CN109575230A - A kind of multifunctional polyurethane derivative and its preparation method and application - Google Patents
A kind of multifunctional polyurethane derivative and its preparation method and application Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3215—Polyhydroxy compounds containing aromatic groups or benzoquinone groups
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3237—Polyamines aromatic
- C08G18/3243—Polyamines aromatic containing two or more aromatic rings
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent 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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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1408—Carbocyclic compounds
- C09K2211/1416—Condensed systems
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1408—Carbocyclic compounds
- C09K2211/1433—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
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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"
- G01N2021/6432—Quenching
Abstract
A kind of multifunctional polyurethane derivative and its preparation method and application, the present invention relates to a kind of multifunctional polyurethane derivatives and its preparation method and application.The present invention is in order to which the functional type for solving the problems, such as that existing multifunctional material has is few.The present invention has synthesized two kinds of monomers of triphenylamine that triphenylamine and tert-butyl replace and 1 containing hydroxyl structure first, bis- (4- hydroxy phenyl) -1, the 2- diphenylethlenes of 2-, while introducing 4,4 '-'-diphenylmethane diisocyanates are prepared by the means of combined polymerization.The material has the function of electrochromism, fluorescence sense hole transport, can be used as automobile rearview mirror material, display material；And it can be used for preparing explosive detection and memory performance device.Present invention application multifunctional material field.
Description
Technical field
The present invention relates to a kind of multifunctional polyurethane derivatives and its preparation method and application.
Background technique
Polyurethane (PU) has many ideal performances, such as better flexibility, and bigger tensile strength is higher hard
Degree, more resistant to chemical solvent and temperature condition, higher wearability, higher oil resistivity and longer fatigue life.Due to good
Mechanically and chemically performance, polyurethane is also the potential candidate of film preparation.Although polyurethane excellent combination property, tradition PU
There are some disadvantages, and such as the problems such as difficulty of processing is high, dissolubility is poor, which greatly limits polyurethane material answering industrially
With.Therefore, recent years, more and more researchers begin to focus on the preparation of polyurethane and research and the related material of modified aspect
The application of material.
For multifunctional material by it in sensor, actuator stores the outstanding use in equipment and high-contrast display
Ability and rapidly develop.Outside stimulus, such as chemicals, soda acid, temperature, light and electricity can change the chemistry or object of these materials
Rationality matter.Preparing thorniness to swash the common method of responsive materials is to introduce to have specific function and sensitivity on same molecular skeleton
Group.In the past decade, although having made great progress in this field, there are three types of above functions to polymerize for simultaneously synthesizing tool
Object is still a challenge.
Summary of the invention
The present invention is provided a kind of multi-functional in order to which the functional type for solving the problems, such as that existing multifunctional material has is few
Urethane derivative and its preparation method and application.
A kind of multifunctional polyurethane derivative of the present invention is that the multifunctional polyurethane containing triphenylamine and tetraphenyl ethylene group spreads out
The multifunctional polyurethane derivative of biology or the triphenylamine and tetraphenyl ethylene group that replace containing tert-butyl；
Structural formula wherein containing triphenylamine and the multifunctional polyurethane derivative of tetraphenyl ethylene group is as follows:
The integer that n is 3~10 in formula；
The structural formula of the triphenylamine and the multifunctional polyurethane derivative of tetraphenyl ethylene group of the substitution containing tert-butyl is as follows:
,
The integer that n is 3~10 in formula.
A kind of multifunctional polyurethane derivative of the present invention the preparation method comprises the following steps: one, by bis- (4- the hydroxy phenyl) -1,2- of 1,2-
Diphenylethlene and 4,4 '-'-diphenylmethane diisocyanates are mixed with solvent n,N-dimethylacetamide, are stirred under room temperature
Flow back 5-15h, and mixing speed is 800r/min~900r/min, obtains presoma；Two, will replace containing triphenylamine or tert-butyl
The diamine monomer of triphenylamine be added in the presoma of step 1 preparation, be warming up to 70-120 DEG C, be stirred at reflux 5-15h, it is cooling
After pour into methanol, using filter, by obtained solid formation be dried in vacuo, obtain containing triphenylamine or containing tert-butyl replace triphen
The multifunctional polyurethane derivative of amine and the tetraphenyl ethylene group for having aggregation-induced emission performance；
Bis- (4- the hydroxy phenyl) -1,2- of diamine monomer, 1,2- of the triphenylamine wherein replaced containing triphenylamine or tert-butyl
Diphenylethlene, 4,4 '-'-diphenylmethane diisocyanate molar ratios are as follows: (0.5-2.5): 1:2；
The amount of DMAC N,N' dimethyl acetamide solvent and the diamine monomer of the triphenylamine replaced containing triphenylamine or tert-butyl
Volume mass ratio is (10-30) mL:(0.5-2.5g).
A kind of application of the multifunctional polyurethane derivative of the present invention as electrochromic material.
A kind of application of the multifunctional polyurethane derivative of the present invention as electroluminescent fluorescent materials.
A kind of application of the multifunctional polyurethane derivative of the present invention as explosive detection material.
Beneficial effects of the present invention:
To there is the present invention triaryl amine group for destroying bulk property to be introduced into polyurethane structural, not only be able to maintain original poly-
The high thermal stability of urethane, and being capable of increasing its solubility enhances film forming ability, and this is not only advantageous to manufacture large area
Film electrochromic device additionally provides electric activity center to promote the processing and application of electrochromic device；Containing there are four can
The tetraphenyl ethylene (TPE) for rotating phenyl ring has obtained sufficient development due to its aggregation inducing transmitting (AIE) activity.TPE is derivative
Object can overcome the problems, such as that (ACQ) is quenched caused by the aggregation of conventional organic luminescence body, this is greatly promoted it in bioprobe,
The various applications of chemical sensitisation and photoelectric device.Urethane derivative prepared by the present invention is single with the triaryl amine of propeller type
Body can be effectively reduced the strong effect power between polymer molecular chain, increase the dissolubility of polymer, while triaryl amine is easy
The triaryl amine different from middle condition is showed in forming radical cation.In the present invention containing electroactive triphenylamine or contain uncle
The multifunctional polyurethane derivative of triphenylamine and the tetraphenyl ethylene group for having aggregation-induced emission performance that butyl replaces has very high
Performance resistant to high temperature, generally under the atmosphere of nitrogen, decomposition temperature at 350 DEG C or more, be suitble to use in the devices.This is sent out
It is bright to gather containing triphenylamine or the triphenylamine replaced containing tert-butyl with the multi-functional of tetraphenyl ethylene group for having aggregation-induced emission performance
Film is made in urethane derivant material, does not have big clustering phenomena and Fragmentation Phenomena on ITO substrate, also shows on ITO substrate
Good wet ability is shown.This means that multifunctional polyurethane derivant material has good film Formation and characteristics, can be used to
Make the film of large area.After application of a voltage, the transmitance of film still can achieve 50%, and transparency is relatively good, and
Thin polymer film is able to maintain circulating ring and has good stability during applying voltage, be recycled 20 times or more and transparency not
Become.
The triphenylamine replaced containing triphenylamine or containing tert-butyl of the invention and the tetraphenyl ethylene for having aggregation-induced emission performance
The multifunctional polyurethane derivative of group has following superiority in practical applications: (1) having good electrochemical oxidation also
Former invertibity is still able to maintain reversible after tens redox cycles；(2) response time of color change is fast, is adding
After voltage, it can change colour rapidly within 2 seconds；(3) variation of color is reversible；(4) color change high sensitivity；(5)
There is higher cycle life；(6) have storing memory function, before responding after, reset condition or discoloration can be stably maintained at
State afterwards, can maintain several months to several years after discoloration, color can be remained unchanged and is up to after electrochromism in this experiment
As long as half a year；(7) there is a preferable chemical stability in material discoloration front and back, under normal temperature and pressure, may be stabilized in air.(8)
To explosive TNT, picric acid has response, and it is 1 × 10 that picric acid and TNT, which can detect concentration,-12Mol/L, sensitivity are good.(9)
There is good electroluminescent fluorescent performance, during applying voltage, fluorescence intensity can be quenched, and fluorescent switch contrast
It can reach 100 or more, there is very big application potential in terms of intelligent opto-electrical and sensor.(10) there is good photoelectric respone energy
Power keeps stablizing in the cyclic process of 500s.
In conclusion triphenylamine and the tetraphenyl ethylene group of the invention replaced containing triphenylamine or containing tert-butyl is multi-functional
Urethane derivative has the function of 10 kinds.
Detailed description of the invention
Fig. 1 is the proton magnetic of the multifunctional polyurethane derivative containing triphenylamine and tetraphenyl ethylene group prepared by embodiment one
Spectrogram；
Fig. 2 is the circulation volt of the multifunctional polyurethane derivative containing triphenylamine and tetraphenyl ethylene group prepared by embodiment one
Antu；
Fig. 3 is that the multifunctional polyurethane derivative containing triphenylamine and tetraphenyl ethylene group prepared by embodiment one is applying electricity
Stability and transmitance figure after pressure；
Fig. 4 is the electroluminescent change of the multifunctional polyurethane derivative containing triphenylamine and tetraphenyl ethylene group prepared by embodiment one
Chromatic graph；
Fig. 5 is the electroluminescent glimmering of the multifunctional polyurethane derivative containing triphenylamine and tetraphenyl ethylene group prepared by embodiment one
Light figure；
Fig. 6 is the thermal weight loss of the multifunctional polyurethane derivative containing triphenylamine and tetraphenyl ethylene group prepared by embodiment one
Curve graph；
Fig. 7 is that the aggregation of the multifunctional polyurethane derivative containing triphenylamine and tetraphenyl ethylene group prepared by embodiment one lures
Lead figure；
Fig. 8 is the multifunctional polyurethane derivative containing triphenylamine and tetraphenyl ethylene group prepared by embodiment one to explosion
The picric detection figure of object；
Fig. 9 is the multifunctional polyurethane derivative containing triphenylamine and tetraphenyl ethylene group prepared by embodiment one to explosion
The detection figure of object TNT；
Figure 10 is the memory of the multifunctional polyurethane derivative containing triphenylamine and tetraphenyl ethylene group prepared by embodiment one
Performance map；
Figure 11 is the photoelectricity of the multifunctional polyurethane derivative containing triphenylamine and tetraphenyl ethylene group prepared by embodiment one
Performance map；
Figure 12 is the multifunctional polyurethane of the triphenylamine replaced containing tert-butyl and tetraphenyl ethylene group prepared by embodiment two
The hydrogen nuclear magnetic spectrogram of derivative；
Figure 13 is the multifunctional polyurethane of the triphenylamine replaced containing tert-butyl and tetraphenyl ethylene group prepared by embodiment two
The cyclic voltammogram of derivative；
Figure 14 is the multifunctional polyurethane of the triphenylamine replaced containing tert-butyl and tetraphenyl ethylene group prepared by embodiment two
Derivative stability after application of a voltage and transmitance figure；
Figure 15 is the multifunctional polyurethane of the triphenylamine replaced containing tert-butyl and tetraphenyl ethylene group prepared by embodiment two
The electrochromism figure of derivative；
Figure 16 is the multifunctional polyurethane of the triphenylamine replaced containing tert-butyl and tetraphenyl ethylene group prepared by embodiment two
The electroluminescent fluorescent figure of derivative；
Figure 17 is the multifunctional polyurethane of the triphenylamine replaced containing tert-butyl and tetraphenyl ethylene group prepared by embodiment two
The thermogravimetric curve figure of derivative；
Figure 18 is the multifunctional polyurethane of the triphenylamine replaced containing tert-butyl and tetraphenyl ethylene group prepared by embodiment two
The aggregation inducing figure of derivative；
Figure 19 is the multifunctional polyurethane of the triphenylamine replaced containing tert-butyl and tetraphenyl ethylene group prepared by embodiment two
The detection picric to explosive of derivative is schemed；
Figure 20 is the multifunctional polyurethane of the triphenylamine replaced containing tert-butyl and tetraphenyl ethylene group prepared by embodiment two
The detection figure to explosive TNT of derivative；
Figure 21 is the multifunctional polyurethane of the triphenylamine replaced containing tert-butyl and tetraphenyl ethylene group prepared by embodiment two
The memory performance figure of derivative；
Figure 22 is the multifunctional polyurethane of the triphenylamine replaced containing tert-butyl and tetraphenyl ethylene group prepared by embodiment two
The photoelectric properties figure of derivative.
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: present embodiment multifunctional polyurethane derivative is containing triphenylamine and tetraphenyl ethylene group
The multifunctional polyurethane derivative of multifunctional polyurethane derivative or the triphenylamine and tetraphenyl ethylene group that replace containing tert-butyl；
Structural formula wherein containing triphenylamine and the multifunctional polyurethane derivative of tetraphenyl ethylene group is as follows:
The integer that n is 3~10 in formula；
The structural formula of the triphenylamine and the multifunctional polyurethane derivative of tetraphenyl ethylene group of the substitution containing tert-butyl is as follows:
,
The integer that n is 3~10 in formula.
To there is present embodiment the triaryl amine group for destroying bulk property to be introduced into polyurethane structural, not only be able to maintain original
There is the high thermal stability of polyurethane, and being capable of increasing its solubility enhances film forming ability, this is not only advantageous to manufacture big face
Long-pending film electrochromic device additionally provides electric activity center to promote the processing and application of electrochromic device；Contain four
The tetraphenyl ethylene (TPE) of a rotatable phenyl ring has obtained sufficient development due to its aggregation inducing transmitting (AIE) activity.TPE
Derivative can overcome the problems, such as that (ACQ) is quenched caused by the aggregation of conventional organic luminescence body, this is greatly promoted it in biology
The various applications of probe, chemical sensitisation and photoelectric device.The urethane derivative of present embodiment preparation is with the three of propeller type
Arylamine is monomer, and the strong effect power between polymer molecular chain can be effectively reduced, increase the dissolubility of polymer, simultaneously
Triaryl amine is easily formed radical cation and shows triaryl amine different from middle condition.In present embodiment containing triphenylamine or
The multifunctional polyurethane derivative of the triphenylamine and the tetraphenyl ethylene group for having aggregation-induced emission performance of the substitution containing tert-butyl has
Very high performance resistant to high temperature, generally under the atmosphere of nitrogen, decomposition temperature is suitble to use in the devices at 350 DEG C or more.It will
The triphenylamine that present embodiment replaces containing triphenylamine or containing tert-butyl and the tetraphenyl ethylene group for having aggregation-induced emission performance
Film is made in multifunctional polyurethane derivant material, does not have big clustering phenomena and Fragmentation Phenomena on ITO substrate, serves as a contrast in ITO
Good wet ability is also shown on bottom.This means that multifunctional polyurethane derivant material has good film Formation and characteristics,
The film of large area can be used to make.After application of a voltage, the transmitance of film still can achieve 50%, and transparency compares
It is good, and thin polymer film is able to maintain circulating ring and has good stability during applying voltage, is recycled 20 times or more and saturating
Lightness is constant.
The triphenylamine of present embodiment replaced containing triphenylamine or containing tert-butyl with have four benzene of aggregation-induced emission performance
The multifunctional polyurethane derivative of vinyl group has following superiority in practical applications: (1) having good electrochemistry oxygen
Change reduction invertibity, is still able to maintain after tens redox cycles reversible；(2) response time of color change is fast,
After making alive, it can change colour rapidly within 2 seconds；(3) variation of color is reversible；(4) color change high sensitivity；
(5) there is higher cycle life；(6) have storing memory function, before responding after, reset condition or change can be stably maintained at
State after color can maintain several months to several years after discoloration, and color can remain unchanged length after electrochromism in this experiment
For half a year；(7) there is a preferable chemical stability in material discoloration front and back, under normal temperature and pressure, may be stabilized in air.
(8) to explosive TNT, picric acid has response, and it is 1 × 10 that picric acid and TNT, which can detect concentration,-12Mol/L, sensitivity are good.
(9) there is good electroluminescent fluorescent performance, during applying voltage, fluorescence intensity can be quenched, and fluorescent switch pair
It can reach 100 or more than degree, there is very big application potential in terms of intelligent opto-electrical and sensor.(10) there is good photoelectric respone
Ability keeps stablizing in the cyclic process of 500s.
The four benzene second present embodiment triphenylamine containing triphenylamine or the substitution containing tert-butyl and have aggregation-induced emission performance
The multifunctional polyurethane derivative of alkenyl group has the function of ten kinds.
Specific embodiment 2: present embodiment multifunctional polyurethane derivative the preparation method comprises the following steps: one, 1,2- is bis-
(4- hydroxy phenyl) -1,2- diphenylethlene and 4,4 '-'-diphenylmethane diisocyanates and solvent DMAC N,N' dimethyl acetamide
(DMAC) it mixes, is stirred at reflux 5-15h under room temperature, mixing speed is 800r/min~900r/min, obtains presoma；
Two, the diamine monomer of the triphenylamine replaced containing triphenylamine or tert-butyl is added in the presoma of step 1 preparation, is warming up to
70-120 DEG C, it is stirred at reflux 5-15h, is poured into methanol after cooling, is dried in vacuo, obtain using filter, by obtained solid formation
Multifunctional polyurethane derivative；
Bis- (4- the hydroxy phenyl) -1,2- of diamine monomer, 1,2- of the triphenylamine wherein replaced containing triphenylamine or tert-butyl
Diphenylethlene, 4,4 '-'-diphenylmethane diisocyanate molar ratios are as follows: (0.5-2.5): 1:2；
The diamine monomer of solvent DMAC N,N' dimethyl acetamide (DMAC) and the triphenylamine replaced containing triphenylamine or tert-butyl
Volume mass ratio be (10-30) mL (0.5-2.5g).
Specific embodiment 3: present embodiment is unlike specific embodiment two: it is described in step 1 containing
Diamine monomer, 1,2- bis- (4- the hydroxy phenyl) -1,2- diphenylethlenes, 4,4 '-for the triphenylamine that triphenylamine or tert-butyl replace
'-diphenylmethane diisocyanate molar ratio is 2:1:2.Other are identical with embodiment two.
Specific embodiment 4: present embodiment is unlike specific embodiment two or three: containing in step 2
Diamine monomer, 1,2- bis- (4- the hydroxy phenyl) -1,2- diphenylethlenes, 4,4 '-for the triphenylamine that triphenylamine or tert-butyl replace
'-diphenylmethane diisocyanate, solvent DMAC N,N' dimethyl acetamide (DMAC) molar ratio be 1:1:2:20.Other and specific reality
It is identical to apply mode two or three.
Specific embodiment 5: the multifunctional polyurethane derivative of present embodiment is in answering as electrochromic material
With.
Specific embodiment 6: present embodiment is unlike specific embodiment five: multifunctional polyurethane derivative
Application method as electrochromic material is: multifunctional polyurethane derivative being dissolved in organic solvent, polyurethane is obtained and spreads out
Then urethane derivative solution is carried out on electro-conductive glass film, obtains electrochromic material by biological solution；It is wherein organic
Solvent is tetrahydrofuran, chloroform, N, N '-dimethyl acetamide, N, N '-dimethylformamide or N-Methyl pyrrolidone.Other
It is identical as specific embodiment five.
Specific embodiment 7: present embodiment is containing triphenylamine and the triphenylamine and tetraphenyl ethylene group that replace containing tert-butyl
Multifunctional polyurethane derivative in the application as electroluminescent fluorescent materials.
Specific embodiment 8: present embodiment is unlike specific embodiment seven: multifunctional polyurethane derivative
Application method as electroluminescent fluorescent materials is: multifunctional polyurethane derivative being dissolved in organic solvent, polyurethane is obtained and spreads out
Then urethane derivative solution is carried out on electro-conductive glass film, obtains electroluminescent fluorescent materials by biological solution；It is wherein organic
Solvent is tetrahydrofuran, chloroform, N, N '-dimethyl acetamide, N, N '-dimethylformamide or N-Methyl pyrrolidone.Other
It is identical as specific embodiment seven.
Specific embodiment 9: present embodiment is containing triphenylamine and the triphenylamine and tetraphenyl ethylene group that replace containing tert-butyl
Application of the multifunctional polyurethane derivative as explosive detection material.
Specific embodiment 10: present embodiment is unlike specific embodiment nine: multifunctional polyurethane derivative
Application method as explosive detection are as follows: multifunctional polyurethane derivative is dissolved in organic solvent, obtains multi-functional poly- ammonia
Ester derivant solution, then the solution by tool containing explosive is added dropwise in urethane derivative solution, strong using solution fluorescence
The variation of degree whether there is explosive to detect in solution.Other are identical as specific embodiment nine.
It is 1 × 10 that picric acid and TNT, which can detect concentration, in present embodiment explosive-12Mol/L, sensitivity are good.
Beneficial effects of the present invention are verified using following embodiment:
Embodiment one: the multifunctional polyurethane derivative containing triphenylamine and tetraphenyl ethylene group the preparation method comprises the following steps: by 1,
Bis- (4- the hydroxy phenyl) -1,2- diphenylethlenes (5mmol, 0.2g) of 2- and 4,4 '-'-diphenylmethane diisocyanates (10mmol,
It 0.25g) is mixed with solvent n,N-dimethylacetamide DMAC 10mL, is stirred at reflux 10h under room temperature, mixing speed is
Then 800r/min the diamine monomer (10mmol, 0.43g) containing triphenylamine is added in previously prepared presoma, rise
Temperature is stirred at reflux 10h, pours into methanol after cooling to 80 DEG C, is dried in vacuo, is contained using filter, by obtained solid formation
The multifunctional polyurethane derivative of triphenylamine and tetraphenyl ethylene group；Its chemical structural formula are as follows:
,
The integer that n is 3~10 in formula.
Preparation method of the multifunctional polyurethane derivative containing triphenylamine and tetraphenyl ethylene group as electrochromic material
It is: the multifunctional polyurethane derivative containing triphenylamine and tetraphenyl ethylene group is dissolved in organic solvent, obtains multi-functional poly- ammonia
Then multifunctional polyurethane derivative solution is carried out film by ester derivant solution on electro-conductive glass, obtain electrochromism material
Material；Wherein organic solvent is tetrahydrofuran, chloroform, N, N '-dimethyl acetamide, N, N '-dimethylformamide or N- methyl pyrrole
Pyrrolidone.
Application method of the multifunctional polyurethane derivative containing triphenylamine and tetraphenyl ethylene group as electroluminescent fluorescent materials
It is: the multifunctional polyurethane derivative containing triphenylamine and tetraphenyl ethylene group is dissolved in organic solvent, it is derivative obtains polyurethane
Then urethane derivative solution is carried out on electro-conductive glass film, obtains electroluminescent fluorescent materials by object solution；It is wherein organic molten
Agent is tetrahydrofuran, chloroform, N, N '-dimethyl acetamide, N, N '-dimethylformamide or N-Methyl pyrrolidone.
Application method of the multifunctional polyurethane derivative containing triphenylamine and tetraphenyl ethylene group as explosive detection are as follows:
Multifunctional polyurethane derivative containing triphenylamine and tetraphenyl ethylene group is dissolved in organic solvent, multifunctional polyurethane is obtained and spreads out
Biological solution, then the solution by tool containing explosive is added dropwise in multifunctional polyurethane derivative solution, utilizes solution fluorescence
The variation of intensity whether there is explosive to detect in solution.
Multifunctional polyurethane derivative containing triphenylamine and tetraphenyl ethylene group is coated and is formed a film, its performance is surveyed
Examination:
Fig. 1 is the proton magnetic of the multifunctional polyurethane derivative containing triphenylamine and tetraphenyl ethylene group prepared by embodiment one
Spectrogram；From fig. 1, it can be seen that1H-NMR (DMSO, TMS): the peak at δ=9.4ppm is the chemical shift of the H on CO-NH, δ=6.4-
7.60ppm is the chemical shift of H on phenyl ring, it is believed that embodiment one has synthesized more function containing triphenylamine and tetraphenyl ethylene group
It can urethane derivative.
Fig. 2 is the circulation volt of the multifunctional polyurethane derivative containing triphenylamine and tetraphenyl ethylene group prepared by embodiment one
Antu；As can be seen from Figure 2, occur two oxidation peaks at 0.75V respectively, occur two reduction peaks at 0.55V；Exist respectively
Occur two oxidation peaks at 0.85V, occurs two reduction peaks at 0.62V
Fig. 3 is that the multifunctional polyurethane derivative containing triphenylamine and tetraphenyl ethylene group prepared by embodiment one is applying electricity
Stability and transmitance figure after pressure；It is multi-functional containing triphenylamine and tetraphenyl ethylene group from the figure 3, it may be seen that after application of a voltage
The transmitance of urethane derivative film still can achieve 50%, illustrate that transparency is relatively good, and apply alive process
Middle thin polymer film is able to maintain circulating ring and has good stability, and is recycled 20 times or more and transparency is constant.
Fig. 4 is the electroluminescent change of the multifunctional polyurethane derivative containing triphenylamine and tetraphenyl ethylene group prepared by embodiment one
Chromatic graph；As can be seen from Figure 4, before not applying voltage, prepared by embodiment one gathers containing triphenylamine and the multi-functional of tetraphenyl ethylene group
Urethane derivative has absorption peak at 352nm, and when applied voltage is from 0.0V to 1.6V, absorption peak is gradually increasing at 352nm,
Occur new absorption peak at 560nm, 735nm and is gradually increasing；Electrochromic color is from faint yellow to navy blue.
Fig. 5 is the electroluminescent glimmering of the multifunctional polyurethane derivative containing triphenylamine and tetraphenyl ethylene group prepared by embodiment one
Light figure；Before not applying voltage, fluorescence intensity reaches highest level, when with applied voltage by 0.0V to 1.5V, polymer
Fluorescence intensity is gradually reduced, and finally almost levels off to zero.
Fig. 6 is the thermal weight loss of the multifunctional polyurethane derivative containing triphenylamine and tetraphenyl ethylene group prepared by embodiment one
Curve graph；As can be seen from Figure 6, the multifunctional polyurethane derivative containing triphenylamine and tetraphenyl ethylene group that prepared by embodiment one is about
Start a large amount of weightlessness at 300 DEG C or so, when temperature is at 308 DEG C, weight loss 5%, when temperature is 330 DEG C, weight loss is
10%；When temperature be 367 DEG C when, weight loss 20%, when temperature reaches 800 DEG C embodiment one prepare containing electroactive three
Aniline and have aggregation-induced emission performance tetraphenyl ethylene group multifunctional polyurethane derivative carbon residual volume be 30 have compared with
Good high temperature resistance.
Fig. 7 is the multifunctional polyurethane derivative aggregation inducing containing triphenylamine and tetraphenyl ethylene group prepared by embodiment one
Luminescent effect figure；As seen from Figure 7 with the increase of the mass fraction of dampening, the fluorescence intensity of polymer is gradually increasing；Wherein a
For 80%, b 60%, c 40%, d 20%, e 0%.
Fig. 8 is the multifunctional polyurethane derivative containing triphenylamine and tetraphenyl ethylene group of the preparation of embodiment one to picric acid
The fluorogram of response；As seen from Figure 8 with the increase of bitter taste acid concentration, the fluorescence intensity of polymer solution gradually weakens.
Fig. 9 is that the multifunctional polyurethane derivative containing triphenylamine and tetraphenyl ethylene group prepared by embodiment one rings TNT
The fluorogram answered；As seen from Figure 9 with the increase of TNT concentration, the fluorescence intensity of polymer solution gradually weakens.
Figure 10 is the memory of the multifunctional polyurethane derivative containing triphenylamine and tetraphenyl ethylene group prepared by embodiment one
Performance map；As seen from Figure 10 in first time voltage scanning, from 0 to -6V (scanning 1), when negative threshold voltage is -1.0 simultaneously
And memory device observes sharply increasing for electric current when being switched to highly conductive state (ON) from low conductivity state (OFF).This
Conversion process can be used as " write-in " process of ITO/PI/Al device.During scan next time (scanning 2), electric current still in
ON state, device still keep high on state.In the third time scanning of from 0 to+6V (scanning 3), it is observed that+3.6
Threshold voltage under electric current unexpected decline, this show memory device experience from ON state to the transformation of original OFF state.It is this
Conversion from ON to OFF can be used as " erasing " process.As forward bias is applied, electric current (is swept in subsequent voltage scanning
It retouches in 4) and stills remain in low on state.Therefore, the storage equipment manufactured with PU is binary system flash memory data storage device.
Figure 11 is the multifunctional polyurethane derivative photo electric containing triphenylamine and tetraphenyl ethylene group prepared by embodiment one
It can figure；As seen from Figure 11 illumination and in the case where be protected from light polymer photoelectric properties it is sufficiently stable.
The preparation of embodiment two, the triphenylamine and the multifunctional polyurethane derivative of tetraphenyl ethylene group that replace containing tert-butyl
Method are as follows: by bis- (4- the hydroxy phenyl) -1,2- diphenylethlenes (5mmol, 0.2g) of 1,2- and 4,4 '-diphenylmethane diisocyanates
Ester (10mmol, 0.25g) is mixed with solvent n,N-dimethylacetamide DMAC 10mL, is stirred at reflux 10h under room temperature, is stirred
Mixing speed is 800r/min, and previous institute then is added in the diamine monomer (10mmol, 0.45g) of the triphenylamine replaced containing tert-butyl
In the presoma of preparation, 80 DEG C are warming up to, 10h is stirred at reflux, is poured into methanol after cooling, using filter, the solid phase that will be obtained
Object vacuum drying obtains the multifunctional polyurethane derivative of the triphenylamine and tetraphenyl ethylene group that replace containing tert-butyl；Its chemistry
Structural formula are as follows:
,
The integer that n is 3~10 in formula.
Multifunctional polyurethane containing triphenylamine and the tetraphenyl ethylene group for having aggregation-induced emission performance that tert-butyl replaces
Derivative is as the preparation method of electrochromic material: by the triphenylamine replaced containing tert-butyl and having aggregation-induced emission performance
The multifunctional polyurethane derivative of tetraphenyl ethylene group be dissolved in organic solvent, obtain urethane derivative solution, then will
Urethane derivative solution carries out film on electro-conductive glass, obtains electrochromic material；Wherein organic solvent be tetrahydrofuran,
Chloroform, N, N '-dimethyl acetamide, N, N '-dimethylformamide or N-Methyl pyrrolidone.
Multifunctional polyurethane containing triphenylamine and the tetraphenyl ethylene group for having aggregation-induced emission performance that tert-butyl replaces
Derivative is as the application method of electroluminescent fluorescent materials: by the triphenylamine replaced containing tert-butyl and having aggregation-induced emission performance
The multifunctional polyurethane derivative of tetraphenyl ethylene group be dissolved in organic solvent, obtain urethane derivative solution, then will
Urethane derivative solution carries out film on electro-conductive glass, obtains electroluminescent fluorescent materials；Wherein organic solvent be tetrahydrofuran,
Chloroform, N, N '-dimethyl acetamide, N, N '-dimethylformamide or N-Methyl pyrrolidone.
Multifunctional polyurethane containing triphenylamine and the tetraphenyl ethylene group for having aggregation-induced emission performance that tert-butyl replaces
Application method of the derivative as explosive detection are as follows: by the triphenylamine replaced containing tert-butyl and have aggregation-induced emission performance
The multifunctional polyurethane derivative of tetraphenyl ethylene group is dissolved in organic solvent, obtains urethane derivative solution, then will tool
Solution containing explosive is added dropwise in urethane derivative solution, and the variation using solution fluorescence intensity is to detect in solution
It is no that there are explosives.
The multifunctional polyurethane derivative of the triphenylamine replaced containing tert-butyl and tetraphenyl ethylene group is coated and is formed a film, to it
Performance is tested:
Figure 12 is the multifunctional polyurethane of the triphenylamine replaced containing tert-butyl and tetraphenyl ethylene group prepared by embodiment two
The hydrogen nuclear magnetic spectrogram of derivative；From fig. 1, it can be seen that1H-NMR (DMSO, TMS): the peak at δ=9.4ppm is the change of the H on CO-NH
Displacement study, δ=6.4-7.60ppm are the chemical shift of H on phenyl ring, it is believed that embodiment two has synthesized the substitution containing tert-butyl
The multifunctional polyurethane derivative of triphenylamine and the tetraphenyl ethylene group for having aggregation-induced emission performance.
Figure 13 is the multifunctional polyurethane of the triphenylamine replaced containing tert-butyl and tetraphenyl ethylene group prepared by embodiment two
The cyclic voltammogram of derivative；As can be seen from Figure 13, occur two oxidation peaks at 1.02V respectively, occur two at 0.99V
A reduction peak；Occur two oxidation peaks at 1.1V respectively, occurs two reduction peaks at 0.97V
Figure 14 is the multifunctional polyurethane of the triphenylamine replaced containing tert-butyl and tetraphenyl ethylene group prepared by embodiment two
Derivative stability after application of a voltage and transmitance figure；As shown in Figure 14, after application of a voltage, three replaced containing tert-butyl
The transmitance of aniline and the multifunctional polyurethane derivative film for the tetraphenyl ethylene group for having aggregation-induced emission performance still may be used
To reach 45%, illustrate that transparency is relatively good, and thin polymer film is able to maintain circulating ring stabilization during applying voltage
Property it is good, be recycled 20 times or more and transparency it is constant.
Figure 15 is the multifunctional polyurethane of the triphenylamine replaced containing tert-butyl and tetraphenyl ethylene group prepared by embodiment two
The electrochromism figure of derivative；From figure 15, it can be known that before not applying voltage, the triphen of the substitution containing tert-butyl prepared by embodiment two
Amine and there is the multifunctional polyurethane derivative of the tetraphenyl ethylene group of aggregation-induced emission performance to have absorption peak at 350nm, when
When applied voltage is from 0.0V to 1.6V, absorption peak is gradually increasing at 350nm, occurs new suction at 520nm, 640nm, 784nm
It receives peak and is gradually increasing；Electrochromic color is from faint yellow to navy blue.
Figure 16 is the multifunctional polyurethane of the triphenylamine replaced containing tert-butyl and tetraphenyl ethylene group prepared by embodiment two
The electroluminescent fluorescent figure of derivative；Before not applying voltage, fluorescence intensity reaches highest level, with applied voltage by 0.0V to
When 1.5V, the fluorescence intensity of polymer is gradually reduced, and finally almost levels off to zero.
Figure 17 is the multifunctional polyurethane of the triphenylamine replaced containing tert-butyl and tetraphenyl ethylene group prepared by embodiment two
The thermogravimetric curve figure of derivative；As can be seen from Figure 17, the triphenylamine and tetraphenyl ethylene replaced containing tert-butyl prepared by embodiment two
The multifunctional polyurethane derivative of group about starts a large amount of weightlessness at 300 DEG C or so, when temperature is 336；5% DEG C of weight loss
When, weight loss 5%, when temperature is 351 DEG C；When weight loss 10%, weight loss 10%；The implementation when temperature reaches 800 DEG C
The multi-functional poly- ammonia of the triphenylamine replaced containing tert-butyl and the tetraphenyl ethylene group for having aggregation-induced emission performance prepared by example one
Ester derivant carbon residual volume is 30%, has preferable high temperature resistance.
Figure 18 is the multifunctional polyurethane of the triphenylamine replaced containing tert-butyl and tetraphenyl ethylene group prepared by embodiment two
Derivative aggregation-induced emission effect figure；As seen from Figure 18 with the increase of the mass fraction of dampening, the fluorescence of polymer is strong
Degree is gradually increasing；Wherein a is 80%, b 60%, c 40%, d 20%, e 0%.
Figure 19 is the multifunctional polyurethane of the triphenylamine replaced containing tert-butyl and tetraphenyl ethylene group prepared by embodiment two
The fluorogram that derivative responds picric acid；As seen from Figure 19 with the increase of bitter taste acid concentration, polymer solution it is glimmering
Luminous intensity gradually weakens.
Figure 20 is the multifunctional polyurethane of the triphenylamine replaced containing tert-butyl and tetraphenyl ethylene group prepared by embodiment two
The fluorogram that derivative responds TNT；As seen from Figure 20 with the increase of TNT concentration, the fluorescence intensity of polymer solution
Gradually weaken.
Figure 21 is the multifunctional polyurethane of the triphenylamine replaced containing tert-butyl and tetraphenyl ethylene group prepared by embodiment two
The memory performance figure of derivative；As seen from Figure 21 in first time voltage scanning, from 0 to -6V (scanning 1), work as negative threshold value
Voltage is that -1.2V and memory device observe electric current when being switched to highly conductive state (ON) from low conductivity state (OFF)
It sharply increases.This conversion process can be used as " write-in " process of ITO/PI/Al device.(the scanning during scan next time
2), electric current still keeps high on state still in ON state, device.In the third time scanning of from 0 to+6V (scanning 3), we
Observe the unexpected decline of the electric current under the threshold voltage of+3.2V, this shows memory device experience from ON state to original OFF shape
The transformation of state.This conversion from ON to OFF can be used as " erasing " process.As forward bias is applied, electric current is subsequent
Voltage scanning (scanning 4) in still remain in low on state.Therefore, the storage equipment manufactured with PU is binary system flash memory number
According to storage equipment.
Figure 22 is the multifunctional polyurethane of the triphenylamine replaced containing tert-butyl and tetraphenyl ethylene group prepared by embodiment two
Derivative photoelectric properties figure；As seen from Figure 22 illumination and in the case where be protected from light polymer photoelectric properties it is sufficiently stable.
Test multifunctional polyurethane derivative containing triphenylamine and the tetraphenyl ethylene group for having aggregation-induced emission performance and
The dissolubility of the multifunctional polyurethane derivative of the triphenylamine and tetraphenyl ethylene group that replace containing tert-butyl, the results are shown in Table 1,
As shown in Table 1, the multifunctional polyurethane containing triphenylamine Yu the tetraphenyl ethylene group for having aggregation-induced emission performance of the present embodiment
The multifunctional polyurethane derivative of the triphenylamine and tetraphenyl ethylene group of derivative and the substitution containing tert-butyl has good dissolution
Property.
Table 1
By the test of embodiment one and two it is found that will there is the present embodiment the triaryl amine group for destroying bulk property to introduce poly- ammonia
In ester structure, it is not only able to maintain the high thermal stability of original polyurethane, but also being capable of increasing its solubility enhances film forming ability,
This is not only advantageous to the film electrochromic device of manufacture large area, additionally provides electric activity center to promote electrochromic device
Processing and application；Containing there are four the tetraphenyl ethylene of rotatable phenyl ring (TPE) due to its aggregation inducing transmitting (AIE) activity and obtain
Sufficient development is arrived.TPE derivative can overcome the problems, such as that (ACQ) is quenched caused by the aggregation of conventional organic luminescence body, this pole
The earth promotes it in bioprobe, the various applications of chemical sensitisation and photoelectric device.Polyurethane manufactured in the present embodiment is derivative
The strong effect power between polymer molecular chain can be effectively reduced using the triaryl amine of propeller type as monomer in object, increases poly-
The dissolubility of object is closed, while triaryl amine is easily formed radical cation and shows triaryl amine different from middle condition.This implementation
More function containing triphenylamine or the triphenylamine and the tetraphenyl ethylene group for having aggregation-induced emission performance that replace containing tert-butyl in example
Energy urethane derivative has very high performance resistant to high temperature, and generally under the atmosphere of nitrogen, decomposition temperature is fitted at 350 DEG C or more
Conjunction uses in the devices.By triphenylamine that the present embodiment replaces containing triphenylamine or containing tert-butyl and there is aggregation-induced emission performance
Film is made in the multifunctional polyurethane derivant material of tetraphenyl ethylene group, does not have big clustering phenomena on ITO substrate and breaks
Broken phenomenon also shows good wet ability on ITO substrate.This means that multifunctional polyurethane derivant material has well
Film Formation and characteristics, can be used to make the film of large area.After application of a voltage, the transmitance of film still can achieve
50%, transparency is relatively good, and thin polymer film is able to maintain circulating ring and has good stability during applying voltage, can follow
Ring 20 times or more and transparency it is constant.
The multifunctional polyurethane containing triphenylamine and the triphenylamine and tetraphenyl ethylene group that replace containing tert-butyl of the present embodiment
Derivative has following superiority in practical applications: (1) having good electrochemical redox invertibity, by tens times
It is still able to maintain after redox cycle reversible；(2) response time of color change is fast, after making alive, within 2 seconds i.e.
It can change colour rapidly；(3) variation of color is reversible；(4) color change high sensitivity；(5) there is higher cycle life；(6)
Have storing memory function, before responding after, can be stably maintained at reset condition or discoloration after state, can be tieed up after discoloration
It holds several months to several years, color can be remained unchanged up to as long as half a year after electrochromism in this experiment；(7) before material discoloration
After have a preferable chemical stability, under normal temperature and pressure, may be stabilized in air.(8) to explosive TNT, picric acid has
Response.(9) there is good electroluminescent fluorescent performance, during applying voltage, fluorescence intensity can be quenched, and fluorescence is opened
Closing contrast can reach 100 or more, there is very big application potential in terms of intelligent opto-electrical and sensor.(10) there is good photoelectricity
Responding ability keeps stablizing in the cyclic process of 500s.
In conclusion multifunctional polyurethane derivative prepared by embodiment one and two has the function of ten kinds, function has been prepared
It can the more multifunctional material of type.
Claims (9)
1. a kind of multifunctional polyurethane derivative, it is characterised in that multifunctional polyurethane derivative is containing triphenylamine and tetraphenyl ethylene
The multifunctional polyurethane of the multifunctional polyurethane derivative of group or the triphenylamine and tetraphenyl ethylene group of the substitution containing tert-butyl spreads out
Biology；
Structural formula wherein containing triphenylamine and the multifunctional polyurethane derivative of tetraphenyl ethylene group is as follows:
The integer that n is 3~10 in formula；
The structural formula of the triphenylamine and the multifunctional polyurethane derivative of tetraphenyl ethylene group of the substitution containing tert-butyl is as follows:
,
The integer that n is 3~10 in formula.
2. the method for preparing multifunctional polyurethane derivative as described in claim 1, it is characterised in that this method are as follows: one, general
Bis- (4- the hydroxy phenyl) -1,2- diphenylethlenes of 1,2-, 4,4 '-'-diphenylmethane diisocyanates and solvent N, N- dimethylacetamide
Amine mixing is stirred at reflux 5-15h under room temperature, and mixing speed is 800r/min~900r/min, obtains presoma；Two, will
The diamine monomer of triphenylamine containing triphenylamine or tert-butyl substitution is added in the presoma of step 1 preparation, is warming up to 70-120
DEG C, it is stirred at reflux 5-15h, is poured into methanol after cooling, using filter, obtained solid formation is dried in vacuo, is obtained multi-functional
Urethane derivative；
Bis- (4- the hydroxy phenyl) -1,2- hexichol of diamine monomer, 1,2- of the triphenylamine wherein replaced containing triphenylamine or tert-butyl
Base ethylene, 4,4 '-'-diphenylmethane diisocyanate molar ratios are as follows: (0.5-2.5): 1:2；
Solvent DMAC N,N' dimethyl acetamide and the volume mass ratio of the triphen amine monomers containing triphenylamine or tert-butyl substitution are
(10-30)mL:(0.5-2.5)g。
3. a kind of preparation method of multifunctional polyurethane derivative according to claim 2, it is characterised in that contain triphenylamine
Or triphen amine monomers, bis- (4- the hydroxy phenyl) -1,2- diphenylethlenes of 1,2- and the 4,4 '-diphenyl-methanes two that tert-butyl replaces are different
The molar ratio of cyanate are as follows: 2:1:2.
4. a kind of application of multifunctional polyurethane derivative as described in claim 1, it is characterised in that multifunctional polyurethane spreads out
Application of the biology as electrochromic material.
5. a kind of application of multifunctional polyurethane derivative according to claim 4, it is characterised in that multifunctional polyurethane
Derivative is as the application method of electrochromic material: multifunctional polyurethane derivative being dissolved in organic solvent, is gathered
Then urethane derivative solution is carried out on electro-conductive glass film, obtains electrochromic material by urethane derivative solution；Its
Middle organic solvent is tetrahydrofuran, chloroform, N, N '-dimethyl acetamide, N, N '-dimethylformamide or N- crassitude
Ketone.
6. a kind of application of multifunctional polyurethane derivative as described in claim 1, it is characterised in that multifunctional polyurethane spreads out
Application of the biology as electroluminescent fluorescent materials.
7. a kind of application of multifunctional polyurethane derivative according to claim 6, it is characterised in that multifunctional polyurethane
Derivative is as the application method of electroluminescent fluorescent materials: multifunctional polyurethane derivative being dissolved in organic solvent, is gathered
Then urethane derivative solution is carried out on electro-conductive glass film, obtains electroluminescent fluorescent materials by urethane derivative solution；Its
Middle organic solvent is tetrahydrofuran, chloroform, N, N '-dimethyl acetamide, N, N '-dimethylformamide or N- crassitude
Ketone.
8. a kind of application of multifunctional polyurethane derivative as described in claim 1, it is characterised in that multifunctional polyurethane spreads out
Application of the biology as explosive detection material.
9. a kind of application of multifunctional polyurethane derivative according to claim 8, it is characterised in that multifunctional polyurethane
Application method of the derivative as explosive detection are as follows: multifunctional polyurethane derivative is dissolved in organic solvent, obtains poly
Urethane derivative solution, then the solution by tool containing explosive is added dropwise in urethane derivative solution, utilizes solution fluorescence
The variation of intensity whether there is explosive to detect in solution.
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