CN106905551B - A kind of counter opal structure temperature-sensitive material and preparation method thereof - Google Patents
A kind of counter opal structure temperature-sensitive material and preparation method thereof Download PDFInfo
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- CN106905551B CN106905551B CN201710070396.0A CN201710070396A CN106905551B CN 106905551 B CN106905551 B CN 106905551B CN 201710070396 A CN201710070396 A CN 201710070396A CN 106905551 B CN106905551 B CN 106905551B
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- temperature
- counter opal
- sensitive material
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- opal structure
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- 239000000463 material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000004038 photonic crystal Substances 0.000 claims abstract description 38
- 239000011022 opal Substances 0.000 claims abstract description 31
- 239000000126 substance Substances 0.000 claims abstract description 16
- 230000036413 temperature sense Effects 0.000 claims abstract description 15
- 238000011049 filling Methods 0.000 claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 96
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 67
- 239000000377 silicon dioxide Substances 0.000 claims description 48
- 239000000178 monomer Substances 0.000 claims description 40
- 235000019441 ethanol Nutrition 0.000 claims description 29
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 claims description 24
- 239000011521 glass Substances 0.000 claims description 21
- 239000004005 microsphere Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 21
- 229920006254 polymer film Polymers 0.000 claims description 21
- 235000012239 silicon dioxide Nutrition 0.000 claims description 21
- -1 alkenyl carbonate Chemical compound 0.000 claims description 19
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000005530 etching Methods 0.000 claims description 13
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 12
- UVZUFUGNHDDLRQ-LLHZKFLPSA-N cholesteryl benzoate Chemical compound O([C@@H]1CC2=CC[C@H]3[C@@H]4CC[C@@H]([C@]4(CC[C@@H]3[C@@]2(C)CC1)C)[C@H](C)CCCC(C)C)C(=O)C1=CC=CC=C1 UVZUFUGNHDDLRQ-LLHZKFLPSA-N 0.000 claims description 11
- WCLNGBQPTVENHV-MKQVXYPISA-N cholesteryl nonanoate Chemical compound C([C@@H]12)C[C@]3(C)[C@@H]([C@H](C)CCCC(C)C)CC[C@H]3[C@@H]1CC=C1[C@]2(C)CC[C@H](OC(=O)CCCCCCCC)C1 WCLNGBQPTVENHV-MKQVXYPISA-N 0.000 claims description 11
- 150000002148 esters Chemical class 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 239000000908 ammonium hydroxide Substances 0.000 claims description 8
- 235000012000 cholesterol Nutrition 0.000 claims description 8
- 238000005538 encapsulation Methods 0.000 claims description 8
- 239000003921 oil Substances 0.000 claims description 8
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 claims description 7
- 239000004973 liquid crystal related substance Substances 0.000 claims description 7
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 claims description 6
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 6
- OTVRYZXVVMZHHW-FNOPAARDSA-N (8s,9s,10r,13r,14s,17r)-3-chloro-10,13-dimethyl-17-[(2r)-6-methylheptan-2-yl]-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1h-cyclopenta[a]phenanthrene Chemical compound C1C=C2CC(Cl)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 OTVRYZXVVMZHHW-FNOPAARDSA-N 0.000 claims description 5
- AMKBITCLNBJPEW-UHFFFAOYSA-N C(O)(O)=O.C(CCCCCCC)CC1=CC=CC=C1 Chemical compound C(O)(O)=O.C(CCCCCCC)CC1=CC=CC=C1 AMKBITCLNBJPEW-UHFFFAOYSA-N 0.000 claims description 5
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 claims description 4
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 claims description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 229940117958 vinyl acetate Drugs 0.000 claims description 4
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 claims description 3
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 3
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 3
- FIOCEWASVZHBTK-UHFFFAOYSA-N 2-[2-(2-oxo-2-phenylacetyl)oxyethoxy]ethyl 2-oxo-2-phenylacetate Chemical compound C=1C=CC=CC=1C(=O)C(=O)OCCOCCOC(=O)C(=O)C1=CC=CC=C1 FIOCEWASVZHBTK-UHFFFAOYSA-N 0.000 claims description 2
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 claims description 2
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 125000004386 diacrylate group Chemical group 0.000 claims description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 2
- 210000000232 gallbladder Anatomy 0.000 claims description 2
- 238000003780 insertion Methods 0.000 claims description 2
- 230000037431 insertion Effects 0.000 claims description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims 1
- 239000007983 Tris buffer Substances 0.000 claims 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims 1
- 125000004494 ethyl ester group Chemical group 0.000 claims 1
- FBUKVWPVBMHYJY-UHFFFAOYSA-M nonanoate Chemical compound CCCCCCCCC([O-])=O FBUKVWPVBMHYJY-UHFFFAOYSA-M 0.000 claims 1
- 238000005507 spraying Methods 0.000 claims 1
- 150000003431 steroids Chemical class 0.000 claims 1
- 239000003086 colorant Substances 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 39
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 13
- 238000001704 evaporation Methods 0.000 description 12
- 230000008020 evaporation Effects 0.000 description 12
- 238000000059 patterning Methods 0.000 description 11
- 230000035945 sensitivity Effects 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 238000005457 optimization Methods 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 6
- 239000008236 heating water Substances 0.000 description 6
- 238000010907 mechanical stirring Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 5
- 230000000087 stabilizing effect Effects 0.000 description 5
- 230000001939 inductive effect Effects 0.000 description 4
- 239000004575 stone Substances 0.000 description 4
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000004986 Cholesteric liquid crystals (ChLC) Substances 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 230000003098 cholesteric effect Effects 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- XBTXTLKLSHACSS-WDSKDSINSA-N (2S,3S)-2,3-dihydro-3-hydroxyanthranilic acid Chemical compound [NH3+][C@@H]1[C@@H](O)C=CC=C1C([O-])=O XBTXTLKLSHACSS-WDSKDSINSA-N 0.000 description 1
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 229930182558 Sterol Natural products 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000036760 body temperature Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 description 1
- MHMNJMPURVTYEJ-UHFFFAOYSA-N fluorescein-5-isothiocyanate Chemical compound O1C(=O)C2=CC(N=C=S)=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 MHMNJMPURVTYEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000011540 sensing material Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 235000003702 sterols Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/109—Esters; Ether-esters of carbonic acid, e.g. R-O-C(=O)-O-R
-
- 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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
- G01K13/00—Thermometers specially adapted for specific purposes
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
- G01K13/00—Thermometers specially adapted for specific purposes
- G01K13/20—Clinical contact thermometers for use with humans or animals
Abstract
The present invention relates to a kind of counter opal structure temperature-sensitive materials and preparation method thereof.Using the porous microstructure of inverse opal photonic crystal, by temperature sense substance selective filling in the porous microstructure of counter opal, and it is encapsulated, then obtains temperature-sensitive material.Different according to the temperature sense substance of filling, temperature-sensitive material shows different colours at different temperatures.Counter opal temperature-sensitive material prepared by the present invention has high flexibility, high sensitive, and preparation process is simple, and controllability is strong, easy to industrialized production.
Description
Technical field:
The present invention relates to a kind of counter opal structure temperature-sensitive materials and preparation method thereof, belong to counter opal structure light
Sub- crystalline material and temperature sensing material field.
Background technique:
Photonic crystal is the structure of the material periodic arrangement in space of differing dielectric constant.Utilize photonic crystal refractive power
The cyclically-varying of index can regulate and control prohibiting for certain wavelength light, i.e. photon band gap.Photonic crystal three-dimensional order from group
Another material is filled in the opal structural gap of dress, then removes primary photon crystal mould using chemical etching or calcining
Plate to get arrive counter opal.
Porous material since with nanoscale cellular structure, specific surface area is high, and aperture is uniform adjustable and dimension is orderly,
There is important answer in fields such as biocatalysis, the assembling of functional polymer compound, chemical sensitisation, adsorbing separation and micro elements
Use prospect.Photonic crystal with inverse opal structure has been widely used as a kind of superhigh specific surface area material, as catalyst and
The purposes such as its carrier, biosensor are continuously developed out.Patent CN101870866A is by silica counter opal photon
Plane of crystal modifies upper fluorescein FITC, successfully prepares the counter opal structure silica fluorescent to TNT steam recognition reaction
Film forms highly selective, high sensitivity, has molecular recognition performance nanostructure probe.Patent CN103257123A will be weighed
Metal incudes base group modification to inverse opal photonic crystal surface, is prepared for a kind of photon crystal film weight with multilevel structure
Metal sensor, the analysis detection for predetermined substance can greatly improve sensitivity, selectivity and the scope of application of detection.Specially
Sharp CN102193213B fills the thermosetting of contact lenses standard using hydrogel as inverse opal photonic crystal skeleton in hole
Colorful contact lens are dazzled in liquid, acquisition.For other colorful contact lens, it is more beautiful and generous to dazzle colorful contact lens,
And good biocompatibility, there is good practicability.Multiple material be used to modify inverse opal photonic crystal, make anti-albumen
Stone photonic crystal shows a variety of properties.But in previous counter opal structure application, it yet there are no filling temp sensitivity object
Report of the matter as temperature-sensitive material.Traditional thermometer is made using mercury and glass, is easily damaged, mercury is caused to volatilize
And leakage, it causes damages to human body and environment；Thermometer form is fixed, and cannot be bent, and complex condition is unable to satisfy, and temperature is surveyed
Amount.Since film liquid crystal thermometer is flow morphology, it is easy leakage, is caused damages.In order to solve the temperature under complex environment
Inductive material missing wherein by temperature-sensitivmaterial material encapsulation has obtained a kind of anti-egg using counter opal structure porosity characteristic
White stone structure temperature-sensitive material.
Summary of the invention:
The present invention relates to a kind of counter opal structure temperature-sensitive materials and preparation method thereof, brilliant using counter opal photon
The porous microstructure of body by temperature sense substance selective filling in the porous microstructure of counter opal, and is encapsulated, after
And obtain temperature-sensitive material.
A kind of counter opal structure temperature-sensitive material provided by the invention: silicon dioxide microsphere vertical sedimentation is assembled into
Silica photonic crystal is embedded in thin polymer film, will be embedded in the thin polymer film selective etch shape of silica photonic crystal
At counter opal region, the counter opal area filling temperature sense substance formed after the etching is encapsulated, forms counter opal
Structure temperature inductive material.
The temperature sense substance is cholesteric liquid crystal；Selected from one of following liquid crystal or their mixture: gallbladder
Sterol oleyl carbonic ester, cholesteryl nonanoate, cholesteryl benzoate, cholesteryl chloride, cholesteryl carbonic ester or cholesteric
Alkenyl is to nonyl benzol carbonate.
A kind of preparation method of counter opal structure temperature-sensitive material provided by the invention, specific steps and condition are as follows:
(1) preparation of silicon dioxide microsphere
Using the Stober method of optimization, ethyl alcohol is mixed with the ammonium hydroxide of mass concentration 25% according to volume ratio 45:1-3:1,
100 mass parts are taken, under stirring and steady temperature (25-50 DEG C), 3-30 mass parts tetraethyl orthosilicate is added dropwise.It is small by 6-48
Product washing, drying are obtained the silicon dioxide microsphere of uniform particle diameter, for use by Shi Fanying.
(2) assembling of silica photonic crystal
The silicon dioxide microsphere that step (1) obtains is configured to the alcohol dispersion liquid of mass concentration 0.1-5%, preferred mass
The glass substrate of surface hydrophilic is put into dispersion liquid by concentration 1-3%, under the conditions of constant temperature and humidity, stands 24-96 hours,
Silica photonic crystal is obtained in substrate surface (two-sided).
The constant temperature and humidity condition are as follows: temperature is 10-80 DEG C, preferably 30-50 DEG C；Humidity is 5-80%, preferably 30-
50%.
(3) it is embedded in the preparation of the thin polymer film of silica photonic crystal
Separation pad is sticked to photonic crystal glass substrate two sides, another piece of glass substrate is covered and forms cavity.It will be polymerizable
After monomer adds the photoinitiator of mass ratio 1%-5%, it is packed into cavity.(the ultraviolet ray intensity 5- under ultraviolet light
50mw/cm2, irradiation time is 5-200 minutes preferred) and solidification, cavity is placed in 60-95 DEG C of hot water and is impregnated 1-24 hours, general
The thin polymer film of formation takes out from cavity, obtains the thin polymer film that one side is embedded in silica photonic crystal.
The polymerisable monomer is selected from one of following monomer or their mixture: methyl methacrylate, first
Base ethyl acrylate, n-BMA, Isobutyl methacrylate, hexyl methacrylate, methacrylic acid hydroxypropyl
Ester, glycidyl methacrylate, vinylacetate, methyl acrylate, ethyl acrylate, Hexyl 2-propenoate, acrylic acid are different
Monooctyl ester, isodecyl acrylate, lauryl acrylate, hexanediyl ester, polyethyleneglycol diacrylate, trihydroxy methyl third
Alkane triacrylate, A6OCB, AC-6CN, 6CB, 5CB, C3M, C4M, C6M.
The photoinitiator be selected from following photoinitiator one of or their mixture: Irgacure651,
Irgacure 1717、Irgacure 1173、Irgacure 2959、Irgacure 184、Irgacure 907、Irgacure
369、Irgacure 819、Irgacure 754、TPO、MBF。
(4) selective etch prepares pattern
Under exposure mask covering, with the photonic crystal of hydrofluoric acid weak solution etching polymer film surface, in thin polymer film
Photon crystal surface obtains patterned flexible counter opal structure gap.Hydrofluoric acid weak solution mass concentration is 0.05-5%, excellent
1-3% is selected, etching period is preferably 1-30 minutes.
(5) filling and encapsulation of temperature sense substance
In counter opal structure gap after temperature sense substance filling is etched, then is sprayed in film surface and be added to light
The polymerizable encapsulation monomer of initiator, after ultraviolet lighting solidifies, temperature-sensitivmaterial material is encapsulated in counter opal structure, is obtained
To counter opal structure temperature-sensitive material.
The liquid crystal compound of the preferably following mass ratio of temperature sense substance:
Cholesteryl is to nonyl benzol carbonate: cholesteryl nonanoate: cholesteryl benzoate: cholesteryl chloride: cholesteric
Alkenyl carbonic ester=(20-30): (30-50): (0-20): (0-10): (0-25)
Or cholesterol oil alkenyl carbonate: cholesteryl nonanoate: cholesteryl benzoate=(30-45): (45-60):
10
The polymerizable encapsulation monomer be mass ratio 10:1~1:10 1,6 hexanediol diacrylate (HDDA) with
The mixture of one of following monomer: methyl methacrylate, ethyl methacrylate, n-BMA, methyl
Isobutyl acrylate, hexyl methacrylate, hydroxy propyl methacrylate, glycidyl methacrylate, vinylacetate,
Methyl acrylate, ethyl acrylate, Hexyl 2-propenoate, Isooctyl acrylate monomer；Photoinitiator is in following photoinitiator
A kind of or their mixture: Irgacure 651, Irgacure 1717, Irgacure 1173, Irgacure 2959,
Irgacure184, TPO, the additional amount of photoinitiator are the 1-4% of monomer gross mass.
Effect of the invention: temperature-sensitive material produced by the present invention has good biocompatibility, non-stimulated, environmental-friendly
The characteristics of, and there is high flexibility, material foundation is provided for design temperature sensor.The present invention can also obtain according to actual needs
It can be applied to multiple use according to temperature sensor range to the inductive material for incuding different assigned temperatures, such as detect body
Temperature, alcohol product temperature and other narrow range temperature detection fields.Compared with traditional mercurial thermometer, counter opal structure temperature
Degree inductive material can be used for the preparation of flexible temperature measuring device；Compared with traditional mercurial thermometer, more environmentally friendly, applicable scene
More；Compared with electronic thermometer, price is less expensive.
Specific embodiment:
Embodiment 1:
Silicon dioxide microsphere is synthesized using the Stober method of optimization.Firstly, by 75ml ethyl alcohol, 7ml mass concentration 25%
Ammonium hydroxide mixing is added in reactor, and heating water bath is to 30 DEG C；Mechanical stirring is carried out with 300rpm revolving speed.Controlling reaction temperature is
30 DEG C, into system with 1 drop/s rate of addition, 6ml tetraethyl orthosilicate is added.After being added dropwise, 12h is reacted.It will produce
After object centrifugation, washed repeatedly four times with ethyl alcohol, deionized water respectively, it is dry, silicon dioxide microsphere is obtained, for use.
In ethanol with 1.2% ultrasonic disperse of mass concentration by silicon dioxide microsphere.The glass that will be handled through surface hydrophilicity
Glass substrate (glass substrate is put into 12h in the mixed solution of 37% hydrogen peroxide of mass concentration and 98% concentrated sulfuric acid volume ratio 3:7,
To enhance its surface hydrophilicity), it is vertically put into silica-alcohol dispersion liquid reservoir.35 DEG C of temperature of control, humidity
25%, stand 48h, take out, to ethanol evaporation after, obtain silica photonic crystal template.
Polymerisable monomer C4M, C6M, A6OCB are added 2% light of monomer mass gross mass and are drawn with mass ratio 4:4:2 mixing
After sending out agent Irgacure651, dissolution is sufficiently stirred in methylene chloride.After evaporation under reduced pressure removed solvent, gathering for mixture is obtained
Close monomer.20 microns of separation pad of thickness is sticked to photonic crystal glass substrate two sides, another piece of glass substrate is covered and forms chamber
Body.After polymerisable monomer is added photoinitiator (photoinitiator is 1:50 with polymerisable monomer mass ratio), it is packed into cavity.
Solidify after intensity is ultraviolet light 15 minutes of 15mw/cm2, cavity is placed in 80 DEG C of hot water and is impregnated 5 hours, by shape
At thin polymer film taken out from cavity, obtain one side be embedded in silica photonic crystal thin polymer film.
The thin polymer film of one side insertion photonic crystal prepared by upper step, mask film covering.With the hydrogen fluorine of mass concentration 1%
Acid solution is uniformly applied on exposure mask, carries out local etching.After 1 minute, cleaned with deionized water.It obtains patterning anti-albumen
Stone template.
Cholesterol oil alkenyl carbonate, cholesteryl nonanoate, cholesteryl benzoate are mixed according to mass ratio 45:45:10
Match, after being heated to 90 DEG C, is added in the pattern of patterning counter opal template.One layer of mass ratio 1 is sprayed on Thinfilm pattern surface:
(photoinitiator Irgacure651 mass ratio is 1 1,6 hexanediol diacrylate and methyl methacrylate encapsulation monomer
2%).In 25mw/cm25min cure package under ultraviolet lighting.Obtain counter opal structure temperature-sensitive material.
When temperature is lower than 26.5 DEG C, colorless state is integrally presented in film.At 26.5 DEG C, red pattern is presented in film；
When from being heated to 30.5 DEG C for 26.5 DEG C, film color is successively transformed to red, orange, green, blue.It is higher than 30.5 in temperature
DEG C when, film shows colorless state again.This counter opal structure temperature-sensitive material can refer to 26.5 DEG C to 30.5 DEG C of temperature indicating domain.
Sensitivity is 1 DEG C.
Embodiment 2:
Silicon dioxide microsphere is synthesized using the Stober method of optimization.Tool is added firstly, 75ml ethyl alcohol, 8ml ammonium hydroxide are mixed
Have in churned mechanically reactor, and heating water bath is to 31 DEG C；Control mechanical stirring 310rpm.After stabilizing the temperature, to system
In with 1 drop/s rate of addition, 6ml tetraethyl orthosilicate is added.After being added dropwise, 12h stops reaction.Product is centrifuged
Afterwards, it is washed repeatedly four times with ethyl alcohol, its ionized water respectively.Dried for standby.
In ethanol with 1.5% ultrasonic disperse of mass concentration by silicon dioxide microsphere.The glass that will be handled through surface hydrophilicity
Glass substrate (surface hydrophilic processing is with embodiment 1), is vertically put into silica-alcohol dispersion liquid reservoir.Set temperature 30
DEG C, humidity 35%.Stand 58h, to ethanol evaporation after, obtain silica photonic crystal template.
2% photoinitiator of monomer gross mass is added with mass ratio 8:2 mixing in polymerisable monomer C4M, A6OCB
After Irgacure1173, dissolution is sufficiently stirred in methylene chloride.After evaporation under reduced pressure removed solvent, the polymerizable list of mixture is obtained
Body.Using method same as Example 1, the thin polymer film that one side is embedded in silica photonic crystal is obtained.
Inverse opal film prepared by upper step, mask film covering.With the hydrofluoric acid solution of mass concentration 1.5%, uniformly apply
It is put on exposure mask, carries out local etching.After 1 minute, cleaned with deionized water.Obtain patterning counter opal template.
Cholesterol oil alkenyl carbonate, cholesteryl nonanoate, cholesteryl benzoate are mixed according to mass ratio 44:46:10
Match, after being heated to 95 DEG C, is added in the pattern of patterning counter opal template.With two propylene of 1,6-HD of mass ratio 1:1
Acid esters: acrylic acid mix monomer encapsulates (photoinitiator Irgacure1173, account for monomer mass 2%), the same embodiment of other conditions
1, obtain counter opal structure temperature-sensitive material.
When temperature is lower than 30 DEG C, colorless state is integrally presented in film.At 30 DEG C, red pattern is presented in film；From
30 DEG C when being heated to 33 DEG C, film colour switching is red, orange, green, blue.When temperature is higher than 33 DEG C, film is in again
Reveal colorless state.This counter opal thermometer can refer to 30 DEG C to 33 DEG C of temperature indicating domain.Sensitivity is 1 DEG C.
Embodiment 3:
Silicon dioxide microsphere is synthesized using the Stober method of optimization.Tool is added firstly, 75ml ethyl alcohol, 9ml ammonium hydroxide are mixed
Have in churned mechanically reactor, and heating water bath is to 33 DEG C；Control mechanical stirring 350rpm.After stabilizing the temperature, to system
In with 1 drop/s rate of addition, 6ml tetraethyl orthosilicate is added.After being added dropwise, 12h stops reaction.Product is centrifuged
Afterwards, it is washed repeatedly four times with ethyl alcohol, its ionized water respectively.Dried for standby.
In ethanol with 1.7% ultrasonic disperse of mass concentration by silicon dioxide microsphere.The glass that will be handled through surface hydrophilicity
Glass substrate (surface hydrophilic processing is with embodiment 1), is vertically put into silica-alcohol dispersion liquid reservoir.Set temperature 38
DEG C, humidity 35%.Stand 68h, to ethanol evaporation after, obtain silica photonic crystal template.
By polymerisable monomer C6M, A6OCB is with mass ratio 8:2 mixing, after photoinitiator Irgacure2959 is added, two
Dissolution is sufficiently stirred in chloromethanes.After evaporation under reduced pressure removed solvent, the polymerisable monomer of mixture is obtained.Using with 1 phase of embodiment
Same method obtains the thin polymer film that one side is embedded in silica photonic crystal.
Inverse opal film prepared by upper step, mask film covering.With the hydrofluoric acid solution of mass concentration 1.8%, uniformly apply
It is put on exposure mask, carries out local etching.After 1 minute, cleaned with deionized water.Obtain patterning counter opal template.
Cholesterol oil alkenyl carbonate, cholesteryl nonanoate, cholesteryl benzoate are mixed according to mass ratio 40:50:10
Match, after being heated to 85-95 DEG C, is added in the pattern of patterning counter opal template.With the 1,6-HD dipropyl of mass ratio 1:1
Olefin(e) acid ester: ethyl methacrylate mix monomer encapsulates (photoinitiator Irgacure2959, account for monomer mass 2%), other
Part obtains counter opal structure temperature-sensitive material with embodiment 1.
When temperature is lower than 32 DEG C, colorless state is integrally presented in film.At 32 DEG C, red pattern is presented in film；From
32 DEG C when being heated to 35 DEG C, film colour switching is red, orange, green, blue.When temperature is higher than 35 DEG C, film is in again
Reveal colorless state.This counter opal thermometer can refer to 32 DEG C to 35 DEG C of temperature indicating domain.Sensitivity is 1 DEG C.
Embodiment 4:
Silicon dioxide microsphere is synthesized using the Stober method of optimization.Tool is added firstly, 75ml ethyl alcohol, 10ml ammonium hydroxide are mixed
Have in churned mechanically reactor, and heating water bath is to 34 DEG C；Control mechanical stirring 370rpm.After stabilizing the temperature, to system
In with 1 drop/s rate of addition, 6ml tetraethyl orthosilicate is added.After being added dropwise, 12h stops reaction.Product is centrifuged
Afterwards, it is washed repeatedly four times with ethyl alcohol, its ionized water respectively.Dried for standby.
In ethanol with 2% ultrasonic disperse of mass concentration by silicon dioxide microsphere.The glass that will be handled through surface hydrophilicity
Substrate (surface hydrophilic processing is with embodiment 1), is vertically put into silica-alcohol dispersion liquid reservoir.42 DEG C of set temperature,
Humidity 40%.Stand 68h, to ethanol evaporation after, obtain silica photonic crystal template.
Photoinitiator Irgacure 184 is added with mass ratio 4:4:2 mixing in polymerisable monomer C4M, C6M, AC6CN
Afterwards, dissolution is sufficiently stirred in methylene chloride.After evaporation under reduced pressure removed solvent, the polymerisable monomer of mixture is obtained.Using with reality
The identical method of example 1 is applied, the thin polymer film that one side is embedded in silica photonic crystal is obtained.
Inverse opal film prepared by upper step, mask film covering.With the hydrofluoric acid solution of mass concentration 1%, uniformly smear
On exposure mask, local etching is carried out.After 1 minute, cleaned with deionized water.Obtain patterning counter opal template.
Cholesterol oil alkenyl carbonate, cholesteryl nonanoate, cholesteryl benzoate are mixed according to mass ratio 36:44:10
Match, after being heated to 90-100 DEG C, is added in the pattern of patterning counter opal template.With mass ratio 1:1 1,6-HD dipropyl
Olefin(e) acid ester: methyl acrylate mix monomer encapsulates (photoinitiator Irgacure184, account for monomer mass 2%), and other conditions are the same as real
Example 1 is applied, counter opal structure temperature-sensitive material is obtained.
When temperature is lower than 34 DEG C, colorless state is integrally presented in film.At 34 DEG C, red pattern is presented in film；From
34 DEG C when being heated to 37 DEG C, film colour switching is red, orange, green, blue.When temperature is higher than 37 DEG C, film is in again
Reveal colorless state.This counter opal thermometer can refer to 34 DEG C to 37 DEG C of temperature indicating domain.Sensitivity is 1 DEG C.
Embodiment 5:
Silicon dioxide microsphere is synthesized using the Stober method of optimization.Tool is added firstly, 75ml ethyl alcohol, 11ml ammonium hydroxide are mixed
Have in churned mechanically reactor, and heating water bath is to 32 DEG C；Control mechanical stirring 400rpm.After stabilizing the temperature, to system
In with 1 drop/s rate of addition, 6ml tetraethyl orthosilicate is added.After being added dropwise, 12h stops reaction.Product is centrifuged
Afterwards, it is washed repeatedly four times with ethyl alcohol, its ionized water respectively.Dried for standby.
In ethanol with 1.7% ultrasonic disperse of mass concentration by silicon dioxide microsphere.The glass that will be handled through surface hydrophilicity
Glass substrate (surface hydrophilic processing is with embodiment 1), is vertically put into silica-alcohol dispersion liquid reservoir.Set temperature 45
DEG C, humidity 25%.Stand 48h, to ethanol evaporation after, obtain silica photonic crystal template.
Photoinitiator Irgacure1717 is added with mass ratio 4:4:2 mixing in polymerisable monomer DHHA, C6M, A6OCB
Afterwards, dissolution is sufficiently stirred in methylene chloride.After evaporation under reduced pressure removed solvent, the polymerisable monomer of mixture is obtained.Using with reality
The identical method of example 1 is applied, the thin polymer film that one side is embedded in silica photonic crystal is obtained.
Inverse opal film prepared by upper step, mask film covering.With the hydrofluoric acid solution of mass concentration 3%, uniformly smear
On exposure mask, local etching is carried out.After 1 minute, cleaned with deionized water.Obtain patterning counter opal template.
Cholesterol oil alkenyl carbonate, cholesteryl nonanoate, cholesteryl benzoate are mixed according to mass ratio 32:48:10
Match, after being heated to 90-100 DEG C, is added in the pattern of patterning counter opal template.With mass ratio 1:1 1,6-HD dipropyl
Olefin(e) acid ester: methyl acrylate mix monomer encapsulates (photoinitiator Irgacure1717, account for monomer mass 2%), and other conditions are same
Embodiment 1 obtains counter opal structure temperature-sensitive material.
When temperature is lower than 36 DEG C, colorless state is integrally presented in film.At 36 DEG C, red pattern is presented in film；From
36 DEG C when being heated to 39 DEG C, film colour switching is red, orange, green, blue.When temperature is higher than 39 DEG C, film is in again
Reveal colorless state.This counter opal thermometer can refer to 36 DEG C to 39 DEG C of temperature indicating domain.Sensitivity is 1 DEG C.
Embodiment 6:
Silicon dioxide microsphere is synthesized using the Stober method of optimization.It is added firstly, 75ml ethyl alcohol, 8.5ml ammonium hydroxide are mixed
With in churned mechanically reactor, and heating water bath is to 30 DEG C；Control mechanical stirring 350rpm.After stabilizing the temperature, Xiang Ti
With 1 drop/s rate of addition in system, 6ml tetraethyl orthosilicate is added.After being added dropwise, 12h stops reaction.By product from
After the heart, washed repeatedly four times with ethyl alcohol, its ionized water respectively.Dried for standby.
In ethanol with 1.2% ultrasonic disperse of mass concentration by silicon dioxide microsphere.The glass that will be handled through surface hydrophilicity
Glass substrate (surface hydrophilic processing is with embodiment 1), is vertically put into silica-alcohol dispersion liquid reservoir.Set temperature 38
DEG C, humidity 30%.Stand 52h, to ethanol evaporation after, obtain silica photonic crystal template.
Photoinitiator Irgacure is added with mass ratio 45:35:20 mixing in polymerisable monomer C4M, C6M, A6OCB
After 651, dissolution is sufficiently stirred in methylene chloride.After evaporation under reduced pressure removed solvent, the polymerisable monomer of mixture is obtained.Using with
The identical method of embodiment 1 obtains the thin polymer film that one side is embedded in silica photonic crystal.
Inverse opal film prepared by upper step, mask film covering.With the hydrofluoric acid solution of mass concentration 1%, uniformly smear
On exposure mask, local etching is carried out.After 1 minute, cleaned with deionized water.Obtain patterning counter opal template.
Cholesteric liquid crystal is configured, by cholesteryl to nonyl benzol carbonate, cholesteryl nonanoate, cholesterine benzoic acid
Ester, cholesteryl chloride after being heated to 90-100 DEG C, are added according to mass ratio 36.5:45.3:9.1:9.1 mixture and pattern anti-egg
In the pattern of white stone template.It is encapsulated with mass ratio 1:1 1,6 hexanediol diacrylate: methyl methacrylate mix monomer
(photoinitiator Irgacure651, account for monomer mass 2%), other conditions obtain counter opal structure temperature sense with embodiment 1
Answer material.
When temperature is lower than 33 DEG C, colorless state is integrally presented in film.At 33 DEG C, red pattern is presented in film；From
33 DEG C when being heated to 37 DEG C, film colour switching is red, orange, yellow, green, blue.When temperature is higher than 37 DEG C, film
Colorless state is showed again.This counter opal thermometer can refer to 33 DEG C to 37 DEG C of temperature indicating domain.Sensitivity is 1 DEG C.
Claims (10)
1. a kind of counter opal structure temperature-sensitive material is assembled into silica photon using silicon dioxide microsphere vertical sedimentation
Crystal re-forms the thin polymer film of insertion silica photonic crystal, will be embedded in the thin polymer film of silica photonic crystal
Selective etch forms counter opal region, and the counter opal area filling temperature sense substance formed after the etching is encapsulated,
Form counter opal structure temperature-sensitive material.
2. counter opal structure temperature-sensitive material according to claim 1, it is characterized in that: the temperature sense substance is gallbladder
Steroid phase liquid crystal；Selected from one of following liquid crystal or their mixture: cholesterol oil alkenyl carbonate, cholesteryl nonanoate,
Cholesteryl benzoate, cholesteryl chloride, cholesteryl carbonic ester or cholesteryl are to nonyl benzol carbonate.
3. a kind of preparation method of counter opal structure temperature-sensitive material of any of claims 1 or 2, specific steps and condition
Are as follows:
(1) preparation of silicon dioxide microsphere
Ethyl alcohol is mixed with the ammonium hydroxide of mass concentration 25% according to volume ratio 45:1~3:1,100 mass parts are taken, in stirring and 20-
Under 50 DEG C of steady temperature, 3-30 mass parts tetraethyl orthosilicate is added dropwise, was reacted by 6-48 hours, product is washed, is dry,
Obtain the silicon dioxide microsphere of uniform particle diameter；
(2) assembling of silica photonic crystal
The silicon dioxide microsphere that step (1) obtains is configured to the alcohol dispersion liquid of mass concentration 0.1-5%, by surface hydrophilic
Glass substrate be put into dispersion liquid, under the conditions of constant temperature and humidity, stand 24-96 hours, obtain silica in substrate surface
Photonic crystal；The constant temperature and humidity condition are as follows: temperature is 10-80 DEG C, humidity 5-80%；
(3) it is embedded in the preparation of the thin polymer film of silica photonic crystal
Separation pad is sticked to photonic crystal glass substrate two sides, another piece of glass substrate is covered and forms cavity, by polymerisable monomer
After the photoinitiator for adding mass ratio 1%-5%, it is packed into cavity, solidifies under ultraviolet light, cavity is placed on 60-
It is impregnated 1-24 hours in 95 DEG C of hot water, the thin polymer film of formation is taken out from cavity, obtained one side and be embedded in silica light
The thin polymer film of sub- crystal；
(4) selective etch prepares pattern
Under exposure mask covering, it is embedded in the polymeric film surface of photonic crystal with the etching of hydrofluoric acid weak solution, is patterned
The thin polymer film of flexible counter opal structure；
(5) filling and encapsulation of temperature sense substance
By temperature sense substance filling etching after counter opal structure gap in, then film surface spraying be added to it is light-initiated
The polymerizable encapsulation monomer of agent, after ultraviolet lighting solidifies, temperature-sensitive material is encapsulated in counter opal structure, is obtained anti-
Opal structural temperature-sensitive material.
4. the preparation method of counter opal structure temperature-sensitive material according to claim 3, it is characterized in that: step (3)
Described in polymerisable monomer be selected from one of following monomer or their mixture: methyl methacrylate, metering system
Acetoacetic ester, n-BMA, Isobutyl methacrylate, hexyl methacrylate, hydroxy propyl methacrylate, methyl
Glycidyl acrylate, vinylacetate, methyl acrylate, ethyl acrylate, Hexyl 2-propenoate, Isooctyl acrylate monomer, third
Olefin(e) acid isodecyl ester, lauryl acrylate, hexanediyl ester, polyethyleneglycol diacrylate, trimethylolpropane tris third
Olefin(e) acid ester, A6OCB, AC-6CN, 6CB, 5CB, C3M, C4M, C6M；The photoinitiator in following photoinitiator one
Kind or their mixture: Irgacure 651, Irgacure 1717, Irgacure 1173, Irgacure 2959,
Irgacure 184、Irgacure 907、Irgacure 369、Irgacure 819、Irgacure 754、TPO、MBF。
5. the preparation method of counter opal structure temperature-sensitive material according to claim 3, it is characterized in that: step (3)
It is 5-50mw/cm that middle ultraviolet light condition of cure, which is ultraviolet ray intensity,2, irradiation time is 5-200 minutes.
6. the preparation method of counter opal structure temperature-sensitive material according to claim 3, it is characterized in that: step (5)
Described in temperature sense substance be following mass ratio liquid crystal compound: cholesteryl is to nonyl benzol carbonate: cholesterine
Pelargonate: cholesteryl benzoate: cholesteryl chloride: cholesteryl carbonic ester=(20-30): (30-50): (0-20): (0-
10):(0-25)。
7. the preparation method of counter opal structure temperature-sensitive material according to claim 3, it is characterized in that: step (5)
Described in temperature sense substance be following mass ratio liquid crystal compound: cholesterol oil alkenyl carbonate: cholesteryl nonanoate:
Cholesteryl benzoate=(30-45): (45-60): 10.
8. the preparation method of counter opal structure temperature-sensitive material according to claim 3, it is characterized in that: step (5)
Described in polymerizable encapsulation monomer, be mass ratio 10:1~1:10 1,6- hexanediyl ester and following monomer in
A kind of mixture: methyl methacrylate, ethyl methacrylate, n-BMA, Isobutyl methacrylate,
Hexyl methacrylate, hydroxy propyl methacrylate, glycidyl methacrylate, vinylacetate, methyl acrylate, third
Olefin(e) acid ethyl ester, Hexyl 2-propenoate, Isooctyl acrylate monomer；Photoinitiator be selected from following photoinitiator one of or they mixed
Object: Irgacure 651, Irgacure 1717, Irgacure 1173, Irgacure 2959, Irgacure 184, TPO is closed,
The additional amount of photoinitiator is the 1-4% of monomer gross mass.
9. the preparation method of counter opal structure temperature-sensitive material according to claim 3, it is characterized in that: step (2)
Described in constant temperature and humidity condition are as follows: temperature be 30-50 DEG C, humidity 30-50%.
10. the preparation method of counter opal structure temperature-sensitive material according to claim 3, it is characterized in that: step (4)
Described in hydrofluoric acid mass concentration be 0.05%-5%, etching period be 1-30 minutes.
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