CN105778045A - Polyurethane material with electrochromic property as well as preparation method and application of polyurethane material - Google Patents
Polyurethane material with electrochromic property as well as preparation method and application of polyurethane material Download PDFInfo
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- 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
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- C07C213/02—Preparation 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
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- 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
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- 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
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3802—Low-molecular-weight compounds having heteroatoms other than oxygen having halogens
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3863—Low-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
- C08G18/3865—Low-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
- C08G18/3872—Low-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
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
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Abstract
The invention provides a polyurethane material with an electrochromic property as well as a preparation method and application of the polyurethane material, relates to the polyurethane material with the electrochromic property and the preparation method of the polyurethane material, and aims to solve the problems that common polyurethane is not liable to dissolve and difficult to process and does not have the electrochromic property. The preparation method comprises the following steps: I, adding p-Anisidine and 1-fluoro-4-nitrobenzene into a dimethyl sulfoxide solvent, and performing a reaction so as to prepare methoxyl dinitro triphenylamine; II, reducing the methoxyl dinitro triphenylamine, so as to obtain diamino triphenylamine; III, preparing isocyanate; IV, adding the isocyanate and an aromatic bisphenol monomer into dimethyl formamide, and preparing polyurethane; V, performing drying so as to obtain a polyurethane film. The polyurethane material is applied in such a way that a gel electrolytic solution is applied between the polyurethane film and an ion storing layer, and after encapsulation is performed, a polyurethane device with the electrochromic property is obtained. According to the polyurethane material, as well as the preparation method and the application thereof disclosed by the invention, triphenylamine is introduced into the polyurethane material, so that the processing solubility and the reversible electrochromic property of the polyurethane are realized.
Description
Technical field
The present invention relates to a kind of polyurethane material with electrochromic property and preparation method thereof, and apply this polyurethane material and be assembled into electrochromic device.
Background technology
Metachromatism is prevalent in nature, and such as chameleon, its skin color generally changes along with the change of environment.The material that can realize different colours change by applying different voltage, i.e. electrochromic material is developed according to this phenomenon people.Electrochromic material is because having good optics, and electricity, electrochemical properties is described as one of intellectual material having application prospect most.Now, electrochromic material development is swift and violent, is increasingly widely used in every field, such as fields such as display, smart window, anti-dazzle glasses, sensors.Electrochromic material includes inorganic electrochromic material, organic electrochromic material and conducting polymer etc..Wherein conducting polymer have color change rich colors gorgeous, the advantages such as cyclic reversibility is good, and conversion speed is fast.
Polyurethane, as a kind of emerging high-molecular organic material, is described as " the fifth-largest plastics ", and it is widely used in daily life, can be applicable to the fields such as plastic, adhesive, fabric coating.Between polymer molecule, high forces makes polymer be difficult to dissolve or melted, and this brings very big puzzlement to the processing and forming of polymer.
The main chain of polymer introduces long alkyl group or side chain can change this shortcoming, but make polymer lose stability.Triphenylamine derivative group is a stable spiral pulpous state group with electrochromic property, is incorporated in the main chain of polymer and can make the solvable easy processing of polymer, can give again polymer electrochromic performance simultaneously.
Summary of the invention
The invention aims to solve conventional polyurethanes not readily dissolve, it is difficult to the problem processing and not having electrochromic property, and preparation method and the application thereof of a kind of polyurethane material with electrochromic property are provided.
The present invention has the structural formula of the polyurethane material of electrochromic propertyWherein R represents the repetitive after biphenol monomer polycondensation, and corresponding biphenol monomer is:
N in present configuration formula is the positive integer between 10～30.
The present invention has the preparation method of the polyurethane material of electrochromic property and follows these steps to realize:
One, will methyl oxyaniline and four fluoronitrobenzenes be joined in dimethyl sulfoxide solvent, pass into N2, react 1～2 day at the temperature of 70～190 DEG C, wash after filtration, dry and obtain methoxyl group dinitro triphenylamine (solid product)；
Two, the Pd/C of methoxyl group dinitro triphenylamine and 5wt.% is put in reaction vessel, add dehydrated alcohol and hydrazine hydrate reagent, 20～40h is reacted at the temperature of 70～150 DEG C, cold filtration removes Pd/C, filtrate there is pressed powder precipitate out, then use acetone to carry out recrystallization, obtain diaminourea triphenylamine；
Three, the diaminourea triphenylamine of 0.5～2g and the triphosgene of 1～5g are put in reaction vessel, add toluene reagent, at 0～5 DEG C, stir 1～5h, then heat to 80～150 DEG C and react 1～3 day, filter, after drying, obtain isocyanates (solid product)；
Four, join in dimethylformamide according to the mixture of the isocyanates that mol ratio is 0.5～1.5:1 and aromatic bisphenols monomer, 10～30h is reacted at the temperature of 120～150 DEG C, importing in methanol has solid phase body to precipitate out, and obtains polyurethane after filtration, purification, drying；
Five, polyurethane is dissolved in dimethylformamide, is then spin coated onto on conductive ITO/glass, after vacuum drying, obtain polyurethane film；
Wherein the mol ratio of methyl oxyaniline and four fluoronitrobenzenes is 0.1～0.9:1 by step one；Aromatic bisphenols monomer described in step 4 is 4,4'-(hexafluoro isopropyl) bis-phenol, 4,4' dihydroxydiphenyl sulfone or 4,4'-dihydroxy benaophenonel.
It is that the lithium perchlorate of 1～15g is dissolved in 20～150ml carbonic allyl ester solution that the present invention has the application of the polyurethane material of electrochromic property, it is subsequently adding the polymethyl methacrylate of 1～10g, stir, obtain gel electrolyte solution, gel electrolyte solution is applied between polyurethane film and ion storage layer, after encapsulation, obtains the polyurethane device with electrochromic property.
Polyurethane material prepared by the present invention can make up conventional polyurethanes can not variable color, the shortcoming such as not readily dissolve and be difficult to, it is achieved the processing dissolubility of polyurethane and reversible electrochromic property.Its electrochromism reversibility mechanism is owing to, after applying positive voltage, the nitrogen-atoms in triphenylamine loses electronics and becomes the oxidation state triphenylamine of positive monovalence；When applying negative voltage, the triphenylamine of oxidation state obtains electronics and returns to reduction-state；The different valence state of oxidized and reduced correspond to different colors.
The polyurethane film that the present invention is obtained carries out electrochromism spectrum test (obtaining different ultraviolet figure by adding different voltage), and heretofore described polyurethane absworption peak changes along with the rising of voltage.Peak between 400～800nm gradually rises with the rising of current potential, and the color of polymer is from yellow to aeruginous, it was demonstrated that electrochromism phenomenon can occur this polyurethane.
Accompanying drawing explanation
Fig. 1 is the Infrared Characterization figure of the isocyanates of embodiment one and three kinds of polyurethane；
Fig. 2 is the structural representation of the polyurethane device obtained in Application Example, wherein 1 glass, 2 ITO, 3 polyurethane films, 4 gel electrolytes, 5 ion storage layer, 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.
Detailed description of the invention
Detailed description of the invention one: present embodiment has the preparation method of the polyurethane material of electrochromic property and follows these steps to implement:
One, it is that methyl oxyaniline and four fluoronitrobenzenes will be joined in dimethyl sulfoxide solvent by 0.1～0.9:1 in molar ratio, passes into N2, react 1～2 day at the temperature of 70～190 DEG C, wash after filtration, dry and obtain methoxyl group dinitro triphenylamine (solid product)；
Two, the Pd/C of methoxyl group dinitro triphenylamine and 5wt.% is put in reaction vessel, add dehydrated alcohol and hydrazine hydrate reagent, 20～40h is reacted at the temperature of 70～150 DEG C, cold filtration removes Pd/C, filtrate there is pressed powder precipitate out, then use acetone to carry out recrystallization, obtain diaminourea triphenylamine；
Three, the diaminourea triphenylamine of 0.5～2g and the triphosgene of 1～5g are put in reaction vessel, add toluene reagent, at 0～5 DEG C, stir 1～5h, then heat to 80～150 DEG C and react 1～3 day, filter, after drying, obtain isocyanates (solid product)；
Four, join in dimethylformamide according to the mixture of the isocyanates that mol ratio is 0.5～1.5:1 and aromatic bisphenols monomer, 10～30h is reacted at the temperature of 120～150 DEG C, importing in methanol has solid phase body to precipitate out, and obtains polyurethane after filtration, purification, drying；
Five, polyurethane is dissolved in dimethylformamide, is then spin coated onto on conductive ITO/glass, after vacuum drying, obtain polyurethane film；
Wherein aromatic bisphenols monomer described in step 4 is 4,4'-(hexafluoro isopropyl) bis-phenol, 4,4' dihydroxydiphenyl sulfone or 4,4'-dihydroxy benaophenonel.
Present embodiment has synthesized three kinds of new polyurethanes, has first synthesized a kind of new isocyanate, containing triphenylamine derivative group-methyl triphenylamine, then the dihydroxylic reaction that it is different with 3 kinds is generated polyurethane.Polyurethane carries out infrared, nuclear-magnetism etc. characterize, and to its electrochromism property, stability, spectral characteristic is tested.Polyurethane film is circulated volt-ampere test, and voltage range is 0～2V；Its oxidizing potential, reduction potential are about 0.9～1.1V and 0.5～0.8V, color respectively yellow and aeruginous.
Detailed description of the invention two: present embodiment and detailed description of the invention one the difference is that in dimethyl sulfoxide solvent in step one molar concentration of four fluoronitrobenzenes be 1～4mol/L.Other step and parameter and detailed description of the invention one are identical.
Detailed description of the invention three: present embodiment and detailed description of the invention one or two the difference is that in step 2 the mass ratio of the Pd/C of methoxyl group dinitro triphenylamine and 5wt.% be (0.5～3): (0.5～2).Other step and parameter and detailed description of the invention one or two are identical.
Detailed description of the invention four: one of present embodiment and detailed description of the invention one to three react 20h the difference is that step 2 at the temperature of 80 DEG C.Other step and one of parameter and detailed description of the invention one to three are identical.
Detailed description of the invention five: present embodiment and one of detailed description of the invention one to four are the difference is that step 3 employing apparatus,Soxhlet's purification polyurethane 30～50h.Other step and one of parameter and detailed description of the invention one to four are identical.
Detailed description of the invention six: one of present embodiment and detailed description of the invention one to five the difference is that in step 5 dimethylformamide the concentration of polyurethane be 0.1～1g/ml.Other step and one of parameter and detailed description of the invention one to five are identical.
Detailed description of the invention seven: one of present embodiment and detailed description of the invention one to six the difference is that in step 5 the thickness of polyurethane film be 1～10 μm.Other step and one of parameter and detailed description of the invention one to six are identical.
Detailed description of the invention eight: it is that the lithium perchlorate of 1～15g is dissolved in 20～150ml carbonic allyl ester solution that present embodiment has the application of the polyurethane material of electrochromic property, it is subsequently adding the polymethyl methacrylate of 1～10g, stir, obtain gel electrolyte solution, gel electrolyte solution is applied between polyurethane film and ion storage layer, after encapsulation, obtains the polyurethane device with electrochromic property.
Detailed description of the invention nine: present embodiment and detailed description of the invention eight are the difference is that the lithium perchlorate of 10g is dissolved in 100ml carbonic allyl ester solution, it is subsequently adding the polymethyl methacrylate of 6g, stir, obtain gel electrolyte solution, gel electrolyte solution is applied between polyurethane film and ion storage layer, the both sides of gel electrolyte solution epoxy resin edge sealing, obtains the polyurethane device with electrochromic property after encapsulation.
Present embodiment passes through epoxy resin by two-layer electrode edge sealing, to prevent gel electrolyte volatilization or to flow out impact test effect.
Embodiment one: the present embodiment has the preparation method of the polyurethane material of electrochromic property and follows these steps to implement:
One, will methyl oxyaniline and four fluoronitrobenzenes be joined in dimethyl sulfoxide solvent for 1:2 in molar ratio, pass into N2, react 1 day at the temperature of 120 DEG C, wash after filtration, dry and obtain methoxyl group dinitro triphenylamine (solid product)；
Two, the Pd/C of 1.4g methoxyl group dinitro triphenylamine and 0.5g5wt.% is put in there-necked flask, add 100ml dehydrated alcohol and 5ml hydrazine hydrate reagent, 20h is reacted at the temperature of 80 DEG C, cold filtration removes Pd/C, filtrate there is pressed powder precipitate out, then use acetone to carry out recrystallization, obtain dinitro triphenylamine and the diaminourea triphenylamine of reduction；
Three, the diaminourea triphenylamine of 1.45g and the triphosgene of 1g are put in there-necked flask, add the toluene reagent of 20ml, at 0 DEG C, stir 2h, then heat to 100 DEG C and react 1 day, filter, after drying, obtain isocyanates (solid product)；
Four, join in dimethylformamide according to the mixture of the isocyanates that mol ratio is 1:1 and aromatic bisphenols monomer, 10h is reacted at the temperature of 120 DEG C, importing in methanol has solid phase body to precipitate out, and obtains polyurethane after filtration, purification (apparatus,Soxhlet's purifies polyurethane and is about 50h), drying；
Five, 0.1g polyurethane is dissolved in 3ml dimethylformamide, is then spin coated onto on conductive ITO/glass, after vacuum drying, obtain polyurethane film.
The present embodiment step 4 aromatic bisphenols monomer respectively 4,4'-(hexafluoro isopropyl) bis-phenol, 4,4'-dihydroxydiphenylsulisomer, 4, during 4'-dihydroxy benaophenonel, the polyurethane a that respectively obtains, polyurethane b, polyurethane c Infrared Characterization figure as it is shown in figure 1, in figure d represent isocyanates, a represents polyurethane a, b represents polyurethane b, c and represents polyurethane c.
Application Example: the lithium perchlorate of 10g is dissolved in 100ml carbonic allyl ester solution, it is subsequently adding the polymethyl methacrylate of 6g, stir, obtain gel electrolyte solution, gel electrolyte solution is applied between polyurethane film a and ion storage layer, after encapsulation, obtains the polyurethane device with electrochromic property.
The structure chart of the polyurethane device that the present embodiment obtains is as shown in Figure 2.
The present embodiment polyurethane film is circulated volt-ampere test, and cyclic voltammogram is as it is shown on 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 aeruginous.As shown in Figure 4, the polyurethane absworption peak in the present embodiment changes electrochromism collection of illustrative plates along with the rising of voltage.Peak between 400～800nm gradually rises with the rising of current potential, and the color of polymer is from yellow to aeruginous, it was demonstrated that this polyurethane generation electrochromism phenomenon.
Claims (10)
1. there is the polyurethane material of electrochromic property, it is characterised in that the structural formula of this polyurethane material with electrochromic property isWherein R represents the repetitive after biphenol monomer polycondensation, and corresponding biphenol monomer is:
2. the polyurethane material with electrochromic property according to claim 1, it is characterised in that the n in structural formula is the positive integer between 10～30.
3. the preparation method with the polyurethane material of electrochromic property, it is characterised in that be follow these steps to realize:
One, will methyl oxyaniline and four fluoronitrobenzenes be joined in dimethyl sulfoxide solvent, pass into N2, react 1～2 day at the temperature of 70～190 DEG C, wash after filtration, dry and obtain methoxyl group dinitro triphenylamine；
Two, the Pd/C of methoxyl group dinitro triphenylamine and 5wt.% is put in reaction vessel, add dehydrated alcohol and hydrazine hydrate reagent, 20～40h is reacted at the temperature of 70～150 DEG C, cold filtration removes Pd/C, filtrate there is pressed powder precipitate out, then use acetone to carry out recrystallization, obtain diaminourea triphenylamine；
Three, the diaminourea triphenylamine of 0.5～2g and the triphosgene of 1～5g are put in reaction vessel, add toluene reagent, at 0～5 DEG C, stir 1～5h, then heat to 80～150 DEG C and react 1～3 day, filter, after drying, obtain isocyanates；
Four, join in dimethylformamide according to the mixture of the isocyanates that mol ratio is 0.5～1.5:1 and aromatic bisphenols monomer, 10～30h is reacted at the temperature of 120～150 DEG C, importing in methanol has solid phase body to precipitate out, and obtains polyurethane after filtration, purification, drying；
Five, polyurethane is dissolved in dimethylformamide, is then spin coated onto on conductive ITO/glass, after vacuum drying, obtain polyurethane film；
Wherein the mol ratio of methyl oxyaniline and four fluoronitrobenzenes is 0.1～0.9:1 by step one；Aromatic bisphenols monomer described in step 4 is 4,4'-(hexafluoro isopropyl) bis-phenol, 4,4' dihydroxydiphenyl sulfone or 4,4'-dihydroxy benaophenonel.
4. the preparation method of the polyurethane material with electrochromic property according to claim 3, it is characterised in that in step one, in dimethyl sulfoxide solvent, the molar concentration of four fluoronitrobenzenes is 1～4mol/L.
5. the preparation method of the polyurethane material with electrochromic property according to claim 3, it is characterised in that in step 2, the mass ratio of the Pd/C of methoxyl group dinitro triphenylamine and 5wt.% is (0.5～3): (0.5～2).
6. the preparation method of the polyurethane material with electrochromic property according to claim 3, it is characterised in that step 2 reacts 20h at the temperature of 80 DEG C.
7. the preparation method of the polyurethane material with electrochromic property according to claim 3, it is characterised in that in step 5 dimethylformamide, the concentration of polyurethane is 0.1～1g/ml.
8. the preparation method of the polyurethane material with electrochromic property according to claim 3, it is characterised in that in step 5, the thickness of polyurethane film is 1～10 μm.
9. there is the application of the polyurethane material of electrochromic property as claimed in claim 3, it is characterized in that the lithium perchlorate of 1～15g is dissolved in 20～150ml carbonic allyl ester solution, it is subsequently adding the polymethyl methacrylate of 1～10g, stir, obtain gel electrolyte solution, gel electrolyte solution is applied between polyurethane film and ion storage layer, after encapsulation, obtains the polyurethane device with electrochromic property.
10. the application of the polyurethane material with electrochromic property according to claim 9, it is characterized in that the lithium perchlorate of 10g is dissolved in 100ml carbonic allyl ester solution, it is subsequently adding the polymethyl methacrylate of 6g, stir, obtain gel electrolyte solution, gel electrolyte solution is applied between polyurethane film and ion storage layer, the both sides of gel electrolyte solution epoxy resin edge sealing, obtain the polyurethane device with electrochromic property after encapsulation.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110982064A (en) * | 2019-12-23 | 2020-04-10 | 黑龙江大学 | Triarylamine polyamide containing fused ring anthracenyl side group structure and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675589A (en) * | 2012-05-24 | 2012-09-19 | 黑龙江大学 | Electrochromatic material made of isocyanate-triphenylamine and method for preparing electrochromatic material |
| CN102702461A (en) * | 2012-05-24 | 2012-10-03 | 黑龙江大学 | Polyurethane with electrochromism performance and preparation method thereof |
| 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 |
| CN104877100A (en) * | 2015-05-21 | 2015-09-02 | 黑龙江大学 | Triarylamine-containing polyurethane as well as preparation method and application thereof |
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| CN102675589A (en) * | 2012-05-24 | 2012-09-19 | 黑龙江大学 | Electrochromatic material made of isocyanate-triphenylamine and method for preparing electrochromatic material |
| CN102702461A (en) * | 2012-05-24 | 2012-10-03 | 黑龙江大学 | Polyurethane with electrochromism performance and preparation method thereof |
| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110982064A (en) * | 2019-12-23 | 2020-04-10 | 黑龙江大学 | Triarylamine polyamide containing fused ring anthracenyl side group structure and preparation method and application thereof |
| 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 |
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| CN105778045B (en) | 2018-09-07 |
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