CN112473580A - Preparation method of thermochromic capsules - Google Patents
Preparation method of thermochromic capsules Download PDFInfo
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- CN112473580A CN112473580A CN202011513649.5A CN202011513649A CN112473580A CN 112473580 A CN112473580 A CN 112473580A CN 202011513649 A CN202011513649 A CN 202011513649A CN 112473580 A CN112473580 A CN 112473580A
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- 239000002775 capsule Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000002105 nanoparticle Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000011162 core material Substances 0.000 claims abstract description 14
- 238000004146 energy storage Methods 0.000 claims abstract description 14
- 239000011232 storage material Substances 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 23
- 229910052725 zinc Inorganic materials 0.000 claims description 23
- 239000011701 zinc Substances 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 16
- 239000012621 metal-organic framework Substances 0.000 claims description 16
- 230000008859 change Effects 0.000 claims description 13
- 229920000877 Melamine resin Polymers 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- -1 fatty acid ester Chemical class 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052733 gallium Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000002086 nanomaterial Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 4
- 239000003795 chemical substances by application Substances 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
- 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
- LIZLYZVAYZQVPG-UHFFFAOYSA-N (3-bromo-2-fluorophenyl)methanol Chemical compound OCC1=CC=CC(Br)=C1F LIZLYZVAYZQVPG-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
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 3
- VQMAOMQZXAISMX-UHFFFAOYSA-N C1(=CC=CC=C1)C1C(=CC=C(C1=S(=O)=O)C1=CC=CC=C1)O Chemical compound C1(=CC=CC=C1)C1C(=CC=C(C1=S(=O)=O)C1=CC=CC=C1)O VQMAOMQZXAISMX-UHFFFAOYSA-N 0.000 claims description 3
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 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
- 238000002156 mixing Methods 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
- QIRNGVVZBINFMX-UHFFFAOYSA-N 2-allylphenol Chemical compound OC1=CC=CC=C1CC=C QIRNGVVZBINFMX-UHFFFAOYSA-N 0.000 claims description 2
- WKJNATJKWDKTJH-UHFFFAOYSA-N 3H-2-benzofuran-1-one 2-methyl-1-octylindole Chemical compound C1(=O)OCC2=CC=CC=C12.C(CCCCCCC)N1C(=CC2=CC=CC=C12)C WKJNATJKWDKTJH-UHFFFAOYSA-N 0.000 claims description 2
- HNQMMWIWFNZYRX-UHFFFAOYSA-N 7-[4-(diethylamino)-2-ethoxyphenyl]-7h-furo[3,4-b]pyridin-5-one Chemical compound CCOC1=CC(N(CC)CC)=CC=C1C1C2=NC=CC=C2C(=O)O1 HNQMMWIWFNZYRX-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- KHBAGVIHHCMMKH-UHFFFAOYSA-N CC=1N(C2=CC=CC=C2C1C1=CC=C2C(=N1)COC2=O)CCCCCCCC Chemical compound CC=1N(C2=CC=CC=C2C1C1=CC=C2C(=N1)COC2=O)CCCCCCCC KHBAGVIHHCMMKH-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
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 229920002125 Sokalan® Polymers 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
- DVBJBNKEBPCGSY-UHFFFAOYSA-M cetylpyridinium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 DVBJBNKEBPCGSY-UHFFFAOYSA-M 0.000 claims description 2
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000004945 emulsification Methods 0.000 claims description 2
- 239000000839 emulsion 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
- 239000003446 ligand Substances 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 150000002739 metals Chemical class 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
- 239000012266 salt solution Substances 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- 239000013174 zeolitic imidazolate framework-10 Substances 0.000 claims description 2
- 239000013165 zeolitic imidazolate framework-100 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
- 230000002688 persistence Effects 0.000 claims 1
- 230000000007 visual effect Effects 0.000 abstract description 5
- 239000004753 textile Substances 0.000 abstract 1
- 230000001804 emulsifying effect Effects 0.000 description 4
- 239000007764 o/w emulsion Substances 0.000 description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- HPEUJPJOZXNMSJ-UHFFFAOYSA-N Methyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC HPEUJPJOZXNMSJ-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000004069 differentiation Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- MOVCYDNEZZZSLV-UHFFFAOYSA-N 2-methyl-1-octylindole Chemical compound C1=CC=C2N(CCCCCCCC)C(C)=CC2=C1 MOVCYDNEZZZSLV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 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
- 150000002596 lactones Chemical class 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012782 phase change material Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 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
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012800 visualization Methods 0.000 description 1
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 1
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
- C09K11/661—Chalcogenides
- C09K11/662—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
- C09K11/7701—Chalogenides
- C09K11/7702—Chalogenides 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
- C09K11/7708—Vanadates; Chromates; Molybdates; Tungstates
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Composite Materials (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biophysics (AREA)
- Optics & Photonics (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention relates to a preparation method of a thermochromic capsule, which comprises a shell layer containing long-afterglow nano-particles and a core material consisting of a thermochromic dye, a thermochromic developer and a phase-change energy storage material. The long afterglow nano particle is prepared by a template method, the preparation process is simple, and the particle size is uniform. The capsule provided by the invention not only has the functions of visual temperature indication and energy storage and temperature adjustment, but also has good afterglow luminous capability in a dark environment, and has wide application prospects in the field of textile and clothing.
Description
Technical Field
The invention relates to the field of capsules, in particular to a preparation method of a thermochromic capsule.
Background
Thermochromic materials refer to materials whose color changes with the change of ambient temperature by visual differentiation, and can be classified into organic, inorganic and liquid crystal materials. The inorganic thermochromic material has high color-changing temperature, limits the application range of the inorganic thermochromic material, has high preparation requirement of the liquid crystal thermochromic material, and is not beneficial to wide application.
Although the organic thermochromic material is widely applied, the organic thermochromic 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 thermochromic material as the capsule core, and the polymer material is taken as the capsule wall to prepare the thermochromic energy storage capsule, so that the defects of the organic thermochromic material are overcome, the stability and the application range of the thermochromic energy storage capsule are enhanced, and the thermochromic energy storage capsule has good temperature regulation capability, a visual temperature indication function and a visual differentiated color change effect. In patent CN201811635267.2, the thermochromic capsule is coated with organic silicon, and combined with the phase change capsule to prepare the strawberry-shaped thermochromic energy storage material, so as to realize visualization of phase change energy storage. In patent CN201810839431.5, utilize the shell to cover the granule that contains transparent heat conduction liquid, thermochromism coating and the granule of photochromism picture layer, utilize the influence and the density difference of three density of temperature variation to transparent heat conduction liquid density, realize that thermochromism and photochromism different function show for the tabulation field. In patent CN201610808425.4, reversible thermochromic material microcapsules are coated with polyvinyl butyral. The existing thermochromic capsules can only show the differential color change effect in a bright environment, and any color can not be observed in a dark environment.
Disclosure of Invention
In order to solve the problem that the thermochromic capsule has no color display in a dark environment, the invention provides a preparation method of the thermochromic capsule, which comprises the following specific steps:
(1) heating and dissolving 100 parts by mass of a phase change energy storage material, 0.1-10 parts by mass of a thermochromic dye and 0.1-10 parts by mass of a thermochromic color developing agent until the materials are clear 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 the long-afterglow nano-particles prepared by a template method into the shell layer prepolymer by taking a zinc source MOFs as a template, and uniformly mixing to obtain 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 1-5 h at 60-90 ℃, filtering, cleaning and drying to prepare the thermochromic capsule.
The phase change energy storage material is at least one of fatty acid ester, alkane and fatty alcohol;
the thermochromic dye comprises 2-phenylamino-3-methyl-6-diethylfluorane, 2-phenylamino-3-methyl-6-dibutylfluorane, 3-bis (N-octyl-2-methylindole) phthalide, crystal violet lactone, 3-bis (4-diethylamino-2-ethoxyphenyl) -4-azaphthalide, 4- [ (9-butyl-9H-carbazole-3-yl) methylene ] bis [ N-methyl-N-phenylaniline ], 1, 3-dimethyl-6-diethylaminofluorane, 2 '-chloro-6' - (diethylamino) fluorane, 7- [4- (diethylamino) -2-ethoxyphenyl ] -7- At least one of (2-methyl-1-octyl-1H-indol-3-yl) furo [3, 4-B ] pyridin-5 (7H) -one;
the thermochromism color developing agent is at least one of bisphenol A, bisphenol F, bisphenol S, 2, 4-diphenylsulfuryl phenol and 4, 4' -sulfonyl bis [2- (2-propenyl) ] phenol;
the emulsifier is at least one of alkylphenol ethoxylates, higher alcohol fatty alcohol polyoxyethylene ether, fatty acid polyoxyethylene ester, polyacrylic acid, sodium polyacrylate, polyacrylamide, styrene maleic anhydride copolymer sodium salt, dodecyl ammonium chloride, cetyl trimethyl ammonium bromide, cetyl pyridine bromide nyad, sodium dodecyl benzene sulfonate and sodium dodecyl methyl sulfate.
The long afterglow nano particle in the step (3) is 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 in the zinc gallate, the zinc germanate or the zinc gallium germanate is Dy3+、Pr3+、Cr3+、Mn2+At least one of (1).
The template method in the step (3) comprises the following operation steps: adding zinc source MOFs into a salt solution mixture of long afterglow nano material component metals, uniformly stirring, adjusting the pH value of a system to 8.0 by using ammonia water, and continuously stirring for 1h at room temperature to prepare a precursor dispersion liquid; centrifugally separating the precursor dispersion liquid, drying the solid product at 80 ℃, and then carrying out heat treatment for 1-5 h at 600-1000 ℃ to obtain the long-afterglow nano material;
the zinc source MOFs are 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 shell layer prepolymer in the step (3) is at least one of melamine prepolymer and urea formaldehyde prepolymer.
The invention has the advantages and positive effects that:
1. the long-afterglow nano-particles are combined with the thermochromic energy storage capsule, the used long-afterglow nano-material is displayed in a colorless manner in a bright environment, good afterglow luminescence is realized only in a dark environment, the functions of capsule temperature regulation, visual temperature indication and color change differentiation are not influenced, and meanwhile, the afterglow luminescence function in the dark environment is increased, so that the capsule disclosed by the invention has good color expression in the bright and dark environment conditions, two color development modes are compounded into the same capsule, the later product application difficulty is reduced, and the material is ensured to have more excellent expression and wider application prospect in the color change field.
2. The zinc source MOFs is used as a template, the particle size of the long afterglow nano particles can be effectively regulated and controlled through the size of the template, the long afterglow nano particles prepared by using the template method 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, the afterglow luminescence uniformity is guaranteed, the defect that the afterglow intensity is influenced due to the fact that the crystal form of the conventional crushed and screened nano particles is damaged is avoided, meanwhile, zinc ions in the MOFs serve as a component of a long afterglow material, the step of removing the template is avoided, and the preparation process is simplified.
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, 0.1g of 2-phenylamino-3-methyl-6-diethylfluorane and 0.1g of bisphenol A until the mixture is clear, thus obtaining 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-8 as a template through a template method3+Adding the doped zinc gallate long-afterglow nanoparticles into the melamine prepolymer and uniformly mixing to obtain a shell layer prepolymer C, wherein the heat treatment temperature is 600 ℃ and the heat treatment time is 2 hours;
(4) slowly adding the core material A into the continuous phase B, mechanically or ultrasonically emulsifying to obtain an oil-in-water emulsion, slowly adding the melamine prepolymer C, reacting at a constant temperature of 60 ℃ for 5 hours, filtering, cleaning, and drying to obtain the thermochromic capsule.
Example 2
(1) Heating and dissolving 200g of octadecanol, 10g of 2-phenylamino-3-methyl-6-diethylfluorane and 20g of bisphenol F until the mixture is clear, and preparing 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 a template method by taking TIF-5 as a template2+Adding the doped zinc gallium germanate long-afterglow nano-particles into melamine prepolymer to be uniformly mixed to prepare a shell layer prepolymer C, wherein the heat treatment temperature is 900 ℃ and the heat treatment time is 3 hours;
(4) slowly adding the core material A into the continuous phase B, mechanically or ultrasonically emulsifying to obtain oil-in-water emulsion, slowly adding the melamine prepolymer C, reacting at a constant temperature of 70 ℃ for 3h, filtering, cleaning, and drying to obtain the thermochromic capsule.
Example 3
(1) Heating and dissolving 1000g of methyl stearate, 40g of 3, 3-bis (N-octyl-2-methylindole) phthalic lactone and 80g of bisphenol S until the materials are clear 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 Pr by using ZIF-20 as a template through a template method3+Adding the doped zinc gallate long-afterglow nano particles into the urea formaldehyde prepolymer to be uniformly mixed to prepare a 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, mechanically or ultrasonically emulsifying to obtain an oil-in-water emulsion, slowly adding the urea formaldehyde prepolymer C, reacting at the constant temperature of 80 ℃ for 2 hours, filtering, cleaning, and drying to obtain the thermochromic capsule.
Example 4
(1) Heating and dissolving 500g of octadecanol, 40g of crystal violet lactone and 20g of 2, 4-diphenylsulfuryl phenol until the mixture is clear, and preparing 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-64 as a template through a template method3+And Pr3+Co-doped zinc germanate long afterglow nano particles are subjected to heat treatment at 800 ℃ for 5 hours, and the obtained long afterglow nano particles are added into melamine prepolymer and mixed uniformly to prepare a shell layer prepolymer C;
(4) slowly adding the core material A into the continuous phase B, mechanically or ultrasonically emulsifying to obtain an oil-in-water emulsion, slowly adding the melamine prepolymer C, reacting at a constant temperature of 90 ℃ for 1h, filtering, cleaning, and drying to obtain the thermochromic 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 (6)
1. A preparation method of a thermochromic capsule comprises the following specific steps:
(1) heating and dissolving 100 parts by mass of a phase change energy storage material, 0.1-10 parts by mass of a thermochromic dye and 0.1-10 parts by mass of a thermochromic color developing agent until the materials are clear 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 the long-afterglow nano-particles prepared by a template method into the shell layer prepolymer by taking a zinc source MOFs as a template, and uniformly mixing to obtain 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 1-5 h at 60-90 ℃, filtering, cleaning and drying to prepare the thermochromic 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 thermochromic dye comprises 2-phenylamino-3-methyl-6-diethylfluorane, 2-phenylamino-3-methyl-6-dibutylfluorane, 3-bis (N-octyl-2-methylindole) phthalide, crystal violet lactone, 3-bis (4-diethylamino-2-ethoxyphenyl) -4-azaphthalide, 4- [ (9-butyl-9H-carbazole-3-yl) methylene ] bis [ N-methyl-N-phenylaniline ], 1, 3-dimethyl-6-diethylaminofluorane, 2 '-chloro-6' - (diethylamino) fluorane, 7- [4- (diethylamino) -2-ethoxyphenyl ] -7- At least one of (2-methyl-1-octyl-1H-indol-3-yl) furo [3, 4-B ] pyridin-5 (7H) -one;
the thermochromism color developing agent is at least one of bisphenol A, bisphenol F, bisphenol S, 2, 4-diphenylsulfuryl phenol and 4, 4' -sulfonyl bis [2- (2-propenyl) ] phenol;
the emulsifier is at least one of alkylphenol ethoxylates, higher alcohol fatty alcohol polyoxyethylene ether, fatty acid polyoxyethylene ester, polyacrylic acid, sodium polyacrylate, polyacrylamide, styrene maleic anhydride copolymer sodium salt, dodecyl ammonium chloride, cetyl trimethyl ammonium bromide, cetyl pyridine bromide nyad, sodium dodecyl benzene sulfonate and sodium dodecyl methyl sulfate.
3. The method according to claim 1, wherein the long persistence nanoparticles in step (3) 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.
4. The method according to claim 3, wherein the doped metal ion in the zinc gallate, zinc germanate or zinc gallium germanate is Dy3+、Pr3+、Cr3+、Mn2+At least one of (1).
5. The method according to claim 1, wherein the template method in step (3) is performed by the steps of: adding zinc source MOFs into a salt solution mixture of long afterglow nano material component metals, uniformly stirring, adjusting the pH value of a system to 8.0 by using ammonia water, and continuously stirring for 1h at room temperature to prepare a precursor dispersion liquid; centrifugally separating the precursor dispersion liquid, drying the solid product at 80 ℃, and then carrying out heat treatment for 1-5 h at 600-1000 ℃ to obtain the long-afterglow nano material;
the zinc source MOFs are 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.
6. The method according to claim 1, wherein the shell prepolymer in the step (3) is at least one of melamine prepolymer and urea-formaldehyde prepolymer.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113372864A (en) * | 2021-07-09 | 2021-09-10 | 西安交通大学 | Intelligent epoxy packaging material with temperature real-time early warning function and preparation method and application thereof |
| CN115466611A (en) * | 2022-10-13 | 2022-12-13 | 中国南方电网有限责任公司超高压输电公司天生桥局 | Thermochromic particle and preparation method thereof, thermochromic coating and application 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 |
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2020
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113372864A (en) * | 2021-07-09 | 2021-09-10 | 西安交通大学 | Intelligent epoxy packaging material with temperature real-time early warning function and preparation method and application thereof |
| CN115466611A (en) * | 2022-10-13 | 2022-12-13 | 中国南方电网有限责任公司超高压输电公司天生桥局 | Thermochromic particle and preparation method thereof, thermochromic coating and application 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 |
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