CN109593171A - Multi-functional quasi polymer of oxazines containing triarylamine of one kind and its preparation method and application - Google Patents
Multi-functional quasi polymer of oxazines containing triarylamine of one kind and its preparation method and application Download PDFInfo
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- CN109593171A CN109593171A CN201811525792.9A CN201811525792A CN109593171A CN 109593171 A CN109593171 A CN 109593171A CN 201811525792 A CN201811525792 A CN 201811525792A CN 109593171 A CN109593171 A CN 109593171A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
- C07D265/04—1,3-Oxazines; Hydrogenated 1,3-oxazines
- C07D265/12—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems
- C07D265/14—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring
- C07D265/16—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring with only hydrogen or carbon atoms directly attached in positions 2 and 4
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
Abstract
Multi-functional quasi polymer of oxazines containing triarylamine of one kind and its preparation method and application, the present invention relates to a kind of multi-functional quasi polymers of oxazines containing triarylamine 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 N4,N4- two-naphthalene -2- bases-biphenyl -4,4- diamines is then raw material reacts realization nitration with p-fluoronitrobenzene, nitro is then reduced to amino again, with bisphenol-A, paraformaldehyde, the triphenylamine base class monomer of preparation is raw material, pass through condensation reaction synthetic polymer under certain condition, Inventive polymers have excellent electrochromic property and memory performance, can be applied to electrochromism field, also have good performance in explosive detection；Present invention application electrochromic polymeric compounds field.
Description
Technical field
The present invention relates to a kind of multi-functional quasi polymers of oxazines containing triarylamine 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 multi-functional quasi polymer of oxazines containing triarylamine of one kind and its preparation method and application.
A kind of structural formula of multi-functional quasi polymer of oxazines containing triarylamine of the invention is as follows:
N is 3~10 in formula
Integer.
The multi-functional quasi polymer of oxazines containing triarylamine of the invention a kind of the preparation method comprises the following steps:
One, bis- (4- aminophenyl)-N, N '-two -2- naphthalenes-Isosorbide-5-Nitrae-benzidines of N, N ' -
In N2Under atmosphere, by N4,N4- two-naphthalene -2- bases-biphenyl -4,4- diamine monomer, sodium hydride and anhydrous N, N- dimethyl
Formamide 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, it 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, is then filtered
Resulting crude product is put and is dried in a vacuum drying oven with water washing crude product 2~3 times of 99~100 DEG C by crude product out
It is dry, then recrystallized using ethyl alcohol, crystallized product is filtered out after recrystallization, and crystallized product is dried in vacuo to obtain powder
M2；The wherein volume and N of anhydrous n,N-Dimethylformamide4,N4- two-naphthalene -2- bases-biphenyl -4,4- diamine monomer substance
The ratio of amount is (200~250) mL:4.50mmol；Sodium hydride and N4,N4- two-naphthalene -2- bases-biphenyl -4,4- diamine monomer substance
Amount ratio be 39.0mmol:4.50mmol；P-fluoronitrobenzene and N4,N4- two-naphthalene -2- bases-biphenyl -4,4- diamine monomer rubs
You are than being 13.50mmol:4.50mmol；The volume and N of 24~25 DEG C of water4,N4- two-naphthalene -2- bases-biphenyl -4,4- diamine monomer
Substance amount ratio be (500~800) mL:4.50mmol；The vacuum drying temperature is 99~100 DEG C, vacuum drying
Time be 40~48 hours, vacuum drying pressure be -30~-29KPa；
2., under room temperature, dehydrated alcohol, Pd/C and 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 solid M22；
Wherein the volume mass ratio of dehydrated alcohol and powder M2 are (200~300) mL:2g；The quality of Pd/C and powder M2
Than for (0.70~0.80) g:2g；The volume mass ratio of hydrazine hydrate and powder M2 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 quasi polymer of oxazines containing triarylamine is prepared
In N2Under atmosphere, dehydrated alcohol and the mixed solution except water-toluene are added into there-necked flask, 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 oxazines containing triarylamine
Quasi polymer；Wherein the volume ratio of the amount of solid M22 substance and dehydrated alcohol and water removal toluene mixed solution is 0.6mmol:
Dehydrated alcohol and the volume ratio except water-toluene are 1:2 in 13mL, dehydrated alcohol and water removal toluene mixed solution；Solid M22 and double
The amount of substance ratio of phenol fluorenes is 0.6mmol:0.7mmol；The amount of substance of solid M22 and paraformaldehyde ratio is 0.6mmol:2.6mmol；
The vacuum drying temperature is 29~30 DEG C, and the vacuum drying time is 24 hours, and 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, and the time of Soxhlet extraction is 48h.
A kind of multi-functional quasi polymer of oxazines containing triarylamine of the invention is as the electrochromic layer in electrochromic device
Application in electrochromism.
A kind of multi-functional quasi polymer of oxazines containing triarylamine of the invention 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 N4,N4- two-naphthalene -2- bases-biphenyl -4,4- diamines
Then react with p-fluoronitrobenzene realization nitration for raw material, nitro is then reduced to amino again, with bisphenol-A, paraformaldehyde,
The triphenylamine base class monomer of preparation is raw material, is synthesized under certain condition by Mannich condensation reaction, is synthesized a series of opposite
The lesser polymer of molecular weight, the quasi polymer can ring-opening polymerisations under the action of heating or catalyst.
The present invention has following special-effect:
One, the present invention, which has, introduces benzoxazine class formation in the triphenylamine base class molecular formula of electrochromic property, design
And a series of polymer of triphenylamine 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 triphenylamine base 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 0.60~1.80V voltage range, and the coloration time of Inventive polymers is 1.7~1.9s；When bleaching
Between be 1.8~2.0s；The combination of oxazines and the unit containing triphenylamine base promotes electronics transfer between the two to make containing three
The color change of anilino- and the conjugated polymer of oxazines structure is more obvious；It is navy blue when coloring to peony, when bleaching
It is colourless to approach, therefore contrast is very high when electrochromism；
Three, Inventive polymers have very strong fluorescence, and Inventive polymers are matched with explosive 2,4,6-trinitrotoluene
At the fluorescence of solution contact post-consumer polymer be gradually reduced until disappearing, therefore Inventive polymers can be used for detecting explosive
2,4,6- trinitrotoluene；
Four, by thermogravimetric curve it is found that oxazines containing triarylamine prepared by the present invention quasi polymer is with heat-resisting well
Performance.
Detailed description of the invention
Fig. 1 is the hydrogen nuclear magnetic spectrogram of the multi-functional quasi polymer of oxazines containing triarylamine prepared by embodiment one；
Fig. 2 is the cyclic voltammogram of the multi-functional quasi polymer of oxazines containing triarylamine prepared by embodiment one；
Fig. 3 is the electrochromism figure of the multi-functional quasi polymer of oxazines containing triarylamine prepared by embodiment one；
Fig. 4 is the thermogravimetric curve figure of the multi-functional quasi polymer of oxazines containing triarylamine prepared by embodiment one；
Fig. 5 is the fluorogram that the multi-functional quasi polymer of oxazines containing triarylamine prepared by embodiment one responds TNT；
Fig. 6 is the fluorogram that the multi-functional quasi polymer of oxazines containing triarylamine prepared by embodiment one responds TNP；
Fig. 7 is the memory performance figure of the multi-functional quasi polymer of oxazines containing triarylamine prepared by embodiment one.
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: a kind of structural formula of the multi-functional quasi polymer of oxazines containing triarylamine of present embodiment is such as
Under:N is 3~10 integers in formula.
In present embodiment, triphenylamine base class monomer is prepared first, present embodiment is with N4,N4- two-naphthalene -2- bases-biphenyl -
4,4- diamines are then raw material react realization nitration with p-fluoronitrobenzene, and nitro is then reduced to amino again, with bisphenol-A,
Paraformaldehyde, the triphenylamine base class monomer of preparation are raw material, are synthesized under certain condition by Mannich condensation reaction, synthesis
A series of lesser polymer of relative molecular weight, the quasi polymer can ring-opening polymerisations under the action of heating or catalyst.
Present embodiment has following special-effect:
One, present embodiment, which has, introduces benzoxazine class formation in the triphenylamine base class molecular formula of electrochromic property,
The polymer for designing and preparing a series of triphenylamine 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
The interior active site for generating stable polymer of the reversible change containing triphenylamine base 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 embodiment
Color change is obvious in polymer 0.60~1.80V voltage range, and the coloration time of present embodiment polymer is 1.7~
1.9s；Bleaching time is 1.8~2.0s；The combination of oxazines and the unit containing triphenylamine base promotes electronics transfer between the two
To keep the color change of the conjugated polymer containing triphenylamine base and oxazines structure 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, present embodiment polymer has very strong fluorescence, present embodiment polymer and 2,4,6- tri- nitre of explosive
The fluorescence for the solution contact post-consumer polymer that base toluene is made into is gradually reduced until disappearing, therefore present embodiment polymer can be used
In detection explosive 2,4,6- trinitrotoluene；
Four, by thermogravimetric curve it is found that the quasi polymer of oxazines containing triarylamine of present embodiment preparation has well
Heat resistance.
Specific embodiment 2: a kind of preparation method of the multi-functional quasi polymer of oxazines containing triarylamine of present embodiment
Are as follows:
One, bis- (4- aminophenyl)-N, N '-two -2- naphthalenes-Isosorbide-5-Nitrae-benzidines of N, N ' -
In N2Under atmosphere, by N4,N4- two-naphthalene -2- bases-biphenyl -4,4- diamine monomer, sodium hydride and anhydrous N, N- dimethyl
Formamide 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, it 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, is then filtered
Resulting crude product is put and is dried in a vacuum drying oven with water washing crude product 2~3 times of 99~100 DEG C by crude product out
It is dry, then recrystallized using ethyl alcohol, crystallized product is filtered out after recrystallization, and crystallized product is dried in vacuo to obtain powder
M2；The wherein volume and N of anhydrous n,N-Dimethylformamide4,N4- two-naphthalene -2- bases-biphenyl -4,4- diamine monomer substance
The ratio of amount is (200~250) mL:4.50mmol；Sodium hydride and N4,N4- two-naphthalene -2- bases-biphenyl -4,4- diamine monomer substance
Amount ratio be 39.0mmol:4.50mmol；P-fluoronitrobenzene and N4,N4- two-naphthalene -2- bases-biphenyl -4,4- diamine monomer rubs
You are than being 13.50mmol:4.50mmol；The volume and N of 24~25 DEG C of water4,N4- two-naphthalene -2- bases-biphenyl -4,4- diamine monomer
Substance amount ratio be (500~800) mL:4.50mmol；The vacuum drying temperature is 99~100 DEG C, vacuum drying
Time be 40~48 hours, vacuum drying pressure be -30~-29KPa；
2., under room temperature, dehydrated alcohol, Pd/C and 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 solid M22；
Wherein the volume mass ratio of dehydrated alcohol and powder M2 are (200~300) mL:2g；The quality of Pd/C and powder M2
Than for (0.70~0.80) g:2g；The volume mass ratio of hydrazine hydrate and powder M2 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 quasi polymer of oxazines containing triarylamine is prepared
In N2Under atmosphere, dehydrated alcohol and the mixed solution except water-toluene are added into there-necked flask, 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 oxazines containing triarylamine
Quasi polymer；Wherein the volume ratio of the amount of solid M22 substance and dehydrated alcohol and water removal toluene mixed solution is 0.6mmol:
Dehydrated alcohol and the volume ratio except water-toluene are 1:2 in 13mL, dehydrated alcohol and water removal toluene mixed solution；Solid M22 and double
The amount of substance ratio of phenol fluorenes is 0.6mmol:0.7mmol；The amount of substance of solid M22 and paraformaldehyde ratio is 0.6mmol:2.6mmol；
The vacuum drying temperature is 29~30 DEG C, and the vacuum drying time is 24 hours, and 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, and the time of Soxhlet extraction is 48h.
Specific embodiment 3: present embodiment is unlike specific embodiment two: 1. middle powder M2 is step 1
Bis- (4- nitrobenzophenone)-N, N '-two -2- naphthalenes-Isosorbide-5-Nitrae-benzidines of N, N ' -.Other are identical with embodiment two.
Specific embodiment 4: present embodiment is unlike specific embodiment two or three: step 1 2. in solid
M22 is N, bis- (4- aminophenyl)-N, N '-two -2- naphthalenes-Isosorbide-5-Nitrae-benzidines of N ' -.Other and specific embodiment two or three
It is identical.
Specific embodiment 5: unlike one of present embodiment and specific embodiment two to four: step 1 2. in
The heating rate being warming up to when solution flows back is 9~10 DEG C of heating per minute.Other and specific embodiment two to four it
One is identical.
Specific embodiment 6: the multi-functional quasi polymer of oxazines containing triarylamine of present embodiment is as electrochromic device
In application of the electrochromic layer in electrochromism.
Specific embodiment 7: present embodiment is unlike specific embodiment six: oxazines containing triarylamine is birdsed of the same feather flock together
Close application method of the object as the electrochromic layer in electrochromic device in electrochromism:
Using the quasi polymer of oxazines containing triarylamine as the electrochromic layer in electrochromic device, electrochromic layer coating
Electrochromic device is prepared on conducting base, electrochromic layer generates electrochromism under the action of extra electric field.Other
It is identical as specific embodiment six.
Specific embodiment 8: present embodiment is unlike specific embodiment six or seven: conducting base is conduction
Glass.Other are identical as specific embodiment six or seven.
Specific embodiment 9: unlike one of present embodiment and specific embodiment six to eight: containing triarylamine
Application method of the oxazines quasi polymer as the electrochromic layer in electrochromic device in electrochromism: triarylamine will be contained
As the electrochromic layer in electrochromic device, electrochromic layer is coated on conducting base and is prepared into electricity oxazines quasi polymer
Mutagens color device, electrochromic layer generate electrochromism under the action of extra electric field.Other and specific embodiment six to eight
One of it is identical.
Specific embodiment 10: the multi-functional quasi polymer of oxazines containing triarylamine of present embodiment is used for explosive 2,4,6-
The detection of trinitrotoluene.
Beneficial effects of the present invention are verified using following embodiment:
Embodiment one: the structural formula of the multi-functional quasi polymer of oxazines containing triarylamine is as follows:
N is 3~10 in formula
Integer.
A kind of multi-functional quasi polymer of oxazines containing triarylamine of the present embodiment the preparation method comprises the following steps:
One, bis- (4- aminophenyl)-N, N '-two -2- naphthalenes-Isosorbide-5-Nitrae-benzidines of N, N ' -
In N2Under atmosphere, by N4,N4- two-naphthalene -2- bases-biphenyl -4,4- diamine monomer, sodium hydride and anhydrous N, N- dimethyl
Formamide 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, it 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, is then filtered
Resulting crude product is put and is dried in a vacuum drying oven with water washing crude product 2~3 times of 99~100 DEG C by crude product out
It is dry, then recrystallized using ethyl alcohol, crystallized product is filtered out after recrystallization, and crystallized product is dried in vacuo to obtain powder
M2；The wherein volume and N of anhydrous n,N-Dimethylformamide4,N4- two-naphthalene -2- bases-biphenyl -4,4- diamine monomer substance
The ratio of amount is 200mL:4.50mmol；Sodium hydride and N4,N4The amount of-two-naphthalene -2- bases-biphenyl -4,4- diamine monomer substance
Than for 39.0mmol:4.50mmol；P-fluoronitrobenzene and N4,N4- two-naphthalene -2- bases-biphenyl -4,4- diamine monomer molar ratio is
13.50mmol:4.50mmol；The volume and N of 24~25 DEG C of water4,N4- two-naphthalene -2- bases-biphenyl -4,4- diamine monomer substance
Amount ratio be 750mL:4.50mmol；The vacuum drying temperature is 99~100 DEG C, and the vacuum drying time is 40~48
Hour, vacuum drying pressure is -30~-29KPa；
2., under room temperature, dehydrated alcohol, Pd/C and 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 solid M22；
Wherein the volume mass ratio of dehydrated alcohol and powder M2 are 250mL:2g；The mass ratio of Pd/C and powder M2 is
(0.70~0.80) g:2g；The volume mass ratio of hydrazine hydrate and powder M2 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 quasi polymer of oxazines containing triarylamine is prepared
In N2Under atmosphere, dehydrated alcohol and the mixed solution except water-toluene are added into there-necked flask, 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 oxazines containing triarylamine
Quasi polymer；Wherein the volume ratio of the amount of solid M22 substance and dehydrated alcohol and water removal toluene mixed solution is 0.6mmol:
Dehydrated alcohol and the volume ratio except water-toluene are 1:2 in 13mL, dehydrated alcohol and water removal toluene mixed solution；Solid M22 and double
The amount of substance ratio of phenol fluorenes is 0.6mmol:0.7mmol；The amount of substance of solid M22 and paraformaldehyde ratio is 0.6mmol:2.6mmol；
The vacuum drying temperature is 29~30 DEG C, and the vacuum drying time is 24 hours, and 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, and the time of Soxhlet extraction is 48h.
Wherein powder M2 is N, and bis- (4- nitrobenzophenone)-N, N '-two -2- naphthalenes-Isosorbide-5-Nitrae-benzidines of N ' -, yield is
60%.Solid M22 is that N, bis- (4- aminophenyl)-N, N '-two -2- naphthalenes-Isosorbide-5-Nitrae-benzidines of N ' -, and yield are 60%.
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 quasi polymer of oxazines containing triarylamine manufactured in the present embodiment is more soluble, every 10 milliliters of pole in polar solvent
Solvable 1.5 grams in property solution；It is slightly soluble in nonpolar solvent, solvable 0.2 gram in every 10 milliliters of polar solvents.
Fig. 1 is the hydrogen nuclear magnetic spectrogram of the multi-functional quasi polymer of oxazines containing triarylamine prepared by embodiment one；It can from Fig. 1
Know, chemical shift δ is shown in 4.50,5.30ppm, the i.e. chemical shift of oxazines characteristic peak in Fig. 1, illustrates that embodiment one synthesizes
The quasi polymer of oxazines containing triarylamine；
Fig. 2 is the cyclic voltammogram of the multi-functional quasi polymer of oxazines containing triarylamine prepared by embodiment one；It can from Fig. 2
Know, it is each at 1.14V, 0.86V an oxidation peak and a reduction peak occur；Illustrate that the multi-functional of the preparation of embodiment one contains three
Redox reaction has occurred in the case where applying voltage conditions in aryl amine oxazines quasi polymer, and triaryl amine is contained in oxidation-reduction process
Base oxazines quasi polymer can generate the variation of color, and the quasi polymer of oxazines containing triarylamine for illustrating prepared by embodiment one has electricity
Cause discoloration；
Fig. 3 is the electrochromism figure of the multi-functional quasi polymer of oxazines containing triarylamine prepared by embodiment one；Curve in Fig. 3
1 is the ultraviolet absorption curve applied when voltage is 2.0V-0.0V；As can be seen from Figure 3, before not applying voltage, prepared by embodiment one
The quasi polymer of oxazines containing triarylamine have absorption peak at 330nm, when applied voltage is from 0.0V to 2.0V, in 450nm and
Occur new absorption peak at 850nm and is gradually increasing；The quasi polymer of oxazines containing triarylamine for illustrating prepared by embodiment one has
Electrochromism function, color is from faint yellow to orange red to navy blue again to cerise；
Fig. 4 is the thermogravimetric curve figure of the multi-functional quasi polymer of oxazines containing triarylamine prepared by embodiment one；It can from Fig. 4
Know, the multi-functional quasi polymer of oxazines containing triarylamine prepared by embodiment one about starts a large amount of weightlessness at 300 DEG C or so, works as temperature
For degree at 395 DEG C, carbon residual volume is 95%, and when temperature is 442 DEG C, carbon residual volume is 90%；When temperature is 546 DEG C, carbon
Residual volume is 80%, and the multi-functional quasi polymer of oxazines containing the triarylamine carbon that when temperature reaches 800 DEG C prepared by embodiment one is residual
Surplus is 67%；And then can illustrate the series polymer have good thermal stability, can in the higher environment of temperature work
Make, such as space industry.
1 milligram of the quasi polymer of oxazines containing triarylamine is dissolved in the N-Methyl pyrrolidone of 20mL, obtaining concentration is 1
The quasi polymer solution of oxazines containing triarylamine of × 10-5M adds 2 microlitres of hardships into the quasi polymer solution of oxazines containing triarylamine
It is sour；Fig. 5 is the fluorogram that the multi-functional quasi polymer of oxazines containing triarylamine prepared by embodiment one responds TNT；It is bent in figure
Line 1 is the fluorescence intensity curves for being not added with the quasi polymer solution of oxazines containing triarylamine of TNT, and curve 2 to 8 respectively corresponds addition
2 microlitres of concentration are 1 × 10-10M、1×10-9M、1×10-8M、1×10-7M、1×10-6M、1×10-5M、1×10-4M, TNT
The quasi polymer solution of oxazines containing triarylamine fluorescence intensity curves；As seen from Figure 5 with the increase of TNT concentration, gather
The fluorescence intensity of polymer solution gradually weakens；Illustrate that the polymer can generate response to TNT, that is, whether passes through the polymerization fluorescence
Decline is to judge that TNT whether there is；
1 milligram of the quasi polymer of oxazines containing triarylamine is dissolved in the N-Methyl pyrrolidone of 20mL, obtaining concentration is 1
The quasi polymer solution of oxazines containing triarylamine of × 10-5M adds 2 microlitre three into the quasi polymer solution of oxazines containing triarylamine
Nitrophenol；Fig. 6 is the fluorogram that the multi-functional quasi polymer of oxazines containing triarylamine prepared by embodiment one responds TNP；Figure
Middle curve 1 is the fluorescence intensity curves for being not added with the quasi polymer solution of oxazines containing triarylamine of TNP, and curve 2 to 8 respectively corresponds
Being added to 2 microlitres of concentration is 1 × 10-10M、1×10-9M、1×10-8M、1×10-7M、1×10-6M、1×10-5M、1×10-4M's
The fluorescence intensity curves of the quasi polymer solution of oxazines containing triarylamine of TNP；As seen from Figure 6 with the increase of TNP concentration,
The fluorescence intensity of polymer solution gradually weakens；And then can illustrate that the polymer can generate response to TNP, it is glimmering by the polymerization
Whether light declines to judge that TNP whether there is；
Fig. 7 is the memory performance figure of the multi-functional quasi polymer of oxazines containing triarylamine prepared by embodiment one；It can be with by Fig. 7
Find out in first time voltage scanning, from 0 to -8V (scanning 2), when negative threshold voltage is -2.8V 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 3), electric current is still in ON state, device
Still keep high on state.In the third time scanning of from 0 to+8V (scanning 4), electric current is prominent under the threshold voltage of+3.2V
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 1)
Logical state.Therefore, the storage equipment manufactured with the polymer is binary system flash memory data storage device.
Claims (10)
1. a kind of multi-functional quasi polymer of oxazines containing triarylamine, it is characterised in that the multi-functional quasi polymer of oxazines containing triarylamine
Structural formula it is as follows:
N is 3~10 integers in formula.
2. the method for preparing the multi-functional quasi polymer of oxazines containing triarylamine as described in claim 1, it is characterised in that contain three
Aryl amine oxazines quasi polymer the preparation method comprises the following steps:
One, bis- (4- aminophenyl)-N, N '-two -2- naphthalenes-Isosorbide-5-Nitrae-benzidines of N, N ' -
In N2Under atmosphere, by N4,N4- two-naphthalene -2- bases-biphenyl -4,4- diamine monomer, sodium hydride and anhydrous N, N- dimethyl formyl
Amine 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 114~115 DEG C
After carry out isothermal reaction, then cool down；Reaction product is placed in 24~25 DEG C of water to crude product and is precipitated, thick production is then filtered out
Resulting crude product is put and is dried in a vacuum drying oven with water washing crude product 2~3 times of 99~100 DEG C by product, then
It is recrystallized using ethyl alcohol, crystallized product is filtered out after recrystallization, crystallized product is dried in vacuo to obtain powder M2；Its
In anhydrous n,N-Dimethylformamide volume and N4,N4The ratio of the amount of-two-naphthalene -2- bases-biphenyl -4,4- diamine monomer substance
For (200~250) mL:4.50mmol；Sodium hydride and N4,N4The amount of-two-naphthalene -2- bases-biphenyl -4,4- diamine monomer substance
Than for 39.0mmol:4.50mmol；P-fluoronitrobenzene and N4,N4- two-naphthalene -2- bases-biphenyl -4,4- diamine monomer molar ratio is
13.50mmol:4.50mmol；The volume and N of 24~25 DEG C of water4,N4- two-naphthalene -2- bases-biphenyl -4,4- diamine monomer substance
Amount ratio be (500~800) mL:4.50mmol；The vacuum drying temperature is 99~100 DEG C, the vacuum drying time
It is 40~48 hours, vacuum drying pressure is -30~-29KPa；
2., under room temperature, dehydrated alcohol, Pd/C and powder M2 are added in there-necked flask, N is passed through into there-necked flask2, use
Constant pressure funnel is added dropwise in the mixed solution in hydrazine hydrate to there-necked flask with the rate of addition of 1~2 drop per second；Solution is warming up to return
It flows, stops heating after back flow reaction, be filtered to remove at 79~80 DEG C except Pd/C, filtrate poured into 4~5 DEG C of water,
Sodium chloride is added to solid is precipitated simultaneously in stirring, filters out solid and with ethanol washing, after being dried in vacuo to the solid filtered out
Obtain solid M22；
Wherein the volume mass ratio of dehydrated alcohol and powder M2 are (200~300) mL:2g；The mass ratio of Pd/C and powder M2 is
(0.70~0.80) g:2g；The volume mass ratio of hydrazine hydrate and powder M2 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 quasi polymer of oxazines containing triarylamine is prepared
In N2Under atmosphere, dehydrated alcohol and the mixed solution except water-toluene are added into there-necked flask, solid M22, bisphenol fluorene is added,
10~20min is stirred, paraformaldehyde is added into there-necked flask, then heats to 85 DEG C, reaction time 48h obtains 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 carries out
It filters, obtained product is dried in a vacuum drying oven, and then Soxhlet extraction is purified, and is obtained oxazines containing triarylamine and is birdsed of the same feather flock together
Close object；Wherein the volume ratio of the amount of solid M22 substance and dehydrated alcohol and water removal toluene mixed solution is 0.6mmol:13mL, nothing
Dehydrated alcohol and the volume ratio except water-toluene are 1:2 in water-ethanol and water removal toluene mixed solution；The object of solid M22 and bisphenol fluorene
Mass ratio is 0.6mmol:0.7mmol；The amount of substance of solid M22 and paraformaldehyde ratio is 0.6mmol:2.6mmol；The vacuum
Dry temperature is 29~30 DEG C, and the vacuum drying time is 24 hours, and the control of time, vacuum drying are paid attention in drying process
Pressure be -30~-29KPa；The temperature of Soxhlet extraction is 70 DEG C, and the time of Soxhlet extraction is 48h.
3. the preparation method of the multi-functional quasi polymer of oxazines containing triarylamine of one kind according to claim 2, feature exist
In step 1,1. middle powder M2 is N, bis- (4- nitrobenzophenone)-N, N '-two -2- naphthalenes-Isosorbide-5-Nitrae-benzidines of N ' -.
4. the preparation method of the multi-functional quasi polymer of oxazines containing triarylamine of one kind according to claim 2, feature exist
In step 1,2. middle solid M22 is N, bis- (4- aminophenyl)-N, N '-two -2- naphthalenes-Isosorbide-5-Nitrae-benzidines of N ' -.
5. the preparation method of the multi-functional quasi polymer of oxazines containing triarylamine of one kind according to claim 2, feature exist
In step 1 2. described in be warming up to solution reflux when heating rate be per minute heating 9~10 DEG C.
6. the application of the multi-functional quasi polymer of oxazines containing triarylamine as described in claim 1, it is characterised in that contain triaryl amine
Application of the base oxazines quasi polymer as the electrochromic layer in electrochromic device in electrochromism.
7. the application of the multi-functional quasi polymer of oxazines containing triarylamine of one kind according to claim 6, it is characterised in that contain
Application method of the triarylamine oxazines quasi polymer as the electrochromic layer in electrochromic device in electrochromism:
Using the quasi polymer of oxazines containing triarylamine as the electrochromic layer in electrochromic device, electrochromic layer is coated in and leads
Electrochromic device is prepared on electric matrix, electrochromic layer generates electrochromism under the action of extra electric field.
8. the application of the multi-functional quasi polymer of oxazines containing triarylamine of one kind according to claim 7, it is characterised in that lead
Electric matrix is electro-conductive glass.
9. the application of the multi-functional quasi polymer of oxazines containing triarylamine of one kind according to claim 7, it is characterised in that outer
The voltage of added electric field is 0.60~1.80V.
10. the application of the multi-functional quasi polymer of oxazines containing triarylamine as described in claim 1, it is characterised in that contain triaryl amine
Base oxazines quasi polymer is used for the detection of explosive 2,4,6- trinitrotoluene.
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| CN111019125B (en) * | 2019-12-23 | 2022-05-03 | 黑龙江大学 | Multifunctional triarylamine polyamide containing fused ring naphthyl side group structure and preparation method and application thereof |
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