CN104479114A - CT-(MIO) modified polythiophene as well as synthesis method and application thereof - Google Patents
CT-(MIO) modified polythiophene as well as synthesis method and application thereof Download PDFInfo
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Abstract
The invention discloses CT-(MIO) modified polythiophene as well as a synthesis method and application thereof. The CT-(MIO) modified polythiophene is obtained by chemically modifying side groups at 3- site and 4- site in the thiophene repetition structure unit of a polythiophene high-polymer material by CT-(MIO) derivatives, or obtained by chemically modifying the side groups at 3- site and 4- site of a thiophene monomer by CT-(MIO) derivatives, and then carrying out a polymerization reaction. According to the CT-(MIO) modified polythiophene disclosed by the invention, free radicals with a proper redox potential are fixed to a conducting polythiophene side chain in a conjugating manner to form a stable free radical polymer, wherein each free radical unit is capable of participating in an electrode reaction, and reaction electronics can be rapidly transmitted through the main chain of the polymer, so that the CT-(MIO) modified polythiophene has excellent electrochemical performance, conductive performance, charge storage density, capacitance retention rate and electrode reaction dynamic performance, and has good rate performance and circulation stability during a charge-discharge circulation process.
Description
Technical field
The invention belongs to material, technical field of chemistry, be specifically related to class benzazine nitric oxide radical modified polythiophene and a preparation method and use.
Background technology
Conducting polymer composite, also can be called conductive polymers, is the macromolecular material that a class has height π key conjugated polymer chain.It had both possessed the electrochemical properties of metal and semi-conductor, possessed again organic macromolecular mechanical property.U.S. Alan J.Heeger, Alan G.MacDiarmid in 1977 and Japanese Hideki Shirakawa three scientists find that crystalline state polyacetylene has obvious electroconductibility, jointly obtain Nobel chemistry Prize in 2000.Over nearly 30 years, conductive polymers extensively causes attention and the interest of chemist and physicist as a class new function material, also becomes the Some Questions To Be Researched of domestic and international field of polymer chemical industry.In succession have developed again the conducting polymer composites such as polypyrrole, polyphenylene sulfide, Polythiophene, polyaniline, poly-phenylene vinylene (ppv), poly-phthalocyanine-like compound at present.
Polythiophene (PTh) is a kind of conducting polymer composite with similar aromatic ring structure, have good environmental stability, less size, be easy to preparation, doping after there is higher electroconductibility and luminescent properties.Its conductive capability can regulate and control from insulation to close in range of metal, and electric conductivity can reach 10
-8~ 10
2s/cm, and the characteristics such as the good electricity of material, optics and mechanics can also be given through processing.Therefore PTh is widely used in different field, as thin film transistor, and battery, antistatic coating, electromagnetic shielding, artificial-muscle, photodiode, gas and biosensor, fuel and solar cell, filler and anticorrosive coating etc.
Be a kind of insoluble not molten polymer without substituting polythiophene, although through doped with higher electric conductivity, processing characteristics is generally poor, is not thus widely used.Compared with other conducting polymer composite, substituting polythiophene derivative has high electrical conductivity and stability, preferably solvability.Alkyl substituted polythiophene derivative has higher solubleness in common organic solvents, is because weaken the interaction between Polythiophene molecular chain introduce alkyl on the 3-position of thiophene after.Along with the increase of alkyl chain, solubility property increases, but electric conductivity reduces, when alkyl is-CH
3,-C
2h
5time electric conductivity reach 10
2s/cm.
Some new substituted base polythiophene conductive macromolecular materials, reach the practical stage gradually in recent years.But the application example with substituent Polythiophenes such as chiral substituent, carboxylic acid or carboxylic acid ester groups is also more limited.Simultaneously, the series of problems occurred in application process, new technical need is proposed to the performance of Polythiophene, as the raising of polymer purity, masking and the processing technology requirement etc. making luminescent device, therefore the application of novel synthesis, material modification improve or give new performance, will promote that polythiophene conducting polymer demonstrates stronger competitive power, thus meet the demand of various high-tech sector.
But the electrochemical doping degree due to conventional conductive polymer is lower and decay is very fast, causes its energy density and cyclical stability to be difficult to meet application requiring.
Summary of the invention
The object of the invention is to overcome current existing Polythiophene (PTh), and to there is electric conductivity lower, electrochemical doping degree is lower and decay is very fast, charging and discharging capacity is lower, efficiency for charge-discharge is lower, solvability and processing characteristics poor, its energy density and cyclical stability is caused to be difficult to meet the problem of application requiring, a kind of polythiophene conductive material containing benzazine nitric oxide radical group and its production and use is provided, thus acquisition one class has high electrochemical redox active, high power density, long circulation life, good dissolving and processing characteristics, and in energy storage density and resource environment benefit etc., have more the free radical polyalcohol material of application advantage.
For achieving the above object, adopt technical scheme as follows:
One class benzazine nitric oxide radical modified polythiophene, it has following structural formula:
Wherein, R
1represent secondary amine atom, phenyl, allyl group or butadienyl equiconjugate group;
R
2, R
3, R
4represent respectively
H，
-R
5,-OR
6,-NR
7r
8, or-NHR
9; R
5, R
6, R
7, R
8, R
9represent hydrogen atom, alkyl, aryl or the alkyl with one or more hydroxyl, alkoxyl group, aryl or aryloxy respectively, n is natural number.
A kind of benzazine nitric oxide radical modified polythiophene, it has following structural formula:
n is natural number.
A kind of benzazine nitric oxide radical modified polythiophene, it has following structural formula:
n is natural number.
A kind of benzazine nitric oxide radical modified polythiophene, it has following structural formula:
n is natural number.
A kind of benzazine nitric oxide radical modified polythiophene, it has following structural formula:
n is natural number.
The synthetic method of above-mentioned benzazine nitric oxide radical modified polythiophene, comprises the following steps:
Carry out chemical modification by benzazine nitric oxide radical derivative to side, 3-, 4-position base in the thiophene repeated structural unit of Polythiophene macromolecular material to get.
The synthetic method of above-mentioned benzazine nitric oxide radical modified polythiophene, comprises the following steps:
By benzazine nitric oxide radical derivative, chemical modification is carried out to thiophene monomer 3-, 4-side, position base, then carry out polyreaction and get.
Above-mentioned benzazine nitric oxide radical modified polythiophene is used as conducting polymer composite.
Above-mentioned benzazine nitric oxide radical modified polythiophene is used as polymer battery material; Described battery material is made up of benzazine nitric oxide radical modified polythiophene and at least one carrier or electro-conductive material; Described benzazine nitric oxide radical modified polythiophene mass percent is 0.1-95%.
By such scheme, described carrier is polyoxyethylene (PEO), polymethylmethacrylate (PMMA), polyacrylonitrile (PAN), polystyrene (PS), polyvinyl acetate (PVA) (PVAc), poly(vinylidene fluoride) (PVDF), polyvinylidene difluoride (PVDF)-R 1216 P (VDF-HFP) or its multipolymer.
By such scheme, described electro-conductive material is LiN, LiAlO, LiCoO
2, LiClO
4, LiFePO
4, Graphene, Graphene, carbon nanotube, soccerballene C
60, C
70one in solid electrolyte, or SiO
2, TiO
2, ZrO
2, Al
2o
3, MgO, Fe
2o
3, MnO
2one in electrochemicaUy inert filler.
Benzazine nitric oxide radical modified polythiophene free radical polyalcohol electro-conductive material can dense arrangement free radical group (active redox point), redox reaction can thoroughly be carried out, and therefore has the advantage such as High Density Charge storage, high power charging-discharging, easily processing.Select of the same race or different free radical polyalcohols as positive and negative electrode, the discharge and recharge reaction on positive pole is R+e=R
-, the discharge and recharge reaction simultaneously carried out at negative pole is R-e=R
+.These two kinds reactions all do not relate to the altered chemical structure of active substance, thus ensure that long term reversibility and the charge-discharge magnification performance of cell reaction.Therefore it has high electrochemical redox active, high power density, long circulation life, good dissolving and processing characteristics, and in energy storage density and resource environment benefit etc., have more the polymer materials of application advantage, the electrode active material of high-performance secondary cell can be used as.The isoparametric size of its electric conductivity in addition, can carry out regulable control by the charge capacity of benzazine nitric oxide radical.
Compared with prior art, beneficial effect of the present invention is as follows:
1) the free radical conjugation with suitable redox electromotive force is fixed on conductive polythiophene side chain and forms stable free radical polyalcohol, wherein each free radical unit can participate in electrode reaction, and reaction electronics can pass through main polymer chain fast transport, therefore benzazine nitric oxide radical modified polythiophene has excellent chemical property, there is good conductivity, higher Charge Storage density, preferably capacity retention, fast electrode reaction dynamic performance, in the process of charge and discharge cycles, there is good high rate performance and cyclical stability.
2) there is the redox property similar with benzazine nitric oxide radical and feature three-wire electronic paramagnetic resonance spectral line.
3) there is excellent Thermal Synthetic mechanical property, physical and mechanical properties.
4) there are excellent solvability and machine-shaping property etc.
Accompanying drawing illustrates:
Accompanying drawing 1: electric capacity-current density plot;
Accompanying drawing 2: electric capacity-scanning turn graph;
Accompanying drawing 3: electron paramagnetic resonance collection of illustrative plates.
Embodiment
Following examples explain technical scheme of the present invention further, but not as limiting the scope of the invention.
Embodiment 1
(3,4-bis-benzazine nitric oxide radical amido)-thiophene copolymers
Two (the three normal-butyl first stannanes) thiophene (1.8392g of N.N-two (tert-butoxycarbonyl)-3,4-diaminothiophen-2,5-, 2.0603mmol) with 2,5-dibromo thiophene (0.499g, 2.0603mmol) is dissolved in 5ml tetrahydrofuran (THF), Pd
2(dba)
3(0.0377g, 0.0412mmol), CuI (0.0393g, 0.2063mmol) and AsPh
3(0.0252g, 0.0824mmol) joins in reaction flask, and drying nitrogen is protected, and reacts 72h at 80 DEG C.After reaction cooling, reaction solution is poured in the KF aqueous solution (10mL, 1.00mol/L), stirs 30 minutes, filters out insoluble white solid.Filtrate, with dichloromethane extraction three times, merges organic layer, anhydrous sodium sulfate drying, solvent removed in vacuo.Add 5mL acetone solution solid, be slowly added drop-wise in 200mL normal hexane, solid collected by filtration, vacuum-drying obtains two (tert-butoxycarbonyl) polythiophene copolymer product.
1.5mL trifluoroacetic acid is joined gained thiophene copolymers (0.1852g, in methylene dichloride (1.5mL) 0.4505mmol) and methyl-phenoxide (1.0mL), stirred at ambient temperature 12h, after reaction terminates, reaction solution is poured into stirring at room temperature 1h in the saturated sodium bicarbonate solution of 10mL, solvent removed in vacuo and water, vacuum-drying obtains the thiophene copolymers product sloughing tert-butoxycarbonyl.
Polythiophene (the 0.031g of tert-butoxycarbonyl will be sloughed, 0.158mmol) join in 5mL toluene, with triethylamine, its pH is transferred to 7-8, by 5-bromo-1,1,3,3-tetramethyl-benzazine nitroxyl free radical (0.085g, 0.316mmol), cesium carbonate (0.164g, 0.5mmol), Pd
2(dba)
3(0.014g, 0.0158mmol) and BINAP (0.006g, 0.00948mmol) join in reaction flask, and drying nitrogen is protected, and is heated to back flow reaction 48h, and filter, filter residue methylene dichloride is washed, and filtrate is spin-dried for.Add 10mL water, dialyse 7 days with dialysis tubing, solvent removed in vacuo, vacuum-drying obtains (3,4-bis-benzazine nitric oxide radical amido)-thiophene copolymers.
Embodiment 2
Poly-(3,4-bis-benzazine nitric oxide radical amido-thiophene)
Two (tert-butoxycarbonyl)-3 of N.N-; 4-diaminothiophen-2; two (the three normal-butyl first stannanes) thiophene (0.9201g of 5-; 1.0301mmol) protect thiophene (0.4862g with bromo tert-butoxycarbonyl; 1.0301mmol) be dissolved in 5mL tetrahydrofuran (THF), Pd
2(dba)
3(0.0185g, 0.0206mmol), CuI (0.0195g, 0.1030mmol) and AsPh
3(0.0126g, 0.0412mmol) joins in reaction flask, and drying nitrogen is protected, and reacts 72h at 80 DEG C.After reaction cooling, reaction solution is poured in the KF aqueous solution (5mL, 1.00mol/L), stirs 30 minutes, filters out insoluble white solid.Filtrate, with dichloromethane extraction three times, merges organic layer, anhydrous sodium sulfate drying, solvent removed in vacuo.Add 3ml acetone solution solid, be slowly added drop-wise in 100mL normal hexane, solid collected by filtration, vacuum-drying obtains tert-butoxycarbonyl Polythiophene product.
3mL trifluoroacetic acid is joined tert-butoxycarbonyl Polythiophene (0.5787g, in methylene dichloride (3.0mL) 0.9000mmol) and methyl-phenoxide (2.0mL), stirred at ambient temperature 12h, after reaction terminates, reaction solution is poured into stirring at room temperature 1h in the saturated sodium bicarbonate solution of 20mL, solvent removed in vacuo and water, vacuum-drying obtains amido substituting polythiophene product.
Amido substituting polythiophene (0.036g will be sloughed, 0.158mmol) join in 10mL toluene, with triethylamine, its pH is transferred to 7-8, by 5-bromo-1,1,3,3-tetramethyl-benzazine nitroxyl free radical (0.170g, 0.651mmol), cesium carbonate (0.328g, 1.0mmol), Pd
2(dba)
3(0.028g, 0.0316mmol) and BINAP (0.012g, 0.0190mmol) join in reaction flask, and drying nitrogen is protected, and is heated to back flow reaction 48h, and filter, filter residue methylene dichloride is washed, and filtrate is spin-dried for.Add 15mL water, dialyse 7 days with dialysis tubing, solvent removed in vacuo, vacuum-drying is gathered (3,4-bis-benzazine nitric oxide radical amido-thiophene).
With reference to shown in accompanying drawing 1, electric capacity-the current density plot of embodiment 1 gained electro-conductive material TMIO-PTh (1), embodiment 2 gained electro-conductive material TMIO-PTh (2), benzazine nitric oxide radical TMIO, Polythiophene PTh, the electric capacity-scanning turn graph of attached 2 gained electro-conductive materials embodiment illustrated in fig. 2.Benzazine nitric oxide radical modified polythiophene of the present invention can be obtained there is excellent chemical property, there is good conductivity, higher Charge Storage density, preferably capacity retention, fast electrode reaction dynamic performance, in the process of charge and discharge cycles, there is good high rate performance and cyclical stability; Within 1000 weeks, charge and discharge cycles still can keep the coulombic efficiency of more than 87%.
With reference to the electron paramagnetic resonance collection of illustrative plates of attached 2 gained electro-conductive materials embodiment illustrated in fig. 3, it has the redox property similar with benzazine nitric oxide radical and feature three-wire electronic paramagnetic resonance spectral line.
Embodiment 3
Poly-(3,4-bis-benzazine nitric oxide radical vinyl-thiophene)
(2,5-dibromo thiophene-3-methylene radical)-phosphoric acid ester (0.062g, 0.158mmol) is dissolved in DMF (2mL), is joined in reaction solution by sodium methylate (0.008mg is in 1mL DMF) under ice bath.5-bromo-1,1,3,3-tetramethyl-benzazine nitroxyl free radical (0.03g, 0.1376mmol) joins in reaction solution and reacts 30 minutes.Pour in frozen water by solution after reaction terminates, extracted with diethyl ether, washing, anhydrous magnesium sulfate drying, filter, solvent removed in vacuo, column chromatography (methylene dichloride) is purified and is obtained radical modification thiophene product.
Radical modification thiophene (0.114g, 0.25mmol) is dissolved in 5mL tetrahydrofuran (THF), and drying nitrogen is protected, by CH
3mgBr (ether solution of 0.12mL, 0.25mmol, 2.1mol/L) is added drop-wise in reaction flask, by Ni (dppp) Cl after back flow reaction 1h
2(0.15mg) be added in reaction flask and react 2h.After reaction terminates, reaction solution is poured in 100mL methyl alcohol, filter, collect filter residue.10mL water is added in solid, dialyses 7 days with dialysis tubing, solvent removed in vacuo, and vacuum-drying is gathered (3,4-bis-benzazine nitric oxide radical vinyl-thiophene).
Embodiment 4
(3,4-bis-benzazine nitric oxide radical vinyl)-thiophene copolymers
(2,5-dibromo thiophene-3-methylene radical)-phosphoric acid ester (0.062g, 0.158mmol) is dissolved in DMF (2ml), is joined in reaction solution by sodium methylate (0.008mg is in 1mL DMF) under ice bath.5-bromo-1,1,3,3-tetramethyl-benzazine nitroxyl free radical (0.03g, 0.1376mmol) joins in reaction solution and reacts 30 minutes.Pour in frozen water by solution after reaction terminates, extracted with diethyl ether, washing, anhydrous magnesium sulfate drying, filter, solvent removed in vacuo, column chromatography (methylene dichloride) is purified and is obtained radical modification thiophene product.
Radical modification thiophene (0.114g, 0.25mmol) and 2,5-(3-butyl tin) thiophene (0.166g, 0.25mmol) is dissolved in 3mL tetrahydrofuran (THF), Pd
2(dba)
3(0.0050g, 0.0055mmol), CuI (0.004g, 0.0257mmol) and AsPh
3(0.0032g, 0.0103mmol) joins in reaction flask, and drying nitrogen is protected, and reacts 72h at 80 DEG C.After reaction cooling, reaction solution is poured in the KF aqueous solution (3mL, 1.00mol/L), stirs 30 minutes, filters out insoluble white solid.Filtrate, with dichloromethane extraction three times, merges organic layer, anhydrous sodium sulfate drying, solvent removed in vacuo.Add 2mL acetone solution solid, be slowly added drop-wise in 100mL normal hexane, solid collected by filtration, vacuum-drying obtains (3,4-bis-benzazine nitric oxide radical vinyl)-thiophene copolymers product.
Embodiment 5
(3,4-bis-benzazine nitric oxide radical amido)-thiophene copolymers 0.2g, polyoxyethylene (PEO, molecular weight is 2000) 0.05g, γ-Fe in Example 1
2o
30.1g adds in 20mL tetrahydrofuran (THF), adds 20mL distilled water with vigorous stirring, and stir 3 hours, pressure reducing and steaming solvent, vacuum-drying obtains Fe
2o
3/ polythiophene composite material.
Embodiment 6
(3 are gathered in Example 2,4-bis-benzazine nitric oxide radical amido-thiophene) 0.05g, polyvinylidene difluoride (PVDF)-R 1216 P (VDF-HFP) 0.05g add 10mLN, in dinethylformamide, stir 2 hours, pressure reducing and steaming solvent, vacuum-drying obtains polyvinylidene difluoride (PVDF)-R 1216/polythiophene composite material.
Embodiment 7
Poly-(3,4-bis-benzazine nitric oxide radical vinyl-thiophene) 1.0g, polyacrylonitrile (PAN) 0.2g, SiO in Example 3
20.2g adds in 20mL tetrahydrofuran (THF), and stir 4 hours, pressure reducing and steaming solvent, vacuum-drying obtains polyacrylonitrile/Fe
2o
3/ polythiophene composite material.
Embodiment 8
In Example 4 (3,4-bis-benzazine nitric oxide radical vinyl)-thiophene copolymers 0.5g, LiAlO 0.01g adds in 20mL dimethyl sulfoxide (DMSO), stir 1 hour, pressure reducing and steaming solvent, vacuum-drying obtains LiAlO/ polythiophene composite material.
Claims (10)
1. a class benzazine nitric oxide radical modified polythiophene, is characterized in that having following structural formula:
Wherein, R
1represent secondary amine atom, phenyl, allyl group or butadienyl equiconjugate group;
R
2, R
3, R
4represent respectively
-R
5,-OR
6,-NR
7r
8, or-NHR
9; R
5, R
6, R
7, R
8, R
9represent hydrogen atom, alkyl, aryl or the alkyl with one or more hydroxyl, alkoxyl group, aryl or aryloxy respectively, n is natural number.
2. a benzazine nitric oxide radical modified polythiophene, is characterized in that having following structural formula:
n is natural number.
3. a benzazine nitric oxide radical modified polythiophene, is characterized in that having following structural formula:
n is natural number.
4. a benzazine nitric oxide radical modified polythiophene, is characterized in that having following structural formula:
n is natural number.
5. a benzazine nitric oxide radical modified polythiophene, is characterized in that having following structural formula:
n is natural number.
6. the synthetic method of benzazine nitric oxide radical modified polythiophene described in any one of claim 1-5, comprises the following steps:
Carry out chemical modification by benzazine nitric oxide radical derivative to side, 3-, 4-position base in the thiophene repeated structural unit of Polythiophene macromolecular material to get.
7. the synthetic method of benzazine nitric oxide radical modified polythiophene described in any one of claim 1-5, comprises the following steps:
By benzazine nitric oxide radical derivative, chemical modification is carried out to thiophene monomer 3-, 4-side, position base, then carry out polyreaction and get.
8. benzazine nitric oxide radical modified polythiophene described in any one of claim 1-5 is as the purposes of conducting polymer composite.
9. benzazine nitric oxide radical modified polythiophene described in any one of claim 1-5 is as the purposes of polymer battery material.
10. benzazine nitric oxide radical modified polythiophene, as the purposes of polymer battery material, is characterized in that described battery material is made up of benzazine nitric oxide radical modified polythiophene and at least one carrier or electro-conductive material as claimed in claim 9; Described benzazine nitric oxide radical modified polythiophene mass percent is 0.1-95%; Described carrier is polyoxyethylene, polymethylmethacrylate, polyacrylonitrile, polystyrene, polyvinyl acetate (PVA), poly(vinylidene fluoride), polyvinylidene difluoride (PVDF)-R 1216 or its multipolymer; Described electro-conductive material is LiN, LiAlO, LiCoO
2, LiClO
4, LiFePO
4, Graphene, Graphene, carbon nanotube, soccerballene C
60, C
70one in solid electrolyte, or SiO
2, TiO
2, ZrO
2, Al
2o
3, MgO, Fe
2o
3, MnO
2one in electrochemicaUy inert filler.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113423755A (en) * | 2019-02-07 | 2021-09-21 | 马丁·舍丁 | Conductive redox oligomers |
| CN114106032A (en) * | 2021-12-15 | 2022-03-01 | 江西省科学院应用化学研究所 | Preparation method of thiophene monomer and application of thiophene monomer in preparation of polythiophene anticorrosive paint |
| CN115093549A (en) * | 2022-08-04 | 2022-09-23 | 浙江吉泰新材料股份有限公司 | Polythiophene with side chain containing ABNO, and preparation method and application thereof |
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| CN1951155A (en) * | 2004-05-14 | 2007-04-18 | 出光兴产株式会社 | Organic electroluminescent device |
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| CN1951155A (en) * | 2004-05-14 | 2007-04-18 | 出光兴产株式会社 | Organic electroluminescent device |
Non-Patent Citations (1)
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| 沈艳春等: "异氮杂茚自由基改性聚噻吩及其导电性能", 《2014年全国高分子材料科学与工程研讨会学术论文集（下册）》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113423755A (en) * | 2019-02-07 | 2021-09-21 | 马丁·舍丁 | Conductive redox oligomers |
| CN114106032A (en) * | 2021-12-15 | 2022-03-01 | 江西省科学院应用化学研究所 | Preparation method of thiophene monomer and application of thiophene monomer in preparation of polythiophene anticorrosive paint |
| CN114106032B (en) * | 2021-12-15 | 2023-10-03 | 江西省科学院应用化学研究所 | Preparation method of thiophene monomer and application of thiophene monomer in preparation of polythiophene anti-corrosion coating |
| CN115093549A (en) * | 2022-08-04 | 2022-09-23 | 浙江吉泰新材料股份有限公司 | Polythiophene with side chain containing ABNO, and preparation method and application thereof |
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