CN102275357A - 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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- CN102275357A CN102275357A CN2011101230806A CN201110123080A CN102275357A CN 102275357 A CN102275357 A CN 102275357A CN 2011101230806 A CN2011101230806 A CN 2011101230806A CN 201110123080 A CN201110123080 A CN 201110123080A CN 102275357 A CN102275357 A CN 102275357A
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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 be induced down in external electric field, produces deformation, thereby produces the material of mechanical response.The response forms of electroactive material can have bending, contraction or expansion etc., thereby can realize driving, function such as fastening, sensing.Because being stimulated by outer signals directly, this class material produces motion, can be configured to novel product, Mechatronic Systems or robot (animal) with this class material as drive unit, wherein do not need the conventional mechanical drive unit, such as motor, arbor, gear etc., alleviated the weight of system greatly, changed the notion of traditional machine, special-shaped machine or system will provide wide innovative space for future, thereby cause numerous researchers and engineer, technical staff's concern.According to the mechanism that deformation produces, the electroactive polymer material can be divided into electron type and ionic two big classes.Electron type is also referred to as does the driving system, mainly comprises dielectric elastomers, piezopolymer, ferroelectric polymers, electrostrictive polymers etc.; Ionic also claims wet driving system because system needs to work under the hygrometric state environment, mainly comprise ionomer, polymer dielectric gel, conducting polymer etc.Two kinds of electric living polymerization rerum natura materials of electron type and ionic respectively have pluses and minuses.The advantage of electron type electricity living polymerization rerum natura material is that it can drive for a long time under indoor environment, response speed fast (response time is the microsecond level), can produce relatively large driving force; Shortcoming be need be very high driving voltage (generally more than kilovolt).The advantage of ionic electricity living polymerization rerum natura material is can produce big bending strain under low-voltage; Shortcoming be must under the hygrometric state environment, work, response speed is slow, stress that produce is less relatively and be difficult to obtain uniform material.
At present, the research of electroactive material all concentrates on these synthesizing polymeric materials in the world, the resource and these materials all need consume petroleum, and discarded object also can cause environmental disruption, and manufacturing expense is also very high, is a key factor of restriction electroactive polymer large-scale application.Cellulose is the natural biological source macromolecular material the widest, that annual production is maximum that distributes on the earth, is truly sustainable, the natural material that can not consume.As far back as eighties of last century the fifties, people just have been found that cellulose has piezo-electric effect.Found again afterwards that oriented crystalline had partly shown stronger shearing piezo-electric effect in the plant cellulose, this makes cellulose can be used as the electron type electroactive material and is applied.How electron type and two kinds of electric living polymerization rerum natura materials of ionic are combined, design a kind of novel electric living polymerization rerum natura material, make it both have the advantage of electron type electricity living polymerization rerum natura material, have the advantage of ionic electricity living polymerization rerum natura material again, so this electric living polymerization rerum natura material will have broad application prospects.Based on this thinking, the present invention prepares a kind of cellulose membrane electroactive material that contains poly-indoles coating from the angle of structural design.
Summary of the invention
The purpose of this invention is to provide novel poly-indoles coating cellulose film electroactive material, and the preparation method of this electroactive material.This method forms poly-indoles coating by electrochemical polymerization on cellulose membrane, be compounded on the cellulose membrane thereby will gather the electroactive of indoles.The poly-indoles coating cellulose film electroactive material of the present invention's preparation has had the advantage of electron type and two kinds of electric living polymerization rerum natura materials of ionic concurrently, has advantages such as raw material sources are extensive, cost is low, technology is simple simultaneously again.
Novel poly-indoles coating cellulose film electroactive material of the present invention adopts following technical scheme to realize:
(1) be that 200000～600000 cellulose is dissolved in and is configured to 0.1%～5% (mass ratio in the solvent with molecular weight, solution down together), solvent can be selected N, N-dimethylacetylamide/lithium chloride, methyl oxidation beautiful jade or trifluoroacetic acid, to fully dissolving back filtration, the cast of gained filtering solution film forming, at room temperature finish-drying;
(2) dried film is placed the aqueous solution that contains 0.5%～2% NaOH, soak under the room temperature to take out after 2～6 hours and wash repeatedly with deionized water;
(3) again film is placed the aqueous solution that contains 0.1%～1% hydrogen chloride, soaked under the room temperature 4～12 hours, surperficial only after taking out with deionized water rinsing, finish-drying under the room temperature;
(4) under vacuum condition (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) with the cellulose membrane that plated metal electrode as working electrode, platinum electrode is an auxiliary electrode, saturated sweet tribute electrode is that reference electrode is formed three-electrode cell, to form electrolyte in indoles monomer, electroanalysis solvent and the electrolyte adding three-electrode cell, adopt potentiostatic method to carry out polymerization, the poly-indoles of electro-deposition on working electrode surface.The initial concentration of described monomer is 10
-2～1mol/L, monomer can select 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; When adopting potentiostatic method to carry out polymerization, concrete steps are as follows: working electrode is applied the constant potential signal, and the constant potential range of signal is 0.7～1.2V, and the time is 1～8 hour.
(6) cleaning fluid with 50～200ml cleans 2～4 times the poly-indoles coating that deposition on the working electrode obtains, and surperficial adsorbate is removed, and washes in deionized water at last, obtains poly-indoles coating cellulose film electroactive material after the vacuum drying.Cleaning fluid can be selected acetonitrile, methyl alcohol, ethanol, propene carbonate.
The invention has the beneficial effects as follows
1. be raw material with cellulose and indoles, prepared novel poly-indoles coating cellulose film electroactive material, this electroactive material have driving voltage low, the response deformation greatly, do not need hygrometric state environment etc., had the advantage of two kinds of electric living polymerization rerum natura materials of electron type ionic concurrently.
2. cellulose is the natural biological source macromolecular material the widest, that annual production is maximum that distributes on the earth, all has every year the over ten billion ton to produce, and is real continuable, the natural material that can not consume, raw material be easy to obtain and price lower.
3. electrochemical polymerization is simple and practical, and is with low cost, is easy to suitability for industrialized production.
Description of drawings
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 ℃; Environment temperature: 30% relative temperature);
The specific embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is described further:
With molecular weight is that 350000 paper celluloses are cut into segment, is placed on the vacuum drying chamber inner drying 24 hours, guarantees no residual moisture content; Take by weighing 4.5g and be placed in the 100ml tetrafluoro acetate, sealing back room temperature left standstill 7 days; Filter after treating to dissolve fully, and in the tetrafluoroethene model, pour into a mould film forming; Air dry is after 2 days under the room temperature, dried film is put into 200ml contains in 1.5% the sodium hydrate aqueous solution, soaks 3 hours under the room temperature; Deionized water with 3000ml washes repeatedly then, film is put into to contain in 0.5% the hydrochloride aqueous solution again, soaks 6 hours under the room temperature; It is surperficial only with the deionized water rinsing of 500ml that film takes out the back, shakeouts on the tetrafluoroethene plate, and air dry is 2 days under the room temperature; Under vacuum condition (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 the three-electrode cell, wherein working electrode is the cellulose membrane that has plated gold electrode; Auxiliary electrode is a platinum electrode; Reference electrode is saturated sweet tribute electrode.Adopt potentiostatic method to carry out polymerization, the polymerization current potential is 0.8V, and the time is 3 hours.After treating that polymerization is finished, use 50ml washed with methanol surface 2 times, with washing in the deionized water, vacuum drying obtains poly-indoles coating cellulose film electroactive material again.
With molecular weight is that 300000 paper celluloses are cut into segment, is placed on the vacuum drying chamber inner drying 24 hours, guarantees no residual moisture content; Take by weighing 2.0g and be placed on 100ml N, in N-dimethylacetylamide and the 9.0g lithium chloride solution, stirred 2 days under the room temperature of sealing back, be warming up to 150 ℃ then and stirred 3 days down; Filter after treating to dissolve fully, and on the tetrafluoroethene model, pour into film; Air dry is after 2 days under the room temperature, dried film is put into 100ml contains in 1.0% the sodium hydrate aqueous solution, soaks 4 hours under the room temperature; Deionized water with 3000ml washes repeatedly then, film is put into to contain in 0.5% the hydrochloride aqueous solution again, soaks 4 hours under the room temperature; It is surperficial only with the deionized water rinsing of 300ml that film takes out the back, shakeouts on the tetrafluoroethene plate, and air dry is 2 days under the room temperature; Under vacuum condition (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 the three-electrode cell, wherein working electrode is the cellulose membrane that has plated copper electrode; Auxiliary electrode is a platinum electrode; Reference electrode is saturated sweet tribute electrode.Adopt potentiostatic method to carry out polymerization, the polymerization current potential is 0.9V, and the time is 6 hours.After treating that polymerization is finished, use 100ml acetonitrile clean surface 2 times, with washing in the deionized water, vacuum drying obtains poly-indoles coating cellulose film electroactive material again.
With molecular weight is that 400000 paper celluloses are cut into segment, is placed on the vacuum drying chamber inner drying 24 hours, guarantees no residual moisture content; Take by weighing 1.0g and be placed in the 100ml methyl oxidation beautiful jade, stirred 2 days under the room temperature of sealing back; Filter after treating to dissolve fully, and on the tetrafluoroethene model, pour into film; Air dry is after 2 days under the room temperature, dried film is put into 100ml contains in 0.5% the sodium hydrate aqueous solution, soaks 4 hours under the room temperature; Deionized water with 3000ml washes repeatedly then, film is put into to contain in 0.1% the hydrochloride aqueous solution again, soaks 5 hours under the room temperature; Film takes out the back with the deionized water rinsing of 100ml surface only, pushes away flatly on the tetrafluoroethene plate, and air dry is 2 days under the room temperature; Under vacuum condition (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 the three-electrode cell, wherein working electrode is the cellulose membrane that has plated silver electrode; Auxiliary electrode is a platinum electrode; Reference electrode is saturated sweet tribute electrode.Adopt potentiostatic method to carry out polymerization, the polymerization current potential is 0.95V, and the time is 7 hours.After treating that polymerization is finished, use 50ml ethanol clean surface 2 times, with washing in the deionized water, vacuum drying obtains poly-indoles coating cellulose film electroactive material again.
Embodiment 4
With molecular weight is that 600000 paper celluloses are cut into segment, is placed on the vacuum drying chamber inner drying 24 hours, guarantees no residual moisture content; Take by weighing 3.0g and be placed in the 100ml tetrafluoro acetate, sealing back room temperature left standstill 7 days; Row filters when treating to dissolve fully the back, and pours into a mould film forming in the tetrafluoroethene model; Air dry is after 2 days under the room temperature, dried film is put into 200ml contains in 20% the sodium hydrate aqueous solution, soaks 2 hours under the room temperature; Deionized water with 3000ml washes repeatedly then, film is put into to contain in 1% the hydrochloride aqueous solution again, soaks 3 hours under the room temperature; It is surperficial only with the deionized water rinsing of 1000ml that film takes out the back, shakeouts on the tetrafluoroethene plate, and air dry is 2 days under the room temperature; Under vacuum condition (less than 4 * 10
4Pa) to film surface platinized electrode, thickness is less than 0.1 micron.Nitroindoline (0.05mol/L) is dissolved in the carbonic acid of lithium hexafluoro phosphate in the alkene ester solution (0.005mol/L), joins in the three-electrode cell, wherein working electrode is the cellulose membrane that has plated platinum electrode; Auxiliary electrode is a platinum electrode; Reference electrode is saturated sweet tribute electrode.Adopt potentiostatic method to carry out polymerization, the polymerization current potential is 0.9V, and the time is 8 hours.After treating that polymerization is finished, use 100ml propene carbonate clean surface 2 times, with washing in the deionized water, vacuum drying obtains poly-indoles coating cellulose film electroactive material again.
Claims (10)
1. an electroactive polymer material is characterized by, and it is 200000～600000 cellulose membrane by molecular weight and constitutes at the poly-indoles of its surface deposition.
2. an electroactive polymer preparation methods is characterized in that it comprises the following steps:
(1) is that 200000～600000 cellulose is dissolved in and is configured to 0.1%～5% in the solvent solution of (mass ratio, down with) with molecular weight, filters the cast of gained filtering solution film forming, at room temperature finish-drying to abundant dissolving back;
(2) dried film is placed the aqueous solution that contains 0.5%～2% NaOH, soak 2～6 hours under the room temperature after, take out and to wash repeatedly with deionized water;
(3) again film is placed the aqueous solution that contains 0.1%～1% hydrogen chloride, soaked under the room temperature 4～12 hours, surperficial only after taking out with deionized water rinsing, finish-drying under the room temperature;
(4) under vacuum condition (less than 4 * 10
4Pa) to film plating metal on surface electrode, electrode layers thickness is less than 0.1 micron;
(5) with the cellulose membrane that plated metal electrode as working electrode, platinum electrode is an auxiliary electrode, saturated sweet tribute electrode is that reference electrode is formed three-electrode cell, to form electrolyte in indoles monomer, electroanalysis solvent and the electrolyte adding three-electrode cell, adopt potentiostatic method to carry out polymerization, the poly-indoles of electro-deposition on working electrode surface.
(6) cleaning fluid with 50～200ml cleans 2～4 times the poly-indoles coating that deposition on the working electrode obtains, and surperficial adsorbate is removed, and washes in deionized water at last, obtains poly-indoles coating cellulose film electroactive material after the vacuum drying.
3. electroactive polymer preparation methods according to claim 2 is characterized in that described solvent is N, N-dimethylacetylamide/lithium chloride, methyl oxidation beautiful jade or trifluoroacetic acid.
4. electroactive polymer preparation methods according to claim 2 is characterized in that described metal electrode is copper, silver, gold or platinum.
5. electroactive polymer preparation methods according to claim 2, it is characterized in that described indoles monomer is one of following: alkyl indoles, nitroindoline, chloro indoles, the initial concentration of monomer are 10
-2～1mol/L.
6. electroactive polymer preparation methods according to claim 2 is characterized in that described is that electrolyte is one of following: lithium perchlorate, LiBF4 or lithium hexafluoro phosphate.
7. electroactive polymer preparation methods according to claim 6 is characterized in that described is that electrolytical concentration is 10 in the described electrolyte
-3～10
-1Mol/L.
8. electroactive polymer preparation methods according to claim 2 is characterized in that described is that electroanalysis solvent is one of following: acetonitrile, methyl alcohol, ethanol or propene carbonate.
9. electroactive polymer preparation methods according to claim 2, it is characterized in that described is to adopt potentiostatic method to carry out polymerization, concrete steps are as follows: working electrode is applied the constant potential signal, and the constant potential range of signal is 0.7～1.2V, and the time is 1～8 hour.
10. electroactive polymer preparation methods according to claim 2, it is characterized in that post processing adopts following method: with cleaning fluid the poly-indoles coating that deposition on the working electrode obtains is cleaned, described cleaning fluid adopts following solvent: acetonitrile, methyl alcohol, ethanol, propene carbonate.
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Cited By (4)
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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 |
| CN112126103A (en) * | 2020-08-24 | 2020-12-25 | 浙江长宇新材料有限公司 | Metal evaporation composite nano cellulose membrane current collector and preparation method thereof |
| CN114933724A (en) * | 2022-06-21 | 2022-08-23 | 陕西科技大学 | Preparation method of nonionic cellulose/polycaprolactone-based antibacterial film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN112126103A (en) * | 2020-08-24 | 2020-12-25 | 浙江长宇新材料有限公司 | Metal evaporation composite nano cellulose membrane current collector 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 |
| CN114933724A (en) * | 2022-06-21 | 2022-08-23 | 陕西科技大学 | Preparation method of nonionic cellulose/polycaprolactone-based antibacterial film |
| CN114933724B (en) * | 2022-06-21 | 2023-09-22 | 陕西科技大学 | Preparation method of nonionic cellulose/polycaprolactone-based antibacterial film |
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