CN103059273A - Novel water-soluble thiofuran acetylene and phenylacetylene copolymer precursor, preparation method and application thereof - Google Patents
Novel water-soluble thiofuran acetylene and phenylacetylene copolymer precursor, preparation method and application thereof Download PDFInfo
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- CN103059273A CN103059273A CN2013100325973A CN201310032597A CN103059273A CN 103059273 A CN103059273 A CN 103059273A CN 2013100325973 A CN2013100325973 A CN 2013100325973A CN 201310032597 A CN201310032597 A CN 201310032597A CN 103059273 A CN103059273 A CN 103059273A
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Abstract
The invention belongs to the field of organic photoelectricity, and particularly relates to a novel water-soluble thiofuran acetylene and phenylacetylene copolymer precursor, a preparation method thereof and application of the novel water-soluble thiofuran acetylene and phenylacetylene copolymer precursor in a water-phase hybridized battery and a field-effect transistor. The preparation method comprises the following steps of: accessing a certain amount of hydrogen chloride gases into a hydrochloric acid solution containing a certain amount of paraformaldehyde and zinc chloride till saturation; adding a certain amount of 3,4-dibromo-thiophene to obtain a chloromethylation product; adding the chloromethylation product to a p-chlorobenzyl methanol solution; adding alkali liquor at certain temperature; polymerizing; and then finishing reaction by using acid to obtain the needed polymer precursor. The novel water-soluble thiofuran acetylene and phenylacetylene copolymer precursor disclosed by the invention can be applied to the preparation of the field-effect transistor and obtain higher carrier mobility, can be used for preparing the water-soluble hybridized solar battery without using a highly toxic organic solvent by being hybridized with a CdTe nanocrystalline and obtain considerable photoelectric conversion efficiency and can widen the absorption spectrum to 600-1000 nanometers.
Description
Technical field
The invention belongs to the organic photoelectric field, be specifically related to a kind of new type water-solubility thiophene acetylene and phenylacetylene presoma, preparation method and the application in water hybrid battery and field-effect transistor thereof.
Background technology
Water miscible conjugated polymers has very important application in the organic photoelectric field, and this water-soluble material is clean environment firendly not only, and also has good photoelectric properties.Although currently reported water miscible polymkeric substance is used in the organic photoelectric field, the electric charge on this base polymer all is difficult to slough, and affects the further transmission of current carrier.Nguyen group has prepared a kind of water miscible Polythiophene PTEBS:Na
+Although polymkeric substance can effectively be dissolved in the water, owing to there being the electric charge that can not remove, this polymkeric substance can not be used as effective electron donor(ED), because in the transmittance process in hole, the surface charge meeting cancellation hole on the polymer chain causes the again combination of current carrier.Finally cause electricity conversion lower.
Thiphene ring widely is applied in organic solar batteries field by what people were used as electronics to body because its electron density will be higher than phenyl ring.But how to prepare the water miscible conjugated polymers that contains thiphene ring, and the electricity conversion that how to improve battery remains a difficult problem.
Summary of the invention
The invention provides a kind of effective ways prepares the water miscible conjugated polymers PBTPV presoma that contains thiphene ring (its structural formula is as follows, annealing can obtain conjugated polymers PBTPV under the nitrogen, n is positive integer), this conjugated polymer can be effectively soluble in water, good film-forming properties is arranged, thermostability.At first: a certain amount of hydrogen chloride gas is passed in the hydrochloric acid soln that contains a certain amount of Paraformaldehyde 96 and zinc chloride to saturated, add a certain amount of 3, the 4-dibromo thiophene, can obtain the product of chloromethylation, in the methanol solution of its adding to benzyl chloride, at a certain temperature, add alkali lye, polymerization can obtain required polymer precursor (Fig. 1 and Fig. 2) with sour termination reaction again.This polymkeric substance can be applied in the preparation of field-effect transistor, and the higher carrier mobility (Fig. 3) of acquisition, and this water miscible polymkeric substance and CdTe nano-crystal hybrid, can prepare water miscible hybrid solar cell, do not use highly toxic organic solvent.And obtain considerable electricity conversion (Fig. 4).Its absorption spectrum can be widened 600nm to 1000nm.
The preparation method of copolymer p BTPV presoma of the present invention and device preparation method, concrete steps are as follows:
1) in the solution of 0.1～5g Paraformaldehyde 96 and 0.1～5g zinc chloride, adds 1～10mL concentrated hydrochloric acid, pass into HCl gas to saturated; At 30～60 degrees centigrade of lower reaction 30min～6h, can obtain 3,4-two bromo-2,5-dichloromethyl thiophene; Then under 0～20 degree centigrade, to 3,4-two bromo-2, the NaOH that adds 0.1～4mol/L in 5-dichloromethyl thiophene and the equimolar ratio methanol solution to benzyl chloride, behind the reaction 30min to 3h with the HCl termination reaction of 0.1～4mol/L, one week of dialysis, namely prepare copolymer p BTPV presoma, wherein 3,4-two bromo-2, the mol ratio of 5-dichloromethyl thiophene and NaOH is 1:1～1:5; The molecular weight of the water solubility copolymer presoma of preparation is greater than 2000;
2) water-soluble PBTPV presoma prepares the field-effect transistor method and is: at Si/SiO
2In the substrate, the polymethylmethacrylate of spin coating 50～500nm, and then spin coating 80～100nm PBTPV presoma (concentration be after 1～5mg/mL) in 100～300 degrees centigrade of annealing 10～60min, evaporation 60～100nm gold electrode namely gets field-effect transistor again;
3) preparation method of water-soluble hybrid battery is: at the TiO of ITO surface spin coating one deck 10～50nm
2Colloidal sol, TiO
2Colloidal sol is to get in 17uL concentrated hydrochloric acid Water Under solution by the 4mL tetrabutyl titanate.The PBTPV presoma is mixed with mass ratio 1:5～1:50 with CdTe is nanocrystalline, then at TiO
2Surface spin coating 80～100nm thick film, last 100～300 degrees centigrade of annealing, 10～60min namely obtain can photoelectric conversion active coating, last evaporation 60～100nm gold electrode namely gets water-soluble hybrid battery.
Description of drawings
The flight time mass spectrum of the PBTPV presoma of Fig. 1: embodiment 1 preparation, its molecular weight is greater than 2000;
The nuclear magnetic spectrogram of Fig. 2: embodiment 1 prepared PBTPV presoma; Show and obtained the object construction product;
(left figure is that leakage current is with the change curve of drain voltage to the output sign of the field-effect transistor for preparing with PBTPV among Fig. 3: the embodiment 1, right figure is that leakage current is with the change curve of gate voltage), show that it has good transmittability to the hole, and higher carrier mobility.
The current-voltage of the water-soluble hybrid battery among Fig. 4: the embodiment 1 characterizes (left figure is the I-V curve, and right figure is the external quantum efficiency curve), and its photoelectric transformation efficiency can reach 3.5%.
Embodiment
In the solution of 0.1g Paraformaldehyde 96 and 0.1g zinc chloride, add the 1mL concentrated hydrochloric acid, pass into HCl gas 30min.At 30 degrees centigrade of lower reaction 30min, can obtain 3,4-two bromo-2,5-dichloromethyl thiophene.Under 0 degree centigrade, to 3,4-two bromo-2,5-dichloromethyl thiophene with to adding the NaOH of 0.1mol/L, 3,4-, two bromo-2 in the methanol solution of benzyl chloride, the mol ratio of 5-dichloromethyl thiophene and NaOH is 1:1, with the HCl termination reaction of 0.1mol/L, in one week of dialysis, namely prepare copolymer p BTPV presoma behind the reaction 30min.
Water-soluble PBTPV presoma prepares the field-effect transistor method: at Si/SiO
2The surface, the polymethylmethacrylate of spin coating 50nm, 100 degrees centigrade of about 80nm of annealing 10min thickness behind the spin coating PBTPV presoma.The thick gold electrode of evaporation 80nm gets final product again.
The preparation method of water-soluble hybrid battery is: at the TiO of ITO surface spin coating one deck 10nm
2After, mix with mass ratio 1:5 PBTPV and CdTe are nanocrystalline, at TiO
2The surface spin coating become behind the 80nm film 100 degrees centigrade of annealing 10min be can photoelectric conversion active coating.Last evaporation 80nm gold electrode namely gets water-soluble hybrid battery.
In the solution of 1g Paraformaldehyde 96 and 1g zinc chloride, add the 2mL concentrated hydrochloric acid, pass into HCl gas to saturated.At 60 degrees centigrade of lower reaction 3h, can obtain 3,4-two bromo-2,5-dichloromethyl thiophene.Under 10 degrees centigrade, to 3,4-two bromo-2,5-dichloromethyl thiophene with to adding the NaOH of 0.4mol/L, 3,4-, two bromo-2 in the methanol solution of benzyl chloride, the mol ratio of 5-dichloromethyl thiophene and NaOH is 1:3, with the HCl termination reaction of 0.4mol/L, in one week of dialysis, namely prepare copolymer p BTPV presoma behind the reaction 30min.
Water-soluble PBTPV presoma prepares the field-effect transistor method: at Si/SiO
2The surface, the polymethylmethacrylate of spin coating 100nm, 200 degrees centigrade of about 80nm of annealing 30min thickness behind the spin coating PBTPV presoma.The thick gold electrode of evaporation 80nm gets final product again.
The preparation method of water-soluble hybrid battery is: at the TiO of ITO surface spin coating one deck 30nm
2After, mix with mass ratio 1:30 PBTPV and CdTe are nanocrystalline, at TiO
2The surface spin coating become behind the 90nm film 200 degrees centigrade of annealing 30min be can photoelectric conversion active coating.Last evaporation 80nm gold electrode namely gets water-soluble hybrid battery.
In the solution of 1.5g Paraformaldehyde 96 and 2g zinc chloride, add the 2.5mL concentrated hydrochloric acid, pass into HCl gas to saturated.At 60 degrees centigrade of lower reaction 30min, can obtain 3,4-two bromo-2,5-dichloromethyl thiophene.Under 20 degrees centigrade, to 3,4-two bromo-2,5-dichloromethyl thiophene with to adding the NaOH of 4mol/L, 3,4-, two bromo-2 in the methanol solution of benzyl chloride, the mol ratio of 5-dichloromethyl thiophene and NaOH is 1:5, with the HCl termination reaction of 4mol/L, in one week of dialysis, namely prepare copolymer p BTPV presoma behind the reaction 30min.
Water-soluble PBTPV presoma prepares the field-effect transistor method: at Si/SiO
2The surface, the polymethylmethacrylate of spin coating 500nm, 300 degrees centigrade of about 80nm of annealing 60min thickness behind the spin coating PBTPV presoma.The thick gold electrode of evaporation 80nm gets final product again.
The preparation method of water-soluble hybrid battery is: at the TiO of ITO surface spin coating one deck 50nm
2After, mix with mass ratio 1:50 PBTPV and CdTe are nanocrystalline, at TiO
2The surface spin coating become behind the 100nm film 300 degrees centigrade of annealing 60min be can photoelectric conversion active coating.Last evaporation 80nm gold electrode namely gets water-soluble hybrid battery.
Claims (8)
1. a water-soluble thiophene acetylene and phenylacetylene presoma, its structural formula is as follows:
2. a water-soluble thiophene acetylene and phenylacetylene, its structural formula is as follows:
3. the preparation method of water-soluble thiophene acetylene claimed in claim 1 and phenylacetylene presoma, it is characterized in that: be in the solution of 0.1～5g Paraformaldehyde 96 and 0.1～5g zinc chloride, to add 1～10mL concentrated hydrochloric acid, pass into HCl gas 30min to saturated, again at 30～60 degrees centigrade of lower reaction 30min～6h, can obtain 3,4-two bromo-2,5-dichloromethyl thiophene; Then under 0～20 degree centigrade, to 3,4-two bromo-2, the NaOH that adds 0.1～4mol/L in 5-dichloromethyl thiophene and the equimolar ratio methanol solution to benzyl chloride, behind the reaction 30min to 3h with the HCl termination reaction of 0.1～4mol/L, one week of dialysis, namely prepare water-soluble thiophene acetylene and phenylacetylene presoma, wherein 3,4-two bromo-2, the mol ratio of 5-dichloromethyl thiophene and NaOH is 1:1～1:5.
4. the preparation method of water-soluble thiophene acetylene claimed in claim 2 and phenylacetylene presoma, it is characterized in that: be in the solution of 0.1～5g Paraformaldehyde 96 and 0.1～5g zinc chloride, to add 1～10mL concentrated hydrochloric acid, pass into HCl gas 30min to saturated, again at 30～60 degrees centigrade of lower reaction 30min～6h, can obtain 3,4-two bromo-2,5-dichloromethyl thiophene; Then under 0～20 degree centigrade, to 3,4-two bromo-2, the NaOH that adds 0.1～4mol/L in 5-dichloromethyl thiophene and the equimolar ratio methanol solution to benzyl chloride, behind the reaction 30min to 3h with the HCl termination reaction of 0.1～4mol/L, one week of dialysis, namely prepare water-soluble thiophene acetylene and phenylacetylene presoma, wherein 3,4-two bromo-2, the mol ratio of 5-dichloromethyl thiophene and NaOH is 1:1～1:5; Then water-soluble thiophene acetylene and phenylacetylene presoma are annealed under nitrogen and obtain.
5. water-soluble thiophene acetylene claimed in claim 1 and the phenylacetylene presoma application aspect the preparation field-effect transistor.
6. water-soluble thiophene acetylene as claimed in claim 5 and the phenylacetylene presoma application aspect the preparation field-effect transistor is characterized in that: at Si/SiO
2In the substrate, the polymethylmethacrylate of spin coating 50～500nm, spin coating 80～100nm PBTPV presoma again, then in 100～300 degrees centigrade of annealing 10～60min, evaporation 60～100nm gold electrode namely gets field-effect transistor more at last.
7. water-soluble thiophene acetylene claimed in claim 1 and the phenylacetylene presoma application aspect the water-soluble hybrid battery of preparation.
8. water-soluble thiophene acetylene as claimed in claim 7 and the phenylacetylene presoma application aspect the water-soluble hybrid battery of preparation is characterized in that: at the TiO of ITO surface spin coating one deck 10～50nm
2Colloidal sol mixes with CdTe is nanocrystalline the PBTPV presoma, more then at TiO with mass ratio 1:5～1:50
2Surface spin coating 80～100nm thick film, last 100～300 degrees centigrade of annealing 10～60min obtain the active coating of photoelectric conversion, and last evaporation 60～100nm gold electrode namely gets water-soluble hybrid battery.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103613740A (en) * | 2013-11-22 | 2014-03-05 | 吉林大学 | Water-soluble polythiophene acetylene conjugated polymer and preparation method and applications thereof |
| CN103880741A (en) * | 2014-02-28 | 2014-06-25 | 安徽国星生物化学有限公司 | Preparation method of 2-chloromethyl-3,5-dimethyl-4-alkoxypyridyl-N-oxide |
| CN107406586A (en) * | 2015-03-27 | 2017-11-28 | 综研化学株式会社 | Polymer, oxypolymer, polymer composition, gelatinous polymer composition and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006049579A1 (en) * | 2004-11-01 | 2006-05-11 | Agency For Science, Technology And Research | Poly(arylenevinylene) and poly(heteroarylenevinylene) light emitting polymers and polymer light-emitting devices |
| CN1861659A (en) * | 2006-04-27 | 2006-11-15 | 复旦大学 | Polyphenylene ethylene and its derivant, preparation process and application |
| CN101803051A (en) * | 2007-09-14 | 2010-08-11 | 3M创新有限公司 | Polythienylenevinylene thermoelectric conversion material |
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- 2013-01-28 CN CN2013100325973A patent/CN103059273A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006049579A1 (en) * | 2004-11-01 | 2006-05-11 | Agency For Science, Technology And Research | Poly(arylenevinylene) and poly(heteroarylenevinylene) light emitting polymers and polymer light-emitting devices |
| CN1861659A (en) * | 2006-04-27 | 2006-11-15 | 复旦大学 | Polyphenylene ethylene and its derivant, preparation process and application |
| CN101803051A (en) * | 2007-09-14 | 2010-08-11 | 3M创新有限公司 | Polythienylenevinylene thermoelectric conversion material |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103613740A (en) * | 2013-11-22 | 2014-03-05 | 吉林大学 | Water-soluble polythiophene acetylene conjugated polymer and preparation method and applications thereof |
| CN103880741A (en) * | 2014-02-28 | 2014-06-25 | 安徽国星生物化学有限公司 | Preparation method of 2-chloromethyl-3,5-dimethyl-4-alkoxypyridyl-N-oxide |
| CN107406586A (en) * | 2015-03-27 | 2017-11-28 | 综研化学株式会社 | Polymer, oxypolymer, polymer composition, gelatinous polymer composition and application thereof |
| CN107406586B (en) * | 2015-03-27 | 2020-03-27 | 综研化学株式会社 | Polymer, oxidized polymer, polymer composition, gel-like polymer composition, and use thereof |
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Application publication date: 20130424 |