CN105778045B - Polyurethane material and its preparation method and application with electrochromic property - Google Patents

Polyurethane material and its preparation method and application with electrochromic property Download PDF

Info

Publication number
CN105778045B
CN105778045B CN201610264711.9A CN201610264711A CN105778045B CN 105778045 B CN105778045 B CN 105778045B CN 201610264711 A CN201610264711 A CN 201610264711A CN 105778045 B CN105778045 B CN 105778045B
Authority
CN
China
Prior art keywords
polyurethane
electrochromic property
triphenylamine
preparation
polyurethane material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201610264711.9A
Other languages
Chinese (zh)
Other versions
CN105778045A (en
Inventor
赵九蓬
张坤
李垚
马晓轩
王月敏
强亮生
李新刚
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Harbin Institute of Technology
Original Assignee
Harbin Institute of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Harbin Institute of Technology filed Critical Harbin Institute of Technology
Priority to CN201610264711.9A priority Critical patent/CN105778045B/en
Publication of CN105778045A publication Critical patent/CN105778045A/en
Application granted granted Critical
Publication of CN105778045B publication Critical patent/CN105778045B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72Polyisocyanates or polyisothiocyanates
    • C08G18/77Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78Nitrogen
    • C08G18/785Nitrogen containing tertiary amino groups
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/02Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C263/00Preparation of derivatives of isocyanic acid
    • C07C263/10Preparation of derivatives of isocyanic acid by reaction of amines with carbonyl halides, e.g. with phosgene
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C265/00Derivatives of isocyanic acid
    • C07C265/12Derivatives of isocyanic acid having isocyanate groups bound to carbon atoms of six-membered aromatic rings
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30Low-molecular-weight compounds
    • C08G18/32Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203Polyhydroxy compounds
    • C08G18/3215Polyhydroxy compounds containing aromatic groups or benzoquinone groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30Low-molecular-weight compounds
    • C08G18/38Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3802Low-molecular-weight compounds having heteroatoms other than oxygen having halogens
    • C08G18/3804Polyhydroxy compounds
    • C08G18/3812Polyhydroxy compounds having fluorine atoms
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30Low-molecular-weight compounds
    • C08G18/38Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3855Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
    • C08G18/3863Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms
    • C08G18/3865Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms
    • C08G18/3872Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms the sulfur atom belonging to a sulfoxide or sulfone group
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K9/00Tenebrescent 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
    • C09K9/02Organic tenebrescent materials
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04Polyurethanes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14Macromolecular compounds
    • C09K2211/1408Carbocyclic compounds
    • C09K2211/1433Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B

Abstract

Polyurethane material and its preparation method and application with electrochromic property, the present invention relates to the polyurethane materials and preparation method thereof with electrochromic property, it is not readily dissolved to solve conventional polyurethanes, it is difficult to process and not have the problem of electrochromic property.Preparation method:One, methyl oxyaniline and four fluoronitrobenzenes will be added in dimethyl sulfoxide solvent, reaction prepares methoxyl group dinitro triphenylamine;Two, reduction dinitro triphenylamine obtains diamino triphenylamine;Three, isocyanates is prepared;Four, isocyanates and aromatic bisphenols monomer are added in dimethylformamide, prepare polyurethane;Five, drying obtains polyurethane film.Using being that gel electrolyte solution is applied between polyurethane film and ion storage layer, the polyurethane device with electrochromic property is obtained after encapsulation.The present invention realizes the processing dissolubility of polyurethane and reversible electrochromic property by introducing triphenylamine into polyurethane material.

Description

Polyurethane material and its preparation method and application with electrochromic property
Technical field
The present invention relates to a kind of polyurethane material and preparation method thereof with electrochromic property, and apply the polyurethane Material is assembled into electrochromic device.
Background technology
Metachromatism is prevalent in nature, such as chameleon, its skin color usually with the variation of environment and It changes.The material of different colours variation can be realized by applying different voltages by being developed according to this phenomenon people, i.e., Electrochromic material.Electrochromic material is because having good optics, electricity, electrochemical properties to be known as most having application prospect One of intellectual material.Now, electrochromic material development is swift and violent, is more and more widely used in every field, such as display, Smart window, anti-dazzle glasses, the fields such as sensor.Electrochromic material includes inorganic electrochromic material, organic electrochromic material Material and conducting polymer etc..Wherein conducting polymer has color change rich colors gorgeous, and cyclic reversibility is good, conversion speed The advantages that fast.
Polyurethane is known as " the fifth-largest plastics ", in daily life as a kind of emerging high-molecular organic material It is widely used, can be applied to plastic products, adhesive, the fields such as fabric coating.High forces to polymerize between polymer molecule Object is difficult dissolving or melting, this brings prodigious puzzlement to the processing and forming of polymer.
Long alkyl group or side chain are introduced on the main chain of polymer can change this disadvantage, but polymer is made to lose Stability is gone.Triphenylamine derivative group is a stable spiral pulpous state group with electrochromic property, it is drawn Enter to make in the main chain of polymer the solvable easy processing of polymer, while polymer electrochromic performance can be assigned again.
Invention content
The purpose of the present invention is to solve conventional polyurethanes to not readily dissolve, it is difficult to process and not have electrochromism The problem of energy, and a kind of preparation method and applications of the polyurethane material with electrochromic property are provided.
There is the present invention structural formula of polyurethane material of electrochromic property to beWherein R represents the repetitive unit after biphenol monomer polycondensation, corresponding Biphenol monomer is:
N in structure of the invention formula is the positive integer between 10~30.
There is the present invention preparation method of the polyurethane material of electrochromic property to follow these steps to realize:
One, methyl oxyaniline and four fluoronitrobenzenes will be added in dimethyl sulfoxide solvent, and will be passed through N2, at 70~190 DEG C At a temperature of react 1~2 day, washed after filtering, drying obtain methoxyl group dinitro triphenylamine (solid product);
Two, the Pd/C of methoxyl group dinitro triphenylamine and 5wt.% is put into reaction vessel, absolute ethyl alcohol and water is added Hydrazine reagent is closed, 20~40h is reacted at a temperature of 70~150 DEG C, cold filtration removes Pd/C, has solid powder analysis in filtrate Go out, then recrystallized using acetone, obtains diamino triphenylamine;
Three, the triphosgene of the diamino triphenylamine of 0.5~2g and 1~5g is put into reaction vessel, toluene reagent is added, At 0~5 DEG C stir 1~5h, then heat to 80~150 DEG C react 1~3 day, filtering, obtained after drying isocyanates (Gu Body product);
Four, it is 0.5~1.5 according to molar ratio:1 isocyanates and the mixture of aromatic bisphenols monomer are added to dimethyl In formamide, 10~30h is reacted at a temperature of 120~150 DEG C, importing in methanol has the precipitation of solid phase body, and filtering, is dried at purification Polyurethane is obtained after dry;
Five, polyurethane is dissolved in dimethylformamide, is then spin coated onto on conductive ITO/glass, is obtained after vacuum drying Polyurethane film;
It is 0.1~0.9 to the molar ratio of methyl oxyaniline and four fluoronitrobenzenes wherein in step 1:1;It is fragrant described in step 4 Biphenol monomer is 4,4'- (hexafluoro isopropyl) bis-phenol, 4,4' dihydroxydiphenyl sulfone or 4,4'- dihydroxy benaophenonels.
The present invention have the application of the polyurethane material of electrochromic property be the lithium perchlorate of 1~15g is dissolved in 20~ Then 150ml carbonic allyl ester solutions are added the polymethyl methacrylate of 1~10g, stir evenly, obtain gel electrolyte Gel electrolyte solution is applied between polyurethane film and ion storage layer by solution, is obtained with electrochromism after encapsulation The polyurethane device of energy.
Polyurethane material prepared by the present invention, which can make up conventional polyurethanes, cannot change colour, not readily dissolves and be difficult to The shortcomings of, realize the processing dissolubility of polyurethane and reversible electrochromic property.Its electrochromism invertibity mechanism be due to After applying positive voltage, the nitrogen-atoms in triphenylamine loses the oxidation state triphenylamine that electronics becomes positive monovalence;When applying negative voltage, oxygen The triphenylamine of change state obtains electronics and is restored to reduction-state;The different valence state of oxidized and reduced corresponds to different colors.
It is (different by adding different voltage to obtain that electrochromism spectrum test is carried out to the polyurethane film that the present invention obtains Ultraviolet figure), heretofore described polyurethane absorption peak changes with the raising of voltage.Between 400~800nm Peak gradually rises with the raising of current potential, and the color of polymer is from yellow to blue-green, it was demonstrated that the polyurethane can occur electroluminescent Metachromatism.
Description of the drawings
Fig. 1 is the IR Characterization figure of the isocyanates and three kinds of polyurethane of embodiment one;
Fig. 2 is the structural schematic diagram of the polyurethane device obtained in Application Example, wherein 1-glass, 2-ITO, 3- Polyurethane film, 4-gel electrolytes, 5-ion storage layers, 6-epoxy resin;
Fig. 3 is the cyclic voltammogram of polyurethane film a;
Fig. 4 is the electrochromism collection of illustrative plates of polyurethane film a.
Specific implementation mode
Specific implementation mode one:Present embodiment has the preparation method of the polyurethane material of electrochromic property by following Step is implemented:
One, it is 0.1~0.9 in molar ratio:1 will be added to dimethyl sulfoxide solvent to methyl oxyaniline and four fluoronitrobenzenes In, it is passed through N2, react 1~2 day at a temperature of 70~190 DEG C, washed after filtering, drying obtains methoxyl group dinitro triphenylamine (solid product);
Two, the Pd/C of methoxyl group dinitro triphenylamine and 5wt.% is put into reaction vessel, absolute ethyl alcohol and water is added Hydrazine reagent is closed, 20~40h is reacted at a temperature of 70~150 DEG C, cold filtration removes Pd/C, has solid powder analysis in filtrate Go out, then recrystallized using acetone, obtains diamino triphenylamine;
Three, the triphosgene of the diamino triphenylamine of 0.5~2g and 1~5g is put into reaction vessel, toluene reagent is added, At 0~5 DEG C stir 1~5h, then heat to 80~150 DEG C react 1~3 day, filtering, obtained after drying isocyanates (Gu Body product);
Four, it is 0.5~1.5 according to molar ratio:1 isocyanates and the mixture of aromatic bisphenols monomer are added to dimethyl In formamide, 10~30h is reacted at a temperature of 120~150 DEG C, importing in methanol has the precipitation of solid phase body, and filtering, is dried at purification Polyurethane is obtained after dry;
Five, polyurethane is dissolved in dimethylformamide, is then spin coated onto on conductive ITO/glass, is obtained after vacuum drying Polyurethane film;
Wherein aromatic bisphenols monomer described in step 4 be 4,4'- (hexafluoro isopropyl) bis-phenol, 4,4' dihydroxydiphenyl sulfone or 4,4'- dihydroxy benaophenonels.
Present embodiment has synthesized three kinds of new polyurethanes, has synthesized a kind of new isocyanate first, has contained triphenylamine Then its dihydroxylic reaction different with 3 kinds is generated polyurethane by derivatives group-methyl triphenylamine.Polyurethane is carried out The characterizations such as infrared, nuclear-magnetism, and to its electrochromism property, stability, spectral characteristic is tested.Polyurethane film is carried out Cyclic voltammetry, voltage range are 0~2V;Its oxidizing potential, reduction potential are about 0.9~1.1V and 0.5~0.8V, color Respectively yellow and blue-green.
Specific implementation mode two:The present embodiment is different from the first embodiment in that dimethyl sulfoxide (DMSO) is molten in step 1 The molar concentration of four fluoronitrobenzenes is 1~4mol/L in agent.Other steps and parameter are same as the specific embodiment one.
Specific implementation mode three:The present embodiment is different from the first and the second embodiment in that methoxyl group two in step 2 The mass ratio of the Pd/C of nitrotrianiline and 5wt.% are (0.5~3):(0.5~2).Other steps and parameter and specific implementation Mode one or two is identical.
Specific implementation mode four:Step 2 is at 80 DEG C unlike one of present embodiment and specific implementation mode one to three At a temperature of react 20h.Other steps and parameter are identical as one of specific implementation mode one to three.
Specific implementation mode five:Step 3 uses rope unlike one of present embodiment and specific implementation mode one to four Family name's extractor purifies 30~50h of polyurethane.Other steps and parameter are identical as one of specific implementation mode one to four.
Specific implementation mode six:Step 5 dimethyl unlike one of present embodiment and specific implementation mode one to five A concentration of 0.1~1g/ml of polyurethane in formamide.Other steps and parameter are identical as one of specific implementation mode one to five.
Specific implementation mode seven:Poly- ammonia in step 5 unlike one of present embodiment and specific implementation mode one to six The thickness of ester film is 1~10 μm.Other steps and parameter are identical as one of specific implementation mode one to six.
Specific implementation mode eight:It is by 1~15g that present embodiment, which has the application of the polyurethane material of electrochromic property, Lithium perchlorate be dissolved in 20~150ml carbonic allyl ester solutions, the polymethyl methacrylate of 1~10g is then added, stirring is equal It is even, gel electrolyte solution is obtained, gel electrolyte solution is applied between polyurethane film and ion storage layer, after encapsulation To the polyurethane device with electrochromic property.
Specific implementation mode nine:The lithium perchlorate of 10g is dissolved in by present embodiment unlike specific implementation mode eight Then 100ml carbonic allyl ester solutions are added the polymethyl methacrylate of 6g, stir evenly, obtain gel electrolyte solution, Gel electrolyte solution is applied between polyurethane film and ion storage layer, the both sides epoxy resin of gel electrolyte solution Edge sealing obtains the polyurethane device with electrochromic property after encapsulation.
Present embodiment, by two layers of electrode edge sealing, influences to survey by epoxy resin to prevent gel electrolyte from volatilizing or flow out Try effect.
Embodiment one:There is the present embodiment the preparation method of the polyurethane material of electrochromic property to follow these steps reality It applies:
One, it is 1 in molar ratio:2 will be added in dimethyl sulfoxide solvent methyl oxyaniline and four fluoronitrobenzenes, be passed through N2, react 1 day at a temperature of 120 DEG C, washed after filtering, drying obtains methoxyl group dinitro triphenylamine (solid product);
Two, the Pd/C of 1.4g methoxyl group dinitro triphenylamines and 0.5g 5wt.% is put into there-necked flask, 100ml is added Absolute ethyl alcohol and 5ml are hydrated hydrazine reagent, and 20h is reacted at a temperature of 80 DEG C, and cold filtration removes Pd/C, has solid powder in filtrate End is precipitated, and is then recrystallized using acetone, the dinitro triphenylamine restored i.e. diamino triphenylamine;
Three, the triphosgene of the diamino triphenylamine of 1.45g and 1g is put into there-necked flask, the toluene reagent of 20ml is added, 2h is stirred at 0 DEG C, 100 DEG C is then heated to and reacts 1 day, filtering obtains isocyanates (solid product) after drying;
Four, it is 1 according to molar ratio:1 isocyanates and the mixture of aromatic bisphenols monomer are added to dimethylformamide In, 10h is reacted at a temperature of 120 DEG C, importing in methanol has the precipitation of solid phase body, and (Soxhlet extractor purifies poly- ammonia for filtering, purification Ester about 50h), drying after obtain polyurethane;
Five, 0.1g polyurethane is dissolved in 3ml dimethylformamides, is then spin coated onto on conductive ITO/glass, vacuum drying After obtain polyurethane film.
The present embodiment step 4 aromatic bisphenols monomer is respectively 4,4'- (hexafluoro isopropyl) bis-phenol, 4,4'- dihydroxy hexichol When sulfone, 4,4'- dihydroxy benaophenonels, IR Characterization figure such as Fig. 1 institutes of the polyurethane a, polyurethane b, polyurethane c that respectively obtain Show, d represents isocyanates in figure, and a represents polyurethane a, and b represents polyurethane b, c and represents polyurethane c.
Application Example:The lithium perchlorate of 10g is dissolved in 100ml carbonic allyl ester solutions, the poly- methyl of 6g is then added Methyl acrylate stirs evenly, and obtains gel electrolyte solution, and gel electrolyte solution is applied to polyurethane film a and ion The polyurethane device with electrochromic property is obtained between storage layer, after encapsulation.
The structure chart for the polyurethane device that the present embodiment obtains is as shown in Figure 2.
Cyclic voltammetry is carried out to the present embodiment polyurethane film, cyclic voltammogram is as shown in figure 3, voltage range is 0 ~1.5V;Its oxidizing potential, reduction potential are about 1.1V and 0.6V, and color is yellow and blue-green.Electrochromism collection of illustrative plates such as Fig. 4 Shown, the polyurethane absorption peak in the present embodiment changes with the raising of voltage.Peak between 400~800nm with The raising of current potential and gradually rise, the color of polymer is from yellow to blue-green, it was demonstrated that the polyurethane occur electrochromism phenomenon.

Claims (9)

1. the polyurethane material with electrochromic property, it is characterised in that should be with the polyurethane material of electrochromic property Structural formula isWherein R represents the repetition list after biphenol monomer polycondensation Member, corresponding biphenol monomer are:
N wherein in structural formula is the positive integer between 10~30.
2. as described in claim 1 with electrochromic property polyurethane material preparation method, it is characterised in that be by The following steps are realized:
One, methyl oxyaniline and 4- fluoronitrobenzenes will be added in dimethyl sulfoxide solvent, and will be passed through N2, in 70~190 DEG C of temperature Lower reaction 1~2 day, is washed after filtering, and drying obtains methoxyl group dinitro triphenylamine;
Two, the Pd/C of methoxyl group dinitro triphenylamine and 5wt.% is put into reaction vessel, absolute ethyl alcohol and hydrazine hydrate is added Reagent, reacts 20~40h at a temperature of 70~150 DEG C, and cold filtration removes Pd/C, has solid powder precipitation in filtrate, so It is recrystallized afterwards using acetone, obtains methoxyl group diamino triphenylamine;
Three, the triphosgene of the methoxyl group diamino triphenylamine of 0.5~2g and 1~5g is put into reaction vessel, toluene examination is added 1~5h is stirred in agent at 0~5 DEG C, is then heated to 80~150 DEG C and is reacted 1~3 day, and filtering obtains isocyanates after drying;
Four, it is 0.5~1.5 according to molar ratio:1 isocyanates and the mixture of aromatic bisphenols monomer are added to dimethyl formyl In amine, 10~30h is reacted at a temperature of 120~150 DEG C, importing in methanol has the precipitation of solid phase body, after filtering, purification, drying Obtain polyurethane;
Five, polyurethane is dissolved in dimethylformamide, is then spin coated onto in obtaining poly- ammonia on conductive ITO/glass, after vacuum drying Ester film;
It is 0.1~0.9 to the molar ratio of methyl oxyaniline and 4- fluoronitrobenzenes wherein in step 1:1;Aromatic bisphenols described in step 4 Monomer is 4,4 '-(hexafluoro isopropyl) bis-phenols, 4,4 '-dihydroxydiphenylsulisomers or 4,4 '-dihydroxy benaophenonels.
3. the preparation method of the polyurethane material according to claim 2 with electrochromic property, it is characterised in that step The molar concentration of 4- fluoronitrobenzenes is 1~4mol/L in dimethyl sulfoxide solvent in rapid one.
4. the preparation method of the polyurethane material according to claim 2 with electrochromic property, it is characterised in that step The mass ratio of the Pd/C of methoxyl group dinitro triphenylamine and 5wt.% are (0.5~3) in rapid two:(0.5~2).
5. the preparation method of the polyurethane material according to claim 2 with electrochromic property, it is characterised in that step Rapid two react 20h at a temperature of 80 DEG C.
6. the preparation method of the polyurethane material according to claim 2 with electrochromic property, it is characterised in that step A concentration of 0.1~1g/ml of polyurethane in rapid five dimethylformamide.
7. the preparation method of the polyurethane material according to claim 2 with electrochromic property, it is characterised in that step The thickness of polyurethane film is 1~10 μm in rapid five.
8. the application of the polyurethane material with electrochromic property as described in claim 1, it is characterised in that be by 1~ The lithium perchlorate of 15g is dissolved in 20~150ml carbonic allyl ester solutions, and the polymethyl methacrylate of 1~10g is then added, stirs It mixes uniformly, obtains gel electrolyte solution, gel electrolyte solution is applied between polyurethane film and ion storage layer, encapsulate The polyurethane device with electrochromic property is obtained afterwards.
9. the application of the polyurethane material according to claim 8 with electrochromic property, it is characterised in that by 10g's Lithium perchlorate is dissolved in 100ml carbonic allyl ester solutions, and the polymethyl methacrylate of 6g is then added, stirs evenly, is coagulated Glue electrolyte solution, gel electrolyte solution is applied between polyurethane film and ion storage layer, gel electrolyte solution Both sides epoxy resin edge sealing obtains the polyurethane device with electrochromic property after encapsulation.
CN201610264711.9A 2016-04-25 2016-04-25 Polyurethane material and its preparation method and application with electrochromic property Active CN105778045B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610264711.9A CN105778045B (en) 2016-04-25 2016-04-25 Polyurethane material and its preparation method and application with electrochromic property

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610264711.9A CN105778045B (en) 2016-04-25 2016-04-25 Polyurethane material and its preparation method and application with electrochromic property

Publications (2)

Publication Number Publication Date
CN105778045A CN105778045A (en) 2016-07-20
CN105778045B true CN105778045B (en) 2018-09-07

Family

ID=56399541

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610264711.9A Active CN105778045B (en) 2016-04-25 2016-04-25 Polyurethane material and its preparation method and application with electrochromic property

Country Status (1)

Country Link
CN (1) CN105778045B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110982064B (en) * 2019-12-23 2022-05-03 黑龙江大学 Triarylamine polyamide containing fused ring anthracenyl side group structure and preparation method and application thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102702461B (en) * 2012-05-24 2013-12-25 黑龙江大学 Polyurethane with electrochromism performance and preparation method thereof
CN102675589B (en) * 2012-05-24 2013-08-07 黑龙江大学 Electrochromatic material made of isocyanate-triphenylamine and method for preparing electrochromatic material
CN104610544A (en) * 2015-02-16 2015-05-13 哈尔滨工业大学 Preparation method of thermal-control polyimide material and method for preparing devices from material
CN104877100B (en) * 2015-05-21 2017-10-10 黑龙江大学 A kind of polyurethane containing triaryl amine and its preparation method and application

Also Published As

Publication number Publication date
CN105778045A (en) 2016-07-20

Similar Documents

Publication Publication Date Title
CN103469272B (en) Tungsten trioxide/polyanilinecore-shell core-shell nanowire array radiochromic film and preparation method thereof
CN102352109B (en) Organic-inorganic composite electrochromic film and preparation method thereof
CN106543415B (en) Thin polymer film and the preparation method and application thereof based on intersection construction conjugated molecule
CN101824145B (en) Electrochromic conducting polymer and preparation method as well as application thereof
WO2019014370A9 (en) Electrochromic polymer and synthesis and uses thereof
CN110592609B (en) Method for improving cycling stability of polymer electrochromic film
CN109683416B (en) Double-color adjustable electrochromic thin film device
CN114907551B (en) Red electrochromic polymer, preparation method, film and device
CN110928095A (en) Dual electrochromic layer device capable of realizing conversion between any colors and assembling method
CN110716360B (en) High-performance all-solid-state polymer electrochromic device and preparation method thereof
Zeng et al. Benzodifuranone based color-changing epoxy-polyamine coating
Zhu et al. Multicolored and high contrast electrochromic devices based on viologen derivatives with various substituents
CN105778045B (en) Polyurethane material and its preparation method and application with electrochromic property
Ye et al. Multicolored and high optical contrast flexible electrochromic devices based on viologen derivatives
CN108957895A (en) Acid-base response electrochomeric films, preparation method and application and electrochromic device
CN110501852B (en) Electrochromic device based on high-concentration aqueous electrolyte and preparation method thereof
CN112898543B (en) Thiophene polymer film and preparation method and application thereof
Cao et al. Hyperbranched and viologen-functionalized polyglycerols: preparation, photo-and electrochromic performance
Qian et al. High-contrast energy-efficient flexible electrochromic devices based on viologen derivatives and their application in smart windows and electrochromic displayers
JP2023512976A (en) Electrochromic device and method of discoloration thereof
CN106831545B (en) A kind of multicoloured electrochromic material of four-membered ring pyridine based on different substituents
CN110713493B (en) Electrochemical polymerization preparation and application of triphenylamine derivative conjugated polymer material
Meng Organic Electronics for Electrochromic Materials and Devices
CN104829817B (en) A kind of aromatic polyester containing triphenylamine and its preparation method and application
CN102675580B (en) Electrochromatic epoxy resin polymer and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant