CN111718450B - Organic-inorganic electrically polarized particle and preparation method and application thereof - Google Patents
Organic-inorganic electrically polarized particle and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an organic-inorganic electric polarized particle, a preparation method thereof and application thereof in an electric polarized color-changing device, comprising the following steps: 1) preparing titanium oxide nanorods; 2) grafting dye molecules with polymerizable groups onto the surface of the titanium oxide nanorod by utilizing polymerization reaction to obtain the organic-inorganic electrically polarized particles. The invention specifically relates to a method for grafting dye molecules with different colors by utilizing the surface polymerization reaction of a titanium oxide nanorod to realize multicolor organic-inorganic electrically polarized particles and an electrically polarized color-changing device. The organic-inorganic electrically polarized particles have the characteristics of simple operation, wide color adjustable range, simple preparation, easy large-scale preparation and the like; the electric polarization color-changing device prepared by the method has the advantages of high response speed, wide color-changing range and the like.
Description
Technical Field
The invention relates to the technical field of an electric polarization color-changing device, in particular to organic-inorganic electric polarization particles, a preparation method thereof and application thereof in the electric polarization color-changing device.
Background
The electrochromic window can provide a plurality of functions such as heat insulation, temperature control, energy conservation, privacy and the like, so the electrochromic window is widely applied to the fields of buildings, houses, automobiles and the like, and has high social significance and commercial significance. The intelligent light adjusting film technology is long-term developed and extremely challenging. At present, two intelligent glass technologies based on polymer dispersed liquid crystal color change (PDLC) and an intelligent glass technology based on conductive polymer Electrochromism (EC) are mainly available on the market. The polymer dispersed liquid crystal technology is to disperse liquid crystal small molecular droplets in an organic solid polymer matrix. The free orientation of liquid crystal small molecules is realized through the change of voltage, and an opaque milky white state or a semitransparent state is realized. The PDLC intelligent glass technology has the disadvantages of unsatisfactory minimum transmittance, small maximum/minimum transmittance ratio and limited application scene. Although the conductive polymer electrochromic technology can solve the problem of the lowest transmittance of the PDLC, the conductive polymer electrochromic technology has the advantages of complex processing technology, low color-changing speed, short service life, higher cost and high price, and is only used on a few devices such as high-end sports cars, boeing planes and the like. In addition, the traditional color changing device has single color change. There is therefore a need to develop electrochromic devices of different colors.
Disclosure of Invention
The invention provides an organic-inorganic electrically polarized particle, a preparation method thereof and application thereof in an electrically polarized color-changing device, and particularly relates to an organic-inorganic electrically polarized particle with multiple colors and an electrically polarized color-changing device, which are realized by grafting dye molecules with different colors by utilizing the surface polymerization reaction of a titanium oxide nanorod.
The preferable length of the titanium oxide nano rod is 300-500nm, the length-diameter ratio is 3-5, and the surface of the titanium oxide nano rod is coated by adopting a specific surfactant and dye molecules. The titanium oxide nano rod can be polarized under an electric field and shows electric polarization and color change performance.
A method for preparing organic-inorganic electrically polarized particles, comprising the steps of:
1) preparing titanium oxide nanorods;
2) grafting dye molecules with polymerizable groups onto the surface of the titanium oxide nanorod by utilizing polymerization reaction to obtain the organic-inorganic electrically polarized particles.
In the step 1), the preparation of the titanium oxide nanorod specifically comprises the following steps:
adding titanium sulfate and citric acid into water, performing ultrasonic dispersion and dissolution, adding ethylenediamine, stirring for 0.5-2 hours, transferring into a hydrothermal reaction kettle, reacting for 4-8 hours at 150-250 ℃, washing the obtained precipitate with deionized water to obtain a wet titanium oxide product, adding ethylene glycol monomethyl ether, and performing ultrasonic dispersion to obtain a titanium oxide nanorod solution.
The dosage ratio of the titanium sulfate, the citric acid, the water and the ethylenediamine is 1.5-4 g: 4.7-8.7 g: 10 mL-18 mL: 6-10 mL. More preferably, the dosage ratio of the titanium sulfate, the citric acid, the water and the ethylenediamine is 2.4 g: 6.7 g: 14mL of: 8 mL.
Further preferably, the reaction is carried out at 180 to 220 ℃ for 5 to 7 hours, and most preferably at 200 ℃ for 6 hours.
In step 2), the dye molecules with polymerizable groups are dye molecules with different colors and are one or more of the following structures:
the polymerization reaction needs to add a surfactant, the surfactant is an amphiphilic molecule with a polymerization group, and the surfactant is one or a combination of more of the following structures:
an initiator is required to be added in the polymerization reaction, and the initiator is Azobisisobutyronitrile (AIBN).
The polymerization conditions are as follows: the reaction is carried out for 3-6 h at 70-80 ℃, and the temperature is continuously increased to 81-90 ℃ for 0.5-2 h.
The ratio of the dosage of the titanium oxide nano rod, the dye molecule with polymerizable group, the surfactant and the initiator to be added is 100-200 mg: 15-100 mg: 200-300 mg: 1-10 mg.
The application of the organic-inorganic electrically polarized particles in preparing an electrochromic device specifically comprises the following steps:
dispersing organic-inorganic electrically polarized particles in an oligomer (oligomer) and a solvent, blending with a cross-linkable polymer to obtain a coating slurry, coating the coating slurry on a substrate with a conductive film, and curing and packaging another conductive film and a protective film to obtain the electrically polarized color-changing device.
The oligomer is poly (octyl methacrylate), and the preparation of the poly (octyl methacrylate) comprises the following steps:
adding butyl methacrylate and acryloyloxypropyltrimethoxysilane into ethyl acetate, adding Azobisisobutyronitrile (AIBN), deoxidizing, heating to 70-80 ℃ for reaction for 2-6 h, cooling to 55-65 ℃, adding triethylene glycol dimethacrylate for end capping reaction for 0.2-1.5 h, and precipitating a polymer in methanol after the reaction is finished to obtain the octyl polymethacrylate.
The mass ratio of the butyl methacrylate, the acryloyloxypropyl trimethoxysilane, the ethyl acetate, the Azobisisobutyronitrile (AIBN) and the triethylene glycol dimethacrylate is 12-18 g: 8-13 g: 100-150 mL: 135-210 mg: 0.2 to 0.8 g. Most preferably, the mass ratio of the butyl methacrylate, the acryloxypropyltrimethoxysilane, the ethyl acetate, the Azobisisobutyronitrile (AIBN) and the triethylene glycol dimethacrylate is 15.2 g: 10.5 g: 125 mL: 175 mg: 0.5 g.
Most preferably, the temperature is increased to 75 ℃ for reaction for 4h, the temperature is reduced to 60 ℃, 0.5g of triethylene glycol dimethacrylate is added for end capping reaction for 0.5h,
the solvent is ethyl acetate.
The crosslinkable polymer is a crosslinkable polystyrene solution, and the specific preparation comprises the following steps: adding styrene into ethyl acetate, adding Azobisisobutyronitrile (AIBN), deoxidizing, heating to 80-90 ℃, reacting for 1.5-5 h, cooling to 60-70 ℃, adding 0.1-0.6 g of triethylene glycol dimethacrylate, carrying out end-capping reaction for 1h, precipitating a polymer in ethanol after the reaction is finished, drying to obtain polystyrene, and further preparing a dichloromethane solution for use to obtain a crosslinkable polystyrene solution.
The mass ratio of the styrene to the ethyl acetate to the Azodiisobutyronitrile (AIBN) to the triethylene glycol dimethacrylate is 5-15 g: 100-150 mL: 120-180 mg: 0.1 to 0.6 g. Most preferably, the mass ratio of the styrene to the ethyl acetate to the Azobisisobutyronitrile (AIBN) to the triethylene glycol dimethacrylate is 10 g: 125 mL: 152 mg: 0.3 g.
In the preparation of the crosslinkable polystyrene solution, most preferably, the temperature is increased to 85 ℃ for reaction for 2.5 hours, and the temperature is reduced to 65 ℃ for adding the triethylene glycol dimethacrylate for end capping reaction for 1 hour.
The substrate is a transparent substrate, and is one or a combination of glass, a PET (polyethylene terephthalate) substrate and a PMMA (polymethyl methacrylate) substrate.
The conductive film can be one of ITO, silver nanowire, copper nanowire, ZnO and other conductive films and a combination thereof.
The front conductive film and the back conductive film can be one of ITO, silver nanowires, copper nanowires, ZnO and other conductive films and a combination thereof.
The electrochromic device comprises a transparent substrate, a front conductive film, an electrochromic film formed by coating slurry, a back conductive film and a back protective film in sequence.
Most preferably, a method for preparing an electrochromic device having a deep blue-transparent color change and a transmittance (T%) (105V) of 1.8 to 52.1 with excellent properties, the method comprising the steps of:
1) preparing a titanium oxide nanorod, wherein the preparation of the titanium oxide nanorod specifically comprises the following steps:
adding titanium sulfate and citric acid into water, performing ultrasonic dispersion and dissolution, adding ethylenediamine, stirring for 0.5-2 hours, transferring into a hydrothermal reaction kettle, reacting for 6 hours at 200 ℃, washing the obtained precipitate with deionized water to obtain a wet titanium oxide product, adding ethylene glycol monomethyl ether, and performing ultrasonic dispersion to obtain a titanium oxide nanorod solution;
the dosage ratio of the titanium sulfate, the citric acid, the water and the ethylenediamine is 2.4 g: 6.7 g: 14mL of: 8 mL;
2) grafting dye molecules with polymerizable groups onto the surface of a titanium oxide nanorod by using a polymerization reaction, and adding hydroxypropyl acrylate and Azobisisobutyronitrile (AIBN) into the polymerization reaction to obtain organic-inorganic electrically polarized particles;
the dye molecule with the polymerizable group has a structure shown as a formula B:
the dosage ratio of the titanium oxide nano rod, the dye molecule with polymerizable group, hydroxypropyl acrylate and azodiisobutyronitrile is 150 mg: 50 mg: 203 mg: 2.3 mg;
the polymerization conditions are as follows: firstly reacting for 4.5h at 75 ℃, and continuously heating to 85 ℃ for reacting for 1 h;
3) dispersing organic-inorganic electrically polarized particles in the poly octyl methacrylate and the ethyl acetate, blending the organic-inorganic electrically polarized particles with a cross-linkable polymer to obtain coating slurry, coating the coating slurry on a substrate with a conductive film, and curing and packaging the other conductive film and the protective film to obtain the electrically polarized color-changing device.
The preparation of the poly octyl methacrylate comprises the following steps:
adding butyl methacrylate and acryloyloxypropyltrimethoxysilane into ethyl acetate, adding Azobisisobutyronitrile (AIBN), deoxidizing, heating to 75 ℃ for reaction for 4 hours, cooling to 60 ℃, adding 0.5g of triethylene glycol dimethacrylate for end capping reaction for 0.5 hour, and precipitating the polymer in methanol after the reaction is finished to obtain the octyl polymethacrylate.
In the preparation of the octyl polymethacrylate, the mass ratio of butyl methacrylate, acryloxypropyltrimethoxysilane, ethyl acetate, Azobisisobutyronitrile (AIBN) and triethylene glycol dimethacrylate is 15.2 g: 10.5 g: 125 mL: 175 mg: 0.5 g.
The crosslinkable polymer is a crosslinkable polystyrene solution, and the specific preparation comprises the following steps: adding styrene into ethyl acetate, adding Azobisisobutyronitrile (AIBN), deoxidizing, heating to 85 ℃, reacting for 2.5 hours, cooling to 65 ℃, adding triethylene glycol dimethacrylate to perform end capping reaction for 1 hour, precipitating a polymer in ethanol after the reaction is finished, drying to obtain polystyrene, and further preparing a dichloromethane solution for use to obtain a crosslinkable polystyrene solution.
In the preparation of the crosslinkable polystyrene solution, the mass ratio of styrene, ethyl acetate, Azobisisobutyronitrile (AIBN) and triethylene glycol dimethacrylate is 10 g: 125 mL: 152 mg: 0.3 g.
Compared with the traditional electric polarization color-changing device, the invention has the advantages that:
1. compared with the traditional color change device which has single color change, the invention can easily realize the color change particles with different colors on the surface of the titanium oxide nano rod by an interfacial polymerization method.
2. By means of interfacial polymerization, dye molecules can be wrapped around the particles well, the stability of the electrically polarized particles can be improved, and the device also shows good stability.
3. The method of the invention has better compatibility, and various surfactants and modified dye molecules can be applied, which can greatly expand the universality of the technology to realize different applications.
4. The particles with different colors are further combined to realize more color changes, the polychromaticity of the electric polarization color changing device can be obviously improved, and almost any color requirement can be realized.
5. Compared with the electrochromism technology adopting the redox principle, the electrochromism particles and the device do not generate redox reaction when voltage is applied, have good stability and are beneficial to practical application.
6. The invention specifically relates to a method for grafting dye molecules with different colors by utilizing the surface polymerization reaction of a titanium oxide nanorod to realize multicolor organic-inorganic electrically polarized particles and an electrically polarized color-changing device. The organic-inorganic electrically polarized particles have the characteristics of simple operation, wide color adjustable range, simple preparation, easy large-scale preparation and the like; the electric polarization color-changing device prepared by the method has the advantages of high response speed, wide color-changing range and the like.
Drawings
FIG. 1 is a structural formula of a modified dye in an example;
FIG. 2 is a synthesis scheme of electrically polarized particles (i.e., organic-inorganic electrically polarized particles);
FIG. 3 is a graph showing the molecular weight and distribution of octyl polymethacrylate prepared in the examples;
FIG. 4 is a graph showing the molecular weights and distributions of polystyrene prepared in examples.
FIG. 5 is the electron microscope scanning image of the titanium oxide nanorods in the titanium oxide nanorod solution.
FIG. 6 is an electron microscope scan of nanorods in organic-inorganic electrically polarized particles.
Detailed Description
The titanium oxide nanorod solution, the octyl polymethacrylate and the cross-linkable polystyrene solution adopted in the embodiment of the invention are prepared by the following method:
the preparation method of the titanium oxide nanorod solution comprises the following steps: 2.4g of titanium sulfate and 6.7g of citric acid were added to 14mL of deionized water, and dissolved by ultrasonic dispersion. 8mL of ethylenediamine was added, stirred for 1 hour, and then transferred to a 50mL hydrothermal reaction vessel to react at 200 ℃ for 6 hours. The resulting precipitate was washed three more times with deionized water to yield about 1.1g of wet titanium oxide product. 500mg of the mixture was added to 100mL of ethylene glycol monomethyl ether, and after removing a part of water, the mixture was ultrasonically dispersed for 3 hours. The concentration was 3.0mg/mL by heating.
The self-making method of the poly octyl methacrylate (Mn ═ 4300) comprises the following steps: 15.2g of butyl methacrylate and 10.5g of acryloyloxypropyltrimethoxysilane were added to 125mL of ethyl acetate, 175mg of AIBN were added, oxygen was removed, and the reaction was allowed to warm to 75 ℃ for 4 hours. Cooling to 60 ℃, adding 0.5g of triethylene glycol dimethacrylate to carry out end capping reaction for 0.5 h. After the reaction is finished, the polymer is precipitated in methanol, and a small part of insoluble substances are removed to obtain the poly octyl methacrylate. The molecular weight and the distribution diagram of the poly (octyl methacrylate) are shown in FIG. 3. The characterization data of the octyl polymethacrylate are as follows:1H-NMR(300MHz，CDCl3，δ)4.2-3.9(3H)，3.8-3.4(1H),2.5-1.8(10H)，0.8-1.4(5H)。GPC(THF),Mn＝4300。
the crosslinkable polystyrene solution (dichloromethane solution, concentration 200mg/mL, Mn 4400) is prepared by the following steps: 10g of styrene were added to 125mL of ethyl acetate, 152mg of AIBN (azobisisobutyronitrile) was added, oxygen was removed, and the reaction was carried out at 85 ℃ for 2.5 hours. Cooling to 65 ℃, adding 0.3g of triethylene glycol dimethacrylate to carry out end capping reaction for 1 h. After the reaction is finished, the polymer is precipitated in ethanol, a small part of insoluble substances are removed, and the polystyrene is obtained after drying. The characterization data for polystyrene are as follows:1H-NMR(300MHz，CDCl3delta) 6.8-7.3(5H), 2.5-1.9 (3H). Gpc (thf), Mn 4400. The solution is further prepared into a dichloromethane solution for use, and a crosslinkable polystyrene solution is obtained.
Example 1
1) Dye molecule a was prepared according to literature [ ACS appl.mater.interfaces 2013,5,7086 ]: a100 mL single neck round bottom flask was charged with 2.6g of indigo starting material (CAS: 482-89-3; Tokyo chemical Co., Ltd.), 4.1g of ethyl 2-chloromethacrylate (Afahesar chemical Co., Ltd., 98%), 2.5g of potassium carbonate (analytical grade) and 50mL of N, N-dimethylformamide were added to dissolve it. The reaction was then warmed to 110 ℃ and purged with nitrogen for 15 minutes. After 12 hours of reaction, the temperature is reduced, 100mL of deionized water is added, and a blue blocky solid is separated out. The blue solid was then collected, 120mL of dichloromethane was added, stirred for 30 minutes, and insoluble material was removed. Crude product in petroleum ether: dichloromethane ═ 2: 1 to give 2.0g of solid powder dye molecule a in 76% yield.
2) As shown in fig. 2, organic-inorganic electrically polarized particles were prepared: to the titanium oxide nanorod solution (50.0mL,3.0mg/mL, ethylene glycol methyl ether solution) prepared in preparation example 1, dye molecule A (25.0mg), hydroxypropyl acrylate (225mg, CAS:25584-83-2) was added, and aeration was performed for 15 min. AIBN2.5mg (dissolved in 1mL tetrahydrofuran) was added and reacted at 75 ℃ for 4 hours. The temperature is continuously increased to 85 ℃, and the reaction is carried out for 1 h. Concentrating the reaction liquid to 10mL, pouring 100mL of n-hexane, separating out blue powder solid, washing twice with n-hexane and then with ethanol, and blow-drying the obtained solid with nitrogen for later use to obtain the organic-inorganic electrically-polarized particles.
FIG. 5 is the electron microscope scanning image of the titanium oxide nanorods in the titanium oxide nanorod solution, and FIG. 6 is the electron microscope scanning image of the nanorods in the organic-inorganic polarized particles. As shown in FIG. 5, the surface of the titanium oxide nanorods can be seen to have substantially no polymer attached. As shown in fig. 6, the titanium oxide surface-coated polymer sample: most of the nano-rod surfaces have certain polymer adhesion, and the particle surfaces become smoother.
3) About 100mg of the blue solid powder of the previous step was dispersed in ethyl acetate (15mL), 270mg of the octyl polymethacrylate (Mn ═ 4300) prepared in preparation example was added, and after stirring at a high speed for 2 hours, the ethyl acetate was removed in vacuo to obtain a blue slurry. The blue paste was mixed with 1.7mL of a crosslinkable polystyrene solution (dichloromethane solution, concentration 200mg/mL, Mn 4400), photoinitiator 907(1.0mg) was added, the mixture was stirred at a low speed for 2 hours, and then dichloromethane was removed in vacuo to obtain a blue viscous paste.
4) Coating the blue viscous slurry on the surface of the ITO film by a blade coating mode, and preparing a wet film with the thickness of 90-100 mu m by controlling the distance between a scraper and the ITO film. And then curing for 60s by adopting a UV light source to obtain a blue electric polarization discoloring layer. And superposing another ITO film on the prepared electric polarization color changing layer to obtain an electric polarization color changing device, and then contacting the optical film with an electrode to test.
Example 2
1) Preparation of organic-inorganic electrically polarized particles: dye molecule A (75.0mg), hydroxypropyl acrylate (178.0mg) were added to a solution of titanium oxide nanorods (50.0mL,3.0mg/mL, ethylene glycol methyl ether solution, made by Dow.) and aerated for 15 min. AIBN 2.3mg (dissolved in 1mL tetrahydrofuran) was added and the reaction was carried out at 75 ℃ for 4 hours. The temperature is continuously increased to 85 ℃, and the reaction is carried out for 1 h. Concentrating the reaction solution to 10mL, pouring 100mL of n-hexane, separating out dark blue powder solid, washing twice with n-hexane and then with ethanol, and drying the obtained solid by blowing with nitrogen for later use.
2) About 100mg of the blue solid powder of the previous step was dispersed in ethyl acetate (15mL), 270mg of octyl polymethacrylate (Mn 4300, manufactured by oneself) was added, and after stirring at a high speed for 2 hours, ethyl acetate was removed in vacuo to obtain a blue slurry. The blue slurry was mixed with 1.7mL of a crosslinkable polystyrene solution (dichloromethane solution, concentration 200mg/mL, Mn 4400, homemade), photoinitiator 907(1.0mg) was added, the mixture was stirred at a low speed for 2 hours, and then dichloromethane was removed in vacuo to obtain a blue viscous slurry.
3) Coating the blue viscous slurry on the surface of the ITO film by a blade coating mode, and preparing a wet film with the thickness of 90-100 mu m by controlling the distance between a scraper and the ITO film. And then curing for 60s by adopting a UV light source to obtain a blue electric polarization discoloring layer. And superposing the other ITO film on the prepared electric polarization color changing layer to obtain an electric polarization color changing device, and then contacting the optical film with an electrode for testing.
Example 3
1) Dye molecule B was prepared according to literature [ ACS appl.mater.interfaces 2013,5,7086 ]: a100 mL single neck round bottom flask was charged with 2.6g of indigo starting material (CAS: 482-89-3; Tokyo chemical Co., Ltd.), 8.3g of 2-chloromethyl ethyl acrylate (Afahesa chemical Co., Ltd., 98%), 5.0g of potassium carbonate (analytical grade) and 50mL of N, N-dimethylformamide were added and dissolved. The reaction was then warmed to 120 ℃ and purged with nitrogen for 15 minutes. After reacting for 36 hours, the temperature is reduced, and 150mL of deionized water is added to precipitate a blue blocky solid. The blue solid was then collected and washed three times with ethanol (150 mL. times.3). Crude product in petroleum ether: methanol 1: 2.5 to give 3.7g of solid powder dye molecule B in 72% yield.
2) Preparation of organic-inorganic electrically polarized particles: to a titanium oxide nanorod solution (50.0mL,3.0mg/mL, ethylene glycol methyl ether solution) was added dye molecule B (50.0mg), hydroxypropyl acrylate (203.0mg), and aeration was carried out for 15 min. AIBN 2.3mg (dissolved in 1mL tetrahydrofuran) was added and the reaction was carried out at 75 ℃ for 4.5 h. The temperature is continuously increased to 85 ℃, and the reaction is carried out for 1 h. Concentrating the reaction liquid to 10mL, pouring 100mL of n-hexane, separating out green powder solid, washing twice with n-hexane and then with ethanol, and blow-drying the obtained solid with nitrogen for later use to obtain the organic-inorganic electrically-polarized particles.
3) About 100mg of the blue solid powder of the previous step was dispersed in ethyl acetate (15mL), 270mg of octyl polymethacrylate (Mn 4300, manufactured by oneself) was added, and after stirring at a high speed for 2 hours, ethyl acetate was removed in vacuo to obtain a blue slurry. The blue slurry was mixed with 1.7mL of a crosslinkable polystyrene solution (dichloromethane solution, concentration 200mg/mL, Mn 4400, homemade), photoinitiator 907(1.0mg) was added, the mixture was stirred at a low speed for 2 hours, and then dichloromethane was removed in vacuo to obtain a blue viscous slurry.
4) Coating the blue viscous slurry on the surface of the ITO film by a blade coating mode, and preparing a wet film with the thickness of 90-100 mu m by controlling the distance between a scraper and the ITO film. And then curing for 60s by adopting a UV light source to obtain a blue electric polarization discoloring layer. And superposing the other ITO film on the prepared electric polarization color changing layer to obtain an electric polarization color changing device, and then contacting the optical film with an electrode for testing.
Example 4
1) Dye molecule C was prepared according to the literature [ Bioconjugate chem.2015,26, 1328-: a100 mL single neck round bottom flask was charged with 6.4g of the acid dye eosin (CAS: 482-89-3; Sigma Aldrich), 8.3g of 2-chloromethyl ethyl acrylate (Afaeangsa chemical Co., Ltd., 98%), 2.5g of potassium carbonate (analytical purity), and 50mL of N, N-dimethylformamide. The reaction solution was then warmed to 90 ℃ and purged with nitrogen for 15 minutes. After reacting for 18 hours, the temperature is reduced, and 150mL of deionized water is added to precipitate a dark red solid. The red solid was then collected and washed three times with methanol (150 mL. times.3). Crude product in petroleum ether: methanol 1: 3 to give 4.9g of solid powder dye molecule C in a yield of 64%.
2) Preparation of organic-inorganic electrically polarized particles: to a titanium oxide nanorod solution (50.0mL,3.0mg/mL, ethylene glycol methyl ether solution) was added dye molecule C (25.0mg), hydroxypropyl acrylate (225mg), and aeration was carried out for 15 min. AIBN2.5mg (dissolved in 1mL tetrahydrofuran) was added and reacted at 75 ℃ for 4 hours. The temperature is continuously increased to 85 ℃, and the reaction is carried out for 1 h. Concentrating the reaction solution to 10mL, pouring 100mL of n-hexane, separating out red powder solid, washing twice with n-hexane and then with ethanol, and drying the obtained solid by blowing with nitrogen for later use.
3) About 100mg of the red solid powder of the previous step was dispersed in ethyl acetate (15mL), 270mg of octyl polymethacrylate (Mn 4300, manufactured by oneself, same as above) was added, and after stirring at a high speed for 2 hours, ethyl acetate was removed in vacuo to obtain a red slurry. The red paste was mixed with 1.7mL of a crosslinkable polystyrene solution (dichloromethane solution, 200mg/mL, Mn 4400, homemade), photoinitiator 907(1.0mg) was added, the mixture was stirred at a low speed for 2 hours, and then dichloromethane was removed in vacuo to obtain a red viscous paste.
4) Coating the red viscous slurry on the surface of the ITO film by a blade coating mode, and preparing a wet film with the thickness of 90-100 mu m by controlling the distance between a scraper and the ITO film. And then curing for 60s by adopting a UV light source to obtain the red electric polarization discoloring layer. And superposing the other ITO film on the prepared electric polarization color changing layer to obtain an electric polarization color changing device, and then contacting the optical film with an electrode for testing.
Example 5
1) Preparation of organic-inorganic electrically polarized particles: to a titanium oxide nanorod solution (50.0mL,3.0mg/mL, ethylene glycol methyl ether solution) was added dye molecule C (50.0mg), methyl acrylate (203.0mg), and aeration was carried out for 15 min. AIBN 2.3mg (dissolved in 1mL tetrahydrofuran) was added and the reaction was carried out at 75 ℃ for 4.5 h. The temperature is continuously increased to 85 ℃, and the reaction is carried out for 1 h. Concentrating the reaction solution to 10mL, pouring 100mL of n-hexane, separating out green powder solid, washing twice with n-hexane, then washing once with ethanol, and drying the obtained solid by blowing with nitrogen for later use.
2) About 100mg of the red solid powder of the previous step was dispersed in ethyl acetate (15mL), 270mg of octyl polymethacrylate (Mn 4300, manufactured by oneself) was added, and after stirring at a high speed for 2 hours, ethyl acetate was removed in vacuo to obtain a red slurry. The red paste was mixed with 1.7mL of a crosslinkable polystyrene solution (dichloromethane solution, 200mg/mL, Mn 4400, homemade), photoinitiator 907(1.0mg) was added, the mixture was stirred at a low speed for 2 hours, and then dichloromethane was removed in vacuo to obtain a red viscous paste.
3) Coating the red viscous slurry on the surface of the ITO film by a blade coating mode, and preparing a wet film with the thickness of 90-100 mu m by controlling the distance between a scraper and the ITO film. And then curing for 60s by adopting a UV light source to obtain the red electric polarization discoloring layer. And superposing the other ITO film on the prepared electric polarization color changing layer to obtain an electric polarization color changing device, and then contacting the optical film with an electrode for testing.
Example 6
1) Dye molecule D was prepared according to the literature [ Dyes and Pigments,2015,121,328-335 ]: in a 100mL single neck round bottom flask was added 3.1g quinacridone (CAS: 1047-16-1; Sigma Aldrich), 2.1g 2-chloromethyl ethyl acrylate (Afaeangsa chemical Co., Ltd., 98%) and 25mL ultra dry N, N-dimethylformamide. After 15 minutes of introduction of nitrogen gas, 260mg of sodium hydride was slowly added in 3 portions, and the reaction was carried out at room temperature for 5 hours, followed by heating to 50 ℃ and reacting for 1 hour. After the reaction was completed, 10mL of ethanol was added to quench the reaction, and 100mL of ionized water was added to precipitate a black solid. The dark red is dried and separated by chromatography (eluent petroleum ether: ethyl acetate: 6: 1) to give 2.4g of dye molecule D as a purple solid in 57% yield.
2) Preparation of organic-inorganic electrically polarized particles: to a titanium oxide nanorod solution (50.0mL,3.0mg/mL, ethylene glycol methyl ether solution) was added dye molecule D (25.0mg), methyl acrylate (225mg), and aeration was carried out for 15 min. AIBN2.5mg (dissolved in 1mL tetrahydrofuran) was added and reacted at 75 ℃ for 4 hours. The temperature is continuously increased to 85 ℃, and the reaction is carried out for 1 h. Concentrating the reaction solution to 10mL, pouring 100mL of n-hexane, separating out purple powder solid, washing twice with n-hexane and then with ethanol, and drying the obtained solid by blowing with nitrogen for later use.
3) About 100mg of the purple solid powder of the previous step was dispersed in ethyl acetate (15mL), 270mg of octyl polymethacrylate (Mn 4300, manufactured by seiko) was added, and after stirring at a high speed for 2 hours, ethyl acetate was removed in vacuo to obtain a purple slurry. The purple slurry was mixed with 1.7mL of a cross-linkable polystyrene solution (dichloromethane solution, concentration 200mg/mL, Mn 4400, homemade), photoinitiator 907(1.0mg) was added, the mixture was stirred at a low speed for 2 hours, and then dichloromethane was removed in vacuo to obtain a purple viscous slurry.
4) Coating the purple viscous slurry on the surface of the ITO film by a blade coating mode, and preparing a wet film with the thickness of 90-100 mu m by controlling the distance between a scraper and the ITO film. And then curing for 60s by adopting a UV light source to obtain the purple (red) electric polarization color changing layer. And superposing the other ITO film on the prepared electric polarization color changing layer to obtain an electric polarization color changing device, and then contacting the optical film with an electrode for testing.
Example 7
1) Preparation of organic-inorganic electrically polarized particles: to a titanium oxide nanorod solution (50.0mL,3.0mg/mL, ethylene glycol methyl ether solution) was added dye molecule D (50.0mg), methyl acrylate (203.0mg), and aeration was carried out for 15 min. AIBN 2.3mg (dissolved in 1mL tetrahydrofuran) was added and the reaction was carried out at 75 ℃ for 4.5 h. The temperature is continuously increased to 85 ℃, and the reaction is carried out for 1 h. Concentrating the reaction solution to 10mL, pouring 100mL of n-hexane, separating out purple powder solid, washing twice with n-hexane and then with ethanol, and drying the obtained solid by blowing with nitrogen for later use.
2) About 100mg of the above-obtained solid powder was dispersed in ethyl acetate (15mL), 270mg of octyl polymethacrylate (Mn 4300, manufactured by seiko) was added, and after stirring at a high speed for 2 hours, ethyl acetate was removed in vacuo to obtain a purple slurry. The red slurry was mixed with 1.7mL of a cross-linkable polystyrene solution (dichloromethane solution, concentration 200mg/mL, Mn 4400, homemade), photoinitiator 907(1.0mg) was added, the mixture was stirred at a low speed for 2 hours, and then dichloromethane was removed in vacuo to obtain a purple viscous slurry.
3) Coating the purple viscous slurry on the surface of the ITO film by a blade coating mode, and preparing a wet film with the thickness of 90-100 mu m by controlling the distance between a scraper and the ITO film. And then curing for 60s by adopting a UV light source to obtain the purple (red) electric polarization color changing layer. And superposing the other ITO film on the prepared electric polarization color changing layer to obtain an electric polarization color changing device, and then contacting the optical film with an electrode for testing.
Example 8
1) Dye molecule D was prepared according to the literature [ Dyes and Pigments,2015,121,328-335 ]: a25 mL single neck round bottom flask was charged with 0.58g N, N '-bis (2, 4-nitrophenyl) -3,3' -dimethoxy [1, 1 '-biphenyl-4, 4' -diamine (CAS:29398-96-7), 2.1g of 2-chloromethylacrylic acid ethyl ester (AlfaElsa chemical Co., Ltd., 98%) and 8mL of ultra dry N, N-dimethylformamide. After introducing nitrogen for 15 minutes, 240mg of potassium tert-butoxide was slowly added in 3 portions and reacted at room temperature for 3 hours. After the reaction was completed, 3mL of ethanol was added to quench the reaction, and 250mL of ionized water was added to precipitate a brownish black solid. The crude product was dried and separated by column chromatography (eluent petroleum ether: ethyl acetate 1: 1) to give 220mg of dye molecule E as a brown solid in 32% yield.
2) Preparation of organic-inorganic electrically polarized particles: to a solution of titanium oxide nanorods (50.0mL,3.0mg/mL, ethylene glycol methyl ether solution) was added dye molecule E (25.0mg), methyl acrylate (225mg), and aeration was carried out for 15 min. AIBN2.5mg (dissolved in 1mL tetrahydrofuran) was added and reacted at 75 ℃ for 4 hours. The temperature is continuously increased to 85 ℃, and the reaction is carried out for 1 h. Concentrating the reaction solution to 10mL, pouring 100mL of n-hexane, separating out brown powder solid, washing twice with n-hexane and then with ethanol, and drying the obtained solid by blowing with nitrogen for later use.
3) About 100mg of the brown solid powder of the previous step was dispersed in ethyl acetate (15mL), 270mg of octyl polymethacrylate (Mn 4300, manufactured by oneself) was added, and after stirring at a high speed for 2 hours, ethyl acetate was removed in vacuo to obtain a brown slurry. The brown slurry was mixed with 1.7mL of a cross-linkable polystyrene solution (dichloromethane solution, 200mg/mL, Mn 4400, homemade), photoinitiator 907(1.0mg) was added, the mixture was stirred at low speed for 2h, and then dichloromethane was removed in vacuo to give a brown viscous slurry.
4) Coating the brown viscous slurry on the surface of the ITO film by a blade coating mode, and preparing a wet film with the thickness of 90-100 mu m by controlling the distance between a scraper and the ITO film. And then curing for 60s by adopting a UV light source to obtain the purple (red) electric polarization color changing layer. And superposing the other ITO film on the prepared electric polarization color changing layer to obtain an electric polarization color changing device, and then contacting the optical film with an electrode for testing.
Performance testing
The electrical polarization discoloration properties of the device reflect the change between the energized and de-energized states of the particles based on titanium oxide and dye molecules. The light transmittance of the device was measured by an LS183 spectrometer, ranging from 380nm to 760 nm. The frequency of the applied voltage of the AC power supply is 60Hz, the voltage is adjustable within the range of 0-150V, and the test results of the voltage prepared in examples 1-8 are shown in Table 1.
TABLE 1
From the test results, the good coating of the titanium oxide particle surface and the excellent performance of the electric polarization color changing device can be realized by adopting different modified dye molecules. The adjustment of the uniform color depth can be realized by adjusting the proportion of the surface dye molecules. As in examples 1 and 2, and examples 4 and 5, when the ratio of the dye molecules used is large, the lowest transmittance is decreased, and the light-shielding property is better. When the bifunctional modified dye molecule B is adopted, the lowest transmittance is lower, and the highest transmittance is higher. This may be due to the higher efficiency of bifunctional modified molecules in the polymerization of titanium oxide surface, denser dye layer, and fewer participating unencapsulated dye molecules. However, when the concentration of the dye molecules was further increased on the basis of example 3, it was found that the polymerization rate of the dye was too fast, and it was difficult to obtain well-dispersed electrically polarized particles. This also laterally demonstrates the high efficiency of the polymerization of the bifunctional dye molecules on the titanium oxide surface. When red or magenta dye molecules are used (examples 4-7), the lowest transmittance of the electrochromic device is higher, which may be the result of its narrower spectral range. When brown dye D (example 8) was used, the device performance was comparable to the blue electrochromic device.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change or modification made to the above embodiments according to the technical principle of the present invention still falls within the scope of the technical solution of the present invention.
Claims (9)
1. A method for preparing organic-inorganic electrically polarized particles, comprising the steps of:
1) preparing titanium oxide nanorods;
2) grafting dye molecules with polymerizable groups onto the surface of the titanium oxide nanorod by utilizing a polymerization reaction to obtain organic-inorganic electrically polarized particles;
the dye molecule with the polymerizable group is one or more of the following structures:
2. the method for preparing organic-inorganic electrically polarized particles according to claim 1, wherein the step 1) of preparing the titanium oxide nanorods specifically comprises:
adding titanium sulfate and citric acid into water, performing ultrasonic dispersion and dissolution, adding ethylenediamine, stirring for 0.5-2 hours, transferring into a hydrothermal reaction kettle, reacting for 4-8 hours at 150-250 ℃, washing the obtained precipitate with deionized water to obtain a wet titanium oxide product, adding ethylene glycol monomethyl ether, and performing ultrasonic dispersion to obtain a titanium oxide nanorod solution.
3. The method for preparing organic-inorganic electrically polarized particles according to claim 2, wherein in the step 1), the ratio of the amounts of the titanium sulfate, the citric acid, the water and the ethylenediamine is 1.5-4 g: 4.7-8.7 g: 10 mL-18 mL: 6-10 mL;
reacting for 5-7 h at 180-220 ℃.
4. The method for preparing organic-inorganic electrically polarized particles according to claim 1, wherein in step 2), the polymerization reaction requires the addition of a surfactant having one or more of the following structures:
an initiator is required to be added in the polymerization reaction, and the initiator is azobisisobutyronitrile.
5. The method for preparing organic-inorganic electrically polarized particles according to claim 1, wherein the polymerization conditions in step 2) are as follows: the reaction is carried out for 3-6 h at 70-80 ℃, and the temperature is continuously increased to 81-90 ℃ for 0.5-2 h.
6. The method for preparing organic-inorganic electrically polarized particles according to claim 4, wherein in the step 2), the ratio of the titanium oxide nanorods, the dye molecules having polymerizable groups, and the surfactant and the initiator which need to be added is 100-200 mg: 15-100 mg: 200-300 mg: 1-10 mg.
7. The organic-inorganic electrically polarized particles prepared by the preparation method according to any one of claims 1 to 6.
8. Use of organic-inorganic electrically polarized particles according to claim 7 for the preparation of an electrochromic device, comprising in particular:
dispersing organic-inorganic electrically polarized particles in an oligomer and a solvent, blending with a cross-linkable polymer to obtain a coating slurry, coating the coating slurry on a substrate with a conductive film, and curing and packaging another conductive film and a protective film to obtain the electrically polarized color-changing device.
9. The use of claim 8, wherein the oligomer is poly (octyl methacrylate) and the poly (octyl methacrylate) is prepared by:
adding butyl methacrylate and acryloyloxypropyltrimethoxysilane into ethyl acetate, adding Azobisisobutyronitrile (AIBN), deoxidizing, heating to 70-80 ℃ for reaction for 2-6 h, cooling to 55-65 ℃, adding triethylene glycol dimethacrylate for end capping reaction for 0.2-1.5 h, and precipitating a polymer in methanol after the reaction is finished to obtain the poly octyl methacrylate;
the solvent is ethyl acetate;
the crosslinkable polymer is a crosslinkable polystyrene solution, and the specific preparation comprises the following steps: adding styrene into ethyl acetate, adding azobisisobutyronitrile, deoxidizing, heating to 80-90 ℃, reacting for 1.5-5 h, cooling to 60-70 ℃, adding 0.1-0.6 g of triethylene glycol dimethacrylate, performing end capping reaction for 1h, precipitating a polymer in ethanol after the reaction is finished, drying to obtain polystyrene, adding a solvent to prepare a dichloromethane solution, and obtaining a crosslinkable polystyrene solution.
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