CN105175716A - Triphenylamino group-containing polyamide film, and production method and application thereof - Google Patents

Triphenylamino group-containing polyamide film, and production method and application thereof Download PDF

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CN105175716A
CN105175716A CN201510556845.3A CN201510556845A CN105175716A CN 105175716 A CN105175716 A CN 105175716A CN 201510556845 A CN201510556845 A CN 201510556845A CN 105175716 A CN105175716 A CN 105175716A
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volume ratio
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CN105175716B (en
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牛海军
吴晓彤
盘清江
郑冰
纪艳
王曙重
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Heilongjiang University
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Heilongjiang University
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Abstract

The invention relates to a polyamide film, and a production method and an application thereof, and concretely relates to a triphenylamino group-containing polyamide film, and a production method and an application thereof. The purpose of the invention is to solve the problems of low solubility in organic solvents, difficult film formation processing and low photoelectrochromic response sensitivity of present polyamide. The structural formula of the triphenylamino group-containing polyamide film is shown in the specification. The production method comprises the following steps: 1, carrying out a polymerization reaction; and 2, carrying out curing film formation to obtain the triphenylamino group-containing polyamide film. The triphenylamino group-containing polyamide film can be applied in electrochromic materials, photochromic materials, hole transporting materials, third order nonlinear materials, anti-counterfeit and camouflage materials and display materials as a photoelectric material. The triphenylamino group-containing polyamide film can be obtained in the invention.

Description

A kind of polyamide layer containing trianilino group and its preparation method and application
Technical field
The present invention relates to a kind of polyamide layer and its preparation method and application.
Background technology
Can form radical cation containing triphenylamine base polymer under the effect of electric field, be the important raw and processed materials preparing charge transfer material, electroluminescent material, electrochromic material, also can make organic dye and medicine intermediate simultaneously.Aromaticity polymeric amide is high performance polymer, and they have good mechanical property and electrochromic property, is expected to be used in optical storage, light memory, optics computing, optical Limiting lasing safety.But it is low that existing polymeric amide still exists solvability, be difficult to film forming processing, the problem that light-spot positioning response sensitivity is low, needs to study raising further.Main solution is on main chain, introduce large group.On the other hand, by changing chemical structure and composition, improving solubility property and the film-forming properties of polymeric amide, further increasing the Application Areas of polymeric amide: as light active material, fluorescence, electrically active films and ion-exchange membrane etc.
Summary of the invention
Solubleness is low in organic solvent to the object of the invention is to solve existing polymeric amide, is difficult to process film forming and the low problem of light-spot positioning response sensitivity, and provides a kind of polyamide layer containing trianilino group and its preparation method and application.
A kind of structural formula of the polyamide layer containing trianilino group is:
wherein, described R 1for described R 2for described n 1value be 1≤n 1≤ 100, and n 1for integer; Described n 2value be 1≤n 2≤ 100, and n 2for integer.
A preparation method for polyamide layer containing trianilino group, completes according to the following steps:
One, polyreaction:
By N, N '-two (Alpha-Naphthyl)-N, N '-two (4-aniline) benzidine monomer or N, N '-phenylbenzene-N, N '-two (4-aniline) benzidine monomer, diacid monomer and calcium chloride adds in organic solvent, then reacts 5h ~ 7h at temperature is 120 DEG C ~ 150 DEG C, re-use methyl alcohol to settle out reactant I, carry out suction filtration again, discard filtrate, obtain reactant I; Recycling Soxhlet extraction method is purified to reactant I, then the reactant I after purifying is dried 3h ~ 5h at temperature is 30 ~ 40 DEG C, obtains the polymeric amide containing triphenylamine;
N described in step one, N '-two (Alpha-Naphthyl)-N, the mol ratio of N '-two (4-aniline) benzidine monomer and diacid monomer is 1:1 or N, N '-phenylbenzene-N, N '-two the mol ratio of (4-aniline) benzidine monomer and diacid monomer be 1:1;
N described in step one, N '-two (Alpha-Naphthyl)-N, N '-two (4-aniline) benzidine monomer or N, the volume ratio of N '-phenylbenzene-N, N '-two (4-aniline) benzidine monomer and organic solvent is (0.001mol ~ 0.05mol): 3mL;
The quality of the calcium chloride described in step one and the volume ratio of organic solvent are (0.2g ~ 0.3g): 3mL;
Two, film-forming: be dissolved in organic solvent by the polymeric amide containing triphenylamine, obtains the polyamide solution containing triphenylamine; Be be coated on ito glass under the condition of 1500r/min ~ 2500r/min at rotating speed by the polyamide solution containing trianilino group, then at temperature is 80 DEG C ~ 100 DEG C dry 8 ~ 10h, obtain the polyamide layer containing trianilino group;
The thickness of the polyamide layer containing trianilino group described in step 2 is 0.5 μm ~ 5 μm;
The quality of polymeric amide containing triphenylamine described in step 2 and the volume ratio of organic solvent are (0.0001 ~ 0.0005g): 1mL;
The structural formula of the polyamide layer containing trianilino group described in step 2 is:
wherein, described R 1for described R 2for described n 1value be 1≤n 1≤ 100, and n 1for integer; Described n 2value be 1≤n 2≤ 100, and n 2for integer.
Advantage of the present invention:
One, the polyamide layer containing trianilino group the present invention prepared is dissolved in dimethyl sulfoxide (DMSO), can carry out film on conductive glass; Polyamide layer containing trianilino group prepared by the present invention is as working electrode, and saturated calomel electrode is reference electrode, and platinum filament is to electrode, and ionogen is the electrochromic device of lithium perchlorate acetonitrile solution composition;
Two, the polyamide layer containing trianilino group that prepared by the present invention can be applied in electrochromic material, photochromic material, hole mobile material, third-order non-linear material, false proof, camouflage material and display material as photoelectric material;
Three, the polyamide layer containing trianilino group that prepared by the present invention has good reversibility, and solvability is large;
Four, the polyamide layer containing trianilino group that prepared by the present invention has a pair redox peak, and this polymkeric substance has good reversibility;
Five, the ultraviolet-ray visible absorbing peak value containing the polyamide layer of trianilino group that prepared by the present invention is 360nm ~ 370nm, and the peak value of fluorescence spectrum is 496nm ~ 506nm, and these are all conjugation triphenylamine π-π *the result of transition of electron gained.
The present invention can obtain a kind of polyamide layer containing trianilino group.
Accompanying drawing explanation
Fig. 1 is the dinitrile monomer that 1. embodiment one step 2 obtains infrared spectrum;
Fig. 2 is the N that 2. embodiment one step 2 obtains, N '-two (betanaphthyl)-N, N '-two (4-carboxyl benzene) Ursol D monomer infrared spectrogram;
Fig. 3 is the N that 2. embodiment one step 2 obtains, N '-two (betanaphthyl)-N, N '-two (4-carboxyl benzene) Ursol D monomer h nuclear magnetic spectrum figure;
Fig. 4 is the N that 2. embodiment one step 2 obtains, N '-two (betanaphthyl)-N, N '-two (4-carboxyl benzene) Ursol D monomer c nuclear magnetic spectrum figure;
Fig. 5 is the infrared spectrogram of the polyamide layer containing trianilino group that embodiment one step 4 obtains;
Fig. 6 is the cyclic voltammogram of the polyamide layer containing trianilino group that embodiment one step 4 obtains;
Fig. 7 is the ultraviolet spectrogram of the polyamide layer containing trianilino group that embodiment one step 4 obtains;
Fig. 8 is the fluorescence spectrum figure of the polyamide layer containing trianilino group that embodiment one step 4 obtains;
Fig. 9 is the dinitrile monomer that 1. embodiment two step 2 obtains infrared spectrogram;
Figure 10 is the N that 2. embodiment two step 2 obtains, N '-two (Alpha-Naphthyl)-N, N '-two (4-carboxyl benzene) benzidine monomer infrared spectrogram;
Figure 11 is the N that 2. embodiment two step 2 obtains, N '-two (Alpha-Naphthyl)-N, N '-two (4-carboxyl benzene) benzidine monomer h nuclear magnetic spectrum figure;
Figure 12 is the infrared spectrogram of the polyamide layer containing trianilino group that embodiment two step 4 obtains;
Figure 13 is the cyclic voltammetric spectrogram of the polyamide layer containing trianilino group that embodiment two step 4 obtains;
Figure 14 is the ultraviolet spectrogram of the polyamide layer containing trianilino group that embodiment two step 4 obtains;
Figure 15 is the fluorescence spectrum figure of the polyamide layer containing trianilino group that embodiment two step 4 obtains;
The infrared spectrogram of the polyamide layer containing trianilino group obtained in Figure 16 embodiment three step 4;
The cyclic voltammogram of the polyamide layer containing trianilino group obtained in Figure 17 embodiment three step 4;
The ultraviolet spectrogram of the polyamide layer containing trianilino group obtained in Figure 18 embodiment three step 4;
The fluorescence spectrum figure of the polyamide layer containing trianilino group obtained in Figure 19 embodiment three step 4;
Figure 20 is the infrared spectrogram of the polyamide layer containing trianilino group that embodiment four step 4 obtains;
Figure 21 is the cyclic voltammogram of the polyamide layer containing trianilino group that embodiment four step 4 obtains;
Figure 22 is the ultraviolet spectrogram of the polyamide layer containing trianilino group that embodiment four step 4 obtains;
Figure 23 is the fluorescence spectrum figure of the polyamide layer containing trianilino group that embodiment four step 4 obtains.
Embodiment
Embodiment one: to be a kind of structural formula of the polyamide layer containing trianilino group be present embodiment:
wherein, described R 1for described R 2for described n 1value be 1≤n 1≤ 100, and n 1for integer; Described n 2value be 1≤n 2≤ 100, and n 2for integer.
Embodiment two: present embodiment is that a kind of preparation method of the polyamide layer containing trianilino group completes according to the following steps:
One, polyreaction:
By N, N '-two (Alpha-Naphthyl)-N, N '-two (4-aniline) benzidine monomer or N, N '-phenylbenzene-N, N '-two (4-aniline) benzidine monomer, diacid monomer and calcium chloride adds in organic solvent, then reacts 5h ~ 7h at temperature is 120 DEG C ~ 150 DEG C, re-use methyl alcohol to settle out reactant I, carry out suction filtration again, discard filtrate, obtain reactant I; Recycling Soxhlet extraction method is purified to reactant I, then the reactant I after purifying is dried 3h ~ 5h at temperature is 30 ~ 40 DEG C, obtains the polymeric amide containing triphenylamine;
N described in step one, N '-two (Alpha-Naphthyl)-N, the mol ratio of N '-two (4-aniline) benzidine monomer and diacid monomer is 1:1 or N, N '-phenylbenzene-N, N '-two the mol ratio of (4-aniline) benzidine monomer and diacid monomer be 1:1;
N described in step one, N '-two (Alpha-Naphthyl)-N, N '-two (4-aniline) benzidine monomer or N, the volume ratio of N '-phenylbenzene-N, N '-two (4-aniline) benzidine monomer and organic solvent is (0.001mol ~ 0.05mol): 3mL;
The quality of the calcium chloride described in step one and the volume ratio of organic solvent are (0.2g ~ 0.3g): 3mL;
Two, film-forming: be dissolved in organic solvent by the polymeric amide containing triphenylamine, obtains the polyamide solution containing triphenylamine; Be be coated on ito glass under the condition of 1500r/min ~ 2500r/min at rotating speed by the polyamide solution containing trianilino group, then at temperature is 80 DEG C ~ 100 DEG C dry 8 ~ 10h, obtain the polyamide layer containing trianilino group;
The thickness of the polyamide layer containing trianilino group described in step 2 is 0.5 μm ~ 5 μm;
The quality of polymeric amide containing triphenylamine described in step 2 and the volume ratio of organic solvent are (0.0001g ~ 0.0005g): 1mL
The structural formula of the polyamide layer containing trianilino group described in step 2 is:
wherein, described R 1for described R 2for described n 1value be 1≤n 1≤ 100, and n 1for integer; Described n 2value be 1≤n 2≤ 100, and n 2for integer.
The advantage of present embodiment:
One, the polyamide layer containing trianilino group present embodiment prepared is dissolved in dimethyl sulfoxide (DMSO), can carry out film on conductive glass; Polyamide layer containing trianilino group prepared by present embodiment is as working electrode, and saturated calomel electrode is reference electrode, and platinum filament is to electrode, and ionogen is the electrochromic device of lithium perchlorate acetonitrile solution composition;
Two, the polyamide layer containing trianilino group that prepared by present embodiment can be applied in electrochromic material, photochromic material, hole mobile material, third-order non-linear material, false proof, camouflage material and display material as photoelectric material;
Three, the polyamide layer containing trianilino group that prepared by present embodiment has good reversibility, and solvability is large;
Four, the polyamide layer containing trianilino group that prepared by present embodiment has a pair redox peak, and this polymkeric substance has good reversibility;
Five, the ultraviolet-ray visible absorbing peak value containing the polyamide layer of trianilino group that prepared by present embodiment is 360nm ~ 370nm, and the peak value of fluorescence spectrum is 496nm ~ 506nm, and these are all conjugation triphenylamine π-π *the result of transition of electron gained.
Present embodiment can obtain a kind of polyamide layer containing trianilino group.
Embodiment three: the difference of present embodiment and embodiment two is: the N described in step one, N '-two (Alpha-Naphthyl)-N, N '-two (4-aniline) benzidine monomer is prepared by the following method:
1., in a nitrogen atmosphere N, N-bis-(Alpha-Naphthyl)-4,4-benzidine is dissolved in dimethyl sulfoxide (DMSO), then adds p-fluoronitrobenzene and sodium hydride, then react 24h ~ 30h at 100 DEG C, obtain reaction solution; Reaction solution is joined in cold water, then carries out suction filtration, discard filtrate, obtain yellow mercury oxide material; Use acetonitrile to clean 2 times ~ 4 times to yellow mercury oxide material, then at temperature is 30 DEG C ~ 40 DEG C dry 8 ~ 15h, obtain reaction product A;
Step 1. described in N, the amount of substance of N-bis-(Alpha-Naphthyl)-4,4-benzidine and p-fluoronitrobenzene is than being 1:2;
Step 1. described in N, the amount of substance of N-bis-(Alpha-Naphthyl)-4,4-benzidine and the volume ratio of dimethyl sulfoxide (DMSO) are 1mol:(100mL ~ 200mL);
Step 1. described in the quality of sodium hydride and the volume ratio of dimethyl sulfoxide (DMSO) be (1g ~ 3g): 100mL;
2., reaction product A and Pd/C catalyzer are joined N, in N '-dimethyl formamide, in a hydrogen atmosphere, pressure is 7MPa ~ 9MPa, stirring velocity be 120r/min ~ 150r/min and temperature is react 40h ~ 45h under the condition of 70 DEG C ~ 90 DEG C, obtains yellow-green precipitate material; Yellow-green precipitate material is carried out suction filtration, discards filtrate, obtain reactant B; Re-use toluene cleaning reaction thing B2 time ~ 4 times, then dry 3h ~ 5h at temperature is 30 DEG C ~ 40 DEG C, obtain N, N '-two (Alpha-Naphthyl)-N, N '-two (4-aniline) benzidine monomer;
Step 2. described in the quality of reaction product A and the volume ratio of N, N '-dimethyl formamide be (3g ~ 5g): 250mL;
Step 2. described in the quality of Pd/C catalyzer and the volume ratio of N, N '-dimethyl formamide be (0.5g ~ 2g): 250mL;
Step 2. described in Pd/C catalyzer in the massfraction of Pd be 10%.Other are identical with embodiment two.
Embodiment four: the difference of present embodiment and embodiment two or three is: the N described in step one, N '-phenylbenzene-N, N '-two (4-aniline) benzidine monomer is prepared by the following method:
1., in a nitrogen atmosphere N, N-biphenyl diamine is dissolved in dimethyl sulfoxide (DMSO), then adds p-fluoronitrobenzene and sodium hydride, then react 24h ~ 30h at 100 DEG C, obtain reaction solution; Reaction solution is joined in cold water, then carries out suction filtration, discard filtrate, obtain yellow mercury oxide material; Use acetonitrile to clean 2 times ~ 4 times to yellow mercury oxide material, then at temperature is 30 DEG C ~ 40 DEG C dry 8 ~ 15h, obtain reaction product C;
Step 1. described in N, the quality of N-biphenyl diamine and the volume ratio of dimethyl sulfoxide (DMSO) are (6g ~ 8g): 100mL;
Step 1. described in the quality of p-fluoronitrobenzene and the volume ratio of dimethyl sulfoxide (DMSO) be (6g ~ 8g): 100mL;
Step 1. described in the quality of sodium hydride and the volume ratio of dimethyl sulfoxide (DMSO) be (2g ~ 3g): 100mL;
2., reaction product C and Pd/C catalyzer are joined N, in N '-dimethyl formamide, in a hydrogen atmosphere, pressure is 7MPa ~ 9MPa, stirring velocity be 120r/min ~ 150r/min and temperature is react 40h ~ 45h under the condition of 70 DEG C ~ 90 DEG C, obtains yellow-green precipitate material; Yellow-green precipitate material is carried out suction filtration, discards filtrate, obtain reactant D; Re-use toluene cleaning reaction thing B2 time ~ 4 times, then dry 3h ~ 5h at temperature is 30 DEG C ~ 40 DEG C, obtain N, N '-phenylbenzene-N, N '-two (4-aniline) benzidine monomer;
Step 2. described in the quality of reaction product C and the volume ratio of N, N '-dimethyl formamide be (3g ~ 4g): 200mL;
Step 2. described in the quality of Pd/C catalyzer and the volume ratio of N, N '-dimethyl formamide be (0.5g ~ 1.5g): 200mL;
Step 2. described in Pd/C catalyzer in the massfraction of Pd be 10%.Other are identical with embodiment two or three.
Embodiment five: the difference of present embodiment and embodiment two to four is: the diacid monomer described in step one is N, N'-bis-(betanaphthyl)-N, N '-two (4-carboxyl benzene) Ursol D monomer or N, N'-bis-(Alpha-Naphthyl)-N, N '-two (4-carboxyl benzene) benzidine monomer; Described diacid monomer is the structural formula of N, N'-bis-(betanaphthyl)-N, N '-two (4-carboxyl benzene) Ursol D monomer the structural formula of described N, N'-bis-(Alpha-Naphthyl)-N, N '-two (4-carboxyl benzene) benzidine monomer is other are identical with embodiment two to four.
Embodiment six: the difference of present embodiment and embodiment two to five is: described N, N'-bis-(betanaphthyl)-N, N '-two (4-carboxyl benzene) Ursol D monomer is prepared by the following method:
1., in a nitrogen atmosphere, by N, N '-two (betanaphthyl) Ursol D is dissolved in anhydrous DMF, then adds fluorobenzonitrile and sodium hydride, 15h ~ 20h is reacted again at temperature is 120 DEG C ~ 130 DEG C, re-using temperature is that the distilled water of 0 DEG C ~ 5 DEG C is settled out reactant E, then carries out suction filtration to reactant E, discards filtrate, at temperature is 30 DEG C ~ 35 DEG C, carry out dry 24h ~ 30h again, obtain dried reactant E; Use acetone recrystallization is carried out to dried reactant E, then at temperature is 30 DEG C ~ 35 DEG C dry 6h ~ 8h, obtain dinitrile monomer;
Step 1. described in N, the quality of N '-two (betanaphthyl) Ursol D and the volume ratio of anhydrous DMF are 5g:(70mL ~ 100mL);
Step 1. described in the quality to fluorobenzonitrile and the volume ratio of anhydrous DMF be 4g:(70mL ~ 100mL);
Step 1. described in the quality of sodium hydride and the volume ratio of anhydrous DMF be 2g:(70mL ~ 100mL);
2., dinitrile monomer, potassium hydroxide, methyl alcohol and distilled water are mixed, stirring reaction 5 days ~ 6 days under be 100 DEG C ~ 110 DEG C and stirring velocity being the condition of 120r/min ~ 150r/min in temperature again, re-using temperature is 0 DEG C ~ 5 DEG C, pH value be 2 ~ 3 distilled water be settled out reactant F; Again suction filtration is carried out to reactant F, discards filtrate, then at temperature is 30 DEG C ~ 35 DEG C dry 24h ~ 30h, obtain dried reactant F; Functional quality mark be 6% ~ 8% Glacial acetic acid recrystallization is carried out to dried reactant F, obtain N, N '-two (betanaphthyl)-N, N '-two (4-carboxyl benzene) Ursol D monomer;
Step 2. described in the quality of dinitrile monomer and the volume ratio of methyl alcohol be 3g:(8mL ~ 10mL);
Step 2. described in the quality of potassium hydroxide and the volume ratio of methyl alcohol be 2g:(8mL ~ 10mL);
Step 2. described in methyl alcohol and the volume ratio of distilled water be (0.5 ~ 1.5): 1.Other are identical with embodiment two to five.
Embodiment seven: the difference of present embodiment and embodiment two to six is: described N, N'-bis-(Alpha-Naphthyl)-N, N '-two (4-carboxyl benzene) benzidine monomer is prepared by the following method:
1., in a nitrogen atmosphere, N, N '-two (1-naphthyl)-4,4-benzidines are dissolved into anhydrous N, in dinethylformamide, add fluorobenzonitrile and sodium hydride again, then react 15h ~ 20h at temperature is 120 DEG C ~ 130 DEG C, re-using temperature is that the distilled water of 0 DEG C ~ 5 DEG C is settled out reactant G, again suction filtration is carried out to reactant G, discard filtrate, then carry out dry 24h ~ 30h at temperature is 30 DEG C ~ 35 DEG C, obtain dried reactant G; Use acetone recrystallization is carried out to dried reactant G, then at temperature is 30 DEG C ~ 35 DEG C dry 6h ~ 8h, obtain dinitrile monomer;
Step 1. described in N, the quality of N '-two (1-naphthyl)-4,4-benzidines and the volume ratio of anhydrous DMF are 5g:(70mL ~ 100mL);
Step 1. described in the quality to fluorobenzonitrile and the volume ratio of anhydrous DMF be 4g:(70mL ~ 100mL);
Step 1. described in the quality of sodium hydride and the volume ratio of anhydrous DMF be 2g:(70mL ~ 100mL);
2., dinitrile monomer, potassium hydroxide, methyl alcohol and distilled water are mixed, stirring reaction 5 days ~ 6 days under be 100 DEG C ~ 110 DEG C and stirring velocity being the condition of 120r/min ~ 150r/min in temperature again, re-using temperature is 0 DEG C ~ 5 DEG C, pH value be 2 ~ 3 distilled water be settled out reactant H; Again suction filtration is carried out to reactant H, discards filtrate, then at temperature is 30 DEG C ~ 35 DEG C dry 24h ~ 30h, obtain dried reactant H; Functional quality mark be 6% ~ 8% Glacial acetic acid recrystallization is carried out to dried reactant H, obtain N, N '-two (Alpha-Naphthyl)-N, N '-two (4-carboxyl benzene) benzidine monomer;
Step 2. described in the quality of dinitrile monomer and the volume ratio of methyl alcohol be 3g:(8mL ~ 10mL);
Step 2. described in the quality of potassium hydroxide and the volume ratio of methyl alcohol be 2g:(8mL ~ 10mL);
Step 2. described in methyl alcohol and the volume ratio of distilled water be (0.5 ~ 1.5): 1.Other are identical with embodiment two to six.
Embodiment eight: present embodiment with the difference of embodiment two to seven is: the organic solvent described in step one is a kind of in triphenyl phosphite, pyridine and N-Methyl pyrrolidone or wherein severally mixes.Other are identical with embodiment two to seven.
Embodiment nine: the difference of present embodiment and embodiment two to eight is: the organic solvent described in step 2 is N, a kind of or wherein several mixing in N '-N,N-DIMETHYLACETAMIDE, N, N '-dimethyl formamide and N-Methyl pyrrolidone.Other are identical with embodiment two to eight.
Embodiment ten: to be a kind of polyamide layer containing trianilino group apply in electrochromic material, photochromic material, hole mobile material, third-order non-linear material, false proof, camouflage material and display material as photoelectric material present embodiment.
Adopt following verification experimental verification beneficial effect of the present invention:
Embodiment one: a kind of preparation method of the polyamide layer containing trianilino group, completes according to the following steps:
One, the N described in synthesis step one, N '-two (Alpha-Naphthyl)-N, N '-two (4-aniline) benzidine:
1., in a nitrogen atmosphere 1molN, N-bis-(Alpha-Naphthyl)-4,4-benzidine is dissolved in 100mL dimethyl sulfoxide (DMSO), then adds 2mol p-fluoronitrobenzene and 2.5g sodium hydride, then react 28h at 100 DEG C, obtain reaction solution; Reaction solution is joined in cold water, then carries out suction filtration, discard filtrate, obtain yellow mercury oxide material; Use acetonitrile 3 times are cleaned to yellow mercury oxide material, then at temperature is 38 DEG C dry 11h, obtain reaction product A;
2., by reaction product A and Pd/C catalyzer join N, in N '-dimethyl formamide, in a hydrogen atmosphere, pressure is 8.5MPa, stirring velocity be 150r/min and temperature is react 45h under the condition of 85 DEG C, obtains yellow-green precipitate material; Yellow-green precipitate material is carried out suction filtration, discards filtrate, obtain reactant B; Re-use toluene cleaning reaction thing B3 time, then dry 3.5h at temperature is 40 DEG C, obtain N, N '-two (Alpha-Naphthyl)-N, N '-two (4-aniline) benzidine monomer;
Step one 2. described in the quality of reaction product A and the volume ratio of N, N '-dimethyl formamide be 5g:250mL;
Step one 2. described in the quality of Pd/C catalyzer and the volume ratio of N, N '-dimethyl formamide be 2g:250mL;
Step one 2. described in Pd/C catalyzer in the massfraction of Pd be 10%;
Two, N, N'-bis-(betanaphthyl)-N, N '-two (4-carboxyl benzene) Ursol D monomer is prepared:
1., in a nitrogen atmosphere, by 5gN, N '-two (betanaphthyl) Ursol D is dissolved in the anhydrous DMF of 80mL, then adds 4g to fluorobenzonitrile and 2g sodium hydride, 15h is reacted again at temperature is 120 DEG C, re-using temperature is that the distilled water of 3 DEG C is settled out reactant E, then carries out suction filtration to reactant E, discards filtrate, at temperature is 35 DEG C, carry out dry 24h again, obtain dried reactant E; Use acetone recrystallization is carried out to dried reactant E, then at temperature is 35 DEG C dry 7h, obtain dinitrile monomer;
2., by 3g dinitrile monomer, 2g potassium hydroxide, 8mL methyl alcohol and 6mL distilled water mix, then stirring reaction 5 days under be 100 DEG C and stirring velocity being the condition of 120r/min in temperature, re-using temperature is 3 DEG C, pH value be 3 distilled water be settled out reactant F; Again suction filtration is carried out to reactant F, discards filtrate, then at temperature is 35 DEG C dry 24h, obtain dried reactant F; Functional quality mark be 8% Glacial acetic acid recrystallization is carried out to dried reactant F, obtain N, N '-two (betanaphthyl)-N, N '-two (4-carboxyl benzene) Ursol D monomer;
Three, polyreaction:
N, N '-two (Alpha-Naphthyl)-N, N '-two (4-aniline) benzidine monomer, diacid monomer and calcium chloride are added in organic solvent, at temperature is 120 DEG C, react 5h again, re-use methyl alcohol and to settle out reactant I, then carry out suction filtration, discard filtrate, obtain reactant I; Recycling Soxhlet extraction method is purified to reactant I, then the reactant I after purifying is dried 5h at temperature is 35 DEG C, obtains the polymeric amide containing triphenylamine;
The mol ratio of the N described in step 3, N '-two (Alpha-Naphthyl)-N, N '-two (4-aniline) benzidine monomer and diacid monomer is 1:1;
The volume ratio of the N described in step 3, N '-two (Alpha-Naphthyl)-N, N '-two (4-aniline) benzidine monomer and organic solvent is 0.001mol:3mL;
The quality of the calcium chloride described in step 3 and the volume ratio of organic solvent are 0.25g:3mL;
Organic solvent described in step 3 is pyridine, tricresyl phosphite aniline and N-Methyl pyrrolidone are that 3:3:5 mixes according to the volume ratio of pyridine, tricresyl phosphite aniline and N-Methyl pyrrolidone;
Four, film-forming: be dissolved in organic solvent by the polymeric amide containing triphenylamine, obtains the polyamide solution containing triphenylamine; Be be coated on ito glass under the condition of 2000r/min at rotating speed by the polyamide solution containing trianilino group, then at temperature is 80 DEG C dry 10h, obtain the polyamide layer containing trianilino group;
The thickness of the polyamide layer containing trianilino group described in step 4 is 1 μm;
Organic solvent described in step 4 is N, N '-N,N-DIMETHYLACETAMIDE;
The quality of polymeric amide containing triphenylamine described in step 4 and the volume ratio of organic solvent are 0.0001g:1mL.
Embodiment one step one 1. described in N, the structural formula of N-bis-(Alpha-Naphthyl)-4,4-benzidine is
The N that 2. embodiment one step one obtains, the structural formula of N '-two (Alpha-Naphthyl)-N, N '-two (4-aniline) benzidine monomer is
Embodiment one step one 1. in reaction formula be:
Embodiment one step one 2. in reaction formula be:
The N that 2. embodiment one step 2 obtains, the structure of N '-two (betanaphthyl)-N, N '-two (4-carboxyl benzene) Ursol D monomer is
Embodiment one step 2 1. described in N, the structural formula of N '-two (betanaphthyl) Ursol D is:
Embodiment one step 2 1. in reaction formula be:
Embodiment one step 2 2. in reaction formula be:
Reaction formula in embodiment one step 3 is:
The structural formula of the polyamide layer containing trianilino group obtained in embodiment one step 4 is: the span of described n is 3≤n≤10, and n is integer.
Fig. 1 is the dinitrile monomer that 1. embodiment one step 2 obtains infrared spectrum; As can be seen from Figure 1, at 2246cm -1characteristic peak is the CN stretching vibration on main chain, and this explanation has prepared dinitrile monomer.
Fig. 2 is the N that 2. embodiment one step 2 obtains, N '-two (betanaphthyl)-N, N '-two (4-carboxyl benzene) Ursol D monomer infrared spectrogram; As can be seen from Figure 2, at 2500cm -1~ 3100cm -1place's characteristic peak is the O-H stretching vibration on main chain, at 1680cm -1place is owing to C=O stretching vibration peak, and this peak, two places illustrates obtained N, N '-two (betanaphthyl)-N, N '-two (4-carboxyl benzene) Ursol D monomer.
Fig. 3 is the N that 2. embodiment one step 2 obtains, N '-two (betanaphthyl)-N, N '-two (4-carboxyl benzene) Ursol D monomer h nuclear magnetic spectrum figure; As can be seen from Figure 3, what 12 places represented is carboxyl peak, and the area ratio at peak and N, N '-two (betanaphthyl)-N, the hydrogen number of N '-two (4-carboxyl benzene) Ursol D monomer is consistent, this illustrates the N that obtained structure is consistent, N '-two (betanaphthyl)-N, N '-two (4-carboxyl benzene) Ursol D monomer.
Fig. 4 is the N that 2. embodiment one step 2 obtains, N '-two (betanaphthyl)-N, N '-two (4-carboxyl benzene) Ursol D monomer c nuclear magnetic spectrum figure; As can be seen from Figure 4, the area ratio at peak and N, N '-two (betanaphthyl)-N, the carbon number of N '-two (4-carboxyl benzene) Ursol D monomer is consistent, this illustrates the N that obtained structure is consistent, N '-two (betanaphthyl)-N, N '-two (4-carboxyl benzene) Ursol D monomer.
Fig. 5 is the infrared spectrogram of the polyamide layer containing trianilino group that embodiment one step 4 obtains; As can be seen from Figure 5, the polyamide layer containing trianilino group of embodiment one preparation is at 3220cm -1characteristic peak is the N-H stretching vibration on main chain, at 1675cm -1place can be classified as C=O stretching vibration peak, and this peak, two places illustrates the polymeric amide being polymerized and having generated containing trianilino group.
Fig. 6 is the cyclic voltammogram of the polyamide layer containing trianilino group that embodiment one step 4 obtains; As can be seen from Figure 6, the cyclic voltammetric spectrogram of polyamide layer under impressed voltage containing trianilino group obtained in embodiment one step 4, having a pair redox peak, is oxidation peak at the peak of 1.20V, and simultaneous color from pale yellow look becomes redness; Have 1 corresponding reduction peak at 0.50V place, now color is become light yellow from redness; Illustrate that this polymkeric substance has good reversibility.
Fig. 7 is the ultraviolet spectrogram of the polyamide layer containing trianilino group that embodiment one step 4 obtains;
Fig. 8 is the fluorescence spectrum figure of the polyamide layer containing trianilino group that embodiment one step 4 obtains;
As can be seen from Fig. 7 and Fig. 8, the ultraviolet-ray visible absorbing peak value of the polyamide layer containing trianilino group that embodiment one step 4 obtains is 370nm, and the peak value of fluorescence spectrum is 502nm, and these are all conjugation triphenylamine π-π *the result of transition of electron gained.
Embodiment two: a kind of preparation method of the polyamide layer containing trianilino group, completes according to the following steps:
One, the N described in synthesis step one, N '-two (Alpha-Naphthyl)-N, N '-two (4-aniline) benzidine:
1., in a nitrogen atmosphere 1molN, N-bis-(Alpha-Naphthyl)-4,4-benzidine is dissolved in 100mL dimethyl sulfoxide (DMSO), then adds 2mol p-fluoronitrobenzene and 2.5g sodium hydride, then react 28h at 100 DEG C, obtain reaction solution; Reaction solution is joined in cold water, then carries out suction filtration, discard filtrate, obtain yellow mercury oxide material; Use acetonitrile 3 times are cleaned to yellow mercury oxide material, then at temperature is 38 DEG C dry 11h, obtain reaction product A;
2., by reaction product A and Pd/C catalyzer join N, in N '-dimethyl formamide, in a hydrogen atmosphere, pressure is 8.5MPa, stirring velocity be 150r/min and temperature is react 45h under the condition of 85 DEG C, obtains yellow-green precipitate material; Yellow-green precipitate material is carried out suction filtration, discards filtrate, obtain reactant B; Re-use toluene cleaning reaction thing B3 time, then dry 3.5h at temperature is 40 DEG C, obtain N, N '-two (Alpha-Naphthyl)-N, N '-two (4-aniline) benzidine monomer;
Step one 2. described in the quality of reaction product A and the volume ratio of N, N '-dimethyl formamide be 5g:250mL;
Step one 2. described in the quality of Pd/C catalyzer and the volume ratio of N, N '-dimethyl formamide be 2g:250mL;
Step one 2. described in Pd/C catalyzer in the massfraction of Pd be 10%;
Two, N, N'-bis-(Alpha-Naphthyl)-N, N '-two (4-carboxyl benzene) benzidine monomer is prepared:
1., in a nitrogen atmosphere, 5gN, N '-two (1-naphthyl)-4,4-benzidines are dissolved into the anhydrous N of 80mL, in dinethylformamide, add 4.2g again to fluorobenzonitrile and 2.3g sodium hydride, then react 16h at temperature is 120 DEG C, re-using temperature is that the distilled water of 2 DEG C is settled out reactant G, again suction filtration is carried out to reactant G, discard filtrate, then carry out dry 26h at temperature is 35 DEG C, obtain dried reactant G; Use acetone recrystallization is carried out to dried reactant G, then at temperature is 35 DEG C dry 8h, obtain dinitrile monomer;
2., 3.2g dinitrile monomer, 2g potassium hydroxide, 10mL methyl alcohol and 10mL distilled water are mixed, stirring reaction 6 days under be 100 DEG C and stirring velocity being the condition of 120r/min in temperature again, re-using temperature is 3 DEG C, pH value be 2 distilled water be settled out reactant H; Again suction filtration is carried out to reactant H, discards filtrate, then at temperature is 35 DEG C dry 24h, obtain dried reactant H; Functional quality mark be 8% Glacial acetic acid recrystallization is carried out to dried reactant H, obtain N, N '-two (Alpha-Naphthyl)-N, N '-two (4-carboxyl benzene) benzidine monomer;
Three, polyreaction:
N, N '-two (Alpha-Naphthyl)-N, N '-two (4-aniline) benzidine monomer, diacid monomer and calcium chloride are added in organic solvent, at temperature is 120 DEG C, react 6h again, re-use methyl alcohol and to settle out reactant I, then carry out suction filtration, discard filtrate, obtain reactant I; Recycling Soxhlet extraction method is purified to reactant I, then the reactant I after purifying is dried 5h at temperature is 40 DEG C, obtains the polymeric amide containing triphenylamine;
The mol ratio of the N described in step 3, N '-two (Alpha-Naphthyl)-N, N '-two (4-aniline) benzidine monomer and diacid monomer is 1:1;
The volume ratio of the N described in step 3, N '-two (Alpha-Naphthyl)-N, N '-two (4-aniline) benzidine monomer and organic solvent is 0.05mol:3mL;
The quality of the calcium chloride described in step 3 and the volume ratio of organic solvent are 0.3g:3mL;
Four, film-forming: be dissolved in organic solvent by the polymeric amide containing triphenylamine, obtains the polyamide solution containing triphenylamine; Be be coated on ito glass under the condition of 2000r/min at rotating speed by the polyamide solution containing trianilino group, then at temperature is 80 DEG C dry 10h, obtain the polyamide layer containing trianilino group;
The thickness of the polyamide layer containing trianilino group described in step 4 is 1 μm;
Organic solvent described in step 4 is N, N '-N,N-DIMETHYLACETAMIDE;
The quality of polymeric amide containing triphenylamine described in step 4 and the volume ratio of organic solvent are 0.0001g:1mL.
The diacid monomer that 2. embodiment two step 2 obtains is N, N '-two (Alpha-Naphthyl)-N, N '-two (4-carboxyl benzene) benzidine monomer; The structural formula of described N, N '-two (Alpha-Naphthyl)-N, N '-two (4-carboxyl benzene) benzidine monomer is
Embodiment two step 2 1. in reaction formula be:
Embodiment two step 2 2. in reaction formula be:
The structural formula of the polyamide layer containing trianilino group obtained in embodiment two step 4 is: the span of described n is 3≤n≤8, and n is integer.
Reaction formula in embodiment two step 3 is:
Fig. 9 is the dinitrile monomer that 1. embodiment two step 2 obtains infrared spectrogram; As can be seen from Figure 9, at 2246cm -1characteristic peak is the CN stretching vibration on main chain, and this explanation has prepared dinitrile monomer.
Figure 10 is the N that 2. embodiment two step 2 obtains, N '-two (Alpha-Naphthyl)-N, N '-two (4-carboxyl benzene) benzidine monomer infrared spectrogram; As can be seen from Figure 10, monomer is at 3100cm -1place's characteristic peak is the O-H stretching vibration on main chain, at 1700cm -1place is owing to C=O stretching vibration peak, and this peak, two places illustrates obtained N, N '-two (Alpha-Naphthyl)-N, N '-two (4-carboxyl benzene) benzidine monomer.
Figure 11 is the N that 2. embodiment two step 2 obtains, N '-two (Alpha-Naphthyl)-N, N '-two (4-carboxyl benzene) benzidine monomer h nuclear magnetic spectrum figure; As can be seen from Figure 11, what 12 places represented is carboxyl peak, and the area ratio at peak and N, N '-two (betanaphthyl)-N, the hydrogen number of N '-two (4-carboxyl benzene) Ursol D monomer is consistent, this illustrates the N that obtained structure is consistent, N '-two (Alpha-Naphthyl)-N, N '-two (4-carboxyl benzene) benzidine monomer.
Figure 12 is the infrared spectrogram of the polyamide layer containing trianilino group that embodiment two step 4 obtains; As can be seen from Figure 12, embodiment two step 4 obtain containing the polyamide layer of trianilino group at 3108cm -1characteristic peak is the N-H stretching vibration on main chain, at 1678cm -1place can be classified as C=O stretching vibration peak, and this peak, two places illustrates the polyamide layer being polymerized and having generated containing trianilino group.
Figure 13 is the cyclic voltammetric spectrogram of the polyamide layer containing trianilino group that embodiment two step 4 obtains; As can be seen from Figure 13, the cyclic voltammetric spectrogram of polyamide layer under impressed voltage containing trianilino group that embodiment two step 4 obtains, having a pair redox peak, is oxidation peak at the peak of 1.28V, and simultaneous color from pale yellow look becomes redness; Have 1 corresponding reduction peak at 0.70V place, now color is become light yellow from redness; Illustrate that this polymkeric substance has good reversibility.
Figure 14 is the ultraviolet spectrogram of the polyamide layer containing trianilino group that embodiment two step 4 obtains;
Figure 15 is the fluorescence spectrum figure of the polyamide layer containing trianilino group that embodiment two step 4 obtains;
As can be seen from Figure 14 and Figure 15, the ultraviolet-ray visible absorbing peak value of the polyamide layer containing trianilino group that embodiment two step 4 obtains is 368nm, and the peak value of fluorescence spectrum is 498nm, and these are all conjugation triphenylamine π-π *the result of transition of electron gained.
Embodiment three: a kind of preparation method of the polyamide layer containing trianilino group, completes according to the following steps:
One, N, N is prepared '-phenylbenzene-N, N '-two (4-aniline) benzidine monomer:
1., in a nitrogen atmosphere N, N-biphenyl diamine is dissolved in dimethyl sulfoxide (DMSO), then adds p-fluoronitrobenzene and sodium hydride, then react 26h at 100 DEG C, obtain reaction solution; Reaction solution is joined in cold water, then carries out suction filtration, discard filtrate, obtain yellow mercury oxide material; Use acetonitrile 2 times ~ 4 times are cleaned to yellow mercury oxide material, then at temperature is 35 DEG C dry 12h, obtain reaction product C;
Step one 1. described in N, the quality of N-biphenyl diamine and the volume ratio of dimethyl sulfoxide (DMSO) are 7g:100mL;
Step one 1. described in the quality of p-fluoronitrobenzene and the volume ratio of dimethyl sulfoxide (DMSO) be 6.5g:100mL;
Step one 1. described in the quality of sodium hydride and the volume ratio of dimethyl sulfoxide (DMSO) be 2.5g:100mL;
2., by reaction product C and Pd/C catalyzer join N, in N '-dimethyl formamide, in a hydrogen atmosphere, pressure is 8MPa, stirring velocity be 150r/min and temperature is react 45h under the condition of 80 DEG C, obtains yellow-green precipitate material; Yellow-green precipitate material is carried out suction filtration, discards filtrate, obtain reactant D; Re-use toluene cleaning reaction thing B3 time, then dry 4h at temperature is 35 DEG C, obtain N, N '-phenylbenzene-N, N '-two (4-aniline) benzidine monomer;
Step one 2. described in the quality of reaction product C and the volume ratio of N, N '-dimethyl formamide be 3.5g:200mL;
Step one 2. described in the quality of Pd/C catalyzer and the volume ratio of N, N '-dimethyl formamide be 1.0g:200mL;
Step one 2. described in Pd/C catalyzer in the massfraction of Pd be 10%;
Two, N, N'-bis-(betanaphthyl)-N, N '-two (4-carboxyl benzene) Ursol D monomer is prepared:
1., in a nitrogen atmosphere, by 5gN, N '-two (betanaphthyl) Ursol D is dissolved in the anhydrous DMF of 80mL, then adds 4g to fluorobenzonitrile and 2g sodium hydride, 15h is reacted again at temperature is 120 DEG C, re-using temperature is that the distilled water of 3 DEG C is settled out reactant E, then carries out suction filtration to reactant E, discards filtrate, at temperature is 35 DEG C, carry out dry 24h again, obtain dried reactant E; Use acetone recrystallization is carried out to dried reactant E, then at temperature is 35 DEG C dry 7h, obtain dinitrile monomer;
2., by 3g dinitrile monomer, 2g potassium hydroxide, 8mL methyl alcohol and 6mL distilled water mix, then stirring reaction 5 days under be 100 DEG C and stirring velocity being the condition of 120r/min in temperature, re-using temperature is 3 DEG C, pH value be 3 distilled water be settled out reactant F; Again suction filtration is carried out to reactant F, discards filtrate, then at temperature is 35 DEG C dry 24h, obtain dried reactant F; Functional quality mark be 8% Glacial acetic acid recrystallization is carried out to dried reactant F, obtain N, N '-two (betanaphthyl)-N, N '-two (4-carboxyl benzene) Ursol D monomer;
Three, polyreaction:
By N, N '-phenylbenzene-N, N '-two (4-aniline) benzidine monomer, diacid monomer and calcium chloride adds in organic solvent, at temperature is 120 DEG C, react 5h again, re-use methyl alcohol and to settle out reactant I, then carry out suction filtration, discard filtrate, obtain reactant I; Recycling Soxhlet extraction method is purified to reactant I, then the reactant I after purifying is dried 5h at temperature is 35 DEG C, obtains the polymeric amide containing triphenylamine;
N described in step 3, N '-phenylbenzene-N, N '-two the mol ratio of (4-aniline) benzidine monomer and diacid monomer be 1:1;
N described in step 3, N '-phenylbenzene-N, N '-two the volume ratio of (4-aniline) benzidine monomer and organic solvent be 0.001mol:3mL;
The quality of the calcium chloride described in step 3 and the volume ratio of organic solvent are 0.23g:3mL;
Organic solvent described in step 3 is pyridine, tricresyl phosphite aniline and N-Methyl pyrrolidone are that 3:3:5 mixes according to the volume ratio of pyridine, tricresyl phosphite aniline and N-Methyl pyrrolidone;
Four, film-forming: be dissolved in organic solvent by the polymeric amide containing triphenylamine, obtains the polyamide solution containing triphenylamine; Be be coated on ito glass under the condition of 2000r/min at rotating speed by the polyamide solution containing trianilino group, then at temperature is 80 DEG C dry 10h, obtain the polyamide layer containing trianilino group;
The thickness of the polyamide layer containing trianilino group described in step 4 is 1 μm;
Organic solvent described in step 4 is N, N '-N,N-DIMETHYLACETAMIDE;
The quality of polymeric amide containing triphenylamine described in step 4 and the volume ratio of organic solvent are 0.0001g:1mL.
Embodiment three step one 1. in the structural formula of N, N-phenylbenzene-4,4-benzidine be:
Embodiment three step one 1. in reaction formula be:
Embodiment three step one 2. in reaction formula be:
The reaction formula of embodiment three step 3 is:
The structural formula of the polyamide layer containing trianilino group obtained in embodiment three step 4 is the span of described n is 3≤n≤10, and n is integer.
The infrared spectrogram of the polyamide layer containing trianilino group obtained in Figure 16 embodiment three step 4;
As can be seen from Figure 16, the polyamide layer containing trianilino group obtained in embodiment three step 4 is at 3112cm -1characteristic peak is the N-H stretching vibration on main chain, at 1665cm -1place can be classified as C=O stretching vibration peak, and this peak, two places illustrates the polyamide layer being polymerized and having generated containing trianilino group.
The cyclic voltammogram of the polyamide layer containing trianilino group obtained in Figure 17 embodiment three step 4; As can be seen from Figure 17, the cyclic voltammetric spectrogram of polyamide layer under impressed voltage containing trianilino group obtained in embodiment three step 4, having a pair redox peak, is oxidation peak at the peak of 1.21V, and simultaneous color from pale yellow look becomes redness; Have 1 corresponding reduction peak at 0.58V place, now color is become light yellow from redness; Illustrate that this polymkeric substance has good reversibility.
The ultraviolet spectrogram of the polyamide layer containing trianilino group obtained in Figure 18 embodiment three step 4;
The fluorescence spectrum figure of the polyamide layer containing trianilino group obtained in Figure 19 embodiment three step 4;
As can be seen from Figure 18 and Figure 19, the ultraviolet-ray visible absorbing peak value of the polyamide layer containing trianilino group obtained in embodiment three step 4 is 360nm, and the peak value of fluorescence spectrum is 506nm, and these are all conjugation triphenylamine π-π *the result of transition of electron gained.
Embodiment four: a kind of preparation method of the polyamide layer containing trianilino group, completes according to the following steps:
One, N, N is prepared '-phenylbenzene-N, N '-two (4-aniline) benzidine monomer:
1., in a nitrogen atmosphere N, N-biphenyl diamine is dissolved in dimethyl sulfoxide (DMSO), then adds p-fluoronitrobenzene and sodium hydride, then react 26h at 100 DEG C, obtain reaction solution; Reaction solution is joined in cold water, then carries out suction filtration, discard filtrate, obtain yellow mercury oxide material; Use acetonitrile 2 times ~ 4 times are cleaned to yellow mercury oxide material, then at temperature is 35 DEG C dry 12h, obtain reaction product C;
Step one 1. described in N, the quality of N-biphenyl diamine and the volume ratio of dimethyl sulfoxide (DMSO) are 7g:100mL;
Step one 1. described in the quality of p-fluoronitrobenzene and the volume ratio of dimethyl sulfoxide (DMSO) be 6.5g:100mL;
Step one 1. described in the quality of sodium hydride and the volume ratio of dimethyl sulfoxide (DMSO) be 2.5g:100mL;
2., by reaction product C and Pd/C catalyzer join N, in N '-dimethyl formamide, in a hydrogen atmosphere, pressure is 8MPa, stirring velocity be 150r/min and temperature is react 45h under the condition of 80 DEG C, obtains yellow-green precipitate material; Yellow-green precipitate material is carried out suction filtration, discards filtrate, obtain reactant D; Re-use toluene cleaning reaction thing B3 time, then dry 4h at temperature is 35 DEG C, obtain N, N '-phenylbenzene-N, N '-two (4-aniline) benzidine monomer;
Step one 2. described in the quality of reaction product C and the volume ratio of N, N '-dimethyl formamide be 3.5g:200mL;
Step one 2. described in the quality of Pd/C catalyzer and the volume ratio of N, N '-dimethyl formamide be 1.0g:200mL;
Step one 2. described in Pd/C catalyzer in the massfraction of Pd be 10%;
Two, N, N'-bis-(Alpha-Naphthyl)-N, N '-two (4-carboxyl benzene) benzidine monomer is prepared:
1., in a nitrogen atmosphere, 5gN, N '-two (1-naphthyl)-4,4-benzidines are dissolved into the anhydrous N of 80mL, in dinethylformamide, add 4.2g again to fluorobenzonitrile and 2.3g sodium hydride, then react 16h at temperature is 120 DEG C, re-using temperature is that the distilled water of 2 DEG C is settled out reactant G, again suction filtration is carried out to reactant G, discard filtrate, then carry out dry 26h at temperature is 35 DEG C, obtain dried reactant G; Use acetone recrystallization is carried out to dried reactant G, then at temperature is 35 DEG C dry 8h, obtain dinitrile monomer;
2., 3.2g dinitrile monomer, 2g potassium hydroxide, 10mL methyl alcohol and 10mL distilled water are mixed, stirring reaction 6 days under be 100 DEG C and stirring velocity being the condition of 120r/min in temperature again, re-using temperature is 3 DEG C, pH value be 2 distilled water be settled out reactant H; Again suction filtration is carried out to reactant H, discards filtrate, then at temperature is 35 DEG C dry 24h, obtain dried reactant H; Functional quality mark be 8% Glacial acetic acid recrystallization is carried out to dried reactant H, obtain N, N '-two (Alpha-Naphthyl)-N, N '-two (4-carboxyl benzene) benzidine monomer;
Three, polyreaction:
By N, N '-two (Alpha-Naphthyl)-N, N '-two (4-aniline) benzidine monomer or N, N '-phenylbenzene-N, N '-two (4-aniline) benzidine monomer, diacid monomer and calcium chloride adds in organic solvent, then react 5h at temperature is 120 DEG C, re-use methyl alcohol to settle out reactant I, carry out suction filtration again, discard filtrate, obtain reactant I; Recycling Soxhlet extraction method is purified to reactant I, then the reactant I after purifying is dried 5h at temperature is 35 DEG C, obtains the polymeric amide containing triphenylamine;
N described in step 3, N '-phenylbenzene-N, N '-two the mol ratio of (4-aniline) benzidine monomer and diacid monomer be 1:1;
N described in step 3, N '-phenylbenzene-N, N '-two the volume ratio of (4-aniline) benzidine monomer and organic solvent be 0.001mol:3mL;
The quality of the calcium chloride described in step 3 and the volume ratio of organic solvent are 0.26g:3mL;
Organic solvent described in step 3 is pyridine, tricresyl phosphite aniline and N-Methyl pyrrolidone are that 3:3:5 mixes according to the volume ratio of pyridine, tricresyl phosphite aniline and N-Methyl pyrrolidone;
Four, film-forming: be dissolved in organic solvent by the polymeric amide containing triphenylamine, obtains the polyamide solution containing triphenylamine; Be be coated on ito glass under the condition of 2000r/min at rotating speed by the polyamide solution containing trianilino group, then at temperature is 80 DEG C dry 10h, obtain the polyamide layer containing trianilino group;
The thickness of the polyamide layer containing trianilino group described in step 4 is 1 μm;
Organic solvent described in step 4 is N, N '-N,N-DIMETHYLACETAMIDE;
The quality of polymeric amide containing triphenylamine described in step 4 and the volume ratio of organic solvent are 0.0001g:1mL.
The structural formula of the polymeric amide containing triphenylamine obtained in embodiment four step 3 is
Reaction formula in embodiment four step 3 is:
Figure 20 is the infrared spectrogram of the polyamide layer containing trianilino group that embodiment four step 4 obtains; As can be seen from Figure 20, embodiment four step 4 obtain containing the polyamide layer of trianilino group at 3122cm -1characteristic peak is the N-H stretching vibration on main chain, at 1668cm -1place can be classified as C=O stretching vibration peak, and this peak, two places illustrates the polyamide layer being polymerized and having generated containing trianilino group.
Figure 21 is the cyclic voltammogram of the polyamide layer containing trianilino group that embodiment four step 4 obtains; As can be seen from Figure 21, the cyclic voltammetric spectrogram of polyamide layer under impressed voltage containing trianilino group that embodiment four step 4 obtains, having a pair redox peak, is oxidation peak at the peak of 1.12V, and simultaneous color from pale yellow look becomes redness; Have 1 corresponding reduction peak at 0.78V place, now color is become light yellow from redness; Illustrate that this polymkeric substance has good reversibility.
Figure 22 is the ultraviolet spectrogram of the polyamide layer containing trianilino group that embodiment four step 4 obtains;
Figure 23 is the fluorescence spectrum figure of the polyamide layer containing trianilino group that embodiment four step 4 obtains;
As can be seen from Figure 22 and Figure 23, the ultraviolet-ray visible absorbing peak value of the polyamide layer containing trianilino group that embodiment four step 4 obtains is 365nm, and the peak value of fluorescence spectrum is 496nm, and these are all conjugation triphenylamine π-π *the result of transition of electron gained.

Claims (10)

1. the polyamide layer containing trianilino group, is characterized in that a kind of structural formula of the polyamide layer containing trianilino group is:
wherein, described R 1for described R 2for described n 1value be 1≤n 1≤ 100, and n 1for integer; Described n 2value be 1≤n 2≤ 100, and n 2for integer.
2. a preparation method for the polyamide layer containing trianilino group, is characterized in that a kind of preparation method of the polyamide layer containing trianilino group completes according to the following steps:
One, polyreaction:
By N, N '-two (Alpha-Naphthyl)-N, N '-two (4-aniline) benzidine monomer or N, N '-phenylbenzene-N, N '-two (4-aniline) benzidine monomer, diacid monomer and calcium chloride adds in organic solvent, then reacts 5h ~ 7h at temperature is 120 DEG C ~ 150 DEG C, re-use methyl alcohol to settle out reactant I, carry out suction filtration again, discard filtrate, obtain reactant I; Recycling Soxhlet extraction method is purified to reactant I, then the reactant I after purifying is dried 3h ~ 5h at temperature is 30 ~ 40 DEG C, obtains the polymeric amide containing triphenylamine;
N described in step one, N '-two (Alpha-Naphthyl)-N, the mol ratio of N '-two (4-aniline) benzidine monomer and diacid monomer is 1:1 or N, N '-phenylbenzene-N, N '-two the mol ratio of (4-aniline) benzidine monomer and diacid monomer be 1:1;
N described in step one, N '-two (Alpha-Naphthyl)-N, N '-two (4-aniline) benzidine monomer or N, the volume ratio of N '-phenylbenzene-N, N '-two (4-aniline) benzidine monomer and organic solvent is (0.001mol ~ 0.05mol): 3mL;
The quality of the calcium chloride described in step one and the volume ratio of organic solvent are (0.2g ~ 0.3g): 3mL;
Two, film-forming: be dissolved in organic solvent by the polymeric amide containing triphenylamine, obtains the polyamide solution containing triphenylamine; Be be coated on ito glass under the condition of 1500r/min ~ 2500r/min at rotating speed by the polyamide solution containing trianilino group, then at temperature is 80 DEG C ~ 100 DEG C dry 8 ~ 10h, obtain the polyamide layer containing trianilino group;
The thickness of the polyamide layer containing trianilino group described in step 2 is 0.5 μm ~ 5 μm;
The quality of polymeric amide containing triphenylamine described in step 2 and the volume ratio of organic solvent are (0.0001g ~ 0.0005g): 1mL;
The structural formula of the polyamide layer containing trianilino group described in step 2 is:
wherein, described R 1for described R 2for described n 1value be 1≤n 1≤ 100, and n 1for integer; Described n 2value be 1≤n 2≤ 100, and n 2for integer.
3. the preparation method of a kind of polyamide layer containing trianilino group according to claim 2, it is characterized in that the N described in step one, N '-two (Alpha-Naphthyl)-N, N '-two (4-aniline) benzidine monomer is prepared by the following method:
1., in a nitrogen atmosphere N, N-bis-(Alpha-Naphthyl)-4,4-benzidine is dissolved in dimethyl sulfoxide (DMSO), then adds p-fluoronitrobenzene and sodium hydride, then react 24h ~ 30h at 100 DEG C, obtain reaction solution; Reaction solution is joined in cold water, then carries out suction filtration, discard filtrate, obtain yellow mercury oxide material; Use acetonitrile to clean 2 times ~ 4 times to yellow mercury oxide material, then at temperature is 30 DEG C ~ 40 DEG C dry 8 ~ 15h, obtain reaction product A;
Step 1. described in N, the amount of substance of N-bis-(Alpha-Naphthyl)-4,4-benzidine and p-fluoronitrobenzene is than being 1:2;
Step 1. described in N, the amount of substance of N-bis-(Alpha-Naphthyl)-4,4-benzidine and the volume ratio of dimethyl sulfoxide (DMSO) are 1mol:(100mL ~ 200mL);
Step 1. described in the quality of sodium hydride and the volume ratio of dimethyl sulfoxide (DMSO) be (1g ~ 3g): 100mL;
2., reaction product A and Pd/C catalyzer are joined N, in N '-dimethyl formamide, in a hydrogen atmosphere, pressure is 7MPa ~ 9MPa, stirring velocity be 120r/min ~ 150r/min and temperature is react 40h ~ 45h under the condition of 70 DEG C ~ 90 DEG C, obtains yellow-green precipitate material; Yellow-green precipitate material is carried out suction filtration, discards filtrate, obtain reactant B; Re-use toluene cleaning reaction thing B2 time ~ 4 times, then dry 3h ~ 5h at temperature is 30 DEG C ~ 40 DEG C, obtain N, N '-two (Alpha-Naphthyl)-N, N '-two (4-aniline) benzidine monomer;
Step 2. described in the quality of reaction product A and the volume ratio of N, N '-dimethyl formamide be (3g ~ 5g): 250mL;
Step 2. described in the quality of Pd/C catalyzer and the volume ratio of N, N '-dimethyl formamide be (0.5g ~ 2g): 250mL;
Step 2. described in Pd/C catalyzer in the massfraction of Pd be 10%.
4. the preparation method of a kind of polyamide layer containing trianilino group according to claim 2, it is characterized in that the N described in step one, N '-phenylbenzene-N, N '-two (4-aniline) benzidine monomer is prepared by the following method:
1., in a nitrogen atmosphere N, N-biphenyl diamine is dissolved in dimethyl sulfoxide (DMSO), then adds p-fluoronitrobenzene and sodium hydride, then react 24h ~ 30h at 100 DEG C, obtain reaction solution; Reaction solution is joined in cold water, then carries out suction filtration, discard filtrate, obtain yellow mercury oxide material; Use acetonitrile to clean 2 times ~ 4 times to yellow mercury oxide material, then at temperature is 30 DEG C ~ 40 DEG C dry 8 ~ 15h, obtain reaction product C;
Step 1. described in N, the quality of N-biphenyl diamine and the volume ratio of dimethyl sulfoxide (DMSO) are (6g ~ 8g): 100mL;
Step 1. described in the quality of p-fluoronitrobenzene and the volume ratio of dimethyl sulfoxide (DMSO) be (6g ~ 8g): 100mL;
Step 1. described in the quality of sodium hydride and the volume ratio of dimethyl sulfoxide (DMSO) be (2g ~ 3g): 100mL;
2., reaction product C and Pd/C catalyzer are joined N, in N '-dimethyl formamide, in a hydrogen atmosphere, pressure is 7MPa ~ 9MPa, stirring velocity be 120r/min ~ 150r/min and temperature is react 40h ~ 45h under the condition of 70 DEG C ~ 90 DEG C, obtains yellow-green precipitate material; Yellow-green precipitate material is carried out suction filtration, discards filtrate, obtain reactant D; Re-use toluene cleaning reaction thing B2 time ~ 4 times, then dry 3h ~ 5h at temperature is 30 DEG C ~ 40 DEG C, obtain N, N '-phenylbenzene-N, N '-two (4-aniline) benzidine monomer;
Step 2. described in the quality of reaction product C and the volume ratio of N, N '-dimethyl formamide be (3g ~ 4g): 200mL;
Step 2. described in the quality of Pd/C catalyzer and the volume ratio of N, N '-dimethyl formamide be (0.5g ~ 1.5g): 200mL;
Step 2. described in Pd/C catalyzer in the massfraction of Pd be 10%.
5. the preparation method of a kind of polyamide layer containing trianilino group according to claim 2, it is characterized in that the diacid monomer described in step one is N, N'-bis-(betanaphthyl)-N, N '-two (4-carboxyl benzene) Ursol D monomer or N, N'-bis-(Alpha-Naphthyl)-N, N '-two (4-carboxyl benzene) benzidine monomer; Described diacid monomer is the structural formula of N, N'-bis-(betanaphthyl)-N, N '-two (4-carboxyl benzene) Ursol D monomer
the structural formula of described N, N'-bis-(Alpha-Naphthyl)-N, N '-two (4-carboxyl benzene) benzidine monomer is
6. the preparation method of a kind of polyamide layer containing trianilino group according to claim 5, it is characterized in that described N, N'-bis-(betanaphthyl)-N, N '-two (4-carboxyl benzene) Ursol D monomer is prepared by the following method:
1., in a nitrogen atmosphere, by N, N '-two (betanaphthyl) Ursol D is dissolved in anhydrous DMF, then adds fluorobenzonitrile and sodium hydride, 15h ~ 20h is reacted again at temperature is 120 DEG C ~ 130 DEG C, re-using temperature is that the distilled water of 0 DEG C ~ 5 DEG C is settled out reactant E, then carries out suction filtration to reactant E, discards filtrate, at temperature is 30 DEG C ~ 35 DEG C, carry out dry 24h ~ 30h again, obtain dried reactant E; Use acetone recrystallization is carried out to dried reactant E, then at temperature is 30 DEG C ~ 35 DEG C dry 6h ~ 8h, obtain dinitrile monomer;
Step 1. described in N, the quality of N '-two (betanaphthyl) Ursol D and the volume ratio of anhydrous DMF are 5g:(70mL ~ 100mL);
Step 1. described in the quality to fluorobenzonitrile and the volume ratio of anhydrous DMF be 4g:(70mL ~ 100mL);
Step 1. described in the quality of sodium hydride and the volume ratio of anhydrous DMF be 2g:(70mL ~ 100mL);
2., dinitrile monomer, potassium hydroxide, methyl alcohol and distilled water are mixed, stirring reaction 5 days ~ 6 days under be 100 DEG C ~ 110 DEG C and stirring velocity being the condition of 120r/min ~ 150r/min in temperature again, re-using temperature is 0 DEG C ~ 5 DEG C, pH value be 2 ~ 3 distilled water be settled out reactant F; Again suction filtration is carried out to reactant F, discards filtrate, then at temperature is 30 DEG C ~ 35 DEG C dry 24h ~ 30h, obtain dried reactant F; Functional quality mark be 6% ~ 8% Glacial acetic acid recrystallization is carried out to dried reactant F, obtain N, N '-two (betanaphthyl)-N, N '-two (4-carboxyl benzene) Ursol D monomer;
Step 2. described in the quality of dinitrile monomer and the volume ratio of methyl alcohol be 3g:(8mL ~ 10mL);
Step 2. described in the quality of potassium hydroxide and the volume ratio of methyl alcohol be 2g:(8mL ~ 10mL);
Step 2. described in methyl alcohol and the volume ratio of distilled water be (0.5 ~ 1.5): 1.
7. the preparation method of a kind of polyamide layer containing trianilino group according to claim 5, it is characterized in that described N, N'-bis-(Alpha-Naphthyl)-N, N '-two (4-carboxyl benzene) benzidine monomer is prepared by the following method:
1., in a nitrogen atmosphere, N, N '-two (1-naphthyl)-4,4-benzidines are dissolved into anhydrous N, in dinethylformamide, add fluorobenzonitrile and sodium hydride again, then react 15h ~ 20h at temperature is 120 DEG C ~ 130 DEG C, re-using temperature is that the distilled water of 0 DEG C ~ 5 DEG C is settled out reactant G, again suction filtration is carried out to reactant G, discard filtrate, then carry out dry 24h ~ 30h at temperature is 30 DEG C ~ 35 DEG C, obtain dried reactant G; Use acetone recrystallization is carried out to dried reactant G, then at temperature is 30 DEG C ~ 35 DEG C dry 6h ~ 8h, obtain dinitrile monomer;
Step 1. described in N, the quality of N '-two (1-naphthyl)-4,4-benzidines and the volume ratio of anhydrous DMF are 5g:(70mL ~ 100mL);
Step 1. described in the quality to fluorobenzonitrile and the volume ratio of anhydrous DMF be 4g:(70mL ~ 100mL);
Step 1. described in the quality of sodium hydride and the volume ratio of anhydrous DMF be 2g:(70mL ~ 100mL);
2., dinitrile monomer, potassium hydroxide, methyl alcohol and distilled water are mixed, stirring reaction 5 days ~ 6 days under be 100 DEG C ~ 110 DEG C and stirring velocity being the condition of 120r/min ~ 150r/min in temperature again, re-using temperature is 0 DEG C ~ 5 DEG C, pH value be 2 ~ 3 distilled water be settled out reactant H; Again suction filtration is carried out to reactant H, discards filtrate, then at temperature is 30 DEG C ~ 35 DEG C dry 24h ~ 30h, obtain dried reactant H; Functional quality mark be 6% ~ 8% Glacial acetic acid recrystallization is carried out to dried reactant H, obtain N, N '-two (Alpha-Naphthyl)-N, N '-two (4-carboxyl benzene) benzidine monomer;
Step 2. described in the quality of dinitrile monomer and the volume ratio of methyl alcohol be 3g:(8mL ~ 10mL);
Step 2. described in the quality of potassium hydroxide and the volume ratio of methyl alcohol be 2g:(8mL ~ 10mL);
Step 2. described in methyl alcohol and the volume ratio of distilled water be (0.5 ~ 1.5): 1.
8. the preparation method of a kind of polyamide layer containing trianilino group according to claim 2, is characterized in that the organic solvent described in step one is a kind of or wherein several mixing in triphenyl phosphite, pyridine and N-Methyl pyrrolidone.
9. the preparation method of a kind of polyamide layer containing trianilino group according to claim 2, it is characterized in that the organic solvent described in step 2 is N, a kind of or wherein several mixing in N '-N,N-DIMETHYLACETAMIDE, N, N '-dimethyl formamide and N-Methyl pyrrolidone.
10. the application of polyamide layer containing trianilino group, is characterized in that a kind of polyamide layer containing trianilino group is applied in electrochromic material, photochromic material, hole mobile material, third-order non-linear material, false proof, camouflage material and display material as photoelectric material.
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