CN107759789A - A kind of polysilsesquioxane with electrochromic property and its preparation method and application - Google Patents
A kind of polysilsesquioxane with electrochromic property and its preparation method and application Download PDFInfo
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- CN107759789A CN107759789A CN201711030897.2A CN201711030897A CN107759789A CN 107759789 A CN107759789 A CN 107759789A CN 201711030897 A CN201711030897 A CN 201711030897A CN 107759789 A CN107759789 A CN 107759789A
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- 0 C*C1=CCCC=C1 Chemical compound C*C1=CCCC=C1 0.000 description 3
- OZVXBXKVMMIGDV-UHFFFAOYSA-N Cc(cc1)ccc1-[n]1c(cccc2)c2c2c1cccc2 Chemical compound Cc(cc1)ccc1-[n]1c(cccc2)c2c2c1cccc2 OZVXBXKVMMIGDV-UHFFFAOYSA-N 0.000 description 1
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
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Abstract
A kind of polysilsesquioxane with electrochromic property and its preparation method and application, it is related to a kind of polysilsesquioxane and preparation method thereof.Easily come off in organic solution the invention aims to solve existing thin polymer film, it is difficult to determine the problem of coloured under its electrochromic property and natural mode.A kind of molecular formula of the polysilsesquioxane with electrochromic property is Tn(OH)x(OR)y, T=RSiO1.5‑(x+y)/2n；Method：First, solution A is prepared；2nd, solution B is prepared；3rd, monomer is prepared；4th, it polymerize, obtains the polysilsesquioxane with electrochromic property.The color change of polysilsesquioxane with electrochromic property prepared by the present invention is obvious；Δ T (%) is larger, most of to be more than 40%, it was demonstrated that transmitance changes it is obvious that reflection color change is obvious.The present invention can obtain a kind of polysilsesquioxane with electrochromic property.
Description
Technical field
The present invention relates to a kind of polysilsesquioxane and preparation method thereof.
Background technology
Electrochromic material is to change people life style to have very much a new function material using future, and application field is wide
Wealthy, it will change understanding and Land use systems of the people to the energy, significant to national economy.Electrochromic material has knot
The features such as structure is controllable, rich in color, cost is cheap, low energy, it is current most one of intellectual material of application prospect.Due to
Electrochromic device has the spies such as optical property continuously adjustabe, low-work voltage, low-power consumption, radiationless, wide viewing angle, open circuit memory
Point, many countries are all in device of the development based on electrochromism phenomenon in recent years.Mainly there are electrochromic, electrochromism storage
Device, electrochromic display device (ECD), intelligent dimming automobile rearview mirror, electron beam printing technology and sensor, camouflage clothes etc..Polymerization
Thing electrochromic material is easy to modulate due to being easy to large area production, spectrum, and structure can flexibly be cut, thus by extensive
Concern.
Electrochromic material is broadly divided into inorganic electrochromic material and organic electrochromic material by material type.Nothing
Machine material is the electrochromic material being more early studied, and with color contrast is high, cyclical stability is high, adhesive force is strong and heat
The advantages that stability is high, caused by the change of its light absorbs is due to the Dual Implantations of ion and electronics and black soy sauce goes out.With without electromechanics
Off-color material is caused to compare, conducting polymer electrochromic material has abundant fast response time, color change, easy processing, easily divided
The advantages that son design and cheap cost, the change of its light absorbs come from redox reaction.Although conducting polymer electrochromism material
Material research is started late, but has become the focus of electrochromic material research field at present.But many electrochromism gather
Compound material has that film forming is difficult, and the problems such as easily come off in organic solvent after film forming, simultaneously as the reason for conjugation,
The application that deeper color directly limit conducting polymer electrochromic material is presented under natural mode.
The content of the invention
Easily come off in organic solution the invention aims to solve existing thin polymer film, it is difficult to it is electroluminescent to determine its
The problem of coloured under discoloration and natural mode, and a kind of polysilsesquioxane and its system with electrochromic property are provided
Preparation Method and application.
A kind of molecular formula of the polysilsesquioxane with electrochromic property is Tn(OH)x(OR)y；Described T=
RSiO1.5-[(x+y)/2n]；Described n >=4；Described x >=0；Described y >=0；A kind of poly- sesquialter silicon with electrochromic property
The structural formula of oxygen alkane is：
Wherein, described R is
A kind of preparation method of the polysilsesquioxane with electrochromic property, is specifically realized by the following steps：
First, 1., by an amino aniline derivative it is dissolved into DMF, then low whipping speed is 20r/
Stirring reaction 20min~40min under min~50r/min, obtains solution A；
Step 1 1. described in the quality of an amino aniline derivative and the volume ratio of N,N-dimethylformamide be (4g
~8g):100mL；
2nd, under nitrogen protection, into solution A add isocyanates propyl-triethoxysilicane, then be warming up to 50 DEG C~
70 DEG C, then under conditions of temperature is 50 DEG C~70 DEG C and mixing speed is 20r/min~50r/min stirring reaction 18h~
30h, obtain solution B；
The material of an amino aniline derivative and isocyanates propyl-triethoxysilicane in solution A described in step 2
Amount ratio be 1:2；
3rd, solution B is poured into petroleum ether, then stands 1h~3h, then taken out under conditions of vacuum is 0.09MPa
Filter, solid is collected, the solid of collection is put into vacuum drying oven, in vacuum be 0.09MPa and temperature is 50 DEG C~70 DEG C
Under the conditions of be dried in vacuo 6h~12h, produce monomer；
The volume ratio of solution B and petroleum ether described in step 3 is 1:(8~10)；
4th, 1., by the monomer obtained in step 3 be dissolved in tetrahydrofuran, then low whipping speed be 20r/min~
Stirring reaction 5min~10min under 50r/min, obtains solution C；
The quality of monomer described in step 4 and the volume ratio of tetrahydrofuran are (1g~5g):(50mL~150mL)；
2., into solution C be added dropwise concentration be 1mol/L hydrochloric acid, then temperature be 50 DEG C~70 DEG C at stirring reaction 18h
~30h, obtains solution D；
Step 4 2. described in concentration be 1mol/L hydrochloric acid and the volume ratio of solution C be (0.5~1):(50~
150)；
3., the potassium hydroxide aqueous solution that concentration is 1mol/L the pH value of solution D is adjusted to 8~10, then stirring
Speed is to be stirred under 50r/min~200r/min, until there is flocculent deposit, stops stirring；Obtain the molten of flocculent deposit occur
Liquid D；
4., the solution D that will appear from flocculent deposit pours into petroleum ether, then stands 1h~3h, then in vacuum be 0.09MPa
Under conditions of filtered, collect solid, solid will be collected and be put into vacuum drying oven, then in vacuum be 0.09MPa and temperature
To be dried in vacuo 6h~12h under conditions of 30 DEG C~50 DEG C, the polysilsesquioxane with electrochromic property is obtained；
Step 4 4. described in appearance flocculent deposit solution D and petroleum ether volume ratio be 1:(8~10).
Advantages of the present invention：
First, the polysilsesquioxane with electrochromic property prepared by the present invention is with good electrochemical redox
Invertibity；
2nd, the color change response time of the polysilsesquioxane with electrochromic property prepared by the present invention is fast；Profit
With the present invention obtain with electrochromic property polysilsesquioxane preparation polysilsesquioxane film coloration time with
It is shorter compared to other polymers coloring fading time and fading time is close to 3s；
3rd, the change of the polysilsesquioxane color with electrochromic property prepared by the present invention should be reversible；
4th, the color change of the polysilsesquioxane with electrochromic property prepared by the present invention is obvious；Δ T (%) compared with
Greatly, it is most of to be more than 40%, it was demonstrated that transmitance changes it is obvious that reflection color change is obvious；
5th, the polysilsesquioxane with electrochromic property prepared by the present invention has higher cycle life；
6th, the circle of the circulation of the polysilsesquioxane with electrochromic property 100 prepared by the present invention, electric current and transmitance
Do not change significantly, it was demonstrated that the polysilsesquioxane with electrochromic property prepared by the present invention is with good oxidation
Reduce invertibity；
7th, the polysilsesquioxane with electrochromic property prepared by the present invention has preferable chemical stability, because of it
Contain rigid radical phenyl ring, and inorganic silicon oxygen groups in structure, be not susceptible to react, chemical stability is good；
8th, the polysilsesquioxane dissolubility with electrochromic property that prepared by the present invention is good, spiral helicine triphenylamine
And the presence of flexible alkyl chains effectively reduces interchain interaction, raising moves freely volume, improves solubility；
9th, the polysilsesquioxane natural mode with electrochromic property prepared by the present invention is colourless.
The present invention can obtain a kind of polysilsesquioxane with electrochromic property.
Brief description of the drawings
Fig. 1 is infrared spectrogram, and 1 is the polysilsesquioxane with electrochromic property prepared by embodiment one in Fig. 1
Infrared spectrum curve, 2 be embodiment two prepare the polysilsesquioxanes with electrochromic property infrared spectrum curve,
3 be the infrared spectrum curve of the polysilsesquioxane with electrochromic property prepared by embodiment three, and 4 be the tool of example IV
There is the infrared spectrum curve of the polysilsesquioxane of electrochromic property；
Fig. 2 is thermogravimetric curve, and 1 is the polysilsesquioxane with electrochromic property prepared by embodiment one in Fig. 2
Thermogravimetric curve, 2 be embodiment two prepare the polysilsesquioxanes with electrochromic property thermogravimetric curve, 3 are
The thermogravimetric curve of polysilsesquioxane with electrochromic property prepared by embodiment three, 4 be tool prepared by example IV
There is the thermogravimetric curve of the polysilsesquioxane of electrochromic property；
Fig. 3 is poly- silsesquioxane prepared by the polysilsesquioxane with electrochromic property obtained using embodiment one
The cyclic voltammogram of alkane film；
Fig. 4 is poly- silsesquioxane prepared by the polysilsesquioxane with electrochromic property obtained using embodiment two
The cyclic voltammogram of alkane film；
Fig. 5 is poly- silsesquioxane prepared by the polysilsesquioxane with electrochromic property obtained using embodiment three
The cyclic voltammogram of alkane film；
Fig. 6 is poly- silsesquioxane prepared by the polysilsesquioxane with electrochromic property obtained using example IV
The cyclic voltammogram of alkane film；
Fig. 7 is poly- silsesquioxane prepared by the polysilsesquioxane with electrochromic property obtained using embodiment one
The uv atlas of alkane film, 1 is 0V in Fig. 7, and 2 be 1V, and 3 be 1.25V, and 4 be 1.75V；
Fig. 8 is poly- silsesquioxane prepared by the polysilsesquioxane with electrochromic property obtained using embodiment two
The uv atlas of alkane film, 1 is 0V in Fig. 8, and 2 be 1.1V, and 3 be 1.3V, and 4 be 1.55V, and 5 be 1.85V；
Fig. 9 is poly- silsesquioxane prepared by the polysilsesquioxane with electrochromic property obtained using embodiment three
The uv atlas of alkane film, 1 is 0V in Fig. 9, and 2 be 0.5V, and 3 be 1.1V, and 4 be 1.5V；
Figure 10 is poly- sesquialter silicon prepared by the polysilsesquioxane with electrochromic property obtained using example IV
The uv atlas of oxygen alkane film, 1 is 0V in Figure 10, and 2 be 1.05V, and 3 be 1.4V, and 4 be 1.6V；
Figure 11 is that absorbance-curent change of the polysilsesquioxane with electrochromic property prepared by embodiment one is bent
Line；
Figure 12 is that absorbance-curent change of the polysilsesquioxane with electrochromic property prepared by embodiment two is bent
Line；
Figure 13 is that absorbance-curent change of the polysilsesquioxane with electrochromic property prepared by embodiment three is bent
Line；
Figure 14 is that absorbance-curent change of the polysilsesquioxane with electrochromic property prepared by example IV is bent
Line.
Embodiment
Embodiment one：Present embodiment is a kind of molecular formula of the polysilsesquioxane with electrochromic property
For Tn(OH)x(OR)y；Described T=RSiO1.5-[(x+y)/2n]；Described n >=4；Described x >=0；Described y >=0；One kind tool
The structural formula for having the polysilsesquioxane of electrochromic property is：
Wherein, described R is
Embodiment two：Present embodiment is a kind of preparation side of the polysilsesquioxane with electrochromic property
Method, it is specifically realized by the following steps：
First, 1., by an amino aniline derivative it is dissolved into DMF, then low whipping speed is 20r/
Stirring reaction 20min~40min under min~50r/min, obtains solution A；
Step 1 1. described in the quality of an amino aniline derivative and the volume ratio of N,N-dimethylformamide be (4g
~8g):100mL；
2nd, under nitrogen protection, into solution A add isocyanates propyl-triethoxysilicane, then be warming up to 50 DEG C~
70 DEG C, then under conditions of temperature is 50 DEG C~70 DEG C and mixing speed is 20r/min~50r/min stirring reaction 18h~
30h, obtain solution B；
The material of an amino aniline derivative and isocyanates propyl-triethoxysilicane in solution A described in step 2
Amount ratio be 1:2；
3rd, solution B is poured into petroleum ether, then stands 1h~3h, then taken out under conditions of vacuum is 0.09MPa
Filter, solid is collected, the solid of collection is put into vacuum drying oven, in vacuum be 0.09MPa and temperature is 50 DEG C~70 DEG C
Under the conditions of be dried in vacuo 6h~12h, produce monomer；
The volume ratio of solution B and petroleum ether described in step 3 is 1:(8~10)；
4th, 1., by the monomer obtained in step 3 be dissolved in tetrahydrofuran, then low whipping speed be 20r/min~
Stirring reaction 5min~10min under 50r/min, obtains solution C；
The quality of monomer described in step 4 and the volume ratio of tetrahydrofuran are (1g~5g):(50mL~150mL)；
2., into solution C be added dropwise concentration be 1mol/L hydrochloric acid, then temperature be 50 DEG C~70 DEG C at stirring reaction 18h
~30h, obtains solution D；
Step 4 2. described in concentration be 1mol/L hydrochloric acid and the volume ratio of solution C be (0.5~1):(50~
150)；
3., the potassium hydroxide aqueous solution that concentration is 1mol/L the pH value of solution D is adjusted to 8~10, then stirring
Speed is to be stirred under 50r/min~200r/min, until there is flocculent deposit, stops stirring；Obtain the molten of flocculent deposit occur
Liquid D；
4., the solution D that will appear from flocculent deposit pours into petroleum ether, then stands 1h~3h, then in vacuum be 0.09MPa
Under conditions of filtered, collect solid, solid will be collected and be put into vacuum drying oven, then in vacuum be 0.09MPa and temperature
To be dried in vacuo 6h~12h under conditions of 30 DEG C~50 DEG C, the polysilsesquioxane with electrochromic property is obtained；
Step 4 4. described in appearance flocculent deposit solution D and petroleum ether volume ratio be 1:(8~10).
The advantages of present embodiment：
First, the polysilsesquioxane with electrochromic property prepared by present embodiment is with good electrochemical oxidation
Reduce invertibity；
2nd, the color change response time of the polysilsesquioxane with electrochromic property prepared by present embodiment
It hurry up；Polysilsesquioxane film prepared by the polysilsesquioxane with electrochromic property obtained using present embodiment
Color time and fading time are shorter compared to other polymers coloring fading time close to 3s；
3rd, the change of the polysilsesquioxane color with electrochromic property prepared by present embodiment should be reversible
's；
4th, the color change of the polysilsesquioxane with electrochromic property prepared by present embodiment is obvious；ΔT
(%) is larger, most of to be more than 40%, it was demonstrated that transmitance changes it is obvious that reflection color change is obvious；
5th, the polysilsesquioxane with electrochromic property prepared by present embodiment has higher cycle life；
6th, the circle of the circulation of the polysilsesquioxane with electrochromic property 100 prepared by present embodiment, electric current and saturating
Cross rate not change significantly, it was demonstrated that the polysilsesquioxane with electrochromic property for preparing of the present invention is with well
Redox reversible；
7th, the polysilsesquioxane with electrochromic property prepared by present embodiment has preferable chemical stability,
Because containing rigid radical phenyl ring, and inorganic silicon oxygen groups in its structure, it is not susceptible to react, chemical stability is good；
8th, the polysilsesquioxane dissolubility with electrochromic property that prepared by present embodiment is good, and spiral helicine three
The presence of aniline and flexible alkyl chains effectively reduces interchain interaction, and raising moves freely volume, improves solubility；
9th, the polysilsesquioxane natural mode with electrochromic property prepared by present embodiment is colourless.
Present embodiment can obtain a kind of polysilsesquioxane with electrochromic property.
Embodiment three：The difference of present embodiment and embodiment two is：Step 1 1. described in
One amino aniline derivative is 4- amino-triphenylamine, 9- (4- aminophenyls) carbazole, 4- aminophenyl-N- phenthazine or N- (2
(9,9- dimethyl -9H- fluorenes))-N- phenyl-pphenylenediamines.Other steps are identical with embodiment two.
Embodiment four：Present embodiment is with one of embodiment two to three difference：Described 4- ammonia
The structural formula of base-triphenylamine isSpecific preparation method is as follows：
First, in a nitrogen atmosphere, diphenylamines, p-fluoronitrobenzene and NaH are added in dimethyl sulfoxide (DMSO), then are in temperature
100 DEG C~110 DEG C are back flow reaction 15h~18h under 100r/min~300r/min with mixing speed, obtain reaction product I；Will
Reaction product I is sunk in saturated aqueous common salt, then is filtered, and the solid matter that suction filtration obtains is dried, reused anhydrous
Ethyl alcohol recrystallization, obtain product II；
The quality of diphenylamines described in step 1 and the volume ratio of dimethyl sulfoxide (DMSO) are (4g~8g):(70mL~
100mL)；
The quality of p-fluoronitrobenzene described in step 1 and the volume ratio of dimethyl sulfoxide (DMSO) are (2g~5g):(70mL~
100mL)；
The quality of NaH described in step 1 and the volume ratio of dimethyl sulfoxide (DMSO) are (0.5g~2g):(70mL~
100mL)；
2nd, product II is added in absolute ethyl alcohol, adds Pd/C catalyst and hydrazine hydrate, then temperature be 70 DEG C~
Reductase 12 0h~28h at 90 DEG C, obtains product III；Product III is sunk in saturated aqueous common salt, then filtered, will be filtrated to get
Solid matter be dried, reuse absolute ethyl alcohol and recrystallized, obtain 4- amino-triphenylamine；
The quality of product II described in step 2 and the volume ratio of absolute ethyl alcohol are (5g~10g):(80mL~
150mL)；
The mass ratio of product II and Pd/C catalyst described in step 2 is (5~10):(0.5~1)；
The mass ratio of product II and hydrazine hydrate described in step 2 is (5~10):(10~14).Other steps with it is specific
Embodiment two to three is identical.
Embodiment five：Present embodiment is with one of embodiment two to four difference：Described 9- (4-
Aminophenyl) structural formula of carbazole isSpecific preparation method is as follows：
First, in a nitrogen atmosphere, carbazole, p-fluoronitrobenzene and NaH are added in dimethyl sulfoxide (DMSO), then are in temperature
100 DEG C~110 DEG C are back flow reaction 15h~18h under 100r/min~300r/min with mixing speed, obtain reaction product I；Will
Reaction product I is sunk in saturated aqueous common salt, then is filtered, and the solid matter that suction filtration obtains is dried, reused anhydrous
Ethyl alcohol recrystallization, obtain product II；
The quality of carbazole described in step 1 and the volume ratio of dimethyl sulfoxide (DMSO) are (4g~8g):(70mL~100mL)；
The quality of p-fluoronitrobenzene described in step 1 and the volume ratio of dimethyl sulfoxide (DMSO) are (2g~5g):(70mL~
100mL)；
The quality of NaH described in step 1 and the volume ratio of dimethyl sulfoxide (DMSO) are (0.5g~2g):(70mL~
100mL)；
2nd, product II is added in absolute ethyl alcohol, adds Pd/C catalyst and hydrazine hydrate, then temperature be 70 DEG C~
Reductase 12 0h~28h at 90 DEG C, obtains product III；Product III is sunk in saturated aqueous common salt, then filtered, will be filtrated to get
Solid matter be dried, reuse absolute ethyl alcohol and recrystallized, obtain 9- (4- aminophenyls) carbazole；
The quality of product II described in step 2 and the volume ratio of absolute ethyl alcohol are (5g~10g):(80mL~
150mL)；
The mass ratio of product II and Pd/C catalyst described in step 2 is (5~10):(0.5~1)；
The mass ratio of product II and hydrazine hydrate described in step 2 is (5~10):(10~14).Other steps with it is specific
Embodiment two to four is identical.
Embodiment six：Present embodiment is with one of embodiment two to five difference：Described 4- ammonia
The structural formula of base phenyl-N- phenthazine isSpecific preparation method is as follows：
First, in a nitrogen atmosphere, phenthazine, p-fluoronitrobenzene and NaH are added in dimethyl sulfoxide (DMSO), then are in temperature
100 DEG C~110 DEG C are back flow reaction 15h~18h under 100r/min~300r/min with mixing speed, obtain reaction product I；Will
Reaction product I is sunk in saturated aqueous common salt, then is filtered, and the solid matter that suction filtration obtains is dried, reused anhydrous
Ethyl alcohol recrystallization, obtain product II；
The quality of phenthazine described in step 1 and the volume ratio of dimethyl sulfoxide (DMSO) are (4g~8g):(70mL~
100mL)；
The quality of p-fluoronitrobenzene described in step 1 and the volume ratio of dimethyl sulfoxide (DMSO) are (2g~5g):(70mL~
100mL)；
The quality of NaH described in step 1 and the volume ratio of dimethyl sulfoxide (DMSO) are (0.5g~2g):(70mL~
100mL)；
2nd, product II is added in absolute ethyl alcohol, adds Pd/C catalyst and hydrazine hydrate, then temperature be 70 DEG C~
Reductase 12 0h~28h at 90 DEG C, obtains product III；Product III is sunk in saturated aqueous common salt, then filtered, will be filtrated to get
Solid matter be dried, reuse absolute ethyl alcohol and recrystallized, obtain 4- aminophenyl-N- phenthazine；
The quality of product II described in step 2 and the volume ratio of absolute ethyl alcohol are (5g~10g):(80mL~
150mL)；
The mass ratio of product II and Pd/C catalyst described in step 2 is (5~10):(0.5~1)；
The mass ratio of product II and hydrazine hydrate described in step 2 is (5~10):(10~14).Other steps with it is specific
Embodiment two to five is identical.
Embodiment seven：Present embodiment is with one of embodiment two to six difference：Described N- (2
(9,9- dimethyl -9H- fluorenes)) structural formula of-N- phenyl-pphenylenediamines isSpecific preparation side
Method is as follows：
First, in a nitrogen atmosphere, N- phenyl -2 (9,9- dimethyl -9H- fluorenes) amine, p-fluoronitrobenzene and NaH is added to
In dimethyl sulfoxide (DMSO), then the back flow reaction in the case where temperature is 100 DEG C~110 DEG C and mixing speed is 100r/min~300r/min
15h~18h, obtain reaction product I；Reaction product I is sunk in saturated aqueous common salt, then filtered, is consolidated what suction filtration obtained
Body material is dried, and reuses absolute ethyl alcohol recrystallization, obtains product II；
(9,9- dimethyl -9H- fluorenes) quality of amine of N- phenyl -2 and the volume ratio of dimethyl sulfoxide (DMSO) described in step 1
For (4g~8g):(70mL~100mL)；
The quality of p-fluoronitrobenzene described in step 1 and the volume ratio of dimethyl sulfoxide (DMSO) are (2g~5g):(70mL~
100mL)；
The quality of NaH described in step 1 and the volume ratio of dimethyl sulfoxide (DMSO) are (0.5g~2g):(70mL~
100mL)；
2nd, product II is added in absolute ethyl alcohol, adds Pd/C catalyst and hydrazine hydrate, then temperature be 70 DEG C~
Reductase 12 0h~28h at 90 DEG C, obtains product III；Product III is sunk in saturated aqueous common salt, then filtered, will be filtrated to get
Solid matter be dried, reuse absolute ethyl alcohol and recrystallized, obtain N- (2 (9,9- dimethyl -9H- fluorenes))-N- benzene
Base-p-phenylenediamine；
The quality of product II described in step 2 and the volume ratio of absolute ethyl alcohol are (5g~10g):(80mL~
150mL)；
The mass ratio of product II and Pd/C catalyst described in step 2 is (5~10):(0.5~1)；
The mass ratio of product II and hydrazine hydrate described in step 2 is (5~10):(10~14).Other steps with it is specific
Embodiment two to six is identical.
Embodiment eight：Present embodiment is with one of embodiment two to seven difference：In step 2
Under nitrogen protection, isocyanates propyl-triethoxysilicane is added into solution A, then is warming up to 60 DEG C, then in temperature be 60 DEG C
Stirring reaction 18h~24h under conditions of being 30r/min~50r/min with mixing speed, obtains solution B.Other steps with it is specific
Embodiment two to seven is identical.
Embodiment nine：Present embodiment is with one of embodiment two to eight difference：Step 4 2. in
The hydrochloric acid that concentration is 1mol/L is added dropwise into solution C, then distilled water is added dropwise, then stirring reaction 18h at being 60 DEG C in temperature~
24h, obtain solution D.Other steps are identical with embodiment two to eight.
Embodiment ten：Present embodiment is with one of embodiment two to nine difference：One kind has electricity
The polysilsesquioxane of discoloration is caused to be applied as electrochromic material in smart window.Other steps and embodiment
Two to nine is identical.
Beneficial effects of the present invention are verified using following examples：
Embodiment one：A kind of preparation method of the polysilsesquioxane with electrochromic property, specifically by following step
Suddenly complete：
First, 4- amino-triphenylamine is prepared：
In a nitrogen atmosphere, 5.96g diphenylamines, 4.1716g p-fluoronitrobenzenes and 1.4g NaH are added to 70mL diformazans
In base sulfoxide, then the back flow reaction 17h in the case where temperature is 110 DEG C and mixing speed is 200r/min, obtain reaction product I；Will be anti-
Answer product I to sink in saturated aqueous common salt, then filtered, the solid matter that suction filtration obtains is dried, reuses anhydrous second
Alcohol recrystallizes, and obtains product II；
2nd, 7g products II are added in 100mL absolute ethyl alcohols, add 1g Pd/C catalyst and 12g hydrazine hydrates, then
Reductase 12 4h at being 80 DEG C in temperature, obtains product III；Product III is sunk in saturated aqueous common salt, then filtered, will be filtered
To solid matter be dried, reuse absolute ethyl alcohol and recrystallized, obtain 4- amino-triphenylamine；
3rd, 1., by 5.1g 4- amino-triphenylamine it is dissolved into 100mL DMFs, then low whipping speed
For stirring reaction 30min under 50r/min, solution A is obtained；
4th, under nitrogen protection, isocyanates propyl-triethoxysilicane is added into solution A, then is warming up to 60 DEG C, then
Stirring reaction 24h under conditions of being 60 DEG C and mixing speed 50r/min in temperature, obtains solution B；
4- amino-triphenylamine and the material of isocyanates propyl-triethoxysilicane in solution A described in step 4
Amount is than being 1:2；
5th, solution B is poured into petroleum ether, then stands 2h, then filtered under conditions of vacuum is 0.09MPa,
Solid is collected, the solid of collection is put into vacuum drying oven, the vacuum under conditions of vacuum is 0.09MPa and temperature is 60 DEG C
10h is dried, produces monomer；
The volume ratio of solution B and petroleum ether described in step 5 is 1:10；
6th, 1., by the monomer obtained in 1g step 3 it is dissolved in 60mL tetrahydrofurans, then low whipping speed is 50r/
Stirring reaction 10min under min, obtains solution C；
2., into 60mL solution Cs be added dropwise concentration be 0.6mL 1mol/L hydrochloric acid, then temperature be 60 DEG C at stirring reaction
24h, obtain solution D；
3., concentration be 1mol/L potassium hydroxide aqueous solution the pH value of solution D is adjusted to 9, then low whipping speed
To be stirred under 100r/min, until there is flocculent deposit, stop stirring；Obtain the solution D for flocculent deposit occur；
4., the solution D that will appear from flocculent deposit pour into petroleum ether, then stand 2h, then in the bar that vacuum is 0.09MPa
Filtered under part, collect solid, solid will be collected and be put into vacuum drying oven, then be 0.09MPa in vacuum and temperature is 50
10h is dried in vacuo under conditions of DEG C, obtains the polysilsesquioxane with electrochromic property；
Step 6 4. described in appearance flocculent deposit solution D and petroleum ether volume ratio be 1:10.
The structural formula of 4- amino-triphenylamine described in the step 2 of embodiment one is
The synthetic reaction formula of monomer is in the step 5 of embodiment one：
The polymerisation formula of the polysilsesquioxane with electrochromic property is in embodiment one：
The molecular formula of the polysilsesquioxane with electrochromic property is T in embodiment onen(OH)x(OR)y；Described T=
RSiO1.5-[(x+y)/2n], structural formula isn≥4；x≥
0；y≥0.
Embodiment two：A kind of preparation method of the polysilsesquioxane with electrochromic property, specifically by following step
Suddenly complete：
First, 9- (4- aminophenyls) carbazole is prepared：
In a nitrogen atmosphere, 5.84g carbazoles, 4.1716g p-fluoronitrobenzenes and 1.4g NaH are added to 70mL dimethyl
In sulfoxide, then the back flow reaction 17h in the case where temperature is 110 DEG C and mixing speed is 200r/min, obtain reaction product I；Will reaction
Product I is sunk in saturated aqueous common salt, then is filtered, and the solid matter that suction filtration obtains is dried, reuses absolute ethyl alcohol
Recrystallization, obtains product II；
2nd, 6.95g products II are added in 100mL absolute ethyl alcohols, add 1g Pd/C catalyst and 12g hydrazine hydrates,
Reductase 12 4h at being again 80 DEG C in temperature, obtains product III；Product III is sunk in saturated aqueous common salt, then filtered, will be filtered
Obtained solid matter is dried, and reuses absolute ethyl alcohol and is recrystallized, and obtains 9- (4- aminophenyls) carbazole；
3rd, 1., by 5.1g 9- (4- aminophenyls) carbazole it is dissolved into 100mL DMFs, then is stirring
Speed is mixed as stirring reaction 30min under 50r/min, obtains solution A；
4th, under nitrogen protection, isocyanates propyl-triethoxysilicane is added into solution A, then is warming up to 60 DEG C, then
Stirring reaction 24h under conditions of being 60 DEG C and mixing speed 50r/min in temperature, obtains solution B；
The thing of 9- (4- aminophenyls) carbazoles and isocyanates propyl-triethoxysilicane in solution A described in step 4
The amount ratio of matter is 1:2；
5th, solution B is poured into petroleum ether, then stands 2h, then filtered under conditions of vacuum is 0.09MPa,
Solid is collected, the solid of collection is put into vacuum drying oven, the vacuum under conditions of vacuum is 0.09MPa and temperature is 60 DEG C
10h is dried, produces monomer；
The volume ratio of solution B and petroleum ether described in step 5 is 1:10；
6th, 1., by the monomer obtained in 1g step 3 it is dissolved in 60mL tetrahydrofurans, then low whipping speed is 50r/
Stirring reaction 10min under min, obtains solution C；
2., into 60mL solution Cs be added dropwise concentration be 0.6mL 1mol/L hydrochloric acid, then temperature be 60 DEG C at stirring reaction
24h, obtain solution D；
3., concentration be 1mol/L potassium hydroxide aqueous solution the pH value of solution D is adjusted to 9, then low whipping speed
To be stirred under 100r/min, until there is flocculent deposit, stop stirring；Obtain the solution D for flocculent deposit occur；
4., the solution D that will appear from flocculent deposit pour into petroleum ether, then stand 2h, then in the bar that vacuum is 0.09MPa
Filtered under part, collect solid, solid will be collected and be put into vacuum drying oven, then be 0.09MPa in vacuum and temperature is 50
10h is dried in vacuo under conditions of DEG C, obtains the polysilsesquioxane with electrochromic property；
Step 6 4. described in appearance flocculent deposit solution D and petroleum ether volume ratio be 1:10.
The structural formula of 9- (4- aminophenyls) carbazole described in the step 2 of embodiment two is
The synthetic reaction formula of monomer is in the step 5 of embodiment two：
The polymerisation formula of the polysilsesquioxane with electrochromic property is in embodiment two：
The molecular formula of the polysilsesquioxane with electrochromic property is T in embodiment twon(OH)x(OR)y；Described T
=RSiO1.5-[(x+y)/2n], structural formula isn≥4x≥0；y
≥0。
Embodiment three：A kind of preparation method of the polysilsesquioxane with electrochromic property, specifically by following step
Suddenly complete：
First, 4- aminophenyl-N- phenthazine is prepared：
In a nitrogen atmosphere, 5.96g phenthazine, 4.1716g p-fluoronitrobenzenes and 1.4g NaH are added to 70mL diformazans
In base sulfoxide, then the back flow reaction 17h in the case where temperature is 110 DEG C and mixing speed is 200r/min, obtain reaction product I；Will be anti-
Answer product I to sink in saturated aqueous common salt, then filtered, the solid matter that suction filtration obtains is dried, reuses anhydrous second
Alcohol recrystallizes, and obtains product II；
2nd, 6.95g products II are added in 100mL absolute ethyl alcohols, add 1g Pd/C catalyst and 12g hydrazine hydrates,
Reductase 12 4h at being again 80 DEG C in temperature, obtains product III；Product III is sunk in saturated aqueous common salt, then filtered, will be filtered
Obtained solid matter is dried, and reuses absolute ethyl alcohol and is recrystallized, and obtains 4- aminophenyl-N- phenthazine；
3rd, 1., by 5.1g 4- aminophenyl-N- phenthazine it is dissolved into 100mL DMFs, then is stirring
Speed is mixed as stirring reaction 30min under 50r/min, obtains solution A；
4th, under nitrogen protection, isocyanates propyl-triethoxysilicane is added into solution A, then is warming up to 60 DEG C, then
Stirring reaction 24h under conditions of being 60 DEG C and mixing speed 50r/min in temperature, obtains solution B；
4- aminophenyls-N- phenthazine and isocyanates propyl-triethoxysilicane in solution A described in step 4
The amount ratio of material is 1:2；
5th, solution B is poured into petroleum ether, then stands 2h, then filtered under conditions of vacuum is 0.09MPa,
Solid is collected, the solid of collection is put into vacuum drying oven, the vacuum under conditions of vacuum is 0.09MPa and temperature is 60 DEG C
10h is dried, produces monomer；
The volume ratio of solution B and petroleum ether described in step 5 is 1:10；
6th, 1., by the monomer obtained in 1g step 3 it is dissolved in 60mL tetrahydrofurans, then low whipping speed is 50r/
Stirring reaction 10min under min, obtains solution C；
2., into 60mL solution Cs be added dropwise concentration be 0.6mL 1mol/L hydrochloric acid, then temperature be 60 DEG C at stirring reaction
24h, obtain solution D；
3., concentration be 1mol/L potassium hydroxide aqueous solution the pH value of solution D is adjusted to 9, then low whipping speed
To be stirred under 100r/min, until there is flocculent deposit, stop stirring；Obtain the solution D for flocculent deposit occur；
4., the solution D that will appear from flocculent deposit pour into petroleum ether, then stand 2h, then in the bar that vacuum is 0.09MPa
Filtered under part, collect solid, solid will be collected and be put into vacuum drying oven, then be 0.09MPa in vacuum and temperature is 50
10h is dried in vacuo under conditions of DEG C, obtains the polysilsesquioxane with electrochromic property；
Step 6 4. described in appearance flocculent deposit solution D and petroleum ether volume ratio be 1:10.
The structural formula of 4- amino-triphenylamine described in the step 2 of embodiment three is the knot of 4- aminophenyl-N- phenthazine
Structure formula is：
The synthetic reaction formula of monomer is in the step 5 of embodiment three：
The polymerisation formula of the polysilsesquioxane with electrochromic property is in embodiment three：
The molecular formula of the polysilsesquioxane with electrochromic property is T in embodiment threen(OH)x(OR)y；Described T
=RSiO1.5-[(x+y)/2n], structural formula is
n≥4；x≥0；y≥0.
Example IV：A kind of preparation method of the polysilsesquioxane with electrochromic property, specifically by following step
Suddenly complete：
First, N- (2 (9,9- dimethyl -9H- fluorenes))-N- phenyl-pphenylenediamines are prepared：
In a nitrogen atmosphere, by 5.71g N- phenyl -2 (9,9- dimethyl -9H- fluorenes) amine, 4.1716g p-fluoronitrobenzenes and
1.4g NaH are added in 70mL dimethyl sulfoxide (DMSO)s, then the back flow reaction in the case where temperature is 110 DEG C and mixing speed is 200r/min
17h, obtain reaction product I；Reaction product I is sunk in saturated aqueous common salt, then filtered, the solid matter that suction filtration is obtained
It is dried, reuses absolute ethyl alcohol recrystallization, obtain product II；
2nd, 6.95g products II are added in 100mL absolute ethyl alcohols, add 1g Pd/C catalyst and 12g hydrazine hydrates,
Reductase 12 4h at being again 80 DEG C in temperature, obtains product III；Product III is sunk in saturated aqueous common salt, then filtered, will be filtered
Obtained solid matter is dried, and reuses absolute ethyl alcohol and is recrystallized, obtain N- (2 (9,9- dimethyl -9H- fluorenes)) -
N- phenyl-pphenylenediamines；
3rd, 100mL N, N- 1., by 5.1g N- (2 (9,9- dimethyl -9H- fluorenes))-N- phenyl-pphenylenediamines are dissolved into
In dimethylformamide, then low whipping speed is stirring reaction 30min under 50r/min, obtains solution A；
4th, under nitrogen protection, isocyanates propyl-triethoxysilicane is added into solution A, then is warming up to 60 DEG C, then
Stirring reaction 24h under conditions of being 60 DEG C and mixing speed 50r/min in temperature, obtains solution B；
N- (2 (9,9- dimethyl -9H- fluorenes))-N- phenyl-pphenylenediamines and isocyanic acid in solution A described in step 4
The amount ratio of the material of ester propyl-triethoxysilicane is 1:2；
5th, solution B is poured into petroleum ether, then stands 2h, then filtered under conditions of vacuum is 0.09MPa,
Solid is collected, the solid of collection is put into vacuum drying oven, the vacuum under conditions of vacuum is 0.09MPa and temperature is 60 DEG C
10h is dried, produces monomer；
The volume ratio of solution B and petroleum ether described in step 5 is 1:10；
6th, 1., by the monomer obtained in 1g step 3 it is dissolved in 60mL tetrahydrofurans, then low whipping speed is 50r/
Stirring reaction 10min under min, obtains solution C；
2., into 60mL solution Cs be added dropwise concentration be 0.6mL 1mol/L hydrochloric acid, then temperature be 60 DEG C at stirring reaction
24h, obtain solution D；
3., concentration be 1mol/L potassium hydroxide aqueous solution the pH value of solution D is adjusted to 9, then low whipping speed
To be stirred under 100r/min, until there is flocculent deposit, stop stirring；Obtain the solution D for flocculent deposit occur；
4., the solution D that will appear from flocculent deposit pour into petroleum ether, then stand 2h, then in the bar that vacuum is 0.09MPa
Filtered under part, collect solid, solid will be collected and be put into vacuum drying oven, then be 0.09MPa in vacuum and temperature is 50
10h is dried in vacuo under conditions of DEG C, obtains the polysilsesquioxane with electrochromic property；
Step 6 4. described in appearance flocculent deposit solution D and petroleum ether volume ratio be 1:10.
The structural formula of N- (2 (9,9- dimethyl -9H- fluorenes))-N- phenyl-pphenylenediamines described in example IV step 2
For
The synthetic reaction formula of monomer is in example IV step 5：
The polymerisation formula of the polysilsesquioxane with electrochromic property is in example IV：
The molecular formula of the polysilsesquioxane with electrochromic property is T in example IVn(OH)x(OR)y；Described T=
RSiO1.5-[(x+y)/2n], structural formula is
n≥4；x≥0；y≥0.
Fig. 1 is infrared spectrogram, and 1 is the polysilsesquioxane with electrochromic property prepared by embodiment one in Fig. 1
Infrared spectrum curve, 2 be embodiment two prepare the polysilsesquioxanes with electrochromic property infrared spectrum curve,
3 be the infrared spectrum curve of the polysilsesquioxane with electrochromic property prepared by embodiment three, and 4 be the tool of example IV
There is the infrared spectrum curve of the polysilsesquioxane of electrochromic property；
As can be known from Fig. 1, the polysilsesquioxane with electrochromic property that prepared by embodiment one to four is in 3330cm-1
Place, occurs that N-H stretching vibration peaks；In 1511cm-1Place, occur that N-H flexural vibrations absworption peak；In 1660cm-1
Place, the C=O stretching vibration peaks of appearance, illustrates the presence of amide group；In 3058cm-1Place, occurs that the C-H on phenyl ring
Stretching vibration absworption peak；In 2927cm-1And 2867cm-1Place, occurs that the C-H asymmetric stretching vibrations of methyl and methylene
Absworption peak；In 1604cm-1The absworption peak at place absorbs for the skeleton stretching vibration of phenyl ring；In 1000-1100cm-1Between it is wide and strong
Multi-absorption peak be caused by Si-O-Si stretching vibration.
Fig. 2 is thermogravimetric curve, and 1 is the polysilsesquioxane with electrochromic property prepared by embodiment one in Fig. 2
Thermogravimetric curve, 2 be embodiment two prepare the polysilsesquioxanes with electrochromic property thermogravimetric curve, 3 are
The thermogravimetric curve of polysilsesquioxane with electrochromic property prepared by embodiment three, 4 be tool prepared by example IV
There is the thermogravimetric curve of the polysilsesquioxane of electrochromic property；
It was found from the curve 1 in Fig. 2, the polysilsesquioxane with electrochromic property prepared by embodiment one is from room temperature
During being warming up to 800 DEG C, there is an obvious weightless region；Weightlessness 5% temperature be 297 DEG C, weightlessness 10% when temperature
Degree at 323 DEG C or so, weightlessness 20% when temperature at 353 DEG C or so, illustrate embodiment one preparation there is electrochromic property
Polysilsesquioxane hot property it is preferable.
It was found from the curve 2 in Fig. 2, the polysilsesquioxane with electrochromic property prepared by embodiment two is from room temperature
During being warming up to 800 DEG C, there is an obvious weightless region；Weightlessness 5% temperature be 270 DEG C, weightlessness 10% when temperature
Degree at 303 DEG C or so, weightlessness 20% when temperature at 336 DEG C or so, illustrate embodiment two preparation there is electrochromic property
Polysilsesquioxane hot property it is preferable.
It was found from the curve 3 in Fig. 2, the polysilsesquioxane with electrochromic property prepared by embodiment three is from room temperature
During being warming up to 800 DEG C, there is an obvious weightless region, the temperature of weightlessness 5% is 308 DEG C, temperature during weightlessness 10%
The temperature at 335 DEG C or so, 20% is spent at 361 DEG C or so, illustrates that embodiment three is prepared poly- with electrochromic property
Silsesquioxane hot property is preferable.
It was found from the curve 4 in Fig. 2, the polysilsesquioxane with electrochromic property prepared by example IV is from room temperature
During being warming up to 800 DEG C, there is an obvious weightless region；Weightlessness 5% temperature be 340 DEG C, weightlessness 10% when temperature
Degree at 365 DEG C or so, weightlessness 20% when temperature at 391 DEG C or so, illustrate example IV preparation there is electrochromic property
Polysilsesquioxane hot property it is preferable.
Embodiment five：The polysilsesquioxane with electrochromic property prepared using embodiment one is prepared with electroluminescent
What the polysilsesquioxane film of discoloration was specifically realized by the following steps：
Polysilsesquioxane with electrochromic property prepared by embodiment one is dissolved into N,N-dimethylformamide
In, obtain solution；Solution is uniformly applied on ITO electro-conductive glass, then it is 0.09MPa that ITO electro-conductive glass is put into vacuum
Vacuum drying chamber in, then vacuum dries film 2h at being 180 DEG C in temperature, and be utilized that embodiment one obtains has electrochromism
Polysilsesquioxane film prepared by the polysilsesquioxane of performance；Prepared by described embodiment one has electrochromic property
The quality of polysilsesquioxane and the volume ratio of N,N-dimethylformamide be 0.05g:1mL.
Embodiment six：The polysilsesquioxane with electrochromic property prepared using embodiment two is prepared with electroluminescent
What the polysilsesquioxane film of discoloration was specifically realized by the following steps：
Polysilsesquioxane with electrochromic property prepared by embodiment two is dissolved into N,N-dimethylformamide
In, obtain solution；Solution is uniformly applied on ITO electro-conductive glass, then it is 0.09MPa that ITO electro-conductive glass is put into vacuum
Vacuum drying chamber in, then vacuum dries film 2h at being 180 DEG C in temperature, and be utilized that embodiment two obtains has electrochromism
Polysilsesquioxane film prepared by the polysilsesquioxane of performance；Prepared by described embodiment two has electrochromic property
The quality of polysilsesquioxane and the volume ratio of N,N-dimethylformamide be 0.05g:1mL.
Embodiment seven：The polysilsesquioxane with electrochromic property prepared using embodiment three is prepared with electroluminescent
What the polysilsesquioxane film of discoloration was specifically realized by the following steps：
Polysilsesquioxane with electrochromic property prepared by embodiment three is dissolved into N,N-dimethylformamide
In, obtain solution；Solution is uniformly applied on ITO electro-conductive glass, then it is 0.09MPa that ITO electro-conductive glass is put into vacuum
Vacuum drying chamber in, then vacuum dries film 2h at being 180 DEG C in temperature, and be utilized that embodiment three obtains has electrochromism
Polysilsesquioxane film prepared by the polysilsesquioxane of performance；Prepared by described embodiment three has electrochromic property
The quality of polysilsesquioxane and the volume ratio of N,N-dimethylformamide be 0.05g:1mL.
Embodiment eight：The polysilsesquioxane with electrochromic property prepared using example IV is prepared with electroluminescent
What the polysilsesquioxane film of discoloration was specifically realized by the following steps：
Polysilsesquioxane with electrochromic property prepared by example IV is dissolved into N,N-dimethylformamide
In, obtain solution；Solution is uniformly applied on ITO electro-conductive glass, then it is 0.09MPa that ITO electro-conductive glass is put into vacuum
Vacuum drying chamber in, then vacuum dries film 2h at being 180 DEG C in temperature, and be utilized that example IV obtains has electrochromism
Polysilsesquioxane film prepared by the polysilsesquioxane of performance；Prepared by described example IV has electrochromic property
The quality of polysilsesquioxane and the volume ratio of N,N-dimethylformamide be 0.05g:1mL.
The polysilsesquioxane with electrochromic property obtained using electrochemical workstation test using embodiment one
Cyclic voltammetric performance of the polysilsesquioxane film of preparation in the acetonitrile solution of lithium perchlorate, as a result as shown in Figure 3；
Fig. 3 is poly- silsesquioxane prepared by the polysilsesquioxane with electrochromic property obtained using embodiment one
The cyclic voltammogram of alkane film；
As can be seen from Figure 3, there is an oxidation peak in 1.09V, corresponding reduction peak occur in 0.65V, illustrate to be sent out
Raw reaction is reversible, during cyclic voltammetry scan, has the poly- of electrochromic property using what embodiment one obtained
The color of polysilsesquioxane film prepared by silsesquioxane is also by colourless change au bleu, and with the loading of backward voltage
The color of film returns to original state.Therefore, the polysilsesquioxane with electrochromic property that prepared by embodiment one can
To be used as electrochromic material.
The polysilsesquioxane with electrochromic property obtained using electrochemical workstation test using embodiment two
Cyclic voltammetric performance of the polysilsesquioxane film of preparation in the acetonitrile solution of lithium perchlorate, as a result as shown in Figure 4；
Fig. 4 is poly- silsesquioxane prepared by the polysilsesquioxane with electrochromic property obtained using embodiment two
The cyclic voltammogram of alkane film；
As shown in Figure 4, there is an oxidation peak in 1.46V, corresponding reduction peak occur in 0.94V, illustrate to be sent out
Raw reaction is reversible.During cyclic voltammetry scan, there is the poly- of electrochromic property using what embodiment two obtained
The color of polysilsesquioxane film prepared by silsesquioxane is also by colourless change au bleu, and with the loading of backward voltage
The color of film returns to original state.Therefore, the polysilsesquioxane with electrochromic property that prepared by embodiment two can
To be used as electrochromic material.
The polysilsesquioxane with electrochromic property obtained using electrochemical workstation test using embodiment three
Cyclic voltammetric performance of the polysilsesquioxane film of preparation in the acetonitrile solution of lithium perchlorate, as a result as shown in Figure 5；
Fig. 5 is poly- silsesquioxane prepared by the polysilsesquioxane with electrochromic property obtained using embodiment three
The cyclic voltammogram of alkane film；
As shown in Figure 5, there is an oxidation peak in 0.84V, corresponding reduction peak occur in 0.70V, illustrate to be sent out
Raw reaction is reversible.During cyclic voltammetry scan, there is the poly- of electrochromic property using what embodiment three obtained
The color of polysilsesquioxane film prepared by silsesquioxane also becomes red by colourless, and with the loading of backward voltage
The color of film returns to original state.Therefore, the polysilsesquioxane with electrochromic property that prepared by embodiment three can
To be used as electrochromic material.
The polysilsesquioxane with electrochromic property obtained using electrochemical workstation test using example IV
Cyclic voltammetric performance of the polysilsesquioxane film of preparation in the acetonitrile solution of lithium perchlorate, as a result as shown in Figure 6；
Fig. 6 is poly- silsesquioxane prepared by the polysilsesquioxane with electrochromic property obtained using example IV
The cyclic voltammogram of alkane film；
It will be appreciated from fig. 6 that there is an oxidation peak in 0.97V, there is corresponding reduction peak in 0.52V, illustrate to be sent out
Raw reaction is reversible.During cyclic voltammetry scan, there is the poly- of electrochromic property using what example IV obtained
The color of polysilsesquioxane film prepared by silsesquioxane also becomes blue-green, and adding with backward voltage by colourless
The color for carrying film returns to original state.Therefore, the polysilsesquioxane with electrochromic property that prepared by example IV
Electrochromic material can be used as.
Fig. 7 is poly- silsesquioxane prepared by the polysilsesquioxane with electrochromic property obtained using embodiment one
The uv atlas of alkane film, 1 is 0V in Fig. 7, and 2 be 1V, and 3 be 1.25V, and 4 be 1.75V；
As can be seen from Figure 7, as the loading of different voltages, ultraviolet spectra curve illustrate using real there occurs obvious change
The color of polysilsesquioxane film prepared by the polysilsesquioxane with electrochromic property that example one obtains is applied in voltage
Loading under changed, illustrate that this polymer can be used as electrochromic material.
Fig. 8 is poly- silsesquioxane prepared by the polysilsesquioxane with electrochromic property obtained using embodiment two
The uv atlas of alkane film, 1 is 0V in Fig. 8, and 2 be 1.1V, and 3 be 1.3V, and 4 be 1.55V, and 5 be 1.85V；
As it can be observed in the picture that with the loading of different voltages, ultraviolet spectra curve illustrates using real there occurs obvious change
The color of polysilsesquioxane film prepared by the polysilsesquioxane with electrochromic property that example two obtains is applied in voltage
Loading under changed, illustrate that this polymer can be used as electrochromic material.
Fig. 9 is poly- silsesquioxane prepared by the polysilsesquioxane with electrochromic property obtained using embodiment three
The uv atlas of alkane film, 1 is 0V in Fig. 9, and 2 be 0.5V, and 3 be 1.1V, and 4 be 1.5V；
As can be seen from Figure 9, as the loading of different voltages, ultraviolet spectra curve illustrate using real there occurs obvious change
The color of polysilsesquioxane film prepared by the polysilsesquioxane with electrochromic property that example three obtains is applied in voltage
Loading under changed, illustrate that this polymer can be used as electrochromic material.
Figure 10 is poly- sesquialter silicon prepared by the polysilsesquioxane with electrochromic property obtained using example IV
The uv atlas of oxygen alkane film, 1 is 0V in Figure 10, and 2 be 1.05V, and 3 be 1.4V, and 4 be 1.6V；
As can be seen from Figure 10, as the loading of different voltages, ultraviolet spectra curve illustrate using real there occurs obvious change
The color of polysilsesquioxane film prepared by the polysilsesquioxane with electrochromic property that example four obtains is applied in voltage
Loading under changed, illustrate that this polymer can be used as electrochromic material.
Figure 11 is that absorbance-curent change of the polysilsesquioxane with electrochromic property prepared by embodiment one is bent
Line；
As can be seen from Figure 11, the polysilsesquioxane with electrochromic property that prepared by embodiment one passes through continuous 100
After circulation, obvious change does not occur for transmitance and size of current, show material have good cyclical stability with
And longer service life.
Figure 12 is that absorbance-curent change of the polysilsesquioxane with electrochromic property prepared by embodiment two is bent
Line；
As can be seen from Figure 12, the polysilsesquioxane with electrochromic property that prepared by embodiment two passes through continuous 100
After circulation, obvious change does not occur for transmitance and size of current, show material have good cyclical stability with
And longer service life.
Figure 13 is that absorbance-curent change of the polysilsesquioxane with electrochromic property prepared by embodiment three is bent
Line；
As can be seen from Figure 13, the polysilsesquioxane with electrochromic property that prepared by embodiment three passes through continuous 100
After circulation, obvious change does not occur for transmitance and size of current, show material have good cyclical stability with
And longer service life.
Figure 14 is that absorbance-curent change of the polysilsesquioxane with electrochromic property prepared by example IV is bent
Line.
As can be seen from Figure 14, the polysilsesquioxane with electrochromic property that prepared by embodiment five passes through continuous 100
After circulation, obvious change does not occur for transmitance and size of current, show material have good cyclical stability with
And longer service life.
Table 1 is that the polysilsesquioxane with electrochromic property prepared by embodiment one to four is molten in different solvents
Xie Xing；
Table 1
Note：Dissolubility in table 1 is to be dissolved in 1mL solvents by 5mg sample to measure, ++, room temperature is solvable；+, heating can
It is molten；+-, heating part is solvable or is swelled；-, heating is insoluble；A is gathering with electrochromic property prepared by embodiment one
Silsesquioxane；B is the polysilsesquioxane with electrochromic property prepared by embodiment two；C is prepared by embodiment three
Polysilsesquioxane with electrochromic property；D is the poly- silsesquioxane with electrochromic property prepared by example IV
Alkane.
Claims (10)
1. a kind of molecular formula of the polysilsesquioxane with electrochromic property is Tn(OH)x(OR)y；Described T=
RSiO1.5-[(x+y)/2n]；Described n >=4；Described x >=0；Described y >=0；A kind of poly- sesquialter silicon with electrochromic property
The structural formula of oxygen alkane is：
Wherein, described R is
2. a kind of preparation method of the polysilsesquioxane with electrochromic property as claimed in claim 1, its feature exist
It is specifically realized by the following steps in a kind of preparation method of the polysilsesquioxane with electrochromic property：
First, 1., by an amino aniline derivative be dissolved into DMF, then low whipping speed be 20r/min~
Stirring reaction 20min~40min under 50r/min, obtains solution A；
Step 1 1. described in an amino aniline derivative quality and N,N-dimethylformamide volume ratio for (4g~
8g):100mL；
2nd, under nitrogen protection, isocyanates propyl-triethoxysilicane is added into solution A, then is warming up to 50 DEG C~70 DEG C,
Stirring reaction 18h~30h under conditions of temperature is 50 DEG C~70 DEG C and mixing speed is 20r/min~50r/min again, is obtained
Solution B；
The amount of an amino aniline derivative and the material of isocyanates propyl-triethoxysilicane in solution A described in step 2
Than for 1:2；
3rd, solution B is poured into petroleum ether, then stands 1h~3h, then filtered under conditions of vacuum is 0.09MPa,
Solid is collected, the solid of collection is put into vacuum drying oven, in the condition that vacuum is 0.09MPa and temperature is 50 DEG C~70 DEG C
Lower vacuum drying 6h~12h, produces monomer；
The volume ratio of solution B and petroleum ether described in step 3 is 1:(8~10)；
4th, 1., by the monomer obtained in step 3 it is dissolved in tetrahydrofuran, then low whipping speed is 20r/min~50r/min
Lower stirring reaction 5min~10min, obtains solution C；
The quality of monomer described in step 4 and the volume ratio of tetrahydrofuran are (1g~5g):(50mL~150mL)；
2., into solution C be added dropwise concentration be 1mol/L hydrochloric acid, then temperature be 50 DEG C~70 DEG C at stirring reaction 18h~
30h, obtain solution D；
Step 4 2. described in concentration be 1mol/L hydrochloric acid and the volume ratio of solution C be (0.5~1):(50~150)；
3., concentration be 1mol/L potassium hydroxide aqueous solution the pH value of solution D is adjusted to 8~10, then low whipping speed
To be stirred under 50r/min~200r/min, until there is flocculent deposit, stop stirring；Obtain the solution D for flocculent deposit occur；
4., the solution D that will appear from flocculent deposit pour into petroleum ether, then stand 1h~3h, then in the bar that vacuum is 0.09MPa
Filtered under part, collect solid, solid will be collected and be put into vacuum drying oven, then be 0.09MPa in vacuum and temperature is 30
DEG C~50 DEG C under conditions of be dried in vacuo 6h~12h, obtain the polysilsesquioxane with electrochromic property；
Step 4 4. described in appearance flocculent deposit solution D and petroleum ether volume ratio be 1:(8~10).
3. a kind of preparation method of polysilsesquioxane with electrochromic property according to claim 2, its feature
An amino aniline derivative described in being step 1 1. is 4- amino-triphenylamine, 9- (4- aminophenyls) carbazole, 4- amino
Phenyl-N- phenthazine or N- (2 (9,9- dimethyl -9H- fluorenes))-N- phenyl-pphenylenediamines.
4. a kind of preparation method of polysilsesquioxane with electrochromic property according to claim 3, its feature
The structural formula for being described 4- amino-triphenylamine isSpecific preparation method is as follows：
First, in a nitrogen atmosphere, diphenylamines, p-fluoronitrobenzene and NaH are added in dimethyl sulfoxide (DMSO), then temperature be 100
DEG C~110 DEG C and mixing speed be back flow reaction 15h~18h under 100r/min~300r/min, obtain reaction product I；Will be anti-
Answer product I to sink in saturated aqueous common salt, then filtered, the solid matter that suction filtration obtains is dried, reuses anhydrous second
Alcohol recrystallizes, and obtains product II；
The quality of diphenylamines described in step 1 and the volume ratio of dimethyl sulfoxide (DMSO) are (4g~8g):(70mL~100mL)；
The quality of p-fluoronitrobenzene described in step 1 and the volume ratio of dimethyl sulfoxide (DMSO) are (2g~5g):(70mL~
100mL)；
The quality of NaH described in step 1 and the volume ratio of dimethyl sulfoxide (DMSO) are (0.5g~2g):(70mL~100mL)；
2nd, product II is added in absolute ethyl alcohol, adds Pd/C catalyst and hydrazine hydrate, then in temperature be 70 DEG C~90 DEG C
Lower reductase 12 0h~28h, obtains product III；Product III is sunk in saturated aqueous common salt, then filtered, is consolidated what is be filtrated to get
Body material is dried, and reuses absolute ethyl alcohol and is recrystallized, and obtains 4- amino-triphenylamine；
The quality of product II described in step 2 and the volume ratio of absolute ethyl alcohol are (5g~10g):(80mL~150mL)；
The mass ratio of product II and Pd/C catalyst described in step 2 is (5~10):(0.5~1)；
The mass ratio of product II and hydrazine hydrate described in step 2 is (5~10):(10~14).
5. a kind of preparation method of polysilsesquioxane with electrochromic property according to claim 3, its feature
The structural formula for being described 9- (4- aminophenyls) carbazole isSpecific preparation method is as follows：
First, in a nitrogen atmosphere, carbazole, p-fluoronitrobenzene and NaH are added in dimethyl sulfoxide (DMSO), then temperature be 100 DEG C
~110 DEG C are back flow reaction 15h~18h under 100r/min~300r/min with mixing speed, obtain reaction product I；Will reaction
Product I is sunk in saturated aqueous common salt, then is filtered, and the solid matter that suction filtration obtains is dried, reuses absolute ethyl alcohol
Recrystallization, obtains product II；
The quality of carbazole described in step 1 and the volume ratio of dimethyl sulfoxide (DMSO) are (4g~8g):(70mL~100mL)；
The quality of p-fluoronitrobenzene described in step 1 and the volume ratio of dimethyl sulfoxide (DMSO) are (2g~5g):(70mL~
100mL)；
The quality of NaH described in step 1 and the volume ratio of dimethyl sulfoxide (DMSO) are (0.5g~2g):(70mL~100mL)；
2nd, product II is added in absolute ethyl alcohol, adds Pd/C catalyst and hydrazine hydrate, then in temperature be 70 DEG C~90 DEG C
Lower reductase 12 0h~28h, obtains product III；Product III is sunk in saturated aqueous common salt, then filtered, is consolidated what is be filtrated to get
Body material is dried, and reuses absolute ethyl alcohol and is recrystallized, and obtains 9- (4- aminophenyls) carbazole；
The quality of product II described in step 2 and the volume ratio of absolute ethyl alcohol are (5g~10g):(80mL~150mL)；
The mass ratio of product II and Pd/C catalyst described in step 2 is (5~10):(0.5~1)；
The mass ratio of product II and hydrazine hydrate described in step 2 is (5~10):(10~14).
6. a kind of preparation method of polysilsesquioxane with electrochromic property according to claim 3, its feature
The structural formula for being described 4- aminophenyl-N- phenthazine isSpecific preparation method is as follows：
First, in a nitrogen atmosphere, phenthazine, p-fluoronitrobenzene and NaH are added in dimethyl sulfoxide (DMSO), then temperature be 100
DEG C~110 DEG C and mixing speed be back flow reaction 15h~18h under 100r/min~300r/min, obtain reaction product I；Will be anti-
Answer product I to sink in saturated aqueous common salt, then filtered, the solid matter that suction filtration obtains is dried, reuses anhydrous second
Alcohol recrystallizes, and obtains product II；
The quality of phenthazine described in step 1 and the volume ratio of dimethyl sulfoxide (DMSO) are (4g~8g):(70mL~100mL)；
The quality of p-fluoronitrobenzene described in step 1 and the volume ratio of dimethyl sulfoxide (DMSO) are (2g~5g):(70mL~
100mL)；
The quality of NaH described in step 1 and the volume ratio of dimethyl sulfoxide (DMSO) are (0.5g~2g):(70mL~100mL)；
2nd, product II is added in absolute ethyl alcohol, adds Pd/C catalyst and hydrazine hydrate, then in temperature be 70 DEG C~90 DEG C
Lower reductase 12 0h~28h, obtains product III；Product III is sunk in saturated aqueous common salt, then filtered, is consolidated what is be filtrated to get
Body material is dried, and reuses absolute ethyl alcohol and is recrystallized, and obtains 4- aminophenyl-N- phenthazine；
The quality of product II described in step 2 and the volume ratio of absolute ethyl alcohol are (5g~10g):(80mL~150mL)；
The mass ratio of product II and Pd/C catalyst described in step 2 is (5~10):(0.5~1)；
The mass ratio of product II and hydrazine hydrate described in step 2 is (5~10):(10~14).
7. a kind of preparation method of polysilsesquioxane with electrochromic property according to claim 3, its feature exist
It is in the structural formula of described N- (2 (9,9- dimethyl -9H- fluorenes))-N- phenyl-pphenylenediamines
Specific preparation method is as follows：
First, in a nitrogen atmosphere, N- phenyl -2 (9,9- dimethyl -9H- fluorenes) amine, p-fluoronitrobenzene and NaH is added to diformazan
In base sulfoxide, then in the case where temperature is 100 DEG C~110 DEG C and mixing speed is 100r/min~300r/min back flow reaction 15h~
18h, obtain reaction product I；Reaction product I is sunk in saturated aqueous common salt, then filtered, the solid matter that suction filtration is obtained
It is dried, reuses absolute ethyl alcohol recrystallization, obtain product II；
(9,9- dimethyl -9H- fluorenes) quality of amine of N- phenyl -2 and the volume ratio of dimethyl sulfoxide (DMSO) described in step 1 are (4g
~8g):(70mL~100mL)；
The quality of p-fluoronitrobenzene described in step 1 and the volume ratio of dimethyl sulfoxide (DMSO) are (2g~5g):(70mL~
100mL)；
The quality of NaH described in step 1 and the volume ratio of dimethyl sulfoxide (DMSO) are (0.5g~2g):(70mL~100mL)；
2nd, product II is added in absolute ethyl alcohol, adds Pd/C catalyst and hydrazine hydrate, then in temperature be 70 DEG C~90 DEG C
Lower reductase 12 0h~28h, obtains product III；Product III is sunk in saturated aqueous common salt, then filtered, is consolidated what is be filtrated to get
Body material is dried, and reuses absolute ethyl alcohol and is recrystallized, and obtains N- (2 (9,9- dimethyl -9H- fluorenes))-N- phenyl-right
Phenylenediamine；
The quality of product II described in step 2 and the volume ratio of absolute ethyl alcohol are (5g~10g):(80mL~150mL)；
The mass ratio of product II and Pd/C catalyst described in step 2 is (5~10):(0.5~1)；
The mass ratio of product II and hydrazine hydrate described in step 2 is (5~10):(10~14).
8. a kind of preparation method of polysilsesquioxane with electrochromic property according to claim 2, its feature
Under nitrogen protection, isocyanates propyl-triethoxysilicane is being added into solution A in step 2, then is being warming up to 60 DEG C,
Stirring reaction 18h~24h under conditions of temperature is 60 DEG C and mixing speed is 30r/min~50r/min again, obtains solution B.
9. a kind of preparation method of polysilsesquioxane with electrochromic property according to claim 2, its feature
In step 4 2. in the hydrochloric acid that concentration is 1mol/L is added dropwise into solution C, then distilled water is added dropwise, then stirred at being 60 DEG C in temperature
Reaction 18h~24h is mixed, obtains solution D.
10. a kind of polysilsesquioxane with electrochromic property as claimed in claim 1, it is characterised in that one kind has
The polysilsesquioxane of electrochromic property is applied in smart window as electrochromic material.
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| CN108503839A (en) * | 2018-03-23 | 2018-09-07 | 吉林大学 | Multifunctional mesh shaped polymer and the application of film, preparation method and the film in terms of electrochromism or automatically controlled fluorescence |
| CN110698509A (en) * | 2019-10-23 | 2020-01-17 | 华南理工大学 | Triphenylamine derivative electrochromic composite material and preparation method thereof |
| CN110759953A (en) * | 2019-10-23 | 2020-02-07 | 华南理工大学 | Ferrocene-improved triphenylamine derivative electrochromic composite material and preparation method thereof |
| CN114920910A (en) * | 2022-06-29 | 2022-08-19 | 中国人民解放军96901部队25分队 | Solution-processable yellow-blue electrochromic polymer and preparation method and application thereof |
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