CN109593172A - Triarylamine quasi polymer of structure containing benzoxazine and its preparation method and application - Google Patents
Triarylamine quasi polymer of structure containing benzoxazine and its preparation method and application Download PDFInfo
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Abstract
Triarylamine quasi polymer of structure containing benzoxazine and its preparation method and application, the present invention relates to triarylamine quasi polymers of structure containing benzoxazine and its preparation method and application.The present invention is, the problem of electrochromic polymeric compounds film membrane ability difference poor in order to solve previous triarylamine quasi polymer heat resistance.The present invention is with N, N- diphenyl-Isosorbide-5-Nitrae-phenylenediamine, N, N'- diphenyl-benzidine is then raw material reacts realization nitration with p-fluoronitrobenzene, nitro is then reduced to amino again, with bisphenol-A, paraformaldehyde, the triaryl amine base class monomer of preparation is raw material, passes through condensation reaction synthetic polymer under certain condition, and Inventive polymers have excellent electrochromic property and memory performance, it can be applied to electrochromism field, also there is good performance in explosive detection；Present invention application electrochromic polymeric compounds field.
Description
Technical field
The present invention relates to triarylamine quasi polymers of structure containing benzoxazine and its preparation method and application.
Background technique
Electrochromic polymeric compounds are the polymer that color change can occur when changing voltage or electric current.Polythiophene, poly- pyrrole
It coughs up, the conducting polymers such as polyacetylene and certain liquid crystal polymers can be used as electrochromic material.Conducting polymer itself is
The conjugated structure of delocalization, the energy gap very little between valence band and conduction, if being doped (electron donor or receptor in the polymer
Ionic compound), band structure also changes therewith, by applying external electrical field, further changes the absorption to light, leads
Cause the change of color.Electrochromic polymeric compounds have broad application prospects as a kind of emerging functional polymer material.
Currently, electrochromism quasi polymer still has, heat resistance is poor, and the electrochromic polymeric compounds formed are thin
Film is easier the problems such as falling off, while electrochromism quasi polymer has largely only probed into the performance in terms of electrochromism,
Other than electrochromic property, this quasi polymer still obtains development and exploration there are many performance number.
Summary of the invention
The present invention is that there are heat resistances in order to solve existing triarylamine quasi polymer poor, electrochromic polymeric compounds film
The problem of membrane ability difference provides triarylamine quasi polymer of structure containing benzoxazine and its preparation method and application.
The present invention triarylamine quasi polymer of structure containing benzoxazine is the triarylamine of structure containing benzoxazine quasi polymer
The P1 or triarylamine quasi polymer of structure containing benzoxazine P2；
Wherein the structural formula of the triarylamine quasi polymer of structure containing benzoxazine P1 is as follows:
The integer that n is 3~10 in formula；
The structural formula of the triarylamine quasi polymer of structure containing benzoxazine P2 is as follows:
, n is 3~10 in formula integer.
The present invention triarylamine of structure containing benzoxazine quasi polymer P1's the preparation method comprises the following steps: one, synthesis N, the bis- (4- of N '-
Aminophenyl)-N, N '-diphenyl-Isosorbide-5-Nitrae-phenylenediamine monomer: 1., in N2Under atmosphere, by N, N- diphenyl-Isosorbide-5-Nitrae-phenylenediamine list
Body, sodium hydride and anhydrous n,N-Dimethylformamide are placed in there-necked flask, and stirring is added simultaneously with the rate of addition of 1~2 drop per second
Enter p-fluoronitrobenzene, carries out isothermal reaction after being warming up to 114~115 DEG C, then cool down；Reaction product is placed in 24~25 DEG C of water
In be precipitated to crude product, crude product is then filtered out, with water washing crude product 2~3 times of 99~100 DEG C, by resulting thick production
Product are put is dried in a vacuum drying oven, then is recrystallized using ethyl alcohol, and crystallized product is filtered out after recrystallization, will be crystallized
Product is dried in vacuo to obtain yellow powder M1；The wherein volume and N of anhydrous n,N-Dimethylformamide, diphenyl -1 N-,
The ratio of the amount of the substance of 4- phenylenediamine monomer is (200~250) mL:7.5mmol；Sodium hydride and N, N- diphenyl-Isosorbide-5-Nitrae-benzene two
The ratio of the amount of the substance of amine monomers is 66.6mmol:7.5mmol；P-fluoronitrobenzene and N, N- diphenyl-Isosorbide-5-Nitrae-phenylenediamine monomer
Molar ratio be 20.0mmol:7.5mmol；The volume and N of 24~25 DEG C of water, N- diphenyl-Isosorbide-5-Nitrae-phenylenediamine monomeric substance
The ratio of amount is (500~800) mL:7.5mmol；The vacuum drying temperature is 99~100 DEG C, and the vacuum drying time is 40
~48 hours, vacuum drying pressure was -30~-29KPa；
2., under room temperature, dehydrated alcohol, Pd/C and yellow powder M1 are added in there-necked flask, into there-necked flask lead to
Enter N2, it is added dropwise in the mixed solution in hydrazine hydrate to there-necked flask using constant pressure funnel with the rate of addition of 1~2 drop per second；Heating
It flows back to solution, stops heating after back flow reaction, be filtered to remove at 79~80 DEG C except Pd/C, filtrate is poured into 4~5 DEG C
Water in, stirring while sodium chloride is added to solid is precipitated, filters out solid and with ethanol washing, to the solid vacuum filtered out
Shallow white solid M11 is obtained after drying；
Wherein the volume mass ratio of dehydrated alcohol and yellow powder M1 are (200~300) mL:2g；Pd/C and yellow powder
The mass ratio of M1 is (0.70~0.80) g:2g；The volume mass ratio of hydrazine hydrate and yellow powder M1 are (18~20) mL:2g；Filter
The volume ratio of liquid and 4~5 DEG C of water is 1:(3~4)；The Pd/C is the C doped and compounded material of Pd, the mass fraction of Pd in Pd/C
It is 10%；The vacuum drying temperature be 29~30 DEG C, the vacuum drying time be 24 hours, vacuum drying pressure be-
30~-29KPa；
Two, the triarylamine quasi polymer of structure containing benzoxazine P1 is prepared
In N2Under atmosphere, dehydrated alcohol and the mixed solution except water-toluene are added into there-necked flask, shallow white solid is added
M11, bisphenol fluorene stir 10~20min, paraformaldehyde are added into there-necked flask, then heats to 85 DEG C, reaction time 48h,
Obtain polymer solution；By volume it is that the ratio of 7:40 is poured into methanol by polymer solution, carries out product precipitation, then use first
Alcohol washing is filtered, and obtained product is dried in a vacuum drying oven, and then Soxhlet extraction is purified, and obtains disliking containing benzo
Piperazine structure triarylamine quasi polymer P1；Wherein the amount of shallow white solid M11 substance and dehydrated alcohol and except water-toluene mix it is molten
The volume ratio of liquid is 1.0mmol:15mL, dehydrated alcohol and the volume for removing water-toluene in dehydrated alcohol and water removal toluene mixed solution
Than for 1:2；The amount of substance ratio of shallow white solid M11 and bisphenol fluorene is 1.0mmol:1.2mmol；Shallow white solid M11 and poly
The amount of substance ratio of formaldehyde is 1.0mmol:4.55mmol；The vacuum drying temperature is 29~30 DEG C, the vacuum drying time
It is 24 hours, the control of time is paid attention in drying process, vacuum drying pressure is -30~-29KPa；The temperature of Soxhlet extraction
It is 70 DEG C, the time of Soxhlet extraction is 48h.
The present invention triarylamine of structure containing benzoxazine quasi polymer P2's the preparation method comprises the following steps: one, synthesis N, the bis- (4- of N '-
Aminophenyl)-N, N '-diphenyl-Isosorbide-5-Nitrae-benzidine: a, in N2Under atmosphere, by N, N'- diphenyl-benzidine monomer, hydrogen
Change sodium and anhydrous n,N-Dimethylformamide is placed in there-necked flask, stirring is added with the rate of addition of 1~2 drop per second to fluorine simultaneously
Nitrobenzene carries out isothermal reaction after being warming up to 114~115 DEG C, then cools down；Reaction product is placed in 24~25 DEG C of water to thick
Product is precipitated, and then filters out crude product, with water washing crude product 2~3 times of 99~100 DEG C, resulting crude product is placed on
Dried in vacuum oven, then recrystallized using ethyl alcohol, crystallized product filtered out after recrystallization, by crystallized product into
Row vacuum drying obtains buff powder M2；The wherein volume and N of anhydrous n,N-Dimethylformamide, N'- diphenyl-biphenyl two
The ratio of the amount of the substance of amine monomers is (200~250) mL:5.95mmol；Sodium hydride and N, N'- diphenyl-benzidine monomer
Substance amount ratio be 51.46mmol:5.95mmol；P-fluoronitrobenzene and N, N'- diphenyl-benzidine monomer mole
Than for 15.47mmol:5.95mmol；24~25 DEG C of water and N, N'- diphenyl-benzidine monomer volume mass ratio are (500
~800) mL:5.95mmol；The vacuum drying temperature is 99~100 DEG C, and the vacuum drying time is 40~48 hours, very
The dry pressure of sky is -30~-29KPa；
B, under room temperature, dehydrated alcohol, Pd/C and buff powder M2 are added in there-necked flask, led into there-necked flask
Enter N2, it is added dropwise in the mixed solution in hydrazine hydrate to there-necked flask using constant pressure funnel with the rate of addition of 1~2 drop per second；Heating
It flows back to solution, stops heating after back flow reaction, be filtered to remove at 79~80 DEG C except Pd/C, filtrate is poured into 4~5 DEG C
Water in, stirring while sodium chloride is added to solid is precipitated, filters out solid and with ethanol washing, to the solid vacuum filtered out
Shallow white solid M22 is obtained after drying；The volume mass of dehydrated alcohol and M2 ratio are (200~300) mL:2g；Pd/C's and M2
Mass ratio is (0.70~0.80) g:2g；The volume mass of hydrazine hydrate and M2 ratio are (18~20) mL:2g；Filtrate and 4~5 DEG C of water
Volume ratio be 1:(3~4)；The Pd/C is the C doped and compounded material of Pd, and the mass fraction of Pd is 10% in Pd/C；It is described
Vacuum drying temperature is 29~30 DEG C, and the vacuum drying time is 24 hours, and vacuum drying pressure is -30~-29KPa；
Two, the triarylamine quasi polymer of structure containing benzoxazine P2 is prepared
In N2Under atmosphere, dehydrated alcohol and the mixed solution except water-toluene are added into there-necked flask, shallow white solid is added
M22, bisphenol fluorene stir 10~20min, paraformaldehyde are added into there-necked flask, then heats to 85 DEG C, reaction time 48h,
Obtain polymer solution；By volume it is that the ratio of 7:40 is poured into methanol by polymer solution, carries out product precipitation, then use first
Alcohol washing is filtered, and obtained product is dried in a vacuum drying oven, and then Soxhlet extraction is purified, and obtains disliking containing benzo
Piperazine structure triarylamine quasi polymer P2；Wherein the amount of shallow white solid M22 substance and dehydrated alcohol and except water-toluene mix it is molten
The volume ratio of liquid is 0.7mmol:10mL, dehydrated alcohol and the volume for removing water-toluene in dehydrated alcohol and water removal toluene mixed solution
Than for 1:2；The amount of substance ratio of shallow white solid M22 and bisphenol fluorene is 0.7mmol:0.8mmol；Shallow white solid M22 and poly
The amount of substance ratio of formaldehyde is 0.7mmol:3mmol；The vacuum drying temperature is 29~30 DEG C, and the vacuum drying time is 24
Hour, the control of time is paid attention in drying process, vacuum drying pressure is -30~-29KPa；The temperature of Soxhlet extraction is 70
DEG C, the time of Soxhlet extraction is 48h.
The present invention triarylamine quasi polymer of structure containing benzoxazine exists as the electrochromic layer in electrochromic device
Application in electrochromism.
Present invention structure containing benzoxazine triarylamine quasi polymer P2 is used for the inspection of explosive 2,4,6- trinitrotoluene
It surveys.
The principle of the invention are as follows:
In the present invention, triphenylamine base class monomer is prepared first, the present invention is with N, N- diphenyl-Isosorbide-5-Nitrae-phenylenediamine, N, N'- bis-
Phenyl-benzidine is then raw material reacts realization nitration with p-fluoronitrobenzene, nitro is then reduced to amino again, with double
Phenol A, paraformaldehyde, the triphenylamine base class monomer of preparation are raw material, are synthesized under certain condition by Mannich condensation reaction,
A series of lesser polymer of relative molecular weights is synthesized, which can gather in open loop under the action of heating or catalyst
It closes.
The present invention has following special-effect:
One, the present invention, which has, introduces benzoxazine class formation in the triaryl amine base class molecular formula of electrochromic property, design
And a series of polymer of triaryl amine base class benzoxazine structures with new function is prepared, not only remain electrochromism material
The performance of material, while being introduced into benzoxazine class formation can make script have larger rigid polymer in common organic solvents
There is preferable dissolubility.During heat treatment, ring-opening reaction can occur for the oxazines ring in polymer, crosslink.It improves
Coating and substrate adhesive strength, the filming performance of polymer are more conducive to the test in terms of the electrochemistry of polymer；
Two, Inventive polymers have excellent electrochromic property and memory performance, can be applied to electrochromism neck
Domain also has good performance in explosive detection；
Electrochromism refers to that under the driving of external voltage or current, substance occurs electrochemical redox reaction and draws
The phenomenon that playing color change.I.e. under DC Electric Field, the chemical property (transmissivity, reflectivity etc.) of substance is in visible light model
The interior active site for generating stable polymer of the reversible change containing triarylamine and containing electron-transport and electron transition is enclosed, when
Electron transition then occurs to generate the variation of color in polymeric inner when applying certain voltage to polymer.Present invention polymerization
Color change is obvious in object 0.60~1.40V voltage range, and the coloration time of Inventive polymers is 2.6~2.8s；When bleaching
Between be 2.3~2.5s；The combination of oxazines structure and the unit containing triarylamine promotes electronics transfer between the two to make
The color change of conjugated polymer containing triarylamine and oxazines group is more obvious；It is navy blue to peony when coloring, drift
Bai Shiwei is close to colourless, therefore contrast is very high when electrochromism；
Three, the P2 in Inventive polymers has very strong fluorescence, P2 and explosive 2,4,6- in Inventive polymers
The fluorescence for the solution contact post-consumer polymer that trinitrotoluene is made into is gradually reduced until disappearing, therefore Inventive polymers can be used
In detection explosive 2,4,6- trinitrotoluene；And since the structure conjugated degree ratio P2 of polymer P 1 is weak, fluorescence is more likely to
It is conjugated group and is unfavorable for the detection of explosive so the fluorescence of polymer P 1 is fainter.
Four, by thermogravimetric curve it is found that structure containing benzoxazine prepared by the present invention triarylamine quasi polymer has very
Good heat resistance.
Detailed description of the invention
Fig. 1 is the hydrogen nuclear magnetic spectrogram of the triarylamine quasi polymer of structure containing benzoxazine P1 prepared by embodiment one；
Fig. 2 is the cyclic voltammogram of the triarylamine quasi polymer of structure containing benzoxazine P1 prepared by embodiment one；
Fig. 3 is the electrochromism figure of the triarylamine quasi polymer of structure containing benzoxazine P1 prepared by embodiment one；
Fig. 4 is the memory performance figure of the triarylamine quasi polymer of structure containing benzoxazine P1 prepared by embodiment one；
Fig. 5 is the hydrogen nuclear magnetic spectrogram of the triarylamine quasi polymer of structure containing benzoxazine P2 prepared by embodiment two；
Fig. 6 is the cyclic voltammogram of the triarylamine quasi polymer of structure containing benzoxazine P2 prepared by embodiment two；
Fig. 7 is the electrochromism figure of the triarylamine quasi polymer of structure containing benzoxazine P2 prepared by embodiment two；
Fig. 8 is the fluorogram that the triarylamine quasi polymer P2 of structure containing benzoxazine prepared by embodiment two responds TNT；
Fig. 9 is the fluorescence that the triarylamine quasi polymer P2 of structure containing benzoxazine prepared by embodiment two responds picric acid
Figure；
Figure 10 is the memory performance figure of the triarylamine quasi polymer of structure containing benzoxazine P2 prepared by embodiment two；
Figure 11 is the thermal weight loss of the triarylamine quasi polymer of structure containing benzoxazine prepared by embodiment one and embodiment two
Curve graph.
Specific embodiment
Technical solution of the present invention is not limited to the specific embodiment of act set forth below, further include each specific embodiment it
Between any combination.
Specific embodiment 1: the present embodiment triarylamine quasi polymer of structure containing benzoxazine is knot containing benzoxazine
The structure triarylamine quasi polymer P1 or triarylamine quasi polymer of structure containing benzoxazine P2；
Wherein the structural formula of the triarylamine quasi polymer of structure containing benzoxazine P1 is as follows:
The integer that n is 3~10 in formula；
The structural formula of the triarylamine quasi polymer of structure containing benzoxazine P2 is as follows:
, n is 3~10 in formula
Integer.
In present embodiment, triphenylamine base class monomer is prepared first, present embodiment is with N, N- diphenyl-Isosorbide-5-Nitrae-benzene two
Amine, N, N'- diphenyl-benzidine are then raw material reacts realization nitration with p-fluoronitrobenzene, then again restore nitro
For amino, with bisphenol-A, paraformaldehyde, the triphenylamine base class monomer of preparation is raw material, is contracted under certain condition by Mannich
Reaction synthesis is closed, synthesizes a series of lesser polymer of relative molecular weights, which can be in heating or the work of catalyst
With lower ring-opening polymerisation.
Present embodiment has following special-effect:
One, present embodiment, which has, introduces benzoxazine class formation in the triaryl amine base class molecular formula of electrochromic property,
The polymer for designing and preparing a series of triaryl amine base class benzoxazine structures with new function, not only remains electroluminescent change
The performance of color material, while introducing benzoxazine class formation can make script have larger rigid polymer general organic molten
There is preferable dissolubility in agent.During heat treatment, ring-opening reaction can occur for the oxazines ring in polymer, crosslink.
Coating and substrate adhesive strength are improved, the filming performance of polymer is more conducive to the test in terms of the electrochemistry of polymer；
Two, present embodiment polymer has excellent electrochromic property and memory performance, can be applied to electroluminescent change
Color field also has good performance in explosive detection；
Electrochromism refers to that under the driving of external voltage or current, substance occurs electrochemical redox reaction and draws
The phenomenon that playing color change.I.e. under DC Electric Field, the chemical property (transmissivity, reflectivity etc.) of substance is in visible light model
Enclose the stable reversible change of interior generation.Polymer containing triarylamine contains the active site of electron-transport and electron transition, when
Electron transition then occurs to generate the variation of color in polymeric inner when applying certain voltage to polymer.Present embodiment
Color change is obvious in polymer 0.60~1.40V voltage range, and the coloration time of Inventive polymers is 2.6~2.8s；Drift
The white time is 2.3~2.5s；The combination of oxazines structure and the unit containing triarylamine promote electronics transfer between the two from
And keep the color change of the conjugated polymer containing triarylamine and oxazines group more obvious；It is navy blue when coloring to dark red
Color, for close to colourless when bleaching, therefore contrast is very high when electrochromism；
Three, the P2 in present embodiment polymer has very strong fluorescence, P2 and explosion in present embodiment polymer
The fluorescence for the solution contact post-consumer polymer that object 2,4,6-trinitrotoluene is made into is gradually reduced up to disappearing, therefore present embodiment
Polymer can be used for detecting explosive 2,4,6- trinitrotoluene；And since the structure conjugated degree ratio P2 of polymer P 1 is weak,
Fluorescence is more likely to conjugation group and is unfavorable for the detection of explosive so the fluorescence of polymer P 1 is fainter.
Four, by thermogravimetric curve it is found that the triarylamine quasi polymer of structure containing the benzoxazine tool of present embodiment preparation
There is good heat resistance.
Specific embodiment 2: the preparation method of the present embodiment triarylamine quasi polymer of structure containing benzoxazine P1
Are as follows: one, synthesis N, bis- (4- aminophenyl)-N, N '-diphenyl-Isosorbide-5-Nitrae-phenylenediamine monomers of N '-: 1., in N2Under atmosphere, by N, N-
Diphenyl-Isosorbide-5-Nitrae-phenylenediamine monomer, sodium hydride and anhydrous n,N-Dimethylformamide are placed in there-necked flask, and stirring is simultaneously with per second
P-fluoronitrobenzene is added in the rate of addition of 1~2 drop, carries out isothermal reaction after being warming up to 114~115 DEG C, then cools down；It will reaction
Product is placed in 24~25 DEG C of water to crude product and is precipitated, and crude product is then filtered out, with 99~100 DEG C of water washing crude product 2
~3 times, resulting crude product is put and is dried in a vacuum drying oven, then is recrystallized using ethyl alcohol, mistake after recrystallization
Crystallized product is filtered out, crystallized product is dried in vacuo to obtain yellow powder M1；Wherein anhydrous n,N-Dimethylformamide
Volume and N, the ratio of the amount of the substance of N- diphenyl-Isosorbide-5-Nitrae-phenylenediamine monomer are (200~250) mL:7.5mmol；Sodium hydride with
The ratio of the amount of the substance of N, N- diphenyl-Isosorbide-5-Nitrae-phenylenediamine monomer is 66.6mmol:7.5mmol；P-fluoronitrobenzene and N, N- bis-
The molar ratio of phenyl -1,4- phenylenediamine monomer is 20.0mmol:7.5mmol；The volume and N of 24~25 DEG C of water, diphenyl -1 N-,
The ratio of the amount of 4- phenylenediamine monomeric substance is (500~800) mL:7.5mmol；The vacuum drying temperature is 99~100 DEG C,
The vacuum drying time is 40~48 hours, and vacuum drying pressure is -30~-29KPa；
2., under room temperature, dehydrated alcohol, Pd/C and yellow powder M1 are added in there-necked flask, into there-necked flask lead to
Enter N2, it is added dropwise in the mixed solution in hydrazine hydrate to there-necked flask using constant pressure funnel with the rate of addition of 1~2 drop per second；Heating
It flows back to solution, stops heating after back flow reaction, be filtered to remove at 79~80 DEG C except Pd/C, filtrate is poured into 4~5 DEG C
Water in, stirring while sodium chloride is added to solid is precipitated, filters out solid and with ethanol washing, to the solid vacuum filtered out
Shallow white solid M11 is obtained after drying；
Wherein the volume mass ratio of dehydrated alcohol and yellow powder M1 are (200~300) mL:2g；Pd/C and yellow powder
The mass ratio of M1 is (0.70~0.80) g:2g；The volume mass ratio of hydrazine hydrate and yellow powder M1 are (18~20) mL:2g；Filter
The volume ratio of liquid and 4~5 DEG C of water is 1:(3~4)；The Pd/C is the C doped and compounded material of Pd, the mass fraction of Pd in Pd/C
It is 10%；The vacuum drying temperature be 29~30 DEG C, the vacuum drying time be 24 hours, vacuum drying pressure be-
30~-29KPa；
Two, the triarylamine quasi polymer of structure containing benzoxazine P1 is prepared
In N2Under atmosphere, dehydrated alcohol and the mixed solution except water-toluene are added into there-necked flask, shallow white solid is added
M11, bisphenol fluorene stir 10~20min, paraformaldehyde are added into there-necked flask, then heats to 85 DEG C, reaction time 48h,
Obtain polymer solution；By volume it is that the ratio of 7:40 is poured into methanol by polymer solution, carries out product precipitation, then use first
Alcohol washing is filtered, and obtained product is dried in a vacuum drying oven, and then Soxhlet extraction is purified, and obtains disliking containing benzo
Piperazine structure triarylamine quasi polymer P1；Wherein the amount of shallow white solid M11 substance and dehydrated alcohol and except water-toluene mix it is molten
The volume ratio of liquid is 1.0mmol:15mL, dehydrated alcohol and the volume for removing water-toluene in dehydrated alcohol and water removal toluene mixed solution
Than for 1:2；The amount of substance ratio of shallow white solid M11 and bisphenol fluorene is 1.0mmol:1.2mmol；Shallow white solid M11 and poly
The amount of substance ratio of formaldehyde is 1.0mmol:4.55mmol；The vacuum drying temperature is 29~30 DEG C, the vacuum drying time
It is 24 hours, the control of time is paid attention in drying process, vacuum drying pressure is -30~-29KPa；The temperature of Soxhlet extraction
It is 70 DEG C, the time of Soxhlet extraction is 48h.
1. present embodiment step judges whether isothermal reaction terminates with thin-layered chromatography, 2. step is sentenced with thin-layered chromatography
Whether disconnected back flow reaction terminates.
Specific embodiment 3: present embodiment is unlike specific embodiment two: step 1 1. described in yellow
Powder M1 is N, bis- (4- nitrobenzophenone)-N, N '-diphenyl-Isosorbide-5-Nitrae-phenylenediamines of N '-.Other are identical with embodiment two.
Specific embodiment 4: present embodiment is unlike specific embodiment two or three: step 1 2. described in
Shallow white solid M11 is N, bis- (4- aminophenyl)-N, N '-diphenyl-Isosorbide-5-Nitrae-phenylenediamines of N '-.Other and specific embodiment
Two or three is identical.
Specific embodiment 5: the preparation method of the present embodiment triarylamine quasi polymer of structure containing benzoxazine P2
Are as follows: one, synthesis N, bis- (4- aminophenyl)-N, N '-diphenyl-Isosorbide-5-Nitrae-benzidines of N '-: a, in N2Under atmosphere, by N, N'- bis-
Phenyl-benzidine monomer, sodium hydride and anhydrous n,N-Dimethylformamide are placed in there-necked flask, and stirring is simultaneously with per second 1~2
P-fluoronitrobenzene is added in the rate of addition of drop, carries out isothermal reaction after being warming up to 114~115 DEG C, then cools down；By reaction product
It is placed in 24~25 DEG C of water to crude product and is precipitated, crude product is then filtered out, with 99~100 DEG C of water washing crude product 2~3
It is secondary, resulting crude product is put and is dried in a vacuum drying oven, then is recrystallized using ethyl alcohol, is filtered out after recrystallization
Crystallized product is dried in vacuo to obtain buff powder M2 by crystallized product；The wherein body of anhydrous n,N-Dimethylformamide
The ratio of long-pending and N, N'- diphenyl-benzidine monomer substance amount is (200~250) mL:5.95mmol；Sodium hydride and N,
The ratio of the amount of N'- diphenyl-benzidine monomer substance is 51.46mmol:5.95mmol；P-fluoronitrobenzene and N, N'- bis-
Phenyl-benzidine monomer molar ratio is 15.47mmol:5.95mmol；24~25 DEG C of water and N, N'- diphenyl-biphenyl two
The volume mass ratio of amine monomers is (500~800) mL:5.95mmol；The vacuum drying temperature is 99~100 DEG C, vacuum
The dry time is 40~48 hours, and vacuum drying pressure is -30~-29KPa；
B, under room temperature, dehydrated alcohol, Pd/C and buff powder M2 are added in there-necked flask, led into there-necked flask
Enter N2, it is added dropwise in the mixed solution in hydrazine hydrate to there-necked flask using constant pressure funnel with the rate of addition of 1~2 drop per second；Heating
It flows back to solution, stops heating after back flow reaction, be filtered to remove at 79~80 DEG C except Pd/C, filtrate is poured into 4~5 DEG C
Water in, stirring while sodium chloride is added to solid is precipitated, filters out solid and with ethanol washing, to the solid vacuum filtered out
Shallow white solid M22 is obtained after drying；The volume mass of dehydrated alcohol and M2 ratio are (200~300) mL:2g；Pd/C's and M2
Mass ratio is (0.70~0.80) g:2g；The volume mass of hydrazine hydrate and M2 ratio are (18~20) mL:2g；Filtrate and 4~5 DEG C of water
Volume ratio be 1:(3~4)；The Pd/C is the C doped and compounded material of Pd, and the mass fraction of Pd is 10% in Pd/C；It is described
Vacuum drying temperature is 29~30 DEG C, and the vacuum drying time is 24 hours, and vacuum drying pressure is -30~-29KPa；
Two, the triarylamine quasi polymer of structure containing benzoxazine P2 is prepared
In N2Under atmosphere, dehydrated alcohol and the mixed solution except water-toluene are added into there-necked flask, shallow white solid is added
M22, bisphenol fluorene stir 10~20min, paraformaldehyde are added into there-necked flask, then heats to 85 DEG C, reaction time 48h,
Obtain polymer solution；By volume it is that the ratio of 7:40 is poured into methanol by polymer solution, carries out product precipitation, then use first
Alcohol washing is filtered, and obtained product is dried in a vacuum drying oven, and then Soxhlet extraction is purified, and obtains disliking containing benzo
Piperazine structure triarylamine quasi polymer P2；Wherein the amount of shallow white solid M22 substance and dehydrated alcohol and except water-toluene mix it is molten
The volume ratio of liquid is 0.7mmol:10mL, dehydrated alcohol and the volume for removing water-toluene in dehydrated alcohol and water removal toluene mixed solution
Than for 1:2；The amount of substance ratio of shallow white solid M22 and bisphenol fluorene is 0.7mmol:0.8mmol；Shallow white solid M22 and poly
The amount of substance ratio of formaldehyde is 0.7mmol:3mmol；The vacuum drying temperature is 29~30 DEG C, and the vacuum drying time is 24
Hour, the control of time is paid attention in drying process, vacuum drying pressure is -30~-29KPa；The temperature of Soxhlet extraction is 70
DEG C, the time of Soxhlet extraction is 48h.
Present embodiment step a thin-layered chromatography judges whether isothermal reaction terminates, and step b is judged with thin-layered chromatography
Whether back flow reaction terminates.
Specific embodiment 6: present embodiment is unlike specific embodiment five: buff powder M2 is N, N '-
Bis- (4- nitrobenzophenone)-N, N '-diphenyl-Isosorbide-5-Nitrae-benzidines.Other are identical as specific embodiment five.
Specific embodiment 7: present embodiment is unlike specific embodiment five or six: shallow white solid M22 is
Bis- (4- aminophenyl)-N, N '-diphenyl-Isosorbide-5-Nitrae-benzidines of N, N '-.Other are identical as specific embodiment five or six.
Specific embodiment 8: the present embodiment triarylamine quasi polymer of structure containing benzoxazine is as electrochromism device
Application of the electrochromic layer in electrochromism in part.
Specific embodiment 9: present embodiment is unlike specific embodiment eight: three virtue of structure containing benzoxazine
Application method of the amido quasi polymer as the electrochromic layer in electrochromic device in electrochromism: benzoxazine will be contained
Structure triarylamine quasi polymer is coated on conducting base as the electrochromic layer in electrochromic device, electrochromic layer
It is prepared into electrochromic device, electrochromic layer generates electrochromism under the action of extra electric field.Other and specific embodiment party
Formula eight is identical.
Conducting base described in present embodiment is electro-conductive glass, and the voltage of extra electric field is 0.60~1.80V.
Specific embodiment 10: present embodiment structure containing benzoxazine triarylamine quasi polymer P2 is used for explosive 2,
The detection of 4,6- trinitrotoluene.
Beneficial effects of the present invention are verified using following embodiment:
Embodiment one: the structural formula of the triarylamine quasi polymer of structure containing benzoxazine P1 is as follows:
N is 3~10 integers in formula；
The triarylamine of structure containing benzoxazine quasi polymer P1's the preparation method comprises the following steps: one, synthesis N, bis- (the 4- aminobenzenes of N '-
Base)-N, N '-diphenyl-Isosorbide-5-Nitrae-phenylenediamine monomer: 1., in N2Under atmosphere, by N, N- diphenyl-Isosorbide-5-Nitrae-phenylenediamine monomer, hydrogenation
Sodium and anhydrous n,N-Dimethylformamide are placed in there-necked flask, and stirring is added with the rate of addition of 1~2 drop per second to fluorine nitre simultaneously
Base benzene carries out isothermal reaction after being warming up to 114~115 DEG C, then cools down；Reaction product is placed in 24~25 DEG C of water to thick and is produced
Product are precipitated, and then filter out crude product, with water washing crude product 2~3 times of 99~100 DEG C, resulting crude product is placed on very
It is dried in empty drying box, then is recrystallized using ethyl alcohol, crystallized product is filtered out after recrystallization, crystallized product is carried out
Vacuum drying obtains yellow powder M1；The wherein volume and N of anhydrous n,N-Dimethylformamide, N- diphenyl-Isosorbide-5-Nitrae-phenylenediamine
The ratio of the amount of the substance of monomer is 200mL:7.5mmol；Sodium hydride and N, the amount of the substance of N- diphenyl-Isosorbide-5-Nitrae-phenylenediamine monomer
Ratio be 66.6mmol:7.5mmol；The molar ratio of p-fluoronitrobenzene and N, N- diphenyl-Isosorbide-5-Nitrae-phenylenediamine monomer is
20.0mmol:7.5mmol；The ratio of the volume and N of 24~25 DEG C of water, the amount of the substance of N- diphenyl-Isosorbide-5-Nitrae-phenylenediamine monomer is
750mL:7.5mmol；The vacuum drying temperature is 99~100 DEG C, and the vacuum drying time is 40 hours, vacuum drying
Pressure is -30~-29KPa；
2., under room temperature, dehydrated alcohol, Pd/C and yellow powder M1 are added in there-necked flask, into there-necked flask lead to
Enter N2, it is added dropwise in the mixed solution in hydrazine hydrate to there-necked flask using constant pressure funnel with the rate of addition of 1~2 drop per second；Heating
It flows back to solution, stops heating after back flow reaction, be filtered to remove at 79~80 DEG C except Pd/C, filtrate is poured into 4~5 DEG C
Water in, stirring while sodium chloride is added to solid is precipitated, filters out solid and with ethanol washing, to the solid vacuum filtered out
Shallow white solid M11 is obtained after drying；
Wherein the volume mass ratio of dehydrated alcohol and yellow powder M1 are 200mL:2g；The quality of Pd/C and yellow powder M1
Than for 0.8g:2g；The volume mass ratio of hydrazine hydrate and yellow powder M1 are 18mL:2g；Filtrate and the volume ratio of 4~5 DEG C of water are
1:(3~4)；The Pd/C is the C doped and compounded material of Pd, and the mass fraction of Pd is 10% in Pd/C；It is described vacuum drying
Temperature is 29~30 DEG C, and the vacuum drying time is 24 hours, and vacuum drying pressure is -30~-29KPa；
Step 1 1. described in yellow powder M1 be N, bis- (4- nitrobenzophenone)-N, N '-diphenyl-Isosorbide-5-Nitrae-phenylenediamines of N '-,
And yield is 75%.Step 1 2. described in shallow white solid M11 be N, bis- (4- the aminophenyl)-N of N ' -, diphenyl -1 N ' -,
4- phenylenediamine, and yield is 69%.
Two, the triarylamine quasi polymer of structure containing benzoxazine P1 is prepared
In N2Under atmosphere, dehydrated alcohol and the mixed solution except water-toluene are added into there-necked flask, shallow white solid is added
M11, bisphenol fluorene stir 20min, paraformaldehyde are added into there-necked flask, then heats to 85 DEG C, reaction time 48h is obtained
Polymer solution；By volume it is that the ratio of 7:40 is poured into methanol by polymer solution, carries out product precipitation, again with methanol is washed
It washs and is filtered, obtained product is dried in a vacuum drying oven, and then Soxhlet extraction is purified, and obtains knot containing benzoxazine
Structure triarylamine quasi polymer P1；Wherein the amount of shallow white solid M11 substance and dehydrated alcohol and remove water toluene mixed solution
Volume ratio is 1.0mmol:15mL, and dehydrated alcohol is with the volume ratio except water-toluene in dehydrated alcohol and water removal toluene mixed solution
1:2；The amount of substance ratio of shallow white solid M11 and bisphenol fluorene is 1.0mmol:1.2mmol；Shallow white solid M11 and paraformaldehyde
Amount of substance ratio be 1.0mmol:4.55mmol；The vacuum drying temperature is 29~30 DEG C, and the vacuum drying time is 24
Hour, the control of time is paid attention in drying process, vacuum drying pressure is -30~-29KPa；The temperature of Soxhlet extraction is 70
DEG C, the time of Soxhlet extraction is 48h.
1. the present embodiment step judges whether isothermal reaction terminates with thin-layered chromatography, 2. step is judged with thin-layered chromatography
Whether back flow reaction terminates.
The triarylamine of structure containing benzoxazine quasi polymer manufactured in the present embodiment in polar solvent to be more soluble, often
Solvable 1.5 grams in 10 milliliters of polar solvents；It is slightly soluble in nonpolar solvent, solvable 0.2 gram in every 10 milliliters of polar solvents；
Benzoxazine structure triarylamine quasi polymer P1 coating film forming will be contained, its performance will be tested:
Fig. 1 is the hydrogen nuclear magnetic spectrogram of the triarylamine quasi polymer of structure containing benzoxazine P1 prepared by embodiment one；From Fig. 1
It is found that chemical shift δ is 4.50 in Fig. 1~5.50ppm, the i.e. chemical shift of oxazines characteristic peak illustrate that embodiment one has synthesized and contain
Benzoxazine structure triarylamine quasi polymer；
Fig. 2 is the cyclic voltammogram of the triarylamine quasi polymer of structure containing benzoxazine P1 prepared by embodiment one；From Fig. 2
It is found that occurring two oxidation peaks in 0.86V, at 1.12V, occur two reduction peaks at 0.56V and 0.88V；Illustrate reality
Redox reaction has occurred in the case where applying voltage conditions in the triarylamine quasi polymer of structure containing benzoxazine for applying the preparation of example one,
The triarylamine of structure containing benzoxazine quasi polymer can generate the variation of color in oxidation-reduction process, illustrate that embodiment one is made
The standby triarylamine quasi polymer of structure containing benzoxazine P1 has electrochromic property.
Fig. 3 is the electrochromism figure of the triarylamine quasi polymer of structure containing benzoxazine P1 prepared by embodiment one；In Fig. 3
Curve is the ultraviolet absorption curve applied when voltage is 2.1V-0.0V；As can be seen from Figure 3, before not applying voltage, embodiment one is made
The standby triarylamine quasi polymer of structure containing benzoxazine has absorption peak at 342nm, when applied voltage is from 0.0V to 1.4V,
Occur new absorption peak at 420nm and 1200nm and is gradually increasing；Illustrate structure containing benzoxazine three prepared by embodiment one
Aryl amine quasi polymer has the function of electrochromism, color from it is faint yellow to navy blue again to peony；
Fig. 4 is the memory performance figure of the triarylamine quasi polymer of structure containing benzoxazine P1 prepared by embodiment one；By Fig. 4
It can be seen that in voltage scanning, from 0 to -8V (scanning 1), when negative threshold voltage is -2.2V and memory device is from low conductance
Rate state (OFF) observes sharply increasing for electric current when being switched to highly conductive state (ON).This conversion process can be used as
" write-in " process of ITO/Polymer/Al device.During scan next time (scanning 2), electric current is still in ON state, device
Still keep high on state.In the third time scanning of from 0 to+8V (scanning 3), it is observed that in the threshold voltage of+4.0V
The unexpected decline of lower electric current, this shows memory device experience from ON state to the transformation of original OFF state.It is this from ON to OFF
Conversion can be used as " erasing " process.As forward bias is applied, electric current in subsequent voltage scanning (scanning 4) still
It is maintained at low on state.Therefore, the storage equipment manufactured with the polymer is binary system flash memory data storage device.
Embodiment two, the structural formula of the triarylamine quasi polymer of structure containing benzoxazine P2 are as follows:
, n is 3~10 in formula
Integer.
The triarylamine of structure containing benzoxazine quasi polymer P2's the preparation method comprises the following steps: one, synthesis N, bis- (the 4- aminobenzenes of N '-
Base)-N, N '-diphenyl-Isosorbide-5-Nitrae-benzidine: a, in N2Under atmosphere, by N, N'- diphenyl-benzidine monomer, sodium hydride and
Anhydrous n,N-Dimethylformamide is placed in there-necked flask, and stirring is added with the rate of addition of 1~2 drop per second to fluorine nitro simultaneously
Benzene carries out isothermal reaction after being warming up to 114~115 DEG C, then cools down；Reaction product is placed in 24~25 DEG C of water to crude product
It is precipitated, then filters out crude product, with water washing crude product 2~3 times of 99~100 DEG C, resulting crude product is placed on vacuum
It is dried in drying box, then is recrystallized using ethyl alcohol, crystallized product is filtered out after recrystallization, crystallized product is carried out true
Sky is dried to obtain buff powder M2；The wherein volume and N of anhydrous n,N-Dimethylformamide, N'- diphenyl-benzidine list
The ratio of the amount of the substance of body is 200mL:5.95mmol；Sodium hydride and N, the amount of N'- diphenyl-benzidine monomer substance
Than for 51.46mmol:5.95mmol；P-fluoronitrobenzene and N, N'- diphenyl-benzidine monomer molar ratio are
15.47mmol:5.95mmol；24~25 DEG C of water and N, N'- diphenyl-benzidine monomer volume mass ratio are 800mL:
5.95mmol；The vacuum drying temperature is 99~100 DEG C, and the vacuum drying time is 40~48 hours, vacuum drying
Pressure is -30~-29KPa；
B, under room temperature, dehydrated alcohol, Pd/C and buff powder M2 are added in there-necked flask, led into there-necked flask
Enter N2, it is added dropwise in the mixed solution in hydrazine hydrate to there-necked flask using constant pressure funnel with the rate of addition of 1~2 drop per second；Heating
It flows back to solution, stops heating after back flow reaction, be filtered to remove at 79~80 DEG C except Pd/C, filtrate is poured into 4~5 DEG C
Water in, stirring while sodium chloride is added to solid is precipitated, filters out solid and with ethanol washing, to the solid vacuum filtered out
Shallow white solid M22 is obtained after drying；The volume mass of dehydrated alcohol and M2 ratio are 200mL:2g；The mass ratio of Pd/C and M2 is
0.8g:2g；The volume mass of hydrazine hydrate and M2 ratio are 18mL:2g；The volume ratio of filtrate and 4~5 DEG C of water is 1:(3~4)；It is described
Pd/C is the C doped and compounded material of Pd, and the mass fraction of Pd is 10% in Pd/C；The vacuum drying temperature is 29~30
DEG C, the vacuum drying time is 24 hours, and vacuum drying pressure is -30~-29KPa；Wherein step a is sentenced with thin-layered chromatography
Whether disconnected isothermal reaction terminates, and step b thin-layered chromatography judges whether back flow reaction terminates.
Two, the triarylamine quasi polymer of structure containing benzoxazine P2 is prepared
In N2Under atmosphere, dehydrated alcohol and the mixed solution except water-toluene are added into there-necked flask, shallow white solid is added
M22, bisphenol fluorene stir 20min, paraformaldehyde are added into there-necked flask, then heats to 85 DEG C, reaction time 48h is obtained
Polymer solution；By volume it is that the ratio of 7:40 is poured into methanol by polymer solution, carries out product precipitation, again with methanol is washed
It washs and is filtered, obtained product is dried in a vacuum drying oven, and then Soxhlet extraction is purified, and obtains knot containing benzoxazine
Structure triarylamine quasi polymer P2；Wherein the amount of shallow white solid M22 substance and dehydrated alcohol and remove water toluene mixed solution
Volume ratio is 0.7mmol:10mL, and dehydrated alcohol is with the volume ratio except water-toluene in dehydrated alcohol and water removal toluene mixed solution
1:2；The amount of substance ratio of shallow white solid M22 and bisphenol fluorene is 0.7mmol:0.8mmol；Shallow white solid M22 and paraformaldehyde
Amount of substance ratio be 0.7mmol:3mmol；The vacuum drying temperature is 29~30 DEG C, and the vacuum drying time is 24 small
When, the control of time is paid attention in drying process, vacuum drying pressure is -30~-29KPa；The temperature of Soxhlet extraction is 70 DEG C,
The time of Soxhlet extraction is 48h.
The triarylamine of structure containing benzoxazine quasi polymer manufactured in the present embodiment in polar solvent to be more soluble, often
Solvable 1.5 grams in 10 milliliters of polar solvents；It is slightly soluble in nonpolar solvent, solvable 0.2 gram in every 10 milliliters of polar solvents；
Buff powder M2 is N, bis- (4- nitrobenzophenone)-N, N '-diphenyl-Isosorbide-5-Nitrae-benzidines of N '-, and yield is
70%.Shallow white solid M22 is N, bis- (4- aminophenyl)-N, N '-diphenyl-Isosorbide-5-Nitrae-benzidines of N '-, and yield is
60%.
Fig. 5 is the hydrogen nuclear magnetic spectrogram of the triarylamine quasi polymer of structure containing benzoxazine P2 prepared by embodiment two；From Fig. 5
It is found that chemical shift δ is 4.50 in Fig. 5~5.50ppm, the i.e. chemical shift of oxazines characteristic peak illustrate embodiment two at containing
Benzoxazine structure triarylamine quasi polymer；
Fig. 6 is the cyclic voltammogram of the triarylamine quasi polymer of structure containing benzoxazine P2 prepared by embodiment two；From Fig. 6
In it is found that this polymer has a pair of of redox peaks, oxygen may be had occurred simultaneously due to polymer according to the structure of this polymer
Change reduction process, so there are a pair of of redox peaks, redox reaction and polymer have occurred under corresponding voltage
The variation that color has occurred illustrates the triarylamine quasi polymer P2 of structure containing benzoxazine of preparation while also having electrochromism
Performance.
Fig. 7 is the electrochromism figure of the triarylamine quasi polymer of structure containing benzoxazine P2 prepared by embodiment two；In Fig. 7
Curve is the ultraviolet absorption curve applied when voltage is 2.0V-0.0V；As can be seen from Figure 7, before not applying voltage, embodiment two is made
The standby triarylamine quasi polymer of structure containing benzoxazine has absorption peak at 322nm, when applied voltage is from 0.0V to 2.0V,
Occur new absorption peak at 410nm and 850nm and is gradually increasing；Illustrate three virtue of structure containing benzoxazine prepared by embodiment two
Amido quasi polymer P2 has the function of electrochromism, color from it is faint yellow to navy blue again to peony；
1 milligram of the triarylamine quasi polymer of structure containing benzoxazine P2 is dissolved in the N-Methyl pyrrolidone of 20mL,
The triarylamine quasi polymer solution of structure containing benzoxazine that concentration is 1 × 10-5M is obtained, to the triaryl amine of structure containing benzoxazine
2 microlitres of picric acid are added in base class polymer solution；Fig. 8 is that the triarylamine of structure containing benzoxazine prepared by embodiment two is birdsed of the same feather flock together
Close the fluorogram that object P2 responds TNT；Curve 1 is the triarylamine quasi polymer of structure containing benzoxazine for being not added with TNT in figure
The fluorescence intensity curves of solution, it is 1 × 10-10M, 1 × 10-9M, 1 × 10- that curve 2 to 8, which respectively corresponds and is added to 2 microlitres of concentration,
The triarylamine quasi polymer of structure containing benzoxazine of 8M, 1 × 10-7M, 1 × 10-6M, 1 × 10-5M, 1 × 10-4M, TNT
The fluorescence intensity curves of solution；As seen from Figure 5 with the increase of TNT concentration, the fluorescence intensity of polymer solution gradually subtracts
It is weak；Illustrate that the polymer can generate response to TNT, i.e., judges that TNT whether there is by the way that whether the polymerization fluorescence declines；
1 milligram of the triarylamine quasi polymer of structure containing benzoxazine P2 is dissolved in the N-Methyl pyrrolidone of 20mL,
The triarylamine quasi polymer solution of structure containing benzoxazine that concentration is 1 × 10-5M is obtained, to the triaryl amine of structure containing benzoxazine
2 microlitres of picric acid are added in base class polymer solution；Fig. 9 is that the triarylamine of structure containing benzoxazine prepared by embodiment two is birdsed of the same feather flock together
Close the fluorogram that object P2 responds picric acid；Curve 1 is to be not added with the picric triaryl amine of structure containing benzoxazine base class in figure
The fluorescence intensity curves of polymer solution, curve 2 to 8 respectively correspond be added to 2 microlitres of concentration be 1 × 10-10M, 1 × 10-9M,
1 × 10-8M, 1 × 10-7M, 1 × 10-6M, 1 × 10-5M, 1 × 10-4M, picric structure containing benzoxazine triarylamine
The fluorescence intensity curves of quasi polymer solution；As seen from Figure 6 with the increase of bitter taste acid concentration, the fluorescence of polymer solution
Intensity gradually weakens；And then can illustrate the polymer can to picric acid generate response, by the polymerization fluorescence whether decline come
Judge that picric acid whether there is；
Figure 10 is the memory performance figure of the triarylamine quasi polymer of structure containing benzoxazine P2 prepared by embodiment two；By scheming
10 it can be seen that in voltage scanning, from 0 to -8V (scanning 1), when negative threshold voltage is -2.2V and memory device is from low electricity
Conductance state (OFF) observes sharply increasing for electric current when being switched to highly conductive state (ON).This conversion process can be used as
" write-in " process of ITO/Polymer/Al device.During scan next time (scanning 2), electric current is still in ON state, device
Still keep high on state.In the third time scanning of from 0 to+8V (scanning 3), electric current is prominent under the threshold voltage of+4.0V
So decline, this shows memory device experience from ON state to the transformation of original OFF state.This conversion from ON to OFF can be with
As " erasing " process.As forward bias is applied, electric current stills remain in low lead in subsequent voltage scanning (scanning 4)
Logical state.Therefore, the storage equipment manufactured with the polymer is binary system flash memory data storage device.
Figure 11 is the thermal weight loss of the triarylamine quasi polymer of structure containing benzoxazine prepared by embodiment one and embodiment two
Curve graph；From curve a it is found that the triarylamine quasi polymer of structure containing the benzoxazine P1 of the preparation of embodiment one is about at 300 DEG C
Left and right starts a large amount of weightlessness, and when temperature is at 367 DEG C, carbon residual volume is 95%, and when temperature is 418 DEG C, carbon residual volume is
90%；When temperature is 519 DEG C, carbon residual volume is 80%, and what when temperature reaches 800 DEG C prepared by embodiment one contains benzoxazine
Structure triarylamine quasi polymer carbon residual volume is 63%.
From curve b it is found that the triarylamine quasi polymer of structure containing the benzoxazine P2 of the preparation of embodiment two is about at 300 DEG C
Left and right starts a large amount of weightlessness, and when temperature is at 370 DEG C, carbon residual volume is 95%, and when temperature is 414 DEG C, carbon residual volume is
90%；When temperature is 490 DEG C, carbon residual volume is 80%, and what when temperature reaches 800 DEG C prepared by embodiment one contains benzoxazine
Structure triarylamine quasi polymer carbon residual volume is 60%；And then can illustrate that the series polymer has good thermal stability,
It can work in the higher environment of temperature, such as space industry.
Claims (10)
1. the triarylamine quasi polymer of structure containing benzoxazine, it is characterised in that the triarylamine quasi polymer of structure containing benzoxazine
For the triarylamine quasi polymer P1 of structure containing the benzoxazine or triarylamine quasi polymer of structure containing benzoxazine P2；
Wherein the structural formula of the triarylamine quasi polymer of structure containing benzoxazine P1 is as follows:
N is 3~10 integers in formula；
The structural formula of the triarylamine quasi polymer of structure containing benzoxazine P2 is as follows:
, n is 3~10 in formula integer.
2. the method for preparing the triarylamine of structure containing benzoxazine quasi polymer as described in claim 1, it is characterised in that contain
Benzoxazine structure triarylamine quasi polymer P1's the preparation method comprises the following steps: one, synthesis N, N '-bis- (4- aminophenyl)-N, N '-two
Phenyl -1,4- phenylenediamine monomer: 1., in N2Under atmosphere, by N, N- diphenyl-Isosorbide-5-Nitrae-phenylenediamine monomer, sodium hydride and anhydrous N,
Dinethylformamide is placed in there-necked flask, and p-fluoronitrobenzene, heating is added simultaneously with the rate of addition of 1~2 drop per second in stirring
Isothermal reaction is carried out after to 114~115 DEG C, is then cooled down；Reaction product is placed in 24~25 DEG C of water to crude product and is precipitated, so
After filter out crude product, with water washing crude product 2~3 times of 99~100 DEG C, resulting crude product is put in a vacuum drying oven
It is dried, then is recrystallized using ethyl alcohol, crystallized product is filtered out after recrystallization, crystallized product be dried in vacuo
To yellow powder M1；The wherein volume and N of anhydrous n,N-Dimethylformamide, the substance of N- diphenyl-Isosorbide-5-Nitrae-phenylenediamine monomer
Amount ratio be (200~250) mL:7.5mmol；Sodium hydride and N, the amount of the substance of N- diphenyl-Isosorbide-5-Nitrae-phenylenediamine monomer
Than for 66.6mmol:7.5mmol；The molar ratio of p-fluoronitrobenzene and N, N- diphenyl-Isosorbide-5-Nitrae-phenylenediamine monomer are 20.0mmol:
7.5mmol；The volume and N of 24~25 DEG C of water, the ratio of the amount of N- diphenyl-Isosorbide-5-Nitrae-phenylenediamine monomeric substance are (500~800)
ML:7.5mmol；The vacuum drying temperature is 99~100 DEG C, and the vacuum drying time is 40~48 hours, vacuum drying
Pressure be -30~-29KPa；
2., under room temperature, dehydrated alcohol, Pd/C and yellow powder M1 are added in there-necked flask, N is passed through into there-necked flask2,
It is added dropwise in the mixed solution in hydrazine hydrate to there-necked flask using constant pressure funnel with the rate of addition of 1~2 drop per second；It is warming up to solution
It flows back, stops heating after back flow reaction, be filtered to remove at 79~80 DEG C except Pd/C, filtrate is poured into 4~5 DEG C of water
In, sodium chloride is added to solid is precipitated simultaneously in stirring, filters out solid and the solid vacuum drying with ethanol washing, to filtering out
After obtain shallow white solid M11；
Wherein the volume mass ratio of dehydrated alcohol and yellow powder M1 are (200~300) mL:2g；Pd/C's and yellow powder M1
Mass ratio is (0.70~0.80) g:2g；The volume mass ratio of hydrazine hydrate and yellow powder M1 are (18~20) mL:2g；Filtrate with
The volume ratio of 4~5 DEG C of water is 1:(3~4)；The Pd/C is the C doped and compounded material of Pd, and the mass fraction of Pd is in Pd/C
10%；The vacuum drying temperature is 29~30 DEG C, and the vacuum drying time is 24 hours, and vacuum drying pressure is -30
~-29KPa；
Two, the triarylamine quasi polymer of structure containing benzoxazine P1 is prepared
In N2Under atmosphere, dehydrated alcohol and the mixed solution except water-toluene are added into there-necked flask, shallow white solid M11, double is added
Phenol fluorenes stirs 10~20min, paraformaldehyde is added into there-necked flask, then heats to 85 DEG C, reaction time 48h is gathered
Polymer solution；By volume it is that the ratio of 7:40 is poured into methanol by polymer solution, carries out product precipitation, again with methanol washing
It is filtered, obtained product is dried in a vacuum drying oven, and then Soxhlet extraction is purified, and obtains structure containing benzoxazine
Triarylamine quasi polymer P1；The wherein body of the amount of shallow white solid M11 substance and dehydrated alcohol and water removal toluene mixed solution
Product is than being 1.0mmol:15mL, and dehydrated alcohol and the volume ratio except water-toluene are 1 in dehydrated alcohol and water removal toluene mixed solution:
2；The amount of substance ratio of shallow white solid M11 and bisphenol fluorene is 1.0mmol:1.2mmol；Shallow white solid M11 and paraformaldehyde
Amount of substance ratio is 1.0mmol:4.55mmol；The vacuum drying temperature is 29~30 DEG C, and the vacuum drying time is 24 small
When, the control of time is paid attention in drying process, vacuum drying pressure is -30~-29KPa；The temperature of Soxhlet extraction is 70 DEG C,
The time of Soxhlet extraction is 48h.
3. the preparation method of the triarylamine of structure containing benzoxazine quasi polymer according to claim 2, it is characterised in that
Step 1 1. described in yellow powder M1 be N, bis- (4- nitrobenzophenone)-N, N '-diphenyl-Isosorbide-5-Nitrae-phenylenediamines of N '-.
4. the preparation method of the triarylamine of structure containing benzoxazine quasi polymer according to claim 2, it is characterised in that
Step 1 2. described in shallow white solid M11 be N, bis- (4- aminophenyl)-N, N '-diphenyl-Isosorbide-5-Nitrae-phenylenediamines of N '-.
5. the method for preparing the triarylamine of structure containing benzoxazine quasi polymer as described in claim 1, it is characterised in that contain
Benzoxazine structure triarylamine quasi polymer P2's the preparation method comprises the following steps: one, synthesis N, N '-bis- (4- aminophenyl)-N, N '-two
Phenyl -1,4- benzidine: a, in N2Under atmosphere, by N, N'- diphenyl-benzidine monomer, sodium hydride and anhydrous N, N- bis-
Methylformamide is placed in there-necked flask, and p-fluoronitrobenzene is added simultaneously with the rate of addition of 1~2 drop per second in stirring, is warming up to 114
Isothermal reaction is carried out after~115 DEG C, is then cooled down；Reaction product is placed in 24~25 DEG C of water to crude product and is precipitated, then mistake
Crude product is filtered out, with water washing crude product 2~3 times of 99~100 DEG C, resulting crude product is put and is carried out in a vacuum drying oven
Drying, then recrystallized using ethyl alcohol, crystallized product is filtered out after recrystallization, and crystallized product is dried in vacuo to obtain depth
Yellow powder M2；The wherein volume and N of anhydrous n,N-Dimethylformamide, the amount of N'- diphenyl-benzidine monomer substance
Ratio be (200~250) mL:5.95mmol；The ratio of sodium hydride and N, the amount of N'- diphenyl-benzidine monomer substance is
51.46mmol:5.95mmol；P-fluoronitrobenzene and N, N'- diphenyl-benzidine monomer molar ratio are 15.47mmol:
5.95mmol；24~25 DEG C of water and N, N'- diphenyl-benzidine monomer volume mass ratio are (500~800) mL:
5.95mmol；The vacuum drying temperature is 99~100 DEG C, and the vacuum drying time is 40~48 hours, vacuum drying
Pressure is -30~-29KPa；
B, under room temperature, dehydrated alcohol, Pd/C and buff powder M2 are added in there-necked flask, N is passed through into there-necked flask2,
It is added dropwise in the mixed solution in hydrazine hydrate to there-necked flask using constant pressure funnel with the rate of addition of 1~2 drop per second；It is warming up to solution
It flows back, stops heating after back flow reaction, be filtered to remove at 79~80 DEG C except Pd/C, filtrate is poured into 4~5 DEG C of water
In, sodium chloride is added to solid is precipitated simultaneously in stirring, filters out solid and the solid vacuum drying with ethanol washing, to filtering out
After obtain shallow white solid M22；The volume mass of dehydrated alcohol and M2 ratio are (200~300) mL:2g；The quality of Pd/C and M2
Than for (0.70~0.80) g:2g；The volume mass of hydrazine hydrate and M2 ratio are (18~20) mL:2g；The body of filtrate and 4~5 DEG C of water
Product is than being 1:(3~4)；The Pd/C is the C doped and compounded material of Pd, and the mass fraction of Pd is 10% in Pd/C；The vacuum
Dry temperature is 29~30 DEG C, and the vacuum drying time is 24 hours, and vacuum drying pressure is -30~-29KPa；
Two, the triarylamine quasi polymer of structure containing benzoxazine P2 is prepared
In N2Under atmosphere, dehydrated alcohol and the mixed solution except water-toluene are added into there-necked flask, shallow white solid M22, double is added
Phenol fluorenes stirs 10~20min, paraformaldehyde is added into there-necked flask, then heats to 85 DEG C, reaction time 48h is gathered
Polymer solution；By volume it is that the ratio of 7:40 is poured into methanol by polymer solution, carries out product precipitation, again with methanol washing
It is filtered, obtained product is dried in a vacuum drying oven, and then Soxhlet extraction is purified, and obtains structure containing benzoxazine
Triarylamine quasi polymer P2；The wherein body of the amount of shallow white solid M22 substance and dehydrated alcohol and water removal toluene mixed solution
Product is than being 0.7mmol:10mL, and dehydrated alcohol and the volume ratio except water-toluene are 1 in dehydrated alcohol and water removal toluene mixed solution:
2；The amount of substance ratio of shallow white solid M22 and bisphenol fluorene is 0.7mmol:0.8mmol；Shallow white solid M22 and paraformaldehyde
Amount of substance ratio is 0.7mmol:3mmol；The vacuum drying temperature is 29~30 DEG C, and the vacuum drying time is 24 hours,
The control of time is paid attention in drying process, vacuum drying pressure is -30~-29KPa；The temperature of Soxhlet extraction is 70 DEG C, rope
The time that family name extracts is 48h.
6. the preparation method of the triarylamine of structure containing benzoxazine quasi polymer according to claim 5, it is characterised in that
Buff powder M2 is N, bis- (4- nitrobenzophenone)-N, N '-diphenyl-Isosorbide-5-Nitrae-benzidines of N '-.
7. the preparation method of the triarylamine of structure containing benzoxazine quasi polymer according to claim 5, it is characterised in that
Shallow white solid M22 is N, bis- (4- aminophenyl)-N, N '-diphenyl-Isosorbide-5-Nitrae-benzidines of N '-.
8. the application of the triarylamine of structure containing benzoxazine quasi polymer as described in claim 1, it is characterised in that contain benzo
Application of the oxazines structure triarylamine quasi polymer as the electrochromic layer in electrochromic device in electrochromism.
9. a kind of application of the triarylamine of structure containing benzoxazine quasi polymer according to claim 8, it is characterised in that
The triarylamine quasi polymer of structure containing benzoxazine answering in electrochromism as the electrochromic layer in electrochromic device
With method:
Using the triarylamine quasi polymer of structure containing benzoxazine as the electrochromic layer in electrochromic device, electrochromic layer
Coated in electrochromic device is prepared on conducting base, electrochromic layer generates electrochromism under the action of extra electric field.
10. the application of the triarylamine of structure containing benzoxazine quasi polymer as described in claim 1, it is characterised in that contain benzo
Oxazines structure triarylamine quasi polymer P2 is used for the detection of explosive 2,4,6- trinitrotoluene.
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