CN115572513A - Fulgide photochromic exterior wall coating and preparation method thereof - Google Patents
Fulgide photochromic exterior wall coating and preparation method thereof Download PDFInfo
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- CN115572513A CN115572513A CN202211270833.0A CN202211270833A CN115572513A CN 115572513 A CN115572513 A CN 115572513A CN 202211270833 A CN202211270833 A CN 202211270833A CN 115572513 A CN115572513 A CN 115572513A
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- 238000000576 coating method Methods 0.000 title claims abstract description 55
- 239000011248 coating agent Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title abstract description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000003094 microcapsule Substances 0.000 claims abstract description 48
- 150000001875 compounds Chemical class 0.000 claims abstract description 38
- 239000001023 inorganic pigment Substances 0.000 claims abstract description 33
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 30
- 239000002270 dispersing agent Substances 0.000 claims abstract description 24
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 23
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 23
- 239000002775 capsule Substances 0.000 claims abstract description 20
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 17
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 17
- 238000001914 filtration Methods 0.000 claims abstract description 16
- 238000000227 grinding Methods 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims description 26
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000003973 paint Substances 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 15
- 239000003963 antioxidant agent Substances 0.000 claims description 12
- 230000003078 antioxidant effect Effects 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- MDWJZBVEVLTXDE-UHFFFAOYSA-N 2-methyl-1h-indol-5-ol Chemical compound OC1=CC=C2NC(C)=CC2=C1 MDWJZBVEVLTXDE-UHFFFAOYSA-N 0.000 claims description 10
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 10
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 10
- 239000010445 mica Substances 0.000 claims description 10
- 229910052618 mica group Inorganic materials 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 9
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical group CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 claims description 8
- 239000005995 Aluminium silicate Substances 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 8
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 8
- 235000012211 aluminium silicate Nutrition 0.000 claims description 8
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 8
- 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 8
- 239000010452 phosphate Substances 0.000 claims description 8
- 229920000570 polyether Polymers 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 239000004408 titanium dioxide Substances 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 4
- 239000001384 succinic acid Substances 0.000 claims description 3
- 230000002441 reversible effect Effects 0.000 abstract description 3
- 230000007774 longterm Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- MOMKPYAIESLQSC-UHFFFAOYSA-N C(CCCC(=O)O)(=O)O.C(CCCCCCC(=O)O)(=O)O.C(CCC(=O)O)(=O)O Chemical compound C(CCCC(=O)O)(=O)O.C(CCCCCCC(=O)O)(=O)O.C(CCC(=O)O)(=O)O MOMKPYAIESLQSC-UHFFFAOYSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
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- 238000012360 testing method Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
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- 239000000049 pigment Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
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- 238000013112 stability test Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- VCMLCMCXCRBSQO-UHFFFAOYSA-N 3h-benzo[f]chromene Chemical compound C1=CC=CC2=C(C=CCO3)C3=CC=C21 VCMLCMCXCRBSQO-UHFFFAOYSA-N 0.000 description 1
- SKVLBFICUWJKDV-UHFFFAOYSA-N 5-oxaspiro[2.4]heptane-4,6-dione Chemical class O=C1OC(=O)CC11CC1 SKVLBFICUWJKDV-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- JGLMVXWAHNTPRF-CMDGGOBGSA-N CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O Chemical compound CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O JGLMVXWAHNTPRF-CMDGGOBGSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- XLXOGJYARRBRPZ-UHFFFAOYSA-N [2,3-di(prop-2-enoyloxy)-3-propoxypropyl] prop-2-enoate Chemical compound CCCOC(OC(=O)C=C)C(OC(=O)C=C)COC(=O)C=C XLXOGJYARRBRPZ-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical group C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 150000001988 diarylethenes Chemical class 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- -1 phosphate ester Chemical class 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000011257 shell material Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003419 tautomerization reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
- C09D133/12—Homopolymers or copolymers of methyl methacrylate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
The invention discloses a fulgide photochromic exterior wall coating and a preparation method thereof, wherein the fulgide photochromic exterior wall coating is prepared by taking photochromic microcapsules, inorganic pigment, polymethyl methacrylate, a dispersing agent, a defoaming agent, ethyl acetate, an auxiliary agent and 1wt% of potassium hydroxide solution as raw materials, measuring, premixing, grinding, dispersing, adjusting pH and filtering, wherein the capsule core of the photochromic microcapsules contains fulgide photochromic compounds. The fulgide photochromic exterior wall coating prepared by the invention can realize reversible photochromic after being irradiated by sunlight, has better thermal stability and can meet the requirement of long-term use of exterior walls of buildings.
Description
Technical Field
The invention belongs to the technical field of photochromic coatings, and particularly relates to a fulgide photochromic exterior wall coating and a preparation method thereof.
Background
The photochromic phenomenon is that one substance can perform a specific chemical reaction under the irradiation of light with a certain wavelength to obtain another substance, namely, a photochromic body, the absorption spectrum of the substance changes due to the change of the substance structure, namely, the color changes, and the photochromic body can recover the form of the substance under the irradiation of light with another wavelength or the action of heat. Photochromic compounds refer to a class of compounds that are capable of undergoing a photochromic phenomenon. Photochromic compounds are widely applied to the fields of information storage, molecular switching, imaging, anti-counterfeiting identification and the like at present, and have extremely high potential application prospects in the field of preparation of photochromic coatings.
The photochromic compound is mainly divided into an inorganic photochromic compound and an organic photochromic compound, wherein the inorganic photochromic compound has the advantages of good thermal stability and fatigue resistance, high strength, easiness in forming and chemical corrosion resistance, but the optical response speed of the inorganic photochromic compound is relatively slow, the organic photochromic compound has the advantage of high optical response speed, and part of the organic photochromic compound has poor thermal stability and fatigue resistance. The organic photochromic compound can be divided into two types from the aspect of thermal stability, the first type is a thermal unstable type, is called T type, and has the problems of unstable photochromic body, easy fading and the like; the second type is thermostable, called P-type, and is characterized by bistability, i.e., thermodynamic stability in both the photochromogen and proto-species forms. Fulgide photochromic compounds belong to one of organic photochromic compounds, and are a general name of aromatic substituted dimethylene succinic anhydride compounds. The fulgide photochromic compound belongs to P type, and usually does not generate active free radical, ion or dipole intermediate in the reaction process, so that the fulgide photochromic compound has high thermal stability and fatigue resistance, and can generate photochromic phenomena in a large temperature range and different media. The photochromic fulgide compound has the color change mechanism that under the excitation light, the photochromic fulgide compound induces the inner circumference ring reaction of molecules through valence bond tautomerism, and the structural change before and after color change is as follows:
at present, fulgide photochromic compounds are mainly applied to optical information recording and anti-counterfeiting materials, and have potential application prospects in preparation of photochromic coatings with good thermal stability. For example, chinese patent CN 112724808A discloses a photochromic coating and a preparation method thereof, which comprises the following raw material components by weight: 15-25% of pentaerythritol tetraacrylate, 10-20% of tetrafunctional polyester acrylate, 20-35% of 3 (propoxy) glycerol triacrylate, 0.5-5% of photochromic microcapsules, 5-15% of rare earth powder, 10-20% of porous powder, 0.2-3% of photoinitiator, 0.5-2% of photocatalyst and 5-10% of water, wherein each photochromic microcapsule comprises a capsule wall and a capsule core wrapped in the capsule wall, each capsule core comprises a photochromic material and an antioxidant, and the photochromic material comprises one or more of naphthopyran photochromic compounds, diarylethene photochromic compounds, azobenzene photochromic compounds, fulgide photochromic compounds, spiropyran photochromic compounds and spirooxazine photochromic compounds. The invention also provides a preparation method of the photochromic coating. The photochromic coating provided by the invention not only has good stability, adhesion and hardness, but also has the functions of generating negative ions and regulating humidity, and the photochromic effect can be obtained by adding the photochromic microcapsules; meanwhile, the preparation method of the photochromic coating is simple, and the coating has high curing speed by adopting photocuring, is suitable for mass production, and can be widely applied to the fields of buildings and decoration.
The photochromic exterior wall coating for coating the exterior wall of the building can enable the exterior wall of the building to show different colors according to the intensity of light rays in different time in the environment, and is used for decorating the building. However, the existing fulgide photochromic coatings applied to the building field are mainly suitable for building interior walls, the variety of the coatings applied to exterior walls is less, and the effective period of most fulgide photochromic exterior wall coatings is usually shorter, because the fulgide photochromic compounds belong to a thermal stability type, and if the existing fulgide photochromic coatings are in an outdoor high-temperature environment for a long time, the fulgide photochromic compounds are easy to degrade and lose efficacy. Therefore, the thermal stability of the photochromic exterior wall coating containing the fulgide photochromic compound needs to be further improved so as to prolong the service life of the photochromic exterior wall coating and reduce the times of recoating or refinishing the coating.
Disclosure of Invention
In order to solve the technical problems, the invention provides a fulgide photochromic exterior wall coating and a preparation method thereof.
In order to achieve the purpose, the invention provides the following technical scheme:
a fulgide photochromic exterior wall coating comprises the following raw materials in percentage by weight: 0.5 to 2 percent of photochromic microcapsule, 21 to 23.5 percent of inorganic pigment, 40 to 45 percent of polymethyl methacrylate, 0.6 to 1.0 percent of dispersant, 0.2 to 0.8 percent of defoaming agent, 29 to 30 percent of ethyl acetate, 3.5 to 7 percent of auxiliary agent and 1 to 1.2 percent of 1 weight percent of potassium hydroxide solution, wherein the sum of the weight percentages is 100 percent;
the capsule core of the photochromic microcapsule contains fulgide photochromic compounds.
Preferably, the fulgide photochromic compound is 5-hydroxy-2-methylindole.
Preferably, the capsule core of the photochromic microcapsule also contains an antioxidant, and the mass ratio of the antioxidant to the fulgide photochromic compound is 1; the antioxidant is dibutylhydroxytoluene.
Preferably, the photochromic microcapsules use polymethyl methacrylate as the capsule wall.
Preferably, the mass ratio of the core to the wall of the photochromic microcapsule is 3.
Preferably, the particle size of the photochromic microcapsule is less than or equal to 4 mu m.
Preferably, the inorganic pigment consists of titanium dioxide and calcined kaolin according to a mass ratio of 2.
Preferably, the dispersant is a polyether phosphate dispersant.
Preferably, the auxiliary agent consists of erucamide, tetrahydrofuran, succinic acid, octanedioic glutarate and mica powder in a mass ratio of 3.
The preparation method of the fulgide photochromic exterior wall coating comprises the following steps:
1) Measuring: taking photochromic microcapsules, inorganic pigment, polymethyl methacrylate, a dispersing agent, a defoaming agent, ethyl acetate, an auxiliary agent and 1wt% of potassium hydroxide solution according to the weight proportion;
2) Premixing: taking the auxiliary agent and ethyl acetate accounting for 20 percent of the raw material, and mixing at the rotating speed of 500-700r/min for 15-20min to obtain a premixed solution;
3) Grinding: grinding inorganic pigment to a particle size of 0.2-0.4 μm;
4) Dispersing: mixing the ground inorganic pigment with the rest ethyl acetate, photochromic microcapsules, polymethyl methacrylate, a dispersing agent and a defoaming agent, oscillating and mixing for 10-15min at the frequency of 660-740 times/min, adding the premixed liquid obtained in the step 2), and dispersing for 15-30min at the rotating speed of 1200-1450 r/min;
5) Adjusting the pH value: adjusting the pH value of the mixed solution to 8-9 by using 1wt% of potassium hydroxide solution;
6) And (3) filtering: filtering with a paint filter to obtain a paint finished product.
Compared with the prior art, the invention has the beneficial effects that:
1. the fulgide photochromic exterior wall coating provided by the invention adopts 5-hydroxy-2 methyl indole as a photochromic compound to prepare photochromic microcapsules, takes inorganic pigment as a pigment matrix, takes polymethyl methacrylate with good thermal stability as a film forming substance, and adopts auxiliary agents consisting of erucamide, tetrahydrofuran, succinic acid octanedioic glutarate and mica powder to form a light-transmitting antioxidation layer outside the photochromic microcapsules so as to inhibit oxidation components in the air from entering a capsule core through the capsule wall of the photochromic microcapsules, thereby avoiding the phenomenon that a colored cyclohexadiene structure and the oxidation components in the air undergo a thermodynamic ring-opening reaction under the action of heat to lose photochromic capacity. Experiments prove that the fulgide photochromic exterior wall coating can realize reversible photochromic after being irradiated by sunlight, has better thermal stability and can meet the requirement of long-time use of a building exterior wall.
2. According to the invention, titanium dioxide and calcined kaolin with high content and without hydroxyl groups are used as a white pigment matrix, so that cost is saved, meanwhile, the loading of photochromic microcapsules containing fulgide photochromic compounds with small particle size is facilitated, and the good chromaticity of the coating can be maintained by adopting the polyether phosphate ester dispersing agent, so that the coating can show a good color change effect to the greatest extent.
3. The invention mixes the auxiliary agent and part of ethyl acetate into a premixed liquid, and firstly oscillates and disperses the rest substances to break up agglomerated particles, so that the photochromic microcapsule containing the fulgide photochromic compound and the inorganic pigment used as the pigment matrix which can present the color are fully mixed with the polymethyl methacrylate used as the film forming substance, and then the premixed liquid containing the auxiliary agent is added and dispersed by a high-speed dispersion machine, which is beneficial to uniformly distributing the auxiliary agent outside the capsule wall of the photochromic microcapsule, thereby forming double-layer protection for the fulgide photochromic compound in the coating and improving the thermal stability of the fulgide photochromic exterior wall coating.
Detailed Description
A preparation method of a fulgide photochromic exterior wall coating comprises the following steps:
1) Measuring: taking 0.5-2% of photochromic microcapsule, 21-23.5% of inorganic pigment, 40-45% of polymethyl methacrylate, 0.6-1.0% of dispersing agent, 0.2-0.8% of defoaming agent, 29-30% of ethyl acetate, 3.5-7% of auxiliary agent and 1-1.2% of 1wt% of potassium hydroxide solution according to the weight percentage sum of 100% respectively;
2) Pre-mixing: taking the auxiliary agent and ethyl acetate accounting for 20 percent of the raw material, and mixing the auxiliary agent and the ethyl acetate in a stirring device at a rotating speed of 500-700r/min for 15-20min to obtain a premixed solution;
3) Grinding: grinding the inorganic pigment to a particle size of 0.2-0.4 μm;
4) Dispersing: mixing the ground inorganic pigment with the rest ethyl acetate, photochromic microcapsules, polymethyl methacrylate, a dispersing agent and a defoaming agent, oscillating and mixing for 10-15min by using oscillating equipment at the frequency of 660-740 times/min, then adding the premixed liquid obtained in the step 2), and dispersing for 15-30min by using a high-speed dispersion machine at the rotating speed of 1200-1450 r/min;
5) Adjusting the pH value: adjusting the pH value of the mixed solution to 8-9 by using 1wt% of potassium hydroxide solution;
6) And (3) filtering: filtering with a paint filter to obtain a paint finished product.
The photochromic microcapsule is prepared by preparing 5-hydroxy-2-methylindole and antioxidant dibutylhydroxytoluene into a capsule core according to the mass ratio of 3 to 1, taking polymethyl methacrylate as a capsule wall, and mixing the two according to the mass ratio of 4; it is prepared by solvent evaporation method. Mixing 0.30g of 5-hydroxy-2-methylindole, 0.10g of dibutylhydroxytoluene and 0.10g of polymethyl methacrylate in 5g of dichloromethane, adding 20g of aqueous solution containing 3wt% of polyvinyl alcohol 1788, forming emulsion through high-speed shearing, removing dichloromethane through rotary evaporation at 40 ℃ to obtain suspension containing microspheres, filtering, washing with deionized water and drying to gradually solidify shell materials, thereby obtaining the photochromic microcapsule. The grain diameter of the obtained photochromic microcapsule is less than or equal to 4 mu m.
The crystal structure of the 5-hydroxy-2-methylindole is in s-cis conformation, which is beneficial to the generation of cyclization reaction, and the light color quantum yield is better, so that the photochromic material has better photochromic performance.
The inorganic pigment is composed of titanium dioxide and calcined kaolin according to the mass ratio of 2.
The dispersant is a polyether phosphate dispersant.
The auxiliary agent consists of erucamide, tetrahydrofuran, succinic acid octanedioate glutarate and mica powder according to a mass ratio of 3.
In order to make the content of the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1:
the preparation method of the fulgide photochromic exterior wall coating comprises the following steps:
1) Measuring: taking 2% of photochromic microcapsule, 22% of inorganic pigment, 41% of polymethyl methacrylate, 0.6% of polyether phosphate dispersing agent, 0.4% of defoaming agent Byk028, 29% of ethyl acetate, 4% of auxiliary agent and 1% of potassium hydroxide solution by weight according to the weight ratio;
2) Premixing: taking an auxiliary agent and ethyl acetate accounting for 20% of the raw material, and mixing for 16min in a stirring device at a rotating speed of 600r/min to obtain a premixed solution;
3) Grinding: grinding the inorganic pigment to a particle size of 0.2 μm;
4) Dispersing: mixing the ground inorganic pigment with the rest ethyl acetate, photochromic microcapsules, polymethyl methacrylate, a dispersing agent and a defoaming agent, firstly oscillating and mixing for 10min by using a YJ200 high-speed oscillator at the frequency of 700 times/min, then adding the premixed liquid obtained in the step 2), and then dispersing for 20min by using a TGM-FL high-speed dispersing machine at the rotating speed of 1350 r/min;
5) Adjusting the pH value: adjusting the pH value of the mixed solution to 8 by using 1wt% of potassium hydroxide solution;
6) And (3) filtering: and filtering the insoluble solid by using a paint filter to obtain a paint finished product.
The photochromic microcapsule is prepared by preparing 5-hydroxy-2-methylindole and an antioxidant dibutylhydroxytoluene into a capsule core according to a mass ratio of 3. The particle size of the obtained photochromic microcapsule was 4 μm.
The inorganic pigment consists of titanium dioxide and calcined kaolin according to the mass ratio of 2.
The auxiliary agent consists of erucamide, tetrahydrofuran, succinic acid octanedioate glutarate and mica powder according to a mass ratio of 3.
Comparative example:
according to the steps of example 1, the fulgide photochromic exterior wall coating is prepared by adopting an auxiliary agent consisting of erucamide, tetrahydrofuran, succinic acid, octanedionate, and mica powder according to a mass ratio of 1.
Example 2:
the preparation method of the fulgide photochromic exterior wall coating comprises the following steps:
1) Measuring: taking 1% of photochromic microcapsule, 21% of inorganic pigment, 41% of polymethyl methacrylate, 0.6% of polyether phosphate dispersing agent, 0.6% of defoaming agent Byk028, 30% of ethyl acetate, 4.6% of auxiliary agent and 1.2% of potassium hydroxide solution according to weight percentage;
2) Premixing: taking the auxiliary agent and ethyl acetate accounting for 20 percent of the raw material, and mixing for 20min in stirring equipment at the rotating speed of 500r/min to obtain a premixed solution;
3) Grinding: grinding the inorganic pigment to a particle size of 0.4 μm;
4) Dispersing: mixing the ground inorganic pigment with the rest ethyl acetate, photochromic microcapsules, polymethyl methacrylate, a dispersing agent and a defoaming agent, firstly oscillating and mixing for 15min by using a YJ200 high-speed oscillator at the frequency of 660 times/min, then adding the premixed liquid obtained in the step 2), and then dispersing for 20min by using a TGM-FL high-speed dispersing machine at the rotating speed of 1450 r/min;
5) Adjusting the pH value: adjusting the pH value of the mixed solution to 9 by using 1wt% of potassium hydroxide solution;
6) And (3) filtering: and filtering the insoluble solid by using a paint filter to obtain a paint finished product.
The photochromic microcapsule is prepared by preparing 5-hydroxy-2-methylindole and antioxidant dibutylhydroxytoluene into a capsule core according to the mass ratio of 3. The particle size of the obtained photochromic microcapsule was 3 μm.
The inorganic pigment is composed of titanium dioxide and calcined kaolin according to the mass ratio of 2.
The auxiliary agent consists of erucamide, tetrahydrofuran, succinic acid octanedioate glutarate and mica powder according to a mass ratio of 3.
Example 3:
the preparation method of the fulgide photochromic exterior wall coating comprises the following steps:
1) Measuring: taking 0.5 percent of photochromic microcapsule, 22.5 percent of inorganic pigment, 41 percent of polymethyl methacrylate, 0.9 percent of polyether phosphate dispersing agent, 0.7 percent of defoaming agent Byk028, 29 percent of ethyl acetate, 4.4 percent of auxiliary agent and 1 percent of potassium hydroxide solution by weight percent;
2) Pre-mixing: taking the auxiliary agent and ethyl acetate accounting for 20% of the raw material, and mixing for 15min in a stirring device at the rotating speed of 700r/min to obtain a premixed solution;
3) Grinding: grinding the inorganic pigment to a particle size of 0.2 μm;
4) Dispersing: mixing the ground inorganic pigment with the rest ethyl acetate, photochromic microcapsules, polymethyl methacrylate, a dispersing agent and a defoaming agent, oscillating and mixing for 15min by using a YJ200 high-speed oscillator at a frequency of 740 times/min, then adding the premixed liquid obtained in the step 2), and dispersing for 22min by using a TGM-FL high-speed dispersion machine at a rotating speed of 1200 r/min;
5) Adjusting the pH value: adjusting the pH value of the mixed solution to 8 by using 1wt% of potassium hydroxide solution;
6) And (3) filtering: and filtering the insoluble solid by using a paint filter to obtain a paint finished product.
The photochromic microcapsule is prepared by preparing 5-hydroxy-2-methylindole and antioxidant dibutylhydroxytoluene into a capsule core according to the mass ratio of 3. The particle size of the obtained photochromic microcapsule was 3 μm.
The inorganic pigment is composed of titanium dioxide and calcined kaolin according to the mass ratio of 2.
The auxiliary agent consists of erucamide, tetrahydrofuran, succinic acid octanedioate glutarate and mica powder according to a mass ratio of 3.
Example 4:
the preparation method of the fulgide photochromic exterior wall coating comprises the following steps:
1) Measuring: taking 2% of photochromic microcapsule, 21% of inorganic pigment, 39% of polymethyl methacrylate, 1.0% of polyether phosphate dispersing agent, 0.6% of defoaming agent Byk028, 30% of ethyl acetate, 5.2% of auxiliary agent and 1.2% of potassium hydroxide solution by weight according to the weight ratio;
2) Premixing: taking the auxiliary agent and ethyl acetate accounting for 20 percent of the raw material, and mixing for 20min in stirring equipment at the rotating speed of 650r/min to obtain a premixed solution;
3) Grinding: grinding the inorganic pigment to a particle size of 0.4 μm;
4) Dispersing: mixing the ground inorganic pigment with the rest ethyl acetate, photochromic microcapsules, polymethyl methacrylate, a dispersing agent and a defoaming agent, oscillating and mixing for 15min by using a YJ200 high-speed oscillator at a frequency of 740 times/min, then adding the premixed liquid obtained in the step 2), and then dispersing for 20min by using a TGM-FL high-speed dispersion machine at a rotating speed of 1350 r/min;
5) Adjusting the pH value: adjusting the pH value of the mixed solution to 8 by using 1wt% of potassium hydroxide solution;
6) And (3) filtering: and filtering the insoluble solid by using a paint filter to obtain a paint finished product.
The photochromic microcapsule is prepared by preparing 5-hydroxy-2-methylindole and an antioxidant dibutylhydroxytoluene into a capsule core according to a mass ratio of 3. The particle size of the obtained photochromic microcapsule was 4 μm.
The inorganic pigment is composed of titanium dioxide and calcined kaolin according to the mass ratio of 2.
The auxiliary agent consists of erucamide, tetrahydrofuran, succinic acid octanedioic glutarate and mica powder in a mass ratio of 3.
Heat stability test
The coatings obtained in examples and comparative examples were applied to 2 silica glass pieces 4cm × 4cm and 10mm thick by a 20 μm thick coater, respectively, to obtain 10 silica glass pieces supporting the coatings, one group of the silica glass pieces on which the coatings obtained in examples and comparative examples were applied was set as control groups A, B, C, D, and E, and the other group was set as experimental groups F, G, H, I, and J (i.e., A and F were coated with the coating of example 1, B and G were coated with the coating of example 2, and so on). Drying the control group by using a hot air oven at 40 ℃ for 10min, standing for 8h after drying to restore the temperature to room temperature, respectively irradiating the control group by using UVA-340 lamp tubes for 1h, testing the color of the control group when the control group is irradiated by using an Agera colorimeter, and observing whether the control group has the damage phenomena of light loss, decoloration and chalking or not in the process; and drying the experimental group by a hot air oven at 50 ℃ for 8h, standing for 8h after drying is finished to restore the temperature to room temperature, respectively irradiating the experimental group by UVA-340 lamp tubes for 1h, testing the color of the experimental group when the experimental group is irradiated by an Agera colorimeter, observing whether the experimental group has the damage phenomena of light loss, decoloration and chalking or not in the process, and comparing the colors of the control group and the experimental group to obtain the color difference of the corresponding coating, wherein the experimental results are shown in tables 1 and 2.
Table 1 film stability test statistics
TABLE 2 film color difference test statistics
As can be seen from tables 1 and 2, the fulgide photochromic exterior wall coating provided in embodiments 1 to 4 has better thermal stability and can realize reversible photochromic after simulated sunlight irradiation, and the color difference is less than 1.5, which indicates that the requirement of long-term use of the exterior wall of a building can be met, and also indicates that the thermal stability of the fulgide photochromic exterior wall coating can be significantly improved by adopting the adjuvant consisting of erucamide, tetrahydrofuran, succinic acid, adipic acid, diacid salt and mica powder in a mass ratio of 3.
The above description is only a preferred embodiment of the present invention, and all the equivalent changes and modifications made according to the claims of the present invention should be covered by the present invention.
Claims (10)
1. A fulgide photochromic exterior wall coating is characterized in that the used raw materials and the weight percentage of the raw materials are as follows: 0.5 to 2 percent of photochromic microcapsule, 21 to 23.5 percent of inorganic pigment, 40 to 45 percent of polymethyl methacrylate, 0.6 to 1.0 percent of dispersant, 0.2 to 0.8 percent of defoaming agent, 29 to 30 percent of ethyl acetate, 3.5 to 7 percent of auxiliary agent and 1 to 1.2 percent of 1 weight percent of potassium hydroxide solution, wherein the sum of the weight percentages is 100 percent;
the capsule core of the photochromic microcapsule contains fulgide photochromic compounds.
2. The photochromic external wall paint of claim 1, wherein the photochromic fulgide compound is 5-hydroxy-2-methylindole.
3. The photochromic external wall coating of claim 1, wherein the capsule core of the photochromic microcapsules further comprises an antioxidant, and the mass ratio of the antioxidant to the photochromic compound of the fulgide is 1;
the antioxidant is dibutylhydroxytoluene.
4. The photochromic external wall coating of claim 1, wherein the photochromic microcapsules use polymethyl methacrylate as the capsule wall.
5. The fulgide-based photochromic exterior-wall coating of claim 1, wherein the mass ratio of the core to the wall of the photochromic microcapsule is 3.
6. The photochromic external wall coating of fulgide type according to claim 1, wherein the photochromic microcapsules have particle size not greater than 4 μm.
7. The fulgide-based photochromic exterior wall coating of claim 1, wherein the inorganic pigment consists of titanium dioxide and calcined kaolin in a mass ratio of 2.
8. The photochromic external wall coating of fulgide type according to claim 1, wherein the dispersant is polyether phosphate dispersant.
9. The fulgide-based photochromic exterior wall coating of claim 1, wherein the auxiliary agent consists of erucamide, tetrahydrofuran, succinic acid octanedionate, and mica powder in a mass ratio of 3.
10. A method for preparing a fulgide-based photochromic exterior wall coating according to any one of claims 1 to 9, comprising the steps of:
1) Measuring: taking photochromic microcapsules, inorganic pigment, polymethyl methacrylate, a dispersing agent, a defoaming agent, ethyl acetate, an auxiliary agent and 1wt% of potassium hydroxide solution according to the weight proportion;
2) Pre-mixing: taking the auxiliary agent and ethyl acetate accounting for 20 percent of the raw material, and mixing at the rotating speed of 500-700r/min for 15-20min to obtain a premixed solution;
3) Grinding: grinding inorganic pigment to a particle size of 0.2-0.4 μm;
4) Dispersing: mixing the ground inorganic pigment with the rest of ethyl acetate, photochromic microcapsules, polymethyl methacrylate, a dispersing agent and a defoaming agent, oscillating and mixing for 10-15min at the frequency of 660-740 times/min, adding the premixed liquid obtained in the step 2), and dispersing for 15-30min at the rotating speed of 1200-1450 r/min;
5) Adjusting the pH value: adjusting the pH value of the mixed solution to 8-9 by using 1wt% of potassium hydroxide solution;
6) And (3) filtering: filtering with a paint filter to obtain a paint finished product.
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| CN105482597A (en) * | 2016-01-07 | 2016-04-13 | 上海华谊（集团）公司 | Ultra-stain-resistant self-cleaning paint and preparation method thereof |
| CN109876743A (en) * | 2019-03-05 | 2019-06-14 | 上海甘田光学材料有限公司 | A kind of light-sensitive microcapsule and the preparation method and application thereof containing photosensitive colour-changing material |
| CN111621285A (en) * | 2020-04-30 | 2020-09-04 | 江南大学 | Organic/inorganic double-shell photochromic microcapsule and preparation method thereof |
| CN112724808A (en) * | 2020-12-25 | 2021-04-30 | 上海甘田光学材料有限公司 | Photochromic coating and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105482597A (en) * | 2016-01-07 | 2016-04-13 | 上海华谊（集团）公司 | Ultra-stain-resistant self-cleaning paint and preparation method thereof |
| CN109876743A (en) * | 2019-03-05 | 2019-06-14 | 上海甘田光学材料有限公司 | A kind of light-sensitive microcapsule and the preparation method and application thereof containing photosensitive colour-changing material |
| CN111621285A (en) * | 2020-04-30 | 2020-09-04 | 江南大学 | Organic/inorganic double-shell photochromic microcapsule and preparation method thereof |
| CN112724808A (en) * | 2020-12-25 | 2021-04-30 | 上海甘田光学材料有限公司 | Photochromic coating and preparation method thereof |
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Application publication date: 20230106 |