CN108623790A - A kind of conjugated polymer and its preparation method and application containing triaryl amine and fluorenes unit - Google Patents
A kind of conjugated polymer and its preparation method and application containing triaryl amine and fluorenes unit Download PDFInfo
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- CN108623790A CN108623790A CN201810440510.9A CN201810440510A CN108623790A CN 108623790 A CN108623790 A CN 108623790A CN 201810440510 A CN201810440510 A CN 201810440510A CN 108623790 A CN108623790 A CN 108623790A
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- triaryl amine
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- POPZQKSCLJBCAG-UHFFFAOYSA-N Brc(cc1)ccc1-c(cc1)ccc1N(c(cc1)ccc1-c(cc1)ccc1Br)c(cc1)ccc1N(c1ccccc1)c1ccccc1 Chemical compound Brc(cc1)ccc1-c(cc1)ccc1N(c(cc1)ccc1-c(cc1)ccc1Br)c(cc1)ccc1N(c1ccccc1)c1ccccc1 POPZQKSCLJBCAG-UHFFFAOYSA-N 0.000 description 1
- KQIUXKYDGQRIBV-UHFFFAOYSA-N Nc(cc1)ccc1N(Cc1ccccc1)c1ccccc1 Chemical compound Nc(cc1)ccc1N(Cc1ccccc1)c1ccccc1 KQIUXKYDGQRIBV-UHFFFAOYSA-N 0.000 description 1
- WFQDTOYDVUWQMS-UHFFFAOYSA-N [O-][N+](c(cc1)ccc1F)=O Chemical compound [O-][N+](c(cc1)ccc1F)=O WFQDTOYDVUWQMS-UHFFFAOYSA-N 0.000 description 1
- UQOKZDUUBVGFAK-UHFFFAOYSA-N [O-][N+](c(cc1)ccc1N(c1ccccc1)c1ccccc1)=O Chemical compound [O-][N+](c(cc1)ccc1N(c1ccccc1)c1ccccc1)=O UQOKZDUUBVGFAK-UHFFFAOYSA-N 0.000 description 1
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- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/314—Condensed aromatic systems, e.g. perylene, anthracene or pyrene
- C08G2261/3142—Condensed aromatic systems, e.g. perylene, anthracene or pyrene fluorene-based, e.g. fluorene, indenofluorene, or spirobifluorene
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Abstract
A kind of conjugated polymer and its preparation method and application containing triaryl amine and fluorenes unit is related to a kind of conjugated polymer and its preparation method and application containing triaryl amine and fluorenes unit.The present invention is to solve the single technical problems of existing electrochromic material performance.The structural formula of the conjugated polymer containing triaryl amine and fluorenes unit of the present invention is as follows：Wherein n is positive integer.The preparation method of the conjugated polymer containing triaryl amine and fluorenes unit of the present invention is as follows：One, triaryl amine monomer is synthesized；Two, suzuki reaction.The conjugated polymer containing triaryl amine and fluorenes unit of the present invention is applied to be used as electrochromic material, electroluminescent properties material, resistance memory material or sensor function material.The present invention extends the application range of electrochromic material, and the fluorenes triaryl amine system of foundation fully combines the advantages of triaryl amine and fluorenes unit and overcome the two disadvantage, the emission effciency with stronger cavity transmission ability and enhancing device.
Description
Technical field
The present invention relates to a kind of conjugated polymer and its preparation method and application containing triaryl amine and fluorenes unit
Background technology
With the development of science and technology, requirement of the mankind for material is also higher and higher.Simple electrochromic material is increasingly
Growing needs cannot be fully met, it is intended that electrochromic material also has more functions, such as Electroluminescence
Energy, resistance memory, sensor function etc. reach the integrated target of device.Since triaryl amine has unique conjugated structure, and
Very special electron can be readily formed amine radical cation under electric field action, and there is higher hole to move
Shifting rate, so being a kind of excellent electrochromic material.However the most of electrochromic materials based on triaryl amine reported
It is three phenyl ring of connection centered on N atoms mostly.And the aromatic compound based on biphenyl has the p electrons of high degree of polarization
System, plays an important role in the application of Organic Light Emitting Diode, dyestuff and pigment, however is but seldom applied to electroluminescent change
Color field.Polyfluorene is that one in conjugated polymer research enlivens type, can be especially useful for display application field.They are with it
Good processing performance, high luminous efficiency and good carrier mobility and by academia and industrial quarters researcher
Extensive concern.However, still there is some problems anxious to be resolved.On the one hand, polyfluorene tend to solid-state formed excimers and/or
Aggregation.On the other hand, the ionization potential of polyfluorene is up to 5.8eV, to generate high driving voltage.
Invention content
The present invention is to solve the single technical problems of existing electrochromic material performance, and provide a kind of containing triaryl amine
With the conjugated polymer of fluorenes unit and its preparation method and application.
The structural formula of the conjugated polymer containing triaryl amine and fluorenes unit of the present invention is as follows：
Wherein n is positive integer.
The preparation method of the conjugated polymer containing triaryl amine and fluorenes unit of the present invention is as follows：
One, triaryl amine monomer is synthesized：
1., in N2Under atmosphere, diphenylamines, sodium hydride and anhydrous n,N-Dimethylformamide are sequentially added in three-necked bottle,
P-fluoronitrobenzene is added dropwise after stirring evenly, then oil bath heating is to 115 DEG C~120 DEG C, the item for being 115 DEG C~120 DEG C in temperature
Continue reaction under part and stop heating to diphenlyamine reaction is complete, in N2Natural cooling under atmosphere, by reaction solution after cooling
It is placed in distilled water, sodium chloride is added under stirring conditions and is filtered to solid, standing sedimentation 12h~14h is precipitated, washing, 50
The drying of DEG C vacuum drying oven, then recrystallizes in ethanol, filters, washing, and 50 DEG C of vacuum drying ovens drying obtain yellow solid；Institute
The ratio of the amount of the substance of the diphenylamines and sodium hydride stated is 1:(1.8~2)；The amount of the substance of the diphenylamines and anhydrous N, N-
The volume ratio of dimethylformamide is 1mol:(6.26L~6.3L)；The amount of the substance of the diphenylamines and p-fluoronitrobenzene
Than being 1:(1.2~1.5)；The volume ratio of the anhydrous N,N-dimethylformamide and distilled water is 1:(5~5.5)；
Reaction equation is as follows：
The complete judgment method of the diphenlyamine reaction is：Judge reaction process with thin-layered chromatography.
2., in N2Under atmosphere, it is solid that 1. yellow that absolute ethyl alcohol, palladium carbon and step 1 are prepared is sequentially added in three-necked bottle
Hydrazine hydrate is added dropwise under stirring in body, is warming up to 80 DEG C of reflux for 24 hours, stops heating, filtered immediately, filtrate is poured into
In distilled water, sodium chloride is added under stirring conditions to solid is precipitated, filters, is washed with ethyl alcohol, be dried in vacuo white solid
Body；The mass fraction of palladium is 10% in the palladium carbon；The quality of the palladium carbon and the volume ratio of absolute ethyl alcohol are 1g:
(187mL~190mL)；The mass ratio of 1. yellow solid that the palladium carbon and step 1 is prepared is 1:(3.3~3.5)；It is described
The volume ratio of hydrazine hydrate and absolute ethyl alcohol is 1:(12~15)；
Reaction equation is as follows：
3., under nitrogen protection, it is solid that the white that 2. obtains of step 1 is added into the two mouth flask of the toluene equipped with water removal
Body, the bromo- 4 '-iodine biphenyl of sodium tert-butoxide, 4-, palladium and 1, bis- (diphenylphosphine) ferrocene of 1'- are hidden reactant with tin piece
Light, logical nitrogen reflux reacts for 24 hours under conditions of temperature is 115 DEG C~120 DEG C, and the solution that back flow reaction obtains is used successively
Water, saturated salt solution carry out purification by liquid extraction, and the extract liquor of gained is rotated, and drying, the product after drying is carried out thin with solvent
Layer chromatography detaches, and obtains flaxen triaryl amine monomer；The solvent is petroleum ether and dichloromethane according to volume ratio 5:1
It mixes；The ratio of the amount of the substance of 2. white solid and sodium tert-butoxide that the step one obtains is 1:(3~4)；It is described
The step of one white solid 2. obtained substance amount and toluene volume ratio be 1mol:(2.5L~3L)；The step
The ratio of the amount of the substance of one white solid 2. obtained and the bromo- 4 '-iodine biphenyl of 4- is 1:(2~3)；2. the step one obtains
White solid and palladium substance amount ratio be 1:(0.03~0.04)；2. white solid that the step one obtains
Ratio with the amount of the substance of bis- (diphenylphosphine) ferrocene of 1,1'- is 1:(0.06~0.07)；
Reaction equation is as follows：
Two, suzuki reaction：
By step 1 prepare flaxen triaryl amine monomer, 9,9- dioctyl fluorenes -2,7- bis- (pinacol borates) and
Four (triphenyl phosphorus) palladiums and toluene stir evenly, and add solution of potassium carbonate, under conditions of temperature is 105 DEG C and nitrogen atmosphere
Stir 48h, be cooled to room temperature under nitrogen protection, then with separatory funnel detach organic layer, successively use water, saturated salt solution into
The extract liquor of gained is poured into and yellow polymer is precipitated in methanol by row purification by liquid extraction, is filtered yellow polymer, is finally used first
Alcohol Soxhlet extraction purifies 48h, obtains the conjugated polymer containing triaryl amine and fluorenes unit；
A concentration of 3mol/L of the solution of potassium carbonate；The volume ratio of the solution of potassium carbonate and toluene is 1:1；Institute
The substance of flaxen triaryl amine monomer and 9,9- dioctyl fluorenes -2,7- bis- (pinacol borates) prepared by the step of stating one
The ratio of amount is 1:(1~1.2)；The substance of flaxen triaryl amine monomer and four (triphenyl phosphorus) palladiums prepared by the step one
Amount ratio be 1:(0.04~0.05)；The amount and toluene of the substance of flaxen triaryl amine monomer prepared by the step one
Volume ratio be 1mol:(40L~45L).
Reaction equation is as follows：
The conjugated polymer containing triaryl amine and fluorenes unit of the present invention is applied to as electrochromic material, fluorescence sense material
Material, hole mobile material, anti-fake material, memory resistor, camouflage material, automobile rearview mirror material or display material.
The conjugated polymer containing triaryl amine and fluorenes unit of the present invention is applied to be used as explosive detection material.
Biphenyl structural substituted benzene ring is incorporated on the N atoms of center by the present invention, prepares novel triaryl amine monomer to obtain
More excellent performance is obtained, the multi-functional organic polymer material to design synthesizing new provides basis.
Fluorenes and triaryl amine combined polymerization can be obtained electrochromism and EL function by the present invention；In order to obtain
Effective hole injection, the triaryl amine of the biphenyl type of electron rich is introduced into polyfluorene skeleton, the ionization potential of copolymer is reduced, and
And excimers and/or the tendency of tight agglomerate are formed in solid-state since the introducing of the torsion structure of biphenyl is reduced, make
Molecule has better dissolubility, better electron delocalization range and chemical stabilization compared to containing common tertiary aromatic amine structure
Property.
The conjugated polymer containing triaryl amine and fluorenes unit of the present invention is due to combining biphenyl formula triaryl amine and fluorene structured, together
When have electrochromism, electroluminescent fluorescent, resistance memory and sensor function, the effective integration of device can be reached.
The present invention step one 3. described in water removal toluene preparation method it is as follows：Metallic sodium is added in toluene,
It is heated to reflux, using benzophenone as indicator, becomes the blue toluene for starting to be collected into water removal.
Advantages of the present invention：
The present invention extends the application range of electrochromic material, and fluorenes-triaryl amine system of foundation fully combines triaryl amine
With the advantages of fluorenes unit and both overcome disadvantage, with stronger cavity transmission ability and enhance the emission effciency of device.
In electrochromism field：(1) color change is apparent, from it is faint yellow to green again to navy blue；(2) color change
Response time is fast；(3) variation of color is reversible and good cycling stability.
The electrofluorescence performance of the conjugated polymer containing triaryl amine and fluorenes unit of the present invention can also pass through electrochemical oxidation
It is also original to adjust, there is very high contrast.In addition to this, also there is excellent table in terms of explosive detection and memory performance
It is existing.Multi-functional organic polymer material to design synthesizing new provides certain method and thinking, multi-functional organic to understand
The mechanism of polymer electrochromic performance provides theories integration.
The memory device of the present invention prepared containing the conjugated polymer of triaryl amine and fluorenes unit can be 0-100 with detectable concentration
The presence of TNT in the TNT chloroformic solutions of μ g/mL.
The memory device of the present invention prepared containing the conjugated polymer of triaryl amine and fluorenes unit can be with detectable concentration for 0-70 μ
Picric presence in the picric acid chloroformic solution of g/mL.
Description of the drawings
Fig. 1 is the hydrogen nuclear magnetic spectrogram of the conjugated polymer containing triaryl amine and fluorenes unit prepared by this experiment；
Fig. 2 is the cyclic voltammogram of the conjugated polymer containing triaryl amine and fluorenes unit prepared by this experiment；
Fig. 3 is the electrochromism figure of the conjugated polymer containing triaryl amine and fluorenes unit prepared by this experiment；
Fig. 4 is the electroluminescent fluorescent figure of the conjugated polymer containing triaryl amine and fluorenes unit prepared by this experiment；
Fig. 5 is the thermogravimetric curve figure of the conjugated polymer containing triaryl amine and fluorenes unit prepared by this experiment；
Fig. 6 is the variation diagram for testing conjugated polymer solution fluorescence intensity when explosive is TNT in two；
Fig. 7 is the variation diagram for testing conjugated polymer solution fluorescence intensity when explosive is picric acid in two；
Fig. 8 is the resistance memory performance map for testing the memory device that three prepare；
Fig. 9 is the infrared spectrum of the conjugated polymer containing triaryl amine and fluorenes unit prepared by this experiment.
Specific implementation mode
Specific implementation mode one：Present embodiment is a kind of conjugated polymer containing triaryl amine and fluorenes unit, structural formula
It is as follows：
Wherein n is positive integer.
Specific implementation mode two：The present embodiment is different from the first embodiment in that：The n be 3~10 it is whole
Number.Other are same as the specific embodiment one.
Specific implementation mode three：Present embodiment is the conjugated polymers containing triaryl amine and fluorenes unit of specific implementation mode one
The preparation method of object, is as follows：
One, triaryl amine monomer is synthesized：
1., in N2Under atmosphere, diphenylamines, sodium hydride and anhydrous n,N-Dimethylformamide are sequentially added in three-necked bottle,
P-fluoronitrobenzene is added dropwise after stirring evenly, then oil bath heating is to 115 DEG C~120 DEG C, the item for being 115 DEG C~120 DEG C in temperature
Continue reaction under part and stop heating to diphenlyamine reaction is complete, in N2Natural cooling under atmosphere, by reaction solution after cooling
It is placed in distilled water, sodium chloride is added under stirring conditions and is filtered to solid, standing sedimentation 12h~14h is precipitated, washing, 50
The drying of DEG C vacuum drying oven, then recrystallizes in ethanol, filters, washing, and 50 DEG C of vacuum drying ovens drying obtain yellow solid；Institute
The ratio of the amount of the substance of the diphenylamines and sodium hydride stated is 1:(1.8~2)；The amount of the substance of the diphenylamines and anhydrous N, N-
The volume ratio of dimethylformamide is 1mol:(6.26L~6.3L)；The amount of the substance of the diphenylamines and p-fluoronitrobenzene
Than being 1:(1.2~1.5)；The volume ratio of the anhydrous N,N-dimethylformamide and distilled water is 1:(5~5.5)；
Reaction equation is as follows：
2., in N2Under atmosphere, it is solid that 1. yellow that absolute ethyl alcohol, palladium carbon and step 1 are prepared is sequentially added in three-necked bottle
Hydrazine hydrate is added dropwise under stirring in body, is warming up to 80 DEG C of reflux for 24 hours, stops heating, filtered immediately, filtrate is poured into
In distilled water, sodium chloride is added under stirring conditions to solid is precipitated, filters, is washed with ethyl alcohol, be dried in vacuo white solid
Body；The mass fraction of palladium is 10% in the palladium carbon；The quality of the palladium carbon and the volume ratio of absolute ethyl alcohol are 1g:
(187mL~190mL)；The mass ratio of 1. yellow solid that the palladium carbon and step 1 is prepared is 1:(3.3~3.5)；It is described
The volume ratio of hydrazine hydrate and absolute ethyl alcohol is 1:(12~15)；
Reaction equation is as follows：
3., under nitrogen protection, it is solid that the white that 2. obtains of step 1 is added into the two mouth flask of the toluene equipped with water removal
Body, the bromo- 4 '-iodine biphenyl of sodium tert-butoxide, 4-, palladium and 1, bis- (diphenylphosphine) ferrocene of 1'- are hidden reactant with tin piece
Light, logical nitrogen reflux reacts for 24 hours under conditions of temperature is 115 DEG C~120 DEG C, and the solution that back flow reaction obtains is used successively
Water, saturated salt solution carry out purification by liquid extraction, and the extract liquor of gained is rotated, and drying, the product after drying is carried out thin with solvent
Layer chromatography detaches, and obtains flaxen triaryl amine monomer；The solvent is petroleum ether and dichloromethane according to volume ratio 5:1
It mixes；The ratio of the amount of the substance of 2. white solid and sodium tert-butoxide that the step one obtains is 1:(3~4)；It is described
The step of one white solid 2. obtained substance amount and toluene volume ratio be 1mol:(2.5L~3L)；The step
The ratio of the amount of the substance of one white solid 2. obtained and the bromo- 4 '-iodine biphenyl of 4- is 1:(2~3)；2. the step one obtains
White solid and palladium substance amount ratio be 1:(0.03~0.04)；2. white solid that the step one obtains
Ratio with the amount of the substance of bis- (diphenylphosphine) ferrocene of 1,1'- is 1:(0.06~0.07)；
Reaction equation is as follows：
Two, suzuki reaction：
By step 1 prepare flaxen triaryl amine monomer, 9,9- dioctyl fluorenes -2,7- bis- (pinacol borates) and
Four (triphenyl phosphorus) palladiums and toluene stir evenly, and add solution of potassium carbonate, under conditions of temperature is 105 DEG C and nitrogen atmosphere
Stir 48h, be cooled to room temperature under nitrogen protection, then with separatory funnel detach organic layer, successively use water, saturated salt solution into
The extract liquor of gained is poured into and yellow polymer is precipitated in methanol by row purification by liquid extraction, is filtered yellow polymer, is finally used first
Alcohol Soxhlet extraction purifies 48h, obtains the conjugated polymer containing triaryl amine and fluorenes unit；
A concentration of 3mol/L of the solution of potassium carbonate；The volume ratio of the solution of potassium carbonate and toluene is 1:1；Institute
The substance of flaxen triaryl amine monomer and 9,9- dioctyl fluorenes -2,7- bis- (pinacol borates) prepared by the step of stating one
The ratio of amount is 1:(1~1.2)；The substance of flaxen triaryl amine monomer and four (triphenyl phosphorus) palladiums prepared by the step one
Amount ratio be 1:(0.04~0.05)；The amount and toluene of the substance of flaxen triaryl amine monomer prepared by the step one
Volume ratio be 1mol:(40L~45L).
Reaction equation is as follows：
Specific implementation mode four：Present embodiment is that the conjugation containing triaryl amine and fluorenes unit in specific implementation mode one is poly-
The application for closing object, is applied particularly to as electrochromic material, fluorescent sensing material, hole mobile material, anti-fake material, memory
Resistance, camouflage material, automobile rearview mirror material or display material.
Specific implementation mode five：Present embodiment is unlike specific implementation mode four：Present embodiment is specific real
The application for applying the conjugated polymer containing triaryl amine and fluorenes unit in mode one, is applied particularly to as explosive detection material.
The present invention is verified with following tests：
Experiment one：This experiment is the preparation method of the conjugated polymer containing triaryl amine and fluorenes unit, is as follows：
One, triaryl amine monomer is synthesized：
1., in N2Under atmosphere, sequentially add the diphenylamines of 23.94mmol in three-necked bottle, the sodium hydride of 43.10mmol and
The p-fluoronitrobenzene of 28.73mmol is added dropwise, then oil bath heating in the anhydrous n,N-Dimethylformamide of 150mL after stirring evenly
To 115 DEG C~120 DEG C, continues reaction under conditions of temperature is 115 DEG C~120 DEG C and stop adding to diphenlyamine reaction is complete
Heat, in N2Reaction solution after cooling is placed in distilled water by natural cooling under atmosphere, and sodium chloride is added extremely under stirring conditions
Solid is precipitated, standing sedimentation 12h~14h is filtered, washing, then 50 DEG C of vacuum drying oven drying are recrystallized, filtered in ethanol,
Washing, 50 DEG C of vacuum drying oven drying, obtains yellow solid, yield 87%；
Reaction equation is as follows：
2., in N2Under atmosphere, sequentially added in three-necked bottle the absolute ethyl alcohol of 150mL, the palladium carbon of 0.8g and 2.7g step
The hydrazine hydrate of 12mL is added dropwise in rapid one yellow solid 1. prepared under stirring, is warming up to 80 DEG C of reflux for 24 hours, stops heating,
It is filtered immediately, filtrate is poured into distilled water, sodium chloride is added under stirring conditions to solid is precipitated, filters, uses second
Alcohol washs, and is dried in vacuo to obtain white solid, yield 72%；The mass fraction of palladium is 10% in the palladium carbon；Reaction equation is as follows：
3., under nitrogen protection, into the two mouth flask of the toluene of the water removal equipped with 30mL be added 3.12g (12mmol) step
Rapid one white solid 2. obtained, the bromo- 4 '-iodine biphenyl of the sodium tert-butoxide of 36mmol, the 4- of 24mmol, 3.6 × 10-1The vinegar of mmol
Sour palladium and 7.2 × 10-1Bis- (diphenylphosphine) ferrocene of 1,1'- of mmol are 115 DEG C in temperature with tin piece by reactant shading
Lead to nitrogen reflux reaction under conditions of~120 DEG C for 24 hours, the solution that back flow reaction is obtained is carried out with water, saturated salt solution successively
Purification by liquid extraction rotates the extract liquor of gained, and drying, the product after drying carries out TLC separation with solvent, obtains light
The triaryl amine monomer of yellow；The solvent is petroleum ether and dichloromethane according to volume ratio 5:1 mixes；
Reaction equation is as follows：
Two, suzuki reaction：
The 9 of flaxen triaryl amine monomer, 0.3739mmol that the step of 0.2403g (0.3739mmol) one is prepared,
9- dioctyl fluorenes -2,7- bis- (pinacol borates) and 1.5 × 10-2The toluene stirring of four (triphenyl phosphorus) palladiums and 15mL of mmol
Uniformly, the solution of potassium carbonate for adding 15mL stirs 48h, in nitrogen protection under conditions of temperature is 105 DEG C and nitrogen atmosphere
Under be cooled to room temperature, then with separatory funnel detach organic layer, purification by liquid extraction is carried out with water, saturated salt solution successively, by gained
Extract liquor pour into yellow polymer be precipitated in methanol, filter yellow polymer, finally purified with methanol Soxhlet extraction
48h obtains the conjugated polymer containing triaryl amine and fluorenes unit；A concentration of 3mol/L of the solution of potassium carbonate.
Reaction equation is as follows：
Fig. 1 is the hydrogen nuclear magnetic spectrogram of the conjugated polymer containing triaryl amine and fluorenes unit prepared by this experiment, as can be seen from Figure 11H
NMR(400MHz,DMSO-d6,δ,ppm):7.81-6.97 (benzene ring hydrogen), 1.97-0.49 (hydrogen on alkyl chain).
Fig. 9 is the infrared spectrum of the conjugated polymer containing triaryl amine and fluorenes unit prepared by this experiment, as we know from the figure IR
(KBr,υ,cm-1):1268(Ar-N),3032(Ar-H stretch)。
The structural formula of the conjugated polymer containing triaryl amine and fluorenes unit prepared by this experiment can be proved by Fig. 1 and Fig. 9
It is as follows：Wherein n is positive integer.
Fig. 2 is the cyclic voltammogram of the conjugated polymer containing triaryl amine and fluorenes unit prepared by this experiment, the electricity of polymer
Chemical property is obtained by cyclic voltammetry (CV) test, and condition used is the NH in a concentration of 0.2mol/L4ClO4's
CH3It is carried out in CN solution, is applying circulating and reversible voltage on the ito glass plate for be coated with thin polymer film.The CV of polymer
Spectrogram occurs as shown, it is observed that occurring two oxidation peaks at 0.99V and 1.31V at 0.76V and 1.07V
Two reduction peaks.
Fig. 3 is the electrochromism figure of the conjugated polymer containing triaryl amine and fluorenes unit prepared by this experiment, in ultraviolet-visible
Light spectrum carries out testing research to the film of conjugated polymer, and wherein test condition is identical as cyclic voltammetry, 0V~1.5V,
In the initial state, the thin polymer film presentation being coated on ITO is faint yellow, in the case where no-voltage applies, in polymer
TPA groups π-π * electron transfer, most strong absworption peak is at 358nm, with applying alive raising, in 506nm and
Absorption peak at 1296nm gradually increases, the variation of thin polymer film simultaneous color, and color is from faint yellow gradual change
Yellow green is turned to, navy blue is eventually become.
Fig. 4 is the electroluminescent fluorescent figure of the conjugated polymer containing triaryl amine and fluorenes unit prepared by this experiment；It can be seen that
Before not applying voltage, fluorescence intensity reaches highest level, when with applied voltage by 0V to 1.5V, the fluorescence intensity of polymer
It is gradually reduced, finally almost levels off to zero.
Fig. 5 is the thermogravimetric curve figure of the conjugated polymer containing triaryl amine and fluorenes unit prepared by this experiment, can from figure
Know, polymer is about starting a large amount of weightlessness, when temperature is at 450 DEG C, weight loss 5%, when temperature is at 430 DEG C or so
At 469 DEG C, weight loss 10%；When temperature is 504 DEG C, weight loss 20%, when temperature reaches 800 DEG C, polymer carbon is residual
Surplus is 63%.
Conjugated polymer containing triaryl amine and fluorenes unit prepared by this experiment is dissolved in organic solvent, obtains 1mg/mL's
Conjugated polymer solution, conjugated polymer solution is then carried out film on electro-conductive glass can be prepared into electrochromism material
Material；The organic solvent is N-Methyl pyrrolidone.
Experiment two：Conjugated polymer containing triaryl amine and fluorenes unit prepared by this experiment is dissolved in the chloroform of 4mL, is obtained
Then the chloroformic solution containing explosive of a drop various concentration is added dropwise to conjugated polymer in the conjugated polymer solution of 5 μ g/mL
In solution, it whether there is explosive in solution using the variation of solution fluorescence intensity to detect；The explosive is TNT or hardship
It is sour.
Fig. 6 is the variation diagram for testing conjugated polymer solution fluorescence intensity when explosive is TNT in two, and arrow representative contains
The increase (0-100 μ g/mL) of TNT concentration in the chloroformic solution of explosive, as seen from Figure 6 with the increase of TNT concentration, altogether
The fluorescence intensity of conjugated polymer solution gradually weakens.
Fig. 7 is the variation diagram for testing conjugated polymer solution fluorescence intensity when explosive is picric acid in two, and arrow represents
The increase (0-70 μ g/mL) of bitter taste acid concentration in chloroformic solution containing explosive, as seen from Figure 7 with bitter taste acid concentration
Increase, the fluorescence intensity of conjugated polymer solution gradually weakens.
Experiment three：Conjugated polymer containing triaryl amine and fluorenes unit prepared by experiment one is dissolved in N-Methyl pyrrolidone
In, the solution of 1mg/mL is obtained, solution is coated on ITO electro-conductive glass, then drying aluminizes, obtains Al/ polymer/ITO
Sandwich type memory device.
Fig. 8 is the resistance memory performance map for testing the memory device that three prepare, which time scanning is the digital representation in figure be,
During in first time, voltage scanning is from 0 to+8V as seen from Figure 8, device is initially at high-impedance state, when threshold voltage be+
Memory device is observed that sharply increasing for electric current, memory device are switched to height from low conductivity state (OFF) and lead when 1.7V
Electricity condition (ON), this transfer process can be as " write-in " (B in Fig. 8) processes of memory device.In subsequent positive scanning
In (second scan), equipment is still within ON states.In the backward voltage scanning from 0 to -8V (third time scans), work as threshold
Threshold voltage declines suddenly close to electric current when -3.9V, this shows memory device experience from ON states to the transformation of original OFF state,
This conversion from ON to OFF can be as " erasing " (A in Fig. 8) process.Similarly, it is scanned from -8 to 0V at the 4th time
When, equipment is closed.Under the threshold voltage of 2.1V (the 5th scanning), the state after erasing can again switch to
Storage state, it means that memory device is rewritable.
Claims (5)
1. a kind of conjugated polymer containing triaryl amine and fluorenes unit, it is characterised in that the conjugated polymer containing triaryl amine and fluorenes unit
Structural formula it is as follows：
Wherein n is positive integer.
2. a kind of conjugated polymer containing triaryl amine and fluorenes unit according to claim 1, it is characterised in that the n is
3~10 integer.
3. a kind of preparation method of the conjugated polymer containing triaryl amine and fluorenes unit as described in claim 1, it is characterised in that
The preparation method of conjugated polymer containing triaryl amine and fluorenes unit is as follows：
One, triaryl amine monomer is synthesized：
1., in N2Under atmosphere, diphenylamines, sodium hydride and anhydrous n,N-Dimethylformamide are sequentially added in three-necked bottle, stirring is equal
P-fluoronitrobenzene is added dropwise after even, then oil bath heating is to 115 DEG C~120 DEG C, under conditions of temperature is 115 DEG C~120 DEG C after
Continuous reacted to diphenlyamine reaction is complete stops heating, in N2Reaction solution after cooling is placed in steaming by natural cooling under atmosphere
In distilled water, sodium chloride is added under stirring conditions and is filtered to solid, standing sedimentation 12h~14h is precipitated, washing, 50 DEG C of vacuum
Baking oven is dried, and is then recrystallized in ethanol, is filtered, washing, and 50 DEG C of vacuum drying oven drying obtain yellow solid；Described two
The ratio of the amount of the substance of aniline and sodium hydride is 1:(1.8~2)；The amount of the substance of the diphenylamines and anhydrous N, N- dimethyl
The volume ratio of formamide is 1mol:(6.26L~6.3L)；The ratio of the amount of the substance of the diphenylamines and p-fluoronitrobenzene is 1:
(1.2~1.5)；The volume ratio of the anhydrous N,N-dimethylformamide and distilled water is 1:(5~5.5)；
2., in N2Under atmosphere, 1. yellow solid that absolute ethyl alcohol, palladium carbon and step 1 are prepared is sequentially added in three-necked bottle, is being stirred
It mixes and hydrazine hydrate is added dropwise under state, be warming up to 80 DEG C of reflux for 24 hours, stop heating, filtered immediately, filtrate is poured into distilled water
In, sodium chloride is added under stirring conditions to solid is precipitated, filters, is washed with ethyl alcohol, be dried in vacuo to obtain white solid；It is described
Palladium carbon in palladium mass fraction be 10%；The quality of the palladium carbon and the volume ratio of absolute ethyl alcohol are 1g:(187mL~
190mL)；The mass ratio of 1. yellow solid that the palladium carbon and step 1 is prepared is 1:(3.3~3.5)；The hydrazine hydrate and
The volume ratio of absolute ethyl alcohol is 1:(12~15)；
3., under nitrogen protection, the white solid that 2. obtains of step 1, uncle are added into the two mouth flask of the toluene equipped with water removal
The bromo- 4 '-iodine biphenyl of sodium butoxide, 4-, palladium and 1, bis- (diphenylphosphine) ferrocene of 1'-, with tin piece by reactant shading, in temperature
Degree leads to nitrogen reflux reaction for 24 hours under conditions of being 115 DEG C~120 DEG C, the solution that back flow reaction is obtained uses water, saturation food successively
Brine carries out purification by liquid extraction, and the extract liquor of gained is rotated, drying, and the product after drying carries out thin-layer chromatography point with solvent
From obtaining flaxen triaryl amine monomer；The solvent is petroleum ether and dichloromethane according to volume ratio 5:1 mixing and
At；The ratio of the amount of the substance of 2. white solid and sodium tert-butoxide that the step one obtains is 1:(3~4)；The step
The amount of the substance of one white solid 2. obtained and the volume ratio of toluene are 1mol:(2.5L~3L)；2. the step one obtains
The ratio of the amount of the substance of the bromo- 4 '-iodine biphenyl of white solid and 4- arrived is 1:(2~3)；2. white that the step one obtains
The ratio of the amount of solid and the substance of palladium is 1:(0.03~0.04)；2. white solid and 1 that the step one obtains,
The ratio of the amount of the substance of bis- (diphenylphosphine) ferrocene of 1'- is 1:(0.06~0.07)；
Two, suzuki reaction：
Flaxen triaryl amine monomer, 9,9- dioctyl fluorenes -2,7- bis- (pinacol borates) and four (three prepared by step 1
Phenyl phosphorus) palladium and toluene stirs evenly, adds solution of potassium carbonate, stirred under conditions of temperature is 105 DEG C and nitrogen atmosphere
48h is cooled to room temperature under nitrogen protection, is then detached organic layer with separatory funnel, is extracted successively with water, saturated salt solution
Purification is taken, the extract liquor of gained is poured into, yellow polymer is precipitated in methanol, filters yellow polymer, finally uses methanol rope
Family name extraction purification 48h obtains the conjugated polymer containing triaryl amine and fluorenes unit；
A concentration of 3mol/L of the solution of potassium carbonate；The volume ratio of the solution of potassium carbonate and toluene is 1:1；Described
The amount of the substance of flaxen triaryl amine monomer and 9,9- dioctyl fluorenes -2,7- bis- (pinacol borates) prepared by step 1
Than being 1:(1~1.2)；The amount of the substance of flaxen triaryl amine monomer and four (triphenyl phosphorus) palladiums prepared by the step one
Ratio be 1:(0.04~0.05)；The body of the amount and toluene of the substance of flaxen triaryl amine monomer prepared by the step one
Product is than being 1mol:(40L~45L).
4. a kind of application of the conjugated polymer containing triaryl amine and fluorenes unit as described in claim 1, it is characterised in that contain three
The conjugated polymer of arylamine and fluorenes unit is applied to as electrochromic material, fluorescent sensing material, hole mobile material, anti-fake
Material, memory resistor, camouflage material, automobile rearview mirror material or display material.
5. a kind of application of the conjugated polymer containing triaryl amine and fluorenes unit as described in claim 1, it is characterised in that contain three
The conjugated polymer of arylamine and fluorenes unit is applied to be used as explosive detection material.
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| CN109880084A (en) * | 2019-02-25 | 2019-06-14 | 黑龙江大学 | Conjugated polymer containing fluorine-triphenylamine structure and tetraphenyl ethylene unit and preparation method thereof and the application in electrochromism |
| CN110951054A (en) * | 2019-12-23 | 2020-04-03 | 黑龙江大学 | Triphenylamine isoindigo polymer containing biphenyl structure and preparation method and application thereof |
| CN111019098A (en) * | 2019-12-23 | 2020-04-17 | 黑龙江大学 | Triphenylamine benzothiadiazole polymer containing biphenyl structure as well as preparation method and application thereof |
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| CN109336787A (en) * | 2018-12-06 | 2019-02-15 | 黑龙江大学 | Multifunctional polyurethane derivative and its preparation method and application containing tertiary aromatic amine structure and tetraphenyl ethylene group |
| CN109880084A (en) * | 2019-02-25 | 2019-06-14 | 黑龙江大学 | Conjugated polymer containing fluorine-triphenylamine structure and tetraphenyl ethylene unit and preparation method thereof and the application in electrochromism |
| CN109880084B (en) * | 2019-02-25 | 2021-03-26 | 黑龙江大学 | Conjugated polymer containing triphenylamine structure and tetraphenylethylene unit, preparation method thereof and application thereof in electrochromism |
| CN110951054A (en) * | 2019-12-23 | 2020-04-03 | 黑龙江大学 | Triphenylamine isoindigo polymer containing biphenyl structure and preparation method and application thereof |
| CN111019098A (en) * | 2019-12-23 | 2020-04-17 | 黑龙江大学 | Triphenylamine benzothiadiazole polymer containing biphenyl structure as well as preparation method and application thereof |
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