CN108727570A - A kind of DPP block polymers, preparation method and application containing trianilino group - Google Patents
A kind of DPP block polymers, preparation method and application containing trianilino group Download PDFInfo
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Abstract
A kind of DPP block polymers, preparation method and application containing trianilino group, the present invention relates to a kind of DPP block polymers, preparation method and application containing trianilino group.There is hyperfluorescence in organic solvent the present invention is to solve DPP but solubility is low, it is difficult to the technical issues of processing forms a film.Method：One, bis- (8- (tributyl tin alkyl) octyl) pyrrolo- [3,4-c] pyrroles-Isosorbide-5-Nitrae (2H, the 5H)-diketone of 3,6- bis- (thiophene -2- bases) -2,5- are synthesized；Two, N1, bis- (4- bromophenyls)-N4, the N4- diphenyl benzene-Isosorbide-5-Nitrae-diamine monomers of N1- are synthesized；Three, the DPP block polymers containing trianilino group are synthesized.This material is applied in photoelectric material, and the preparation of electrochromic material, fluorescent sensing material, hole mobile material, anti-fake material, camouflage material and explosive detection and memory performance original paper is included.
Description
Technical field
The present invention relates to a kind of DPP block polymers, preparation method and application containing trianilino group.
Background technology
It is by structure to-receptor (D-A) structure to prepare the most common method of thermal activation delayed fluorescence material at present, due to
To Intramolecular electron transfer is generated between-receptor, absorption spectrum Einstein shift and energy gap is caused to narrow.Therefore, in organic material application
Aspect has good application prospect.The synthesis of tri-arylamine group compound carries out in-depth study in many articles, and close several
Year tri-arylamine group polymer is just widely studied.Triaryl amine molecule makes it have because having its unique propeller-like structures
Excellent heat resistance, photoconductivity and hole transport performance, and dissolved in most of organic solvents, it is obtained by oxidation-reduction process
To conductor performance.Since DPP groups have strong fluorescent characteristic, wide light abstraction width, good thermal stability and good
Charge transport properties, be used as photoelectric material be applied to organic field effect tube, organic solar batteries, organic electroluminescence
Luminescent material and two-photon material etc. are widely applied.People are concerned organic photovoltaic material of the exploitation containing DPP,
And realize maximum efficiency.But dissolubility is relatively low in organic solvent for the existing compound of class containing DPP, it is difficult to processing film forming.
Invention content
The present invention is to solve the compound of class containing DPP, dissolubility is low in organic solvent, it is difficult to the problem of processing forms a film, and
DPP block polymers, preparation method and application containing trianilino group are provided.
A kind of structural formula of the DPP block polymers containing trianilino group of the present invention is as follows：
,
N is positive integer in formula.
A kind of preparation method of the DPP block polymers containing trianilino group of the present invention carries out according to the following steps：
One, bis- (8- (tributyl tin alkyl) octyl) pyrrolo- [3,4-c] pyrroles of 3,6- bis- (thiophene -2- bases) -2,5- are synthesized
Cough up-Isosorbide-5-Nitrae (2H, 5H)-diketone：1., tert-pentyl alcohol and sodium mixed, 2- cyano thiophenes and dimethyl succinate are added thereto, leads to
Enter N2It is protected, under conditions of temperature is 90~120 DEG C after 18~28h of reaction, reaction temperature is cooled down from 90~120 DEG C
Glacial acetic acid is added dropwise after to 60~80 DEG C dropwise to there is solid evolution reaction liquid sticky, adds first alcohol and water and is diluted, then
It is cooled to room temperature under stirring conditions, first washes 3~5 times and washed 3~5 times using methanol again, obtain dark red solid, as
DPP；2., the DPP that 1. obtains step, potassium tert-butoxide and anhydrous DMF mixing, be passed through N2It is protected, is 100 DEG C in temperature
Under the conditions of 1,8-, bis- bromooctanes are added dropwise thereto after 2~5h of reaction, drip reaction temperature after 1,8-, bis- bromooctanes from 100 DEG C
120~150 DEG C are warming up to, under conditions of temperature is 120~150 DEG C after the reaction was continued 20~28h, cooled to room temperature,
Products therefrom, which pours into ice water, is precipitated solid precipitation, filtering, and filter residue is first washed 3~5 times and washed 3~5 times using methanol again, obtains thick
Product；Gained crude product uses column chromatography for separation, obtains red solid compound；3., in N2By red solid chemical combination under atmosphere
Vacuum nitrogen gas 3~5 times repeatedly after object and the THF of water removal mixing, it is anti-in the isothermal reaction bath that temperature is -70~-80 DEG C
N-BuLi is added after answering 30~50min, reaction temperature is warming up to -40 DEG C from -70~-80 DEG C, the item for being -40 DEG C in temperature
3~5h is reacted under part, and reaction temperature is then cooled to -70~-80 DEG C from -40 DEG C, the condition for being -70~-80 DEG C in temperature
Lower addition tributyltin chloride reacts 30~45min, finally reaction temperature is warming up to from -70~-80 DEG C room temperature reaction 20~
After 28h, tin reagent product is obtained, M1 is denoted as；1. the quality of middle sodium and the volume ratio of tert-pentyl alcohol are 1g to step:(50~90) mL；
1. the volume ratio of middle 2- cyano thiophenes and tert-pentyl alcohol is 1 to step:(7~9)；Step 1. in dimethyl succinate and tert-pentyl alcohol body
Product is than being 1:(10~70)；1. the volume ratio of middle glacial acetic acid and tert-pentyl alcohol is 1 to step:(35~45)；Step 2. in DPP and tertiary fourth
The molar ratio of potassium alcoholate is 1:(2.5~7)；2. the molar ratio of middle DPP and anhydrous DMF is 1 to step:(8~16)；Step 2. in DPP
Molar ratio with bis- bromooctanes of 1,8- is 1:(6~16)；Step 3. in red solid compound quality and water removal THF body
Product is than being 1g:(0.5~1.6) mL；3. the molar ratio of middle red solid compound and n-BuLi is 1 to step:(1.1~4)；Step
Suddenly 3. the molar ratio of middle red solid compound and tributyltin chloride is 1:(3~12)；
Two, N1, bis- (4- bromophenyls)-N4, the N4- diphenyl benzene -1,4- diamine monomers of N1- are synthesized：1., by diamine monomer,
Sodium hydride and anhydrous DMF mixing, obtain reaction system, are added into reaction system to fluorine under conditions of nitrogen atmosphere and stirring
Nitrobenzene is reacted by reaction temperature from room temperature to 115~120 DEG C under conditions of temperature is 115~120 DEG C, with
Thin-layered chromatography judges whether reaction final product generates,, will be cold by reaction solution cooled to room temperature after generating final product
But the reaction solution after pours into and crude product is precipitated in cool brine, filtering, and uses water washing 3~5 times, through ethyl alcohol recrystallization, filters,
Vacuum drying obtains yellow powder compound；2. at ambient temperature, by absolute ethyl alcohol, 10%Pd/C and yellow powder compound
Mixing, then passes to nitrogen and is protected, hydrazine hydrate is slowly added dropwise thereto using constant pressure funnel, by reaction temperature from room
Temperature is warming up to solution reflux, and persistently flow back 24~48h at such a temperature, stops heating and filtering while hot after reaction removing
10%Pd/C pours into filtrate in cold water, and thick sodium chloride is added under stirring conditions to Off-white solid is precipitated, filters, uses
Ethyl alcohol washs 3~5 times, and vacuum drying obtains compound as white solid；3. by dry toluene, to bromo-iodobenzene, white solid chemical combination
Object, Pd (dba) 2, bis- (diphenylphosphine) ferrocene of 1,1'- and sodium tert-butoxide mixing, then pass to nitrogen and are protected, will be reacted
Temperature flows back from room temperature to solution, is persistently stirred to react at such a temperature for 24 hours, cooled to room temperature, and crude product uses
Column chromatography is purified, and vacuum drying obtains white solid, is denoted as Mb；1. the molar ratio of middle diamine monomer and sodium hydride is step
1:(0.7~1.4)；1. the molar ratio of middle diamine monomer and anhydrous DMF is 1 to step:(5~9)；Step 1. in diamine monomer with it is right
The molar ratio of fluoronitrobenzene is 1:(1.4~2.2)；1. the quality of middle diamine monomer and the volume ratio of cool brine are 1g to step:
(175~225) mL；2. the quality of middle 10%Pd/C and the volume ratio of absolute ethyl alcohol are 1g to step:(200~300) mL；Step is 2.
The mass ratio 1 of middle 10%Pd/C and yellow powder compound:(8~12)；Step 3. in bis- (diphenylphosphine) ferrocene of 1,1'- and
Molar ratio to bromo-iodobenzene is 1:(12~15)；Step 3. in bis- (diphenylphosphine) ferrocene of 1,1'- and compound as white solid
Molar ratio be 1:(5~5.5)；3. the molar ratio of middle bis- (diphenylphosphine) ferrocene of 1,1'- and Pd (dba) 2 are 1 to step:
(0.2~0.4)；3. the molar ratio of middle bis- (diphenylphosphine) ferrocene of 1,1'- and sodium tert-butoxide is 1 to step:(20~50)；Step
3. the quality of middle bis- (diphenylphosphine) ferrocene of 1,1'- and the volume ratio of dry toluene are 1g:(50~80) mL；
Three, synthetic polymer：By M1, Mb, tetra-triphenylphosphine palladium and except water-toluene is added in the Lay pipe of SmithKline, it is passed through N2Into
Row protection, the DPP block polymers obtained for 24 hours containing trianilino group are protected from light under the conditions of temperature is 115 DEG C；The M1
Molar ratio with Mb is 1:1；The molar ratio of the tetra-triphenylphosphine palladium and Mb are 1:100；The quality of the Mb with remove water-toluene
Volume ratio be 1g:(10~30) mL.
The DPP block polymers containing trianilino group of the present invention are used for field of photovoltaic materials.
The DPP block polymers containing trianilino group of the present invention are used to prepare explosive detection material.
Beneficial effects of the present invention：
The present invention, which organically combines two kinds of materials progress, forms D-A-D type structures DPP containing there are two mutually conjugate interior
Amide group has very strong electron-withdrawing ability, is typical short of electricity daughter.And it is divided in son knot Ju two amides can be with
Scion grafting alkyl chain improves it in dissolubility and adjusts its assembly behavior.The big portion of visible light region in solar spectrum can be absorbed
Light splitter is a kind of ideal macromolecular architecture unit the characteristics of by its chemical stability and being readily synthesized and modify.It is real
It tests the result shows that the polymer material has excellent electrochromism, memory performance and optical property, in explosive detection
With good performance.Therefore it carries out DPP and triaryl amine organically to combine the advantages of having given full play to the two.
There are two pairs of redox peaks in cyclic voltammetry in polymer prepared by the present invention, and oxidation peak is respectively
0.72V, 1.08V, reduction peak are respectively 0.96V, 1.29V.It is found in electrochromic test process, in 412nm and 938nm
There are two new absorption peaks in place, constantly rises with alive increase absorption peak is applied；Polymer is on ito glass
Color is by colourless to navy blue.
Description of the drawings
Fig. 1 is the hydrogen nuclear magnetic spectrogram for the DPP block polymers containing trianilino group that embodiment one obtains；
Fig. 2 is the cyclic voltammogram for the DPP block polymers containing trianilino group that embodiment one obtains；
Fig. 3 is the electrochromism figure for the DPP block polymers containing trianilino group that embodiment one obtains；
Fig. 4 is the thermogravimetric curve figure for the DPP block polymers containing trianilino group that embodiment one obtains；
Fig. 5 is the response fluorescence to explosive TNT for the DPP block polymers containing trianilino group that embodiment one obtains
Figure；
Fig. 6 is the DPP block polymers containing trianilino group that embodiment one obtains to the picric response of explosive
Fluorogram；
Fig. 7 is the memory performance curve graph for the DPP block polymers containing trianilino group that embodiment one obtains；
Fig. 8 is that the DPP block polymers containing trianilino group that embodiment one obtains change the rank under voltage in 0~1.3V
Jump and current drain curve.
Specific implementation mode
Technical solution of the present invention is not limited to the specific implementation mode of act set forth below, further include each specific implementation mode it
Between arbitrary combination.
Specific implementation mode one：The structural formula of DPP block polymer of the present embodiment containing trianilino group is as follows：
,
N is positive integer in formula.
Specific implementation mode two：Present embodiment from specific implementation mode one unlike：DPP containing trianilino group
The positive integer that n is 3~10 in the structural formula of block polymer.It is same as the specific embodiment one.
Specific implementation mode three：The preparation method of DPP block polymer of the present embodiment containing trianilino group be by with
What lower step carried out：
One, bis- (8- (tributyl tin alkyl) octyl) pyrrolo- [3,4-c] pyrroles of 3,6- bis- (thiophene -2- bases) -2,5- are synthesized
Cough up-Isosorbide-5-Nitrae (2H, 5H)-diketone：1., tert-pentyl alcohol and sodium mixed, 2- cyano thiophenes and dimethyl succinate are added thereto, leads to
Enter N2It is protected, under conditions of temperature is 90~120 DEG C after 18~28h of reaction, reaction temperature is cooled down from 90~120 DEG C
Glacial acetic acid is added dropwise after to 60~80 DEG C dropwise to there is solid evolution reaction liquid sticky, adds first alcohol and water and is diluted, then
It is cooled to room temperature under stirring conditions, first washes 3~5 times and washed 3~5 times using methanol again, obtain dark red solid, as
DPP；2., the DPP that 1. obtains step, potassium tert-butoxide and anhydrous DMF mixing, be passed through N2It is protected, is 100 DEG C in temperature
Under the conditions of 1,8-, bis- bromooctanes are added dropwise thereto after 2~5h of reaction, drip reaction temperature after 1,8-, bis- bromooctanes from 100 DEG C
120~150 DEG C are warming up to, under conditions of temperature is 120~150 DEG C after the reaction was continued 20~28h, cooled to room temperature,
Products therefrom, which pours into ice water, is precipitated solid precipitation, filtering, and filter residue is first washed 3~5 times and washed 3~5 times using methanol again, obtains thick
Product；Gained crude product uses column chromatography for separation, obtains red solid compound；3., in N2By red solid chemical combination under atmosphere
Vacuum nitrogen gas 3~5 times repeatedly after object and the THF of water removal mixing, it is anti-in the isothermal reaction bath that temperature is -70~-80 DEG C
N-BuLi is added after answering 30~50min, reaction temperature is warming up to -40 DEG C from -70~-80 DEG C, the item for being -40 DEG C in temperature
3~5h is reacted under part, and reaction temperature is then cooled to -70~-80 DEG C from -40 DEG C, the condition for being -70~-80 DEG C in temperature
Lower addition tributyltin chloride reacts 30~45min, finally reaction temperature is warming up to from -70~-80 DEG C room temperature reaction 20~
After 28h, tin reagent product is obtained, M1 is denoted as；1. the quality of middle sodium and the volume ratio of tert-pentyl alcohol are 1g to step:(50~90) mL；
1. the volume ratio of middle 2- cyano thiophenes and tert-pentyl alcohol is 1 to step:(7~9)；Step 1. in dimethyl succinate and tert-pentyl alcohol body
Product is than being 1:(10~70)；1. the volume ratio of middle glacial acetic acid and tert-pentyl alcohol is 1 to step:(35~45)；Step 2. in DPP and tertiary fourth
The molar ratio of potassium alcoholate is 1:(2.5~7)；2. the molar ratio of middle DPP and anhydrous DMF is 1 to step:(8~16)；Step 2. in DPP
Molar ratio with bis- bromooctanes of 1,8- is 1:(6~16)；Step 3. in red solid compound quality and water removal THF body
Product is than being 1g:(0.5~1.6) mL；3. the molar ratio of middle red solid compound and n-BuLi is 1 to step:(1.1~4)；Step
Suddenly 3. the molar ratio of middle red solid compound and tributyltin chloride is 1:(3~12)；
Two, N1, bis- (4- bromophenyls)-N4, the N4- diphenyl benzene -1,4- diamine monomers of N1- are synthesized：1., by diamine monomer,
Sodium hydride and anhydrous DMF mixing, obtain reaction system, are added into reaction system to fluorine under conditions of nitrogen atmosphere and stirring
Nitrobenzene is reacted by reaction temperature from room temperature to 115~120 DEG C under conditions of temperature is 115~120 DEG C, with
Thin-layered chromatography judges whether reaction final product generates,, will be cold by reaction solution cooled to room temperature after generating final product
But the reaction solution after pours into and crude product is precipitated in cool brine, filtering, and uses water washing 3~5 times, through ethyl alcohol recrystallization, filters,
Vacuum drying obtains yellow powder compound；2. at ambient temperature, by absolute ethyl alcohol, 10%Pd/C and yellow powder compound
Mixing, then passes to nitrogen and is protected, hydrazine hydrate is slowly added dropwise thereto using constant pressure funnel, by reaction temperature from room
Temperature is warming up to solution reflux, and persistently flow back 24~48h at such a temperature, stops heating and filtering while hot after reaction removing
10%Pd/C pours into filtrate in cold water, and thick sodium chloride is added under stirring conditions to Off-white solid is precipitated, filters, uses
Ethyl alcohol washs 3~5 times, and vacuum drying obtains compound as white solid；3. by dry toluene, to bromo-iodobenzene, white solid chemical combination
Object, Pd (dba) 2, bis- (diphenylphosphine) ferrocene of 1,1'- and sodium tert-butoxide mixing, then pass to nitrogen and are protected, will be reacted
Temperature flows back from room temperature to solution, is persistently stirred to react at such a temperature for 24 hours, cooled to room temperature, and crude product uses
Column chromatography is purified, and vacuum drying obtains white solid, is denoted as Mb；1. the molar ratio of middle diamine monomer and sodium hydride is step
1:(0.7~1.4)；1. the molar ratio of middle diamine monomer and anhydrous DMF is 1 to step:(5~9)；Step 1. in diamine monomer with it is right
The molar ratio of fluoronitrobenzene is 1:(1.4~2.2)；1. the quality of middle diamine monomer and the volume ratio of cool brine are 1g to step:
(175~225) mL；2. the quality of middle 10%Pd/C and the volume ratio of absolute ethyl alcohol are 1g to step:(200~300) mL；Step is 2.
The mass ratio 1 of middle 10%Pd/C and yellow powder compound:(8~12)；Step 3. in bis- (diphenylphosphine) ferrocene of 1,1'- and
Molar ratio to bromo-iodobenzene is 1:(12~15)；Step 3. in bis- (diphenylphosphine) ferrocene of 1,1'- and compound as white solid
Molar ratio be 1:(5~5.5)；3. the molar ratio of middle bis- (diphenylphosphine) ferrocene of 1,1'- and Pd (dba) 2 are 1 to step:
(0.2~0.4)；3. the molar ratio of middle bis- (diphenylphosphine) ferrocene of 1,1'- and sodium tert-butoxide is 1 to step:(20~50)；Step
3. the quality of middle bis- (diphenylphosphine) ferrocene of 1,1'- and the volume ratio of dry toluene are 1g:(50~80) mL；
Three, synthetic polymer：By M1, Mb, tetra-triphenylphosphine palladium and except water-toluene is added in the Lay pipe of SmithKline, it is passed through N2Into
Row protection, the DPP block polymers obtained for 24 hours containing trianilino group are protected from light under the conditions of temperature is 115 DEG C；The M1
Molar ratio with Mb is 1:1；The molar ratio of the tetra-triphenylphosphine palladium and Mb are 1:100；The quality of the Mb with remove water-toluene
Volume ratio be 1g:(10~30) mL.
Specific implementation mode four：Present embodiment from specific implementation mode three unlike：Step 1 1. described in column
Chromatography is used as mobile phase using petroleum ether and dichloromethane mixing, and the wherein volume of petroleum ether and dichloromethane is 3:1.With it is specific
Embodiment three is identical.
Specific implementation mode five：Present embodiment from specific implementation mode three or four unlike：Step 2 3. in institute
It states column chromatography and mobile phase is used as using petroleum ether and dichloromethane mixing, the wherein volume of dichloromethane and petroleum ether is 1:(20
~25).It is identical as specific implementation mode three or four.
Specific implementation mode six：DPP block polymer of the present embodiment containing trianilino group is used for field of photovoltaic materials.
Specific implementation mode seven：Present embodiment from specific implementation mode six unlike：The field of photovoltaic materials
For electrochromic material, fluorescent sensing material, hole mobile material, anti-fake material, camouflage material, automobile rearview mirror material or show
Screen material.It is identical as specific implementation mode six.
Specific implementation mode eight：Present embodiment from specific implementation mode six or seven unlike：Containing trianilino group
DPP block polymers be used to prepare electrochromic material and specifically carry out according to the following steps：DPP containing trianilino group is embedding
Section polymer is dissolved in organic solvent N-Methyl pyrrolidone, block polymer solution is obtained, then by block polymer solution
In rotation figure on electro-conductive glass, it is dried in vacuo at 80 DEG C and obtains electrochromic material.It is identical as specific implementation mode six or seven.
Specific implementation mode nine：DPP block polymer of the present embodiment containing trianilino group is used to prepare explosion quality testing
It measures and monitor the growth of standing timber material.
Specific implementation mode ten：Present embodiment from specific implementation mode nine unlike：DPP containing trianilino group
Block polymer is used to prepare explosive detection material and specifically carries out according to the following steps：By the DPP blocks containing trianilino group
Polymer is dissolved in organic solvent, obtains block polymer solution, then by the N-Methyl pyrrolidone solution containing explosive
It is added dropwise in block polymer solution, detects the variation of solution fluorescence intensity, you can judge in detection solution with the presence or absence of explosion
Object and fluorescent quenching efficiency.It is identical as specific implementation mode nine.
Beneficial effects of the present invention are verified using following embodiment：
Embodiment one：The preparation method of DPP block polymers containing trianilino group carries out according to the following steps：
One, bis- (8- (tributyl tin alkyl) octyl) pyrrolo- [3,4-c] pyrroles of 3,6- bis- (thiophene -2- bases) -2,5- are synthesized
Cough up-Isosorbide-5-Nitrae (2H, 5H)-diketone：1., 40mL tert-pentyl alcohols and 0.5g (5mmol) sodium mixed, 5mL 2- cyano thiophenes are added thereto
Pheno and 2.6mL dimethyl succinates, are passed through N2It is protected, after being reacted for 24 hours under conditions of temperature is 100 DEG C, by reaction temperature
Degree is cooled to after 80 DEG C from 100 DEG C 1mL glacial acetic acid is added dropwise dropwise to there is solid evolution reaction liquid sticky, add first alcohol and water into
Row dilution, is then cooled to room temperature under stirring conditions, first washes 3~5 times and is washed 3~5 times using methanol again, obtains peony
Solid, as DPP, yield 75%；2., by 1.5g DPP, 2.7463g potassium tert-butoxides and 60mL anhydrous DMFs mix, be passed through N2
It is protected, 13.6010g 1 is added dropwise thereto after reaction 3h under conditions of temperature is 100 DEG C, bis- bromooctanes of 8- drip
Reaction temperature is warming up to 120 DEG C from 100 DEG C after 1,8- bis- bromooctane, the reaction was continued under conditions of temperature is 120 DEG C for 24 hours
Afterwards, cooled to room temperature, products therefrom, which pours into ice water, is precipitated solid precipitation, filtering, and filter residue is first washed 3~5 times and used again
Methanol is washed 3~5 times, and crude product is obtained；Gained crude product uses column chromatography for separation, obtains red solid compound, yield is
31%；The column chromatography is used as mobile phase, the wherein volume of petroleum ether and dichloromethane using petroleum ether and dichloromethane mixing
It is 3:1；3., in N2The THF for removing water 2g red solid compounds and 20mL under atmosphere mix after repeatedly vacuum nitrogen gas 3~
5 times, 1.2mL n-BuLis are added after reaction 30min in the isothermal reaction bath that temperature is -78 DEG C, by reaction temperature from -78 DEG C
- 40 DEG C are warming up to, 4h is reacted under conditions of temperature is -40 DEG C, reaction temperature is then cooled to -78 DEG C from -40 DEG C, in temperature
Degree is added 2mL tributyltin chlorides under conditions of being -78 DEG C and reacts 30min, and reaction temperature is finally warming up to room temperature from -78 DEG C
After reaction for 24 hours, tin reagent product is obtained, M1 is denoted as；
Two, N1, bis- (4- bromophenyls)-N4, the N4- diphenyl benzene-Isosorbide-5-Nitrae-diamine monomers of N1- are synthesized：1., by 4g diamines lists
Body, 22mmol sodium hydrides and the mixing of 150mL anhydrous DMFs, obtain reaction system, to reaction under conditions of nitrogen atmosphere and stirring
In system be added 6.21g p-fluoronitrobenzenes, by reaction temperature from room temperature to 115 DEG C, temperature be 115 DEG C under conditions of into
Row reaction is judged to react whether final product generates with thin-layered chromatography, after generating final product, reaction solution is naturally cooled to
Reaction solution after cooling is poured into 700mL cool brines and crude product is precipitated by room temperature, filtering, and uses water washing 3~5 times, through second
Alcohol recrystallizes, and filtering, vacuum drying obtains yellow powder compound, yield 85%；2. at ambient temperature, that 100mL is anhydrous
Ethyl alcohol, the mixing of 0.50g 10%Pd/C and 4g yellow powder compounds, are then passed to nitrogen and are protected, leaked using constant pressure addition
12mL hydrazine hydrates are slowly added dropwise in bucket thereto, and reaction temperature is flowed back from room temperature to solution, is persistently flowed back at such a temperature
For 24 hours, stop heating and filtering while hot after reaction removing 10%Pd/C, filtrate be poured into 700mL cold water, in the item of stirring
Thick sodium chloride is added under part to Off-white solid is precipitated, filters, is washed 3~5 times with ethyl alcohol, vacuum drying obtains white solid
Conjunction object, 79%；3. by 40mL dry toluenes, 3.3948g to bromo-iodobenzene, 1.30065g compound as white solid, 0.21gPd
(dba) 2,0.6g 1, bis- (diphenylphosphine) ferrocene of 1'- and the mixing of 2g sodium tert-butoxides, then pass to nitrogen and are protected, will be anti-
It answers temperature to flow back from room temperature to solution, is persistently stirred to react for 24 hours at such a temperature, cooled to room temperature, crude product is adopted
It is purified with column chromatography, vacuum drying obtains white solid, is denoted as Mb, yield 36%；The column chromatography uses petroleum ether
It is used as mobile phase with dichloromethane mixing, the wherein volume of dichloromethane and petroleum ether is 1:(20~25)；
Three, synthetic polymer：By 1.23g M1,1gMb, 0.01g tetra-triphenylphosphine palladium and 20mL except water-toluene is added to history
In Ke Lai pipes, it is passed through N2It is protected, is protected from light for 24 hours under the conditions of temperature is 115 DEG C, obtains 1.4g containing trianilino group
DPP block polymers；Yield 31%.
Fig. 1 is the hydrogen nuclear magnetic spectrogram for the DPP block polymers containing trianilino group that embodiment one obtains；To polymer into
Row1H-NMR characterization tests can be found that the peak of the range of 1.0~4.0ppm or so is the hydrogen peak of octyl chain from nuclear-magnetism figure, because
Polarity is smaller, and the displacement at peak is also small.Hydrogen within the scope of 1.0~2.0ppm is located at chain middle section, and ambient enviroment has hydrogen.According to
" n+1 principles ", therefore multiplet is presented.And the big group of polarized around the hydrogen at 6.8~8.2, so compared on chain other
Hydrogen shift is larger.Since the polarity of double bond effect and S atom is big, therefore displacement is big compared to the hydrogen peak shift on alkyl chain.Amide groups
Group is because there are substituent groups without hydrogen atom, therefore without peak.Pass through1H-NMR can prove successfully to synthesize target product.
Fig. 2 is the cyclic voltammogram for the DPP block polymers containing trianilino group that embodiment one obtains, and wherein solution is
The Bu of 0.2mol/L4NClO4Acetonitrile solution, sweep speed 50mV/s, scanning range are 0V to 1.7V；From in figure can from
There are two pairs of apparent redox peaks to polymer.The voltage of wherein oxidation peak is respectively 0.72V and 1.08V, reduction peak point
It Wei not 0.96V and 1.29V.It is the color caused by electron exchange in N atoms in polymer TPA groups to generate oxidation peak
Au bleu is become by the light yellow green that becomes again；The color of reduction peak again by blue become green eventually become it is light yellow.Two kinds of face
Color cycle occurs, and illustrates that polymer has good cyclical stability.
Fig. 3 is the electrochromism figure for the DPP block polymers containing trianilino group that embodiment one obtains, external when applying
Voltage is to occur two new absorption peaks and the increase absorption peak with voltage at 412nm and 938nm from 0V-1.4V
It is increasing, electrochromic color is from colourless to navy blue.Before no applied voltage, thin polymer film has by force at 412nm
Absorption peak.With the gradual increase of voltage, there is new peak in 938nm and peak gradually increases, at this time thin polymer film color
Become blue from light yellow.This is because TPA groups are oxidized to caused by ion in polymer, therefore corresponding process
Color is changed by light yellow change au bleu, and the power of absorption peak is also changed.
Fig. 4 is the thermogravimetric curve figure for the DPP block polymers containing trianilino group that embodiment one obtains, can from figure
To find out, the carbon residual volume that polymer measures at 800 DEG C in a nitrogen atmosphere illustrates polymer with high temperature resistant 68%
Characteristic and with than good stability, between the temperature when weightlessness reaches 10% is 380~400 DEG C, 100~300 DEG C of mistakes
Weight is shallower, and 400~600 DEG C of weight loss rates are larger, and when heating reaches 800 DEG C, carbon residual volume is about 68%, has higher
Carbonation rate is because containing more phenyl ring in polymer.From the point of view of thermogravimetric analysis figure, we can obtain containing triphenylamine base
The DPP polymer of group has preferable thermal stability, can do heat-resisting material.
Fig. 5 is the response fluorescence to explosive TNT for the DPP block polymers containing trianilino group that embodiment one obtains
Figure.TNT is with 1 × 10 as can be observed from Figure-5Concentration interval increases as being incremented by for concentration is added in TNT, polymer solution
Fluorescence intensity is in gradually decrease and the more fluorescent quenching efficiency of addition constantly increase, and efficiency is quenched and is up to
82%.Illustrate that polymer there is good response and fluorescent quenching rate can also reach relatively high the detection of explosive.
Fig. 6 is the DPP block polymers containing trianilino group that embodiment one obtains to the picric response of explosive
Fluorogram.TNP is with 1 × 10 as can be observed from Figure-5Concentration interval increases, with the increase that bitter taste acid concentration is added, polymerization
The fluorescence intensity of object solution is gradually weakening, but fluorescent quenching efficiency is constantly increasing, and efficiency is quenched and reaches 87%.It says
Bright polymer has response well to explosive, therefore has good application prospect in context of detection.
Fig. 7 is the memory performance curve graph for the DPP block polymers containing trianilino group that embodiment one obtains；From figure
It is observed that on-off ratio is 2.9 × 103, when the first step, which scans, applies voltage from 0~-8V, memory device is from low conductivity
When state (OFF) is switched to high conductivity state (ON), electric current sharply increases, this process with alive increase is applied at this time
It is named as " write-in " process.Second step scanning apply voltage from 0~-8V when, still in ON states, device still keeps high conducting shape
State.Third step scanning applies voltage from 0~-8V, and from ON condition conversion to OFF state, this process is named as device at this time
" erasing " process.4th step surface sweeping apply voltage from 0V-8V when, be now in low conduction state.Therefore, which prepares
With non-volatile data storage performance.
Fig. 8 is that the DPP block polymers containing trianilino group that embodiment one obtains change the rank under voltage in 0~1.3V
Jump and current drain curve, medium wavelength 598nm, the Bu of period of change 10s, 0.2mol/L4NClO4Acetonitrile solution；Response
Time and stability is one of an important factor for influencing the characteristic of electrochromic material, and the response time refers to polymer from a kind of face
Colour-stable state reaches the time needed for the stable state 90% of another color, it depends on the electrochemistry of electrochromic material
Electronics, ion diffusion velocity etc. in reaction speed, electrode face finish object film.When to the double of polymer application 0.0 to 1.3V
When step voltage, we can be by observing polymer current density change, to be used for judging the stability of polymer.From
We can see that current density is kept not substantially after polymer recycles repeatedly under double step voltages of 0.0V to 1.3V in figure
Become, the generation of thin polymer film color is significantly reversible during the test changes repeatedly, this illustrates that polymer has stable electricity
Cause color shifting properties.
Claims (10)
1. a kind of DPP block polymers containing trianilino group, it is characterised in that the DPP block polymers containing trianilino group
Structural formula is as follows：
,
N is positive integer in formula.
2. a kind of DPP block polymers containing trianilino group according to claim 1, it is characterised in that contain triphenylamine base
The positive integer that n is 3~10 in the structural formula of the DPP block polymers of group.
3. a kind of preparation method of the DPP block polymers containing trianilino group as described in claim 1, it is characterised in that contain
The preparation method of the DPP block polymers of trianilino group carries out according to the following steps：
One, bis- (8- (tributyl tin alkyl) octyl) pyrrolo- [3,4-c] pyrroles -1 of 3,6- bis- (thiophene -2- bases) -2,5- are synthesized,
4 (2H, 5H)-diketone：1., tert-pentyl alcohol and sodium mixed, 2- cyano thiophenes and dimethyl succinate are added thereto, is passed through N2Into
Row protection, under conditions of temperature is 90~120 DEG C after 18~28h of reaction, reaction temperature is cooled to from 90~120 DEG C to 60~
Glacial acetic acid is added dropwise after 80 DEG C dropwise to there is solid evolution reaction liquid sticky, adds first alcohol and water and is diluted, then stirring
Under conditions of be cooled to room temperature, first wash and washed 3~5 times using methanol again for 3~5 times, obtain dark red solid, as DPP；②,
1. DPP, potassium tert-butoxide and anhydrous DMF mixing that step is obtained, is passed through N2It is protected, under conditions of temperature is 100 DEG C
1,8-, bis- bromooctanes are added dropwise thereto after 2~5h of reaction, are warming up to reaction temperature from 100 DEG C after dripping 1,8-, bis- bromooctanes
120~150 DEG C, under conditions of temperature is 120~150 DEG C after the reaction was continued 20~28h, cooled to room temperature, gained production
Object, which pours into ice water, is precipitated solid precipitation, filtering, and filter residue is first washed 3~5 times and washed 3~5 times using methanol again, and crude product is obtained；
Gained crude product uses column chromatography for separation, obtains red solid compound；3., in N2It by red solid compound and is removed under atmosphere
Water THF mixing after vacuum nitrogen gas 3~5 times repeatedly, temperature be -70~-80 DEG C isothermal reaction bath in reaction 30~
N-BuLi is added after 50min, reaction temperature is warming up to -40 DEG C from -70~-80 DEG C, it is anti-under conditions of being -40 DEG C in temperature
3~5h is answered, reaction temperature is then cooled to -70~-80 DEG C from -40 DEG C, is added under conditions of being -70~-80 DEG C in temperature
Tributyltin chloride reacts 30~45min, finally by reaction temperature after -70~-80 DEG C are warming up to 20~28h of room temperature reaction,
Tin reagent product is obtained, M1 is denoted as；1. the quality of middle sodium and the volume ratio of tert-pentyl alcohol are 1g to step:(50~90) mL；Step is 1.
The volume ratio of middle 2- cyano thiophenes and tert-pentyl alcohol is 1:(7~9)；1. the volume ratio of middle dimethyl succinate and tert-pentyl alcohol is step
1:(10~70)；1. the volume ratio of middle glacial acetic acid and tert-pentyl alcohol is 1 to step:(35~45)；Step 2. in DPP and potassium tert-butoxide
Molar ratio is 1:(2.5~7)；2. the molar ratio of middle DPP and anhydrous DMF is 1 to step:(8~16)；Step 2. in DPP and 1,8-
The molar ratio of two bromooctanes is 1:(6~16)；Step 3. in the quality of red solid compound and the volume ratio of THF of water removal be
1g:(0.5~1.6) mL；3. the molar ratio of middle red solid compound and n-BuLi is 1 to step:(1.1~4)；Step 3. in
The molar ratio of red solid compound and tributyltin chloride is 1:(3~12)；
Two, N1, bis- (4- bromophenyls)-N4, the N4- diphenyl benzene -1,4- diamine monomers of N1- are synthesized：1., by diamine monomer, hydrogenation
Sodium and anhydrous DMF mixing, obtain reaction system, are added into reaction system to fluorine nitro under conditions of nitrogen atmosphere and stirring
Benzene is reacted, with thin layer by reaction temperature from room temperature to 115~120 DEG C under conditions of temperature is 115~120 DEG C
Chromatography judges to react whether final product generates, after generating final product, by reaction solution cooled to room temperature, after cooling
Reaction solution pour into crude product be precipitated in cool brine, filter, and using water washing 3~5 times, through ethyl alcohol recrystallization, filtering, vacuum
It is dried to obtain yellow powder compound；2. at ambient temperature, absolute ethyl alcohol, 10%Pd/C and yellow powder compound are mixed
It closes, then passes to nitrogen and protected, hydrazine hydrate is slowly added dropwise using constant pressure funnel thereto, by reaction temperature from room temperature
It is warming up to solution reflux, persistently flow back 24~48h at such a temperature, stops heating and filtering while hot after reaction removing 10%
Pd/C pours into filtrate in cold water, and thick sodium chloride is added under stirring conditions to Off-white solid is precipitated, filters, uses ethyl alcohol
Washing 3~5 times, vacuum drying obtain compound as white solid；3. by dry toluene, to bromo-iodobenzene, compound as white solid, Pd
(dba) 2, bis- (diphenylphosphine) ferrocene of 1,1'- and sodium tert-butoxide mixing, then pass to nitrogen and are protected, by reaction temperature
It flows back, is persistently stirred to react at such a temperature for 24 hours, cooled to room temperature from room temperature to solution, crude product uses column layer
Analysis is purified, and vacuum drying obtains white solid, is denoted as Mb；1. the molar ratio of middle diamine monomer and sodium hydride is 1 to step:
(0.7~1.4)；1. the molar ratio of middle diamine monomer and anhydrous DMF is 1 to step:(5~9)；Step 1. in diamine monomer with to fluorine
The molar ratio of nitrobenzene is 1:(1.4~2.2)；1. the quality of middle diamine monomer and the volume ratio of cool brine are 1g to step:(175
~225) mL；2. the quality of middle 10%Pd/C and the volume ratio of absolute ethyl alcohol are 1g to step:(200~300) mL；Step 2. in
The mass ratio 1 of 10%Pd/C and yellow powder compound:(8~12)；Step 3. in bis- (diphenylphosphine) ferrocene of 1,1'- with it is right
The molar ratio of bromo-iodobenzene is 1:(12~15)；Step 3. in bis- (diphenylphosphine) ferrocene of 1,1'- and compound as white solid
Molar ratio is 1:(5~5.5)；3. the molar ratio of middle bis- (diphenylphosphine) ferrocene of 1,1'- and Pd (dba) 2 are 1 to step:(0.2
~0.4)；3. the molar ratio of middle bis- (diphenylphosphine) ferrocene of 1,1'- and sodium tert-butoxide is 1 to step:(20~50)；Step 3. in
The quality of bis- (diphenylphosphine) ferrocene of 1,1'- and the volume ratio of dry toluene are 1g:(50~80) mL；
Three, synthetic polymer：By M1, Mb, tetra-triphenylphosphine palladium and except water-toluene is added in the Lay pipe of SmithKline, it is passed through N2It is protected
Shield is protected from light the DPP block polymers obtained for 24 hours containing trianilino group under the conditions of temperature is 115 DEG C；The M1 and Mb
Molar ratio be 1:1；The molar ratio of the tetra-triphenylphosphine palladium and Mb are 1:100；The quality of the Mb and the body for removing water-toluene
Product is than being 1g:(10~30) mL.
4. a kind of preparation method of DPP block polymers containing trianilino group according to claim 3, it is characterised in that
Step 1 1. described in column chromatography mobile phase, wherein petroleum ether and dichloromethane are used as using petroleum ether and dichloromethane mixing
Volume is 3:1.
5. a kind of preparation method of DPP block polymers containing trianilino group according to claim 3, it is characterised in that
Step 2 3. described in column chromatography mobile phase, wherein dichloromethane and petroleum ether are used as using petroleum ether and dichloromethane mixing
Volume is 1:(20~25).
6. a kind of application of the DPP block polymers containing trianilino group as described in claim 1, it is characterised in that contain triphen
The DPP block polymers of amine groups are used for field of photovoltaic materials.
7. a kind of application of DPP block polymers containing trianilino group according to claim 6, it is characterised in that described
Field of photovoltaic materials is electrochromic material, after fluorescent sensing material, hole mobile material, anti-fake material, camouflage material, automobile
Visor material or aobvious screen material.
8. a kind of application of DPP block polymers containing trianilino group according to claim 7, it is characterised in that contain three
The DPP block polymers of aniline group are used to prepare electrochromic material and specifically carry out according to the following steps：Triphenylamine base will be contained
The DPP block polymers of group are dissolved in organic solvent N-Methyl pyrrolidone, are obtained block polymer solution, are then gathered block
Polymer solution on electro-conductive glass, is dried in vacuo at 80 DEG C in rotation figure and obtains electrochromic material.
9. a kind of application of the DPP block polymers containing trianilino group as described in claim 1, it is characterised in that contain triphen
The DPP block polymers of amine groups are used to prepare explosive detection material.
10. a kind of application of DPP block polymers containing trianilino group according to claim 9, it is characterised in that contain
The DPP block polymers of trianilino group are used to prepare explosive detection material and specifically carry out according to the following steps：Triphen will be contained
The DPP block polymers of amine groups are dissolved in organic solvent, obtain block polymer solution, then by the N- first containing explosive
Base pyrrolidone solution is added dropwise in block polymer solution, detects the variation of solution fluorescence intensity, you can judges detection solution
In whether there is explosive and fluorescent quenching efficiency.
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| WO2005049695A1 (en) * | 2003-10-28 | 2005-06-02 | Ciba Specialty Chemicals Holding Inc. | Novel diketopyrrolopyrrole polymers |
| CN103665339A (en) * | 2012-09-18 | 2014-03-26 | 海洋王照明科技股份有限公司 | Diketopyrrolopyrrole-base polymer, and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2005049695A1 (en) * | 2003-10-28 | 2005-06-02 | Ciba Specialty Chemicals Holding Inc. | Novel diketopyrrolopyrrole polymers |
| CN103665339A (en) * | 2012-09-18 | 2014-03-26 | 海洋王照明科技股份有限公司 | Diketopyrrolopyrrole-base polymer, and preparation method and application thereof |
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| A.R. RABINDRANATH ET AL.: ""Purple red and luminescent polyiminoarylenes containing the 1,4-diketo-3,6-diphenylpyrrolo[3,4-c]pyrrole (DPP) chromophore"", 《POLYMER》 * |
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