CN104558531A - Synthesis method and application of conjugated polymer - Google Patents
Synthesis method and application of conjugated polymer Download PDFInfo
- Publication number
- CN104558531A CN104558531A CN201510014324.5A CN201510014324A CN104558531A CN 104558531 A CN104558531 A CN 104558531A CN 201510014324 A CN201510014324 A CN 201510014324A CN 104558531 A CN104558531 A CN 104558531A
- Authority
- CN
- China
- Prior art keywords
- carboxylic acid
- aromatic compound
- organic
- alkali
- synthetic method
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention discloses a synthesis method and an application of a conjugated polymer. The method comprises the following steps: dissolving a molar equivalent of aromatic compound containing double carboxylic groups or dual-metal carboxylate-based aromatic compound and 1-3 molar equivalents of aromatic compound containing dual halogen groups or dual-trifluoromethane sulfonic acid ester-based aromatic compound into an organic solvent; adding a metal catalyst, an organic ligand compound, alkali and an additive, heating under the protection of an inert gas, and lastingly reacting under the reaction condition; dropping a reaction liquid into a methyl alcohol or ethyl alcohol solvent, and filtering to obtain a crude product; and purifying to obtain the conjugated polymer. Through polymerization reaction on the aromatic compound containing dual-carboxylic acid or carboxylate functional groups and the aromatic compound containing dual halogen groups or dual-trifluoromethane sulfonic acid ester-based functional groups in catalysis of the catalyst, the conjugated polymer with photoelectric activity is prepared. The method has the advantages of high efficiency, low cost, environmental friendliness and wide applicability.
Description
Technical field
The invention belongs to polymer preparing technical field, be specifically related to a kind of synthetic method and application of conjugated polymers.
Background technology
Conjugated polymers is widely used in organic electro-optic device as the macromolecular material that a class is novel, such as organic electroluminescent LED, organic photovoltaic cell, organic field effect tube and organic infrared detector etc.These conjugated polymerss are all obtained by the polymerization of aromatics unit, such as polyfluorene class, polycarbazole, polythiophene class etc.
At present, method mainly Suzuki polyreaction, Yamamoto polyreaction and the Stille polyreaction etc. of this type of conjugated polymers are synthesized.These synthetic methods mainly by palladium class catalyst, utilize special functional group and Halogen unit to carry out reaction and obtain.Wherein Application comparison widely specific function group be boric acid ester in Suzuki polyreaction and Stille polyreaction and organotin unit.But these groups are prepared expensive, structural instability, easily decomposed, and organotin is a class severe toxicity raw material.So this kind of unit preparation technology containing specific function group is uneconomical and not environmentally.
Therefore, develop a class novel, synthetic method of polymers that is cheap and environmental protection is a very important job.Goo β en etc. utilizes carboxylic unit and halogen-containing unit process, can obtain target coupling compound by high productivity.(Science, 313,2006) based on this, by the aromatic compound with two carboxylic acid functional with the aromatic compound containing Shuan Lu functional group when catalyst, required target conjugated polymers can be obtained.This type of synthetic method without the need to preparing expensive, structural unstable boric acid ester or poisonous organotin unit, thus make such novel method can efficiently, low cost, greenly preparation have the conjugated polymers of photoelectric activity.
Summary of the invention
The present invention by by the aromatic compound containing two carboxylic acid groups or two carboxylic acid metal's alkali with the aromatic compound containing two halogen radical or bis trifluoromethyl sulfonate group in certain organic solvent, metal catalyst, organic ligand compound, alkali and additive; and under the protection of rare gas element; by being heated to certain temperature; and sustained reaction certain hour, preparation has the conjugated polymers of photoelectric characteristic.
The object of the present invention is to provide a kind of preparation method of novel conjugated polymers.
A kind of synthetic method of conjugated polymers: what comprise the steps: a molar equivalent contains two aromatic compound of carboxylic acid group or the aromatic compound of two carboxylic acid metal's alkali, with 1 ~ 3 molar equivalent (containing a molar equivalent and three molar equivalents) be dissolved in organic solvent containing two aromatic compound of halogen radical or the aromatic compound of bis trifluoromethyl sulfonate group, add metal catalyst, organic ligand compound, alkali and additive, under the protection of rare gas element, heated by heater means, and sustained reaction under the reaction conditions, then stopped reaction, reaction solution to be instilled in methyl alcohol or alcohol solvent and to filter, obtain thick product, purify, obtain conjugated polymers.
In aforesaid method, in the aromatic compound of described pair of carboxylic acid metal's alkali carboxylic acid metal's alkali be carboxylic acid lithium, carboxylic acid sodium or the group corresponding to carboxylic acid potassium; Described is fluorine-based, chloro, bromo or iodo containing halogen radical in the aromatic compound of two halogen radical; Described organic solvent is DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), N, N-dimethyl propylene thiazolinyl urea, diglyme or diethyl carbitol; Or the mixed solvent of more than one solvent compositions in above solvent and toluene, dimethylbenzene, trimethylbenzene, chlorobenzene, dichlorobenzene, tetrahydrofuran (THF).
In aforesaid method, described metal catalyst is palladium chloride, dibrominated palladium, palladium diiodide, palladium, palladium acetylacetonate or the palladium compound through organoligand coordination, and the molar content of described metal catalyst accounts for 1% ~ 30% of two aromatic compound of carboxylic acid group or the aromatic content of two carboxylic acid metal's alkali.
In aforesaid method, described organic ligand compound is phosphorous or nitrogenous organic compound; The molar content of described organic ligand compound accounts for 1% ~ 50% of two aromatic compound of carboxylic acid group or the aromatic content of two carboxylic acid metal's alkali; Described alkali is metal carbonate, metal phosphate or metal acetate salt; The molar content of described alkali accounts for 100% ~ 1000% of two aromatic compound of carboxylic acid group or the aromatic content of two carboxylic acid metal's alkali.
In aforesaid method, described additive is Potassium monofluoride, Repone K, Potassium Bromide, potassiumiodide, lithium fluoride, lithium chloride, lithiumbromide, lithium iodide, Sodium Fluoride, sodium-chlor, Sodium Bromide, sodium iodide, cesium fluoride, cesium chloride, cesium bromide or cesium iodide; The molar content of described additive accounts for 100% ~ 1000% of two aromatic compound of carboxylic acid group or the aromatic content of two carboxylic acid metal's alkali.
In aforesaid method, described rare gas element is nitrogen or argon gas; Described heater means is oil bath heating or microwave heating, and Heating temperature is 80 DEG C ~ 200 DEG C; The time of described reaction is 5 minutes ~ 72 hours.
In aforesaid method, described purification is for purify by soxhlet type method, column chromatography method or gel chromatography method.
In aforesaid method, described purification is for purify by soxhlet type method, column chromatography method and gel chromatography method.
In aforesaid method, the number-average molecular weight of described conjugated polymers is 3000 ~ 1000000; And polydispersity coefficient is 1.1 ~ 7.9.
Aforesaid method synthesis product as active coating, interfacial layer or application of electrode in organic/polymer electroluminescence diode, organic/polymer solar cells, organic/polymer field effect transistor, organic/polymer lightguide device, organic/polymkeric substance infrared eye, organic/polymer chemistry sensor and organic/polymer biological sensor.
The advantage that the present invention has and benefit are:
By low price and constitutionally stable carboxylic acid or carboxylate units in the present invention, but not price is higher and structural unstable boric acid ester unit or poisonous organotin unit, carries out copolymerization, prepare conjugated polymers with the cost of cheapness with Halogen unit.
Embodiment
Be described each constituent monomers proposed by the invention below in conjunction with embodiment, the present invention is not limited to this example.
Embodiment 1
The synthesis of polymer P 1
In two mouthfuls of round-bottomed flasks of drying, add 2,7-dicarboxylic acid-9,9-dioctyl fluorene (478.7mg, 1mmol), 2, bromo-9, the 9-dioctyl fluorene (548.4mg, 1mmol) of 7-bis-, palladium (12.2mg, 0.04mmol), copper carbonate (370mg, 3.0mmol), isopropyl biphenyl phosphine (27.4mg, 0.12mmol), KF (174mg, 3.0mmol) and dry
molecular sieve (1.0g).Then in reaction flask, high-purity argon gas 20 minutes are passed into.In reaction flask, add drying again and the N-Methyl pyrrolidone of deaeration (20ml), reacting by heating to 150 DEG C, and react 48 hours.Stopped reaction, instills reaction solution in methyl alcohol, filters, obtains polyfluorene crude product.Utilize soxhlet type method to use methyl alcohol, acetone, normal hexane and tetrahydrofuran (THF) extracting respectively, final tetrahydrofuran solution Precipitation in methyl alcohol, obtains the polyfluorene 645mg after purifying, productive rate 62.6%.Molecular weight characterization result is: number-average molecular weight is 25600, and polydispersity coefficient is 2.65.
Embodiment 2
The synthesis of polymer P 2
In two mouthfuls of round-bottomed flasks of drying, add 2,7-dicarboxylic acid-9-heptadecyl carbazole (493.7mg, 1mmol), 2,7-bis-bromo-9-heptadecyls carbazole (563.5mg, 1mmol), palladium (12.2mg, 0.04mmol), copper carbonate (370mg, 3.0mmol), isopropyl biphenyl phosphine (27.4mg, 0.12mmol), KF (174mg, 3.0mmol) and dry
molecular sieve (1.0g).Then in reaction flask, high-purity argon gas 20 minutes are passed into.In reaction flask, add drying again and the N-Methyl pyrrolidone of deaeration (20ml), reacting by heating to 150 DEG C, and react 48 hours.Stopped reaction, instills reaction solution in methyl alcohol, filters, obtains polyfluorene crude product.Utilize soxhlet type method to use methyl alcohol, acetone, normal hexane and tetrahydrofuran (THF) extracting respectively, final tetrahydrofuran solution Precipitation in methyl alcohol, obtains the polyfluorene 546mg after purifying, productive rate 51.6%.Molecular weight characterization result is: number-average molecular weight is 14800, and polydispersity coefficient is 3.21.
Embodiment 3
The synthesis of polymer P 3
In two mouthfuls of round-bottomed flasks of drying, add 2,5-thiophene dicarboxylate (172.2mg, 1mmol), 2,5-bis-bromo-7,8-bis-(2-ethyl hexyl oxy) benzene 1,4-Dithiapentalene (346.1mg, 1mmol), palladium (12.2mg, 0.04mmol), copper carbonate (370mg, 3.0mmol), isopropyl biphenyl phosphine (27.4mg, 0.12mmol), KF (174mg, 3.0mmol) and dry
molecular sieve (1.0g).Then in reaction flask, high-purity argon gas 20 minutes are passed into.In reaction flask, add drying again and the N-Methyl pyrrolidone of deaeration (20ml), reacting by heating to 150 DEG C, and react 48 hours.Stopped reaction, instills reaction solution in methyl alcohol, filters, obtains polyfluorene crude product.Utilize soxhlet type method to use methyl alcohol, acetone, normal hexane and tetrahydrofuran (THF) extracting respectively, final tetrahydrofuran solution Precipitation in methyl alcohol, obtains the polyfluorene 324mg after purifying, productive rate 62.5%.Molecular weight characterization result is: number-average molecular weight is 15600, and polydispersity coefficient is 2.47.
Embodiment 4
The synthesis of polymer P 4
In two mouthfuls of round-bottomed flasks of drying, add 2,7-dicarboxylic acid-9,9-dioctyl fluorene (478.7mg, 1mmol), 4,7-dibromo diazosulfide (294mg, 1mmol), palladium (12.2mg, 0.04mmol), copper carbonate (370mg, 3.0mmol), isopropyl biphenyl phosphine (27.4mg, 0.12mmol), KF (174mg, 3.0mmol) and dry
molecular sieve (1.0g).Then in reaction flask, high-purity argon gas 20 minutes are passed into.In reaction flask, add drying again and the N-Methyl pyrrolidone of deaeration (20ml), reacting by heating to 150 DEG C, and react 48 hours.Stopped reaction, instills reaction solution in methyl alcohol, filters, obtains polyfluorene crude product.Utilize soxhlet type method to use methyl alcohol, acetone, normal hexane and tetrahydrofuran (THF) extracting respectively, final tetrahydrofuran solution Precipitation in methyl alcohol, obtains the polyfluorene 412mg after purifying, productive rate 53.3%.Molecular weight characterization result is: number-average molecular weight is 34100, and polydispersity coefficient is 3.64.
Embodiment 5
The synthesis of polymer P 5
In two mouthfuls of round-bottomed flasks of drying, add 2,7-dicarboxylic acid-9,9-dioctyl fluorene (478.7mg, 1mmol), 3, two (the 5-bromothiophene base)-2 of 6-, 5-bis-(2-ethylhexyl) [3,4-c] pyrrolo-pyrrole-dione (456.1mg, 1mmol), palladium (12.2mg, 0.04mmol), copper carbonate (370mg, 3.0mmol), isopropyl biphenyl phosphine (27.4mg, 0.12mmol), KF (174mg, 3.0mmol) and dry
molecular sieve (1.0g).Then in reaction flask, high-purity argon gas 20 minutes are passed into.In reaction flask, add drying again and the N-Methyl pyrrolidone of deaeration (20ml), reacting by heating to 150 DEG C, and react 48 hours.Stopped reaction, instills reaction solution in methyl alcohol, filters, obtains polyfluorene crude product.Utilize soxhlet type method to use methyl alcohol, acetone, normal hexane and tetrahydrofuran (THF) extracting respectively, final tetrahydrofuran solution Precipitation in methyl alcohol, obtains the polyfluorene 435mg after purifying, productive rate 46.5%.Molecular weight characterization result is: number-average molecular weight is 17600, and polydispersity coefficient is 2.96.
Embodiment 6
The synthesis of polymer P 6
In two mouthfuls of round-bottomed flasks of drying, add 2,7-dicarboxylic acid-9,9-dioctyl fluorene (478.7mg, 1mmol), 2,7-bis-bromo-9,9-bis-(6-hydroxyl hexyl) fluorenes (524.3mg, 1mmol), palladium (12.2mg, 0.04mmol), copper carbonate (370mg, 3.0mmol), isopropyl biphenyl phosphine (27.4mg, 0.12mmol), KF (174mg, 3.0mmol) and dry
molecular sieve (1.0g).Then in reaction flask, high-purity argon gas 20 minutes are passed into.In reaction flask, add drying again and the N-Methyl pyrrolidone of deaeration (20ml), reacting by heating to 150 DEG C, and react 48 hours.Stopped reaction, instills reaction solution in methyl alcohol, filters, obtains polyfluorene crude product.Utilize soxhlet type method to use methyl alcohol, acetone, normal hexane and tetrahydrofuran (THF) extracting respectively, final tetrahydrofuran solution Precipitation in methyl alcohol, obtains the polyfluorene 459mg after purifying, productive rate 45.8%.Molecular weight characterization result is: number-average molecular weight is 12300, and polydispersity coefficient is 1.86.
Embodiment 7
The synthesis of polymer P 7
In two mouthfuls of round-bottomed flasks of drying, add 2,7-dicarboxylic acid-9,9-dioctyl fluorene (478.7mg, 1mmol), 2,7-bis-bromo-9,9-bis-(N, N-dimethyl propyl-1-amine) fluorenes (494.3mg, 1mmol), palladium (12.2mg, 0.04mmol), copper carbonate (370mg, 3.0mmol), isopropyl biphenyl phosphine (27.4mg, 0.12mmol), KF (174mg, 3.0mmol) and dry
molecular sieve (1.0g).Then in reaction flask, high-purity argon gas 20 minutes are passed into.In reaction flask, add drying again and the N-Methyl pyrrolidone of deaeration (20ml), reacting by heating to 150 DEG C, and react 48 hours.Stopped reaction, instills reaction solution in methyl alcohol, filters, obtains polyfluorene crude product.Utilize soxhlet type method to use methyl alcohol, acetone, normal hexane and tetrahydrofuran (THF) extracting respectively, final tetrahydrofuran solution Precipitation in methyl alcohol, obtains the polyfluorene 524mg after purifying, productive rate 53.9%.Molecular weight characterization result is: number-average molecular weight is 18400, and polydispersity coefficient is 2.38.
Embodiment 8
The synthesis of polymer P 8
In two mouthfuls of round-bottomed flasks of drying, add 2,7-dicarboxylic acid-9,9-dioctyl fluorene (478.7mg, 1mmol), 2,7-bis-(trifluoromethane sulfonic acid ester group)-9,9-dioctyl fluorene (686.8mg, 1mmol), palladium (12.2mg, 0.04mmol), copper carbonate (370mg, 3.0mmol), isopropyl biphenyl phosphine (27.4mg, 0.12mmol), KF (174mg, 3.0mmol) and dry
molecular sieve (1.0g).Then in reaction flask, high-purity argon gas 20 minutes are passed into.In reaction flask, add drying again and the N-Methyl pyrrolidone of deaeration (20ml), reacting by heating to 150 DEG C, and react 48 hours.Stopped reaction, instills reaction solution in methyl alcohol, filters, obtains polyfluorene crude product.Utilize soxhlet type method to use methyl alcohol, acetone, normal hexane and tetrahydrofuran (THF) extracting respectively, final tetrahydrofuran solution Precipitation in methyl alcohol, obtains the polyfluorene 574mg after purifying, productive rate 51.2%.Molecular weight characterization result is: number-average molecular weight is 16600, and polydispersity coefficient is 3.04.
Embodiment 9
The preparation of polymer electroluminescent device
By ITO conductive glass, square resistance ~ 20 Ω/, is precut into 15 millimeters × 15 millimeters square pieces.Use acetone, micron order semi-conductor special purpose detergent, deionized water, Virahol ultrasonic cleaning successively, it is for subsequent use that nitrogen purging is placed on constant temperature oven.Before using, the clean sheet of ITO in oxygen plasma etch instrument with plasma bombardment 10 minutes.And with PEDOT:PSS aqueous dispersions, (about mass concentration is the aqueous solution of 1%, purchased from Bayer company), buffer layer is with the spin coating of sol evenning machine (KW-4A) high speed, thickness is determined by strength of solution and rotating speed, with surface profiler (Tritek company Alpha-Tencor500 type) actual measurement monitoring.After film forming, in constant-temperature vacuum baking oven, drive away solvent residues, post bake.
After conjugated polymers P1 is weighed in clean bottle, proceed to nitrogen protection film forming special gloves case (VAC company), dissolve in dimethylbenzene.Polymer film layer optimum thickness is 100 nanometers.Thickness TENCORALFA-STEP-500 surface profiler measures.In the glove box having nitrogen protection, have spin coating one layer of polymeric P1 thin film layer above the ITO slide of PEDOT:PSS layer in spin coating, and then spin coating one layer of polymeric P7 film is as cathodic modification layer.Aluminium electrode evaporation vacuum tightness in vacuum plating unit reaches 3 × 10
-4complete during below Pa.The thickness of plated film speed and each layer electrode is monitored in real time by quartz resonator film thickness monitor (STM-100 type, Sycon company).All preparation process are all carried out in the glove box providing nitrogen inert atmosphere.The I-E characteristic of device, is recorded by Keithley236 current/voltage source-measuring system and a calibrated silicon photo diode.
Embodiment 10
The preparation of polymer solar cells
By ITO conductive glass, square resistance ~ 20 Ω/, is precut into 15 millimeters × 15 millimeters square pieces.Use acetone, micron order semi-conductor special purpose detergent, deionized water, Virahol ultrasonic cleaning successively, it is for subsequent use that nitrogen purging is placed on constant temperature oven.Before using, the clean sheet of ITO in oxygen plasma etch instrument with plasma bombardment 10 minutes.And with PEDOT:PSS aqueous dispersions, (about mass concentration is the aqueous solution of 1%, purchased from Bayer company), buffer layer is with the spin coating of sol evenning machine (KW-4A) high speed, thickness is determined by strength of solution and rotating speed, with surface profiler (Tritek company Alpha-Tencor500 type) actual measurement monitoring.After film forming, in constant-temperature vacuum baking oven, drive away solvent residues, post bake.
After conjugated polymers P5 donor material is weighed in clean bottle, proceed to nitrogen protection film forming special gloves case (VAC company), dissolve in chlorobenzene, then carry out blended with PCBM, be mixed into necessarily than the mixing solutions of row.Mixed with polymers layer optimum thickness is 100 nanometers.Thickness TENCOR ALFA-STEP-500 surface profiler measures.In the glove box having nitrogen protection, there is spin coating one layer of polymeric P5 and PC above the ITO slide of PEDOT:PSS layer in spin coating
61the mixture film of BM ([6,6]-phenyl C61 methyl-butyrate), and then spin coating one layer of polymeric P7 film is as cathodic modification layer.Aluminium electrode evaporation vacuum tightness in vacuum plating unit reaches 3 × 10
-4complete during below Pa.The thickness of plated film speed and each layer electrode is monitored in real time by quartz resonator film thickness monitor (STM-100 type, Sycon company).All preparation process are all carried out in the glove box providing nitrogen inert atmosphere.The I-E characteristic of device, is recorded by Keithley236 current/voltage source measuring system and a calibrated silicon photo diode.
Following example is the explanation of photoelectric device performance made by conjugated polymers proposed by the invention, but the present invention will be not limited to listed example.
The electroluminescent properties of table 1 polymer P 1
Device architecture A:ITO/PEDOT:PSS/ polymer P 1/P7/Al
Device architecture B:ITO/PEDOT:PSS/PVK/ polymer P 1/P7/Al.
The Photovoltaic Device Performance of table 2 polymer P 5 under 0.66 sunlight intensity
Device architecture: ITO/PEDOT:PSS/ polymer P 5:PC
61bM/P7/Al
To acceptor ratio: polymer P 5:PC
61bM.
The above embodiment of the present invention is only for example of the present invention is clearly described, and is not the restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.All any amendments done within the spirit and principles in the present invention, equivalent to replace and improvement etc., within the protection domain that all should be included in the claims in the present invention.
Claims (10)
1. the synthetic method of a conjugated polymers, it is characterized in that, what comprise the steps: a molar equivalent contains two aromatic compound of carboxylic acid group or the aromatic compound of two carboxylic acid metal's alkali, with 1 ~ 3 molar equivalent be dissolved in organic solvent containing two aromatic compound of halogen radical or the aromatic compound of bis trifluoromethyl sulfonate group, add metal catalyst, organic ligand compound, alkali and additive, under the protection of rare gas element, heated by heater means, and sustained reaction under the reaction conditions, then stopped reaction, reaction solution to be instilled in methyl alcohol or alcohol solvent and to filter, obtain thick product, purify, obtain conjugated polymers.
2., according to the synthetic method described in claim 1, it is characterized in that: in the aromatic compound of described pair of carboxylic acid metal's alkali carboxylic acid metal's alkali be carboxylic acid lithium, carboxylic acid sodium or the group corresponding to carboxylic acid potassium; Described is fluorine-based, chloro, bromo or iodo containing halogen radical in the aromatic compound of two halogen radical; Described organic solvent is DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), N, N-dimethyl propylene thiazolinyl urea, diglyme or diethyl carbitol; Or the mixed solvent of more than one solvent compositions in more than one and toluene in aforementioned solvents, dimethylbenzene, trimethylbenzene, chlorobenzene, dichlorobenzene, tetrahydrofuran (THF).
3. synthetic method according to claim 1, it is characterized in that: described metal catalyst is palladium chloride, dibrominated palladium, palladium diiodide, palladium, palladium acetylacetonate or the palladium compound through organoligand coordination, the molar content of described metal catalyst accounts for 1 % ~ 30 % of two aromatic compound of carboxylic acid group or the aromatic content of two carboxylic acid metal's alkali.
4. synthetic method according to claim 1, is characterized in that: described organic ligand compound is phosphorous or nitrogenous organic compound; The molar content of described organic ligand compound accounts for 1 % ~ 50 % of two aromatic compound of carboxylic acid group or the aromatic content of two carboxylic acid metal's alkali; Described alkali is metal carbonate, metal phosphate or metal acetate salt; The molar content of described alkali accounts for 100 % ~ 1000 % of two aromatic compound of carboxylic acid group or the aromatic content of two carboxylic acid metal's alkali.
5. synthetic method according to claim 1, is characterized in that: described additive is Potassium monofluoride, Repone K, Potassium Bromide, potassiumiodide, lithium fluoride, lithium chloride, lithiumbromide, lithium iodide, Sodium Fluoride, sodium-chlor, Sodium Bromide, sodium iodide, cesium fluoride, cesium chloride, cesium bromide or cesium iodide; The molar content of described additive accounts for 100 % ~ 1000 % of two aromatic compound of carboxylic acid group or the aromatic content of two carboxylic acid metal's alkali.
6. synthetic method according to claim 1, is characterized in that: described rare gas element is nitrogen or argon gas; Described heater means is oil bath heating or microwave heating, and Heating temperature is 80 DEG C ~ 200 DEG C; The time of described reaction is 5 minutes ~ 72 hours.
7. synthetic method according to claim 1, is characterized in that: described purification is for purify by soxhlet type method, column chromatography method or gel chromatography method.
8. synthetic method according to claim 1, is characterized in that: described purification is for purify by soxhlet type method, column chromatography method and gel chromatography method.
9. synthetic method according to claim 1, is characterized in that: the number-average molecular weight of described conjugated polymers is 3000 ~ 1000000; And polydispersity coefficient is 1.1 ~ 7.9.
10. described in claim 1 synthetic method synthesis product as active coating, interfacial layer or application of electrode in organic/polymer electroluminescence diode, organic/polymer solar cells, organic/polymer field effect transistor, organic/polymer lightguide device, organic/polymkeric substance infrared eye, organic/polymer chemistry sensor and organic/polymer biological sensor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510014324.5A CN104558531B (en) | 2015-01-12 | 2015-01-12 | Synthesis method and application of conjugated polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510014324.5A CN104558531B (en) | 2015-01-12 | 2015-01-12 | Synthesis method and application of conjugated polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104558531A true CN104558531A (en) | 2015-04-29 |
| CN104558531B CN104558531B (en) | 2017-02-01 |
Family
ID=53075667
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510014324.5A Active CN104558531B (en) | 2015-01-12 | 2015-01-12 | Synthesis method and application of conjugated polymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104558531B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108192083A (en) * | 2018-01-02 | 2018-06-22 | 苏州大学 | Conjugated polymer containing trifluoromethyl and its preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011060526A1 (en) * | 2009-11-18 | 2011-05-26 | National Research Council Of Canada | Fluorinated monomers, oligomers and polymers for use in organic electronic devices |
| CN102083883A (en) * | 2008-07-02 | 2011-06-01 | 巴斯夫欧洲公司 | High performance solution processable semiconducting polymers based on alternat-ing donor acceptor copolymers |
| CN104119506A (en) * | 2013-04-25 | 2014-10-29 | 海洋王照明科技股份有限公司 | Polymer containing difluoro diazosulfide unit and preparation method thereof and solar cell device |
-
2015
- 2015-01-12 CN CN201510014324.5A patent/CN104558531B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102083883A (en) * | 2008-07-02 | 2011-06-01 | 巴斯夫欧洲公司 | High performance solution processable semiconducting polymers based on alternat-ing donor acceptor copolymers |
| WO2011060526A1 (en) * | 2009-11-18 | 2011-05-26 | National Research Council Of Canada | Fluorinated monomers, oligomers and polymers for use in organic electronic devices |
| CN104119506A (en) * | 2013-04-25 | 2014-10-29 | 海洋王照明科技股份有限公司 | Polymer containing difluoro diazosulfide unit and preparation method thereof and solar cell device |
Non-Patent Citations (2)
| Title |
|---|
| LUKAS J. GOOßEN ET AL.: "Synthesis of Biaryls via Catalytic Decarboxylative Coupling", 《SCIENCE》 * |
| NELLY RAMEAU ET AL.: "Decarboxylative Heterocoupling Coupling of Substituted Benzoic Acids for Biaryl Synthesis", 《TOP CATAL》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108192083A (en) * | 2018-01-02 | 2018-06-22 | 苏州大学 | Conjugated polymer containing trifluoromethyl and its preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104558531B (en) | 2017-02-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xu et al. | Effects of side chain isomerism on the physical and photovoltaic properties of indacenodithieno [3, 2-b] thiophene–quinoxaline copolymers: toward a side chain design for enhanced photovoltaic performance | |
| CN104086752A (en) | Benzodithiophene polymer, its preparation method, semiconductor composition containing it, and solar cell using it | |
| CN106046328B (en) | A kind of two-dimentional conjugated polymer of silane substituted and preparation method thereof and the application in photovoltaic device | |
| Homyak et al. | Systematic fluorination of P3HT: synthesis of P (3HT-co-3H4FT) s by direct arylation polymerization, characterization, and device performance in OPVs | |
| CN101875717A (en) | Copolymer of bithiophene diazosulfide and dibenzothiophene (BDT) and application thereof | |
| TWI523893B (en) | Polymer and the use of its organic thin film solar cells, and with the battery from the electronic machine | |
| He et al. | Synthesis and photovoltaic properties of a low bandgap BODIPY–Pt conjugated polymer | |
| Kurosawa et al. | Understanding the Impact of Oligomeric Polystyrene Side Chain Arrangement on the All‐Polymer Solar Cell Performance | |
| CN103435783A (en) | Conjugated polymer, and preparation method and application thereof | |
| CN106065020A (en) | A kind of preparation method of polymer solar battery small molecule receptor | |
| Bae et al. | Synthesis and photophysical properties of soluble low‐bandgap thienothiophene polymers with various alkyl side‐chain lengths | |
| Leenaers et al. | Structural design of asymmetric diketopyrrolopyrrole polymers for organic solar cells processed from a non-halogenated solvent | |
| Zhao et al. | Direct arylation polycondensation toward water/alcohol-soluble conjugated polymers: influence of side chain functional groups | |
| CN102816298A (en) | Naphtha[2, 3-c]thiophene-4,9-diketone polymer and its application in solar cells | |
| Yang et al. | Impact of isomers on the photovoltaic properties of polymerized small-molecule acceptors | |
| CN102532492B (en) | Crosslinking thiopheno[3,4-b] thiophene conjugated polymer and preparation method and application thereof | |
| CN104530391A (en) | Closed-loop triphenylamine derivative copolymer and preparing method and application thereof | |
| CN104558531A (en) | Synthesis method and application of conjugated polymer | |
| CN103923106B (en) | Conjugated polymer that a kind of mental retardation gap length absorbs and preparation method thereof | |
| Song et al. | Solution-processed interlayer of n-type small molecules for organic photovoltaic devices: Enhancement of the fill factor due to ordered orientation | |
| JP6441196B2 (en) | Polymer and solar cell using the same | |
| CN110734540A (en) | conjugated polymer containing halogen atom substituted thienyl fused thiazole structure and application thereof | |
| CN105622900B (en) | Organic electroluminescence device | |
| CN102786668B (en) | Triphenylamine-based block polymer semiconductor, preparation method and application thereof | |
| CN102643284B (en) | Preparation method and application of 4,9-bisalkylene indene thieno[3,2-b]thiophene derivative and conjugated polymer thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |