CN104479114B - Benzazine nitric oxide radical modified polythiophene and preparation method and use thereof - Google Patents
Benzazine nitric oxide radical modified polythiophene and preparation method and use thereof Download PDFInfo
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- CN104479114B CN104479114B CN201410707973.9A CN201410707973A CN104479114B CN 104479114 B CN104479114 B CN 104479114B CN 201410707973 A CN201410707973 A CN 201410707973A CN 104479114 B CN104479114 B CN 104479114B
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Abstract
The invention discloses class benzazine nitric oxide radical modified polythiophene and a preparation method and use thereof.Carried out chemical modification by 3,4 side bases in the benzazine nitric oxide radical derivative thiophene constitutional repeating unit to polythiophene macromolecular material to get.Or by benzazine nitric oxide radical derivative to thiophene monomer 3,4 side bases carry out chemical modification, then carry out polymerisation and get.The present invention has the free radical conjugation of suitable redox electromotive force and is fixed on conductive polythiophene side chain and forms stable free radical polyalcohol, the most each free radical unit can participate in electrode reaction, and reaction electronics quickly can be transmitted by main polymer chain, therefore benzazine nitric oxide radical modified polythiophene has excellent chemical property, electric conductivity, electric charge storage density, capacity retention, electrode reaction dynamic performance, has good high rate performance and cyclical stability during charge and discharge cycles.
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 conjunction
One-tenth method and purposes.
Background technology
Conducting polymer composite, it is possible to be referred to as conducting polymer, be a class have height π key conjugated polymer chain macromolecular material.
It had both possessed the electrochemical properties of metal and semiconductor, possessed again the mechanical performance of organic macromolecule.U.S. Alan J. in 1977
Heeger, Alan G.MacDiarmid and Japan three scientists of Hideki Shirakawa find that crystalline state polyacetylene has obvious electric conductivity,
Jointly obtain Nobel chemistry Prize in 2000.Over nearly 30 years, conducting polymer the most extensively draws as a class new function material
Play chemist and the attention of physicist and interest, also become the Some Questions To Be Researched of domestic and international field of polymer chemical industry.At present
The most in succession have developed polypyrrole, polyphenylene sulfide, polythiophene, polyaniline, poly-phenylene vinylene (ppv), poly-phthalocyanine-like compound etc. to lead
Electricity macromolecular material.
Polythiophene (PTh) is a kind of conducting polymer composite with similar aromatic ring structure, have preferable environmental stability,
After less size, easily prepared, doping, there is higher electric conductivity and luminescent properties.Its conductive capability can be from insulating to connecing
Regulation and control in nearly range of metal, conductance can reach 10-8～102S/cm, and it is the most electric to can also impart to material through processing
The characteristics such as, optics and mechanics.Therefore PTh is widely used to different field, such as thin film transistor (TFT), battery, antistatic painting
Material, electromagnetic shielding, artificial-muscle, light emitting diode, gas and biology sensor, fuel and solar cell, filler is with anti-
Etching ground etc..
Unsubstituted polythiophene is a kind of insoluble insoluble macromolecule, although pass through doped with higher conductance, but processing characteristics is general
All over poor, thus it is not widely used.Compared with other conducting polymer composite, substituting polythiophene derivative has
High electrical conductivity and stability, preferable dissolubility.Alkyl substituted polythiophene derivative has higher in common organic solvents
Solubility, weakens the interaction of polythiophene molecule interchain after being because on the 3-position of thiophene introducing alkyl.Along with alkyl chain
Increase, solubility property increase, but conductance reduce, when alkyl is-CH3、-C2H5Time conductance reach 102S/cm。
Some new substituted base polythiophene conductive macromolecular materials, have progressivelyed reach the practical stage in recent years.But there is chirality replace
The application example also ratio of the polythiophene of the substituents such as base, carboxylic acid or carboxylic acid ester groups is relatively limited.Meanwhile, occur in application process
Series of problems, the performance of polythiophene is proposed new technical need, such as the raising of polymer purity, masking is sent out with making
The process technology requirement etc. of optical device, the therefore application of novel synthesis, material modification improve or give new performance, will promote
Enter polythiophene conducting polymer and demonstrate higher competitiveness, thus meet the demand of various high-tech sector.
But, owing to the electrochemical doping degree of conventional conductive polymer is relatively low and decay very fast, cause its energy density steady with circulation
Qualitative being difficult to meets application requirement.
Summary of the invention
Present invention aim to overcome that current existing polythiophene (PTh) exists that conductance is relatively low, electrochemical doping degree is relatively low and declines
Subtract very fast, charging and discharging capacity is relatively low, efficiency for charge-discharge is relatively low, dissolubility with processing characteristics is poor, cause its energy density with
Cyclical stability is difficult to meet the problem that application requires, it is provided that a kind of polythiophene containing benzazine nitric oxide radical group is led
Electric material and its production and use, thus obtain a class and there is high electrochemical redox active, high power density, grow and follow
Ring life-span, good dissolving and processing characteristics, and in the freedom of the aspect more application advantages such as energy storage density and resource environment benefit
Base polymeric material.
For reaching above-mentioned purpose, use technical scheme as follows:
One class benzazine nitric oxide radical modified polythiophene, it has a following structural formula:
Wherein, R1Represent secondary amine atom, phenyl, pi-allyl or butadienyl equiconjugate group；
R2、R3、R4Represent respectively
H,
-R5,-OR6,-NR7R8, or-NHR9；R5、R6、R7、R8、R9Represent hydrogen atom, alkyl, aryl respectively
Or the alkyl with one or more hydroxyls, alkoxyl, aryl or aryloxy group, n is natural number.
A kind of benzazine nitric oxide radical modified polythiophene, it has a following structural formula:
N is natural number.
A kind of benzazine nitric oxide radical modified polythiophene, it has a following structural formula:
N is natural number.
A kind of benzazine nitric oxide radical modified polythiophene, it has a following structural formula:
N is natural number.
A kind of benzazine nitric oxide radical modified polythiophene, it has a following structural formula:
N is natural number.
The synthetic method of above-mentioned benzazine nitric oxide radical modified polythiophene, comprises the following steps:
By 3-, 4-side, position in the benzazine nitric oxide radical derivative thiophene constitutional repeating unit to polythiophene macromolecular material
Base carries out chemical modification and gets.
The synthetic method of above-mentioned benzazine nitric oxide radical modified polythiophene, comprises the following steps:
By benzazine nitric oxide radical derivative, thiophene monomer 3-, 4-side, position base is carried out chemical modification, be then polymerized
Reaction gets.
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 by different nitrogen
Miscellaneous indenes nitric oxide radical modified polythiophene and at least one carrier or conductive material composition；Described benzazine nitric oxide radical
Modified polythiophene mass percent is 0.1-95%.
By such scheme, described carrier is polyethylene glycol oxide (PEO), polymethyl methacrylate (PMMA), polyacrylonitrile
(PAN), polystyrene (PS), polyvinyl acetate (PVAc), polyvinylidene fluoride (PVDF), Kynoar-hexafluoro third
Alkene P (VDF-HFP) or its copolymer.
By such scheme, described conductive material is LiN, LiAlO, LiCoO2、LiClO4、LiFePO4, Graphene, stone
Ink alkene, CNT, fullerene C60、C70One in solid electrolyte, or SiO2、TiO2、ZrO2、Al2O3、
MgO、Fe2O3、MnO2One in electrochemicaUy inert filler.
Benzazine nitric oxide radical modified polythiophene free radical polyalcohol conductive material (can be lived with dense arrangement free radical group
Property redox point), redox reaction can thoroughly be carried out, and therefore has High Density Charge storage, high power charging-discharging, easily
The advantages such as processing.Selecting of the same race or different free radical polyalcohols is R+e=as both positive and negative polarity, the discharge and recharge reaction on positive pole
R-, the discharge and recharge reaction simultaneously carried out at negative pole is R-e=R+.Both reactions are all not related to the chemical constitution of active material and become
Change, thus ensure that long term reversibility and the charge-discharge magnification performance of cell reaction.Therefore it has high electrochemical redox work
Property, high power density, long circulation life, good dissolving and processing characteristics, and in sides such as energy storage density and resource environment benefits
The polymeric material of face more application advantage, can serve as the electrode active material of high-performance secondary cell.Additionally its conductance etc.
The size of parameter, can regulate control by the load capacity of benzazine nitric oxide radical.
Compared with prior art, the present invention has the beneficial effect that:
1) the free radical conjugation with suitable redox electromotive force is fixed on conductive polythiophene side chain and forms stable radical polymerization
Thing, the most each free radical unit can participate in electrode reaction, and reaction electronics quickly can be transmitted by main polymer chain, because of
This benzazine nitric oxide radical modified polythiophene has excellent chemical property, has preferable electric conductivity, higher
Electric charge storage density, preferable capacity retention, quick electrode reaction dynamic performance, have during charge and discharge cycles
There are 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 is excellent dissolubility 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.
Detailed description of the invention
Following example explain technical scheme further, but not as limiting the scope of the invention.
Embodiment 1
(3,4-bis-benzazine nitric oxide radical amido)-thiophene copolymers
Double (tert-butoxycarbonyl)-3 of N.N-, 4-diaminothiophen-2, double (the three normal-butyl first stannanes) thiophene of 5-(1.8392g,
2.0603mmol) with 2,5-dibromo thiophene (0.499g, 2.0603mmol) is dissolved in 5ml oxolane, Pd2(dba)3(0.0377g,
0.0412mmol), CuI (0.0393g, 0.2063mmol) and AsPh3(0.0252g, 0.0824mmol) joins reaction bulb
In, drying nitrogen is protected, and reacts 72h at 80 DEG C.After reaction cooling, reactant liquor pours (10mL, 1.00mol/L) in the KF aqueous solution into,
Stir 30 minutes, filter out insoluble white solid.Filtrate extracts three times with dichloromethane, merges organic layer, anhydrous sodium sulfate
It is dried, solvent removed in vacuo.Add 5mL acetone solution solid, be slowly dropped in 200mL n-hexane, solid is collected by filtration,
Vacuum drying obtains double (tert-butoxycarbonyl) polythiophene copolymer product.
1.5mL trifluoroacetic acid is joined the dichloromethane (1.5mL) of gained thiophene copolymers (0.1852g, 0.4505mmol)
With in methyl phenyl ethers anisole (1.0mL), stirring 12h under room temperature, reactant liquor is poured into 10mL by reaction saturated sodium bicarbonate after terminating is molten
1h, solvent removed in vacuo and water are stirred at room temperature in liquid, and vacuum drying obtains sloughing the thiophene copolymers product of tert-butoxycarbonyl.
The polythiophene (0.031g, 0.158mmol) sloughing tert-butoxycarbonyl is joined in 5mL toluene, will with triethylamine
Its pH is transferred to 7-8, by 5-bromo-1,1,3,3-tetramethyl benzazine NO free radical (0.085g, 0.316mmol), cesium carbonate
(0.164g, 0.5mmol), Pd2(dba)3(0.014g, 0.0158mmol) and BINAP (0.006g, 0.00948mmol)
Joining in reaction bulb, drying nitrogen is protected, and is heated to back flow reaction 48h, filters, and filter residue dichloromethane is washed, by filtrate
It is spin-dried for.Adding 10mL water, dialyse 7 days with bag filter, solvent removed in vacuo, vacuum drying obtains (3,4-bis-benzazine oxygen
Change nitrogen free radical amido)-thiophene copolymers.
Embodiment 2
Poly-(3,4-bis-benzazine nitric oxide radical amido-thiophene)
Double (tert-butoxycarbonyl)-3 of N.N-, 4-diaminothiophen-2, double (the three normal-butyl first stannanes) thiophene of 5-(0.9201g,
1.0301mmol) it is dissolved in 5mL oxolane with bromo tert-butoxycarbonyl protection thiophene (0.4862g, 1.0301mmol),
Pd2(dba)3(0.0185g, 0.0206mmol), CuI (0.0195g, 0.1030mmol) and AsPh3(0.0126g, 0.0412mmol)
Joining in reaction bulb, drying nitrogen is protected, and reacts 72h at 80 DEG C.After reaction cooling reactant liquor pour in the KF aqueous solution (5mL,
1.00mol/L), stir 30 minutes, filter out insoluble white solid.Filtrate extracts three times with dichloromethane, merges organic layer,
Anhydrous sodium sulfate is dried, solvent removed in vacuo.Add 3ml acetone solution solid, be slowly dropped in 100mL n-hexane, filter
Collecting solid, vacuum drying obtains tert-butoxycarbonyl polythiophene product.
3mL trifluoroacetic acid is joined the dichloromethane (3.0mL) of tert-butoxycarbonyl polythiophene (0.5787g, 0.9000mmol)
With in methyl phenyl ethers anisole (2.0mL), stirring 12h under room temperature, reactant liquor is poured into 20mL by reaction saturated sodium bicarbonate after terminating is molten
1h, solvent removed in vacuo and water are stirred at room temperature in liquid, and vacuum drying obtains amido substituting polythiophene product.
Amido substituting polythiophene (0.036g, 0.158mmol) will be sloughed and join in 10mL toluene, with triethylamine by its pH
It is transferred to 7-8, by 5-bromo-1,1,3,3-tetramethyl benzazine NO free radical (0.170g, 0.651mmol), cesium carbonate (0.328g,
1.0mmol), Pd2(dba)3(0.028g, 0.0316mmol) and BINAP (0.012g, 0.0190mmol) join reaction
In Ping, drying nitrogen is protected, and is heated to back flow reaction 48h, filters, and filter residue dichloromethane is washed, and filtrate is spin-dried for.Add
15mL water, dialyses 7 days with bag filter, solvent removed in vacuo, and vacuum drying obtains poly-(3,4-bis-benzazine nitrogen oxides freedom
Base amido-thiophene).
Referring to the drawings shown in 1, embodiment 1 gained conductive material TMIO-PTh (1), embodiment 2 gained conductive material TMIO-PTh
(2), the electric capacity-current density plot of benzazine nitric oxide radical TMIO, polythiophene PTh, attached embodiment illustrated in fig. 2
The electric capacity of 2 gained conductive materials-scanning turn graph.Benzazine nitric oxide radical modified polythiophene of the present invention can be obtained and have excellent
Good chemical property, has preferable electric conductivity, higher electric charge storage density, preferable capacity retention, quickly
Electrode reaction dynamic performance, has good high rate performance and cyclical stability during charge and discharge cycles；Within 1000 weeks, fill
Discharge cycles remains to keep the coulombic efficiency of more than 87%.
The electron paramagnetic resonance collection of illustrative plates of 3 illustrated embodiment 2 gained conductive materials referring to the drawings, it has and benzazine nitrogen oxide
The similar redox property of free 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)-phosphate (0.062g, 0.158mmol) is dissolved in DMF (2mL), ice bath
Lower sodium methoxide (0.008mg is in 1mL DMF) is joined in reactant liquor.5-bromo-1,1,3,3-tetramethyl benzazine nitrogen
Oxygen radical (0.03g, 0.1376mmol) joins in reactant liquor and reacts 30 minutes.Reaction pours solution into frozen water after terminating
In, ether extracts, washing, and anhydrous magnesium sulfate is dried, and filters, and solvent removed in vacuo, column chromatography (dichloromethane) purifies
To radical modification thiophene product.
Radical modification thiophene (0.114g, 0.25mmol) is dissolved in 5mL oxolane, and drying nitrogen is protected, by CH3MgBr
(ether solution of 0.12mL, 0.25mmol, 2.1mol/L) is added drop-wise in reaction bulb, by Ni (dppp) Cl after back flow reaction 1h2
(0.15mg) it is added in reaction bulb react 2h.Reactant liquor is poured in 100mL methyl alcohol after terminating by reaction, filters, and collects filter
Slag.10mL water is added in solid, dialyses 7 days with bag filter, solvent removed in vacuo, and vacuum drying obtains poly-(3,4-bis-different nitrogen
Miscellaneous indenes nitric oxide radical vinyl-thiophene).
Embodiment 4
(3,4-bis-benzazine nitric oxide radical vinyl)-thiophene copolymers
(2,5-dibromo thiophene-3-methylene)-phosphate (0.062g, 0.158mmol) is dissolved in DMF (2ml), under ice bath
Sodium methoxide (0.008mg is in 1mL DMF) is joined in reactant liquor.5-bromo-1,1,3,3-tetramethyl benzazine nitrogen oxygen
Free radical (0.03g, 0.1376mmol) joins in reactant liquor and reacts 30 minutes.Solution is poured in frozen water after terminating by reaction,
Ether extracts, washing, and anhydrous magnesium sulfate is dried, and filters, solvent removed in vacuo, and column chromatography (dichloromethane) purifies and obtains certainly
By base modification thiophene product.
Radical modification thiophene (0.114g, 0.25mmol) and 2,5-(3-butyl tin) thiophene (0.166g, 0.25mmol) is molten
In 3mL oxolane, Pd2(dba)3(0.0050g, 0.0055mmol), CuI (0.004g, 0.0257mmol) and AsPh3
(0.0032g, 0.0103mmol) joins in reaction bulb, and drying nitrogen is protected, and reacts 72h at 80 DEG C.After reaction cooling instead
Answer liquid to pour (3mL, 1.00mol/L) in the KF aqueous solution into, stir 30 minutes, filter out insoluble white solid.Filtrate is used
Dichloromethane extracts three times, merges organic layer, and anhydrous sodium sulfate is dried, solvent removed in vacuo.Add 2mL acetone solution solid,
Being slowly dropped in 100mL n-hexane, solid is 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 in Example 1, polyethylene glycol oxide (PEO,
Molecular weight is 2000) 0.05g, γ-Fe2O30.1g adds in 20mL oxolane, adds 20mL distillation with vigorous stirring
Water, stirs 3 hours, and decompression boils off solvent, and vacuum drying prepares Fe2O3/ polythiophene composite material.
Embodiment 6
Poly-(3,4-bis-benzazine nitric oxide radical amido-thiophene) 0.05g, Kynoar-hexafluoropropene in Example 2
P (VDF-HFP) 0.05g adds 10mLN, in dinethylformamide, stirs 2 hours, and decompression boils off solvent, vacuum drying
Prepare Kynoar-hexafluoropropene/polythiophene composite material.
Embodiment 7
Poly-(3,4-bis-benzazine nitric oxide radical vinyl-thiophene) 1.0g in Example 3, polyacrylonitrile (PAN) 0.2g,
SiO20.2g adds in 20mL oxolane, stirs 4 hours, and decompression boils off solvent, and vacuum drying prepares polyacrylonitrile/Fe2O3
/ polythiophene composite material.
Embodiment 8
In Example 4, (3,4-bis-benzazine nitric oxide radical vinyl)-thiophene copolymers 0.5g, LiAlO 0.01g adds
Entering in 20mL dimethyl sulfoxide (DMSO), stir 1 hour, decompression boils off solvent, and vacuum drying prepares LiAlO/ polythiophene composite material.
Claims (6)
1. a benzazine nitric oxide radical modified polythiophene, it is characterised in that there is following structural formula:
N is natural number.
2. a benzazine nitric oxide radical modified polythiophene, it is characterised in that there is following structural formula:
N is natural number.
3. a benzazine nitric oxide radical modified polythiophene, it is characterised in that there is following structural formula:
N is natural number.
4. benzazine nitric oxide radical modified polythiophene described in any one of claim 1-3 is as the use of conducting polymer composite
On the way.
5. benzazine nitric oxide radical modified polythiophene described in any one of claim 1-3 is as the use of polymer battery material
On the way.
6. benzazine nitric oxide radical modified polythiophene as claimed in claim 5 is as the purposes of polymer battery material, its
It is characterised by that described battery material is by benzazine nitric oxide radical modified polythiophene and at least one carrier or conductive material group
Become；Described benzazine nitric oxide radical modified polythiophene mass percent is 0.1-95%；Described carrier is polyoxyethylene
Alkene, polymethyl methacrylate, polyacrylonitrile, polystyrene, polyvinyl acetate, polyvinylidene fluoride, Kynoar-
Hexafluoropropene or its copolymer；Described conductive material is Li3N、LiAlO2、LiCoO2、LiClO4、LiFePO4, Graphene,
CNT, fullerene C60、C70One in solid electrolyte, or SiO2、TiO2、ZrO2、Al2O3、MgO、Fe2O3、
MnO2One in electrochemicaUy inert filler.
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