CN103665348B - Thiophene copolymers and preparation method thereof - Google Patents
Thiophene copolymers and preparation method thereof Download PDFInfo
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- CN103665348B CN103665348B CN201310665212.7A CN201310665212A CN103665348B CN 103665348 B CN103665348 B CN 103665348B CN 201310665212 A CN201310665212 A CN 201310665212A CN 103665348 B CN103665348 B CN 103665348B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/13—Energy storage using capacitors
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Abstract
The invention discloses a kind of thiophene copolymers, there is following structural formula:
Description
Technical field
The present invention relates to technical field of novel high polymer material, particularly relate to a kind of thiophene copolymers and preparation method thereof.
Background technology
Ultracapacitor is a kind of novel energy accumulating device, has the advantage such as high power density, high cycle life.Mesh
The electrode material of front ultracapacitor is mainly porous carbon material, metal-oxide and polymeric material.Relative to first two electricity
Pole material, the ultracapacitor with polymer as electrode material has the advantages such as high-energy-density, light weight and designability are strong.
Polymer conducting material is broadly divided into polypyrrole, polyaniline and polythiophene three class, the wherein electric conductivity of polythiophene
Most preferably, thus become the focus of research.Polymer super capacitor is generally divided into three classes, i.e. I type, II type and type III.I type electricity
Two electrodes of container use the conducting polymer of same p-type doping；II type capacitor uses two kinds of different p-types doping to lead
Electric polymer；Type III capacitor then an electrode p-type doping, another electrode n-type doping.Type III capacitor has than I, II type
Have bigger storage electricity, therefore select a kind of can p-type doping also can the conducting polymer of n-type doping, its energy can be improved
Metric density, can reduce again the preparation cost of electrode material.
Summary of the invention
Based on this, it is necessary to provide a kind of can p-type doping also can the thiophene copolymers and preparation method thereof of n-type doping.
A kind of thiophene copolymers, has a following structural formula:
Wherein, x:y is 1:9～9:1, and n is the integer of 1～20, and-R is
In one embodiment ,-CnH2n+1For straight chained alkyl, n is 4,6,8,12 or 16.
In one embodiment,
-R be
The preparation method of a kind of thiophene copolymers, comprises the steps:
Thering is provided compound A and compound B, the structural formula of described compound A and described compound B is as follows:
Wherein, n is the integer of 1～20, and-R is
At room temperature, under conditions of solvent and catalyst exist, it is x:y by described compound A and described according to mol ratio
Compound B mixes, and fully isolated and purified after reaction obtains described thiophene copolymers, and the structural formula of described thiophene copolymers is as follows:
Thiophene copolymers:Wherein, x:y is 1:9～9:1.
In one embodiment, described compound A is made by the steps and obtains:
3 bromo thiophene and pairs of 2-phenyl-phosphine oxide Nickel Chloride compound are dissolved in oxolane, slowly add after ice bath stirring
Enter CnH2n+1MgBr, fully reacts under stirring condition, isolated and purified after obtain described compound A, wherein, 3 bromo thiophene, double two
Phenylphosphine propane Nickel Chloride compound and CnH2n+1The mol ratio of MgBr is 100:1:120.
In one embodiment ,-CnH2n+1For straight chained alkyl, n is 4,6,8,12 or 16.
In one embodiment, described compound B is made by the steps and obtains:
3 bromo thiophene and pairs of 2-phenyl-phosphine oxide Nickel Chloride compound are dissolved in oxolane, slowly add after ice bath stirring
Enter fluorobenzene magnesium bromide, fully react under stirring condition, isolated and purified after obtain described compound B, wherein, 3 bromo thiophene, double
The mol ratio of diphenylphosphine propane Nickel Chloride compound and fluorobenzene magnesium bromide is 100:1:120, the change of fluorobenzene magnesium bromide
Formula is as follows:
Fluorobenzene magnesium bromide:
In one embodiment, fluorobenzene magnesium bromide is
In one embodiment, described solvent is CHCl3；
Described catalyst is FeCl3, the molal quantity of described catalyst and described compound A and described compound B mole
The ratio of number sum is 10:1.
In one embodiment, isolated and purified obtain described thiophene copolymers operation be: reactant liquor boils off after solvent
Thick product, described thick product volume ratio is that the mixed liquor of the first alcohol and water of 3:1 cleans, and obtains described thiophene copolymers.
Containing long chain alkane group and fluorobenzene group in this thiophene copolymers, long chain alkane group makes thiophene copolymers
Having solubility, the fluorine atom in fluorobenzene group has electronegativity, molecule can be made to have electrophilic characteristic, thus make thiophene altogether
Polymers is provided simultaneously with p-type and n-type doping characteristic.Therefore, this thiophene copolymers can p-type doping also can n-type doping.
Can p-type doping also can this thiophene copolymers of n-type doping when preparing ultracapacitor, can be combined into
Type III capacitor element, makes capacitor have and higher compares electric capacity.
Accompanying drawing explanation
Fig. 1 is the flow chart of the preparation method of the thiophene copolymers of an embodiment.
Detailed description of the invention
Understandable, below in conjunction with the accompanying drawings to the present invention for enabling the above-mentioned purpose of the present invention, feature and advantage to become apparent from
Detailed description of the invention be described in detail.Elaborate a lot of detail in the following description so that fully understanding this
Bright.But the present invention can implement to be much different from alternate manner described here, and those skilled in the art can be not
Doing similar improvement in the case of running counter to intension of the present invention, therefore the present invention is not limited by following public being embodied as.
The thiophene copolymers of one embodiment, has a following structural formula:
X:y is 1:9～9:1, and n is the integer of 1～20, and-R is
Preferably, x:y is 3:7.
Preferably ,-CnH2n+1For straight chained alkyl.The room steric hindrance of straight key alkyl is relatively small, and the productivity when polymerization is compared
In high to alkyl group, n is 4,6,8,12 or 16.Carbon number is the most, and the dissolubility of thiophene copolymers is the best, but electrical conductivity can be by
Gradually reduce, thus affect the performance of capacitor.Particularly preferred, n is 8.
Preferably ,-R is
Fluorine belongs to strong electron-withdrawing group group, beneficially n-type doping, and therefore fluorine atom number is the most, thiophene copolymers n-type doping
Rate is the biggest, and the specific capacity of thiophene copolymers capacitor is the highest.
Particularly preferred ,-R is
Containing long chain alkane group and fluorobenzene group in this thiophene copolymers, long chain alkane group makes thiophene copolymers
Having solubility, the fluorine atom in fluorobenzene group has electronegativity, molecule can be made to have electrophilic characteristic, thus make thiophene altogether
Polymers is provided simultaneously with p-type and n-type doping characteristic.Therefore, this thiophene copolymers can p-type doping also can n-type doping.
Can p-type doping also can this thiophene copolymers of n-type doping when preparing ultracapacitor, can be combined into
Type III capacitor element, makes capacitor have and higher compares electric capacity.
The preparation method of above-mentioned thiophene copolymers as shown in Figure 1, comprises the steps:
S10, offer compound A and compound B.
The structural formula of compound A and compound B is as follows:
Wherein, n is the integer of 1～20, and-R is
Compound A can be made by the steps and obtain: by 3 bromo thiophene and pairs of 2-phenyl-phosphine oxide Nickel Chloride
Compound is dissolved in oxolane, is slowly added into C after ice bath stirringnH2n+1MgBr, fully reacts under stirring condition, isolated and purified after
Obtain described compound A, wherein, 3 bromo thiophene, pairs of 2-phenyl-phosphine oxide Nickel Chloride compound and CnH2n+1MgBr mole
Ratio is 100:1:120.
Shown in the following chemical equation of preparation process of compound A:
The operation obtaining compound A after isolated and purified is: reactant liquor separates organic layer after being neutralized with hydrochloric acid, and boils off solvent and obtains
Thick product, by thick product recrystallization in methanol, obtains compound A.
Preferably ,-CnH2n+1For straight chained alkyl, n is 4,6,8,12 or 16.
Compound B can be made by the steps and obtain: by 3 bromo thiophene and pairs of 2-phenyl-phosphine oxide Nickel Chloride
Compound is dissolved in oxolane, is slowly added into fluorobenzene magnesium bromide, fully reacts under stirring condition after ice bath stirring, isolated and purified after
Obtain described compound B, wherein, rubbing of 3 bromo thiophene, pairs of 2-phenyl-phosphine oxide Nickel Chloride compound and fluorobenzene magnesium bromide
That ratio is 100:1:120, and the chemical formula of fluorobenzene magnesium bromide is as follows:
Fluorobenzene magnesium bromide:
Shown in the following chemical equation of preparation process of compound B:
The operation obtaining compound B after isolated and purified is: reactant liquor separates organic layer after being neutralized with hydrochloric acid, and boils off solvent and obtains
Thick product, by thick product recrystallization in methanol, obtains compound B.
Preferably, fluorobenzene magnesium bromide is
On the one hand, fluorine belongs to strong electron-withdrawing group group, beneficially n-type doping, and therefore fluorine atom number is the most, thiophene copolymers
N-type doping rate is the biggest, and the specific capacity of thiophene copolymers capacitor is the highest.On the other hand, if the 2nd and the 6th quilt of substituent group
Replace, reaction can be caused to be difficult to due to sterically hindered reason or cannot be carried out.
Therefore, fluorobenzene magnesium bromide isFor most preferably scheme.
S20, at room temperature, under conditions of solvent and catalyst exist, be that x:y is by compound A and chemical combination according to mol ratio
Thing B mixes, and fully isolated and purified after reaction obtains thiophene copolymers.
The structural formula of thiophene copolymers is as follows: thiophene copolymers:
Wherein, x:y is 1:9～9:1.
Solvent can be CHCl3。
Catalyst can be FeCl3, the molal quantity of catalyst with the ratio of the molal quantity sum of compound A and compound B is
10:1.
Isolated and purified obtain thiophene copolymers operation be: reactant liquor boils off after solvent to obtain thick product, thick product volume
Clean than methanol and the water mixed liquid for 3:1, obtain thiophene copolymers.
The preparation method of this thiophene copolymers, preparation process is simple, and the thiophene copolymers prepared is applied to capacitor system
There is time standby the advantage that electrode preparation specific capacity convenient, electrode material is high.
The thiophen polymer that the preparation method of this thiophene copolymers prepares dissolves in common organic solvents, and specific capacity is the highest
Up to 285F/g, the capability retention after cycle charge-discharge 500 times is up to 90%.
It it is below specific embodiment.
Embodiment 1
Step one: by 3 bromo thiophene (0.1mol) and NiCl2(dppp)] (1mmol) is dissolved in the THF of 100ml, and ice bath stirs
Mix one hour, magnesium bromide is slowly added to mixed liquor for butane (0.12mol), after stirring is reacted 12 hours, uses 1mol/L hydrochloric acid
Neutralize, separate organic layer, boil off solvent and obtain thick product, then recrystallization in methanol, obtain 3-butyl thiophene monomer.
Step 2: 3-butyl thiophene monomer (0.05mol) is dissolved in 80ml CHCl3In, add the FeCl of 0.08mol3, room
Temperature stirring reaction 24 hours, boils off solvent and obtains thick product, clean with the mixed liquor of the first alcohol and water that volume ratio is 3:1, the most prepared
Thiophen polymer.
Embodiment 2～5
Embodiment 2～5 step method is substantially the same manner as Example 1, and difference is: use bromination in embodiment 2 step one
Magnesium is for hexane；Embodiment 3 step one use magnesium bromide for octane；Embodiment 4 step one use magnesium bromide for n-dodecane；
Embodiment 5 step one use magnesium bromide for hexadecane.
The specific capacity of the capacitor prepared by thiophen polymer that embodiment 1～5 prepares listed by table 1.
| Than electric capacity (F/g) | Capability retention after circulating 500 times | |
| Embodiment 1 | 176 | 91% |
| Embodiment 2 | 172 | 90% |
| Embodiment 3 | 165 | 92% |
| Embodiment 4 | 124 | 92% |
| Embodiment 5 | 88 | 93% |
Table 1
As can be seen from Table 1, falling sharply occurs in the specific capacity of embodiment 3 and embodiment 4, and considers capacity and dissolubility from common
Angle, in preferred embodiment 3 select magnesium bromide for octane.
Embodiment 6～10
Embodiment 6～10 step method is substantially the same manner as Example 1, and difference is: use 1-bromine in embodiment 6 step one
Change magnesium-3 fluorobenzene；Embodiment 7 step one uses 1-magnesium bromide-4 fluorobenzene；In embodiment 8 step one use 1-magnesium bromide-
3,4-difluoro-benzene；Embodiment 9 step one uses 1-magnesium bromide-3,5-difluoro-benzene；Embodiment 10 step one uses 1-
Magnesium bromide-3,4,5-trifluoro-benzene.
The performance of the thiophen polymer that embodiment 6～10 prepares listed by table 2.
| Example | Dissolubility | Than electric capacity (F/g) | Capability retention after circulating 500 times |
| Embodiment 6 | Slightly soluble | 276 | 72% |
| Embodiment 7 | Slightly soluble | 278 | 68% |
| Embodiment 8 | Insoluble | 286 | 52% |
| Embodiment 9 | Insoluble | 282 | 54% |
| Embodiment 10 | Insoluble | 302 | 46% |
Table 2
As can be seen from Table 2, the thiophen polymer that nearly all embodiment 6～10 prepares all shows as being practically insoluble in one
As organic solvent, its electrode plates prepared is due to poor dispersion, and capability retention that its circulation is 500 times is on the low side.
Embodiment 11
Step one: by 3 bromo thiophene (0.1mol) and NiCl2(dppp)] (1mmol) is dissolved in the THF of 100ml, and ice bath stirs
Mix one hour, magnesium bromide is slowly added to mixed liquor for octane (0.12mol), after stirring is reacted 12 hours, uses 1mol/L hydrochloric acid
Neutralize, separate organic layer, boil off solvent and obtain thick product, then recrystallization in methanol, obtain 3-octyl thiophene monomer.
Step 2: by 3 bromo thiophene (0.1mol) and NiCl2(dppp)] (1mmol) is dissolved in the THF of 100ml, and ice bath stirs
Mix one hour, 1-magnesium bromide-3.4.5-trifluoro-benzene (0.12mol) is slowly added to mixed liquor, after stirring is reacted 12 hours, use
1mol/L hydrochloric acid neutralizes, and separates organic layer, boils off solvent and obtain thick product, and then recrystallization in methanol, obtains 3-(3, and 4,5-tri-
Difluorophenyl) thiophene monomer.
Step 3: by 3-octyl thiophene (0.01mol) and 3-(3,4,5-trifluoro-benzene base) thiophene (0.09mol) mixes molten
In 150ml CHCl3In, add FeCl3(0.13mol), reaction 24 hour is stirred at room temperature, boils off solvent and obtain thick product, use volume
Clean than the mixed liquor of the first alcohol and water for 3:1, i.e. obtain thiophene copolymers.
Embodiment 12～19
Embodiment 12～19 step method is substantially the same manner as Example 11, and difference is: monomer in embodiment 12 step 3
Rate of charge is 3-octyl thiophene (0.02mol) and 3-(3,4,5-trifluoro-benzene base) thiophene (0.08mol)；Embodiment 13 step 3
Middle monomeric charge is than for 3-octyl thiophene (0.03mol) and 3-(3,4,5-trifluoro-benzene base) thiophene (0.07mol)；Embodiment 14
In step 3, monomeric charge is than for 3-octyl thiophene (0.04mol) and 3-(3,4,5-trifluoro-benzene base) thiophene (0.06mol)；Real
Execute in example 15 step 3 monomeric charge than for 3-octyl thiophene (0.05mol) and 3-(3,4,5-trifluoro-benzene base) thiophene
(0.05mol)；In embodiment 16 step 3, monomeric charge is than for 3-octyl thiophene (0.06mol) and 3-(3,4,5-trifluoro-benzene
Base) thiophene (0.04mol)；In embodiment 17 step 3, monomeric charge is than for 3-octyl thiophene (0.07mol) and 3-(3,4,5-tri-
Difluorophenyl) thiophene (0.03mol)；In embodiment 18 step 3, monomeric charge is than for 3-octyl thiophene (0.08mol) and 3-(3,
4,5-trifluoro-benzene base) thiophene (0.02mol)；In embodiment 19 step 3, monomeric charge is than for 3-octyl thiophene (0.09mol)
With 3-(3,4,5-trifluoro-benzene base) thiophene (0.01mol).
The performance of the thiophen polymer that embodiment 11～19 prepares listed by table 3.
| Example | Dissolubility | Than electric capacity (F/g) | Capability retention after circulating 500 times |
| Embodiment 11 | Slightly soluble | 278 | 66% |
| Embodiment 12 | Solvable | 282 | 88% |
| Embodiment 13 | Solvable | 285 | 90% |
| Embodiment 14 | Solvable | 263 | 91% |
| Embodiment 15 | Solvable | 246 | 92% |
| Embodiment 16 | Solvable | 221 | 90% |
| Embodiment 17 | Solvable | 211 | 91% |
| Embodiment 18 | Solvable | 188 | 88% |
| Embodiment 19 | Solvable | 169 | 89% |
As can be seen from Table 3, the thiophen polymer that embodiment 11～19 prepares all shows preferable dissolubility, and it is prepared
Electrode plates dispersibility preferable, capability retention that its circulation is 500 times is higher.
Embodiment described above only have expressed the several embodiments of the present invention, and it describes more concrete and detailed, but also
Therefore the restriction to the scope of the claims of the present invention can not be interpreted as.It should be pointed out that, for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, it is also possible to make some deformation and improvement, these broadly fall into the guarantor of the present invention
Protect scope.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (4)
1. a thiophene copolymers, it is characterised in that there is following structural formula:
Wherein, x:y is 3:7～9:1；
-CnH2n+1For straight chained alkyl, n is 8；
-R be
2. the preparation method of a thiophene copolymers, it is characterised in that comprise the steps:
Thering is provided compound A and compound B, the structural formula of described compound A and described compound B is as follows:
At room temperature, under conditions of solvent and catalyst exist, it is that x:y is by described compound A and described chemical combination according to mol ratio
Thing B mixes, and fully isolated and purified after reaction obtains described thiophene copolymers, and the structural formula of described thiophene copolymers is as follows:
Thiophene copolymers:Wherein, x:y is 3:7～9:1；
Described compound A is made by the steps and obtains: by 3 bromo thiophene and pairs of 2-phenyl-phosphine oxide Nickel Chloride compound
It is dissolved in oxolane, after ice bath stirring, is slowly added into CnH2n+1MgBr, fully reacts under stirring condition, isolated and purified after obtain
Described compound A, wherein, 3 bromo thiophene, pairs of 2-phenyl-phosphine oxide Nickel Chloride compound and CnH2n+1The mol ratio of MgBr is
100:1:120；
-CnH2n+1For straight chained alkyl, n is 8；
Described compound B is made by the steps and obtains: by 3 bromo thiophene and pairs of 2-phenyl-phosphine oxide Nickel Chloride compound
Be dissolved in oxolane, be slowly added into fluorobenzene magnesium bromide after ice bath stirring, fully react under stirring condition, isolated and purified after obtain
Described compound B, wherein, 3 bromo thiophene, pairs of 2-phenyl-phosphine oxide Nickel Chloride compound and the mol ratio of fluorobenzene magnesium bromide
For 100:1:120；
Fluorobenzene magnesium bromide is
The preparation method of thiophene copolymers the most according to claim 2, it is characterised in that described solvent is CHCl3；
Described catalyst is FeCl3, the molal quantity of described catalyst and described compound A and the molal quantity sum of described compound B
Ratio be 10:1.
The preparation method of thiophene copolymers the most according to claim 2, it is characterised in that isolated and purified obtain described thiophene
The operation of copolymer is: reactant liquor obtains thick product after boiling off solvent, and described thick product volume ratio is the mixed of the first alcohol and water of 3:1
Conjunction liquid cleans, and obtains described thiophene copolymers.
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Non-Patent Citations (3)
| Title |
|---|
| "Change in Opto-elecrical Characteristics in Poly[3-octylthiophene-co-3-(4-fluorophenyl)thiophene] according to the Copolymerization Ratio";Seon-Ho Shin，et al;《Polymer(Korea)》;20010531;第25卷(第3期);第399-405页 * |
| "ELECTROCHEMICAL COPOLYMERIZATION OF 3-(4-FLUROPHENYL)THIOPHENE AND 3-METHYLTHIOPHENE IN BORON TRIFLUORIDE DIETHYL ETHERATE";Jing-kun Xu，et al;《Chinese Journal of Polymer Science》;20061231;第24卷(第3期);第253-263页 * |
| "Studies on the Synthesis of Poly(3-octylthiophene-co-3-(4-fluorophenyl)thiophene) and Its Opto-electrical Characteristics as a Red Emitting Materical";Seon-Ho Shin，et al;《J. Korean Ind. Eng. Chem.》;20010531;第12卷(第3期);第348-351页 * |
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