CN115558399B - Weather-resistant electrochromic paint and preparation method thereof - Google Patents
Weather-resistant electrochromic paint and preparation method thereof Download PDFInfo
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- CN115558399B CN115558399B CN202211259933.3A CN202211259933A CN115558399B CN 115558399 B CN115558399 B CN 115558399B CN 202211259933 A CN202211259933 A CN 202211259933A CN 115558399 B CN115558399 B CN 115558399B
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- 239000003973 paint Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 54
- 229920001577 copolymer Polymers 0.000 claims abstract description 28
- 239000004593 Epoxy Substances 0.000 claims abstract description 27
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 22
- 239000002608 ionic liquid Substances 0.000 claims abstract description 20
- 239000004020 conductor Substances 0.000 claims abstract description 19
- 239000007822 coupling agent Substances 0.000 claims abstract description 17
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- 229920002635 polyurethane Polymers 0.000 claims abstract description 15
- 239000004814 polyurethane Substances 0.000 claims abstract description 15
- 238000009835 boiling Methods 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
- -1 1-ethyl-3-methylimidazolium tetrafluoroborate Chemical compound 0.000 claims description 18
- 239000003999 initiator Substances 0.000 claims description 17
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 16
- 238000000576 coating method Methods 0.000 claims description 16
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 claims description 16
- GHDIHPNJQVDFBL-UHFFFAOYSA-N methoxycyclohexane Chemical compound COC1CCCCC1 GHDIHPNJQVDFBL-UHFFFAOYSA-N 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 16
- NADYEWVQIJRXJM-UHFFFAOYSA-N 1,3-bis(oxiran-2-ylmethyl)-5-prop-2-enyl-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC=C)C(=O)N1CC1CO1 NADYEWVQIJRXJM-UHFFFAOYSA-N 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 229910021389 graphene Inorganic materials 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- PRXOTZGIQDYFHJ-UHFFFAOYSA-N C1=CC=CC=2C3=CC=CC=C3CC12.C[Si]C=C Chemical compound C1=CC=CC=2C3=CC=CC=C3CC12.C[Si]C=C PRXOTZGIQDYFHJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- 239000011261 inert gas Substances 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- 239000012043 crude product Substances 0.000 claims description 6
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 5
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052754 neon Inorganic materials 0.000 claims description 4
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- BMQZYMYBQZGEEY-UHFFFAOYSA-M 1-ethyl-3-methylimidazolium chloride Chemical compound [Cl-].CCN1C=C[N+](C)=C1 BMQZYMYBQZGEEY-UHFFFAOYSA-M 0.000 claims 1
- LRESCJAINPKJTO-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;1-ethyl-3-methylimidazol-3-ium Chemical class CCN1C=C[N+](C)=C1.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F LRESCJAINPKJTO-UHFFFAOYSA-N 0.000 claims 1
- 239000000178 monomer Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 4
- 125000003700 epoxy group Chemical group 0.000 abstract description 4
- 229910052731 fluorine Inorganic materials 0.000 abstract description 4
- 239000011737 fluorine Substances 0.000 abstract description 4
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical compound C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 abstract description 3
- UTUZBCDXWYMYGA-UHFFFAOYSA-N silafluorene Chemical compound C12=CC=CC=C2CC2=C1C=CC=[Si]2 UTUZBCDXWYMYGA-UHFFFAOYSA-N 0.000 abstract description 3
- 229940117986 sulfobetaine Drugs 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 7
- 238000009472 formulation Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- FQERWQCDIIMLHB-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CC[NH+]1CN(C)C=C1 FQERWQCDIIMLHB-UHFFFAOYSA-N 0.000 description 4
- HLLAFQGXROKYNU-UHFFFAOYSA-N COC1(CCCCC1C=C)F Chemical compound COC1(CCCCC1C=C)F HLLAFQGXROKYNU-UHFFFAOYSA-N 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 229920002799 BoPET Polymers 0.000 description 2
- JEMGWDKEKDZUGI-UHFFFAOYSA-N CC1=C(C=2CC3=CC=CC=C3C2C=C1)C=C Chemical compound CC1=C(C=2CC3=CC=CC=C3C2C=C1)C=C JEMGWDKEKDZUGI-UHFFFAOYSA-N 0.000 description 2
- 239000004992 Ionic Liquid Crystal Substances 0.000 description 2
- 230000005856 abnormality Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- KCXFHTAICRTXLI-UHFFFAOYSA-M propane-1-sulfonate Chemical compound CCCS([O-])(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-M 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 description 1
- QMNWYGTWTXOQTP-UHFFFAOYSA-N 1h-triazin-6-one Chemical group O=C1C=CN=NN1 QMNWYGTWTXOQTP-UHFFFAOYSA-N 0.000 description 1
- BFRDBSBKJUVSNP-UHFFFAOYSA-N 9h-fluorene;silicon Chemical group [Si].C1=CC=C2CC3=CC=CC=C3C2=C1 BFRDBSBKJUVSNP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/085—Copper
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The application discloses a weather-resistant electrochromic paint and a preparation method thereof, which relate to the technical field of functional paint and are prepared from the following components in parts by weight: 40-50 parts of amino-terminated hyperbranched polyurethane, 10-20 parts of epoxy functional copolymer, 15-25 parts of liquid crystal material, 0.1-0.5 part of conductive material, 0.1-0.3 part of coupling agent, 4-7 parts of ionic liquid and 10-15 parts of organic solvent; the epoxy-based functional copolymer includes units formed from monomers including: (1) a radically polymerizable fluorine-containing liquid crystal compound; (2) an unsaturated ethylenic containing silafluorene; (3) a sulfobetaine monomer containing an unsaturated ethylenic bond; (4) other monomers containing an unsaturated ethylenic bond and an epoxy group. The weather-resistant electrochromic paint disclosed by the application has the advantages of good performance stability, sufficient weather resistance and remarkable electrochromic effect.
Description
Technical Field
The application relates to the technical field of functional coatings, in particular to a weather-resistant electrochromic coating and a preparation method thereof.
Background
The electrochromic paint is a novel functional paint, has good indication function and beautifying effect, has excellent optical characteristics, and has wide application in the aspects of high-grade hotels, museums, conference offices, banks, commercial showcases, automobile windows and the like. The material can realize stable and reversible color conversion of reflectivity and transmissivity under the action of an external electric field, and can realize the interconversion between a colorless transparent state and an atomized opaque state.
The existing electrochromic paint has the defects of poor weather resistance, short service life, poor electrochromic effect and reversibility, insufficient adhesion force with a base material, unstable property and easy oxidative decomposition after long-term exposure to air, thereby causing the paint to lose the color-changing property. In order to solve the above problems, chinese patent application CN114163902a discloses an electrochromic layer coating, an electrochromic device and a method for preparing the same. The electrochromic layer coating comprises the following components in parts by weight: 1-60 parts of resin; 0.01-50 parts of functional monomer; 0.01-50 parts of cross-linking agent; 0.001-1.5 parts of conductive material; 0.001-5 parts of initiator; 0.001-0.01 part of UV absorber; 0.01-50 parts of liquid crystal glue. According to the application, the conductive layer is directly compounded into the electrochromic layer for the first time, so that the problem of increase of the b-value of the electrochromic device caused by superposition of the conductive film layer is avoided, the prepared electrochromic device basically does not yellow, has the characteristic of illumination resistance, and has the advantages of high color changing speed, stable performance, long service life, simplicity in preparation, low cost and good application value. However, the paint has insufficient weather resistance, short service life and poor storage and transportation stability.
Therefore, the weather-resistant electrochromic paint with good performance stability, sufficient weather resistance and remarkable electrochromic effect and a preparation method thereof are still needed in the field.
Disclosure of Invention
The application aims to overcome the defects of the prior art and provide the weather-resistant electrochromic paint with good performance stability, sufficient weather resistance and remarkable electrochromic effect and the preparation method thereof.
In order to achieve the above purpose, the application adopts the following technical scheme: a weather-resistant electrochromic paint is prepared from the following components in parts by weight: 40-50 parts of amino-terminated hyperbranched polyurethane, 10-20 parts of epoxy functional copolymer, 15-25 parts of liquid crystal material, 0.1-0.5 part of conductive material, 0.1-0.3 part of coupling agent, 4-7 parts of ionic liquid and 10-15 parts of organic solvent; the epoxy-based functional copolymer includes units formed from monomers including: (1) a radically polymerizable fluorine-containing liquid crystal compound; (2) an unsaturated ethylenic containing silafluorene; (3) a sulfobetaine monomer containing an unsaturated ethylenic bond; (4) other monomers containing an unsaturated ethylenic bond and an epoxy group.
Preferably, the epoxy functional copolymer is formed by polymerizing vinyl fluorine-containing cyclohexyl methyl ether liquid crystal compound, methyl vinyl fluorene, 3- [ N, N-dimethyl- [2- (2-methylpropan-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonate inner salt and 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione according to free radicals.
Preferably, the preparation method of the epoxy functional copolymer comprises the following steps: vinyl fluorine-containing cyclohexyl methyl ether liquid crystal compound, methyl vinyl silicon fluorene, 3- [ N, N-dimethyl- [2- (2-methylpropan-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonic acid inner salt, 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione and an initiator are added into a high boiling point solvent, stirred and reacted for 4-6 hours at 60-80 ℃ in inert gas atmosphere, the reaction is finished and then precipitated in water, then ethanol is used for washing the crude product for 3-6 times, and the crude product is dried to constant weight at 80-90 ℃ in a vacuum drying oven, thus obtaining the epoxy functional copolymer.
Preferably, the vinyl fluorine-containing cyclohexyl methyl ether liquid crystal compound, methyl vinyl silicon fluorene, 3- [ N, N-dimethyl- [2- (2-methylpropan-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonic acid inner salt, 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, an initiator and a high boiling point solvent are mixed according to the mass ratio of 1 (0.8-1.2): (0.5-0.8): (0.3-0.6): (0.03-0.05): (10-20).
Preferably, the initiator is azobisisobutyronitrile; the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide and N-methylpyrrolidone; the inert gas is any one of nitrogen, helium, neon and argon.
Preferably, the vinyl fluorocyclohexyl methyl ether liquid crystal compound is a vinyl fluorocyclohexyl methyl ether liquid crystal compound VC10PUF, and is prepared according to the method of example 1 in chinese patent document CN 103540324B.
Preferably, the amino-terminated hyperbranched polyurethane is prepared according to the method of example 1 in chinese patent document CN 201510141212.6.
Preferably, the liquid crystal material is any one of liquid crystal SLC717, liquid crystal E7, liquid crystal 5CB and liquid crystal 7 CB.
Preferably, the conductive material is a mixture formed by mixing graphene and nano copper powder according to a mass ratio of (3-5) to 1.
Preferably, the graphene is single-layer graphene powder, the sheet diameter is 0.5-5 mu m, the thickness is 0.8-1.2nm, the number is XF001H, and the graphene is provided by Jiangsu Xianfeng nano material science and technology Co., ltd; the diameter of the nanometer copper powder is 150-200nm, and the number is XFJ10, which is provided by Jiangsu Xianfeng nanometer material science and technology Co.
Preferably, the coupling agent is at least one of a silane coupling agent KH550, a silane coupling agent KH560 and a silane coupling agent KH 570.
Preferably, the ionic liquid is at least one of 1-ethyl-3-methylimidazole tetrafluoroborate, 1-ethyl-3-methylimidazole chloride, 1-ethyl-3-methylimidazole hexafluorophosphate and 1-ethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt.
Preferably, the organic solvent is any one of ethylene glycol monobutyl ether, butyl acetate and butanone.
The application also aims at providing a preparation method of the weather-resistant electrochromic paint, which comprises the following steps: the weather-resistant electrochromic paint is prepared by mixing the components in parts by weight and uniformly dispersing the components by ultrasonic.
Detailed Description
The following detailed description of the preferred embodiments of the present application will be provided in connection with.
A weather-resistant electrochromic paint is prepared from the following components in parts by weight: 40-50 parts of amino-terminated hyperbranched polyurethane, 10-20 parts of epoxy functional copolymer, 15-25 parts of liquid crystal material, 0.1-0.5 part of conductive material, 0.1-0.3 part of coupling agent, 4-7 parts of ionic liquid and 10-15 parts of organic solvent; the epoxy-based functional copolymer includes units formed from monomers including: (1) a radically polymerizable fluorine-containing liquid crystal compound; (2) an unsaturated ethylenic containing silafluorene; (3) a sulfobetaine monomer containing an unsaturated ethylenic bond; (4) other monomers containing an unsaturated ethylenic bond and an epoxy group.
Preferably, the epoxy functional copolymer is formed by polymerizing vinyl fluorine-containing cyclohexyl methyl ether liquid crystal compound, methyl vinyl fluorene, 3- [ N, N-dimethyl- [2- (2-methylpropan-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonate inner salt and 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione according to free radicals.
Preferably, the preparation method of the epoxy functional copolymer comprises the following steps: vinyl fluorine-containing cyclohexyl methyl ether liquid crystal compound, methyl vinyl silicon fluorene, 3- [ N, N-dimethyl- [2- (2-methylpropan-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonic acid inner salt, 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione and an initiator are added into a high boiling point solvent, stirred and reacted for 4-6 hours at 60-80 ℃ in inert gas atmosphere, the reaction is finished and then precipitated in water, then ethanol is used for washing the crude product for 3-6 times, and the crude product is dried to constant weight at 80-90 ℃ in a vacuum drying oven, thus obtaining the epoxy functional copolymer.
Preferably, the vinyl fluorine-containing cyclohexyl methyl ether liquid crystal compound, methyl vinyl silicon fluorene, 3- [ N, N-dimethyl- [2- (2-methylpropan-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonic acid inner salt, 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, an initiator and a high boiling point solvent are mixed according to the mass ratio of 1 (0.8-1.2): (0.5-0.8): (0.3-0.6): (0.03-0.05): (10-20).
Preferably, the initiator is azobisisobutyronitrile; the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide and N-methylpyrrolidone; the inert gas is any one of nitrogen, helium, neon and argon.
Preferably, the vinyl fluorocyclohexyl methyl ether liquid crystal compound is a vinyl fluorocyclohexyl methyl ether liquid crystal compound VC10PUF, and is prepared according to the method of example 1 in chinese patent document CN 103540324B.
Preferably, the amino-terminated hyperbranched polyurethane is prepared according to the method of example 1 in chinese patent document CN 201510141212.6.
Preferably, the liquid crystal material is any one of liquid crystal SLC717, liquid crystal E7, liquid crystal 5CB and liquid crystal 7 CB.
Preferably, the conductive material is a mixture formed by mixing graphene and nano copper powder according to a mass ratio of (3-5) to 1.
Preferably, the graphene is single-layer graphene powder, the sheet diameter is 0.5-5 mu m, the thickness is 0.8-1.2nm, the number is XF001H, and the graphene is provided by Jiangsu Xianfeng nano material science and technology Co., ltd; the diameter of the nanometer copper powder is 150-200nm, and the number is XFJ10, which is provided by Jiangsu Xianfeng nanometer material science and technology Co.
Preferably, the coupling agent is at least one of a silane coupling agent KH550, a silane coupling agent KH560 and a silane coupling agent KH 570.
Preferably, the ionic liquid is at least one of 1-ethyl-3-methylimidazole tetrafluoroborate, 1-ethyl-3-methylimidazole chloride, 1-ethyl-3-methylimidazole hexafluorophosphate and 1-ethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt.
Preferably, the organic solvent is any one of ethylene glycol monobutyl ether, butyl acetate and butanone.
The application also aims at providing a preparation method of the weather-resistant electrochromic paint, which comprises the following steps: the weather-resistant electrochromic paint is prepared by mixing the components in parts by weight and uniformly dispersing the components by ultrasonic.
Due to the application of the technical scheme, compared with the prior art, the application has the following advantages: the weather-resistant electrochromic paint provided by the application has the advantages of good performance stability, sufficient weather resistance and remarkable electrochromic effect; by adding amino-terminated hyperbranched polyurethane and epoxy functional copolymer, hyperbranched polyurethane, a zwitterionic salt structure, a triazinone structure, a silicon fluorene structure and a fluorine-containing liquid crystal compound structure are simultaneously introduced into a coating film structure and are matched and acted together, so that the prepared coating has good weather resistance after being cured into a film, and good compatibility with ionic liquid and liquid crystal materials; amino on the amino-terminated hyperbranched polyurethane can be solidified by epoxy ring-opening reaction with epoxy groups on the epoxy functional copolymer to form an interpenetrating network structure, and the ionic liquid and the liquid crystal material are fixed in the interpenetrating network structure, so that the performance stability is improved; the electrochromic effect of the prepared coating is obvious through reasonable selection of the types and the formulas of the components such as the liquid crystal material, the ionic liquid and the like. Meanwhile, the application also provides a preparation method of the weather-resistant electrochromic paint, which is simple, convenient to operate, high in preparation efficiency and finished product qualification rate, low in equipment dependence and suitable for continuous large-scale production. The addition of the conductive material can not only enhance conductivity, but also facilitate the fixation of the ionic liquid and the liquid crystal material, prevent the leakage and improve the performance stability.
The application will be further described with reference to specific examples, but the scope of the application is not limited thereto:
example 1
The weather-resistant electrochromic paint is characterized by being prepared from the following components in parts by weight: 40 parts of amino-terminated hyperbranched polyurethane, 10 parts of epoxy functional copolymer, 15 parts of liquid crystal material, 0.1 part of conductive material, 0.1 part of coupling agent, 4 parts of ionic liquid and 10 parts of organic solvent.
The preparation method of the epoxy functional copolymer comprises the following steps: vinyl fluorine-containing cyclohexyl methyl ether liquid crystal compound, methyl vinyl silicon fluorene and 3- [ N, N-dimethyl- [2- (2-methylprop-2-enoyloxy) ethyl]Ammonium salt]Adding propane-1-sulfonate, 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione and an initiator into a high boiling point solvent, stirring and reacting for 4 hours at 60 ℃ in an inert gas atmosphere, precipitating in water after the reaction is finished, washing a crude product with ethanol for 3 times, and drying to constant weight at 80 ℃ in a vacuum drying oven to obtain an epoxy functional copolymer; the vinyl fluorine-containing cyclohexyl methyl ether liquid crystal compound, methyl vinyl silicon fluorene and 3- [ N, N-dimethyl- [2- (2-methylprop-2-enoyloxy) ethyl]Ammonium salt]Propane-1-sulfonic acid inner salt, 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, an initiator and a high boiling point solvent according to the mass ratio of 1:0.8:0.5:0.3:0.03:10; the initiator is azodiisobutyronitrile; the high boiling point solvent is dimethyl sulfoxide; the inert gas is nitrogen; determination of M of the copolymer by GPC test, U.S. Waters 515-2410 n ＝18620g/mol，M W /M n =1.235; the quantitative analysis of EDX element proves that the copolymer is respectively prepared from vinyl fluorine-containing cyclohexyl methyl ether liquid crystal compound, methyl vinyl silicon fluorene and 3- [ N, N-dimethyl- [2- (2-methylprop-2-enoyloxy) ethyl]Ammonium salt]The mass ratio of the structural units introduced by the propane-1-sulfonate inner salt and the 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione is0.99:0.8:0.48:0.3。
The amino-terminated hyperbranched polyurethane is prepared according to the method of example 1 in Chinese patent document CN 201510141212.6; the liquid crystal material is liquid crystal E7; the conductive material is a mixture formed by mixing graphene and nanometer copper powder according to a mass ratio of 3:1; the graphene is single-layer graphene powder, the sheet diameter is 0.5-5 mu m, the thickness is 0.8-1.2nm, the number is XF001H, and the graphene is provided by Jiangsu Xianfeng nano material science and technology Co Ltd; the diameter of the nanometer copper powder is 150-200nm, and the number is XFJ10, which is provided by Jiangsu Xianfeng nanometer material science and technology Co., ltd; the coupling agent is a silane coupling agent KH550; the ionic liquid is 1-ethyl-3-methylimidazole tetrafluoroborate; the organic solvent is ethylene glycol monobutyl ether.
The preparation method of the weather-resistant electrochromic paint comprises the following steps: the weather-resistant electrochromic paint is prepared by mixing the components in parts by weight and uniformly dispersing the components by ultrasonic.
Example 2
The weather-resistant electrochromic paint provided in the example is basically the same as that in the example 1 in formula and preparation method, except that the weather-resistant electrochromic paint is prepared from the following components in parts by weight: 43 parts of amino-terminated hyperbranched polyurethane, 12 parts of epoxy functional copolymer, 17 parts of liquid crystal material, 0.2 part of conductive material, 0.15 part of coupling agent, 5 parts of ionic liquid and 11 parts of organic solvent; the vinyl fluorine-containing cyclohexyl methyl ether liquid crystal compound, methyl vinyl silicon fluorene, 3- [ N, N-dimethyl- [2- (2-methylpropan-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonic acid inner salt, 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, an initiator and a high boiling point solvent according to the mass ratio of 1:0.9:0.6:0.4:0.035:12; the high boiling point solvent is N, N-dimethylformamide; the inert gas is helium; the conductive material is a mixture formed by mixing graphene and nanometer copper powder according to a mass ratio of 3.5:1; the coupling agent is silane coupling agent KH560; the ionic liquid is 1-ethyl-3-methylimidazole chloride; the organic solvent is butyl acetate.
Example 3
The weather-resistant electrochromic paint provided in the example is basically the same as that in the example 1 in formula and preparation method, except that the weather-resistant electrochromic paint is prepared from the following components in parts by weight: 45 parts of amino-terminated hyperbranched polyurethane, 15 parts of epoxy functional copolymer, 20 parts of liquid crystal material, 0.3 part of conductive material, 0.2 part of coupling agent, 5.5 parts of ionic liquid and 13 parts of organic solvent; the vinyl fluorine-containing cyclohexyl methyl ether liquid crystal compound, methyl vinyl silicon fluorene, 3- [ N, N-dimethyl- [2- (2-methylpropan-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonic acid inner salt, 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, an initiator and a high boiling point solvent according to the mass ratio of 1:1:0.65:0.45:0.04:15; the high boiling point solvent is N-methyl pyrrolidone; the inert gas is neon; the conductive material is a mixture formed by mixing graphene and nanometer copper powder according to a mass ratio of 4:1; the coupling agent is a silane coupling agent KH570; the ionic liquid is 1-ethyl-3-methylimidazole hexafluorophosphate; the organic solvent is butanone.
Example 4
The weather-resistant electrochromic paint provided in the example is basically the same as that in the example 1 in formula and preparation method, except that the weather-resistant electrochromic paint is prepared from the following components in parts by weight: 48 parts of amino-terminated hyperbranched polyurethane, 18 parts of epoxy functional copolymer, 24 parts of liquid crystal material, 0.4 part of conductive material, 0.25 part of coupling agent, 6.5 parts of ionic liquid and 14 parts of organic solvent; the vinyl fluorine-containing cyclohexyl methyl ether liquid crystal compound, methyl vinyl silicon fluorene, 3- [ N, N-dimethyl- [2- (2-methylpropan-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonic acid inner salt, 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, an initiator and a high boiling point solvent according to the mass ratio of 1:1.1:0.75:0.55:0.045:18; the high boiling point solvent is a mixture formed by mixing dimethyl sulfoxide, N-dimethylformamide and N-methylpyrrolidone according to a mass ratio of 1:2:1; the inert gas is argon; the conductive material is a mixture formed by mixing graphene and nanometer copper powder according to a mass ratio of 4.5:1; the coupling agent is a mixture formed by mixing a silane coupling agent KH550, a silane coupling agent KH560 and a silane coupling agent KH570 according to a mass ratio of 1:3:5; the ionic liquid is a mixture formed by mixing 1-ethyl-3-methylimidazole tetrafluoroborate, 1-ethyl-3-methylimidazole chloride salt, 1-ethyl-3-methylimidazole hexafluorophosphate and 1-ethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imine salt according to a mass ratio of 1:1:2:3.
Example 5
The weather-resistant electrochromic paint provided in the example is basically the same as that in the example 1 in formula and preparation method, except that the weather-resistant electrochromic paint is prepared from the following components in parts by weight: 50 parts of amino-terminated hyperbranched polyurethane, 20 parts of epoxy functional copolymer, 25 parts of liquid crystal material, 0.5 part of conductive material, 0.3 part of coupling agent, 7 parts of ionic liquid and 15 parts of organic solvent; the vinyl fluorine-containing cyclohexyl methyl ether liquid crystal compound, methyl vinyl silicon fluorene, 3- [ N, N-dimethyl- [2- (2-methylpropan-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonic acid inner salt, 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, an initiator and a high boiling point solvent according to the mass ratio of 1:1.2:0.8:0.6:0.05:20; the high boiling point solvent is dimethyl sulfoxide; the inert gas is nitrogen; the conductive material is a mixture formed by mixing graphene and nanometer copper powder according to a mass ratio of 5:1; the coupling agent is a silane coupling agent KH550; the ionic liquid is 1-ethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt; the organic solvent is butyl acetate.
Comparative example 1
The formulation and preparation method of the weather-resistant electrochromic paint are basically the same as those of the embodiment 1, except that no vinyl fluorine-containing cyclohexyl methyl ether liquid crystal compound and methyl vinyl silicon fluorene are added in the preparation process of the epoxy functional copolymer.
Comparative example 2
This example provides a weatherable electrochromic coating, the formulation and preparation method of which are substantially the same as example 1, except that 3- [ N, N-dimethyl- [2- (2-methylpropan-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonic acid inner salt and methyl vinyl silafluorene are not added in the preparation process of the epoxy functional copolymer.
In order to further illustrate the beneficial technical effects of the products of the embodiments of the application, the weather-resistant electrochromic coatings prepared by the embodiments are subjected to relevant performance tests, and the test results are shown in Table 1; the test method is as follows:
(1) Transmittance: two rolls of ITO transparent conductive film are arranged on a die clamping machine, weather-proof electrochromic paint in each example is uniformly dripped between the two layers of conductive films, the two layers of conductive films are arranged between two roll shafts on the die clamping machine, and then the roll shafts on the die clamping machine are used for completing the lamination, wherein the distance between the two roll shafts is 15 mu m, and the lamination force is 6kgf/cm 2 And then placing the mixture in an environment of 110 ℃ for 5min for thermal drying and curing, detecting the performance of an electrochromic film formed after the weather-resistant electrochromic paint is cured according to the regulation in GB/T35847-2018 electrochromic film dimming glass, connecting the electrochromic film with an alternating current power supply, regulating the power supply to 50Hz, outputting a sine wave with an output voltage of 36v, and measuring the visible light transmittance of the electrochromic film.
(2) Weather resistance: uniformly coating weather-resistant electrochromic paint prepared in each example on a transparent ITO-PET film, then placing the transparent ITO-PET film in an environment of 110 ℃ for 5min for thermal drying and curing to obtain a template, placing the template in an environment of 85 ℃ multiplied by 85%RH for 1440h, and observing the coating if no abnormality exists, namely, indicating that the coating has good weather resistance; if abnormality occurs, the weather resistance of the coating is not passed.
(3) Adhesion force: the adhesion rating of each example was tested according to the method of GB/T9286-2021.
TABLE 1
| Project | Transmittance (%) | Weather resistance | Adhesion rating (grade) |
| Example 1 | 87 | Good quality | 0 |
| Example 2 | 89 | Good quality | 0 |
| Example 3 | 89 | Good quality | 0 |
| Example 4 | 90 | Good quality | 0 |
| Example 5 | 91 | Good quality | 0 |
| Comparative example 1 | 80 | Not pass through | 0 |
| Comparative example 2 | 83 | Not pass through | 2 |
As can be seen from the data in Table 1, the weather-resistant electrochromic paint product in the examples of the present application has better electrochromic effect and weather resistance and higher adhesion than the comparative examples.
The above embodiments are provided for illustrating the technical concept and features of the present application, and are intended to enable those skilled in the art to understand the present application and to implement the same, but are not intended to limit the scope of the present application, and all equivalent changes or modifications according to the spirit of the present application should be included in the scope of the present application.
Claims (7)
1. The weather-resistant electrochromic paint is characterized by being prepared from the following components in parts by weight: 40-50 parts of amino-terminated hyperbranched polyurethane, 10-20 parts of epoxy functional copolymer, 15-25 parts of liquid crystal material, 0.1-0.5 part of conductive material, 0.1-0.3 part of coupling agent, 4-7 parts of ionic liquid and 10-15 parts of organic solvent;
the preparation method of the epoxy functional copolymer comprises the following steps: adding vinyl fluorine-containing cyclohexyl methyl ether liquid crystal compound, methyl vinyl silicon fluorene, 3- [ N, N-dimethyl- [2- (2-methylpropan-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonate inner salt, 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione and an initiator into a high boiling point solvent, stirring and reacting for 4-6 hours at 60-80 ℃ in an inert gas atmosphere, precipitating in water after the reaction is finished, washing a crude product with ethanol for 3-6 times, and then drying to constant weight at 80-90 ℃ in a vacuum drying oven to obtain an epoxy functional copolymer; the vinyl fluorine-containing cyclohexyl methyl ether liquid crystal compound, methyl vinyl silicon fluorene, 3- [ N, N-dimethyl- [2- (2-methylpropan-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonate inner salt, 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, an initiator and a high boiling point solvent are mixed according to the mass ratio of 1 (0.8-1.2): (0.5-0.8): (0.3-0.6): (0.03-0.05): (10-20); the conductive material is a mixture formed by mixing graphene and nanometer copper powder according to a mass ratio of (3-5): 1.
2. The weatherable electrochromic coating according to claim 1, wherein the initiator is azobisisobutyronitrile; the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide and N-methylpyrrolidone; the inert gas is any one of nitrogen, helium, neon and argon.
3. The weather-resistant electrochromic paint according to claim 1, wherein the liquid crystal material is any one of liquid crystal SLC717, liquid crystal E7, liquid crystal 5CB, and liquid crystal 7 CB.
4. The weather-resistant electrochromic paint according to claim 1, wherein the graphene is single-layer graphene powder, the sheet diameter is 0.5-5 μm, and the thickness is 0.8-1.2nm; the diameter of the nanometer copper powder is 150-200nm.
5. The weather-resistant electrochromic paint according to claim 1, characterized in that the coupling agent is at least one of a silane coupling agent KH550, a silane coupling agent KH560, a silane coupling agent KH 570.
6. The weatherable electrochromic coating according to claim 1, wherein the ionic liquid is at least one of 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt; the organic solvent is any one of ethylene glycol monobutyl ether, butyl acetate and butanone.
7. A method of preparing a weatherable electrochromic coating according to any one of claims 1 to 6, comprising the steps of: the weather-resistant electrochromic paint is prepared by mixing the components in parts by weight and uniformly dispersing the components by ultrasonic.
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| JP4077675B2 (en) * | 2002-07-26 | 2008-04-16 | ナガセケムテックス株式会社 | Aqueous dispersion of complex of poly (3,4-dialkoxythiophene) and polyanion and method for producing the same |
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| JP2001323206A (en) * | 2000-05-11 | 2001-11-22 | Toppan Printing Co Ltd | Glare-proof and antistatic hard coat resin composition, hard coat film and hard coat film molding artilce |
| CN102027079A (en) * | 2008-04-10 | 2011-04-20 | 印可得株式会社 | Ink composition for optoelectronic device |
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