CN109880066A - A kind of Han Xi Pin unit conjugated polymer and the preparation method and application thereof - Google Patents
A kind of Han Xi Pin unit conjugated polymer and the preparation method and application thereof Download PDFInfo
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Abstract
The present invention discloses a kind of Han Xi Pin unit conjugated polymer and the preparation method and application thereof.The Han Xi Pin unit conjugated polymer, structural formula are shown below:Wherein, n is the integer between 35 to 80.Polyselenophenes class material has many advantages, such as that preferable main chain coplanarity, excellent stability, band gap are narrow and mobility is high compared to other conjugated polymers, polymer based on Xi Pin unit and benzene-naphthalene diimide unit equally has relatively narrow band gap, is potential thermoelectric material.Under the conditions of n-type doping, this quasi polymer can act synergistically with carbon nanotube, show N-type semiconductor property stable in air, and widened the research range of N-type Organic thermoelectric material, can be used for preparing relatively stable thermo-electric device.
Description
Technical field
The present invention relates to Organic thermoelectric material field more particularly to a kind of Han Xi Pin unit conjugated polymer and its preparation sides
Method and application.
Background technique
Due to the growing tension of energy supply and being on the rise for environmental pollution, thermoelectric material is because of its internal carrier harmony
Transporting and interacting for son may be implemented mutually to convert between thermal energy and electric energy, and generate electricity to low-grade energy and waste heat
The characteristics of and be concerned.Organic polymer thermoelectric material, as polyaniline, polythiophene, polypyrrole, polycarbazole, polyphenylacetylene and
Its derivative etc., compared to inorganic thermoelectric material (alloy and its solid solution, skutterudite, calcium cobaltate-based oxide, boride, height
Manganese silicide etc.) have it is resourceful, it is low in cost, be easily-synthesized, easy processing and the advantages such as environmental-friendly.It is especially most of poly-
The thermal conductivity for closing object material is very low, only about 0.1~1W/mK, 1~2 order of magnitude lower than inorganic thermoelectric material, therefore organic
The performance of polymer thermoelectric material can be by power factor PF=S2σ is characterized, and wherein S is the Seebeck coefficient of material, and σ is
Conductivity.
Device made of pyroelectric effect using material is known as thermo-electric device, and thermocouple is to being constitute thermo-electric device basic
Unit is generally connected in series by p-type and N-type thermoelectric material through metal electrode.So far, reported organic polymer in document
Most of object thermoelectric material belongs to P-type semiconductor.Such as Zhu etc. is using 3,4-rthylene dioxythiophene as donor, by changing receptor,
Synthesize the conjugated polymer of four kinds of different structures containing donor-acceptor-donor.They all have relatively narrow band gap, respectively
1.19eV, 1.05eV, 1.14eV and 1.07eV.Wherein receptor is that the conjugated polymer thermoelectricity capability of thiazole unit is best, power
The factor is about 0.03 μ W/m K2.Mario etc. has probed into influence of the carbazole polymer structure to thermoelectricity capability.It was found that using FeCl3
Polycarbazole thiadiazoles after doping, conductivity highest can achieve 500S/cm, and possess higher Seebeck coefficient (70 μ
V/K), final power factor is 19 μ W/m K2, illustrate that the introducing of thiadiazole unit can make conjugated polymer show better heat
Electrical property.It is also had made some progress about the research of N-type Organic thermoelectric material in recent years, Pei Jian etc. passes through to based on benzo two
Chlorine atom is introduced on phenylenevinylene's BDPPV skeleton of furasndione, the mode of fluorine atom obtains the new N-type polymer of two classes
ClBDPPV and FBDPPV.Since the higher carrier mobility of polymer itself and efficient doping process make their tables
Reveal higher conductivity, especially FBDPPV, conductivity peak is about 14S/cm, and power factor is 28 μ W/m K2.But
It is that most radical anions generated by n-type doping easily react with oxygen, so leading to N-type thermoelectric material in air very
It is unstable, system is few, performance is low furthermore is also faced to the research of N-type Organic thermoelectric material and the problems such as doping difficulty.
As polythiophene analog, polyselenophenes class material has preferable main chain coplanarity, excellent stability, band gap
The narrow and mobility characteristic for being better than polythiophene class material such as high.And the atomic radius of Se is greater than S, the ability for making it accommodate charge
It is stronger, corresponding polyselenophenes class material can doping level be also higher than polythiophene class material.Polyselenophenes class material is in electroluminescent change
Multiple application fields such as color, field effect transistor, solar battery have been shown good application prospect, and cause scientists
More and more concerns, but up to the present the research about such high mobility narrow band gap polymer thermoelectricity capability also rarely has report
Road.
Therefore, the existing technology needs to be improved and developed.
Summary of the invention
In view of above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a kind of Han Xi Pin unit conjugated polymer and
Preparation method and application, it is intended to solve the radical anion that most n-type dopings generate and easily be reacted with oxygen and lead to N-type thermoelectricity
The problem of material is very unstable in air, and preparation can only be completed with processing in inert atmosphere glove box.
Technical scheme is as follows:
A kind of Han Xi Pin unit conjugated polymer, wherein its structural formula is shown below:
Wherein, n is the integer between 35 to 80.
A kind of preparation method of the Han Xi Pin unit conjugated polymer, wherein comprising steps of
Following monomer is provided:
Monomer I:
Monomer II:
The monomer I and the monomer II are added in organic solvent, and catalyst and ligand is added, carries out Stille
The Han Xi Pin unit conjugated polymer is prepared in coupling reaction.
Further, the catalyst is tris(dibenzylideneacetone) dipalladium.
Further, the ligand is three (o-tolyl) phosphines.
Further, the organic solvent is anhydrous chlorobenzene.
Further, the molar ratio of the monomer I and the monomer II is 1:1.
Further, the temperature of the Stille coupling reaction is 105-115 DEG C.
Further, the time of the Stille coupling reaction is 70-75 hours.
A kind of composite material being combined based on Han Xi Pin unit conjugated polymer of the present invention and carbon nanotube
As the application in thermoelectric material.
The utility model has the advantages that polyselenophenes class material has preferable main chain coplanarity, excellent compared to other conjugated polymers
Stability, the advantages that band gap is narrow and mobility is high, the polymer based on selenium Pin unit and benzene-naphthalene diimide unit equally has
There is relatively narrow band gap, is potential thermoelectric material.Under the conditions of n-type doping, this quasi polymer can act synergistically with carbon nanotube, table
Reveal N-type semiconductor property stable in air, and widened the research range of N-type Organic thermoelectric material, can be used for preparing
Relatively stable thermo-electric device.
Detailed description of the invention
Fig. 1 is the UV-visible-near infrared absorption figure of Han Xi Pin unit conjugated polymer in embodiment.
Fig. 2 is the density functional theory DFT research of Han Xi Pin unit conjugated polymer in embodiment.
Fig. 3 is Han Xi Pin unit conjugated polymer and carbon nanotube composite when content of carbon nanotubes is 10% in embodiment
Expect the thermoelectricity capability figure after doping.
Fig. 4 is Han Xi Pin unit conjugated polymer and carbon nanotube composite when content of carbon nanotubes is 30% in embodiment
Expect the thermoelectricity capability figure after doping.
Fig. 5 is Han Xi Pin unit conjugated polymer and carbon nanotube composite when content of carbon nanotubes is 50% in embodiment
Expect the thermoelectricity capability figure after doping.
Fig. 6 is Han Xi Pin unit conjugated polymer and carbon nanotube composite when content of carbon nanotubes is 70% in embodiment
Expect the thermoelectricity capability figure after doping.
Fig. 7 is Han Xi Pin unit conjugated polymer and carbon nanotube composite when content of carbon nanotubes is 90% in embodiment
Expect the thermoelectricity capability figure after doping.
Specific embodiment
The present invention provides a kind of Han Xi Pin unit conjugated polymer and the preparation method and application thereof, to make mesh of the invention
, technical solution and effect it is clearer, clear, the present invention is described in more detail below.It should be appreciated that described herein
Specific embodiment be only used to explain the present invention, be not intended to limit the present invention.
The embodiment of the present invention provides a kind of Han Xi Pin unit conjugated polymer, wherein its structural formula is shown below:
Wherein, n is the integer between 35 to 80.
Polyselenophenes class material compared to other conjugated polymers have preferable main chain coplanarity, excellent stability,
The advantages that band gap is narrow and mobility is high, the polymer based on selenium Pin unit and benzene-naphthalene diimide unit equally has relatively narrow band
Gap is potential thermoelectric material.Under the conditions of n-type doping, this quasi polymer can act synergistically with carbon nanotube, show in air
Stable N-type semiconductor property, and the research range of N-type Organic thermoelectric material has been widened, it can be used for preparing relatively stable
Thermo-electric device.
The embodiment of the present invention provides the preparation method of Han Xi Pin unit conjugated polymer described in one kind, wherein including step
It is rapid:
Following monomer is provided:
Monomer I:
Monomer II:
The monomer I and the monomer II are added in organic solvent, and catalyst and ligand is added, carries out Stille
The Han Xi Pin unit conjugated polymer is prepared in coupling reaction.
In one embodiment, the catalyst is tris(dibenzylideneacetone) dipalladium.
In one embodiment, the ligand is three (o-tolyl) phosphines, acts on the progress to promote coupling reaction.
In one embodiment, the organic solvent is anhydrous chlorobenzene.
In one embodiment, the molar ratio of the monomer I and the monomer II is 1:1.
In one embodiment, the temperature of the Stille coupling reaction is 105-115 DEG C.
In one embodiment, the time of the Stille coupling reaction is 70-75 hours.
The composite wood that Han Xi Pin unit conjugated polymer described in a kind of embodiment of the present invention and carbon nanotube are combined
Material is as the application in thermoelectric material.
Han Xi Pin unit conjugated polymer of the embodiment of the present invention can act synergistically with carbon nanotube, show to stablize in air
N-type semiconductor property, and widened the research range of N-type Organic thermoelectric material, can be used for preparing relatively stable thermoelectricity
Device.
The present invention is further described in detail below by specific embodiment.
1, the synthesis of Han Xi Pin unit conjugated polymer
(1) 141.93mg monomer I is rapidly joined into dry three-necked flask:81.48mg monomer
II:5.92mg tris(dibenzylideneacetone) dipalladium and 7.88mg tri- (o-tolyl) phosphine,
It is passed through argon gas into flask after connection reflux unit and seals, the anhydrous chlorobenzene of 6ml deoxygenation is added into flask by syringe.
(2) it will be placed in the oil bath pan on magnetic stirring apparatus equipped with the flasks of reaction raw materials, be slowly warming up to 110 DEG C, and
Constant temperature reflux, reacts 72h.
(3) the mixing liquid chloroform being cooled to room temperature is diluted and is washed with deionized water, the organic layer that liquid separation obtains
It is dry with anhydrous magnesium sulfate, and solvent is removed by rotary evaporation and obtains solid.
(4) solid is dissolved in tetrahydrofuran/acetone in the mixed solvent, revolving speed 7000rpm purifies dry after being centrifuged 30 minutes
It is dry to obtain target product.
2, the preparation of Han Xi Pin unit conjugated polymer and carbon nano tube compound material and chemical doping
1 Han Xi Pin unit conjugated polymer of table/carbon nano tube compound material formula table
According to 1 proportionate relationship formula table of table, Han Xi Pin unit conjugated polymer and carbon nanotube are weighed respectively, is placed in
In 30ml sample bottle, 10ml anhydrous chlorobenzene is added, solution is placed in ultrasonic cell disrupte machine ultrasound 60min by stirring at normal temperature 2h.
The glass slide of purchase is cut into 15 × 15mm2Small pieces, successively cleaned with deionized water, acetone and isopropanol,
It is dried with nitrogen.Under room temperature, by the Han Xi Pin unit conjugated polymer/carbon nano tube compound material solution drop coating prepared in
Clean slide surface, until solvent volatilization film forming.
1,3- dimethyl -2- phenyl -2,3- dihydro -1H- benzimidazole (N-DMBI) is dissolved in dehydrated alcohol obtain it is dense
Degree is the solution of 50mmol/l, and laminated film, which is immersed in the solution, carries out chemical doping, takes out after 30 minutes and uses dehydrated alcohol
It sufficiently cleans and is dried in air environment.
3, result and analysis
Fig. 1 is the UV-visible-near infrared absorption figure of Han Xi Pin unit conjugated polymer thin films, which exists
Have maximum absorption band at 717nm, by initial absorption wavelength 892nm can calculate the optical band gap of polymer is about 1.39eV,
Belong to narrow band gap polymer.
Fig. 2 is that the density functional theory DFT of Han Xi Pin unit conjugated polymer studies schematic diagram.Keeping polymer molecule
In the case that chain backbone is constant, the long alkyl side chain on benzene-naphthalene diimide unit is replaced simplifying with methyl, be tied to calculating
Fruit influences little.Polymer molecular structure is carried out in B3LYP/6-31G* level by Spartan software 2016
Optimization.Highest occupied molecular orbital HOMO energy level is -5.4eV, and electron cloud is mainly distributed on diazosulfide He on Xi Pin unit.
Lowest unoccupied molecular orbital lumo energy is -3.5eV, and electron cloud is mainly distributed on benzene-naphthalene diimide unit.By HOMO energy
The band gap that grade and the available DFT of the difference of lumo energy are calculated is about 1.9eV.
Fig. 3 is content of carbon nanotubes when being 10%, and Han Xi Pin unit conjugated polymer and carbon nano tube compound material are adulterating
Thermoelectricity capability variation with temperature situation afterwards.Conductivity is increased with temperature and is increased, and material shows as semiconductor property.
Seebeck coefficient is all negative value within the temperature range of 300K-420K, shows that the composite material belongs to N-type semiconductor.
Seebeck coefficient reaches -51.38 μ V/K of maximum value in 300K, and it is 0.39 μ W/ that power factor then reaches maximum value in 420K
m K2。
Fig. 4 is content of carbon nanotubes when being 30%, and Han Xi Pin unit conjugated polymer and carbon nano tube compound material are adulterating
Thermoelectricity capability variation with temperature situation afterwards.Conductivity is equally increased with temperature and is increased, and Seebeck coefficient is increased with temperature
And reduce, it is -48.11 μ V/K that Seebeck coefficient, which reaches maximum value in 300K, and power factor maximum value in 400K is 7.14
μW/m K2。
Fig. 5 is content of carbon nanotubes when being 50%, and Han Xi Pin unit conjugated polymer and carbon nano tube compound material are adulterating
Thermoelectricity capability variation with temperature situation afterwards.Seebeck coefficient maximum value be -36.93 μ V/K, power factor and conductivity with
The trend of temperature change is consistent, increases and increases with temperature substantially, and power factor maximum value in 420K is 36.13 μ W/m K2。
Fig. 6 is content of carbon nanotubes when being 70%, and Han Xi Pin unit conjugated polymer and carbon nano tube compound material are adulterating
Thermoelectricity capability variation with temperature situation afterwards.Seebeck coefficient reaches -37.57 μ V/K of maximum value, power factor in 300K
In 420K, maximum value is 42.21 μ W/m K2。
Fig. 7 is content of carbon nanotubes when being 90%, and Han Xi Pin unit conjugated polymer and carbon nano tube compound material are adulterating
Thermoelectricity capability variation with temperature situation afterwards.Conductivity maximum value in 420K is 1126S/cm, and Seebeck coefficient is in 300K
When maximum value be -37.29 μ V/K, power factor in 420K maximum value be 78.60 μ W/m K2.It can be seen that with carbon nanometer
The increase of pipe content, Seebeck coefficient when 300K are gradually reduced, and conductivity gradually rises, and power factor is also gradually increased, but
It is that composite material after all doping belongs to N-type thermoelectric material in air environment, even if temperature is increased to 420K, still table
It is now N-type, it is relatively stable.
In conclusion polyselenophenes class material has preferable main chain coplanarity, excellent compared to other conjugated polymers
Stability, the advantages that band gap is narrow and mobility is high, the polymer based on selenium Pin unit and benzene-naphthalene diimide unit equally has
There is relatively narrow band gap, is potential thermoelectric material.Under the conditions of n-type doping, this quasi polymer can act synergistically with carbon nanotube, table
Reveal N-type semiconductor property stable in air, and widened the research range of N-type Organic thermoelectric material, can be used for preparing
Relatively stable thermo-electric device.
It should be understood that the application of the present invention is not limited to the above for those of ordinary skills can
With improvement or transformation based on the above description, all these modifications and variations all should belong to the guarantor of appended claims of the present invention
Protect range.
Claims (9)
1. a kind of Han Xi Pin unit conjugated polymer, which is characterized in that its structural formula is shown below:
Wherein, n is the integer between 35 to 80.
2. a kind of preparation method based on Han Xi Pin unit conjugated polymer described in claim 1, which is characterized in that including step
It is rapid:
Following monomer is provided:
Monomer I:
Monomer II:
The monomer I and the monomer II are added in organic solvent, and catalyst and ligand is added, carries out Stille coupling
The Han Xi Pin unit conjugated polymer is prepared in reaction.
3. the preparation method of Han Xi Pin unit conjugated polymer according to claim 2,
It is characterized in that, the catalyst is tris(dibenzylideneacetone) dipalladium.
4. the preparation method of Han Xi Pin unit conjugated polymer according to claim 2,
It is characterized in that, the ligand is three (o-tolyl) phosphines.
5. the preparation method of Han Xi Pin unit conjugated polymer according to claim 2,
It is characterized in that, the organic solvent is anhydrous chlorobenzene.
6. the preparation method of Han Xi Pin unit conjugated polymer according to claim 2,
It is characterized in that, the molar ratio of the monomer I and the monomer II is 1:1.
7. the preparation method of Han Xi Pin unit conjugated polymer according to claim 2,
It is characterized in that, the temperature of the Stille coupling reaction is 105-115 DEG C.
8. the preparation method of Han Xi Pin unit conjugated polymer according to claim 2,
It is characterized in that, the time of the Stille coupling reaction is 70-75 hours.
9. a kind of composite material being combined based on Han Xi Pin unit conjugated polymer described in claim 1 and carbon nanotube
As the application in thermoelectric material.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111223982A (en) * | 2020-03-03 | 2020-06-02 | 西安交通大学 | Preparation method of n-type multi-walled carbon nanotube thermoelectric material with stable air and high performance |
Citations (2)
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| CN105820316A (en) * | 2016-04-28 | 2016-08-03 | 湘潭大学 | Heteroatom substituted naphthalimide polymer semiconductor as well as preparation method and application thereof |
| CN106229403A (en) * | 2016-08-08 | 2016-12-14 | 中国科学院化学研究所 | N type thermoelectric material that a kind of acid imide or naphthalimide are combined with CNT and preparation method thereof |
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2019
- 2019-02-28 CN CN201910153294.4A patent/CN109880066A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105820316A (en) * | 2016-04-28 | 2016-08-03 | 湘潭大学 | Heteroatom substituted naphthalimide polymer semiconductor as well as preparation method and application thereof |
| CN106229403A (en) * | 2016-08-08 | 2016-12-14 | 中国科学院化学研究所 | N type thermoelectric material that a kind of acid imide or naphthalimide are combined with CNT and preparation method thereof |
Non-Patent Citations (2)
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| RUTH A. SCHLITZ ,ET AL.: "Solubility-Limited Extrinsic n-Type Doping of a High Electron Mobility Polymer for Thermoelectric Applications", 《ADV. MATER.》 * |
| ZHIYUAN ZHAO，ET AL.: "High-Performance, Air-Stable Field-Effect Transistors Based on Heteroatom-Substituted Naphthalenediimide-Benzothiadiazole Copolymers Exhibiting Ultrahigh Electron Mobility up to 8.5 cm V−1s−1", 《ADV. MATER.》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111223982A (en) * | 2020-03-03 | 2020-06-02 | 西安交通大学 | Preparation method of n-type multi-walled carbon nanotube thermoelectric material with stable air and high performance |
| CN111223982B (en) * | 2020-03-03 | 2022-10-25 | 西安交通大学 | Preparation method of n-type multi-walled carbon nanotube thermoelectric material with stable air and high performance |
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Application publication date: 20190614 |