CN112521929A - Preparation method of photochromic energy storage capsule - Google Patents
Preparation method of photochromic energy storage capsule Download PDFInfo
- Publication number
- CN112521929A CN112521929A CN202011513648.0A CN202011513648A CN112521929A CN 112521929 A CN112521929 A CN 112521929A CN 202011513648 A CN202011513648 A CN 202011513648A CN 112521929 A CN112521929 A CN 112521929A
- Authority
- CN
- China
- Prior art keywords
- zif
- energy storage
- photochromic
- shell layer
- mofs
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002775 capsule Substances 0.000 title claims abstract description 34
- 238000004146 energy storage Methods 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000002105 nanoparticle Substances 0.000 claims abstract description 21
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 17
- 239000011701 zinc Substances 0.000 claims abstract description 17
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 16
- 239000011162 core material Substances 0.000 claims abstract description 15
- 230000008859 change Effects 0.000 claims abstract description 12
- 239000011232 storage material Substances 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000004945 emulsification Methods 0.000 claims description 6
- 239000000839 emulsion Substances 0.000 claims description 6
- -1 fatty acid ester Chemical class 0.000 claims description 6
- 239000002086 nanomaterial Substances 0.000 claims description 6
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 150000001988 diarylethenes Chemical class 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 239000003995 emulsifying agent Substances 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 4
- 239000012948 isocyanate Substances 0.000 claims description 4
- 150000002513 isocyanates Chemical class 0.000 claims description 4
- TWBYWOBDOCUKOW-UHFFFAOYSA-N isonicotinic acid Chemical compound OC(=O)C1=CC=NC=C1 TWBYWOBDOCUKOW-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 4
- 239000013165 zeolitic imidazolate framework-100 Substances 0.000 claims description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- TWFQJFPTTMIETC-UHFFFAOYSA-N dodecan-1-amine;hydron;chloride Chemical compound [Cl-].CCCCCCCCCCCC[NH3+] TWFQJFPTTMIETC-UHFFFAOYSA-N 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 3
- 159000000000 sodium salts Chemical class 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- KYNSBQPICQTCGU-UHFFFAOYSA-N Benzopyrane Chemical compound C1=CC=C2C=CCOC2=C1 KYNSBQPICQTCGU-UHFFFAOYSA-N 0.000 claims description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- 102100029880 Glycodelin Human genes 0.000 claims description 2
- 101000585553 Homo sapiens Glycodelin Proteins 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 2
- GYBGISCHRVNSSC-UHFFFAOYSA-N [Na].CCCCCCCCCCCCOS(=O)(=O)OC Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)OC GYBGISCHRVNSSC-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- DVBJBNKEBPCGSY-UHFFFAOYSA-M cetylpyridinium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 DVBJBNKEBPCGSY-UHFFFAOYSA-M 0.000 claims description 2
- 239000000539 dimer Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000003446 ligand Substances 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- 125000003003 spiro group Chemical group 0.000 claims description 2
- 239000013638 trimer Substances 0.000 claims description 2
- 239000013167 zeolitic imidazolate framework-1 Substances 0.000 claims description 2
- 239000013174 zeolitic imidazolate framework-10 Substances 0.000 claims description 2
- 239000013175 zeolitic imidazolate framework-11 Substances 0.000 claims description 2
- 239000013164 zeolitic imidazolate framework-95 Substances 0.000 claims description 2
- YAGCJGCCZIARMJ-UHFFFAOYSA-N N1C(=NC=C1)C=O.[Zn] Chemical compound N1C(=NC=C1)C=O.[Zn] YAGCJGCCZIARMJ-UHFFFAOYSA-N 0.000 claims 1
- 101100018566 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) tif-1 gene Proteins 0.000 claims 1
- 230000002688 persistence Effects 0.000 claims 1
- 239000013160 zeolitic imidazolate framework-70 Substances 0.000 claims 1
- 230000007547 defect Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 239000004814 polyurethane Substances 0.000 abstract description 3
- 229920002635 polyurethane Polymers 0.000 abstract description 3
- 239000000975 dye Substances 0.000 description 10
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000003094 microcapsule Substances 0.000 description 3
- HPEUJPJOZXNMSJ-UHFFFAOYSA-N Methyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC HPEUJPJOZXNMSJ-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- 239000012782 phase change material Substances 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- 229960001124 trientine Drugs 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- CAMHHLOGFDZBBG-UHFFFAOYSA-N epoxidized methyl oleate Natural products CCCCCCCCC1OC1CCCCCCCC(=O)OC CAMHHLOGFDZBBG-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229940038384 octadecane Drugs 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
- B01J13/16—Interfacial polymerisation
-
- 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
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/62—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing gallium, indium or thallium
- C09K11/621—Chalcogenides
- C09K11/623—Chalcogenides with zinc or cadmium
-
- 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
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/67—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals
- C09K11/68—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals containing chromium, molybdenum or tungsten
- C09K11/681—Chalcogenides
- C09K11/682—Chalcogenides with zinc or cadmium
-
- 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
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7707—Germanates
-
- 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
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
-
- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
-
- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention relates to a preparation method of a photochromic energy storage capsule, which consists of an outer shell layer containing long afterglow nano particles, an inner shell layer of polyurethane and a core material of a phase change energy storage material containing photochromic dye. The long-afterglow nano-particles are prepared by using a zinc source MOFs as a template, and have uniform particle size and controllable size. The obtained capsule has a double-shell structure, and the polyurethane inner shell layer makes up the defect of insufficient outer shell layer tightness possibly caused by adding long afterglow nanoparticles. The photochromic energy storage capsule has the effects of ultraviolet intensity indication, energy storage and temperature regulation and afterglow fluorescence, improves the utilization efficiency of sunlight, has good color expression in both bright environment and dark environment, and has wide application prospect.
Description
Technical Field
The invention relates to the field of capsules, in particular to a preparation method of a photochromic energy storage capsule.
Background
Photochromic materials are materials whose color changes visually differently with changes in ambient temperature, and can be classified into organic, inorganic, and liquid crystal. The inorganic photochromic material has higher color-changing temperature, limits the application range thereof, has higher preparation requirement of the liquid crystal photochromic material and is not beneficial to wide application.
Although the organic photochromic material is widely applied, the organic photochromic material has the defects of poor environmental adaptability, poor thermal stability, no acid and alkali resistance, no solvent and the like. The capsule coating technology is adopted to take the phase change material dissolved with the organic photochromic material as the capsule core, and the high polymer material as the capsule wall to prepare the photochromic energy storage capsule, thereby overcoming the defects of the organic photochromic material, enhancing the stability and the application range thereof, and having good temperature regulation capability, visual ultraviolet indication function and visual differentiation discoloration effect. In patent CN201910580016.7, a phase change material, a photosensitizer, an electron donor and a leuco dye are combined and encapsulated to obtain a photo-induced and thermochromic synergistic microcapsule. In patent CN201611008848.4, a photochromic dye and an energy storage material are used as core materials together, and are coated by capsules to prepare the intelligent photochromic energy storage and temperature regulation microcapsule. The existing color-changing energy storage capsule can only show the differentiated color-changing effect in a bright environment, and no color can be observed in a dark environment.
Disclosure of Invention
In order to enrich the functionality of the capsule and solve the problem that the color-changing energy storage capsule has no color display in dark environment, the invention provides a preparation method of a photochromic energy storage capsule, which comprises the following specific steps:
(1) heating and dissolving 100 parts by mass of a phase change energy storage material and 0.1-10 parts by mass of a photochromic dye until the materials are clear, and mixing with isocyanate to prepare a core material A;
(2) heating the aqueous solution containing the emulsifier to a temperature higher than the melting point of the phase change energy storage material to prepare a continuous phase B;
(3) adding long-afterglow nano-particles prepared by a template method into a shell layer prepolymer by using a zinc source MOFs as a template, and then adding water-soluble amine to mix uniformly to prepare a shell layer prepolymer C;
(4) slowly adding the core material A into the continuous phase B, preparing an oil-in-water type emulsion by mechanical or ultrasonic emulsification, slowly adding the shell layer prepolymer C, reacting for 0.5-3 h at 60-90 ℃, then adjusting the pH value of the system to 3.7-6.2, continuously reacting for 1-5 h, performing suction filtration, cleaning and drying to obtain the photochromic energy storage capsule.
The phase change energy storage material is at least one of fatty acid ester, alkane and fatty alcohol;
the photochromic dye comprises at least one of spirooxazine, spiropyran, diarylethene, spiro oh throat, fulgide, azobenzene, benzopyran and phosphomolybdic acid isonicotinic acid;
the emulsifier is at least one of alkylphenol ethoxylates, high-carbon alcohol fatty alcohol polyoxyethylene ether, fatty acid polyoxyethylene ester, polyacrylic acid, sodium polyacrylate, polyacrylamide, styrene maleic anhydride copolymer sodium salt, dodecyl ammonium chloride, hexadecyl trimethyl ammonium bromide, hexadecyl pyridine bromide nyad, sodium dodecyl benzene sulfonate and sodium dodecyl methyl sulfate;
the isocyanate is at least one of IPDI, HMDI, TDI, MDI and corresponding dimer or trimer;
the zinc source MOFs in the step (2) is at least one of ZIF-1-8 series MOFs, TIF-1-5 series MOFs, ZIF-10, ZIF-11, ZIF-14, ZIF-20, ZIF-22, ZIF-23, ZIF-60-62, ZIF-64, ZIF-70-82 series MOFs, ZIF-90-92 series MOFs, ZIF-95 and ZIF-100 which are prepared by taking zinc ions and ligands as raw materials.
The template method in the step (2) comprises the following operation steps: adding zinc source MOFs into the mixed solution containing the long afterglow nano material component ions, uniformly stirring, adjusting the pH value of the system to 8.0 by using ammonia water, and continuously stirring for 1h at room temperature to obtain a precursor dispersion liquid; and (3) centrifugally separating the precursor dispersion liquid, drying the obtained solid product at 80 ℃, and then carrying out heat treatment at 600-1000 ℃ for 1-5 h to obtain the long-afterglow nano material.
The long afterglow nano particles in the step (2) are at least one of zinc gallate, zinc germanate or zinc gallium germanate doped with metal ions;
the particle size of the long-afterglow nano-particles is 10-100 nm.
The doped metal ion is Dy3+、Pr3+、Cr3+、Mn2+At least one of (1).
The water-soluble amine in the step (3) is at least one of diethylenetriamine, triethylene tetramine and tetraethylene pentamine;
the shell layer prepolymer is at least one of melamine prepolymer and urea formaldehyde prepolymer.
The invention has the advantages and positive effects that:
1. combine together long afterglow nanoparticle, photochromic dyestuff and phase change energy storage material utilize the encapsulation technique for the capsule has afterglow in the dark surrounds simultaneously and is luminous, photochromic and phase change energy storage's under the bright environment function, has richened the functionality of capsule, compounds multiple functions to same capsule in, has reduced the later stage product and has used the degree of difficulty, helps enlarging the application range of capsule.
2. The long-afterglow nano-particles prepared by using the template method can effectively regulate and control the particle size of the long-afterglow nano-particles by controlling the size of MOFs serving as a template, and the prepared long-afterglow nano-particles are small in particle size, uniform in distribution, good in dispersity, complete in crystal form and high in afterglow intensity, can be uniformly distributed on a capsule shell layer, ensure the afterglow luminescence uniformity and avoid the defect that the afterglow intensity is influenced because the crystal form of the conventional crushed and screened nano-particles is damaged.
3. The long afterglow nano material used has no color display in bright environment, has good afterglow luminescence only in dark environment, does not influence the photochromic color development effect, and is added into the capsule wall material, so that the long afterglow nano material is prevented from being mixed with the phase change energy storage material to influence the crystallinity of the phase change energy storage material, and further influence the energy storage performance of the phase change energy storage material.
4. The microcapsule with the double-shell structure is prepared, the polyurethane shell layer of the inner layer ensures the tightness of the capsule, and the defect of insufficient tightness of the outer shell layer possibly caused by adding long afterglow nano particles is overcome.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example 1
(1) Heating and dissolving 100g of tetradecanol and 0.1g of spiropyran photochromic dye until the materials are clear, and mixing IPDI to prepare a core material A;
(2) heating the water solution containing sodium polyacrylate to 60 ℃ to obtain a continuous phase B;
(3) preparing Cr by using ZIF-1 as a template and utilizing a template method3+The doped zinc gallate long afterglow nano particle has heat treatment temperature of 820 deg.c for 2.7 hr, and through adding the obtained long afterglow nano particle into melamine prepolymer,adding diethylenetriamine and mixing uniformly to prepare a capsule shell layer prepolymer C;
(4) slowly adding the core material A into the continuous phase B, preparing an oil-in-water type emulsion by mechanical or ultrasonic emulsification, slowly adding the shell layer prepolymer C, reacting for 0.5h at 60 ℃, then adjusting the pH value of the system to 3.7, heating to 60 ℃, continuing to react for 5h, performing suction filtration, cleaning and drying to obtain the photochromic energy storage capsule.
Example 2
(1) Heating and dissolving 200g of octadecanol and 20g of spirooxazine photochromic dye until the mixture is clear, and mixing the octadecanol and the spirooxazine photochromic dye with HMDI to prepare a core material A;
(2) heating the water solution containing the sodium salt of the styrene maleic anhydride copolymer to 70 ℃ to prepare a continuous phase B;
(3) preparing Mn by using a template method by using TIF-3 as a template2+And Dy3+Co-doped zinc gallium germanate long afterglow nano particles are subjected to heat treatment at the temperature of 600 ℃ for 5 hours, the obtained long afterglow nano particles are added into melamine prepolymer, and triethylene tetramine is added and mixed uniformly to obtain capsule shell layer prepolymer C;
(4) slowly adding the core material A into the continuous phase B, preparing an oil-in-water type emulsion by mechanical or ultrasonic emulsification, slowly adding the shell layer prepolymer C, reacting for 3h at 73 ℃, then adjusting the pH value of the system to 4.5, heating to 85 ℃, continuing to react for 2.6h, carrying out suction filtration, cleaning and drying to obtain the photochromic energy storage capsule.
Example 3
(1) Heating and dissolving 50g of methyl stearate and 2g of diarylethene photochromic dye until the materials are clear, and mixing IPDI tripolymer to prepare a core material A;
(2) heating the water solution containing sodium dodecyl benzene sulfonate to 80 ℃ to prepare a continuous phase B;
(3) preparing Mn by using ZIF-100 as a template and utilizing a template method2+Adding the doped zinc gallate long-afterglow nano particles into a urea formaldehyde prepolymer, adding tetraethylenepentamine, and uniformly mixing to obtain a capsule shell layer prepolymer C, wherein the heat treatment temperature is 1000 ℃ and the heat treatment time is 1 h;
(4) slowly adding the core material A into the continuous phase B, preparing an oil-in-water type emulsion by mechanical or ultrasonic emulsification, slowly adding the shell layer prepolymer C, reacting for 0.5h at 90 ℃, then adjusting the pH value of the system to 5.2, continuing to react for 1h at 90 ℃, filtering, cleaning and drying to prepare the photochromic energy storage capsule.
Example 4
(1) Heating and dissolving 50g of octadecane and 4g of diarylethene photochromic dye until the mixture is clear, and mixing IPDI dimer to prepare a core material A;
(2) heating the aqueous solution containing the dodecyl ammonium chloride to 70 ℃ to prepare a continuous phase B;
(3) preparing Cr by using ZIF-100 as a template and utilizing a template method3+Adding the doped zinc germanate long-afterglow nano-particles into a urea formaldehyde prepolymer, adding tetraethylenepentamine, and uniformly mixing to obtain a capsule shell layer prepolymer C, wherein the heat treatment temperature is 930 ℃ and the heat treatment time is 1.8 h;
(4) slowly adding the core material A into the continuous phase B, preparing an oil-in-water type emulsion by mechanical or ultrasonic emulsification, slowly adding the shell layer prepolymer C, reacting for 3h at 70 ℃, then adjusting the pH value of the system to 6.2, continuing to react for 3.9h at 75 ℃, filtering, cleaning and drying to obtain the photochromic energy storage capsule.
The above-mentioned embodiments, objects, technical solutions and advantages of the present invention are further described in detail, it should be understood that the above-mentioned embodiments are only illustrative of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A preparation method of a photochromic energy storage capsule comprises the following specific steps:
(1) heating and dissolving 100 parts by mass of a phase change energy storage material and 0.1-10 parts by mass of a photochromic dye until the materials are clear, and mixing with isocyanate to prepare a core material A;
(2) heating the aqueous solution containing the emulsifier to a temperature higher than the melting point of the phase change energy storage material to prepare a continuous phase B;
(3) adding long-afterglow nano-particles prepared by a template method into a shell layer prepolymer by using a zinc source MOFs as a template, and then adding water-soluble amine to mix uniformly to prepare a shell layer prepolymer C;
(4) slowly adding the core material A into the continuous phase B, preparing an oil-in-water type emulsion by mechanical or ultrasonic emulsification, slowly adding the shell layer prepolymer C, reacting for 0.5-3 h at 60-90 ℃, then adjusting the pH value of the system to 3.7-6.2, continuously reacting for 1-5 h, performing suction filtration, cleaning and drying to obtain the photochromic energy storage capsule.
2. The method according to claim 1, wherein the phase change energy storage material is at least one of fatty acid ester, alkane, and fatty alcohol;
the photochromic dye comprises at least one of spirooxazine, spiropyran, diarylethene, spiro oh throat, fulgide, azobenzene, benzopyran and phosphomolybdic acid isonicotinic acid;
the emulsifier is at least one of alkylphenol ethoxylates, high-carbon alcohol fatty alcohol polyoxyethylene ether, fatty acid polyoxyethylene ester, polyacrylic acid, sodium polyacrylate, polyacrylamide, styrene maleic anhydride copolymer sodium salt, dodecyl ammonium chloride, hexadecyl trimethyl ammonium bromide, hexadecyl pyridine bromide nyad, sodium dodecyl benzene sulfonate and sodium dodecyl methyl sulfate;
the isocyanate is at least one of IPDI, HMDI, TDI, MDI and corresponding dimer or trimer.
3. The method according to claim 1, wherein the MOFs as the zinc source in the step (2) is at least one selected from the group consisting of ZIF-1 to 8 MOFs, TIF-1 to 5 MOFs, ZIF-10, ZIF-11, ZIF-14, ZIF-20, ZIF-22, ZIF-23, ZIF-60 to 62, ZIF-64, ZIF-70 to 82 MOFs, ZIF-90 to 92 MOFs, ZIF-95 and ZIF-100, which are prepared from zinc ions and ligands as raw materials.
4. The method according to claim 1, wherein the template method in step (2) is performed by the steps of: adding zinc source MOFs into the mixed solution containing the long afterglow nano material component ions, uniformly stirring, adjusting the pH value of the system to 8.0 by using ammonia water, and continuously stirring for 1h at room temperature to obtain a precursor dispersion liquid; and (3) centrifugally separating the precursor dispersion liquid, drying the obtained solid product at 80 ℃, and then carrying out heat treatment at 600-1000 ℃ for 1-5 h to obtain the long-afterglow nano material.
5. The method according to claim 1, wherein the long persistence nanoparticles in step (2) are at least one of zinc gallate, zinc germanate or zinc gallium germanate doped with metal ions;
the particle size of the long-afterglow nano-particles is 10-100 nm.
6. The method of claim 5, wherein the doped metal ion is Dy3+、Pr3+、Cr3+、Mn2+At least one of (1).
7. The method according to claim 1, wherein the water-soluble amine in step (3) is at least one of diethylenetriamine, triethylenetetramine, and tetraethylenepentamine;
the shell layer prepolymer is at least one of melamine prepolymer and urea formaldehyde prepolymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011513648.0A CN112521929A (en) | 2020-12-21 | 2020-12-21 | Preparation method of photochromic energy storage capsule |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011513648.0A CN112521929A (en) | 2020-12-21 | 2020-12-21 | Preparation method of photochromic energy storage capsule |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112521929A true CN112521929A (en) | 2021-03-19 |
Family
ID=75001850
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011513648.0A Pending CN112521929A (en) | 2020-12-21 | 2020-12-21 | Preparation method of photochromic energy storage capsule |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112521929A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114307889A (en) * | 2021-12-08 | 2022-04-12 | 武汉中科先进技术研究院有限公司 | Phase-change microcapsule with photochromic function and coated by double-layer wall material and preparation method thereof |
| CN115058231A (en) * | 2022-07-14 | 2022-09-16 | 塔里木大学 | Phase-change material taking MOFs as carrier and preparation method thereof |
| CN116478687A (en) * | 2022-12-01 | 2023-07-25 | 南开大学 | Long afterglow material based on MOF template method and preparation method and application thereof |
-
2020
- 2020-12-21 CN CN202011513648.0A patent/CN112521929A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114307889A (en) * | 2021-12-08 | 2022-04-12 | 武汉中科先进技术研究院有限公司 | Phase-change microcapsule with photochromic function and coated by double-layer wall material and preparation method thereof |
| CN114307889B (en) * | 2021-12-08 | 2024-04-30 | 武汉中科先进材料科技有限公司 | Double-layer wall material coated phase-change microcapsule with photochromic function and preparation method thereof |
| CN115058231A (en) * | 2022-07-14 | 2022-09-16 | 塔里木大学 | Phase-change material taking MOFs as carrier and preparation method thereof |
| CN115058231B (en) * | 2022-07-14 | 2023-08-18 | 塔里木大学 | Phase change material taking MOFs as carrier and preparation method thereof |
| CN116478687A (en) * | 2022-12-01 | 2023-07-25 | 南开大学 | Long afterglow material based on MOF template method and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112521929A (en) | Preparation method of photochromic energy storage capsule | |
| CN112473580A (en) | Preparation method of thermochromic capsules | |
| CN112626721A (en) | Preparation method of composite color-changing nanofiber membrane | |
| CN109505061A (en) | A kind of thermochromism nano fibrous membrane and preparation method thereof | |
| CN102827597A (en) | Thermosensitive discoloring energy-storage material and preparation method thereof | |
| CN102097194A (en) | Method for preparing core-shell structured SiO2/Fe3O4 compound magnetic particle | |
| CN110607015B (en) | Plastic light conversion agricultural film with lasting light conversion effect and preparation method thereof | |
| CN109535691A (en) | A kind of thermochromic thin film and preparation method thereof | |
| CN107771791A (en) | A kind of lignosulfonates mesoporous SiO 2 nanosphere and preparation method thereof | |
| CN115011327B (en) | Packaged photochromic microsphere and preparation method and application thereof | |
| CN105086629A (en) | Preparation method and application of ultraviolet fluorescent powdered ink | |
| CN110578258A (en) | Preparation process of photochromic polypropylene yarn fabric | |
| CN109776586B (en) | Block crystal type organic-rare earth complex, luminescent fiber and preparation method thereof | |
| CN102532943B (en) | Preparation method for reverse phase microemulsion of dye solution | |
| CN1775692B (en) | Nano light-screen zinc-cerium composite oxide and its preparing method | |
| CN108380146A (en) | A kind of preparation method and its ureaformaldehyde photochromic micro-encapsulation of ureaformaldehyde photochromic micro-encapsulation | |
| CN116731575A (en) | Phase-change energy-saving coating and preparation method thereof | |
| CN104383911B (en) | A kind of banded Bi17V3O33/Bi1.7V8O16Photochemical catalyst and its preparation method and application | |
| CN102875822A (en) | Preparation method of photochromic latex emulsion | |
| CN112280353B (en) | Antibacterial and ultraviolet-resistant thermochromic wax color paint and preparation method thereof | |
| CN101235238A (en) | Environmental protection dope and its preparation method | |
| CN105542773B (en) | Quantum dot complex microsphere with bi-component shell and preparation method thereof | |
| CN106366747A (en) | Preparation method of photo-induced repair microcapsules | |
| CN111100604A (en) | Composite color-changing energy storage capsule and preparation method thereof | |
| CN114432979A (en) | Phase-change microcapsule with metal organic framework material as capsule wall |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| DD01 | Delivery of document by public notice | ||
| DD01 | Delivery of document by public notice |
Addressee: Wang Yu Document name: Deemed withdrawal notice |
|
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20210319 |