CN108586309A - A kind of preparation method of pyrroles's oligomer - Google Patents
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- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
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Abstract
The present invention relates to a kind of preparation methods of conducting polymer oligomer, belong to technical field of preparing conductive polymers.A. carrier is added in container；B. pyrroles is added in the container described in step a, container is sealed；C. by mixing in pyrroles and container of the carrier described in step b, curing obtains carrier/pyrroles's oligomerization nanocrystal composition；D. the carrier obtained by step c/pyrroles's oligomerization nanocrystal composition is scattered in organic solvent, closed placement at room temperature makes pyrroles's oligomer be dissolved in organic solvent, is then separated by solid-liquid separation, leaves and takes supernatant；E. supernatant is distilled or is evaporated under reduced pressure, obtain pyrroles's oligomer.The present invention is using the oxygen in air as oxidant, and without metal/transition-metal catalyst auxiliary, using chemical vapour deposition technique, pyrroles's oligomer is synthesized in carbon material substrate surface.Air source is abundant, at low cost, environmental-friendly.
Description
Technical field
The present invention relates to a kind of preparation methods of conducting polymer oligomer, belong to technical field of preparing conductive polymers.
Background technology
Conducting polymer is also known as conducting polymer, and being one kind has big pi-conjugated system molecular skeleton, through chemistry or electrification
Learning doping can make it be changed into the high molecular material of conductor by insulator.Common conducting polymer has polypyrrole, polyaniline, gathers
Thiophene and polyacetylene.
With five yuan of heteroaromatic molecules（Pyrroles, aniline, thiophene）For monomer, by chemistry or electrochemically oxidative polymerization react
Polypyrrole, polyaniline and the polythiophene of acquisition have the advantages that be readily synthesized, conductivity is high, environmental-friendly and biocompatibility
（J. Phys. Chem. C, 2009, 113, 21586-21595.）, prevent in energy storage and conversion, microwave absorption, electrostatic
The fields such as shield, separation of metal ions, organic photovoltaic devices, gas sensing and bioengineered tissue obtain extensive research and answer
With（Chem. Soc. Rev., 2015, 44, 6684-6696; RSC Adv., 2015, 5, 37553-37567; J.
Mater. Chem. A, 2016, 4, 19060-19069; J. Polym. Sci. B, 2012, 50, 1329-
1351.）.But such conducting polymer has the shortcomings that indissoluble solution, is difficult to film forming（Macromolecules, 2009,
42, 8129-8137）, which has limited them in certain fields（Such as energy storage and conversion, microwave absorption, electrostatic protection, organic
Photovoltaic device etc.）Application.
Conducting polymer is difficult to the π pi accumulations being attributed between polymer chain the reason of dissolving（Macromolecules, 2009,
42, 8129-8137）.In terms of the right angle of polymer poly, the degree of polymerization is higher, molecular weight is bigger, then the dissolubility of polymer is got over
Difference.It says from this point on, synthesizes the oligomer of conducting polymer, be conducive to the dissolubility for improving conducting polymer.In addition, conductive
Polymer oligomer has the unique non-linear optical property for being different from conventional polymer amount conducting polymer（Adv.
Mater., 2007, 19, 173-191.）.Therefore, conducting polymer oligomer is synthesized, there is important scientific meaning and is answered
With value.However, the study on the synthesis in relation to conducting polymer, existing literature focuses primarily upon the conducting polymer of conventional polymer amount
Object field.
The synthetic method of the conducting polymer of conventional polymer amount can be divided into two classes：It is that reaction is situated between that one kind, which is with solution,
The chemical oxidising polymerisation and electrochemically oxidative polymerization method of matter（Chem. Soc. Rev., 2015, 44, 6684-6696.）, letter
Claim solwution method；Another kind of is chemical vapour deposition technique（J. Polym. Sci. B, 2012, 50, 1329-1351.）.Two kinds
Method respectively has advantage and disadvantage：The former the advantages of is, the monomer polymerization reactions time is short, the control synthesis that is easy to implement granule-morphology,
The electric conductivity of product is preferable；The disadvantage is that, product be difficult to be dissolved in conventional organic solvent, be not readily available conductive polymer membrane,
Solution post-processing is more troublesome；The advantages of the latter, is that monomer is solvent-free in polymerization process, can gather without conduction
It is realized in the case of closing object dissolving and deposits one layer of conductive polymer membrane in any substrate surface；The disadvantage is that, being plated in substrate surface
It before film, needs first to coat one layer of oxidant film, after reaction, needs to remove oxidant by cleaning.
Conducting polymer is synthesized using chemical vapour deposition technique, 1986 can be traced back to, T. Ono et al. will be coated
FeCl3Polymer film be exposed in pyrroles's steam, obtain polypyrrole（Nippon Kagaku Kaishi, 1986, 348–
355.）；The same year, A. Hohammadi et al. under vacuum, by pyrroles's steam and high temperature FeCl3Steam is introduced into reative cell
In, using chemical vapour deposition technique polypyrrole is obtained in metal or conductive glass surface（Synth. Met., 1986, 14,
189-197.）.2014, Y. Oaki et al. were using transition metal nitrate crystal as oxidant, using oxidant surface to conduction
The activation of polymer monomer obtains conductive polymer membrane by chemical vapor deposition in a variety of substrate surfaces（Chem.
Commun., 2014, 50, 11840-11843.）.The method in substrate surface without coating oxidant, conducting polymer in advance
Synthesis carry out at normal temperatures and pressures.2015, Y. Oaki groups continued to improve the above method, brilliant with transition metal inorganic salts
Body is oxidant and carrier, and a variety of conducting polymers of morphology controllable are obtained on oxidant surface using chemical vapour deposition technique
（Chem. Commun., 2015, 51, 9698-9701.）.
In addition to the oxidant of such non-volatile transition-containing metal ion, bromine is as a kind of oxygen of effumability at room temperature
Agent is also used to synthesize conducting polymer/copolymer by chemical vapour deposition technique（Chem. Mater., 2010, 22,
2864–2868; Chem. Mater., 2011, 23, 2600-2605.）；But bromine toxicity is big, in building-up process there is
Security risk.
Oxygen is a kind of environmental-friendly gaseous oxidizer, and 1994, S. Izumi et al. were with VO (acac)2‒AlCl3For
Catalyst is passed through dioxygen oxidation pyrroles polymerization, obtains polypyrrole in the acetonitrile solution of pyrroles（Bull. Chem. Soc.
Jpn., 1994, 67, 539-545.）.But using oxygen or air as oxidant, synthesized using chemical vapour deposition technique poly-
Pyrroles or pyrroles's oligomer, up to the present, there is not yet document report.
Invention content
In view of the deficiencies of the prior art, the present invention provides one kind using oxygen or air as oxidant, chemical vapour deposition technique
Synthesize the straightforward procedure of pyrroles's oligomer.
Term is explained：
Oligomer：It is a kind of poly that the polymer chain formed by covalent bond repetition connects by small numbers of monomer is shorter
Body, wherein the number of monomer is generally below 20.
Curing：After pyrroles is mixed with carrier in closed container, the evaporation of pyrroles's molecule is deposited on carrier particle surface,
Then nucleation in situ, growth, the process for forming pyrroles's oligomer.
HOMO：Highest occupied molecular orbital (Highest Occupied Molecular Orbital).
LUMO：Lowest unoccupied molecular orbital (Lowest Unoccupied Molecular Orbital).
A kind of preparation method of pyrroles's oligomer, it is characterised in that：
A. carrier is added in container；
B. pyrroles is added in the container described in step a, container is sealed；
C. by mixing in pyrroles and container of the carrier described in step b, curing obtains carrier/pyrroles's oligomerization nanocrystal composition；
D. the carrier obtained by step c/pyrroles's oligomerization nanocrystal composition is scattered in organic solvent, closed placement, makes pyrrole at room temperature
It coughs up oligomer to be dissolved in organic solvent, then be separated by solid-liquid separation, leave and take supernatant；
E. supernatant is distilled or is evaporated under reduced pressure, obtain pyrroles's oligomer.
Obtained pyrroles's oligomer, weight average molecular weight (M w) it is 522 ~ 912；Molecular weight distribution index is 1.1 ~ 1.3, corresponding
Oligomer containing 8 ~ 14 pyrrole rings.Pyrroles's oligomer be p-type semiconductor, charge carrier density be 1.1 ×
1020~2.1 × 1020 cm‒3。
In step a, under room temperature environment air conditions, carrier is added in container；The room temperature environment air item
It is 0 40 °C that part, which refers to range of temperature, and the relative humidity of surrounding air is 20 80%.
Preferably, the container described in step a is salable, with stirring, the container with charge door.
Preferably, the carrier described in step a, for the carrier with big pi-conjugated system.It is furthermore preferred that described in step a
Carrier, be carbon material, including activated carbon powder, granulated carbon, carbon nanotube, graphene, carbon fiber and carbon cloth.
Preferably, the container described in step a, material are stainless steel, enamel, enamel, ceramics, glass or plastics.
Preferably, the carrier and container described in step a, wherein the volume of carrier is no more than the 60% of vessel volume.
Preferably, in step b, the volume mass ratio for referring to pyrroles and carrier is 10 50 mL/kg.It is furthermore preferred that pyrroles is
Pyrroles, i.e., the pyrroles crossed using preceding re-distillation are steamed again.
Preferably, the mixing described in step c, mode are stirring, shake or vibrate.
Preferably, the curing described in step c, curing time are 7 30 days, stir material 24 during curing daily
Secondary, each mixing time is 1 30 min.
Preferably, the organic solvent described in step d is n,N-Dimethylformamide, tetrahydrofuran, N- crassitudes
Ketone, dimethyl sulfoxide, methanol, ethyl alcohol, isobutanol, ethyl acetate, methyl acetate, Ethyl formate, formic acid, acetic acid, ethamine, second two
One or more of amine, triethylamine.
Preferably, the carrier described in step d/pyrroles's oligomerization nanocrystal composition and organic solvent, wherein organic solvent and load
The volume mass ratio of body/pyrroles's oligomer is 5 10 mL/g.
Preferably, the separation of solid and liquid described in step d, mode are filtering, filter or centrifuge.
Advantageous effect
1, the present invention is using the oxygen in air as oxidant, and using chemical vapour deposition technique, pyrrole is synthesized in carbon material substrate surface
Cough up oligomer.Air source is abundant, at low cost, environmental-friendly.
2, the present invention is directly adsorbed on carbon material substrate without metal/transition-metal catalyst auxiliary using air oxidation
The pyrroles on surface, makes it aggregate into oligomer, this is conducive to save metals resources, reduces cost.
Pyrroles's Molecular Adsorption, due to the π π interactions between two kinds of components, leads to pyrroles's molecule after carbon material surface
Energy level difference between HOMO and LUMO is reduced.In other words, the π π interactions between pyrroles's molecule and carbon substrate have activated pyrroles
Molecule, to make pyrroles's molecule become prone to oxidation by air, polymerization.
3, compared to the polypyrrole prepared by conventional solution method, pyrroles's oligomer prepared by the present invention has higher electricity
Charge carrier density, this is conducive to its application in electrochemical energy storage field.
Description of the drawings
Fig. 1 be sample weight average molecular weight (M w) distribution map.
Fig. 2 is the flight time mass spectrum figure of sample.
Fig. 3 is the relation curve reciprocal with potential change of sample space charge capacity square.
Specific implementation mode
It is further elaborated below by specific embodiment and in conjunction with attached drawing to technical scheme of the present invention, these embodiments
It is intended merely to illustrate technical scheme of the present invention, and the limitation to the claims in the present invention content cannot be considered as.
In embodiment
Activated carbon powder is purchased from Huan Shengtan industry factory shop；
Carbon cloth is purchased from flourishing age commerce and trade row；
Pyrroles is purchased from Shanghai Tong Yuan Chemical Co., Ltd.s；
Methanol, N,N-dimethylformamide, tetrahydrofuran, ethyl acetate are purchased from Tianjin great Mao chemical reagent factories；Formic acid, second
Amine, dimethyl sulfoxide are purchased from Sinopharm Chemical Reagent Co., Ltd..
The weight average molecular weight of sample is obtained through the detection of U.S.'s Waters E2695 gel permeation chromatographs in description of the invention
；The flight time mass spectrum figure of sample is obtained through 6520 flight time of German Agilent liquid phase-mass spectrometer detection；Sample
Chemical property through CHI 660E electrochemical analysers detect obtain.
Embodiment is in 0 40 °C of temperature range（Both such as 0 DEG C, 10 DEG C, 20 DEG C, 30 DEG C, 40 DEG C or arbitrary composition
Range）, surrounding air relative humidity 20 80%（Such as 20%, 30%, 40%, 50%, 60%, 70%, 80% or arbitrary the two group
At range）Under conditions of complete, in this condition and range, the purpose of the present invention can be achieved.
Embodiment 1
A kind of preparation method of pyrroles's oligomer, steps are as follows：
(1) 50 μ L pyrroles are added in the 50 mL containers for filling 1 g activated carbon powders, container is sealed, shake container
So that activated carbon powder is uniformly mixed with pyrroles, cures 30 days at room temperature.During curing, it is shaken every day container 2 times, when shaking every time
Between no less than 1 min, after the maturation period activated carbon/pyrroles's oligomerization nanocrystal composition.
(2) activated carbon obtained by step (1)/pyrroles's oligomerization nanocrystal composition is scattered in 10 mL N, N- dimethyl formyls
It in amine aqueous solution, shakes up, is stored at room temperature 24 h；Centrifugation, leaves and takes supernatant.
(3) supernatant vacuum distillation obtained by step (2) is removed into solvent, obtains pyrroles's oligomer sample.
Embodiment 2
A kind of preparation method of pyrroles's oligomer, steps are as follows：
(1) 10 μ L pyrroles are added in the 50 mL containers for filling 1 g carbon cloths, container are sealed, cured 7 days at room temperature,
Obtain carbon cloth/pyrroles's oligomerization nanocrystal composition.
(2) carbon cloth obtained by step (1)/pyrroles's oligomerization nanocrystal composition is impregnated in 5 mL methanol solutions, room temperature is quiet
Set 24 h；Carbon cloth is taken out, liquid is left and taken.
(3) solvent is distilled off in liquid pressure-reducing obtained by step (2), obtains pyrroles's oligomer sample.
Embodiment 3
Other with embodiment 1, the difference is that：
30 μ L pyrroles are added in the 50 mL containers for filling 1 g granulated carbons, and stirring container makes activated carbon powder be mixed with pyrroles
Uniformly, it cures 10 days at room temperature.During curing, it is shaken every day container 3 times, each shake time is no less than 15 min, gained
Compound is impregnated in 5 mL tetrahydrofuran solutions, is stored at room temperature 28 h；Centrifugation, leaves and takes supernatant.
Embodiment 4
Other with embodiment 1, the difference is that：
20 μ L pyrroles are added in the 50 mL containers for filling 1 g carbon nanotubes, and vibration container keeps activated carbon powder mixed with pyrroles
It closes uniformly, cures 20 days at room temperature.During curing, be shaken every day container 4 times, every time shake 30 min of time, gained it is compound
Object is impregnated in 7 mL ethyl acetate solutions, is stored at room temperature 20 h；It filters, leaves and takes supernatant.
Embodiment 5
Other with embodiment 1, the difference is that：
40 μ L pyrroles are added in the 50 mL containers for filling 1 g graphenes, and the compound of gained is impregnated in 8 mL formic acid solutions
In.
Embodiment 6
Other with embodiment 1, the difference is that：
25 μ L pyrroles are added in the 50 mL containers for filling 1 g carbon fibers, and the compound of gained is impregnated in 6 mL ethylamine solutions
In.
Embodiment 7
Other with embodiment 1, the difference is that：
The compound of gained is impregnated in 5 mL dimethyl sulfoxide solutions.
Interpretation of result
By the n,N-Dimethylformamide solution of 1 gained pyrroles's oligomer of embodiment, it is average to detect it through gel permeation chromatograph
Molecular weight.Fig. 1 be sample weight average molecular weight (M w) distribution map.It will be seen from figure 1 that pyrroles's oligomer prepared by the present invention
Weight average molecular weight be 779, the corresponding oligomer containing 12 pyrrole rings.Molecular weight distribution index is 1.27, prepared by explanation
Oligomer range of molecular weight distributions it is relatively narrow.
The methanol solution of 2 gained pyrroles's oligomer of embodiment is subjected to flying time mass spectrum analysis.Fig. 2 is the flight of sample
Time mass spectrum figure.The peak that mass-to-charge ratio is 652 in Fig. 2 corresponds to the oligomer of 10 pyrrole rings.
Using prepared pyrroles's oligomer as positive active material, lithium piece is cathode, the LiPF of 1 mol/L6It is dissolved in carbonic acid
Ethyl：Dimethyl carbonate：Diethyl carbonate（Volume ratio is 1:1:1）For electrolyte, microporous polypropylene membrane is diaphragm, assembling
CR2032 button cells（Int. J. Electrochem. Sci., 2018, 13,1376-1389.）, using impedance-potential
Method tests the impedance of active material with the relation curve of potential change, according to Mott Schottky formula（Electrochimica
Acta, 2011, 56, 9893-9903.）, the relation curve reciprocal with potential change of rendering space charge capacity square（Figure
3）.
From the figure 3, it may be seen that prepared pyrroles's oligomer is p-type semiconductor, charge carrier density is 1.62 × 1020
cm‒3, hence it is evident that higher than according to conventional solution（Electrochimica Acta, 2005, 50, 4649-4654.）Prepared is poly-
The charge carrier density of pyrroles（2.49 × 1019 cm‒3）.The result shows pyrroles's oligomer prepared by the present invention
With the chemical property better than the polypyrrole prepared by conventional solution method.
Claims (10)
1. a kind of preparation method of pyrroles's oligomer, it is characterised in that：
A. carrier is added in container；
B. pyrroles is added in the container described in step a, container is sealed；
C. by mixing in pyrroles and container of the carrier described in step b, curing obtains carrier/pyrroles's oligomerization nanocrystal composition；
D. the carrier obtained by step c/pyrroles's oligomerization nanocrystal composition is scattered in organic solvent, closed placement, makes pyrrole at room temperature
It coughs up oligomer to be dissolved in organic solvent, then be separated by solid-liquid separation, leave and take supernatant；
E. supernatant is distilled or is evaporated under reduced pressure, obtain pyrroles's oligomer.
2. the preparation method of pyrroles's oligomer as described in claim 1, which is characterized in that obtained pyrroles's oligomer, weight are equal
Molecular weight (M w) it is 522 ~ 912；Molecular weight distribution index is 1.1 ~ 1.3, the corresponding oligomer containing 8 ~ 14 pyrrole rings；
Pyrroles's oligomer is p-type semiconductor, and charge carrier density is 1.1 × 1020~2.1 × 1020 cm‒3。
3. the preparation method of pyrroles's oligomer as described in claim 1, which is characterized in that in step a, in room temperature environment air
Under the conditions of, carrier is added in container；It is 0 40 °C that the room temperature environment air conditions, which refer to range of temperature, ring
The relative humidity of border air is 20 80%.
4. the preparation method of pyrroles's oligomer as described in claim 1, which is characterized in that the carrier described in step a, for tool
There is the carrier of big pi-conjugated system；
It is furthermore preferred that the carrier described in step a, is carbon material, including granulated carbon, carbon nanotube, graphene, carbon fiber and carbon
Cloth.
5. the preparation method of pyrroles's oligomer as described in claim 1, which is characterized in that the container described in step a, material
Matter is stainless steel, enamel, enamel, ceramics, glass or plastics；
Carrier described in step a and container, the volume of carrier are no more than the 60% of vessel volume.
6. the preparation method of pyrroles's oligomer as described in claim 1, which is characterized in that in step b, refer to pyrroles and carrier
Volume mass ratio is 10 50 mL/kg.
7. the preparation method of pyrroles's oligomer as described in claim 1, which is characterized in that the mixing described in step c, side
Formula is stirring, shakes or vibrate；
Curing described in step c, curing time are 7 30 days, stir material during curing daily 24 times, every time when stirring
Between be 1 30 min.
8. the preparation method of pyrroles's oligomer as described in claim 1, which is characterized in that the organic solvent described in step d,
For N,N-dimethylformamide, tetrahydrofuran, N-Methyl pyrrolidone, dimethyl sulfoxide, methanol, ethyl alcohol, isobutanol, acetic acid second
One or more of ester, methyl acetate, Ethyl formate, formic acid, acetic acid, ethamine, ethylenediamine, triethylamine.
9. the preparation method of pyrroles's oligomer as described in claim 1, which is characterized in that carrier/pyrroles described in step d
The volume mass ratio of oligomerization nanocrystal composition and organic solvent, wherein organic solvent and carrier/pyrroles's oligomer is 5 10 mL/g.
10. the preparation method of pyrroles's oligomer as described in claim 1, which is characterized in that the solid-liquid point described in step d
From mode is filtering, filters or centrifuge.
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Citations (2)
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|---|---|---|---|---|
| CN102051048A (en) * | 2010-11-10 | 2011-05-11 | 西北师范大学 | Polypyrrole/graphene nano composite and preparation method thereof |
| CN107522269A (en) * | 2017-09-18 | 2017-12-29 | 同济大学 | The preparation method of porous graphene/Platinum material |
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2018
- 2018-02-27 CN CN201810163015.8A patent/CN108586309B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102051048A (en) * | 2010-11-10 | 2011-05-11 | 西北师范大学 | Polypyrrole/graphene nano composite and preparation method thereof |
| CN107522269A (en) * | 2017-09-18 | 2017-12-29 | 同济大学 | The preparation method of porous graphene/Platinum material |
Non-Patent Citations (2)
| Title |
|---|
| YAFEI DAI, ESTELA BLAISTEN-BAROJAS: "Energetics, structure, and charge distribution of reduced and oxidized n-pyrrole oligomers: A density functional approach", 《THE JOURNAL OF CHEMICAL PHYSICS》 * |
| 宫海礁，邬冰，高颖: "聚吡咯碳复合材料的制备及其作为超级电容器电极的性能", 《化学工程师》 * |
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