CN105175716B - A kind of preparation method of the polyamide film containing trianilino group - Google Patents
A kind of preparation method of the polyamide film containing trianilino group Download PDFInfo
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Abstract
A kind of preparation method of the polyamide film containing trianilino group, it is related to a kind of preparation method of polyamide film.The invention aims to solve existing polyamide, solubility is low in organic solvent, it is difficult to process film forming and the low problem of light-spot positioning response sensitivity.The structural formula of the polyamide film containing trianilino group is：Preparation method：First, polymerisation；2nd, film-forming, obtains the polyamide film containing trianilino group；A kind of polyamide film containing trianilino group is applied as photoelectric material in electrochromic material, photochromic material, hole mobile material, third-order non-linear material, false proof, camouflage material and display material.The present invention can obtain a kind of polyamide film containing trianilino group.
Description
Technical field
The present invention relates to a kind of preparation method of polyamide film.
Background technology
Amine polymer containing triphen can form radical cation in the presence of electric field, be to prepare electric charge transmission material
Material, electroluminescent material, the important raw and processed materials of electrochromic material, while can also make organic dyestuff and medicine intermediate.Fragrance
Property polyamide is high performance polymer, and they have good mechanical performance and electrochromic property, it is expected to used in optical storage,
Light memory, optics computing, in optical Limiting lasing safety.But it is low that existing polyamide is still present dissolubility, it is difficult to which film forming adds
Work, the low problem of light-spot positioning response sensitivity needs further research and improves.Main solution is introduced on main chain
Big group.On the other hand, by changing chemical constitution and composition, the solubility property and film forming of polyamide are improved, further
Increase polyamide application field:Such as light active material, fluorescence, electrically active films and amberplex.
The content of the invention
The invention aims to solve existing polyamide, solubility is low in organic solvent, it is difficult to process film forming and photoelectricity
The low problem of discoloration response sensitivity, and a kind of preparation method of the polyamide film containing trianilino group is provided.
A kind of structural formula of the polyamide film containing trianilino group is：
Wherein, described R1ForDescribed R2ForDescribed n1Value be 1≤n1≤ 100, and n1For whole
Number；Described n2Value be 1≤n2≤ 100, and n2It is integer.
A kind of preparation method of the polyamide film containing trianilino group, completes according to the following steps：
First, polymerisation：
By N, N '-two (Alpha-Naphthyl)-N, N '-two (4- aniline) benzidine monomers or N, N '-diphenyl-N, N '-two (4-
Aniline) reacted during benzidine monomer, diacid monomer and calcium chloride adds organic solvent, then at being 120 DEG C~150 DEG C in temperature
5h~7h, reuses methyl alcohol and settles out reactant I, then carries out suction filtration, discards filtrate, obtains reactant I；Recycle surname extraction side
Method is purified to reactant I, then the reactant I after purification is dried into 3h~5h in the case where temperature is for 30~40 DEG C, is contained
The polyamide of triphenylamine；
N described in step one, N '-two (Alpha-Naphthyl)-N, N '-two (4- aniline) benzidine monomers and diacid monomer
Mol ratio is 1:1 or N, N ' mol ratio of-diphenyl-N, N '-two (4- aniline) benzidine monomer and diacid monomer is 1:1；
N described in step one, N '-two (Alpha-Naphthyl)-N, N '-two (4- aniline) benzidine monomers or N, N '-hexichol
Base-N, N '-two (4- aniline) benzidine monomer are (0.001mol~0.05mol) with the volume ratio of organic solvent:3mL；
The quality of the calcium chloride described in step one is (0.2g~0.3g) with the volume ratio of organic solvent:3mL；
2nd, film-forming：Polyamide containing triphenylamine is dissolved into organic solvent, the polyamides containing triphenylamine is obtained
Amine aqueous solution；Polyamide solution containing trianilino group is coated under conditions of rotating speed is 1500r/min~2500r/min
On ito glass, then 8~10h is dried in the case where temperature is for 80 DEG C~100 DEG C, obtain the polyamide film containing trianilino group；
The thickness of the polyamide film containing trianilino group described in step 2 is 0.5 μm~5 μm；
The quality of the polyamide containing triphenylamine described in step 2 and the volume ratio of organic solvent for (0.0001~
0.0005g):1mL；
The structural formula of the polyamide film containing trianilino group described in step 2 is：
Wherein, described R1ForDescribed R2ForDescribed n1Value be 1≤n1≤ 100, and n1For whole
Number；Described n2Value be 1≤n2≤ 100, and n2It is integer.
Advantages of the present invention：
First, the polyamide film containing trianilino group prepared by the present invention is dissolved in dimethyl sulfoxide (DMSO), can be being led
Film is carried out on electric glass；Polyamide film containing trianilino group prepared by the present invention is used as working electrode, saturation calomel
Electrode is reference electrode, and platinum filament is that, to electrode, electrolyte is the electrochromic device of lithium perchlorate acetonitrile solution composition；
2nd, the polyamide film containing trianilino group prepared by the present invention can be as photoelectric material in electrochromism material
Applied in material, photochromic material, hole mobile material, third-order non-linear material, false proof, camouflage material and display material；
3rd, the polyamide film containing trianilino group prepared by the present invention has preferable invertibity, and dissolubility is big；
4th, the polyamide film containing trianilino group prepared by the present invention has a pair of redox peaks, this polymer tool
There is preferable invertibity；
5th, the present invention prepare the polyamide film containing trianilino group ultraviolet-ray visible absorbing peak value for 360nm~
370nm, the peak value of fluorescence spectrum is 496nm~506nm, and these are all conjugation triphenylamine π-π*Result obtained by electron transition.
The present invention can obtain a kind of polyamide film containing trianilino group.
Brief description of the drawings
Fig. 1 is the dinitrile monomer that 1. step 2 of embodiment one obtainsInfrared spectrum；
Fig. 2 is the N that 2. step 2 of embodiment one obtains, N '-two (betanaphthyl)-N, N '-two (4- carboxyls benzene) p-phenylenediamine
MonomerInfrared spectrogram；
Fig. 3 is the N that 2. step 2 of embodiment one obtains, N '-two (betanaphthyl)-N, N '-two (4- carboxyls benzene) p-phenylenediamine
MonomerH nuclear magnetic spectrum figures；
Fig. 4 is the N that 2. step 2 of embodiment one obtains, N '-two (betanaphthyl)-N, N '-two (4- carboxyls benzene) p-phenylenediamine
MonomerC nuclear magnetic spectrum figures；
Fig. 5 is the infrared spectrogram of the polyamide film containing trianilino group that the step 4 of embodiment one is obtained；
Fig. 6 is the cyclic voltammogram of the polyamide film containing trianilino group that the step 4 of embodiment one is obtained；
Fig. 7 is the ultraviolet spectrogram of the polyamide film containing trianilino group that the step 4 of embodiment one is obtained；
Fig. 8 is the fluorescence spectra of the polyamide film containing trianilino group that the step 4 of embodiment one is obtained；
Fig. 9 is the dinitrile monomer that 1. step 2 of embodiment two obtainsInfrared spectrogram；
Figure 10 is the N that 2. step 2 of embodiment two obtains, N '-two (Alpha-Naphthyl)-N, N '-two (4- carboxyls benzene) benzidine
MonomerInfrared spectrogram；
Figure 11 is the N that 2. step 2 of embodiment two obtains, N '-two (Alpha-Naphthyl)-N, N '-two (4- carboxyls benzene) benzidine
MonomerH nuclear magnetic spectrum figures；
Figure 12 is the infrared spectrogram of the polyamide film containing trianilino group that the step 4 of embodiment two is obtained；
Figure 13 is the cyclic voltammetric spectrogram of the polyamide film containing trianilino group that the step 4 of embodiment two is obtained；
Figure 14 is the ultraviolet spectrogram of the polyamide film containing trianilino group that the step 4 of embodiment two is obtained；
Figure 15 is the fluorescence spectra of the polyamide film containing trianilino group that the step 4 of embodiment two is obtained；
The infrared spectrogram of the polyamide film containing trianilino group obtained in the step 4 of Figure 16 embodiments three；
The cyclic voltammogram of the polyamide film containing trianilino group obtained in the step 4 of Figure 17 embodiments three；
The ultraviolet spectrogram of the polyamide film containing trianilino group obtained in the step 4 of Figure 18 embodiments three；
The fluorescence spectra of the polyamide film containing trianilino group obtained in the step 4 of Figure 19 embodiments three；
Figure 20 is the infrared spectrogram of the polyamide film containing trianilino group that example IV step 4 is obtained；
Figure 21 is the cyclic voltammogram of the polyamide film containing trianilino group that example IV step 4 is obtained；
Figure 22 is the ultraviolet spectrogram of the polyamide film containing trianilino group that example IV step 4 is obtained；
Figure 23 is the fluorescence spectra of the polyamide film containing trianilino group that example IV step 4 is obtained.
Specific embodiment
Specific embodiment one：Present embodiment is that a kind of structural formula of the polyamide film containing trianilino group is：
Wherein, it is described
R1ForDescribed R2ForOrDescribed n1Value be 1≤n1≤ 100, and n1It is integer；Described n2Value be 1≤n2
≤ 100, and n2It is integer.
Specific embodiment two：Present embodiment is that a kind of preparation method of the polyamide film containing trianilino group is
Complete according to the following steps：
First, polymerisation：
By N, N '-two (Alpha-Naphthyl)-N, N '-two (4- aniline) benzidine monomers or N, N '-diphenyl-N, N '-two (4-
Aniline) reacted during benzidine monomer, diacid monomer and calcium chloride adds organic solvent, then at being 120 DEG C~150 DEG C in temperature
5h~7h, reuses methyl alcohol and settles out reactant I, then carries out suction filtration, discards filtrate, obtains reactant I；Recycle surname extraction side
Method is purified to reactant I, then the reactant I after purification is dried into 3h~5h in the case where temperature is for 30~40 DEG C, is contained
The polyamide of triphenylamine；
N described in step one, N '-two (Alpha-Naphthyl)-N, N '-two (4- aniline) benzidine monomers and diacid monomer
Mol ratio is 1:1 or N, N ' mol ratio of-diphenyl-N, N '-two (4- aniline) benzidine monomer and diacid monomer is 1:1；
N described in step one, N '-two (Alpha-Naphthyl)-N, N '-two (4- aniline) benzidine monomers or N, N '-hexichol
Base-N, N '-two (4- aniline) benzidine monomer are (0.001mol~0.05mol) with the volume ratio of organic solvent:3mL；
The quality of the calcium chloride described in step one is (0.2g~0.3g) with the volume ratio of organic solvent:3mL；
2nd, film-forming：Polyamide containing triphenylamine is dissolved into organic solvent, the polyamides containing triphenylamine is obtained
Amine aqueous solution；Polyamide solution containing trianilino group is coated under conditions of rotating speed is 1500r/min~2500r/min
On ito glass, then 8~10h is dried in the case where temperature is for 80 DEG C~100 DEG C, obtain the polyamide film containing trianilino group；
The thickness of the polyamide film containing trianilino group described in step 2 is 0.5 μm~5 μm；
The quality of the polyamide containing triphenylamine described in step 2 and the volume ratio of organic solvent for (0.0001g~
0.0005g):1mL
The structural formula of the polyamide film containing trianilino group described in step 2 is：
Wherein, it is described
R1ForDescribed R2For Described n1Value be 1≤n1≤ 100, and n1It is integer；Described n2Value be 1≤n2≤
100, and n2It is integer.
The advantage of present embodiment：
First, the polyamide film containing trianilino group prepared by present embodiment is dissolved in dimethyl sulfoxide (DMSO), can be with
Film is carried out on electro-conductive glass；Present embodiment prepare the polyamide film containing trianilino group as working electrode,
Saturated calomel electrode is reference electrode, and platinum filament is that, to electrode, electrolyte is the electrochromism device of lithium perchlorate acetonitrile solution composition
Part；
2nd, the polyamide film containing trianilino group prepared by present embodiment can be as photoelectric material in electroluminescent change
Should in color material, photochromic material, hole mobile material, third-order non-linear material, false proof, camouflage material and display material
With；
3rd, the polyamide film containing trianilino group prepared by present embodiment has preferable invertibity, and dissolving
Property is big；
4th, the polyamide film containing trianilino group prepared by present embodiment has a pair of redox peaks, this polymerization
Thing has preferable invertibity；
5th, the ultraviolet-ray visible absorbing peak value of the polyamide film containing trianilino group prepared by present embodiment is
360nm~370nm, the peak value of fluorescence spectrum is 496nm~506nm, and these are all conjugation triphenylamine π-π*Electron transition gained
Result.
Present embodiment can obtain a kind of polyamide film containing trianilino group.
Specific embodiment three：Present embodiment is with the difference of specific embodiment two：N described in step one,
N '-two (Alpha-Naphthyl)-N, N '-two (4- aniline) benzidine monomer is prepared as follows：
1., in a nitrogen atmosphere by N, N- bis- (Alpha-Naphthyl) -4,4- benzidines are dissolved into dimethyl sulfoxide (DMSO), add
P-fluoronitrobenzene and sodium hydride, then 24h~30h is reacted at 100 DEG C, obtain reaction solution；Reaction solution is added in cold water, then
Suction filtration is carried out, filtrate is discarded, yellow mercury oxide material is obtained；Yellow mercury oxide material is cleaned 2 times~4 times using acetonitrile, then in temperature
Spend to dry 8~15h at 30 DEG C~40 DEG C, obtain product A；
Step 1. described in N, the amount ratio of the material of (the Alpha-Naphthyl) -4,4- benzidines of N- bis- and p-fluoronitrobenzene is 1:
2；
Step 1. described in N, the amount of the material of N- bis- (Alpha-Naphthyl) -4,4- benzidines and the volume of dimethyl sulfoxide (DMSO)
Than being 1mol:(100mL~200mL)；
Step 1. described in the volume ratio of quality and dimethyl sulfoxide (DMSO) of sodium hydride be (1g~3g):100mL；
2. product A and Pd/C catalyst, is added to N, in N '-dimethylformamide, in a hydrogen atmosphere, pressure
For 7MPa~9MPa, mixing speed be 120r/min~150r/min and temperature be react under conditions of 70 DEG C~90 DEG C 40h~
45h, obtains yellow-green precipitate material；Yellow-green precipitate material is carried out into suction filtration, filtrate is discarded, reactant B is obtained；Reuse first
Benzene cleaning reactant B 2 times~4 times, then dry 3h~5h at being 30 DEG C~40 DEG C in temperature, obtains N, and N '-two (Alpha-Naphthyl)-
N, N '-two (4- aniline) benzidine monomer；
Step 2. described in product A quality and N, N '-dimethylformamide volume ratio be (3g~5g):
250mL；
Step 2. described in Pd/C catalyst quality and N, N '-dimethylformamide volume ratio for (0.5g~
2g):250mL；
Step 2. described in Pd/C catalyst in Pd mass fraction be 10%.Other and specific embodiment two-phase
Together.
Specific embodiment four：Present embodiment is with the difference of specific embodiment two or three：Described in step
N, N '-diphenyl-N, N '-two (4- aniline) benzidine monomer is prepared as follows：
1., in a nitrogen atmosphere by N, N- biphenyl diamines are dissolved into dimethyl sulfoxide (DMSO), are added to fluorine nitro
Benzene and sodium hydride, then 24h~30h is reacted at 100 DEG C, obtain reaction solution；Reaction solution is added in cold water, then is taken out
Filter, discards filtrate, obtains yellow mercury oxide material；Yellow mercury oxide material is cleaned 2 times~4 times using acetonitrile, then is 30 in temperature
DEG C~40 DEG C at dry 8~15h, obtain product C；
Step 1. described in N, the quality of N- biphenyl diamines and the volume ratio of dimethyl sulfoxide (DMSO) are (6g~8g):
100mL；
Step 1. described in the volume ratio of quality and dimethyl sulfoxide (DMSO) of p-fluoronitrobenzene be (6g~8g):100mL；
Step 1. described in the volume ratio of quality and dimethyl sulfoxide (DMSO) of sodium hydride be (2g~3g):100mL；
2. product C and Pd/C catalyst, is added to N, in N '-dimethylformamide, in a hydrogen atmosphere, pressure
For 7MPa~9MPa, mixing speed be 120r/min~150r/min and temperature be react under conditions of 70 DEG C~90 DEG C 40h~
45h, obtains yellow-green precipitate material；Yellow-green precipitate material is carried out into suction filtration, filtrate is discarded, reactant D is obtained；Reuse first
Benzene cleaning reactant B 2 times~4 times, then dry 3h~5h at being 30 DEG C~40 DEG C in temperature, obtains N, and N '-diphenyl-N, N '-
Two (4- aniline) benzidine monomers；
Step 2. described in product C quality and N, N '-dimethylformamide volume ratio be (3g~4g):
200mL；
Step 2. described in Pd/C catalyst quality and N, N '-dimethylformamide volume ratio for (0.5g~
1.5g):200mL；
Step 2. described in Pd/C catalyst in Pd mass fraction be 10%.Other and specific embodiment two or three
It is identical.
Specific embodiment five：Present embodiment is with the difference of specific embodiment two to four：Described in step
Diacid monomer be N, N'- bis- (betanaphthyl)-N, N '-two (4- carboxyls benzene) p-phenylenediamine monomers or N, N'- bis- (Alpha-Naphthyl)-N,
N '-two (4- carboxyls benzene) benzidine monomer；Described diacid monomer is N, N'- bis- (betanaphthyl)-N, N '-two (4- carboxyls benzene)
The structural formula of p-phenylenediamine monomer isDescribed N, N'- bis- (Alpha-Naphthyl)-N, N '-two (4- carboxyls benzene)
The structural formula of benzidine monomer isOther are identical with specific embodiment two to four.
Specific embodiment six：Present embodiment is with the difference of specific embodiment two to five：Described N, N'- bis-
(betanaphthyl)-N, N '-two (4- carboxyls benzene) p-phenylenediamine monomer is prepared as follows：
1., in a nitrogen atmosphere, by N, N '-two (betanaphthyl) p-phenylenediamine is dissolved into anhydrous DMF
In, add to fluorobenzonitrile and sodium hydride, then 15h~20h is reacted in the case where temperature is for 120 DEG C~130 DEG C, it is 0 to reuse temperature
DEG C~5 DEG C of distilled water is settled out reactant E, then carries out suction filtration to reactant E, discards filtrate, then be 30 DEG C~35 in temperature
24h~30h is dried at DEG C, dried reactant E is obtained；Dried reactant E is recrystallized using acetone,
6h~8h is dried at being again 30 DEG C~35 DEG C in temperature, dinitrile monomer is obtained；
Step 1. described in N, the quality of N '-two (betanaphthyl) p-phenylenediamine and the body of anhydrous N,N-dimethylformamide
Product is than being 5g:(70mL~100mL)；
Step 1. described in quality to fluorobenzonitrile and the volume ratio of anhydrous N,N-dimethylformamide be 4g:(70mL
~100mL)；
Step 1. described in sodium hydride quality and anhydrous N,N-dimethylformamide volume ratio be 2g:(70mL~
100mL)；
2., dinitrile monomer, potassium hydroxide, methyl alcohol and distilled water are mixed, then is 100 DEG C~110 DEG C and to stir in temperature
It is stirring reaction 5 days~6 days under conditions of 120r/min~150r/min to mix speed, reuse temperature for 0 DEG C~5 DEG C, pH value
Distilled water for 2~3 is settled out reactant F；Suction filtration is carried out to reactant F again, filtrate is discarded, then is 30 DEG C~35 DEG C in temperature
Under dry 24h~30h, obtain dried reactant F；Use quality fraction be 6%~8% glacial acetic acid to dried anti-
Answer thing F to be recrystallized, obtain N, N '-two (betanaphthyl)-N, N '-two (4- carboxyls benzene) p-phenylenediamine monomer；
Step 2. described in the volume ratio of quality and methyl alcohol of dinitrile monomer be 3g:(8mL~10mL)；
Step 2. described in the volume ratio of quality and methyl alcohol of potassium hydroxide be 2g:(8mL~10mL)；
Step 2. described in the volume ratio of methyl alcohol and distilled water be (0.5~1.5):1.Other and specific embodiment two
It is identical to five.
Specific embodiment seven：Present embodiment is with the difference of specific embodiment two to six：Described N, N'- bis-
(Alpha-Naphthyl)-N, N '-two (4- carboxyls benzene) benzidine monomer is prepared as follows：
1., in a nitrogen atmosphere, by N, N '-two (1- naphthyls) -4,4- benzidines are dissolved into anhydrous N, N- dimethyl methyls
In acid amides, add to fluorobenzonitrile and sodium hydride, then 15h~20h is reacted in the case where temperature is for 120 DEG C~130 DEG C, reuse temperature
For 0 DEG C~5 DEG C of distilled water are settled out reactant G, then suction filtration is carried out to reactant G, discards filtrate, then temperature be 30 DEG C~
24h~30h is dried at 35 DEG C, dried reactant G is obtained；Dried reactant G is tied again using acetone
Crystalline substance, then 6h~8h is dried in the case where temperature is for 30 DEG C~35 DEG C, obtain dinitrile monomer；
Step 1. described in N, the quality and anhydrous N, N- dimethyl formyl of N '-two (1- naphthyls) -4,4- benzidines
The volume ratio of amine is 5g:(70mL~100mL)；
Step 1. described in quality to fluorobenzonitrile and the volume ratio of anhydrous N,N-dimethylformamide be 4g:(70mL
~100mL)；
Step 1. described in sodium hydride quality and anhydrous N,N-dimethylformamide volume ratio be 2g:(70mL~
100mL)；
2., dinitrile monomer, potassium hydroxide, methyl alcohol and distilled water are mixed, then is 100 DEG C~110 DEG C and to stir in temperature
It is stirring reaction 5 days~6 days under conditions of 120r/min~150r/min to mix speed, reuse temperature for 0 DEG C~5 DEG C, pH value
Distilled water for 2~3 is settled out reactant H；Suction filtration is carried out to reactant H again, filtrate is discarded, then is 30 DEG C~35 DEG C in temperature
Under dry 24h~30h, obtain dried reactant H；Use quality fraction be 6%~8% glacial acetic acid to dried anti-
Answer thing H to be recrystallized, obtain N, N '-two (Alpha-Naphthyl)-N, N '-two (4- carboxyls benzene) benzidine monomer；
Step 2. described in the volume ratio of quality and methyl alcohol of dinitrile monomer be 3g:(8mL~10mL)；
Step 2. described in the volume ratio of quality and methyl alcohol of potassium hydroxide be 2g:(8mL~10mL)；
Step 2. described in the volume ratio of methyl alcohol and distilled water be (0.5~1.5):1.Other and specific embodiment two
It is identical to six.
Specific embodiment eight：Present embodiment is with the difference of specific embodiment two to seven：Described in step
Organic solvent be the one kind in triphenyl phosphite, pyridine and 1-METHYLPYRROLIDONE or wherein several mixing.Other with
Specific embodiment two to seven is identical.
Specific embodiment nine：Present embodiment is with the difference of specific embodiment two to eight：Described in step 2
Organic solvent be N, N '-dimethylacetylamide, N, one kind in N '-dimethylformamide and 1-METHYLPYRROLIDONE or wherein
Several mixing.Other are identical with specific embodiment two to eight.
Specific embodiment ten：Present embodiment is a kind of polyamide film containing trianilino group as photoelectric material
In electrochromic material, photochromic material, hole mobile material, third-order non-linear material, false proof, camouflage material and display material
Applied in material.
Beneficial effects of the present invention are verified using tests below：
Embodiment one：A kind of preparation method of the polyamide film containing trianilino group, completes according to the following steps：
First, the N described in synthesis step one, N '-two (Alpha-Naphthyl)-N, N '-two (4- aniline) benzidine：
1., in a nitrogen atmosphere by 1mol N, it is sub- that N- bis- (Alpha-Naphthyl) -4,4- benzidines are dissolved into 100mL dimethyl
In sulfone, 2mol p-fluoronitrobenzenes and 2.5g sodium hydrides are added, then 28h is reacted at 100 DEG C, obtain reaction solution；By reaction solution
It is added in cold water, then carries out suction filtration, discard filtrate, obtains yellow mercury oxide material；3 are cleaned to yellow mercury oxide material using acetonitrile
It is secondary, then 11h is dried in the case where temperature is for 38 DEG C, obtain product A；
2. product A and Pd/C catalyst, is added to N, in N '-dimethylformamide, in a hydrogen atmosphere, pressure
For 8.5MPa, mixing speed are that 150r/min and temperature are to react 45h under conditions of 85 DEG C, yellow-green precipitate material is obtained；Will
Yellow-green precipitate material carries out suction filtration, discards filtrate, obtains reactant B；Reuse toluene cleaning reactant B 3 times, then in temperature
Spend to dry 3.5h at 40 DEG C, obtain N, N '-two (Alpha-Naphthyl)-N, N '-two (4- aniline) benzidine monomer；
Step one 2. described in product A quality and N, N '-dimethylformamide volume ratio be 5g:250mL；
Step one 2. described in Pd/C catalyst quality and N, N '-dimethylformamide volume ratio be 2g:
250mL；
Step one 2. described in Pd/C catalyst in Pd mass fraction be 10%；
2nd, N, N'- bis- (betanaphthyl)-N, N '-two (4- carboxyls benzene) p-phenylenediamine monomer are prepared：
1., in a nitrogen atmosphere, by 5g N, N '-two (betanaphthyl) p-phenylenediamine is dissolved into the anhydrous N of 80mL, N- dimethyl
In formamide, 4g is added to fluorobenzonitrile and 2g sodium hydrides, then react 15h in the case where temperature is for 120 DEG C, reuse temperature for 3 DEG C
Distilled water be settled out reactant E, then suction filtration is carried out to reactant E, discard filtrate, then be dried at being 35 DEG C in temperature
24h, obtains dried reactant E；Dried reactant E is recrystallized using acetone, then in the case where temperature is for 35 DEG C
7h is dried, dinitrile monomer is obtained；
2., by 3g dinitriles monomer, 2g potassium hydroxide, 8mL methyl alcohol and 6mL distilled water mix, then temperature be 100 DEG C and
Mixing speed is stirring reaction 5 days under conditions of 120r/min, and it is 3 DEG C to reuse temperature, and pH value is that 3 distilled water is settled out instead
Answer thing F；Suction filtration is carried out to reactant F again, filtrate is discarded, then 24h is dried in the case where temperature is for 35 DEG C, obtain dried reactant
F；Use quality fraction is that 8% glacial acetic acid is recrystallized to dried reactant F, obtains N, N '-two (betanaphthyl)-N,
N '-two (4- carboxyls benzene) p-phenylenediamine monomer；
3rd, polymerisation：
By N, N '-two (Alpha-Naphthyl)-N, N '-two (4- aniline) benzidine monomer, diacid monomer and calcium chloride are added to be had
5h is reacted in machine solvent, then at being 120 DEG C in temperature, methyl alcohol is reused and is settled out reactant I, then carry out suction filtration, discard filtrate, obtained
To reactant I；Recycle Soxhlet extraction method reactant I is purified, then by the reactant I after purification temperature be 35 DEG C
Lower drying 5h, obtains the polyamide containing triphenylamine；
N described in step 3, N '-two (Alpha-Naphthyl)-N, N '-two (4- aniline) benzidine monomers and diacid monomer
Mol ratio is 1:1；
N described in step 3, N '-two (Alpha-Naphthyl)-N, N '-two (4- aniline) benzidine monomers and organic solvent
Volume ratio is 0.001mol:3mL；
The quality of the calcium chloride described in step 3 is 0.25g with the volume ratio of organic solvent:3mL；
Organic solvent described in step 3 is pyridine, phosphorous acid triphenylamine and 1-METHYLPYRROLIDONE according to pyridine, Asia
The volume ratio of phosphoric acid triphenylamine and 1-METHYLPYRROLIDONE is 3:3:5 mix；
4th, film-forming：Polyamide containing triphenylamine is dissolved into organic solvent, the polyamides containing triphenylamine is obtained
Amine aqueous solution；Polyamide solution containing trianilino group is coated on ito glass under conditions of rotating speed is 2000r/min,
10h is dried at being again 80 DEG C in temperature, the polyamide film containing trianilino group is obtained；
The thickness of the polyamide film containing trianilino group described in step 4 is 1 μm；
Organic solvent described in step 4 is N, N '-dimethylacetylamide；
The quality of the polyamide containing triphenylamine described in step 4 is 0.0001g with the volume ratio of organic solvent:
1mL。
The step one of embodiment one 1. described in N, the structural formula of N- bis- (Alpha-Naphthyl) -4,4- benzidines is
The N that 2. step one of embodiment one obtains, the knot of N '-two (Alpha-Naphthyl)-N, N '-two (4- aniline) benzidine monomer
Structure formula is
The step one of embodiment one 1. in reaction equation be：
The step one of embodiment one 2. in reaction equation be：
The N that 2. step 2 of embodiment one obtains, N '-two (betanaphthyl)-N, N '-two (4- carboxyls benzene) p-phenylenediamine monomer
Structure is
The step 2 of embodiment one 1. described in N, the structural formula of N '-two (betanaphthyl) p-phenylenediamine is：
The step 2 of embodiment one 1. in reaction equation be：
The step 2 of embodiment one 2. in reaction equation be：
Reaction equation in the step 3 of embodiment one is：
The structural formula of the polyamide film containing trianilino group obtained in the step 4 of embodiment one is：
The span of described n is 3≤n≤10, and n is
Integer.
Fig. 1 is the dinitrile monomer that 1. step 2 of embodiment one obtainsInfrared spectrum；From Fig. 1
Understand, in 2246cm-1Characteristic peak is the CN stretching vibrations on main chain, and this explanation has prepared dinitrile monomer.
Fig. 2 is the N that 2. step 2 of embodiment one obtains, N '-two (betanaphthyl)-N, N '-two (4- carboxyls benzene) p-phenylenediamine
MonomerInfrared spectrogram；From figure 2 it can be seen that in 2500cm-1~3100cm-1Locating characteristic peak is
O-H stretching vibrations on main chain, in 1680cm-1Place is attributed to C=O stretching vibration peaks, this explanation prepared N in peak at two, and N '-
Two (betanaphthyl)-N, N '-two (4- carboxyls benzene) p-phenylenediamine monomer.
Fig. 3 is the N that 2. step 2 of embodiment one obtains, N '-two (betanaphthyl)-N, N '-two (4- carboxyls benzene) p-phenylenediamine
MonomerH nuclear magnetic spectrum figures；From figure 3, it can be seen that what is represented at 12 is carboxyl peak, and peak
The hydrogen number of area ratio and N, N '-two (betanaphthyl)-N, N '-two (4- carboxyls benzene) p-phenylenediamine monomer is consistent, and this explanation has been made
Obtain the consistent N of structure, N '-two (betanaphthyl)-N, N '-two (4- carboxyls benzene) p-phenylenediamine monomer.
Fig. 4 is the N that 2. step 2 of embodiment one obtains, N '-two (betanaphthyl)-N, N '-two (4- carboxyls benzene) p-phenylenediamine
MonomerC nuclear magnetic spectrum figures；Figure 4, it is seen that the area ratio and N, N '-two (betanaphthyl) at peak-
The carbon number of N, N '-two (4- carboxyls benzene) p-phenylenediamine monomer is consistent, and this illustrates the consistent N of prepared the structure, (β-naphthalene of N '-two
Base)-N, N '-two (4- carboxyls benzene) p-phenylenediamine monomer.
Fig. 5 is the infrared spectrogram of the polyamide film containing trianilino group that the step 4 of embodiment one is obtained；From Fig. 5
In as can be seen that embodiment one prepare the polyamide film containing trianilino group in 3220cm-1Characteristic peak is on main chain
N-H stretching vibrations, in 1675cm-1Place can be classified as C=O stretching vibration peaks, this at two the peak explanation generation that has been polymerized contain triphenylamine
The polyamide of group.
Fig. 6 is the cyclic voltammogram of the polyamide film containing trianilino group that the step 4 of embodiment one is obtained；From Fig. 6
Understand, cyclic voltammetry spectrum of the polyamide film containing trianilino group obtained in the step 4 of embodiment one under applied voltage
Figure, there is a pair of redox peaks, is oxidation peak at the peak of 1.20V, and simultaneous color is changed into red from light yellow；
There is 1 corresponding reduction peak at 0.50V, now color is changed into light yellow from red；Illustrate that this polymer has preferably reversible
Property.
Fig. 7 is the ultraviolet spectrogram of the polyamide film containing trianilino group that the step 4 of embodiment one is obtained；
Fig. 8 is the fluorescence spectra of the polyamide film containing trianilino group that the step 4 of embodiment one is obtained；
The polyamide film containing trianilino group that the step 4 of embodiment one is obtained is can be seen that from Fig. 7 and Fig. 8
Ultraviolet-ray visible absorbing peak value is 370nm, and the peak value of fluorescence spectrum is 502nm, and these are all conjugation triphenylamine π-π*Electron transition
The result of gained.
Embodiment two：A kind of preparation method of the polyamide film containing trianilino group, completes according to the following steps：
First, the N described in synthesis step one, N '-two (Alpha-Naphthyl)-N, N '-two (4- aniline) benzidine：
1., in a nitrogen atmosphere by 1mol N, it is sub- that N- bis- (Alpha-Naphthyl) -4,4- benzidines are dissolved into 100mL dimethyl
In sulfone, 2mol p-fluoronitrobenzenes and 2.5g sodium hydrides are added, then 28h is reacted at 100 DEG C, obtain reaction solution；By reaction solution
It is added in cold water, then carries out suction filtration, discard filtrate, obtains yellow mercury oxide material；3 are cleaned to yellow mercury oxide material using acetonitrile
It is secondary, then 11h is dried in the case where temperature is for 38 DEG C, obtain product A；
2. product A and Pd/C catalyst, is added to N, in N '-dimethylformamide, in a hydrogen atmosphere, pressure
For 8.5MPa, mixing speed are that 150r/min and temperature are to react 45h under conditions of 85 DEG C, yellow-green precipitate material is obtained；Will
Yellow-green precipitate material carries out suction filtration, discards filtrate, obtains reactant B；Reuse toluene cleaning reactant B 3 times, then in temperature
Spend to dry 3.5h at 40 DEG C, obtain N, N '-two (Alpha-Naphthyl)-N, N '-two (4- aniline) benzidine monomer；
Step one 2. described in product A quality and N, N '-dimethylformamide volume ratio be 5g:250mL；
Step one 2. described in Pd/C catalyst quality and N, N '-dimethylformamide volume ratio be 2g:
250mL；
Step one 2. described in Pd/C catalyst in Pd mass fraction be 10%；
2nd, N, N'- bis- (Alpha-Naphthyl)-N, N '-two (4- carboxyls benzene) benzidine monomer are prepared：
1., in a nitrogen atmosphere, by 5g N, N '-two (1- naphthyls) -4,4- benzidines are dissolved into the anhydrous N of 80mL, N- bis-
In NMF, 4.2g is added to fluorobenzonitrile and 2.3g sodium hydrides, then react 16h in the case where temperature is for 120 DEG C, reuse temperature
The distilled water spent for 2 DEG C is settled out reactant G, then carries out suction filtration to reactant G, discards filtrate, then enter in the case where temperature is for 35 DEG C
Row dries 26h, obtains dried reactant G；Dried reactant G is recrystallized using acetone, then is in temperature
8h is dried at 35 DEG C, dinitrile monomer is obtained；
2., 3.2g dinitriles monomer, 2g potassium hydroxide, 10mL methyl alcohol and 10mL distilled water are mixed, then is 100 in temperature
DEG C and mixing speed be stirring reaction 6 days under conditions of 120r/min, reuse temperature for 3 DEG C, pH value is 2 distillation water sedimentation
Go out reactant H；Suction filtration is carried out to reactant H again, filtrate is discarded, then 24h is dried in the case where temperature is for 35 DEG C, obtain dried anti-
Answer thing H；Use quality fraction is that 8% glacial acetic acid is recrystallized to dried reactant H, obtains the N, (α-naphthalene of N '-two
Base)-N, N '-two (4- carboxyls benzene) benzidine monomer；
3rd, polymerisation：
By N, N '-two (Alpha-Naphthyl)-N, N '-two (4- aniline) benzidine monomer, diacid monomer and calcium chloride are added to be had
6h is reacted in machine solvent, then at being 120 DEG C in temperature, methyl alcohol is reused and is settled out reactant I, then carry out suction filtration, discard filtrate, obtained
To reactant I；Recycle Soxhlet extraction method reactant I is purified, then by the reactant I after purification temperature be 40 DEG C
Lower drying 5h, obtains the polyamide containing triphenylamine；
N described in step 3, N '-two (Alpha-Naphthyl)-N, N '-two (4- aniline) benzidine monomers and diacid monomer
Mol ratio is 1:1；
N described in step 3, N '-two (Alpha-Naphthyl)-N, N '-two (4- aniline) benzidine monomers and organic solvent
Volume ratio is 0.05mol:3mL；
The quality of the calcium chloride described in step 3 is 0.3g with the volume ratio of organic solvent:3mL；
4th, film-forming：Polyamide containing triphenylamine is dissolved into organic solvent, the polyamides containing triphenylamine is obtained
Amine aqueous solution；Polyamide solution containing trianilino group is coated on ito glass under conditions of rotating speed is 2000r/min,
10h is dried at being again 80 DEG C in temperature, the polyamide film containing trianilino group is obtained；
The thickness of the polyamide film containing trianilino group described in step 4 is 1 μm；
Organic solvent described in step 4 is N, N '-dimethylacetylamide；
The quality of the polyamide containing triphenylamine described in step 4 is 0.0001g with the volume ratio of organic solvent:
1mL。
The diacid monomer that 2. step 2 of embodiment two obtains is N, N '-two (Alpha-Naphthyl)-N, N '-two (4- carboxyls benzene) biphenyl
Diamine monomer；The structural formula of described N, N '-two (Alpha-Naphthyl)-N, N '-two (4- carboxyls benzene) benzidine monomer is
The step 2 of embodiment two 1. in reaction equation be：
The step 2 of embodiment two 2. in reaction equation be：
The structural formula of the polyamide film containing trianilino group obtained in the step 4 of embodiment two is：The span of described n is 3≤n≤8, and n is integer.
Reaction equation in the step 3 of embodiment two is：
Fig. 9 is the dinitrile monomer that 1. step 2 of embodiment two obtainsInfrared spectrogram；From figure
9 understand, in 2246cm-1Characteristic peak is the CN stretching vibrations on main chain, and this explanation has prepared dinitrile monomer.
Figure 10 is the N that 2. step 2 of embodiment two obtains, N '-two (Alpha-Naphthyl)-N, N '-two (4- carboxyls benzene) benzidine
MonomerInfrared spectrogram；It can be seen from fig. 10 that monomer is in 3100cm-1Place's characteristic peak is main
O-H stretching vibrations on chain, in 1700cm-1Place is attributed to C=O stretching vibration peaks, this peak explanation prepared N, N '-two at two
(Alpha-Naphthyl)-N, N '-two (4- carboxyls benzene) benzidine monomer.
Figure 11 is the N that 2. step 2 of embodiment two obtains, N '-two (Alpha-Naphthyl)-N, N '-two (4- carboxyls benzene) benzidine
MonomerH nuclear magnetic spectrum figures；It can be seen from fig. 11 that what is represented at 12 is carboxyl peak, Er Qiefeng
Area ratio and N, N '-two (betanaphthyl)-N, N '-two (4- carboxyls benzene) p-phenylenediamine monomer hydrogen number it is consistent, this explanation is
The consistent N of structure, N '-two (Alpha-Naphthyl)-N, N '-two (4- carboxyls benzene) benzidine monomer is obtained.
Figure 12 is the infrared spectrogram of the polyamide film containing trianilino group that the step 4 of embodiment two is obtained；From figure
As can be seen that the polyamide film containing trianilino group that obtains of the step 4 of embodiment two is in 3108cm in 12-1Characteristic peak is
N-H stretching vibrations on main chain, in 1678cm-1Place can be classified as C=O stretching vibration peaks, this at two the peak explanation generation that has been polymerized contain
There is the polyamide film of trianilino group.
Figure 13 is the cyclic voltammetric spectrogram of the polyamide film containing trianilino group that the step 4 of embodiment two is obtained；From
Knowable to Figure 13, cyclic voltammetric of the polyamide film containing trianilino group that the step 4 of embodiment two is obtained under applied voltage
Spectrogram, there is a pair of redox peaks, is oxidation peak at the peak of 1.28V, and simultaneous color is changed into red from light yellow；
There is 1 corresponding reduction peak at 0.70V, now color is changed into light yellow from red；Illustrate that this polymer has preferably reversible
Property.
Figure 14 is the ultraviolet spectrogram of the polyamide film containing trianilino group that the step 4 of embodiment two is obtained；
Figure 15 is the fluorescence spectra of the polyamide film containing trianilino group that the step 4 of embodiment two is obtained；
The polyamide film containing trianilino group that the step 4 of embodiment two is obtained is can be seen that from Figure 14 and Figure 15
Ultraviolet-ray visible absorbing peak value be 368nm, the peak value of fluorescence spectrum is 498nm, and these are all conjugation triphenylamine π-π*Electronics jumps
Move the result of gained.
Embodiment three：A kind of preparation method of the polyamide film containing trianilino group, completes according to the following steps：
First, N, N '-diphenyl-N, N '-two (4- aniline) benzidine monomer are prepared：
1., in a nitrogen atmosphere by N, N- biphenyl diamines are dissolved into dimethyl sulfoxide (DMSO), are added to fluorine nitro
Benzene and sodium hydride, then 26h is reacted at 100 DEG C, obtain reaction solution；Reaction solution is added in cold water, then carries out suction filtration, discarded
Filtrate, obtains yellow mercury oxide material；Yellow mercury oxide material is cleaned 2 times~4 times using acetonitrile, then is dried in the case where temperature is for 35 DEG C
12h, obtains product C；
Step one 1. described in N, the quality of N- biphenyl diamines and the volume ratio of dimethyl sulfoxide (DMSO) are 7g:
100mL；
Step one 1. described in the volume ratio of quality and dimethyl sulfoxide (DMSO) of p-fluoronitrobenzene be 6.5g:100mL；
Step one 1. described in the volume ratio of quality and dimethyl sulfoxide (DMSO) of sodium hydride be 2.5g:100mL；
2. product C and Pd/C catalyst, is added to N, in N '-dimethylformamide, in a hydrogen atmosphere, pressure
For 8MPa, mixing speed are that 150r/min and temperature are to react 45h under conditions of 80 DEG C, yellow-green precipitate material is obtained；By Huang
Green precipitate material carries out suction filtration, discards filtrate, obtains reactant D；Reuse toluene cleaning reactant B 3 times, then in temperature
To dry 4h at 35 DEG C, N, N '-diphenyl-N, N '-two (4- aniline) benzidine monomer are obtained；
Step one 2. described in product C quality and N, N '-dimethylformamide volume ratio be 3.5g:
200mL；
Step one 2. described in Pd/C catalyst quality and N, N '-dimethylformamide volume ratio be 1.0g:
200mL；
Step one 2. described in Pd/C catalyst in Pd mass fraction be 10%；
2nd, N, N'- bis- (betanaphthyl)-N, N '-two (4- carboxyls benzene) p-phenylenediamine monomer are prepared：
1., in a nitrogen atmosphere, by 5g N, N '-two (betanaphthyl) p-phenylenediamine is dissolved into the anhydrous N of 80mL, N- dimethyl
In formamide, 4g is added to fluorobenzonitrile and 2g sodium hydrides, then react 15h in the case where temperature is for 120 DEG C, reuse temperature for 3 DEG C
Distilled water be settled out reactant E, then suction filtration is carried out to reactant E, discard filtrate, then be dried at being 35 DEG C in temperature
24h, obtains dried reactant E；Dried reactant E is recrystallized using acetone, then in the case where temperature is for 35 DEG C
7h is dried, dinitrile monomer is obtained；
2., by 3g dinitriles monomer, 2g potassium hydroxide, 8mL methyl alcohol and 6mL distilled water mix, then temperature be 100 DEG C and
Mixing speed is stirring reaction 5 days under conditions of 120r/min, and it is 3 DEG C to reuse temperature, and pH value is that 3 distilled water is settled out instead
Answer thing F；Suction filtration is carried out to reactant F again, filtrate is discarded, then 24h is dried in the case where temperature is for 35 DEG C, obtain dried reactant
F；Use quality fraction is that 8% glacial acetic acid is recrystallized to dried reactant F, obtains N, N '-two (betanaphthyl)-N,
N '-two (4- carboxyls benzene) p-phenylenediamine monomer；
3rd, polymerisation：
N, N '-diphenyl-N, N '-two (4- aniline) benzidine monomer, diacid monomer and calcium chloride are added organic molten
5h is reacted in agent, then at being 120 DEG C in temperature, methyl alcohol is reused and is settled out reactant I, then carry out suction filtration, discard filtrate, obtain anti-
Answer thing I；Recycle Soxhlet extraction method to purify reactant I, then the reactant I after purification is dried in the case where temperature is for 35 DEG C
Dry 5h, obtains the polyamide containing triphenylamine；
N described in step 3, N '-diphenyl-N, N '-two (4- aniline) benzidine monomer and diacid monomer mole
Than being 1:1；
The volume of the N described in step 3, N '-diphenyl-N, N '-two (4- aniline) benzidine monomer and organic solvent
Than being 0.001mol:3mL；
The quality of the calcium chloride described in step 3 is 0.23g with the volume ratio of organic solvent:3mL；
Organic solvent described in step 3 is pyridine, phosphorous acid triphenylamine and 1-METHYLPYRROLIDONE according to pyridine, Asia
The volume ratio of phosphoric acid triphenylamine and 1-METHYLPYRROLIDONE is 3:3:5 mix；
4th, film-forming：Polyamide containing triphenylamine is dissolved into organic solvent, the polyamides containing triphenylamine is obtained
Amine aqueous solution；Polyamide solution containing trianilino group is coated on ito glass under conditions of rotating speed is 2000r/min,
10h is dried at being again 80 DEG C in temperature, the polyamide film containing trianilino group is obtained；
The thickness of the polyamide film containing trianilino group described in step 4 is 1 μm；
Organic solvent described in step 4 is N, N '-dimethylacetylamide；
The quality of the polyamide containing triphenylamine described in step 4 is 0.0001g with the volume ratio of organic solvent:
1mL。
The step one of embodiment three 1. middle N, the structural formula of N- diphenyl -4,4- benzidines is：
The step one of embodiment three 1. in reaction equation be：
The step one of embodiment three 2. in reaction equation be：
The reaction equation of the step 3 of embodiment three is：
The structural formula of the polyamide film containing trianilino group obtained in the step 4 of embodiment three isThe span of described n is 3≤n≤10, and n
It is integer.
The infrared spectrogram of the polyamide film containing trianilino group obtained in the step 4 of Figure 16 embodiments three；
As can be seen from Figure 16, the polyamide film containing trianilino group for being obtained in the step 4 of embodiment three exists
3112cm-1Characteristic peak is the N-H stretching vibrations on main chain, in 1665cm-1Place can be classified as C=O stretching vibration peaks, this peak at two
Illustrate polyamide film of the generation containing trianilino group that be polymerized.
The cyclic voltammogram of the polyamide film containing trianilino group obtained in the step 4 of Figure 17 embodiments three；From figure
17 understand, cyclic voltammetric of the polyamide film containing trianilino group obtained in the step 4 of embodiment three under applied voltage
Spectrogram, there is a pair of redox peaks, is oxidation peak at the peak of 1.21V, and simultaneous color is changed into red from light yellow；
There is 1 corresponding reduction peak at 0.58V, now color is changed into light yellow from red；Illustrate that this polymer has preferably reversible
Property.
The ultraviolet spectrogram of the polyamide film containing trianilino group obtained in the step 4 of Figure 18 embodiments three；
The fluorescence spectra of the polyamide film containing trianilino group obtained in the step 4 of Figure 19 embodiments three；
As can be seen that the polyamide containing trianilino group obtained in the step 4 of embodiment three is thin from Figure 18 and Figure 19
The ultraviolet-ray visible absorbing peak value of film is 360nm, and the peak value of fluorescence spectrum is 506nm, and these are all conjugation triphenylamine π-π*Electronics
Result obtained by transition.
Example IV：A kind of preparation method of the polyamide film containing trianilino group, completes according to the following steps：
First, N, N '-diphenyl-N, N '-two (4- aniline) benzidine monomer are prepared：
1., in a nitrogen atmosphere by N, N- biphenyl diamines are dissolved into dimethyl sulfoxide (DMSO), are added to fluorine nitro
Benzene and sodium hydride, then 26h is reacted at 100 DEG C, obtain reaction solution；Reaction solution is added in cold water, then carries out suction filtration, discarded
Filtrate, obtains yellow mercury oxide material；Yellow mercury oxide material is cleaned 2 times~4 times using acetonitrile, then is dried in the case where temperature is for 35 DEG C
12h, obtains product C；
Step one 1. described in N, the quality of N- biphenyl diamines and the volume ratio of dimethyl sulfoxide (DMSO) are 7g:
100mL；
Step one 1. described in the volume ratio of quality and dimethyl sulfoxide (DMSO) of p-fluoronitrobenzene be 6.5g:100mL；
Step one 1. described in the volume ratio of quality and dimethyl sulfoxide (DMSO) of sodium hydride be 2.5g:100mL；
2. product C and Pd/C catalyst, is added to N, in N '-dimethylformamide, in a hydrogen atmosphere, pressure
For 8MPa, mixing speed are that 150r/min and temperature are to react 45h under conditions of 80 DEG C, yellow-green precipitate material is obtained；By Huang
Green precipitate material carries out suction filtration, discards filtrate, obtains reactant D；Reuse toluene cleaning reactant B 3 times, then in temperature
To dry 4h at 35 DEG C, N, N '-diphenyl-N, N '-two (4- aniline) benzidine monomer are obtained；
Step one 2. described in product C quality and N, N '-dimethylformamide volume ratio be 3.5g:
200mL；
Step one 2. described in Pd/C catalyst quality and N, N '-dimethylformamide volume ratio be 1.0g:
200mL；
Step one 2. described in Pd/C catalyst in Pd mass fraction be 10%；
2nd, N, N'- bis- (Alpha-Naphthyl)-N, N '-two (4- carboxyls benzene) benzidine monomer are prepared：
1., in a nitrogen atmosphere, by 5g N, N '-two (1- naphthyls) -4,4- benzidines are dissolved into the anhydrous N of 80mL, N- bis-
In NMF, 4.2g is added to fluorobenzonitrile and 2.3g sodium hydrides, then react 16h in the case where temperature is for 120 DEG C, reuse temperature
The distilled water spent for 2 DEG C is settled out reactant G, then carries out suction filtration to reactant G, discards filtrate, then enter in the case where temperature is for 35 DEG C
Row dries 26h, obtains dried reactant G；Dried reactant G is recrystallized using acetone, then is in temperature
8h is dried at 35 DEG C, dinitrile monomer is obtained；
2., 3.2g dinitriles monomer, 2g potassium hydroxide, 10mL methyl alcohol and 10mL distilled water are mixed, then is 100 in temperature
DEG C and mixing speed be stirring reaction 6 days under conditions of 120r/min, reuse temperature for 3 DEG C, pH value is 2 distillation water sedimentation
Go out reactant H；Suction filtration is carried out to reactant H again, filtrate is discarded, then 24h is dried in the case where temperature is for 35 DEG C, obtain dried anti-
Answer thing H；Use quality fraction is that 8% glacial acetic acid is recrystallized to dried reactant H, obtains the N, (α-naphthalene of N '-two
Base)-N, N '-two (4- carboxyls benzene) benzidine monomer；
3rd, polymerisation：
By N, N '-two (Alpha-Naphthyl)-N, N '-two (4- aniline) benzidine monomers or N, N '-diphenyl-N, N '-two (4-
Aniline) 5h is reacted during benzidine monomer, diacid monomer and calcium chloride adds organic solvent, then at being 120 DEG C in temperature, then make
Settled out reactant I with methyl alcohol, then carry out suction filtration, discard filtrate, obtain reactant I；Soxhlet extraction method is recycled to reactant I
Purified, then the reactant I after purification is dried into 5h in the case where temperature is for 35 DEG C, obtained the polyamide containing triphenylamine；
N described in step 3, N '-diphenyl-N, N '-two (4- aniline) benzidine monomer and diacid monomer mole
Than being 1:1；
The volume of the N described in step 3, N '-diphenyl-N, N '-two (4- aniline) benzidine monomer and organic solvent
Than being 0.001mol:3mL；
The quality of the calcium chloride described in step 3 is 0.26g with the volume ratio of organic solvent:3mL；
Organic solvent described in step 3 is pyridine, phosphorous acid triphenylamine and 1-METHYLPYRROLIDONE according to pyridine, Asia
The volume ratio of phosphoric acid triphenylamine and 1-METHYLPYRROLIDONE is 3:3:5 mix；
4th, film-forming：Polyamide containing triphenylamine is dissolved into organic solvent, the polyamides containing triphenylamine is obtained
Amine aqueous solution；Polyamide solution containing trianilino group is coated on ito glass under conditions of rotating speed is 2000r/min,
10h is dried at being again 80 DEG C in temperature, the polyamide film containing trianilino group is obtained；
The thickness of the polyamide film containing trianilino group described in step 4 is 1 μm；
Organic solvent described in step 4 is N, N '-dimethylacetylamide；
The quality of the polyamide containing triphenylamine described in step 4 is 0.0001g with the volume ratio of organic solvent：
1mL。
The structural formula of the polyamide containing triphenylamine obtained in example IV step 3 is
Reaction equation in example IV step 3 is：
Figure 20 is the infrared spectrogram of the polyamide film containing trianilino group that example IV step 4 is obtained；From figure
As can be seen that the polyamide film containing trianilino group that obtains of example IV step 4 is in 3122cm in 20-1Characteristic peak is
N-H stretching vibrations on main chain, in 1668cm-1Place can be classified as C=O stretching vibration peaks, this at two the peak explanation generation that has been polymerized contain
There is the polyamide film of trianilino group.
Figure 21 is the cyclic voltammogram of the polyamide film containing trianilino group that example IV step 4 is obtained；From figure
21 understand, cyclic voltammetry spectrum of the polyamide film containing trianilino group that example IV step 4 is obtained under applied voltage
Figure, there is a pair of redox peaks, is oxidation peak at the peak of 1.12V, and simultaneous color is changed into red from light yellow；
There is 1 corresponding reduction peak at 0.78V, now color is changed into light yellow from red；Illustrate that this polymer has preferably reversible
Property.
Figure 22 is the ultraviolet spectrogram of the polyamide film containing trianilino group that example IV step 4 is obtained；
Figure 23 is the fluorescence spectra of the polyamide film containing trianilino group that example IV step 4 is obtained；
The polyamide film containing trianilino group that example IV step 4 is obtained is can be seen that from Figure 22 and Figure 23
Ultraviolet-ray visible absorbing peak value be 365nm, the peak value of fluorescence spectrum is 496nm, and these are all conjugation triphenylamine π-π*Electronics jumps
Move the result of gained.
Claims (8)
1. a kind of preparation method of the polyamide film containing trianilino group, it is characterised in that a kind of containing trianilino group
The preparation method of polyamide film is completed according to the following steps：
First, polymerisation：
By N, N '-two (Alpha-Naphthyl)-N, N '-two (4- aniline) benzidine monomers or N, N '-diphenyl-N, N '-two (4- benzene
Amine) react 5h during benzidine monomer, diacid monomer and calcium chloride adds organic solvent, then at being 120 DEG C~150 DEG C in temperature
~7h, reuses methyl alcohol and settles out reactant I, then carries out suction filtration, discards filtrate, obtains reactant I；Recycle Soxhlet extraction method
Reactant I is purified, then the reactant I after purification is dried into 3h~5h in the case where temperature is for 30~40 DEG C, obtain containing three
The polyamide of aniline；
N described in step one, N '-two (Alpha-Naphthyl)-N, N '-two (4- aniline) benzidine monomers and diacid monomer mole
Than being 1:1 or N, N ' mol ratio of-diphenyl-N, N '-two (4- aniline) benzidine monomer and diacid monomer is 1:1；
N described in step one, N '-two (Alpha-Naphthyl)-N, N '-two (4- aniline) benzidine monomers or N, N '-diphenyl-N,
(4- aniline) the benzidine monomers of N '-two are (0.001mol~0.05mol) with the volume ratio of organic solvent:3mL；
The quality of the calcium chloride described in step one is (0.2g~0.3g) with the volume ratio of organic solvent:3mL；
2nd, film-forming：Polyamide containing triphenylamine is dissolved into organic solvent, the polyamide containing triphenylamine is obtained molten
Liquid；Polyamide solution containing trianilino group is coated in ITO under conditions of rotating speed is 1500r/min~2500r/min
On glass, then 8~10h is dried in the case where temperature is for 80 DEG C~100 DEG C, obtain the polyamide film containing trianilino group；
The thickness of the polyamide film containing trianilino group described in step 2 is 0.5 μm~5 μm；
The quality of the polyamide containing triphenylamine described in step 2 and the volume ratio of organic solvent for (0.0001g~
0.0005g):1mL；
The structural formula of the polyamide film containing trianilino group described in step 2 is：
Wherein, described R1ForDescribed R2ForDescribed n1Value be 1≤n1≤ 100, and n1For whole
Number；Described n2Value be 1≤n2≤ 100, and n2It is integer.
2. the preparation method of a kind of polyamide film containing trianilino group according to claim 1, it is characterised in that
N described in step one, N '-two (Alpha-Naphthyl)-N, N '-two (4- aniline) benzidine monomer is prepared as follows：
1., in a nitrogen atmosphere by N, N- bis- (Alpha-Naphthyl) -4,4- benzidines are dissolved into dimethyl sulfoxide (DMSO), add to fluorine
Nitrobenzene and sodium hydride, then 24h~30h is reacted at 100 DEG C, obtain reaction solution；Reaction solution is added in cold water, then is carried out
Suction filtration, discards filtrate, obtains yellow mercury oxide material；Yellow mercury oxide material is cleaned 2 times~4 times using acetonitrile, then is in temperature
8~15h is dried at 30 DEG C~40 DEG C, product A is obtained；
Step 1. described in N, the amount ratio of the material of (the Alpha-Naphthyl) -4,4- benzidines of N- bis- and p-fluoronitrobenzene is 1:2；
Step 1. described in N, the amount of material of N- bis- (Alpha-Naphthyl) -4,4- benzidines is with the volume ratio of dimethyl sulfoxide (DMSO)
1mol:(100mL~200mL)；
Step 1. described in the volume ratio of quality and dimethyl sulfoxide (DMSO) of sodium hydride be (1g~3g):100mL；
2. product A and Pd/C catalyst, is added to N, in N '-dimethylformamide, in a hydrogen atmosphere, pressure be
7MPa~9MPa, mixing speed be 120r/min~150r/min and temperature be react under conditions of 70 DEG C~90 DEG C 40h~
45h, obtains yellow-green precipitate material；Yellow-green precipitate material is carried out into suction filtration, filtrate is discarded, reactant B is obtained；Reuse first
Benzene cleaning reactant B 2 times~4 times, then dry 3h~5h at being 30 DEG C~40 DEG C in temperature, obtains N, and N '-two (Alpha-Naphthyl)-
N, N '-two (4- aniline) benzidine monomer；
Step 2. described in product A quality and N, N '-dimethylformamide volume ratio be (3g~5g):250mL；
Step 2. described in Pd/C catalyst quality and N, N '-dimethylformamide volume ratio be (0.5g~2g):
250mL；
Step 2. described in Pd/C catalyst in Pd mass fraction be 10%.
3. the preparation method of a kind of polyamide film containing trianilino group according to claim 1, it is characterised in that
N described in step one, N '-diphenyl-N, N '-two (4- aniline) benzidine monomer are prepared as follows：
1., in a nitrogen atmosphere by N, N- biphenyl diamines are dissolved into dimethyl sulfoxide (DMSO), add p-fluoronitrobenzene and
Sodium hydride, then 24h~30h is reacted at 100 DEG C, obtain reaction solution；Reaction solution is added in cold water, then carries out suction filtration, abandoned
Filtrate is gone, yellow mercury oxide material is obtained；Yellow mercury oxide material is cleaned 2 times~4 times using acetonitrile, then is 30 DEG C~40 in temperature
8~15h is dried at DEG C, product C is obtained；
Step 1. described in N, the quality of N- biphenyl diamines and the volume ratio of dimethyl sulfoxide (DMSO) are (6g~8g):
100mL；
Step 1. described in the volume ratio of quality and dimethyl sulfoxide (DMSO) of p-fluoronitrobenzene be (6g~8g):100mL；
Step 1. described in the volume ratio of quality and dimethyl sulfoxide (DMSO) of sodium hydride be (2g~3g):100mL；
2. product C and Pd/C catalyst, is added to N, in N '-dimethylformamide, in a hydrogen atmosphere, pressure be
7MPa~9MPa, mixing speed be 120r/min~150r/min and temperature be react under conditions of 70 DEG C~90 DEG C 40h~
45h, obtains yellow-green precipitate material；Yellow-green precipitate material is carried out into suction filtration, filtrate is discarded, reactant D is obtained；Reuse first
Benzene cleaning reactant B 2 times~4 times, then dry 3h~5h at being 30 DEG C~40 DEG C in temperature, obtains N, and N '-diphenyl-N, N '-
Two (4- aniline) benzidine monomers；
Step 2. described in product C quality and N, N '-dimethylformamide volume ratio be (3g~4g):200mL；
Step 2. described in Pd/C catalyst quality and N, N '-dimethylformamide volume ratio be (0.5g~1.5g):
200mL；
Step 2. described in Pd/C catalyst in Pd mass fraction be 10%.
4. the preparation method of a kind of polyamide film containing trianilino group according to claim 1, it is characterised in that
Diacid monomer described in step one is N, N'- bis- (betanaphthyl)-N, N '-two (4- carboxyls benzene) p-phenylenediamine monomers or N, N'-
Two (Alpha-Naphthyl)-N, N '-two (4- carboxyls benzene) benzidine monomer；Described diacid monomer be N, N'- bis- (betanaphthyl)-N,
The structural formula of N '-two (4- carboxyls benzene) p-phenylenediamine monomer isDescribed N, N'- bis- (α-
Naphthyl)-N, the structural formula of N '-two (4- carboxyls benzene) benzidine monomer is
5. the preparation method of a kind of polyamide film containing trianilino group according to claim 4, it is characterised in that
Described N, N'- bis- (betanaphthyl)-N, N '-two (4- carboxyls benzene) p-phenylenediamine monomer is prepared as follows：
1., in a nitrogen atmosphere, by N, N '-two (betanaphthyl) p-phenylenediamine is dissolved into anhydrous DMF, then
Add to fluorobenzonitrile and sodium hydride, then 15h~20h is reacted in the case where temperature is for 120 DEG C~130 DEG C, it is 0 DEG C~5 to reuse temperature
DEG C distilled water be settled out reactant E, then suction filtration is carried out to reactant E, discard filtrate, then enter at being 30 DEG C~35 DEG C in temperature
Row dries 24h~30h, obtains dried reactant E；Dried reactant E is recrystallized using acetone, then in temperature
Spend to dry 6h~8h at 30 DEG C~35 DEG C, obtain dinitrile monomer；
Step 1. described in N, the quality of N '-two (betanaphthyl) p-phenylenediamine and the volume ratio of anhydrous N,N-dimethylformamide
It is 5g:(70mL~100mL)；
Step 1. described in quality to fluorobenzonitrile and the volume ratio of anhydrous N,N-dimethylformamide be 4g:(70mL~
100mL)；
Step 1. described in sodium hydride quality and anhydrous N,N-dimethylformamide volume ratio be 2g:(70mL~
100mL)；
2., dinitrile monomer, potassium hydroxide, methyl alcohol and distilled water are mixed, then is 100 DEG C~110 DEG C and stirring speed in temperature
It is stirring reaction 5 days~6 days under conditions of 120r/min~150r/min to spend, and reuses temperature for 0 DEG C~5 DEG C, pH value is 2~
3 distilled water is settled out reactant F；Suction filtration is carried out to reactant F again, filtrate is discarded, then do in the case where temperature is for 30 DEG C~35 DEG C
Dry 24h~30h, obtains dried reactant F；Use quality fraction be 6%~8% glacial acetic acid to dried reactant
F is recrystallized, and obtains N, N '-two (betanaphthyl)-N, N '-two (4- carboxyls benzene) p-phenylenediamine monomer；
Step 2. described in the volume ratio of quality and methyl alcohol of dinitrile monomer be 3g:(8mL~10mL)；
Step 2. described in the volume ratio of quality and methyl alcohol of potassium hydroxide be 2g:(8mL~10mL)；
Step 2. described in the volume ratio of methyl alcohol and distilled water be (0.5~1.5):1.
6. the preparation method of a kind of polyamide film containing trianilino group according to claim 4, it is characterised in that
Described N, N'- bis- (Alpha-Naphthyl)-N, N '-two (4- carboxyls benzene) benzidine monomer is prepared as follows：
1., in a nitrogen atmosphere, by N, N '-two (1- naphthyls) -4,4- benzidines are dissolved into anhydrous DMF
In, add to fluorobenzonitrile and sodium hydride, then 15h~20h is reacted in the case where temperature is for 120 DEG C~130 DEG C, it is 0 to reuse temperature
DEG C~5 DEG C of distilled water is settled out reactant G, then carries out suction filtration to reactant G, discards filtrate, then be 30 DEG C~35 in temperature
24h~30h is dried at DEG C, dried reactant G is obtained；Dried reactant G is recrystallized using acetone,
6h~8h is dried at being again 30 DEG C~35 DEG C in temperature, dinitrile monomer is obtained；
Step 1. described in N, the quality and anhydrous N,N-dimethylformamide of N '-two (1- naphthyls) -4,4- benzidines
Volume ratio is 5g:(70mL~100mL)；
Step 1. described in quality to fluorobenzonitrile and the volume ratio of anhydrous N,N-dimethylformamide be 4g:(70mL~
100mL)；
Step 1. described in sodium hydride quality and anhydrous N,N-dimethylformamide volume ratio be 2g:(70mL~
100mL)；
2., dinitrile monomer, potassium hydroxide, methyl alcohol and distilled water are mixed, then is 100 DEG C~110 DEG C and stirring speed in temperature
It is stirring reaction 5 days~6 days under conditions of 120r/min~150r/min to spend, and reuses temperature for 0 DEG C~5 DEG C, pH value is 2~
3 distilled water is settled out reactant H；Suction filtration is carried out to reactant H again, filtrate is discarded, then do in the case where temperature is for 30 DEG C~35 DEG C
Dry 24h~30h, obtains dried reactant H；Use quality fraction be 6%~8% glacial acetic acid to dried reactant
H is recrystallized, and obtains N, N '-two (Alpha-Naphthyl)-N, N '-two (4- carboxyls benzene) benzidine monomer；
Step 2. described in the volume ratio of quality and methyl alcohol of dinitrile monomer be 3g:(8mL~10mL)；
Step 2. described in the volume ratio of quality and methyl alcohol of potassium hydroxide be 2g:(8mL~10mL)；
Step 2. described in the volume ratio of methyl alcohol and distilled water be (0.5~1.5):1.
7. the preparation method of a kind of polyamide film containing trianilino group according to claim 1, it is characterised in that
Organic solvent described in step one is the one kind or wherein several in triphenyl phosphite, pyridine and 1-METHYLPYRROLIDONE
Mixing.
8. the preparation method of a kind of polyamide film containing trianilino group according to claim 1, it is characterised in that
Organic solvent described in step 2 is N, N '-dimethylacetylamide, N, in N '-dimethylformamide and 1-METHYLPYRROLIDONE
One kind or wherein several mixing.
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