CN106810707B - A kind of preparation method for the swellable colloid crystal film that is powered - Google Patents

A kind of preparation method for the swellable colloid crystal film that is powered Download PDF

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CN106810707B
CN106810707B CN201710045823.XA CN201710045823A CN106810707B CN 106810707 B CN106810707 B CN 106810707B CN 201710045823 A CN201710045823 A CN 201710045823A CN 106810707 B CN106810707 B CN 106810707B
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anhydrous
volume ratio
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mass percent
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CN106810707A (en
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赵九蓬
华春霞
杨大春
侯帅
张盼盼
徐洪波
李垚
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Harbin Institute of Technology
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    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F112/02—Monomers containing only one unsaturated aliphatic radical
    • C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C08J2325/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract

A kind of preparation method for the swellable colloid crystal film that is powered, the present invention relates to the preparation methods of colloid crystal film.The present invention solves the problems, such as that existing electric expansion polymer material preparation is difficult.Method: the one, preparation of monodisperse polystyrene microsphere；Two, the synthesis of ferrocene derivatives；Three, the preparation of electric expansion colloidal crystal material obtains electric expansion colloidal crystal material.A kind of preparation method of the present invention for swellable colloid crystal film that can be powered.

Description

A kind of preparation method for the swellable colloid crystal film that is powered
Technical field
The present invention relates to the preparation methods of colloid crystal film.
Background technique
Colloidal crystal be size 100nm to several microns inorganic or organic colloid micro ball driving force effect It issues and is born from assembly behavior, to form two dimension or three-dimensional ordered structure, the colloid micro ball structure of this ordered arrangement is logical It is commonly referred to as colloidal crystal, photonic crystal or synthetic protein stone structure.Colloidal crystal is due to its excellent optical property Basic material as New Generation Optical electrical part；It is also used as the ideal model system of following fundamemtal phenomena, can be used for molten The mechanism study of the hot issues such as solution preocess, phase transition process；In addition, colloidal crystal itself is alternatively arranged as template, and vapor deposition, light Lithography etc. is perfectly merged, the patterning photonic crystal being used to prepare.Just because of colloidal crystal and its related derivatives Have broad application prospects, just make its in preparation accuracy controlling, the subject crossing of chemical modification and novel application by Greatly concern.
Summary of the invention
The invention solves the difficult problems of existing electric expansion polymer material preparation, and providing one kind can be powered swellable colloid The preparation method of crystal film.
A kind of preparation method being powered swellable colloid crystal film is to sequentially include the following steps:
One, the preparation of monodisperse polystyrene microsphere:
Be added ultrapure water into three mouthfuls of reactors, open condensation cycle water, at the same using mechanical agitator to ultrapure water into Row stirring heats three mouthfuls of reactors to temperature 50 with thermostatic water-circulator bath slot under conditions of revolving speed is 300rpm~3000rpm DEG C~100 DEG C, nitrogen is then led into three mouthfuls of reactors, styrene is added to three mouthfuls of reactors by the oxygen in removing system In, add mass percent be 1%~50% potassium persulfate solution, react 12h~48h, obtain partial size be 200nm~ The monodisperse polystyrene microsphere of 1000nm；
The volume ratio of the styrene and ultrapure water is 1:(30~100)；The styrene is with mass percent The volume ratio of 1%~50% potassium persulfate solution is 1:(0.01~0.1)；
Two, the synthesis of ferrocene derivatives:
By anhydrous AlCl3With anhydrous CH2Cl2It is added in three-necked flask, mixed liquor A is then added dropwise into three-necked flask, to Anhydrous AlCl3After dissolution, mixed liquid B is added dropwise, reacts 2h~5h at room temperature, obtains reaction solution, reaction solution is then poured into ice In water, water layer CH2Cl2Extractant extracts 3 times, merges organic phase, uses anhydrous Na2SO4It dries, filters, solvent is evaporated off, use second Alcohol recrystallization, obtains ferrocene derivatives；
The anhydrous AlCl3Quality and anhydrous CH2Cl2Volume ratio be 1g:(10~100) mL；Described is anhydrous AlCl3Quality and mixed liquor A volume ratio be 1g:(10~100) mL；The anhydrous AlCl3Quality and mixed liquid B Volume ratio is 1g:(20~80) mL；
The mixed liquor A is chloroacetic chloride and anhydrous CH2Cl2Mixture, and chloroacetic chloride and nothing in the mixed liquor A Water CH2Cl2Volume ratio be 1:(10~50)；
The mixed liquid B is ferrocene and anhydrous CH2Cl2Mixture, and in the mixed liquid B ferrocene matter Amount and anhydrous CH2Cl2Volume ratio be 1g:(10~50) mL；
Three, the preparation of electric expansion colloidal crystal material:
The ITO that area is 1cm × 4cm is cleaned up, is 5%~50% by the ITO mass percent cleaned up Hydrogen peroxide and mass percent be 5%~30% the mixture of sulfuric acid impregnate 2h~for 24 hours, be then sonicated 30min~ Then 300min is washed with deionized and is dried with nitrogen, obtain pretreated ITO, is 200nm~1000nm's by partial size Monodisperse polystyrene microsphere is configured to the polystyrene microsphere solution that mass percent is 1%~10% with water, then ultrasonic Disperse 10min~100min, obtain Polystyrene suspension, by 10mL~100mL Polystyrene suspension, dropwise addition is being pre-processed On ITO afterwards, under conditions of spin coating instrument revolving speed is 100rpm~1000rpm, spin coating 10s~100s obtains colloidal crystal mould After dissolving ferrocene derivatives with EtOH Sonicate, it is molten to obtain the ferrocene derivatives that mass percent is 1%~10% for plate The ferrocene derivatives solution that the 10 μ L mass percents of μ L~500 are 1%~10% is added dropwise on colloidal crystal template liquid, Under conditions of spin coating instrument revolving speed is 100rpm~300rpm, spin coating 10s~50s, being subsequently placed in temperature is 30 DEG C~100 DEG C It is dry in incubator, obtain electric expansion colloidal crystal material；
The body for the sulfuric acid that the hydrogen peroxide and mass percent that the mass percent is 5%~50% are 5%~30% Product is than being 1:(3~5).
The beneficial effects of the present invention are: 1, entire technical process is simple, it is not necessarily to special installation and technique；
2, because joined a certain amount of solution of ferrocene in film, film has excellent under the conditions of applying appropriate voltage Electrochromic property, color change interval is wide, reach the multi-color systems such as reddish yellow indigo plant discoloration, can be widely applied to biology, chemical sensor, Photoelectricity equipment etc..
The present invention polystyrene microsphere good using the emulsion polymerization preparation monodispersity of improvement, is then prepared into Colloid monolayer crystal template.Later using ferrocene as raw material, ferrocene derivatives molecule is synthesized using chemical method, is used ethyl alcohol It is filled into colloidal crystal template after completely dissolution, obtains electric expansion colloid crystal film after dry.Applying appropriate voltage feelings Under condition, ferrocene particle volume changes, and the lattice structure of colloidal crystal is made to change, and photon band gap changes to influence Entire colloid crystal film color change.The method simple process, it is reproducible, greatly widen answering for colloidal crystal material Use field.
A kind of preparation method of the present invention for swellable colloid crystal film that can be powered.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of the colloidal crystal template of one step 3 of embodiment preparation；
Fig. 2 is the scanning electron microscope (SEM) photograph of the ferrocene derivatives of two step 2 of embodiment preparation；
Fig. 3 is the scanning electron microscope (SEM) photograph of the electric expansion colloidal crystal material of two step 3 of embodiment preparation；
It is prepared by pure ferrocene derivatives material and embodiment one prepared by comparative test one at 550nm that Fig. 4, which is in wavelength, Electric expansion colloidal crystal material colour fading state and coloured state transmitance variation diagram, a be in the case where voltage is 1V, comparative test one make Standby pure ferrocene derivatives material colour fading state penetrates spectrum, and b is electric expansion colloid prepared by embodiment one in the case where voltage is 1V Crystalline material colour fading state penetrates spectrum, and c is the pure ferrocene derivatives material that in the case where voltage is -1V, prepared by comparative test one Color state penetrates spectrum, and d is that electric expansion colloidal crystal material coloured state prepared by embodiment one penetrates spectrum in the case where voltage is -1V；
It is the transmission at 550nm, under electric expansion colloidal crystal material different voltages prepared by embodiment two that Fig. 5, which is in wavelength, Rate variation diagram, 1 is 2V, and 2 be 1.5V, and 3 be 1V, and 4 be -0.5V, and 5 be -1V, and 6 be -1.5V, and 7 be -2V.
Specific embodiment
Specific embodiment 1: present embodiment one kind can be powered swellable colloid crystal film preparation method be by with Lower step carries out:
One, the preparation of monodisperse polystyrene microsphere:
Be added ultrapure water into three mouthfuls of reactors, open condensation cycle water, at the same using mechanical agitator to ultrapure water into Row stirring heats three mouthfuls of reactors to temperature 50 with thermostatic water-circulator bath slot under conditions of revolving speed is 300rpm~3000rpm DEG C~100 DEG C, nitrogen is then led into three mouthfuls of reactors, styrene is added to three mouthfuls of reactors by the oxygen in removing system In, add mass percent be 1%~50% potassium persulfate solution, react 12h~48h, obtain partial size be 200nm~ The monodisperse polystyrene microsphere of 1000nm；
The volume ratio of the styrene and ultrapure water is 1:(30~100)；The styrene is with mass percent The volume ratio of 1%~50% potassium persulfate solution is 1:(0.01~0.1)；
Two, the synthesis of ferrocene derivatives:
By anhydrous AlCl3With anhydrous CH2Cl2It is added in three-necked flask, mixed liquor A is then added dropwise into three-necked flask, to Anhydrous AlCl3After dissolution, mixed liquid B is added dropwise, reacts 2h~5h at room temperature, obtains reaction solution, reaction solution is then poured into ice In water, water layer CH2Cl2Extractant extracts 3 times, merges organic phase, uses anhydrous Na2SO4It dries, filters, solvent is evaporated off, use second Alcohol recrystallization, obtains ferrocene derivatives；
The anhydrous AlCl3Quality and anhydrous CH2Cl2Volume ratio be 1g:(10~100) mL；Described is anhydrous AlCl3Quality and mixed liquor A volume ratio be 1g:(10~100) mL；The anhydrous AlCl3Quality and mixed liquid B Volume ratio is 1g:(20~80) mL；
The mixed liquor A is chloroacetic chloride and anhydrous CH2Cl2Mixture, and chloroacetic chloride and nothing in the mixed liquor A Water CH2Cl2Volume ratio be 1:(10~50)；
The mixed liquid B is ferrocene and anhydrous CH2Cl2Mixture, and in the mixed liquid B ferrocene matter Amount and anhydrous CH2Cl2Volume ratio be 1g:(10~50) mL；
Three, the preparation of electric expansion colloidal crystal material:
The ITO that area is 1cm × 4cm is cleaned up, is 5%~50% by the ITO mass percent cleaned up Hydrogen peroxide and mass percent be 5%~30% the mixture of sulfuric acid impregnate 2h~for 24 hours, be then sonicated 30min~ Then 300min is washed with deionized and is dried with nitrogen, obtain pretreated ITO, is 200nm~1000nm's by partial size Monodisperse polystyrene microsphere is configured to the polystyrene microsphere solution that mass percent is 1%~10% with water, then ultrasonic Disperse 10min~100min, obtain Polystyrene suspension, by 10mL~100mL Polystyrene suspension, dropwise addition is being pre-processed On ITO afterwards, under conditions of spin coating instrument revolving speed is 100rpm~1000rpm, spin coating 10s~100s obtains colloidal crystal mould After dissolving ferrocene derivatives with EtOH Sonicate, it is molten to obtain the ferrocene derivatives that mass percent is 1%~10% for plate The ferrocene derivatives solution that the 10 μ L mass percents of μ L~500 are 1%~10% is added dropwise on colloidal crystal template liquid, Under conditions of spin coating instrument revolving speed is 100rpm~300rpm, spin coating 10s~50s, being subsequently placed in temperature is 30 DEG C~100 DEG C It is dry in incubator, obtain electric expansion colloidal crystal material；
The body for the sulfuric acid that the hydrogen peroxide and mass percent that the mass percent is 5%~50% are 5%~30% Product is than being 1:(3~5).
Ferrocene, the anhydrous AlCl selected in present embodiment3With anhydrous CH2Cl2Zeolite water removal decompression is all made of to steam After distillation is miscellaneous, sealing is stand-by.
The beneficial effect of present embodiment is: 1, entire technical process is simple, is not necessarily to special installation and technique；
2, because joined a certain amount of solution of ferrocene in film, film has excellent under the conditions of applying appropriate voltage Electrochromic property, color change interval is wide, reach the multi-color systems such as reddish yellow indigo plant discoloration, can be widely applied to biology, chemical sensor, Photoelectricity equipment etc..
The present invention polystyrene microsphere good using the emulsion polymerization preparation monodispersity of improvement, is then prepared into Colloid monolayer crystal template.Later using ferrocene as raw material, ferrocene derivatives molecule is synthesized using chemical method, is used ethyl alcohol It is filled into colloidal crystal template after completely dissolution, obtains electric expansion colloid crystal film after dry.Applying appropriate voltage feelings Under condition, ferrocene particle volume changes, and the lattice structure of colloidal crystal is made to change, and photon band gap changes to influence Entire colloid crystal film color change.The method simple process, it is reproducible, greatly widen answering for colloidal crystal material Use field.
Specific embodiment 2: the present embodiment is different from the first embodiment in that: benzene second described in step 1 The volume ratio of alkene and ultrapure water is 1:(50~100).It is other same as the specific embodiment one.
Specific embodiment 3: unlike one of present embodiment and specific embodiment one or two: institute in step 1 The volume ratio for the potassium persulfate solution that the styrene and mass percent stated are 1%~50% is 1:(0.02~0.1).It is other with Specific embodiment one or two is identical.
Specific embodiment 4: unlike one of present embodiment and specific embodiment one to three: institute in step 2 The anhydrous AlCl stated3Quality and anhydrous CH2Cl2Volume ratio be 1g:(20~100) mL.It is other with specific embodiment one to Three is identical.
Specific embodiment 5: unlike one of present embodiment and specific embodiment one to four: institute in step 2 The anhydrous AlCl stated3Quality and mixed liquor A volume ratio be 1g:(20~100) mL.Other and specific embodiment one to four It is identical.
Specific embodiment 6: unlike one of present embodiment and specific embodiment one to five: institute in step 2 The anhydrous AlCl stated3Quality and mixed liquid B volume ratio be 1g:(30~80) mL.Other and specific embodiment one to five It is identical.
Specific embodiment 7: unlike one of present embodiment and specific embodiment one to six: institute in step 2 The mixed liquor A stated is chloroacetic chloride and anhydrous CH2Cl2Mixture, and chloroacetic chloride and anhydrous CH in the mixed liquor A2Cl2's Volume ratio is 1:(20~50).It is other identical as specific embodiment one to six.
Specific embodiment 8: unlike one of present embodiment and specific embodiment one to seven: institute in step 2 The mixed liquid B stated is ferrocene and anhydrous CH2Cl2Mixture, and the quality of ferrocene and anhydrous in the mixed liquid B CH2Cl2Volume ratio be 1g:(20~50) mL.It is other identical as specific embodiment one to seven.
Specific embodiment 9: unlike one of present embodiment and specific embodiment one to eight: institute in step 3 The volume ratio for the sulfuric acid that the hydrogen peroxide and mass percent that the mass percent stated is 5%~50% are 5%~30% is 1: (3.5~5).It is other identical as specific embodiment one to eight.
Specific embodiment 10: unlike one of present embodiment and specific embodiment one to nine: will in step 3 The ferrocene derivatives solution that the 20 μ L mass percents of μ L~500 are 1%~10% is added dropwise on colloidal crystal template.It is other with Specific embodiment one to nine is identical.
The beneficial effect of present embodiment is:
Beneficial effects of the present invention are verified using following embodiment:
Embodiment one:
A kind of preparation method being powered swellable colloid crystal film is to sequentially include the following steps:
One, the preparation of monodisperse polystyrene microsphere:
Be added ultrapure water into three mouthfuls of reactors, open condensation cycle water, at the same using mechanical agitator to ultrapure water into Row stirring heats three mouthfuls of reactors to temperature 50 C with thermostatic water-circulator bath slot under conditions of revolving speed is 300rpm, then to Lead to nitrogen in three mouthfuls of reactors, styrene is added in three mouthfuls of reactors, adds quality percentage by the oxygen in removing system The potassium persulfate solution that number is 10% reacts 12h, obtains the monodisperse polystyrene microsphere that partial size is 210nm；
The volume ratio of the styrene and ultrapure water is 1:30；The mistake that the styrene and mass percent is 10% The volume ratio of potassium sulfate solution is 1:0.01；
Two, the synthesis of ferrocene derivatives:
By anhydrous AlCl3With anhydrous CH2Cl2It is added in three-necked flask, mixed liquor A is then added dropwise into three-necked flask, to Anhydrous AlCl3After dissolution, mixed liquid B is added dropwise, reacts 2h at room temperature, obtains reaction solution, then pour into reaction solution in ice water, The CH that water layer is 40mL with once used amount2Cl2Extractant extracts 3 times, merges organic phase, uses anhydrous Na2SO4It dries, filters, steams Except solvent obtains ferrocene derivatives with ethyl alcohol recrystallization；
The anhydrous AlCl3Quality and anhydrous CH2Cl2Volume ratio be 1g:10mL；The anhydrous AlCl3Matter The volume ratio of amount and mixed liquor A is 1g:10mL；The anhydrous AlCl3Quality and mixed liquid B volume ratio be 1g:20mL；
The mixed liquor A is chloroacetic chloride and anhydrous CH2Cl2Mixture, and chloroacetic chloride and nothing in the mixed liquor A Water CH2Cl2Volume ratio be 1:10；
The mixed liquid B is ferrocene and anhydrous CH2Cl2Mixture, and in the mixed liquid B ferrocene matter Amount and anhydrous CH2Cl2Volume ratio be 1g:10mL；
Three, the preparation of electric expansion colloidal crystal material:
The ITO that area is 1cm × 4cm is cleaned up, the dioxygen for being 10% by the ITO mass percent cleaned up The mixture for the sulfuric acid that water and mass percent are 20% impregnates for 24 hours, is then sonicated 30min, is then washed with deionized And be dried with nitrogen, pretreated ITO is obtained, the monodisperse polystyrene microsphere that partial size is 210nm is configured to quality with water The polystyrene microsphere solution that percentage is 1%, then ultrasonic disperse 10min, obtains Polystyrene suspension, by 10mL polyphenyl Ethylene suspension is added dropwise on ITO after the pre-treatment, and under conditions of spin coating instrument revolving speed is 100rpm, spin coating 10s obtains glue After dissolving ferrocene derivatives with EtOH Sonicate, it is molten to obtain the ferrocene derivatives that mass percent is 1% for body crystal template The ferrocene derivatives solution that 20 μ L mass percents are 1% is added dropwise on colloidal crystal template, is in spin coating instrument revolving speed by liquid Under conditions of 100rpm, spin coating 10s is subsequently placed in drying in the incubator that temperature is 30 DEG C, obtains electric expansion colloidal crystal material Material；
The volume ratio for the sulfuric acid that the hydrogen peroxide and mass percent that the mass percent is 10% are 20% is 1:3.
The ferrocene derivatives of the present embodiment step 2 preparation are red acicular crystal, yield 77.8%, m.p.126 ℃。
Comparative test one:
One, the synthesis of ferrocene derivatives:
By anhydrous AlCl3With anhydrous CH2Cl2It is added in three-necked flask, mixed liquor A is then added dropwise into three-necked flask, to Anhydrous AlCl3After dissolution, mixed liquid B is added dropwise, reacts 2h at room temperature, obtains reaction solution, then pour into reaction solution in ice water, The CH that water layer is 40mL with once used amount2Cl2Extractant extracts 3 times, merges organic phase, uses anhydrous Na2SO4It dries, filters, steams Except solvent obtains ferrocene derivatives with ethyl alcohol recrystallization；
The anhydrous AlCl3Quality and anhydrous CH2Cl2Volume ratio be 1g:10mL；The anhydrous AlCl3Matter The volume ratio of amount and mixed liquor A is 1g:10mL；The anhydrous AlCl3Quality and mixed liquid B volume ratio be 1g:20mL；
The mixed liquor A is chloroacetic chloride and anhydrous CH2Cl2Mixture, and chloroacetic chloride and nothing in the mixed liquor A Water CH2Cl2Volume ratio be 1:10；
The mixed liquid B is ferrocene and anhydrous CH2Cl2Mixture, and in the mixed liquid B ferrocene matter Amount and anhydrous CH2Cl2Volume ratio be 1g:10mL；
Two, the preparation of electric expansion colloidal crystal material:
The ITO that area is 1cm × 4cm is cleaned up, the dioxygen for being 10% by the ITO mass percent cleaned up The mixture for the sulfuric acid that water and mass percent are 20% impregnates for 24 hours, is then sonicated 30min, is then washed with deionized And be dried with nitrogen, pretreated ITO is obtained, after ferrocene derivatives are dissolved with EtOH Sonicate, obtaining mass percent is The ferrocene derivatives solution that 20 μ L mass percents are 1% is added dropwise after the pre-treatment 1% ferrocene derivatives solution On ITO, under conditions of spin coating instrument revolving speed is 100rpm, spin coating 10s is subsequently placed in drying in the incubator that temperature is 30 DEG C, Obtain pure ferrocene derivatives material；
The volume ratio for the sulfuric acid that the hydrogen peroxide and mass percent that the mass percent is 10% are 20% is 1:3.
Chemical property is tested using three-electrode system.Test uses 600 electrochemical workstation of Shanghai Chen Hua, with poly- carbonic acid Ester is solvent, and lithium perchlorate is solute, and compound concentration is the electrolyte of 0.01mol/L, is prepared respectively with comparative test one pure Electric expansion colloidal crystal material prepared by ferrocene derivatives material or embodiment one is working electrode, and platinum filament is to electrode, silver Silk is reference electrode, tests transmitance change curve.By a large amount of preliminary experiment, the electrochemical window that selects for -2.5V~ 2.5V, the electric expansion colloidal crystal that respectively prepared by the pure ferrocene derivatives material of one preparation of test comparison test and embodiment one Material coloured state and colour fading state are in the variation that wavelength is transmitance at 550nm.When wherein electrochemical window is -1V and 1V, respectively Electric expansion colloidal crystal material coloring prepared by the pure ferrocene derivatives material and embodiment one of one preparation of test comparison test State and colour fading state are in the variation that wavelength is transmitance at 550nm, as shown in Figure 4.
Embodiment two:
A kind of preparation method being powered swellable colloid crystal film is to sequentially include the following steps:
One, the preparation of monodisperse polystyrene microsphere:
Be added ultrapure water into three mouthfuls of reactors, open condensation cycle water, at the same using mechanical agitator to ultrapure water into To 80 DEG C of temperature, then row stirring heats three mouthfuls of reactors with thermostatic water-circulator bath slot under conditions of revolving speed is 3000rpm Lead to nitrogen into three mouthfuls of reactors, styrene is added in three mouthfuls of reactors, adds quality hundred by the oxygen in removing system The potassium persulfate solution that score is 10% reacts 48h, obtains the monodisperse polystyrene microsphere that partial size is 230nm；
The volume ratio of the styrene and ultrapure water is 1:100；The styrene and mass percent is 10% The volume ratio of potassium persulfate solution is 1:0.1；
Two, the synthesis of ferrocene derivatives:
By anhydrous AlCl3With anhydrous CH2Cl2It is added in three-necked flask, mixed liquor A is then added dropwise into three-necked flask, to Anhydrous AlCl3After dissolution, mixed liquid B is added dropwise, reacts 2h at room temperature, obtains reaction solution, then pour into reaction solution in ice water, The CH that water layer is 40mL with once used amount2Cl2Extractant extracts 3 times, merges organic phase, uses anhydrous Na2SO4It dries, filters, steams Except solvent obtains ferrocene derivatives with ethyl alcohol recrystallization；
The anhydrous AlCl3Quality and anhydrous CH2Cl2Volume ratio be 1g:100mL；The anhydrous AlCl3's The volume ratio of quality and mixed liquor A is 1g:100mL；The anhydrous AlCl3Quality and mixed liquid B volume ratio be 1g: 80mL；
The mixed liquor A is chloroacetic chloride and anhydrous CH2Cl2Mixture, and chloroacetic chloride and nothing in the mixed liquor A Water CH2Cl2Volume ratio be 1:50；
The mixed liquid B is ferrocene and anhydrous CH2Cl2Mixture, and in the mixed liquid B ferrocene matter Amount and anhydrous CH2Cl2Volume ratio be 1g:50mL；
Three, the preparation of electric expansion colloidal crystal material:
The ITO that area is 1cm × 4cm is cleaned up, the dioxygen for being 20% by the ITO mass percent cleaned up The mixture for the sulfuric acid that water and mass percent are 15% impregnates 12h, is then sonicated 50min, is then washed with deionized And be dried with nitrogen, pretreated ITO is obtained, the monodisperse polystyrene microsphere that partial size is 230nm is configured to quality with water The polystyrene microsphere solution that percentage is 10%, then ultrasonic disperse 100min, obtains Polystyrene suspension, by 100mL Polystyrene suspension is added dropwise on ITO after the pre-treatment, under conditions of spin coating instrument revolving speed is 1000rpm, spin coating 100s, Colloidal crystal template is obtained, after ferrocene derivatives are dissolved with EtOH Sonicate, obtains the ferrocene that mass percent is 10% The ferrocene derivatives solution that 50 μ L mass percents are 10% is added dropwise on colloidal crystal template, is revolving by derivative solution Instrument revolving speed is applied as under conditions of 300rpm, spin coating 50s is subsequently placed in drying in the incubator that temperature is 30 DEG C, obtains electric expansion Colloidal crystal material；
The volume ratio for the sulfuric acid that the hydrogen peroxide and mass percent that the mass percent is 20% are 15% is 1:5.
The ferrocene derivatives of the present embodiment step 2 preparation are red acicular crystal, yield 77.8%, m.p.126~ 128℃。
Chemical property is tested using three-electrode system.Test uses 600 electrochemical workstation of Shanghai Chen Hua, with poly- carbonic acid Ester is solvent, and lithium perchlorate is solute, and compound concentration is the electrolyte of 0.01mol/L, the electric expansion glue prepared with embodiment two Body crystalline material is working electrode, and platinum filament is to electrode, and filamentary silver is reference electrode, tests transmitance change curve.By a large amount of Preliminary experiment, the electrochemical window selected is -2V~2V, the electric expansion colloidal crystal material that respectively prepared by testing example two Color state and colour fading state are in the variation that wavelength is transmitance at 550nm, and test results are shown in figure 5.
Fig. 1 is the scanning electron microscope (SEM) photograph of the colloidal crystal template of one step 3 of embodiment preparation；As seen from the figure, the colloid obtained Crystal template is face-centred cubic structure, and the degree of order is high.
Fig. 2 is the scanning electron microscope (SEM) photograph of the ferrocene derivatives of two step 2 of embodiment preparation；As seen from the figure, pure ferrocene spreads out Biofilm compact structure, without obvious nanostructure.
Fig. 3 is the scanning electron microscope (SEM) photograph of the electric expansion colloidal crystal material of two step 3 of embodiment preparation；As seen from the figure, two cyclopentadienyl Iron derivant material is attached to Surfaces of Polystyrene Microparticles, and under the action of ferrocene derivatives, polystyrene microsphere it Between distance become larger, entire material have apparent nanostructure.
It is prepared by pure ferrocene derivatives material and embodiment one prepared by comparative test one at 550nm that Fig. 4, which is in wavelength, Electric expansion colloidal crystal material colour fading state and coloured state transmitance variation diagram, a be in the case where voltage is 1V, comparative test one make Standby pure ferrocene derivatives material colour fading state penetrates spectrum, and b is electric expansion colloid prepared by embodiment one in the case where voltage is 1V Crystalline material colour fading state penetrates spectrum, and c is the pure ferrocene derivatives material that in the case where voltage is -1V, prepared by comparative test one Color state penetrates spectrum, and d is that electric expansion colloidal crystal material coloured state prepared by embodiment one penetrates spectrum in the case where voltage is -1V. As seen from the figure, the transmitance variation of electric expansion colloidal crystal material has reached 38%, it is known that, under electrical field stimulation, ferrocene spreads out Volume expansion has occurred in biology, results in the movement of colloidal crystal bandgap center position, and sample generates the change of color, and film transmission rate becomes Change obvious.
It is the transmission at 550nm, under electric expansion colloidal crystal material different voltages prepared by embodiment two that Fig. 5, which is in wavelength, Rate variation diagram, 1 is 2V, and 2 be 1.5V, and 3 be 1V, and 4 be -0.5V, and 5 be -1V, and 6 be -1.5V, and 7 be -2V.As seen from the figure, in electrification Under conditions of window is -2V~2V, apparent change is had occurred in the transmitance of sample.Direction of an electric field from just toward it is negative when, sample Transmitance reduce, color gradually deepens, and illustrates that this electric expansion material is cathodic coloration.

Claims (10)

  1. The preparation method of swellable colloid crystal film 1. one kind can be powered, which is characterized in that sequentially include the following steps:
    One, the preparation of monodisperse polystyrene microsphere:
    Ultrapure water is added into three mouthfuls of reactors, opens condensation cycle water, while stirring ultrapure water using mechanical agitator Mix, revolving speed be 300rpm~3000rpm under conditions of, with thermostatic water-circulator bath slot heat three mouthfuls of reactors to temperature 50 C~ 100 DEG C, nitrogen is then led into three mouthfuls of reactors, styrene is added in three mouthfuls of reactors by the oxygen in removing system, then The potassium persulfate solution that mass percent is 1%~50% is added, reacts 12h~48h, obtaining partial size is 200nm~1000nm Monodisperse polystyrene microsphere；
    The volume ratio of the styrene and ultrapure water is 1:(30~100)；The styrene and mass percent be 1%~ The volume ratio of 50% potassium persulfate solution is 1:(0.01~0.1)；
    Two, the synthesis of ferrocene derivatives:
    By anhydrous AlCl3With anhydrous CH2Cl2It is added in three-necked flask, mixed liquor A is then added dropwise into three-necked flask, to anhydrous AlCl3After dissolution, mixed liquid B is added dropwise, reacts 2h~5h at room temperature, obtains reaction solution, then pour into reaction solution in ice water, Water layer CH2Cl2Extractant extracts 3 times, merges organic phase, uses anhydrous Na2SO4It dries, filters, solvent is evaporated off, tied again with ethyl alcohol Crystalline substance obtains ferrocene derivatives；
    The anhydrous AlCl3Quality and anhydrous CH2Cl2Volume ratio be 1g:(10~100) mL；The anhydrous AlCl3's The volume ratio of quality and mixed liquor A is 1g:(10~100) mL；The anhydrous AlCl3Quality and mixed liquid B volume ratio For 1g:(20~80) mL；
    The mixed liquor A is chloroacetic chloride and anhydrous CH2Cl2Mixture, and in the mixed liquor A chloroacetic chloride with it is anhydrous CH2Cl2Volume ratio be 1:(10~50)；
    The mixed liquid B is ferrocene and anhydrous CH2Cl2Mixture, and in the mixed liquid B quality of ferrocene and Anhydrous CH2Cl2Volume ratio be 1g:(10~50) mL；
    Three, the preparation of electric expansion colloidal crystal material:
    The ITO that area is 1cm × 4cm is cleaned up, pair for being 5%~50% by the ITO mass percent cleaned up The mixture immersion 2h for the sulfuric acid that oxygen water and mass percent are 5%~30%~for 24 hours, it is then sonicated 30min~300min, Then it is washed with deionized and is dried with nitrogen, obtain pretreated ITO, the monodisperse for being 200nm~1000nm by partial size Polystyrene microsphere is configured to the polystyrene microsphere solution that mass percent is 1%~10% with water, then ultrasonic disperse 10min~100min obtains Polystyrene suspension, and 10mL~100mL Polystyrene suspension is added dropwise after the pre-treatment On ITO, under conditions of spin coating instrument revolving speed is 100rpm~1000rpm, spin coating 10s~100s obtains colloidal crystal template, will After ferrocene derivatives are dissolved with EtOH Sonicate, the ferrocene derivatives solution that mass percent is 1%~10% is obtained, by 10 The ferrocene derivatives solution that the μ L mass percent of μ L~500 is 1%~10% is added dropwise on colloidal crystal template, in spin coating instrument Under conditions of revolving speed is 100rpm~300rpm, spin coating 10s~50s is subsequently placed in the incubator that temperature is 30 DEG C~100 DEG C It is dry, obtain the swellable colloid crystal film that can be powered；
    The volume ratio for the sulfuric acid that the hydrogen peroxide and mass percent that the mass percent is 5%~50% are 5%~30% For 1:(3~5).
  2. The preparation method of swellable colloid crystal film 2. one kind according to claim 1 can be powered, it is characterised in that step The volume ratio of styrene described in one and ultrapure water is 1:(50~100).
  3. The preparation method of swellable colloid crystal film 3. one kind according to claim 1 can be powered, it is characterised in that step The volume ratio for the potassium persulfate solution that styrene described in one and mass percent are 1%~50% is 1:(0.02~0.1).
  4. The preparation method of swellable colloid crystal film 4. one kind according to claim 1 can be powered, it is characterised in that step Anhydrous AlCl described in two3Quality and anhydrous CH2Cl2Volume ratio be 1g:(20~100) mL.
  5. The preparation method of swellable colloid crystal film 5. one kind according to claim 1 can be powered, it is characterised in that step Anhydrous AlCl described in two3Quality and mixed liquor A volume ratio be 1g:(20~100) mL.
  6. The preparation method of swellable colloid crystal film 6. one kind according to claim 1 can be powered, it is characterised in that step Anhydrous AlCl described in two3Quality and mixed liquid B volume ratio be 1g:(30~80) mL.
  7. The preparation method of swellable colloid crystal film 7. one kind according to claim 1 can be powered, it is characterised in that step Mixed liquor A described in two is chloroacetic chloride and anhydrous CH2Cl2Mixture, and in the mixed liquor A chloroacetic chloride with it is anhydrous CH2Cl2Volume ratio be 1:(20~50).
  8. The preparation method of swellable colloid crystal film 8. one kind according to claim 1 can be powered, it is characterised in that step Mixed liquid B described in two is ferrocene and anhydrous CH2Cl2Mixture, and in the mixed liquid B quality of ferrocene and Anhydrous CH2Cl2Volume ratio be 1g:(20~50) mL.
  9. The preparation method of swellable colloid crystal film 9. one kind according to claim 1 can be powered, it is characterised in that step The volume ratio for the sulfuric acid that the hydrogen peroxide and mass percent that mass percent described in three is 5%~50% are 5%~30% For 1:(3.5~5).
  10. The preparation method of swellable colloid crystal film 10. one kind according to claim 1 can be powered, it is characterised in that step The ferrocene derivatives solution that the 20 μ L mass percents of μ L~500 are 1%~10% is added dropwise on colloidal crystal template in three.
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CN101006373A (en) * 2003-12-05 2007-07-25 3M创新有限公司 Process for producing photonic crystals
CN101702060A (en) * 2009-11-05 2010-05-05 东南大学 Array type display component and preparation method thereof

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CN101006373A (en) * 2003-12-05 2007-07-25 3M创新有限公司 Process for producing photonic crystals
CN101702060A (en) * 2009-11-05 2010-05-05 东南大学 Array type display component and preparation method thereof

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