CN102304121A - Water-soluble thiophene monomer and water-soluble polythiophene derivative as well as preparation methods of water-soluble thiophene monomer and water-soluble polythiophene derivative - Google Patents
Water-soluble thiophene monomer and water-soluble polythiophene derivative as well as preparation methods of water-soluble thiophene monomer and water-soluble polythiophene derivative Download PDFInfo
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Abstract
The invention provides a water-soluble thiophene monomer and a water-soluble polythiophene derivative as well as preparation methods of the water-soluble thiophene monomer and the water-soluble polythiophene derivative. The preparation method of the water-soluble thiophene monomer n-(3-thiophene oxo)-alkyl-triethyl ammonium bromide (n is 2-6) comprises the following steps: reacting methanol with metal sodium in N-methylpyrrolidone, then reacting with 3-bromothiophene, and purifying so as to obtain 3-methoxythiophene; reacting 3-methoxythiophene with n-bromo-1-alkanol (n is 2-6), and purifying so as to obtain 3-(n-bromo-alkoxyl)-thiophene; and reacting 3-(n-bromo-alkoxyl)-thiophene with triethylamine in acetonitrile, and purifying so as to obtain the water-soluble thiophene monomer. According to the invention, the chloroform solution of the water-soluble thiophene monomer is polymerized in the presence of anhydrous ferric trichloride used as a catalyst so as to obtain the water-soluble polythiophene derivative. The water-soluble polythiophene derivative prepared in the invention not only retains good optical and electrical properties of polythiophene but also has water solubility, and is convenient for processing and manufacturing of organic photovoltaic devices.
Description
Technical field
The present invention relates to organic polymer photoelectric material technical field, be specifically related to water-soluble thiophene monomer and water-soluble poly thiophene derivant and preparation method thereof.
Background technology
Polythiophene and derivative thereof are one type of important organic conjugate polymer functional materialss.On the one hand; In theory; Polythiophene can become the model of research nondegenerate state conducting polymer migration; Because thiophene virtue heterocycle all has advantages of higher stability to oxygen and humidity; Make its derivative more synthetic, and the structure of polythiofuran derivative also have diversity than other fragrant Hete rocyclic derivatives; On the other hand, Polythiophene doping attitude all has good environmental stability with the attitude of going to mix.These have caused that all people more study interest.Therefore; Polythiophene and derivative thereof are used as electro-conductive material, light LED material, lightweight battery material, electromagnetic shielding material, display material, microwave absorbing material, novel material with memory etc., become the focus material that people study organic electrochromic, organic electroluminescent and organic photovoltaic.
In view of polythiofuran derivative is π-Department of Electronics's conjugate beam, the electric material of one type of excellent performance, therefore, the kind and the Application Areas thereof that enlarge polythiofuran derivative seem particularly important.
At present; The polythiofuran derivative that has conducted a research nearly all is not water miscible; In the processing and making process of organic light, electrical part; When utilizing methods such as spin coating to make water-insoluble polythiofuran derivative film forming; Used organic solvent might destroy other the organic membrane in organic light, the electrical part, and this situation will certainly influence the performance of organic light, electrical part.
Summary of the invention
In order to solve the deficiency that exists in the above-mentioned correlation technique, enlarge the kind and the Application Areas thereof of polythiofuran derivative simultaneously, the present invention provides water-soluble thiophene monomer and water-soluble poly thiophene derivant and preparation method thereof.This water-soluble poly thiophene derivant not only keeps Polythiophene excellent light, electrical property, and has water-solublely, helps the processing and fabricating of organic light, electrical part.
Water-soluble thiophene monomer specifically is n-(3-thiophene oxy)-alkyl-triethyl brometo de amonio, has following molecular structure:
N=2～6 wherein.
The preparation method of water-soluble thiophene monomer comprises the steps:
(1) N
2Protection down will
NAfter-methyl-2-pyrrolidone and sodium Metal 99.5 mix, get mixed solution; In mixed solution, slowly drip methyl alcohol, stirring reaction 3h under the room temperature～5 h disappear to sodium Metal 99.5, remove residual methyl alcohol in the dereaction, obtain sodium methylate
N-methyl-2-pyrrolidone solution;
(2) N
2Protection down, with step (1) sodium methylate
N-methyl-2-pyrrolidone solution, cuprous bromide catalyzer, 3 bromo thiophene mix, and at 100 ℃～110 ℃ following stirring reaction 4 h～8 h, get reaction solution; Reaction solution is poured in the methylene dichloride, filtered and obtain sorrel filtrating; After in sorrel filtrating, adding saturated nacl aqueous solution, use dichloromethane extraction, extract organic phase and use anhydrous sodium sulfate drying, remove by filter sodium sulfate then, obtain filtrating; After the methylene dichloride in the filtrating is removed in decompression, promptly obtain the crude product of 3-methoxythiophene; Crude product 78 ℃～80 ℃ with 8kPa under rectifying, obtain pure 3-methoxythiophene;
(3) N
2Protection down; 3-methoxythiophene, n-bromo-1-alkanol, sodium pyrosulfate that toluene, step (2) are obtained mix; At 105 ℃～115 ℃ following stirring reaction 5h～8h; Reaction finishes the back and extracts with saturated nacl aqueous solution; Extract organic layer; And in organic layer, add anhydrous sodium sulfate drying, and remove by filter sodium sulfate then, obtain filtrating; After the toluene in the filtrating is removed in decompression, obtain the crude product of 3-(n-bromo-alkoxyl group)-thiophene; With chromatographic column crude product is separated purification then, obtain pure 3-(n-bromo-alkoxyl group)-thiophene; N=2～6 wherein;
(4) N
2Under the protection, the 3-that step (3) is prepared (n-bromo-alkoxyl group)-thiophene, acetonitrile, triethylamine mix, and 45 ℃～60 ℃ stirring reaction 40 h～45 h obtain reaction solution; Reaction finishes the back decompression remove the acetonitrile and triethylamine in the reaction solution after, obtain thick liquid, with the said thick liquid of petroleum ether, obtain water-soluble thiophene monomer n-(3 '-thiophene oxy)-alkyl-triethyl brometo de amonio; N=2～6 wherein.
It is the mixed solvent of methylene dichloride and sherwood oil that the chromatographic column that said 3-(n-bromo-alkoxyl group)-thiophene crude product is purified is separated the washing fluid that adopts.
Water-soluble poly thiophene derivant by above-mentioned water-soluble thiophene monomer is polymerized has following molecular structure:
N=2～6 wherein.
Preparing method's step of water-soluble thiophene derivant is following:
(1) N
2Protection down adds chloroform and n-(3 '-thiophene oxy)-alkyl-triethyl brometo de amonio successively, must mixing solutions; In mixing solutions, slowly drip the chloroformic solution of FERRIC CHLORIDE ANHYDROUS, stirring reaction 36 h～40h obtain reaction solution; After the chloroform in the reaction solution is removed in decompression, wash remaining reaction solution fast with methyl alcohol, vacuum-drying obtains crude product; N=2～6;
(2) adopt apparatus,Soxhlet's, as solvent above-mentioned crude product is carried out extracting with acetone, till extract is colourless; The gained filter cake carries out extracting with the methanol solution of Hydrazine Hydrate 80 again, collects extract, and after the methanol solution of the Hydrazine Hydrate 80 in the extract was removed in decompression, remaining solid product promptly obtained the water-soluble poly thiophene derivant again through vacuum-drying.
The reaction formula of water-soluble thiophene monomer preparation according to the invention is represented as follows:
Reaction formula by above-mentioned water-soluble thiophene monomer prepares the water-soluble poly thiophene derivant is represented as follows:
(1) the present invention has overcome water-insoluble polythiofuran derivative when utilizing method film forming such as spin coating, and used organic solvent might destroy other the shortcoming of organic membrane in organic light, the electrical part;
(2) water-soluble poly thiophene derivant provided by the present invention not only keeps Polythiophene excellent light, electrical property, but also has water-solublely, helps the processing and fabricating of organic light, electrical part.
Embodiment
Below in conjunction with embodiment, the present invention is done detailed description further.
Embodiment 1
1), the preparation of water-soluble thiophene monomer:
The first step is at N
2Protection down will
N-methyl-2-pyrrolidone and sodium Metal 99.5 add in the there-necked flask, slowly drip methyl alcohol, and stirring reaction 3 h disappear to sodium Metal 99.5 under the room temperature.Underpressure distillation removes residual methyl alcohol, obtains sodium methylate
N-methyl-2-pyrrolidone solution;
Second step, N
2Protection down adds above-mentioned sodium methylate in there-necked flask
N-methyl-2-pyrrolidone solution, cuprous bromide catalyzer and 3 bromo thiophene; Under 100 ℃; Stirring reaction 8 h; Reaction is poured solution in the methylene dichloride into after finishing, and filters and obtains red tan solution, in red tan solution, adds saturated nacl aqueous solution; Use dichloromethane extraction; Extract organic phase, use anhydrous sodium sulfate drying, remove by filter sodium sulfate.The crude product that methylene dichloride in the filtrating obtains the 3-methoxythiophene is removed in decompression.Crude product 78 ℃～80 ℃ with 8kPa under rectifying, obtain pure 3-methoxythiophene;
The 3rd step is at N
2Protection adds toluene, 3-methoxythiophene, 3-bromo-1-propyl alcohol and sodium pyrosulfate, 115 ℃ of following stirring reaction 5 h down in there-necked flask.Reaction finishes the back with the saturated nacl aqueous solution extraction, extracts organic layer, adds anhydrous sodium sulfate drying, removes by filter sodium sulfate then; The toluene in the filtrating is removed in decompression then, obtains the crude product of 3-(3-bromo-propoxy-)-thiophene, with chromatographic column crude product is separated purification then, obtains pure 3-(3-bromo-propoxy-)-thiophene;
The 4th step, N
2Protection adds acetonitrile, 3-(3-bromo-propoxy-)-thiophene and triethylamine, 60 ℃ of stirring reaction 40 h down in the single port flask; Reaction finishes the back decompression and removes acetonitrile and triethylamine, obtains thick liquid, uses petroleum ether, obtains 3-(3 '-thiophene oxy)-propyl group-triethyl brometo de amonio.
The washing fluid that the chromatographic separation of 3-(3-bromo-propoxy-)-thiophene adopts is the mixed solvent of methylene dichloride and sherwood oil.
The preparation of 3 - (3'-thienyl-oxy) - propyl - monomer structure triethylammonium bromide as:
Its structural characterization data are following:
Mass spectrum: m/z 322.5;
Proton nmr spectra: δ (ppm): 7.43 (d, 1H), 6.77 (d, 1H), 6.61 (s, 1H), 4.03 (t, 2H), 3.28 (m, 8H), 2.06 (m, 2H), 1.18 (t, 9H);
Infrared spectra: (KBr method, cm
-1): 1228 (ν
C-N).
2), the preparation process of water-soluble poly thiophene derivant:
At N
2Protection down adds chloroform and 3-(3 '-thiophene oxy)-propyl group-triethyl brometo de amonio in there-necked flask, slowly drip the chloroformic solution of FERRIC CHLORIDE ANHYDROUS, stirring reaction 36 h.After reaction finished, chloroform was removed in decompression, washs fast with methyl alcohol, and vacuum-drying obtains crude product.As solvent, adopt apparatus,Soxhlet's that crude product is carried out extracting with acetone, colourless until solution.After the product drying again the methanol solution with Hydrazine Hydrate 80 carry out extracting, collect extract, the methanol solution of the Hydrazine Hydrate 80 in the extract is removed in decompression, remaining solid product obtains the water-soluble poly thiophene derivant again through vacuum-drying.
Embodiment 2
1), the monomeric preparation of water-soluble thiophene derivant:
The first step is at N
2Protection down will
N-methyl-2-pyrrolidone and sodium Metal 99.5 add in the there-necked flask, slowly drip methyl alcohol, and stirring reaction 4 h disappear to sodium Metal 99.5 under the room temperature.Underpressure distillation removes residual methyl alcohol, obtains sodium methylate
N-methyl-2-pyrrolidone solution;
Second step, N
2Protection down adds above-mentioned sodium methylate in there-necked flask
N-methyl-2-pyrrolidone solution, cuprous bromide catalyzer and 3 bromo thiophene; Under 105 ℃; Stirring reaction 5 h; Reaction is poured solution in the methylene dichloride into after finishing, and filters and obtains red tan solution, in red tan solution, adds saturated nacl aqueous solution; Use dichloromethane extraction; Extract organic phase, use anhydrous sodium sulfate drying, remove by filter sodium sulfate.Decompression is removed methylene dichloride and is obtained 3-methoxythiophene crude product.Crude product 78 ℃～80 ℃ with 10kPa under rectifying, obtain pure 3-methoxythiophene;
The 3rd step is at N
2Protection adds toluene, 3-methoxythiophene, 4-bromo-1-butanols and sodium pyrosulfate, 110 ℃ of following stirring reaction 6 h down in there-necked flask.Reaction finishes the back with the saturated nacl aqueous solution extraction, extracts organic layer, adds anhydrous sodium sulfate drying, removes by filter sodium sulfate then; The toluene in the filtrating is removed in decompression, obtains the crude product of 3-(4-bromo-butoxy)-thiophene; Crude product separates with chromatographic column then purifies, and obtains pure 3-(4-bromo-butoxy)-thiophene;
The 4th step, N
2Protection adds acetonitrile, 3-(4-bromo-butoxy)-thiophene and triethylamine, 50 ℃ of stirring reaction 43 h down in the single port flask; Reaction finishes the back decompression and removes acetonitrile and triethylamine, obtains thick liquid, uses the petroleum ether thick liquid, obtains 4-(3 '-thiophene oxy)-butyl-triethyl brometo de amonio.
The chromatographic column of 3-(4-bromo-butoxy)-thiophene is separated the flushing liquid level methylene dichloride of employing and the mixed solvent of sherwood oil.
The preparation of 4 - (3'-thienyl group) - butyl - triethylammonium bromide molecular structure is as follows:
Its structural characterization data are following:
Mass spectrum: m/z 336.7;
Proton nmr spectra: δ (ppm): 7.44 (d, 1H), 6.77 (d, 1H), 6.62 (s, 1H), 4.03 (t, 2H), 3.26 (m, 10H), 2.04 (m, 2H), 1.16 (t, 9H);
Infrared spectra: (KBr method, cm
-1): 1225 (ν
C-N).
2), the preparation process of water-soluble poly thiophene derivant:
At N
2Protection down adds chloroform and 4-(3 '-thiophene oxy)-butyl-triethyl brometo de amonio in there-necked flask, slowly drip the chloroformic solution of FERRIC CHLORIDE ANHYDROUS, stirring reaction 38 h.After reaction finished, chloroform was removed in decompression, washs fast with methyl alcohol, and vacuum-drying obtains crude product.As solvent, adopt apparatus,Soxhlet's that crude product is carried out extracting with acetone, colourless until solution.After the product drying again the methanol solution with Hydrazine Hydrate 80 carry out extracting, collect extract, after the methanol solution of the Hydrazine Hydrate 80 in the extract was removed in decompression, remaining solid product obtained the water-soluble poly thiophene derivant again through vacuum-drying.
Embodiment 3
1), the monomeric preparation of water-soluble thiophene derivant:
The first step is at N
2Protection down will
N-methyl-2-pyrrolidone and sodium Metal 99.5 add in the there-necked flask, slowly drip methyl alcohol, and stirring reaction 3.5 h disappear to sodium Metal 99.5 under the room temperature.Underpressure distillation removes residual methyl alcohol, obtains sodium methylate
N-methyl-2-pyrrolidone solution.
Second step, N
2Protection down adds above-mentioned sodium methylate in there-necked flask
N-methyl-2-pyrrolidone solution, cuprous bromide catalyzer and 3 bromo thiophene; Under 110 ℃; Stirring reaction 4 h; Reaction is poured solution in the methylene dichloride into after finishing, and filters and obtains red tan solution, in red tan solution, adds saturated nacl aqueous solution; Use dichloromethane extraction; Extract organic phase, use anhydrous sodium sulfate drying, remove by filter sodium sulfate.Decompression is removed methylene dichloride and is obtained 3-methoxythiophene crude product.Crude product 78 ℃～80 ℃ with 8kPa under rectifying, obtain pure 3-methoxythiophene;
The 3rd step is at N
2Protection adds toluene, 3-methoxythiophene, 5-bromo-1-amylalcohol and sodium pyrosulfate, 105 ℃ of following stirring reaction 4h down in there-necked flask.Reaction finishes the back with the saturated nacl aqueous solution extraction, extracts organic layer, adds anhydrous sodium sulfate drying, removes by filter sodium sulfate then; The toluene in the filtrating is removed in decompression, obtains 3-(5-bromo-pentyloxy)-thiophene crude product; With chromatographic column crude product is separated purification then, obtain pure 3-(5-bromo-pentyloxy)-thiophene;
The 4th step, N
2Protection adds acetonitrile, 3-(5-bromo-alkoxyl group)-thiophene and triethylamine down in the single port flask, 45 ℃ of stirring reaction 45 h get reaction solution; Reaction finishes the back decompression and removes acetonitrile and the triethylamine in the reaction solution, obtains thick liquid, uses the petroleum ether thick liquid, obtains 5-(3 '-thiophene oxy)-amyl group-triethyl brometo de amonio.
It is the mixed solvent of methylene dichloride and sherwood oil that the chromatographic column of 3-(5-bromo-pentyloxy)-thiophene is separated the washing fluid that adopts.
Prepared 5-(3 '-thiophene oxy)-amyl group-triethyl brometo de amonio molecular structure is following:
Its structural characterization data are following:
Mass spectrum: m/z 350.1;
Proton nmr spectra: δ (ppm): 7.44 (d, 1H), 6.78 (d, 1H), 6.62 (s, 1H), 4.02 (t, 2H), 3.27 (m, 12H), 2.02 (m, 2H), 1.20 (t, 9H);
Infrared spectra: (KBr method, cm
-1): 1226 (ν
C-N).
2), the preparation process of water-soluble poly thiophene derivant:
At N
2Protection down adds chloroform and 5-(3 '-thiophene oxy)-amyl group-triethyl brometo de amonio in there-necked flask, slowly drip the chloroformic solution of FERRIC CHLORIDE ANHYDROUS, stirring reaction 40 h.After reaction finished, chloroform was removed in decompression, washs fast with methyl alcohol, and vacuum-drying obtains crude product.As solvent, adopt apparatus,Soxhlet's that crude product is carried out extracting with acetone, colourless until solution.After the product drying again the methanol solution with Hydrazine Hydrate 80 carry out extracting, collect extract, after the methanol solution of the Hydrazine Hydrate 80 in the extract was removed in decompression, remaining solid product obtained the water-soluble poly thiophene derivant again through vacuum-drying.
Claims (5)
1. water-soluble thiophene monomer is characterized in that it being n-(3-thiophene oxy)-alkyl-triethyl brometo de amonio, has following molecular structure:
N=2～6 wherein.
2. the preparation method of the said water-soluble thiophene monomer of claim 1 is characterized in that comprising the steps:
(1) N
2Protection down will
NAfter-methyl-2-pyrrolidone and sodium Metal 99.5 mix, get mixed solution; In mixed solution, slowly drip methyl alcohol, stirring reaction 3h under the room temperature～5 h disappear to sodium Metal 99.5, remove residual methyl alcohol in the dereaction, obtain sodium methylate
N-methyl-2-pyrrolidone solution;
(2) N
2Protection down, with step (1) sodium methylate
N-methyl-2-pyrrolidone solution, cuprous bromide catalyzer, 3 bromo thiophene mix, and at 100 ℃～110 ℃ following stirring reaction 4 h～8 h, get reaction solution; Reaction solution is poured in the methylene dichloride, filtered and obtain sorrel filtrating; After in sorrel filtrating, adding saturated nacl aqueous solution, use dichloromethane extraction, extract organic phase and use anhydrous sodium sulfate drying, remove by filter sodium sulfate then, obtain filtrating; After the methylene dichloride in the filtrating is removed in decompression, promptly obtain the crude product of 3-methoxythiophene; Crude product 78 ℃～80 ℃ with 8kPa under rectifying, obtain pure 3-methoxythiophene;
(3) N
2Protection down; 3-methoxythiophene, n-bromo-1-alkanol, sodium pyrosulfate that toluene, step (2) are obtained mix; At 105 ℃～115 ℃ following stirring reaction 5h～8h; Reaction finishes the back and extracts with saturated nacl aqueous solution; Extract organic layer; And in organic layer, add anhydrous sodium sulfate drying, and remove by filter sodium sulfate then, obtain filtrating; After the toluene in the filtrating is removed in decompression, obtain the crude product of 3-(n-bromo-alkoxyl group)-thiophene; With chromatographic column crude product is separated purification then, obtain pure 3-(n-bromo-alkoxyl group)-thiophene; N=2～6 wherein;
(4) N
2Under the protection, the 3-that step (3) is prepared (n-bromo-alkoxyl group)-thiophene, acetonitrile, triethylamine mix, and 45 ℃～60 ℃ stirring reaction 40 h～45 h obtain reaction solution; Reaction finishes the back decompression remove the acetonitrile and triethylamine in the reaction solution after, obtain thick liquid, with the said thick liquid of petroleum ether, obtain water-soluble thiophene monomer n-(3 '-thiophene oxy)-alkyl-triethyl brometo de amonio; N=2～6 wherein.
3. preparation method according to claim 2 is characterized in that it is the mixed solvent of methylene dichloride and sherwood oil that said step (3) chromatographic column is separated the washing fluid that adopts.
4. the water-soluble poly thiophene derivant that is polymerized of the said water-soluble thiophene monomer of claim 1 is characterized in that having following molecular structure:
N=2～6 wherein.
5. the preparation method of the said water-soluble poly thiophene derivant of claim 4 is characterized in that step is following:
(1) N
2Protection down adds chloroform and n-(3 '-thiophene oxy)-alkyl-triethyl brometo de amonio successively, must mixing solutions; In mixing solutions, slowly drip the chloroformic solution of FERRIC CHLORIDE ANHYDROUS, stirring reaction 36 h～40h obtain reaction solution; After the chloroform in the reaction solution is removed in decompression, wash remaining reaction solution fast with methyl alcohol, vacuum-drying obtains crude product; N=2～6;
(2) adopt apparatus,Soxhlet's, as solvent above-mentioned crude product is carried out extracting with acetone, till extract is colourless; The gained filter cake carries out extracting with the methanol solution of Hydrazine Hydrate 80 again, collects extract, and after the methanol solution of the Hydrazine Hydrate 80 in the extract was removed in decompression, remaining solid product promptly obtained the water-soluble poly thiophene derivant again through vacuum-drying.
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| WO2013127227A1 (en) * | 2012-02-29 | 2013-09-06 | 华南理工大学 | Amine-oxide-group-containing conjugated polymer photoelectric material and application thereof |
| CN105860033A (en) * | 2016-04-12 | 2016-08-17 | 南京林业大学 | Polythiophene with side chain containing hydrophilic group, and preparation method thereof |
| CN106045964A (en) * | 2016-07-13 | 2016-10-26 | 南京林业大学 | Preparation method of thiophene compound with side chain with alcohol amine group |
| CN110218298A (en) * | 2019-06-10 | 2019-09-10 | 华东师范大学 | A kind of solubility thiophene copolymers and its preparation method and application |
| CN111138639A (en) * | 2018-11-05 | 2020-05-12 | 天津理工大学 | pH response type conjugated polymer nano particle and preparation method and application thereof |
| CN111269400A (en) * | 2020-01-20 | 2020-06-12 | 中科院广州化学有限公司 | Intrinsic thermoplastic thiophene derivative copolymer heat conduction material and preparation method and application thereof |
| CN114380789A (en) * | 2020-10-06 | 2022-04-22 | 上海漫关越水处理有限公司 | Thiophene dialkoxy fluorine-containing sulfonate compound of sulfur electrode conductive solid electrolyte |
-
2011
- 2011-07-07 CN CN201110188533A patent/CN102304121A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| JUKKA LUKKARI, ET AL.: "Polyelectrolyte Multilayers Prepared from Water-Soluble Poly(alkoxythiophene) Derivatives", 《J. AM. CHEM. SOC.》 * |
Cited By (13)
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|---|---|---|---|---|
| US9159928B2 (en) | 2012-02-29 | 2015-10-13 | South China University Of Technology | Amine-oxide-group-containing conjugated polymer photoelectric material and use thereof |
| WO2013127227A1 (en) * | 2012-02-29 | 2013-09-06 | 华南理工大学 | Amine-oxide-group-containing conjugated polymer photoelectric material and application thereof |
| CN105860033A (en) * | 2016-04-12 | 2016-08-17 | 南京林业大学 | Polythiophene with side chain containing hydrophilic group, and preparation method thereof |
| CN105860033B (en) * | 2016-04-12 | 2018-01-05 | 南京林业大学 | Side chain contains polythiophene of hydrophilic radical and preparation method thereof |
| CN106045964A (en) * | 2016-07-13 | 2016-10-26 | 南京林业大学 | Preparation method of thiophene compound with side chain with alcohol amine group |
| CN106045964B (en) * | 2016-07-13 | 2018-12-14 | 南京林业大学 | Side chain has the preparation method of the thiophene compound of alcohol amine groups |
| CN111138639B (en) * | 2018-11-05 | 2022-04-29 | 天津理工大学 | pH response type conjugated polymer nano particle and preparation method and application thereof |
| CN111138639A (en) * | 2018-11-05 | 2020-05-12 | 天津理工大学 | pH response type conjugated polymer nano particle and preparation method and application thereof |
| CN110218298A (en) * | 2019-06-10 | 2019-09-10 | 华东师范大学 | A kind of solubility thiophene copolymers and its preparation method and application |
| CN110218298B (en) * | 2019-06-10 | 2021-12-24 | 华东师范大学 | Soluble thiophene copolymer and preparation method and application thereof |
| CN111269400A (en) * | 2020-01-20 | 2020-06-12 | 中科院广州化学有限公司 | Intrinsic thermoplastic thiophene derivative copolymer heat conduction material and preparation method and application thereof |
| CN111269400B (en) * | 2020-01-20 | 2023-10-24 | 中科院广州化学有限公司 | Intrinsic thermoplastic thiophene derivative copolymer heat conduction material and preparation method and application thereof |
| CN114380789A (en) * | 2020-10-06 | 2022-04-22 | 上海漫关越水处理有限公司 | Thiophene dialkoxy fluorine-containing sulfonate compound of sulfur electrode conductive solid electrolyte |
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Application publication date: 20120104 |