CN100341906C - Polyethylene acetylene, its production and use thereof - Google Patents
Polyethylene acetylene, its production and use thereof Download PDFInfo
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- CN100341906C CN100341906C CNB2004100098646A CN200410009864A CN100341906C CN 100341906 C CN100341906 C CN 100341906C CN B2004100098646 A CNB2004100098646 A CN B2004100098646A CN 200410009864 A CN200410009864 A CN 200410009864A CN 100341906 C CN100341906 C CN 100341906C
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- phenylene vinylene
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Abstract
The present invention relates to a poly-phenylene vinylene material substituted by sulfenyl, and the sulfenyl is connected with benzene rings of poly-phenylene vinylene. The polymer of the present invention has good photoelectric conversion functions and can be widely applied to polymer solar batteries and polymer light emitting diodes The poly-phenylene vinylene is mixed with C60 and a derivative thereof or other substances used as electron acceptors; the mixture is coated on electric conducting glass to prepare a layer of semitransparent thin film; metal electrodes are prepared on the polymer in a vacuum evaporation plating mode and can be applied to the polymer solar batteries, or the poly-phenylene vinylene is coated on the electric conducting glass to prepare single-layer or multi-layer polymer light emitting diode devices.
Description
Technical field
The present invention relates to a kind of p-phenylene vinylene's material, relate in particular to the poly (p phenylene vinylene) derivatives material that replaces by sulfenyl on a kind of phenyl ring.
The invention still further relates to the application of above-mentioned materials in polymer solar battery and polymer LED.
Background technology
P-phenylene vinylene (PPV) and derivative thereof are the crucial conjugate polymer materials of a class, and it has obtained extensive studies in the application aspect polymer LED and the polymer solar battery in recent years.Aspect material preparation, people are in order to improve the solvability of polymkeric substance to the purpose of PPV research on the one hand, are absorption and the glow color that changes polymkeric substance on the other hand.For example, not having substituent p-phenylene vinylene is a kind of yellowish green, insoluble, infusible solid, and on phenyl ring, introduce alkoxyl group, making poly-[2-methoxyl group-5-(2-ethyl hexyl oxy) is to phenylacetylene] (MEH-PPV) not only makes the solvability of this polymkeric substance improve greatly, dissolve in multiple solvents such as chloroform, toluene, tetrahydrofuran (THF), but also can cause that glow color is moving to red shift.
The synthetic method that is used for PPV class material now has a variety of, and what wherein obtain widespread use mainly contains Wessling precursor process [Batten, J.H.; Duran, R.S.; Macromolecules; 1998,31 (9): 3148-3150], Gilch method [Brink-Spalink, F.; Greiner, A.; Macromolecules; 2002,35 (9): 3315-3317] and Heck method [Pasco, S.T.; Lahti, P.M.; Karasz, F.E.; Macromolecules; 1999,32 (21); 6933-6937] etc.Wherein, although more by the PPV defective of Wessling precursor process preparation, because it can prepare insoluble PPV analog derivative, so this method has still obtained using widely.The Gilch method can prepare high purity, high molecular, and the PPV of low defective, but this polymerization process is not suitable for preparing the PPV derivative of complicated functional group.The PPV of Heck method preparation has regular structure, higher molecular weight, and be fit to the polymkeric substance that preparation has complicated functional group.
For the requirement to material of the opto-electronic device that satisfies difference in functionality, people have prepared the derivative of a variety of PPV by different modifying method, and these have their different separately characteristics through the PPV after modifying.For example, the PPV adopting on the phenyl ring after big steric group replaces can be used as green light material and is applied in the polymer LED; Adopting the PPV after different alkoxyl groups replaces to can be used as the active coating of polymkeric substance photovoltaic cell on the phenyl ring, and can be applied to polymer LED as orange red smooth luminescent material.
Summary of the invention
The purpose of this invention is to provide the poly (p phenylene vinylene) derivatives material that replaces by sulfenyl on a kind of phenyl ring.
Another purpose of the present invention provides the application of above-mentioned materials aspect photoelectric device.
For achieving the above object, sulfenyl provided by the invention replace p-phenylene vinylene's material respectively suc as formula 1, formula 2 and formula 3:
Formula 1. poly-(2-sulfenyl-to phenylacetylene);
Formula 3. poly-(2-sulfenyl-5-sulfenyl-to phenylacetylene);
R in the formula
1, R
2Representation hydrocarbyl or aromatic hydrocarbons.
The present invention is a working medium with above-mentioned polymkeric substance, is applied in polymer solar battery and the polymer LED, and the preparation method is as follows:
The preparation of polymer solar battery:
With above-mentioned polymkeric substance and proper C
60And derivative or other the material mixing that can be used as electron acceptor(EA), add the proper amount of solvent dissolving, prepare the translucent film of one deck by spin coating or other modes on the ITO conductive glass, the mode by vacuum evaporation prepares metal electrode on polymkeric substance then.
The preparation of polymer LED:
Above-mentioned polymkeric substance as luminescent layer, is prepared into film by spin coating or other modes.Can be prepared into the polymer LED device of single or multiple lift according to different needs.
Description of drawings
Fig. 1 is absorption spectrum (solid line) and the fluorescence emission spectrum (dotted line) of polymkeric substance of the present invention in chloroform.
Fig. 2 is the electroluminescent spectrum of the polymer LED for preparing of the present invention.
Fig. 3 is the current-voltage-brightness curve of the polymer LED for preparing of the present invention.
Embodiment
Below enumerate three kinds of concrete polymkeric substance and the application examples on photoelectric device thereof the present invention is specified, and should not regard limitation of the invention as.
Simultaneously in order to be well understood to feature of the present invention and effect more; when describing its structure and using; the poly (p phenylene vinylene) derivatives preparation methods that is replaced by sulfenyl on the phenyl ring that is provided is also made a presentation; but this preparation method is not the emphasis that the present invention protected just with helping understand the present invention.
Below be respectively the example of polymkeric substance shown in formula 1, formula 2 and the formula 3, its structure is as follows:
What it was corresponding respectively is:
Formula 1: poly-(the hot sulfenyl of 2--to phenylacetylene) abbreviation OS-PPV
Formula 2: poly-[2-methoxyl group-5-(the own sulfenyl of 2-ethyl)-to phenylacetylene] abbreviation MOEHS-PPV
Formula 3: poly-(2,5-two hot sulfenyls-to phenylacetylene) abbreviation BOS-PPV
Fig. 1 is absorption spectrum (solid line) and the fluorescence emission spectrum (dotted line) of polymkeric substance of the present invention in chloroform.
As working medium, the method for preparing polymer solar battery is with the poly (p phenylene vinylene) derivatives material in the present invention: with above-mentioned polymkeric substance and proper C
60And derivative or other the material mixing that can be used as electron acceptor(EA), add the proper amount of solvent dissolving, spin coating or other modes by routine are prepared the translucent film of one deck on the ITO conductive glass, the mode by vacuum evaporation prepares metal electrode on polymkeric substance then.
The method that is used to prepare polymer LED is: as luminescent layer, spin coating or other modes by routine are prepared into film with the poly (p phenylene vinylene) derivatives material.Can be prepared into the polymer LED device of single or multiple lift according to different needs.
Embodiment 1: the preparation of polymer solar battery
The OS-PPV of 5mg and the C of 10mg
60Mix, add the dissolving of 0.25ml orthodichlorobenzene, preparing the thick film of the about 40nm of one deck by the spin coating mode on the conductive glass of PEDOT:PSS modified, the mode by vacuum evaporation prepares metal electrode with aluminium on polymkeric substance then.Its device performance shows as:
Short-circuit current=1.038mA/cm
2Open circuit voltage=0.45V; Packing factor=42%;
Simulated solar irradiation (A.M.1.5,80mW/cm
2) under effciency of energy transfer=0.25%
Embodiment 2: the preparation of polymer LED
The OS-PPV of 5mg is dissolved in the toluene of 0.5ml, becomes film by being spin-coated on the ito glass surface preparation, and the mode by vacuum evaporation prepares metal electrode with aluminium on polymkeric substance then.Be prepared into the single polymer layer LED device.Its electroluminescent spectrum and current-voltage-brightness curve are as shown in Figures 2 and 3.
Embodiment 3: substitute OS-PPV as working medium with MOEHS-PPV, all the other conditions are with embodiment 1 and embodiment 2.
Embodiment 4: substitute OS-PPV as working medium with BOS-PPV, all the other conditions are with embodiment 1 and embodiment 2.
P-phenylene vinylene's material provided by the invention has good workability, and has light transfer characteristic preferably through the preliminary proof of attempting, and as the working medium of polymer solar battery and polymer LED wide application prospect is arranged.
Poly (p phenylene vinylene) derivatives material preparation method provided by the invention is to adopt Heck link coupled method with 2,5 the bromostyrene direct polymerization are formed by-oxyl or sulfenyl replacement.
Specifically, the preparation methods key step is among the present invention:
3-sulfenyl-4-bromo-vinylbenzene 1mmol adds palladium diacetate 0.02mmol, three (o-methyl-phenyl-) phosphine 0.08mmol, and DMF 10ml mixes, and under nitrogen protection, is warming up to 80～100 ℃, reacts 48～72 hours.Cooling, in the solution of reaction solution impouring methyl alcohol and concentrated hydrochloric acid, washing is filtered, and solid product is used methyl alcohol successively in apparatus,Soxhlet's, and hexane wash washes residue with chloroform then.The chloroform evaporate to dryness is obtained polymer poly (2-sulfenyl-to phenylacetylene).
Substitute 3-sulfenyl-4-bromo-vinylbenzene in the above-mentioned reaction with equimolar 2--oxyl-4-bromo-5-sulfenyl-vinylbenzene or 2-sulfenyl-5-sulfenyl-4-bromo-vinylbenzene respectively, just can make poly-(2--oxyl-5-sulfenyl-to phenylacetylene) and gather (2-sulfenyl-5-sulfenyl-to phenylacetylene) by same method.
The preparation route of these three kinds of polymer monomers is as shown below:
In the above-mentioned reaction scheme, step 1 to step 5 is precursors of preparation OS-PPV; Step 6 to step 14 is precursors of preparation MOEHS-PPV; Step 15 to step 18 is precursors of preparation BOS-PPV.
Embodiment 5: the preparation of poly-(the hot sulfenyl of 2--to phenylacetylene):
1) paradibromobenzene joins in the chlorsulfonic acid of 4～6 times of molar weights, room temperature reaction 6～8 hours.In product impouring frozen water, obtain white solid 2,5-dibromobenzene SULPHURYL CHLORIDE is directly used in next step reaction.
2) in the sulfuric acid (6mol/L) of zinc powder with 1mol in 0 ℃ of low suspension in 1.2mol, stirred about 10 minutes, with 2 of 0.2mol, 5-dibromobenzene SULPHURYL CHLORIDE slowly adds, and reacts 2 hours down at 0 ℃, be warming up to backflow, after reacting 6 hours again, wet distillation, extraction, decompression distillation obtains 2,5-dibromobenzene thiophenol.
3) 2,5-dibromobenzene thiophenol, n-octane bromide, salt of wormwood mix with equimolar amount, add an amount of N, dinethylformamide (DMF) (every mole of salt of wormwood needs 500ml) is warming up to backflow, reacts after 6 hours, extraction, underpressure distillation obtains 2, the hot thioether of 5-dibromo phenyl.
4) with 2, the hot thioether 0.1～0.2mol of 5-dibromo phenyl is dissolved in 50ml THF, nitrogen protection.Under-70 ℃, add equimolar butyllithium, react after 1～2 hour, add the DMF of equimolar amount, room temperature reaction 1～3 hour, extraction, underpressure distillation obtain the hot sulfenyl of 3--4-bromo-phenyl aldehyde.
5) the bromination three phenyl methyl phosphonium salts of 0.1mol are suspended in the 200ml tetrahydrofuran (THF), add equimolar butyllithium, nitrogen protection.React the hot sulfenyl of the 3-that adds equimolar amount after 1 hour-4-bromo-phenyl aldehyde, back flow reaction extracted after 4 hours, and column chromatography for separation obtains the hot sulfenyl of 3--4-bromo-vinylbenzene.
6) the hot sulfenyl of 3--4-bromo-vinylbenzene 1mmol, palladium diacetate 0.02mmol, three (o-methyl-phenyl-) phosphine 0.08mmol, DMF 10ml mixes, and under nitrogen protection, is warming up to 80～100 ℃, reacts 48～72 hours.Cooling, in the solution of reaction solution impouring 100ml methyl alcohol and 10ml concentrated hydrochloric acid, washing is filtered, and solid product is used methyl alcohol successively in apparatus,Soxhlet's, and hexane wash washes residue with chloroform then.The chloroform evaporate to dryness is obtained polymkeric substance OS-PPV.
Embodiment 6: the preparation of poly-[2-methoxyl group-5-(the own sulfenyl of 2-ethyl)-to phenylacetylene]
1) during the 1mol paradibromobenzene suspends the equimolar vitriol oil,, slowly is warming up to 70 ℃, reacts after 2 hours, in the reaction mixture impouring frozen water, isolate two bromo nitrobenzenes to wherein adding equimolar nitrosonitric acid.
2) iron powder with 0.5mol is suspended in the hydrochloric acid
3) the paradibromobenzene amine with 0.1mol is dissolved in the equimolar sulfuric acid (6mol/L), adds Sodium Nitrite to reaction solution and can make starch potassium iodide paper become blue.This drips of solution is added in the ebullient 200ml sulfuric acid (6mol/L), wet distillation, extraction obtains 2, the 5-dibromophenol.
4) 2,5-dibromophenol, methyl iodide, salt of wormwood mix with equimolar amount, add DMF (every mole of salt of wormwood needs 500ml), are warming up to backflow, react after 6 hours, and extraction, underpressure distillation obtains 2,5-dibromobenzene methyl ether.
5) 2,5-dibromobenzene methyl ether joins in the chlorsulfonic acid of 4～6 times of molar weights, room temperature reaction 6～8 hours.In product impouring frozen water, obtain white waxy solid 2,5-two bromo-4-methoxyl group-benzene sulfonyl chlorides are directly used in next step reaction.
6) in the sulfuric acid (6mol/L) of zinc powder with 1mol in 0 ℃ of low suspension in 1.2mol, stirred about 10 minutes, with 2 of 0.2mol, 5-dibromobenzene SULPHURYL CHLORIDE slowly adds, and reacts 2 hours down at 0 ℃, be warming up to backflow, after reacting 6 hours again, wet distillation, extraction, decompression distillation obtains 2,5-two bromo-4-methoxyl group-thiophenols.
7) 2,5-two bromo-4-methoxyl group-thiophenols, bromo-iso-octane, salt of wormwood mix with equimolar amount, add every mole of salt of wormwood of DMF and need 500ml), be warming up to backflow, react after 6 hours, extraction, underpressure distillation obtains 2,5-two bromo-4-methoxyl groups-iso-octyl phenyl thioether.
8) with 2,5-two bromo-4-methoxyl groups-iso-octyl phenyl thioether 0.1～0.2mol is dissolved in 50ml THF, nitrogen protection.Under-70 ℃, add equimolar butyllithium, react after 1～2 hour, add the DMF of equimolar amount, room temperature reaction 1～3 hour, extraction, column chromatography for separation obtains the hot sulfenyl-phenyl aldehyde of 2-methoxyl group-4-bromo-5-.
9) with the hot sulfenyl of the 3--4-bromo-vinylbenzene in the hot sulfenyl of 2-methoxyl group-4-bromo-5--phenyl aldehyde replacement embodiment 2 steps 6, all the other prepare MOEHS-PPV with the step 6 of embodiment 5.
Embodiment 7: poly-(2,5-two hot sulfenyls-to phenylacetylene)
1) the bromination three phenyl methyl phosphonium salts of 0.1mol are suspended in the 200ml tetrahydrofuran (THF), add equimolar butyllithium, nitrogen protection.React the hot sulfenyl-phenyl aldehyde of the 2-methoxyl group-4-bromo-5-that adds equimolar amount after 1 hour, back flow reaction extracted after 4 hours, and column chromatography for separation obtains the hot sulfenyl-vinylbenzene of 2-methoxyl group-4-bromo-5-.
2) paradiiodobenzene 0.1mol is dissolved in the 50ml tetracol phenixin, adds the liquid bromine of two times of molar weights, and room temperature reaction is not emitted to there being bromize hydrogen gas.Extraction obtains 1 with the tetracol phenixin recrystallization, 4-two iodo-2,5-dibromobenzene.
3) 1,4-two iodo-2, add 50ml quinoline, 10ml pyridine, back flow reaction 4～6 hours at cuprous mixing of hot sulfenyl of 5-dibromobenzene 0.1mol and two times of molar weights.The hydrochloric acid 200ml washed product of 6mol/L, extraction, column chromatography for separation obtain 1,4-two hot sulfenyls-2,5-diiodo-benzene.
4) 1,4-two hot sulfenyls-2,5-diiodo-benzene 0.1～0.2mol is dissolved in 50ml THF, nitrogen protection.Under-70 ℃, add equimolar butyllithium, react after 1～2 hour, add the DMF of equimolar amount, room temperature reaction 1～3 hour, extraction separates obtaining 2,5-two hot sulfenyl-4-bromo-phenyl aldehydes.
5) the bromination three phenyl methyl phosphonium salts of 0.1mol are suspended in the 200ml tetrahydrofuran (THF), add equimolar butyllithium, nitrogen protection.React after 1 hour and to add 2 of equimolar amount, 5-two hot sulfenyl-4-bromo-phenyl aldehydes, back flow reaction is after 4 hours, extraction, column chromatography for separation obtains 2,5-two hot sulfenyl-4-bromo-vinylbenzene.
6) with 2,5-two hot sulfenyls-4-bromo-vinylbenzene replaces the hot sulfenyl of the 3--4-bromo-vinylbenzene in embodiment 5 steps 6, and all the other prepare BOS-PPV with the step 6 of embodiment 5.
Claims (4)
1. p-phenylene vinylene's material is the poly (p phenylene vinylene) derivatives material that is replaced by sulfenyl on phenyl ring, and its structure is as follows:
Formula 1 formula 2 formulas 3
R in the formula
1, R
2Represent alkyl.
2. the application of p-phenylene vinylene's material in polymer solar battery of claim 1 is mixed and made into solution with p-phenylene vinylene's material and electron-acceptor material, is coated in and prepares film on the conductive glass, prepares metal electrode on film;
Described electron acceptor(EA) is C
60And derivative, organism electron acceptor(EA), and inorganicly receive brilliant acceptor.
3. the application of p-phenylene vinylene's material in polymer LED of claim 1 made solution with the p-phenylene vinylene, is coated in conductive glass surface and is prepared into film, prepares metal electrode on film, is prepared into the single polymer layer LED device.
4. the application of claim 3 is characterized in that, is prepared into the multiple layer polymer LED device.
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| CNB2004100098646A CN100341906C (en) | 2004-11-25 | 2004-11-25 | Polyethylene acetylene, its production and use thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2004100098646A CN100341906C (en) | 2004-11-25 | 2004-11-25 | Polyethylene acetylene, its production and use thereof |
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| CN1778825A CN1778825A (en) | 2006-05-31 |
| CN100341906C true CN100341906C (en) | 2007-10-10 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1213672A (en) * | 1997-10-06 | 1999-04-14 | 中国人民解放军国防科工委后勤部军事医学研究所 | Synthetizing of poly-p-phenylacetylene |
| US6403238B1 (en) * | 1998-07-10 | 2002-06-11 | Hoerhold Hans-Heinrich | Organic light-emitting diodes (OLED) including poly[2-methoxy-5-(2′-ethyl-hexyloxy)-1,4-phenylene-1,2-ethenylene-2,5-dimethoxy-1,4-phenylene-1,2-ethenylene] as electroluminescent material |
| CN1389488A (en) * | 2002-06-20 | 2003-01-08 | 华南理工大学 | Polymer containing heterocyclic Se compound and its application in preparing luminous material |
| CN1454961A (en) * | 2003-05-15 | 2003-11-12 | 中国科学院长春应用化学研究所 | Transmission type polymer electroluminescent material and preparing method thereof |
-
2004
- 2004-11-25 CN CNB2004100098646A patent/CN100341906C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1213672A (en) * | 1997-10-06 | 1999-04-14 | 中国人民解放军国防科工委后勤部军事医学研究所 | Synthetizing of poly-p-phenylacetylene |
| US6403238B1 (en) * | 1998-07-10 | 2002-06-11 | Hoerhold Hans-Heinrich | Organic light-emitting diodes (OLED) including poly[2-methoxy-5-(2′-ethyl-hexyloxy)-1,4-phenylene-1,2-ethenylene-2,5-dimethoxy-1,4-phenylene-1,2-ethenylene] as electroluminescent material |
| CN1389488A (en) * | 2002-06-20 | 2003-01-08 | 华南理工大学 | Polymer containing heterocyclic Se compound and its application in preparing luminous material |
| CN1454961A (en) * | 2003-05-15 | 2003-11-12 | 中国科学院长春应用化学研究所 | Transmission type polymer electroluminescent material and preparing method thereof |
Non-Patent Citations (4)
| Title |
|---|
| PPV材料的合成研究进展 陈正勇，刘俊峰，鲁皓，化工新型材料，第32卷第5期 2004 * |
| PPV衍生物的研究进展及应用前景 余淑娴，杨廷达，江西科学，第22卷第1期 2004 * |
| 含PPV结构的电致发光材料 李会学，萧泰，西北师范大学学报(自然科学版)，第39卷第03期 2003 * |
| 富勒烯C_(60)掺杂的共轭高聚物混合薄膜的光谱性质 刘秀，王文军，蔡志岗，姜永强，王恭明，光谱学与光谱分析，第22卷第4期 2002 * |
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