CN102275357B - Polyindole coating cellulose membrane electric active material and preparation method thereof - Google Patents
Polyindole coating cellulose membrane electric active material and preparation method thereof Download PDFInfo
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- CN102275357B CN102275357B CN201110123080.6A CN201110123080A CN102275357B CN 102275357 B CN102275357 B CN 102275357B CN 201110123080 A CN201110123080 A CN 201110123080A CN 102275357 B CN102275357 B CN 102275357B
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Abstract
The invention relates to a polyindole coating cellulose membrane electric active material and a preparation method thereof. The preparation method of the polyindole coating cellulose membrane electric active material comprises the following steps of: dissolving cellulose in a solvent, pouring into a membrane, and drying the membrane at the room temperature; then treating the membrane in a sodium hydroxide solution and a hydrogen chloride solution; and drying the membrane and then plating electrodes on the surface of the membrane in a vacuum condition; adding an indole monomer, an electrolytic solvent and an electrolyte in a three-electrode electrolyzer to form an electrolyte, polymerizing with the cellulose membrane plated with the electrodes as a working electrode by adopting the potentiostatic method, and obtaining the polyindole coating cellulose membrane electric active material through aftertreatment. The novel polyindole coating cellulose membrane electric active material has the advantages of low driving voltage, large response deformation, no need of wet environment, and the like. The preparation method of the polyindole coating cellulose membrane electric active material has simple process and low cost, and is easy to produce industrially.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to the preparation method of poly-indoles coating cellulose film electroactive material and this electroactive material.
Background technology
Electroactive material is that a class can produce deformation under external electric field induction, thereby produces the material of mechanical response.The response forms of electroactive material can have bending, contraction or expansion etc., thereby can realize the functions such as driving, fastening, sensing.Because being stimulated by outer signals directly, this class material produces motion, with this class material, as drive unit, can be configured to novel product, Mechatronic Systems or robot (animal), wherein do not need conventional mechanical drive unit, such as motor, arbor, gear etc., greatly alleviated the weight of system, changed the concept of traditional machine, for future special-shaped machine or system wide innovative space is provided, thereby caused numerous researchers and engineer, technical staff's concern.The mechanism producing according to deformation, electroactive polymer material can be divided into electron type and the large class of ionic two.Electron type is also referred to as dry driving system, mainly comprises dielectric elastomers, piezopolymer, ferroelectric polymers, electrostrictive polymers etc.; Ionic, because system need be worked under wet condition, also claims wet driving system, mainly comprises ionomer, polymer dielectric gel, conducting polymer etc.Two kinds of electric living polymerization physical property materials of electron type and ionic respectively have pluses and minuses.The advantage of electron type electricity living polymerization physical property material be its can be under indoor environment for a long time driving, fast response time (response time is Microsecond grade), can produce relatively large driving force; Shortcoming be need to be very high driving voltage (generally more than kilovolt).The advantage of ionic electricity living polymerization physical property material is can produce large bending strain under low-voltage; Shortcoming be must under wet condition, work, response speed is slow, stress that produce is relatively little and be difficult to obtain uniform material.
At present, the research of electroactive material all concentrates on these synthesizing polymeric materials in the world, and these materials all need to consume petroleum resource, and discarded object also can cause environmental disruption, and manufacturing expense is also very high, it is a key factor of restriction electroactive polymer large-scale application.Cellulose is on the earth, distribute the widest, the maximum natural biological source macromolecular material of annual production, is sustainable, not consumable natural material truly.As far back as eighties of last century the fifties, people just have been found that cellulose has piezo-electric effect.Found again afterwards, in plant cellulose, oriented crystalline has partly shown stronger shearing piezo-electric effect, and this makes cellulose can be used as electron type electroactive material and is applied.How electron type and two kinds of electric living polymerization physical property materials of ionic are combined, design a kind of novel electric living polymerization physical property material, make it both there is electron type electricity living polymerization physical property material, have advantages of again ionic electricity living polymerization physical property material, so this electric living polymerization physical property material will have broad application prospects.Based on this thinking, the present invention, from the angle of structural design, prepares a kind of cellulose membrane electroactive material that contains poly-indoles coating.
Summary of the invention
The object of this invention is to provide novel poly-indoles coating cellulose film electroactive material, and the preparation method of this electroactive material.The method forms poly-indoles coating by electrochemical polymerization on cellulose membrane, thereby poly-the electroactive of indoles is compounded on cellulose membrane.Poly-indoles coating cellulose film electroactive material prepared by the present invention has had the advantage of electron type and two kinds of electric living polymerization physical property materials of ionic concurrently, has again the advantages such as raw material sources are extensive, cost is low, technique is simple simultaneously.
Novel poly-indoles coating cellulose film electroactive material of the present invention adopts following technical scheme to realize:
(1) cellulose that is 200000～600000 by molecular weight is dissolved in and in solvent, is configured to 0.1%～5% (mass ratio, solution down together), solvent can be selected N, N-dimethylacetylamide/lithium chloride, methyl oxidation beautiful jade or trifluoroacetic acid, after fully dissolving, filter, the cast of gained filtering solution film forming, at room temperature finish-drying;
(2) dried film is placed in to the aqueous solution that contains 0.5%～2% NaOH, under room temperature, soaks after 2～6 hours and take out and repeatedly rinse by deionized water;
(3) again film is placed in to the aqueous solution containing 0.1%～1% hydrogen chloride, under room temperature, soaks 4～12 hours, only surperficial with deionized water rinsing after taking-up, finish-drying under room temperature;
(4) under vacuum condition, (be less than 4 * 10
4pa) to film plating metal on surface electrode, institute's plating can be selected copper, silver, gold or platinum, and electrode layers thickness is less than 0.1 micron;
(5) using plated metal electrode cellulose membrane as working electrode, platinum electrode is auxiliary electrode, saturated sweet tribute electrode is that reference electrode forms three-electrode cell, indoles monomer, electroanalysis solvent and electrolyte are added and in three-electrode cell, form electrolyte, adopt potentiostatic method to carry out polymerization, at the poly-indoles of working electrode surface substrates.The initial concentration of described monomer is 10
-2～1mol/L, monomer can be selected alkyl indoles, nitroindoline or chloro indoles; Electrolyte can be selected lithium perchlorate, LiBF4 or lithium hexafluoro phosphate; Electroanalysis solvent can be selected acetonitrile, methyl alcohol, ethanol or propene carbonate; Electrolyte concentration is 10
-3～10
-1mol/L; While adopting potentiostatic method to carry out polymerization, concrete steps are as follows: working electrode is applied to constant potential signal, and constant potential range of signal is 0.7～1.2V, and the time is 1～8 hour.
(6) with the cleaning fluid of 50～200ml, to depositing the poly-indoles coating obtaining on working electrode, clean 2～4 times, adsorption thing is removed, finally in deionized water, rinse, after vacuum drying, obtain poly-indoles coating cellulose film electroactive material.Cleaning fluid can be selected acetonitrile, methyl alcohol, ethanol, propene carbonate.
The invention has the beneficial effects as follows
1. take cellulose and indoles as raw material, prepared novel poly-indoles coating cellulose film electroactive material, this electroactive material have driving voltage low, response deformation greatly, do not need wet condition etc., had the advantage of two kinds of electric living polymerization physical property materials of electron type and ionic concurrently.
2. cellulose is on the earth, distribute the widest, the maximum natural biological source macromolecular material of annual production, has every year over ten billion ton to produce, and is real continuable, not consumable natural material, raw material be easy to obtain and price lower.
3. electrochemical polymerization is simple and practical, with low cost, is easy to suitability for industrialized production.
Accompanying drawing explanation
Structural representation (1 cellulose membrane of the poly-indoles coating cellulose film electroactive material of Fig. 1; 2 metal electrodes; 3 poly-indoles coatings);
The electricity of the poly-indoles coating cellulose film electroactive material of Fig. 2 causes response inflection curves (voltage: ■: 3V; ●: 4V; ▲: 5V;
: 6V;
: 7V) (test condition is: environment temperature: 25 ℃; Ambient humidity: 30% relative humidity);
The specific embodiment
Below in conjunction with specific embodiment, technical scheme of the present invention is described further:
By molecular weight, be that 350000 paper celluloses are cut into segment, be placed on vacuum drying chamber inner drying 24 hours, guarantee without residual moisture content; Take 4.5g and be placed in 100ml tetrafluoro acetic acid, after sealing, room temperature is standing 7 days; Filter until completely dissolved, and in tetrafluoroethene model upper film forming; Under room temperature after natural drying 2 days, dried film is put into 200ml and contains in 1.5% sodium hydrate aqueous solution, under room temperature, soak 3 hours; Then by the deionized water of 3000ml, repeatedly rinse, then film is put into containing in 0.5% hydrochloride aqueous solution, under room temperature, soak 6 hours; After taking out, with the deionized water rinsing of 500ml surface only, on tetrafluoroethene plate, shakeouts film under room temperature natural drying 2 days; Under vacuum condition, (be less than 4 * 10
4pa), to film surface gold-plating electrode, thickness is less than 0.1 micron.Nitroindoline (0.1mol/L) is dissolved in the acetonitrile solution of lithium perchlorate (0.01mol/L), joins in three-electrode cell, wherein working electrode is the cellulose membrane that has plated gold electrode; Auxiliary electrode is platinum electrode; Reference electrode is saturated sweet tribute electrode.Adopt potentiostatic method to carry out polymerization, polymerization current potential is 0.8V, and the time is 3 hours.After polymerization completes, use 50ml washed with methanol surface 2 times, then with washing in deionized water, vacuum drying, obtains poly-indoles coating cellulose film electroactive material.
By molecular weight, be that 300000 paper celluloses are cut into segment, be placed on vacuum drying chamber inner drying 24 hours, guarantee without residual moisture content; Take 2.0g and be placed in 100ml DMA and 9.0g lithium chloride solution, after sealing, under room temperature, stir 2 days, be then warming up at 150 ℃ and stir 3 days; Filter until completely dissolved, and in tetrafluoroethene model upper film forming; Under room temperature after natural drying 2 days, dried film is put into 100ml and contains in 1.0% sodium hydrate aqueous solution, under room temperature, soak 4 hours; Then by the deionized water of 3000ml, repeatedly rinse, then film is put into containing in 0.5% hydrochloride aqueous solution, under room temperature, soak 4 hours; After taking out, with the deionized water rinsing of 300ml surface only, on tetrafluoroethene plate, shakeouts film under room temperature natural drying 2 days; Under vacuum condition, (be less than 4 * 10
4pa), to film copper coating electrode, thickness is less than 0.1 micron.Alkyl indoles (0.5mol/L) is dissolved in the ethanolic solution of LiBF4 (0.05mol/L), joins in three-electrode cell, wherein working electrode is the cellulose membrane that has plated copper electrode; Auxiliary electrode is platinum electrode; Reference electrode is saturated sweet tribute electrode.Adopt potentiostatic method to carry out polymerization, polymerization current potential is 0.9V, and the time is 6 hours.After polymerization completes, use 100ml acetonitrile clean surface 2 times, then with washing in deionized water, vacuum drying, obtains poly-indoles coating cellulose film electroactive material.
Embodiment 3
By molecular weight, be that 400000 paper celluloses are cut into segment, be placed on vacuum drying chamber inner drying 24 hours, guarantee without residual moisture content; Take 1.0g and be placed in 100ml methyl oxidation beautiful jade, after sealing, under room temperature, stir 2 days; Filter until completely dissolved, and in tetrafluoroethene model upper film forming; Under room temperature after natural drying 2 days, dried film is put into 100ml and contains in 0.5% sodium hydrate aqueous solution, under room temperature, soak 4 hours; Then by the deionized water of 3000ml, repeatedly rinse, then film is put into containing in 0.1% hydrochloride aqueous solution, under room temperature, soak 5 hours; After taking out, with the deionized water rinsing of 100ml surface only, on tetrafluoroethene plate, shakeouts film under room temperature natural drying 2 days; Under vacuum condition, (be less than 4 * 10
4pa), to film electroplate electrode, thickness is less than 0.1 micron.Chloro indoles (1mol/L) is dissolved in the acetonitrile solution of LiBF4 (0.1mol/L), joins in three-electrode cell, wherein working electrode is the cellulose membrane that has plated silver electrode; Auxiliary electrode is platinum electrode; Reference electrode is saturated sweet tribute electrode.Adopt potentiostatic method to carry out polymerization, polymerization current potential is 0.95V, and the time is 7 hours.After polymerization completes, use 50ml ethanol clean surface 2 times, then with washing in deionized water, vacuum drying, obtains poly-indoles coating cellulose film electroactive material.
By molecular weight, be that 600000 paper celluloses are cut into segment, be placed on vacuum drying chamber inner drying 24 hours, guarantee without residual moisture content; Take 3.0g and be placed in 100ml tetrafluoro acetic acid, after sealing, room temperature is standing 7 days; Filter until completely dissolved, and in tetrafluoroethene model upper film forming; Under room temperature after natural drying 2 days, dried film is put into 200ml and contains in 20% sodium hydrate aqueous solution, under room temperature, soak 2 hours; Then by the deionized water of 3000ml, repeatedly rinse, then film is put into containing in 1% hydrochloride aqueous solution, under room temperature, soak 3 hours; After taking out, with the deionized water rinsing of 1000ml surface only, on tetrafluoroethene plate, shakeouts film under room temperature natural drying 2 days; Under vacuum condition, (be less than 4 * 10
4pa), to film plated surface platinum electrode, thickness is less than 0.1 micron.Nitroindoline (0.05mol/L) is dissolved in the carbonic acid of lithium hexafluoro phosphate in alkene ester solution (0.005mol/L), joins in three-electrode cell, wherein working electrode is the cellulose membrane that has plated platinum electrode; Auxiliary electrode is platinum electrode; Reference electrode is saturated sweet tribute electrode.Adopt potentiostatic method to carry out polymerization, polymerization current potential is 0.9V, and the time is 8 hours.After polymerization completes, use 100ml propene carbonate clean surface 2 times, then with washing in deionized water, vacuum drying, obtains poly-indoles coating cellulose film electroactive material.
Claims (9)
1. a method of preparing electroactive polymer material, is characterized in that cellulose membrane that electroactive polymer material is 200000～600000 by molecular weight and forms at the poly-indoles of its surface deposition, method comprises the following steps:
(1) cellulose that is 200000～600000 by molecular weight is dissolved in the solution that is configured to 0.1%～5% in solvent, filters gained filtering solution cast film forming, under room temperature natural drying 2 days after fully dissolving;
(2) dried film is placed in to the aqueous solution of the NaOH that contains 0.5%～2%, under room temperature, soaks after 2～6 hours, take out and repeatedly rinse by deionized water;
(3) again film is placed in to the aqueous solution containing 0.1%～1% hydrogen chloride, under room temperature, soaks 4～12 hours, after taking-up with deionized water rinsing surface only, under room temperature natural drying 2 days;
(4) under vacuum condition to film plating metal on surface electrode, electrode layers thickness is less than 0.1 micron;
(5) using plated metal electrode cellulose membrane as working electrode, platinum electrode is auxiliary electrode, saturated sweet tribute electrode is that reference electrode forms three-electrode cell, indoles monomer, electroanalysis solvent and electrolyte are added and in three-electrode cell, form electrolyte, adopt potentiostatic method to carry out polymerization, at the poly-indoles of working electrode surface substrates;
(6) with the cleaning fluid of 50～200ml, to depositing the poly-indoles coating obtaining on working electrode, clean 2～4 times, finally in deionized water, rinse, after vacuum drying, obtain poly-indoles coating cellulose film electroactive material.
2. the preparation method of electroactive polymer material according to claim 1, is characterized in that described solvent is DMA and lithium chloride mixed solvent or methyl oxidation beautiful jade.
3. the preparation method of electroactive polymer material according to claim 1, is characterized in that described metal electrode is copper, silver, gold or platinum.
4. the preparation method of electroactive polymer material according to claim 1, is characterized in that described indoles monomer is one of following: alkyl indoles, nitroindoline, chloro indoles, the initial concentration of monomer is 10
-2～1mol/L.
5. the preparation method of electroactive polymer material according to claim 1, is characterized in that described electrolyte is one of following: lithium perchlorate, LiBF4 or lithium hexafluoro phosphate.
6. the preparation method of electroactive polymer material according to claim 1, is characterized in that in described electrolyte, electrolytical concentration is 10
-3～10
-1mol/L.
7. the preparation method of electroactive polymer material according to claim 1, is characterized in that described electroanalysis solvent is one of following: acetonitrile or ethanol.
8. the preparation method of electroactive polymer material according to claim 1, it is characterized in that described potentiostatic method carries out polymerization, concrete steps are as follows: working electrode is applied to constant potential signal, and constant potential range of signal is 0.7～1.2V, and the time is 1～8 hour.
9. the preparation method of electroactive polymer material according to claim 1, described cleaning fluid adopts one of following solvent: acetonitrile, methyl alcohol, ethanol, propene carbonate.
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| CN102942704A (en) * | 2012-11-20 | 2013-02-27 | 天津工业大学 | Polyurethane/cellulose composite membrane electro-active material and preparation method thereof |
| CN108532014A (en) * | 2018-04-10 | 2018-09-14 | 天津工业大学 | A kind of nanofiber electroactive polymer material and preparation method thereof |
| CN112126103B (en) * | 2020-08-24 | 2022-11-22 | 浙江长宇新材料股份有限公司 | Metal evaporation composite nano cellulose membrane current collector and preparation method thereof |
| CN114933724B (en) * | 2022-06-21 | 2023-09-22 | 陕西科技大学 | Preparation method of nonionic cellulose/polycaprolactone-based antibacterial film |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5211810A (en) * | 1990-08-09 | 1993-05-18 | International Paper Company | Electrically conductive polymeric materials and related method of manufacture |
| EP1139710A2 (en) * | 2000-03-30 | 2001-10-04 | AD-Tech. Co., Ltd. | Wallpaper for shielding electromagnetic waves |
| CN1814652A (en) * | 2006-03-02 | 2006-08-09 | 扬州大学 | Polyaniline with electrochemical activity under high-pH value and preparing method |
| CN101492545A (en) * | 2009-02-17 | 2009-07-29 | 武汉工程大学 | Method of preparing poly-pyrrole/polythiofuran derivative composite conductive macromolecule material for super electrical condenser |
-
2011
- 2011-05-13 CN CN201110123080.6A patent/CN102275357B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5211810A (en) * | 1990-08-09 | 1993-05-18 | International Paper Company | Electrically conductive polymeric materials and related method of manufacture |
| EP1139710A2 (en) * | 2000-03-30 | 2001-10-04 | AD-Tech. Co., Ltd. | Wallpaper for shielding electromagnetic waves |
| CN1814652A (en) * | 2006-03-02 | 2006-08-09 | 扬州大学 | Polyaniline with electrochemical activity under high-pH value and preparing method |
| CN101492545A (en) * | 2009-02-17 | 2009-07-29 | 武汉工程大学 | Method of preparing poly-pyrrole/polythiofuran derivative composite conductive macromolecule material for super electrical condenser |
Non-Patent Citations (9)
| Title |
|---|
| Fabrication of Piezoelectric Cellulose Paper and Audio Application;Jung-Hwan Kim等;《Journal of Bionic Engineering》;20091231(第6期);第19页左栏第1-8行，第20页左栏2-23行及附图5 * |
| Jung-Hwan Kim等.Fabrication of Piezoelectric Cellulose Paper and Audio Application.《Journal of Bionic Engineering》.2009,(第6期),第18-21页. |
| New electro-active paper actuator using conducting polypyrrole: actuation behaviour in LiClO4 acetonitrile solution;S.D.Deshpande等;《Synthetic Metals》;20041213;第149卷;第54页左栏18-31行，第54页左栏41行-右栏9行，第58页左栏25-42行及附图1、4-7 * |
| S.D.Deshpande等.New electro-active paper actuator using conducting polypyrrole: actuation behaviour in LiClO4 acetonitrile solution.《Synthetic Metals》.2004,第149卷第53-58页. |
| 唐致远等.电活性聚合物在锂离子蓄电池中的应用.《电源技术》.2006,第30卷(第12期), |
| 导电聚合物材料在电化学器件中的应用及发展;蔡志江;《电源技术》;20060131;第30卷(第1期);74-77 * |
| 张家鑫.导电高分子纳米材料的电化学合成.《中国优秀博硕士学位论文全文数据库(博士)工程科技Ι辑》.2006, * |
| 电活性聚合物在锂离子蓄电池中的应用;唐致远等;《电源技术》;20061231;第30卷(第12期);1017-1019 * |
| 蔡志江.导电聚合物材料在电化学器件中的应用及发展.《电源技术》.2006,第30卷(第1期), |
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