.
In steps (1) and (4):
preferably, the volume ratio of ethanol to water in the ethanol water solution is 1:1;
preferably, the water in the aqueous ethanol solution is deionized water.
The radiation refrigerant is one or more of silicon dioxide powder, titanium dioxide powder and barium sulfate powder. Preferably, the particle size of the radiant refrigerant is 300 mesh to 1000 mesh.
More preferably, the radiation refrigerant is a polydopamine modified radiation refrigerant; the radiation refrigerant modified by polydopamine is preferably prepared by the following method:
(1) Drying the radiation refrigerant, and uniformly dispersing the radiation refrigerant in the mixed solution to prepare radiation refrigerant dispersion liquid; adding dopamine hydrochloride, and uniformly dispersing in a radiation refrigerant dispersion liquid to obtain a modified solution;
(2) And (3) adding sodium hydroxide solution into the modified solution prepared in the step (2), adjusting the pH value of the modified solution to 8-10, removing the solvent, and drying to obtain the radiation refrigerant modified by polydopamine.
In step (1):
preferably, the radiation refrigerant is dried for 4 hours at 60 ℃;
the mixed solution is formed by mixing Tris-HCl buffer solution and absolute ethyl alcohol; preferably, the volume ratio of the Tris-HCl buffer solution to the absolute ethyl alcohol in the mixed solution is 2-3:1-2; preferably, the Tris-HCl buffer is 2mg/ml,50mM Tris-HCl buffer;
preferably, the mass ratio of the radiation refrigerant to the mixed solution to the dopamine hydrochloride is 5:50-70:1;
preferably, ultrasonic dispersion is used.
In the step (2):
preferably, adding sodium hydroxide solution into the modified solution prepared in the step (2) to be uniformly dispersed so as to adjust the pH value;
preferably, the magnetic stirring is carried out for 2 to 4 hours at 500 to 700rpm, and the dispersion is uniform;
preferably, the mass fraction of sodium hydroxide in the sodium hydroxide solution is 10%;
the solvent is preferably removed by the following method:
centrifuging by using a high-speed centrifuge, and rinsing the centrifuged product with water; preferably, centrifugal treatment is carried out by adopting a high-speed centrifugal machine with the speed of 7000-9000 rpm, and the product after centrifugal treatment is rinsed by deionized water;
preferably, the drying is carried out by adopting an oven at 45-60 ℃ for 20-24 hours.
The latent curing agent is an imine latent curing agent or an oxazolidine latent curing agent.
The defoamer is silicone defoamer. Preferred defoamers are BYK-141 defoamer, BYK-051 defoamer, BYK-065 defoamer or BYK-066N defoamer of Pick chemical.
The leveling agent is cellulose acetate butyrate.
The invention discloses a preparation method of a single-component polyurea waterproof coating with a refrigerating function, which comprises the following steps:
(1) Adding polyether polyol into a closed reaction kettle, heating and stirring, controlling the temperature to be 100-110 ℃, starting a vacuum pump to vacuum for 1.5-2 h, controlling the pressure to be below-0.05 MPa, and controlling the water content to be below 300 ppm;
(2) Cooling to 60-70 ℃, and introducing dry nitrogen to release vacuum;
(3) Adding diisocyanate and a catalyst, controlling the temperature at 80-85 ℃ and carrying out polymerization reaction for 2-3 h;
(4) Cooling to 70 ℃, adding a latent curing agent, and uniformly stirring at 300-400 rpm for 0.5-1 h;
(5) Cooling to 50-55 deg.c, adding fluorescent refrigerant and radiating refrigerant separately into the reaction kettle and stirring at 700-900 rpm for 0.5-1 hr;
(6) Adding the defoaming agent and the leveling agent, uniformly mixing, and stirring at 90-120 rpm for 1-2 h to obtain the single-component polyurea waterproof coating with the refrigerating function.
Advantageous effects
(1) The invention provides a single-component polyurea waterproof coating with a refrigerating function, which realizes a synergistic effect through the design of each component and the content thereof, so that the waterproof coating not only has the function of the traditional single-component polyurea waterproof coating, but also further realizes excellent bonding performance and weather resistance, simultaneously has a cooling effect and a decoration effect, can greatly reduce the indoor temperature in hot summer, is beneficial to reducing the use of an air conditioner, and is energy-saving and environment-friendly.
(2) The invention provides a single-component polyurea waterproof coating with a refrigerating function, which has the advantages that fluorescent refrigerant and radiation refrigerant are introduced into a single-component polyurea waterproof material to enable the waterproof coating to have the refrigerating function, so that the solar reflectivity is not lower than 98%, the infrared emissivity is not lower than 93%, and the sunlight is reflected, so that the sunlight absorptivity is reduced, the coating temperature is reduced, the internal aging rate of the coating is greatly slowed down, the weather resistance is improved, and the service life of the coating is greatly prolonged; the aluminum plate coated with the waterproof coating has extremely obvious passive radiation refrigeration effect in daytime when the surface temperature of the coating is lower than the ambient air temperature (13.5+/-0.45) to (15.2+/-0.45) DEG C under the direct irradiation of noon sunlight; the coating on the surface of the building can effectively reduce the temperature of the surface of the building, particularly in a high-temperature period in summer, can greatly reduce the indoor temperature, is beneficial to reducing the use of air conditioners, and is energy-saving and environment-friendly; the fluorescent refrigerant is long-afterglow fluorescent powder, can continuously emit light at night, and has an excellent night scene decoration effect.
(3) The invention provides a single-component polyurea waterproof coating with a refrigerating function, wherein a latent curing agent in the waterproof coating is beneficial to solving the foaming problem of single-component moisture-cured polyurea in the curing process, after the latent curing agent is added, the latent curing agent is contacted with air to react with water preferentially to generate amine-containing small molecular compounds when the polyurea is cured, the amine-containing small molecular compounds react with NCO groups of a prepolymer again, and the chain extension and crosslinking are carried out to form a polyurea material without CO in the reaction process 2 And (3) generating gas.
(4) The invention provides a single-component polyurea waterproof coating with a refrigerating function, wherein the defoaming agent in the waterproof coating can reduce the surface tension of a polyurea material, can effectively reduce the formation of bubbles, and can form a smooth and flat coating film when the single-component polyurea material is solidified.
(5) The invention provides a single-component polyurea waterproof coating with a refrigerating function, wherein a fluorescent refrigerant in the waterproof coating is preferably a fluorescent refrigerant modified by tetraethoxysilane; as fluorescent refrigerants can suffer from the problems of greatly reduced luminous performance under the conditions of moist or hot environment, such as color coordinate shift, reduced luminous efficiency and even material decomposition, srAl is adopted 2 O 4 :Eu 2+ ,Dy 3+ Green colourFor example, the long afterglow material can contain water molecules in the pore channel environment in the crystal structure, and the strong polarity of the water molecules can cause the destruction of O-Sr-O bonds, so that the material is decomposed; therefore, the fluorescent refrigerant is required to be subjected to ethyl orthosilicate modification treatment, so that heterogeneous nucleation of the ethyl orthosilicate on fluorescent refrigerant powder particles is realized, the problem that the luminous performance of the fluorescent refrigerant is greatly reduced when the fluorescent refrigerant is subjected to humid or hot environment and the like is solved, the water resistance of the fluorescent refrigerant after the ethyl orthosilicate modification is greatly improved, the service life is prolonged, and the weather resistance of the waterproof coating is further improved;
in the modification, since tetraethyl orthosilicate is easily hydrolyzed under acidic conditions and is easily polymerized under alkaline conditions, a modification method in which a polymerization reaction of silane can be initiated by adding nitric acid and ammonium bicarbonate can be adopted: first hydrolysis of ethyl orthosilicate, followed by condensation reaction to form a sol, which causes heterogeneous nucleation of ethyl orthosilicate on the phosphor particles.
(6) The invention provides a single-component polyurea waterproof coating with a refrigerating function, wherein a radiation refrigerant in the waterproof coating is preferably a radiation refrigerant modified by polydopamine; because the polyurea has weak hydrophobicity, the surface of the aqueous radiation refrigerant is difficult to infiltrate, and the aqueous radiation refrigerant cannot be uniformly dispersed in the polyurea; the dopamine is used as a surface polarity modification material, and the polydopamine generated after oxidation and self polymerization contains a large amount of polar groups such as hydroxyl groups, amino groups and the like, so that good interface water wetting modification and cohesiveness can be provided, therefore, the radiation refrigerant is subjected to polydopamine modification, so that the wettability and dispersibility of the radiation refrigerant in polyurea are improved, the cohesive force of the polyurea is improved, the cohesive strength of the waterproof coating is improved, the waterproof coating can be firmly bonded with a base layer without brushing an interface agent, the construction cost can be reduced, and the construction period can be shortened.
(7) The invention provides a preparation method of a single-component polyurea waterproof coating with a refrigerating function, which is mild in technological conditions and convenient for industrial production, and can be used for preparing the single-component polyurea waterproof coating with the refrigerating function.
Detailed Description
The following examples more particularly describe the disclosure of the present application and provide experimental data support, and reagents and instrumentation used in the examples are prior art and are available through published channels.
The sources of some of the raw materials used in the following examples and comparative examples are as follows:
polyether polyol: polyether polyol EP-330N (functionality 3, number average molecular weight 5000) of Shandong blue Star Kogyo Co., ltd, polyether polyol MN1000 (functionality 3, number average molecular weight 1000) of Shandong blue Star Kogyo Co., ltd, polyether polyol DL-2000D (functionality 2, number average molecular weight 2000) of Shandong blue Star Kogyo Co., ltd.
Latent curing agent: the imine latent curing agent BHD-505 and the oxazolidine latent curing agent BHD-808 are all purchased from Beijing North chemical engineering Co.
Defoaming agent: BYK-141 defoamer, BYK-065 defoamer or BYK-066N defoamer of Pick chemical.
Leveling agent: cellulose acetate butyrate, BHD-301, beijing north chemical engineering ltd.
Fluorescent refrigerant: YMC color powder series long afterglow fluorescent powder, YMO yellow-green light series long afterglow fluorescent powder or YMS sky blue light series long afterglow fluorescent powder of Hangzhou luminous science and technology development Co.
Other raw materials not specifically described are all common commercial products.
Example 1
A single-component polyurea waterproof coating with a refrigerating function comprises the following raw material components in parts by weight:
a diisocyanate: hexamethylene Diisocyanate (HDI), 20 parts;
polyether polyol: 25 parts of polyether polyol MN1000 of Shandong Lanxing Dong Co., ltd;
catalyst: 0.4 parts of dibutyl tin dilaurate;
refrigerant: YMC color powder series long afterglow fluorescent powder with particle size of 300 meshes and 15 parts by weight of Hangzhou luminous science and technology development Co., ltd; rutile type R-902+ titanium dioxide powder with the particle size of 500 meshes and 20 parts of Shandong Yousu chemical technology Co., ltd;
latent curing agent: 505,3 parts of imine latent curing agent BHD-505,3;
defoaming agent: 0.5 part of BYK-141 defoamer of Pick chemical;
leveling agent: cellulose acetate butyrate BHD-301,1 parts.
Wherein, the fluorescent refrigerant is modified by tetraethoxysilane, and the modification treatment steps are as follows:
(1) Fully dissolving ethyl orthosilicate with the purity of analytical purity in an ethanol water solution to obtain a mixed solution A;
the volume ratio of the tetraethoxysilane to the ethanol water solution is 1:1;
the ethanol aqueous solution is formed by mixing ethanol and deionized water, and the volume ratio of the ethanol to the deionized water is 1:1.
(2) Adding the nitric acid with the purity of analytical grade into the mixed solution A prepared in the step (1), stirring for 10min, uniformly mixing, and adjusting the pH value of the mixed solution A to 1; and then adding ammonium bicarbonate, uniformly mixing, and adjusting the pH value of the mixed solution A to 8 to obtain the mixed solution A with the adjusted pH value.
(3) Adding urea and fluorescent refrigerant into the mixed solution A with the pH value adjusted, which is prepared in the step (2), and uniformly mixing by adopting a magnetic stirrer to obtain a mixed solution B;
the molar ratio of urea to silicon element in TEOS is 10:1;
the mass ratio of the fluorescent refrigerant to TEOS is 1:2.
(4) Heating the mixed solution B prepared in the step (3) in a water bath at 95 ℃ for reaction for 2 hours, cooling to room temperature, standing for 1 hour, washing with an ethanol water solution, and finally drying at 90 ℃ for 12 hours to prepare a fluorescent refrigerant modified by tetraethoxysilane;
the ethanol aqueous solution is formed by mixing ethanol and deionized water, and the volume ratio of the ethanol to the deionized water is 1:1.
The radiation refrigerant is subjected to polydopamine modification treatment, and the modification treatment comprises the following steps:
(1) Drying the radiation refrigerant at 60 ℃ for 4 hours, adding the radiation refrigerant into the mixed solution, and carrying out ultrasonic treatment for 20min to uniformly disperse to obtain radiation refrigerant dispersion liquid; adding dopamine hydrochloride, and performing ultrasonic treatment in a radiation refrigerant dispersion liquid for 20min to uniformly disperse to obtain a modified solution;
the mixed solution is formed by mixing Tris-HCl buffer solution and absolute ethyl alcohol; the volume ratio of Tris-HCl buffer solution to absolute ethyl alcohol in the mixed solution is 2:1; tris-HCl buffer is 2mg/ml,50mM Tris-HCl buffer;
the mass ratio of the radiation refrigerant to the mixed solution to the dopamine hydrochloride is 5:50:1.
(2) Adding 10% sodium hydroxide solution into the modified solution prepared in the step (2), magnetically stirring for 4 hours at 500rpm to uniformly disperse, adjusting the pH value of the modified solution to 8, centrifuging by adopting a high-speed centrifuge at 7000rpm, rinsing the centrifuged product with deionized water for 3 times, and finally putting the solvent-removed product into a baking oven to dry at 60 ℃ for 20 hours to obtain the polydopamine modified radiation refrigerant.
The preparation method of the single-component polyurea waterproof coating with the refrigerating function comprises the following steps:
(1) Adding polyether polyol into a closed reaction kettle, heating and stirring, controlling the temperature to be 100 ℃, starting a vacuum pump to vacuumize for 2 hours, controlling the pressure to be below-0.05 MPa, and controlling the water content to be below 300 ppm;
(2) Cooling to 70 ℃, and introducing dry nitrogen to release vacuum;
(3) Adding diisocyanate and a catalyst, controlling the temperature at 85 ℃ and carrying out polymerization reaction for 3 hours;
(4) Cooling to 70 ℃, adding a latent curing agent, and uniformly stirring at 400rpm for 1h;
(5) Cooling to 55 ℃, adding the fluorescent refrigerant modified by tetraethoxysilane and the radiation refrigerant modified by polydopamine into a reaction kettle, and uniformly stirring at 900rpm for 1h;
(6) Adding the defoaming agent and the leveling agent, uniformly mixing, and stirring at 120rpm for 2 hours to obtain the single-component polyurea waterproof coating with the refrigerating function.
Example 2
A single-component polyurea waterproof coating with a refrigerating function comprises the following raw material components in parts by weight:
a diisocyanate: 25 parts of diphenylmethane diisocyanate (MDI);
polyether polyol: 30 parts of polyether polyol EP330N of Shandong Lanxing Dong Co., ltd;
catalyst: 0.7 parts of lead isooctanoate;
refrigerant: YMO yellow-green light series long afterglow fluorescent powder with particle size of 500 meshes and 12 parts of Hangzhou luminous science and technology development Co., ltd; rutile type R-258 titanium dioxide powder of Pan Steel group Co., ltd., particle size 800 mesh, 10 parts; barium sulfate powder with particle size of 600 meshes and 3 parts of Shenzhen sea Yangpowder of limited science and technology;
latent curing agent: 505,5 parts of imine latent curing agent BHD-505,5;
defoaming agent: 1.2 parts of BYK-066N defoamer of Pick chemical;
leveling agent: cellulose acetate butyrate BHD-301,1.5 parts.
Wherein, the fluorescent refrigerant is modified by tetraethoxysilane, and the modification treatment steps are as follows:
(1) Fully dissolving ethyl orthosilicate with the purity of analytical purity in an ethanol water solution to obtain a mixed solution A;
the volume ratio of the tetraethoxysilane to the ethanol water solution is 1:1;
the ethanol aqueous solution is formed by mixing ethanol and deionized water, and the volume ratio of the ethanol to the deionized water is 1:1.
(2) Adding the nitric acid with the purity of analytical grade into the mixed solution A prepared in the step (1), stirring for 15min, uniformly mixing, and adjusting the pH value of the mixed solution A to 1; and then adding ammonium bicarbonate, uniformly mixing, and adjusting the pH value of the mixed solution A to 7 to obtain the mixed solution A with the pH value adjusted.
(3) Adding urea and fluorescent refrigerant into the mixed solution A with the pH value adjusted, which is prepared in the step (2), and uniformly mixing by adopting a magnetic stirrer to obtain a mixed solution B;
the molar ratio of urea to silicon element in TEOS is 10:1;
the mass ratio of the fluorescent refrigerant to TEOS is 1:2.5.
(4) Heating the mixed solution B prepared in the step (3) in a water bath at 100 ℃ to react for 1.5 hours, cooling to room temperature, standing for 1 hour, washing with an ethanol water solution, and finally drying at 90 ℃ for 12 hours to prepare a fluorescent refrigerant modified by tetraethoxysilane;
the ethanol aqueous solution is formed by mixing ethanol and deionized water, and the volume ratio of the ethanol to the deionized water is 1:1.
The radiation refrigerant is subjected to polydopamine modification treatment, and the modification treatment comprises the following steps:
(1) Drying the radiation refrigerant at 60 ℃ for 4 hours, adding the radiation refrigerant into the mixed solution, and carrying out ultrasonic treatment for 20min to uniformly disperse to obtain radiation refrigerant dispersion liquid; adding dopamine hydrochloride, and performing ultrasonic treatment in a radiation refrigerant dispersion liquid for 20min to uniformly disperse to obtain a modified solution;
the mixed solution is formed by mixing Tris-HCl buffer solution and absolute ethyl alcohol; the volume ratio of the Tris-HCl buffer solution to the absolute ethyl alcohol in the mixed solution is 2.5:1.5; tris-HCl buffer is 2mg/ml,50mM Tris-HCl buffer;
the mass ratio of the radiation refrigerant to the mixed solution to the dopamine hydrochloride is 5:60:1.
(2) Adding 10% sodium hydroxide solution into the modified solution prepared in the step (2), magnetically stirring at 600rpm for 3 hours to uniformly disperse, adjusting the pH value of the modified solution to 9, centrifuging by adopting a high-speed centrifugal machine at 8000rpm, rinsing the centrifuged product with deionized water for 3 times, and finally putting the solvent-removed product into a drying oven and drying at 50 ℃ for 22 hours to obtain the polydopamine modified radiation refrigerant.
The preparation method of the single-component polyurea waterproof coating with the refrigerating function comprises the following steps:
(1) Adding polyether polyol into a closed reaction kettle, heating and stirring, controlling the temperature at 105 ℃, starting a vacuum pump to vacuumize for 1.8 hours, controlling the pressure below-0.05 MPa, and controlling the water content below 300 ppm;
(2) Cooling to 65 ℃, and introducing dry nitrogen to release vacuum;
(3) Adding diisocyanate and a catalyst, controlling the temperature at 83 ℃ and carrying out polymerization reaction for 2.5 hours;
(4) Cooling to 70 ℃, adding a latent curing agent, and uniformly stirring at 350rpm for 0.8h;
(5) Cooling to 53 ℃, adding the fluorescent refrigerant modified by tetraethoxysilane and the radiation refrigerant modified by polydopamine into a reaction kettle, and uniformly stirring at 800rpm for 0.8h;
(6) Adding the defoaming agent and the leveling agent, uniformly mixing, and stirring at 105rpm for 1.5 hours to obtain the single-component polyurea waterproof coating with the refrigerating function.
Example 3
A single-component polyurea waterproof coating with a refrigerating function comprises the following raw material components in parts by weight:
a diisocyanate: toluene Diisocyanate (TDI), 30 parts;
polyether polyol: 40 parts of polyether polyol DL-2000D of Shandong Lanxing Dong Co., ltd;
catalyst: bismuth isooctanoate, 0.9 part;
refrigerant: YMS sky blue series long afterglow fluorescent powder with particle size of 800 meshes and 16 parts by weight of Hangzhou luminous science and technology development Co., ltd; german wack T40 silica, 24 parts;
latent curing agent: 808,8 parts of oxazolidine latent curing agent BHD-808,8 parts;
defoaming agent: 2 parts of BYK-065 defoamer of Pick chemical;
leveling agent: cellulose acetate butyrate BHD-301,2 parts.
Wherein, the fluorescent refrigerant is modified by tetraethoxysilane, and the modification treatment steps are as follows:
(1) Fully dissolving tetraethoxysilane in an ethanol water solution to obtain a mixed solution A;
the volume ratio of the tetraethoxysilane to the ethanol water solution is 1:1;
the ethanol aqueous solution is formed by mixing ethanol and deionized water, and the volume ratio of the ethanol to the deionized water is 1:1.
(2) Adding the nitric acid with the purity of analytical grade into the mixed solution A prepared in the step (1), stirring for 20min, uniformly mixing, and adjusting the pH value of the mixed solution A to 2; and then adding ammonium bicarbonate, uniformly mixing, and adjusting the pH value of the mixed solution A to 8 to obtain the mixed solution A with the adjusted pH value.
(3) Adding urea and fluorescent refrigerant into the mixed solution A with the pH value adjusted, which is prepared in the step (2), and uniformly mixing by adopting a magnetic stirrer to obtain a mixed solution B;
the molar ratio of urea to silicon element in TEOS is 10:1;
the mass ratio of the fluorescent refrigerant to TEOS is 1:3.
(4) Heating the mixed solution B prepared in the step (3) in a water bath at 90 ℃ to react for 2.5 hours, cooling to room temperature, standing for 1 hour, washing with an ethanol water solution, and finally drying at 90 ℃ for 12 hours to prepare a fluorescent refrigerant modified by tetraethoxysilane;
the ethanol aqueous solution is formed by mixing ethanol and deionized water, and the volume ratio of the ethanol to the deionized water is 1:1.
The radiation refrigerant is subjected to polydopamine modification treatment, and the modification treatment comprises the following steps:
(1) Drying the radiation refrigerant at 60 ℃ for 4 hours, adding the radiation refrigerant into the mixed solution, and carrying out ultrasonic treatment for 20min to uniformly disperse to obtain radiation refrigerant dispersion liquid; adding dopamine hydrochloride, and performing ultrasonic treatment in a radiation refrigerant dispersion liquid for 20min to uniformly disperse to obtain a modified solution;
the mixed solution is formed by mixing Tris-HCl buffer solution and absolute ethyl alcohol; the volume ratio of Tris-HCl buffer solution to absolute ethyl alcohol in the mixed solution is 3:2; tris-HCl buffer is 2mg/ml,50mM Tris-HCl buffer;
the mass ratio of the radiation refrigerant to the mixed solution to the dopamine hydrochloride is 5:70:1.
(2) Adding 10% sodium hydroxide solution into the modified solution prepared in the step (2), magnetically stirring at 700rpm for 2 hours to uniformly disperse, adjusting the pH value of the modified solution to 10, centrifuging by adopting a high-speed centrifugal machine at 9000rpm, rinsing the centrifuged product with deionized water for 3 times, and finally putting the solvent-removed product into a drying oven and drying at 45 ℃ for 24 hours to obtain the polydopamine modified radiation refrigerant.
The preparation method of the single-component polyurea waterproof coating with the refrigerating function comprises the following steps:
(1) Adding polyether polyol into a closed reaction kettle, heating and stirring, controlling the temperature to be 110 ℃, starting a vacuum pump to vacuumize for 1.5h, controlling the pressure to be below-0.05 MPa, and controlling the water content to be below 300 ppm;
(2) Cooling to 60 ℃, and introducing dry nitrogen to release vacuum;
(3) Adding diisocyanate and a catalyst, controlling the temperature at 80 ℃ and carrying out polymerization reaction for 2 hours;
(4) Cooling to 70 ℃, adding a latent curing agent, and uniformly stirring at 300rpm for 0.5h;
(5) Cooling to 50 ℃, adding the fluorescent refrigerant modified by tetraethoxysilane and the radiation refrigerant modified by polydopamine into a reaction kettle, and uniformly stirring at 700rpm for 0.5h;
(6) Adding the defoaming agent and the leveling agent, uniformly mixing, and stirring at 90rpm for 1h to obtain the single-component polyurea waterproof coating with the refrigerating function.
Example 4
The refrigerant was not subjected to the modification treatment, and the rest was the same as in example 1.
Comparative example 1
No refrigerant was present and the remainder was the same as in example 1.
Comparative example 2
A commercially available single-component polyurea waterproof coating KED109, shandong Wangbao waterproof materials Co., ltd.
Test part
The waterproof coatings of examples 1 to 4 and comparative examples 1 and 2 were subjected to performance test, and the results are shown in table 1 below.
TABLE 1 waterproof coating Performance test results
The testing method comprises the following steps:
(1) The bond strength, tensile strength, water impermeability, and low temperature bendability after 5000 hours of artificial weathering in table 1 were tested with reference to GB/T23446-2009 and GB/T19250-2013.
(2) The total solar reflectance test method comprises the following steps: the prepared waterproof paint was applied to a 4cm×4cm aluminum plate by airless spraying, and the total solar reflectance of the paint was measured using an ultraviolet/visible/near infrared spectrophotometer (PekinElmer Lambda, 950).
Comparing the performance data of the waterproof coatings of examples 1 to 4 with those of comparative examples 1 and 2, it can be seen that the adhesive strength, the low-temperature bendability after 5000 hours of artificial weathering, and the overall solar reflectance and other performances of the waterproof coatings of examples 1 to 3 are more excellent than those of example 4 and comparative examples 1 and 2; the waterproof coating in example 4 is lower in adhesive strength, tensile strength, elongation at break, low-temperature flexibility after 5000 hours of artificial weathering and overall solar reflectance than examples 1 to 3; the low temperature flexibility and overall solar reflectance of the waterproof coatings of comparative examples 1 and 2 after 5000 hours of artificial weathering were significantly lower than those of examples 1 to 4.
Adhesive properties:
the water-repellent coatings of examples 1 to 3 were more excellent in adhesion than those of examples 4, comparative examples 1 and 2. Among them, the adhesive strength of the waterproof coating material of example 1 was 4.6MPa, which was improved by 48.4% relative to the adhesive strength of the waterproof coating material of comparative example 2, which was 3.1 MPa.
Weather resistance:
the low temperature flexibility (-30 ℃ C., no crack) of the waterproof coatings of examples 1 to 3 after 5000 hours of artificial weathering is far superior to that of the waterproof coatings of comparative examples 1 (-10 ℃ C., crack) and comparative examples 2 (-10 ℃ C., crack), thus showing that the weather resistance of the waterproof coatings to which the fluorescent refrigerant modified with tetraethoxysilane and the radiation refrigerant modified with polydopamine are added is greatly improved. The weather resistance of the waterproof coating materials after the addition of the unmodified refrigerant can be improved by the low-temperature flexibility after 5000 hours of the artificial weather aging of the waterproof coating materials of comparative examples 1 to 4 and comparative examples 1 and 2, but the weather resistance of the waterproof coating material after the addition of the modified refrigerant is more excellent.
Refrigeration performance:
the overall solar reflectance of the waterproof coatings of examples 1 to 4 was higher than that of comparative examples 1 and 2, and the overall solar reflectance of the waterproof coatings of examples 1 to 3 was higher than that of example 4. Wherein the overall solar reflectance of the waterproof coating material of example 1 was 0.937, an improvement of 43.3% compared to the overall solar reflectance of the waterproof coating material of comparative example 1 of 0.654. The improvement of the total solar reflectivity can reduce the solar energy absorbed by the waterproof coating and reduce the temperature of the waterproof coating, so that the addition of the unmodified refrigerant can improve the refrigerating performance of the waterproof coating, and the refrigerating performance of the waterproof coating is more excellent after the addition of the modified refrigerant.
While the invention has been described with reference to certain preferred embodiments, it will be understood by those skilled in the art that various changes and substitutions of equivalents may be made without departing from the spirit and scope of the invention.
Claims (10)
1. A single-component polyurea waterproof coating with a refrigerating function is characterized in that: the waterproof coating comprises the following raw materials in parts by weight:
the diisocyanate is hexamethylene diisocyanate, diphenylmethane diisocyanate or toluene diisocyanate;
the polyether polyol is more than one of polyether glycol and polyether triol;
the catalyst is more than one of an organic metal catalyst and a tertiary amine catalyst;
the refrigerant consists of fluorescent refrigerant and radiation refrigerant;
the fluorescent refrigerant is long-afterglow fluorescent powder; the radiation refrigerant is more than one of silicon dioxide powder, titanium dioxide powder and barium sulfate powder;
the latent curing agent is an imine latent curing agent or an oxazolidine latent curing agent;
the defoaming agent is an organosilicon defoaming agent;
the leveling agent is cellulose acetate butyrate.
2. The one-component polyurea waterproof coating with a refrigerating function according to claim 1, wherein: the mass ratio of the fluorescent refrigerant to the radiation refrigerant is 2-3:3-4; the particle size of the fluorescent refrigerant is 300-1000 meshes, and the luminous time is more than 8 hours; the particle size of the radiation refrigerant is 300-1000 meshes;
the functionality of the polyether polyol is 2-4; the number average molecular weight of the polyether glycol is 400-4000, and the number average molecular weight of the polyether triol is 2000-5000;
the catalyst is more than one of dibutyl tin dilaurate, lead isooctanoate and bismuth isooctanoate;
the defoamer is BYK-141 defoamer, BYK-051 defoamer, BYK-065 defoamer or BYK-066N defoamer of Pick chemical.
3. A one-component polyurea waterproofing coating having a refrigeration function according to claim 2, characterized in that: the polyether polyol is one or more of polyether polyol EP-330N of Shandong blue Star Dong Co., ltd, polyether polyol MN1000 of Shandong blue Star Dong Co., ltd, polyether polyol DL-2000D of Shandong blue Star Dong Co., ltd, polyethylene glycol and polytetrahydrofuran glycol.
4. A one-component polyurea waterproofing coating having a refrigeration function according to any one of claims 1 to 3, characterized in that: the fluorescent refrigerant is an ethyl orthosilicate modified fluorescent refrigerant; the radiation refrigerant is polydopamine modified radiation refrigerant.
5. The one-component polyurea waterproof coating with a refrigerating function according to claim 4, wherein: the fluorescent refrigerant modified by the tetraethoxysilane is prepared by the following method:
(1) Fully dissolving tetraethoxysilane in an ethanol water solution to obtain a mixed solution A;
(2) Adding nitric acid into the mixed solution A, and adjusting the pH value of the mixed solution A to 1-2; adding ammonium bicarbonate, and adjusting the pH value of the mixed solution A to 7-8 to obtain the mixed solution A with the pH value adjusted;
(3) Adding urea and fluorescent refrigerant into the mixed solution A with the pH value adjusted, and uniformly mixing to obtain a mixed solution B;
(4) And (3) heating the mixed solution B at 90-100 ℃ for reaction for 1.5-2.5 h, cooling to room temperature, standing for more than 1h, washing with ethanol aqueous solution, and drying to obtain the ethyl orthosilicate modified fluorescent refrigerant.
6. The one-component polyurea waterproof coating with a refrigerating function according to claim 5, wherein: in the step (1), the volume ratio of the tetraethoxysilane to the ethanol water solution is 1:1;
in the step (2), adding nitric acid into the mixed solution A, stirring for 10-20 min, uniformly mixing, and adjusting the pH value of the mixed solution A to 1-2; adding ammonium bicarbonate, stirring for 10-20 min, uniformly mixing, and adjusting the pH value of the mixed solution A to 7-8;
in the step (3), the mass ratio of the fluorescent refrigerant to the tetraethoxysilane is 1:2-3; the molar ratio of the urea to the silicon element in the tetraethoxysilane is 10:1; uniformly mixing by adopting a magnetic stirrer;
in the step (4), heating reaction is carried out by adopting water bath heating;
in the steps (1) and (4), the ethanol water solution is prepared by mixing ethanol and deionized water, and the volume ratio of the ethanol to the deionized water is 1:1.
7. The one-component polyurea waterproof coating with a refrigerating function according to claim 4, wherein: the polydopamine modified radiation refrigerant is prepared by the following method:
(1) Drying the radiation refrigerant, and uniformly dispersing the radiation refrigerant in the mixed solution to prepare radiation refrigerant dispersion liquid; adding dopamine hydrochloride, and uniformly dispersing in a radiation refrigerant dispersion liquid to obtain a modified solution; the mixed solution is formed by mixing Tris-HCl buffer solution and absolute ethyl alcohol;
(2) And adding sodium hydroxide solution into the modified solution, adjusting the pH value of the modified solution to 8-10, removing the solvent, and drying to obtain the radiation refrigerant modified by polydopamine.
8. The one-component polyurea waterproof coating with a refrigerating function according to claim 7, wherein: in the step (1), the radiation refrigerant is dried for 4 hours at 60 ℃; the volume ratio of Tris-HCl buffer solution to absolute ethyl alcohol in the mixed solution is 2-3:1-2; the mass ratio of the radiation refrigerant to the mixed solution to the dopamine hydrochloride is 5:50-70:1; uniformly dispersing by adopting ultrasonic waves;
in the step (2), adding sodium hydroxide solution into the modified solution to be uniformly dispersed so as to adjust the pH value; magnetic stirring is carried out for 2 to 4 hours at 500 to 700rpm, and the dispersion is uniform; the solvent removal method comprises the following steps: centrifuging by using a high-speed centrifuge, and rinsing the centrifuged product with water; drying the mixture for 20 to 24 hours at the temperature of between 45 and 60 ℃ by adopting an oven.
9. The one-component polyurea waterproof coating with a refrigerating function according to claim 8, wherein: in the step (1), the Tris-HCl buffer is 2mg/ml,50mM Tris-HCl buffer;
in the step (2), the mass fraction of sodium hydroxide in the sodium hydroxide solution is 10%; the solvent removal method comprises the following steps: centrifugal treatment is carried out by adopting a high-speed centrifugal machine with 7000-9000 rpm, and the centrifugal product is rinsed by deionized water.
10. A method for preparing the single-component polyurea waterproof coating with a refrigerating function as claimed in any one of claims 1 to 9, characterized in that: the method comprises the following steps:
(1) Adding polyether polyol into a closed reaction kettle, heating and stirring, controlling the temperature to be 100-110 ℃, starting a vacuum pump to vacuum for 1.5-2 h, controlling the pressure to be below-0.05 MPa, and controlling the water content to be below 300 ppm;
(2) Cooling to 60-70 ℃, and introducing dry nitrogen to release vacuum;
(3) Adding diisocyanate and a catalyst, controlling the temperature at 80-85 ℃ and carrying out polymerization reaction for 2-3 h;
(4) Cooling to 70 ℃, adding a latent curing agent, and uniformly stirring at 300-400 rpm for 0.5-1 h;
(5) Cooling to 50-55 deg.c, adding fluorescent refrigerant and radiating refrigerant separately into the reaction kettle and stirring at 700-900 rpm for 0.5-1 hr;
(6) Adding the defoaming agent and the leveling agent, uniformly mixing, and stirring at 90-120 rpm for 1-2 h to obtain the single-component polyurea waterproof coating with the refrigerating function.
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| CN103450876A (en) * | 2013-09-13 | 2013-12-18 | 武汉工程大学 | Inorganic oxide coated fluorescent powder and preparation method thereof |
| CN110467779A (en) * | 2019-07-25 | 2019-11-19 | 安徽电缆股份有限公司 | A kind of harsh cable high-performance synthetic rubber of three generations's nuclear power station and preparation method thereof |
| CN110684457A (en) * | 2019-03-19 | 2020-01-14 | 上海固密特新材料科技有限公司 | Single-component polyurethane waterproof coating and preparation method thereof |
| CN111117468A (en) * | 2019-12-30 | 2020-05-08 | 河南东方雨虹建筑材料有限公司 | Semi-submersible curing type single-component polyurethane waterproof coating and preparation method thereof |
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| CN103450876A (en) * | 2013-09-13 | 2013-12-18 | 武汉工程大学 | Inorganic oxide coated fluorescent powder and preparation method thereof |
| CN110684457A (en) * | 2019-03-19 | 2020-01-14 | 上海固密特新材料科技有限公司 | Single-component polyurethane waterproof coating and preparation method thereof |
| CN110467779A (en) * | 2019-07-25 | 2019-11-19 | 安徽电缆股份有限公司 | A kind of harsh cable high-performance synthetic rubber of three generations's nuclear power station and preparation method thereof |
| CN111117468A (en) * | 2019-12-30 | 2020-05-08 | 河南东方雨虹建筑材料有限公司 | Semi-submersible curing type single-component polyurethane waterproof coating and preparation method thereof |
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