CN104558531B - Synthesis method and application of conjugated polymer - Google Patents
Synthesis method and application of conjugated polymer Download PDFInfo
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- CN104558531B CN104558531B CN201510014324.5A CN201510014324A CN104558531B CN 104558531 B CN104558531 B CN 104558531B CN 201510014324 A CN201510014324 A CN 201510014324A CN 104558531 B CN104558531 B CN 104558531B
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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 macromolecule preparing technical field is and in particular to a kind of synthetic method of conjugated polymer and application.
Background technology
Conjugated polymer is widely used in organic electro-optic device as the new macromolecular material of a class, than
As organic electroluminescent LED, organic photovoltaic cell, organic field effect tube and organic infrared detector etc..These are altogether
Conjugated polymer is all to be polymerized by aromatics unit to obtain, such as polyfluorene class, polycarbazole, polythiophene class etc..
At present, synthesize such conjugated polymer method be mainly suzuki polyreaction, yamamoto polyreaction and
Stille polyreaction etc..These synthetic methods mainly pass through palladium class catalyst, using special functional group with contain
Halogen unit carries out reaction and obtains.More extensive specific function group is wherein applied to be suzuki polyreaction and stille polymerization
Borate in reaction and organotin unit.But, these groups prepare expensive, structural instability, easily decomposition, 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, exploitation one class new, cheap and environmental protection synthetic method of polymers be one particularly significant
Work.Goo β en etc. utilizes carboxylic unit and halogen-containing unit process, can obtain target couplingization with high productivity
Compound.(science, 313,2006) be based on this, by have double carboxylic acid functionals aromatic and containing Shuan Lu functional group
Aromatic is in the case of catalyst, it is possible to obtain required target conjugated polymer.Such synthetic method need not be made
Standby expensive, structural unstable borate or poisonous organotin unit, so that such novel method can be high
Effect, low cost, greenly prepare the conjugated polymer with photoelectric activity.
Content of the invention
The present invention passes through by the aromatic containing double carboxylic acid groups or double carboxylic acid metal's alkali and containing double halogen radicals or double three
The aromatic of methyl fluoride sulfonate group is in certain organic solvent, metallic catalyst, organic ligand compound, alkali and additive
In, and under the protection of noble gases, by being heated to uniform temperature, and sustained response certain time, prepare and there is photoelectricity
The conjugated polymer of characteristic.
Object of the present invention is to provide a kind of preparation method of new conjugated polymer.
A kind of synthetic method of conjugated polymer: comprise the steps: the aromatization containing double carboxylic acid groups of a molar equivalent
Compound or the aromatic of double carboxylic acid metal's alkali, with containing of 1～3 molar equivalent (containing a molar equivalent and three molar equivalents)
The aromatic of the aromatic of double halogen radicals or bis trifluoromethyl sulfonate group is dissolved in organic solvent, adds metal
Catalyst, organic ligand compound, alkali and additive, under the protection of noble gases, are heated by heater meanses, and at this
Sustained response under reaction condition, then stopped reaction, reactant liquor is instilled in methanol or alcohol solvent and filters, slightly produced
Product, purification, obtain conjugated polymer.
In said method, in the aromatic of described pair of carboxylic acid metal's alkali, carboxylic acid metal's alkali is carboxylic acid lithium, carboxylic acid
Group corresponding to sodium or carboxylic acid potassium；In the described aromatic containing double halogen radicals halogen radical be fluorine-based, chloro, bromo or
Person's iodo；Described organic solvent is n, n- dimethylformamide, n, n- dimethyl acetylamide, n- methyl pyrrolidone, dimethyl
Sulfoxide, n, n- dimethyl propylene thiazolinyl urea, diethylene glycol dimethyl ether or diethyl carbitol；Or above solvent and toluene, diformazan
The mixed solvent of one or more of benzene, trimethylbenzene, chlorobenzene, dichloro-benzenes, oxolane solvent composition.
In said method, described metallic catalyst is palladium chloride, dibrominated palladium, palladium diiodide, palladium, acetylacetone,2,4-pentanedione
Palladium or the palladium compound through organoligand coordination, the molar content of described metallic catalyst accounts for the aromatic of double carboxylic acid groups
Or the 1%～30% of the aromatic content of double carboxylic acid metal's alkali.
In said method, described organic ligand compound is phosphorous or nitrogenous organic compound；Described organic ligand
The molar content of compound account for the aromatic of double carboxylic acid groups or the aromatic content of double carboxylic acid metal's alkali 1%～
50%；Described alkali is metal carbonate, metal phosphate or metal acetate salt；The molar content of described alkali accounts for double carboxylic acid groups'
The 100%～1000% of the aromatic content of aromatic or double carboxylic acid metal's alkali.
In said method, described additive is potassium fluoride, potassium chloride, potassium bromide, potassium iodide, lithium fluoride, lithium chloride, bromination
Lithium, lithium iodide, sodium fluoride, sodium chloride, sodium bromide, sodium iodide, cesium fluoride, cesium chloride, cesium bromide or cesium iodide；Described interpolation
The molar content of agent account for the aromatic of double carboxylic acid groups or the aromatic content of double carboxylic acid metal's alkali 100%～
1000%.
In said method, described noble gases are nitrogen or argon；Described heater meanses are oil bath heating or microwave
Heating, heating-up temperature is 80 DEG C～200 DEG C；The time of described reaction is 5 minutes～72 hours.
In said method, described purification is to be carried by soxhlet type method, column chromatography method or gel chromatography method
Pure.
In said method, described purification is to be carried by soxhlet type method, column chromatography method and gel chromatography method
Pure.
In said method, the number-average molecular weight of described conjugated polymer is 3000～1000000；And polydispersity coefficient is
1.1～7.9.
The product of said method synthesis is as active layer, boundary layer or application of electrode in organic/polymer electroluminescence
Diode, organic/polymer solar cells, organic/polymer field effect transistor, organic/polymer lightguide device, organic/
In polymer Infrared Detectorss, organic/polymer chemistry sensor and organic/polymer biological sensor.
Advantage for present invention and benefit are:
Pass through low price and constitutionally stable carboxylic acid or carboxylate units in the present invention, rather than price is higher and structure
Unstable boric acid ester units or poisonous organotin unit, carry out copolymerization with halogen unit, are obtained with cheap cost preparation
Obtain conjugated polymer.
Specific embodiment
With reference to embodiment, each constituent monomers proposed by the invention are illustrated, the present invention is not limited to this example.
Embodiment 1
The synthesis of polymer p1
In two mouthfuls of round-bottomed flasks being dried, add 2,7- dicarboxylic acids -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), curpic carbonate (370mg,
3.0mmol), isopropyl biphenyl phosphine (27.4mg, 0.12mmol), kf (174mg, 3.0mmol) and be driedMolecular sieve
(1.0g).Then it is passed through high-purity argon gas toward in reaction bulb 20 minutes.Dry and deaeration n- first is added again toward in reaction bulb
Base ketopyrrolidine (20ml), reacting by heating is to 150 DEG C, and reacts 48 hours.Stopped reaction, reactant liquor is instilled in methanol,
Filter, obtain polyfluorene crude product.Extracted using methanol, acetone, normal hexane and oxolane respectively using soxhlet type method, final four
Hydrogen tetrahydrofuran solution Precipitation in methyl alcohol, obtains polyfluorene 645mg after purification, yield 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 p2
In two mouthfuls of round-bottomed flasks being dried, addition 2,7- dicarboxylic acids -9- heptadecyl carbazole (493.7mg, 1mmol),
2,7- bis- bromo- 9- heptadecyl carbazole (563.5mg, 1mmol), palladium (12.2mg, 0.04mmol), curpic carbonate (370mg,
3.0mmol), isopropyl biphenyl phosphine (27.4mg, 0.12mmol), kf (174mg, 3.0mmol) and be driedMolecular sieve
(1.0g).Then it is passed through high-purity argon gas toward in reaction bulb 20 minutes.Dry and deaeration n- first is added again toward in reaction bulb
Base ketopyrrolidine (20ml), reacting by heating is to 150 DEG C, and reacts 48 hours.Stopped reaction, reactant liquor is instilled in methanol,
Filter, obtain polyfluorene crude product.Extracted using methanol, acetone, normal hexane and oxolane respectively using soxhlet type method, final four
Hydrogen tetrahydrofuran solution Precipitation in methyl alcohol, obtains polyfluorene 546mg after purification, yield 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 p3
In two mouthfuls of round-bottomed flasks being dried, add 2,5- thiophene dicarboxylate (172.2mg, 1mmol), 2,5- bis- bromo- 7,
8- bis- (2- ethyl hexyl oxy) benzene thiophene (346.1mg, 1mmol), palladium (12.2mg, 0.04mmol), curpic carbonate
(370mg, 3.0mmol), isopropyl biphenyl phosphine (27.4mg, 0.12mmol), kf (174mg, 3.0mmol) and dryingPoint
Son sieve (1.0g).Then it is passed through high-purity argon gas toward in reaction bulb 20 minutes.Add dry and deaeration again toward in reaction bulb
N- methyl pyrrolidone (20ml), reacting by heating is to 150 DEG C, and reacts 48 hours.Stopped reaction, reactant liquor is instilled methanol
In, filter, obtain polyfluorene crude product.Extracted using methanol, acetone, normal hexane and oxolane respectively using soxhlet type method,
Whole tetrahydrofuran solution Precipitation in methyl alcohol, obtains polyfluorene 324mg after purification, yield 62.5%.Molecular weight characterization result
For: number-average molecular weight is 15600, and polydispersity coefficient is 2.47.
Embodiment 4
The synthesis of polymer p4
In two mouthfuls of round-bottomed flasks being dried, add 2,7- dicarboxylic acids -9,9- dioctyl fluorene (478.7mg, 1mmol), 4,
7- dibromo diazosulfide (294mg, 1mmol), palladium (12.2mg, 0.04mmol), curpic carbonate (370mg, 3.0mmol),
Isopropyl biphenyl phosphine (27.4mg, 0.12mmol), kf (174mg, 3.0mmol) and dryingMolecular sieve (1.0g).Then past
It is passed through high-purity argon gas 20 minutes in reaction bulb.Dry and deaeration n- methyl pyrrolidone is added again toward in reaction bulb
(20ml), reacting by heating is to 150 DEG C, and reacts 48 hours.Stopped reaction, reactant liquor is instilled in methanol, filters, obtain polyfluorene
Crude product.Extracted using methanol, acetone, normal hexane and oxolane respectively using soxhlet type method, final tetrahydrofuran solution
Precipitation in methyl alcohol, obtains polyfluorene 412mg after purification, yield 53.3%.Molecular weight characterization result is: number-average molecular weight is
34100, polydispersity coefficient is 3.64.
Embodiment 5
The synthesis of polymer p5
In two mouthfuls of round-bottomed flasks being dried, add 2,7- dicarboxylic acids -9,9- dioctyl fluorene (478.7mg, 1mmol), 3,
6- double (5- bromothiophene base) -2,5- bis- (2- ethylhexyl) [3,4-c] pyrrolo-pyrrole-dione (456.1mg, 1mmol), acetic acid
Palladium (12.2mg, 0.04mmol), curpic carbonate (370mg, 3.0mmol), isopropyl biphenyl phosphine (27.4mg, 0.12mmol), kf
(174mg, 3.0mmol) and dryingMolecular sieve (1.0g).Then it is passed through high-purity argon gas toward in reaction bulb 20 minutes.Past again
Dry and deaeration n- methyl pyrrolidone (20ml) is added, reacting by heating is to 150 DEG C, and it is little to react 48 in reaction bulb
When.Stopped reaction, reactant liquor is instilled in methanol, filters, obtain polyfluorene crude product.Using soxhlet type method respectively using methanol,
Acetone, normal hexane and oxolane extracting, final tetrahydrofuran solution Precipitation in methyl alcohol, obtain polyfluorene after purification
435mg, yield 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 p6
In two mouthfuls of round-bottomed flasks being dried, add 2,7- dicarboxylic acids -9,9- dioctyl fluorene (478.7mg, 1mmol), 2,
Bromo- 9,9- bis- (the 6- hydroxyl hexyl) fluorenes (524.3mg, 1mmol) of 7- bis-, palladium (12.2mg, 0.04mmol), curpic carbonate
(370mg, 3.0mmol), isopropyl biphenyl phosphine (27.4mg, 0.12mmol), kf (174mg, 3.0mmol) and dryingPoint
Son sieve (1.0g).Then it is passed through high-purity argon gas toward in reaction bulb 20 minutes.Add dry and deaeration again toward in reaction bulb
N- methyl pyrrolidone (20ml), reacting by heating is to 150 DEG C, and reacts 48 hours.Stopped reaction, reactant liquor is instilled methanol
In, filter, obtain polyfluorene crude product.Extracted using methanol, acetone, normal hexane and oxolane respectively using soxhlet type method,
Whole tetrahydrofuran solution Precipitation in methyl alcohol, obtains polyfluorene 459mg after purification, yield 45.8%.Molecular weight characterization result
For: number-average molecular weight is 12300, and polydispersity coefficient is 1.86.
Embodiment 7
The synthesis of polymer p7
In two mouthfuls of round-bottomed flasks being dried, add 2,7- dicarboxylic acids -9,9- dioctyl fluorene (478.7mg, 1mmol), 2,
Bromo- 9,9- bis- (n, the n- dimethyl propyl -1- amine) fluorenes (494.3mg, 1mmol) of 7- bis-, palladium (12.2mg, 0.04mmol),
Curpic carbonate (370mg, 3.0mmol), isopropyl biphenyl phosphine (27.4mg, 0.12mmol), kf (174mg, 3.0mmol) and dryingMolecular sieve (1.0g).Then it is passed through high-purity argon gas toward in reaction bulb 20 minutes.Add toward in reaction bulb again and be dried and come to nothing
The n- methyl pyrrolidone (20ml) of gas, reacting by heating is to 150 DEG C, and reacts 48 hours.Stopped reaction, reactant liquor is instilled
In methanol, filter, obtain polyfluorene crude product.Taken out using methanol, acetone, normal hexane and oxolane respectively using soxhlet type method
Carry, final tetrahydrofuran solution Precipitation in methyl alcohol, obtain polyfluorene 524mg after purification, yield 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 p8
In two mouthfuls of round-bottomed flasks being dried, add 2,7- dicarboxylic acids -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), carbon
Sour copper (370mg, 3.0mmol), isopropyl biphenyl phosphine (27.4mg, 0.12mmol), kf (174mg, 3.0mmol) and dryingMolecular sieve (1.0g).Then it is passed through high-purity argon gas toward in reaction bulb 20 minutes.Add toward in reaction bulb again and be dried and come to nothing
The n- methyl pyrrolidone (20ml) of gas, reacting by heating is to 150 DEG C, and reacts 48 hours.Stopped reaction, reactant liquor is instilled
In methanol, filter, obtain polyfluorene crude product.Taken out using methanol, acetone, normal hexane and oxolane respectively using soxhlet type method
Carry, final tetrahydrofuran solution Precipitation in methyl alcohol, obtain polyfluorene 574mg after purification, yield 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 electro-conductive glass, square resistance～20 ω/, be precut into 15 millimeters × 15 millimeters square pieces.Successively with third
Ketone, micron level semiconductor special purpose detergent, deionized water, isopropanol are cleaned by ultrasonic, and are placed in constant temperature oven standby after nitrogen purging.
Using front, the net piece of ito is in oxygen plasma etch instrument with plasma bombardment 10 minutes.And with pedot:pss aqueous dispersions
(about mass concentration is 1% aqueous solution, purchased from bayer company), cushion with sol evenning machine (kw-4a) high speed spin coating, thickness by
Solution concentration is determined with rotating speed, surveys monitoring with surface profiler (tritek company alpha-tencor500 type).After film forming,
Drive away solvent residues, post bake in constant-temperature vacuum baking oven.
After conjugated polymer p1 is weighed in the 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 tencor alfa-step-500 surface profile
Instrument measures.In the glove box having nitrogen protection, there is spin coating one layers of polymer above the ito slide of pedot:pss layer in spin coating
Thing p1 thin layer, then again spin coating one layer of polymeric p7 film as cathodic modification layer.Aluminium electrode evaporation is true in vacuum coating equipment
Reciprocal of duty cycle reaches 3 × 10-4Complete during below pa.The thickness of plated film speed and each layer electrode is by quartz vibrator film thickness monitor (stm-
100 types, sycon company) monitor in real time.All preparation process are all carried out in the glove box providing nitrogen inert atmosphere.Device
I-E characteristic, surveyed by the calibrated silicon photo diode of keithley236 current/voltage source-measuring system and
?.
Embodiment 10
The preparation of polymer solar cells
By ito electro-conductive glass, square resistance～20 ω/, be precut into 15 millimeters × 15 millimeters square pieces.Successively with third
Ketone, micron level semiconductor special purpose detergent, deionized water, isopropanol are cleaned by ultrasonic, and are placed in constant temperature oven standby after nitrogen purging.
Using front, the net piece of ito is in oxygen plasma etch instrument with plasma bombardment 10 minutes.And with pedot:pss aqueous dispersions
(about mass concentration is 1% aqueous solution, purchased from bayer company), cushion with sol evenning machine (kw-4a) high speed spin coating, thickness by
Solution concentration is determined with rotating speed, surveys monitoring with surface profiler (tritek company alpha-tencor500 type).After film forming,
Drive away solvent residues, post bake in constant-temperature vacuum baking oven.
After conjugated polymer p5 donor material is weighed in the clean bottle, proceed to nitrogen protection film forming special gloves case (vac
Company), dissolve in chlorobenzene, be then blended with pcbm, be mixed into the mixed solution of definite proportion row.Polymer mixed layer is
Good thickness is 100 nanometers.Thickness is measured with tencor alfa-step-500 surface profiler.In the glove box having nitrogen protection
In, there is spin coating one layer of polymeric p5 and pc above the ito slide of pedot:pss layer in spin coating61Bm ([6,6]-phenyl c61 fourth
Sour methyl ester) mixture film, then again spin coating one layer of polymeric p7 film as cathodic modification layer.Aluminium electrode is deposited with Vacuum Deposition
In film machine, vacuum reaches 3 × 10-4Complete during below pa.The thickness of plated film speed and each layer electrode is by quartz vibrator film thickness monitoring
Instrument (stm-100 type, sycon company) monitor in real time.All preparation process are all entered in the glove box providing nitrogen inert atmosphere
OK.The I-E characteristic of device, by calibrated silicon light two pole of keithley236 current/voltage source measuring system and one
Pipe records.
Example below is the explanation to photoelectric device performance made by conjugated polymer proposed by the invention, but this
Bright it is not limited to listed example.
The electroluminescent properties of table 1 polymer p1
Device architecture a:ito/pedot:pss/ polymer p1/p7/al
Device architecture b:ito/pedot:pss/pvk/ polymer p1/p7/al.
Photovoltaic Device Performance under 0.66 sunlight intensity for the table 2 polymer p5
Device architecture: ito/pedot:pss/ polymer p5:pc61bm/p7/al
To acceptor ratio: polymer p5:pc61bm.
The above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and is not to the present invention
Embodiment restriction.For those of ordinary skill in the field, can also make on the basis of the above description
The change of other multi-forms or variation.There is no need to be exhaustive to all of embodiment.All the present invention's
Any modification, equivalent and improvement made within spirit and principle etc., should be included in the protection of the claims in the present invention
Within the scope of.
Claims (8)
1. a kind of synthetic method of conjugated polymer it is characterised in that comprise the steps: a molar equivalent containing double carboxylic acid groups
Aromatic or double carboxylic acid metal's alkali aromatic, with the aromatics containing double halogen radicals for 1～3 molar equivalent
The aromatic of thing or bis trifluoromethyl sulfonate group is dissolved in organic solvent, adds metallic catalyst, organic ligand
Compound, alkali and additive, under the protection of noble gases, are heated by heater meanses, and continue anti-under the reaction conditions
Should, then stopped reaction, reactant liquor is instilled in methanol or alcohol solvent and filters, obtain crude product, purification, obtain conjugation
Polymer.
2. synthetic method according to claim 1 it is characterised in that: in the aromatic of described pair of carboxylic acid metal's alkali
Carboxylic acid metal's alkali is carboxylic acid lithium, carboxylic acid sodium or the group corresponding to carboxylic acid potassium；The described aromatic containing double halogen radicals
Middle halogen radical is fluorine-based, chloro, bromo or iodo；Described organic solvent is n, n- dimethylformamide, n, n- dimethyl second
Amide, n- methyl pyrrolidone, dimethyl sulfoxide, n, n- dimethyl propylene thiazolinyl urea, diethylene glycol dimethyl ether or diethylene glycol diethyl
Ether；Or one or more of aforementioned solvents and one of toluene, dimethylbenzene, trimethylbenzene, chlorobenzene, dichloro-benzenes, oxolane
The mixed solvent of above solvent composition.
3. synthetic method according to claim 1 it is characterised in that: described metallic catalyst be palladium chloride, dibrominated
Palladium, palladium diiodide, palladium, palladium acetylacetonate or the palladium compound through organoligand coordination, the rubbing of described metallic catalyst
Your content accounts for the 1%～30% of the aromatic of double carboxylic acid groups or the aromatic content of double carboxylic acid metal's alkali.
4. synthetic method according to claim 1 it is characterised in that: described organic ligand compound be phosphorous or nitrogenous
Organic compound；The molar content of described organic ligand compound accounts for the aromatic of double carboxylic acid groups or double carboxylic metallic salt
The 1%～50% of the aromatic content of base；Described alkali is metal carbonate, metal phosphate or metal acetate salt；Institute
State alkali molar content account for the aromatic of double carboxylic acid groups or the aromatic content of double carboxylic acid metal's alkali 100%～
1000%.
5. synthetic method according to claim 1 it is characterised in that: described additive be potassium fluoride, potassium chloride, bromination
Potassium, potassium iodide, lithium fluoride, lithium chloride, lithium bromide, lithium iodide, sodium fluoride, sodium chloride, sodium bromide, sodium iodide, cesium fluoride, chlorination
Caesium, cesium bromide or cesium iodide；The molar content of described additive accounts for the aromatic of double carboxylic acid groups or double carboxylic metallic salt
The 100%～1000% of the aromatic content of base.
6. synthetic method according to claim 1 it is characterised in that: described noble gases be nitrogen or argon；Described
Heater meanses are oil bath heating or microwave heating, and heating-up temperature is 80 DEG C～200 DEG C；The time of described reaction be 5 minutes～
72 hours.
7. synthetic method according to claim 1 it is characterised in that: described purification is by soxhlet type method, post layer
Analysis method or gel chromatography method are purified.
8. synthetic method according to claim 1 it is characterised in that: the number-average molecular weight of described conjugated polymer be 3000
～1000000；And polydispersity coefficient is 1.1～7.9.
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| 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 |
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| 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 |
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