CN103936760B - 噻吩并[2,3-f]苯并呋喃化合物及其聚合物和聚合物的应用 - Google Patents

噻吩并[2,3-f]苯并呋喃化合物及其聚合物和聚合物的应用 Download PDF

Info

Publication number
CN103936760B
CN103936760B CN201410171994.3A CN201410171994A CN103936760B CN 103936760 B CN103936760 B CN 103936760B CN 201410171994 A CN201410171994 A CN 201410171994A CN 103936760 B CN103936760 B CN 103936760B
Authority
CN
China
Prior art keywords
polymer
thieno
polymkeric substance
benzofuran compound
compound
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.)
Expired - Fee Related
Application number
CN201410171994.3A
Other languages
English (en)
Other versions
CN103936760A (zh
Inventor
邹应萍
樊令
郭秀萍
崔锐利
蒋历辉
江文辉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Central South University
Original Assignee
Central South University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Central South University filed Critical Central South University
Priority to CN201410171994.3A priority Critical patent/CN103936760B/zh
Publication of CN103936760A publication Critical patent/CN103936760A/zh
Application granted granted Critical
Publication of CN103936760B publication Critical patent/CN103936760B/zh
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/125—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one oxygen atom in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
    • C08G2261/3241—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more nitrogen atoms as the only heteroatom, e.g. carbazole
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
    • C08G2261/3242—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more oxygen atoms as the only heteroatom, e.g. benzofuran
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
    • C08G2261/3243—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
    • C08G2261/3245—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing nitrogen and oxygen as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
    • C08G2261/3246—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing nitrogen and sulfur as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/90—Applications
    • C08G2261/91—Photovoltaic applications
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

本发明公开了噻吩并[2,3-f]苯并呋喃化合物及其聚合物和聚合物的应用，该噻吩并[2,3-f]苯并呋喃化合物与苯并噻二唑、苯并三氮唑和苯并噁二唑等单体通过Stille偶联聚合方法合成了一系列具有噻吩并[2,3-f]苯并呋喃化合物单元结构的聚合物，该聚合物热稳定性和电化学性能好，可以和常用的富勒烯及有机受体物质混合制备出高光电转换率的聚合物太阳能电池，单层聚合物太阳电池器件光电转换效率高达6.4％，该聚合物材料在太阳电池的应用上有巨大的商业前景。

Description

噻吩并[2,3-f]苯并呋喃化合物及其聚合物和聚合物的应用
技术领域
本发明涉及噻吩并[2,3-f]苯并呋喃化合物及其聚合物和聚合物的应用，属于有机光电材料合成领域。
背景技术
近年来，含有作为给体的苯并[1,2-b；3,4-b]二噻吩(BDT)基的共轭聚合物显示出了优良的光伏性能。杨阳，吴宏斌，侯剑辉等人合成了一系列基于BDT的共轭聚合物，这些聚合物具有非常好的光电性质，报道的叠层器件太阳能电池的最高电转换效率(PCE)为10.6％，但基于BDT材料稳定性能略有欠缺，且叠层器件层数较多，工艺较为复杂。[(1)Z.He,C.Zhong,S.Su,M.Xu,H.Wu,Y.Cao,NaturePhotonics2012,6,591；(2)L.Dou,J.You,J.Yang,C.-C.Chen,Y.He,S.Murase,T.Moriarty,K.Emery,G.Li,Y.Yang,NaturePhotonics2012,6,180]
苯并[1,2-b；3,4-b]二呋喃(BDF)是一个重要的电子给体单元，但是将其作为给体单元与其他稠杂环受体单元聚合后应用于有机电子领域报道不多。[(1)OriGidron,AfshinDadvand,YanaSheynin,MichaelBendikov,DmitriiF.Perepichka.ChemicalCommunications,2011,47,1976-1978.(2)LijunHuo,YeHuang,BenhuFan,XiaGuo,YanJing,MaojieZhang,YongfangLi,JianhuiHou.ChemicalCommunications,2012,48,3318-3320.]
1,2,3-苯并噻二唑,1,2,3-苯并三氮唑，1,2,3-苯并噁二唑是三种常见的重要的电子受体单元，它们的二维结构聚合物近年来在电致变色、聚合物太阳能电池、聚合物发光二极管等方面得到了广泛的研究[BlouinN；MichaudA；LeclercM；etal.Alow-bandgappoly(2，7-carbazole)derivativeforuseinhigh-performancesolarcells.AdvancedMaterials.2007,19,(17),2295-2300.]。
发明内容
本发明的目的是在于提供一种具有新型结构的噻吩并[2,3-f]苯并呋喃化合物，该噻吩并[2,3-f]苯并呋喃化合物可进一步合成热稳定性和电化学性能好，适用于制备高光电转化率太阳能电池的聚合物光伏材料。
本发明的另一个目的是在于提供一种热稳定性和电化学性能好的具有噻吩并[2,3-f]苯并呋喃化合物单元结构的聚合物，该聚合物能用于制备高光电转化率的聚合物太阳能电池。
本发明的第三个目的是在于提供具有噻吩并[2,3-f]苯并呋喃化合物单元结构的聚合物在制备具有高光电转化率的聚合物太阳能电池方面的应用。
本发明提供了噻吩并[2,3-f]苯并呋喃化合物，该噻吩并[2,3-f]苯并呋喃化合物具有式1所示结构：
本发明还提供了具有所述噻吩并[2,3-f]苯并呋喃化合物单元结构的聚合物，该噻吩并[2,3-f]苯并呋喃化合物单元结构的聚合物具有式2、式3、式4或式5所示结构：
其中，n为10～25。
本发明还提供了所述具有噻吩并[2,3-f]苯并呋喃化合物单元结构的聚合物的应用，该应用是将具有噻吩并[2,3-f]苯并呋喃化合物单元结构的聚合物作为光伏层的给体材料应用于制备聚合物太阳能电池。
所述的应用是将所述的具有噻吩并[2,3-f]苯并呋喃化合物单元结构的聚合物与电子受体物质混合后，溶于溶剂，再涂覆在导电玻璃上制成聚合物薄膜，进一步在薄膜上制备金属电极，即制得聚合物太阳能电池器件。
所述电子受体物质为富勒烯C60或含C60基团的化合物、富勒烯C70或含C70基团的化合物，或有机电子受体化合物。
所述的溶剂为邻二氯苯、三氯甲烷、四氢呋喃中一种或几种。
本发明的噻吩并[2,3-f]苯并呋喃化合物合成路线如下：
其中，
反应条件：a为：亚硫酰氯，70℃；b为：二乙胺，二氯甲烷；c为：四氢呋喃，正丁基锂，3-噻吩甲醛；d为：四氢呋喃，正丁基锂，2-异辛基噻吩，二水合氯化亚锡，-78℃。
本发明的具有噻吩并[2,3-f]苯并呋喃化合物单元结构的聚合物由噻吩并[2,3-f]苯并呋喃化合物与其它单体通过Stille偶联反应制备得到，合成路线如下：
其中，
反应条件：e为：四氢呋喃，正丁基锂，三甲基氯化锡，-78℃；f为：甲苯,DMF，四(三苯基膦)钯，110℃。
本发明的有益效果：本发明首次合成出具有新型结构的噻吩并[2,3-f]苯并呋喃化合物(TBF)单体，并进一步将TBF单体与苯并噻二唑、苯并三氮唑和苯并噁二唑等单体采用Stille偶联聚合方法合成了一系列具有噻吩并[2,3-f]苯并呋喃化合物单元结构的聚合物，该聚合物热稳定性和化学稳定性好，可以和常用的富勒烯及有机受体物质等混合制备出高光电转换率的聚合物太阳能电池，单层聚合物太阳电池器件光电转换效率高达6.4％。本发明的聚合物材料在TBF的4,8位引入烷基噻吩，一方面有效改善聚合物的溶解性，有利于聚合物的分散、涂覆；另一方面在支链上添加噻吩类的助色团，使TBF的吸收光谱红移，提高吸收系数，从而吸收更多的光子，有利于提高其能量转换效率。综上所述，本发明首次合成的一系列具有噻吩并[2,3-f]苯并呋喃化合物单元结构的聚合物材料具有良好的可加工性，并将其用于制备聚合物太阳能电池上，经过实验证明具有较好的光电转换特性，这类材料具有好的热稳定性，优越的吸光特性，良好的电化学性能，在太阳电池的应用上有巨大的商业前景。
附图说明
【图1】为本发明实施例1制得的PTBFDTBT聚合物材料的热失重分析图。
【图2】为本发明实施例1制得的PTBFDTBT聚合物材料的紫外-可见光吸收光谱图。
【图3】为本发明实施例1制得的PTBFDTBT聚合物材料的电化学分析图。
【图4】为本发明实施例1制得的PTBFDTBT聚合物材料的空穴迁移率图：a为PTBFDTBT的晶体管转移曲线，b为PTBFDTBT基晶体管的饱和曲线。
【图5】为本发明实施例1制得的PTBFDTBT聚合物材料的光伏性能测试图。
【图6】为本发明实施例1制得的PTBFDTBT聚合物材料的外量子转换效率。
【图7】为本发明实施例1制得的PTBFDTBT聚合物与PCBM共混膜活性层的形貌图：a为高度图，b为相图。
【图8】为本发明实施例2和例3制得的PTBFDTBTz和PTBFDTBO聚合物材料的热失重分析图。
【图9】为本发明实施例2和例3制得的PTBFDTBTz和PTBFDTBO聚合物材料的紫外-可见光吸收光谱图。
【图10】为本发明实施例2和例3制得的PTBFDTBTz和PTBFDTBO聚合物材料的电化学分析图。
【图11】为本发明实施例2和例3制得的PTBFDTBTz和PTBFDTBO光伏性能测试图；a为PTBFTBTz的光电转换效率图，b为PTBFDTBO的光电转换效率图。
【图12】为本发明实施例2制得的PTBFDTBTz聚合物与PCBM共混膜活性层的形貌图；a为高度图，b为相图。
【图13】为本发明实施例3制得的PTBFDTBO聚合物与PCBM共混膜活性层的形貌图；a为高度图，b为相图。
【图14】为本发明实施例4制得的PTBFFBT聚合物材料的热失重分析图。
【图15】为本发明实施例4制得的PTBFFBT聚合物材料的紫外-可见光吸收光谱图。
【图16】为本发明实施例4制得的PTBFFBT聚合物材料的电化学分析图。
【图17】为本发明实施例4制得的PTBFFBT聚合物材料的空穴迁移率图。
【图18】为本发明实施例4制得的PTBFFBT光伏性能测试图。
【图19】为本发明实施例4制得的PTBFFBT的外量子转换效率。
【图20】为本发明实施例4制得的PTBFFBT与PCBM(1:1.5)共混膜活性层的形貌图；a、b分别为PTBFFBT与PC61BM共混膜活性层的高度图和相图；c、d分别为PTBFFBT与PC61BM共混膜活性层(经甲醇处理)的高度图和相图；e、f分别为PTBFFBT与PC71BM共混膜活性层(经3％DIOand甲醇处理)的高度图和相图。
具体实施方式
以下具体实施例旨在进一步说明本发明内容，但不是限制本发明的保护范围。
以下实施例中所述实验方法，如无特殊说明，均为常规方法；所述试剂和材料，如无特殊说明，均可从商业途径获得。
实施例1
a)将亚硫酰氯(65.3mL，0.9mol)逐滴加入到呋喃-3-羧酸(25.1g，0.224mol)的500毫升干燥的圆底烧瓶中，搅拌回流反应4小时后，冷却至室温后，旋干溶剂得到无色油状物化合物1，该产物无需进一步纯化即可用于下一步骤。
b)在0℃下，将化合物1(29.24g，224mmol)滴加到二乙胺(92.6mL)的二氯甲烷(100mL)溶液中，然后将反应混合物升温至室温继续搅拌1小时。冷却至室温，将混合物倒入冰水中，二氯甲烷萃取，有机相水洗2次，无水硫酸镁干燥，旋干溶剂，粗产物过硅胶柱(乙酸乙酯/石油醚洗脱(2:1，V/V)为淋洗液)，得到橙红色油状物化合物2(7.5g，85％)。1HNMR(CDCl3,400MHz)δ7.70(dd,J＝0.9,1.5Hz,1H),7.41(dd,J＝1.5,1.8Hz,1H),6.59(dd,J＝0.9,1.8Hz,1H),3.48(q,J＝7.1Hz,4H),1.21(t,J＝7.1Hz,6H).
c)氮气保护下，将化合物2(8.36g，50mmol)放置在250mL干燥的圆底三口烧瓶中，用注射器加入无水四氢呋喃200mL，冷却至-78℃，缓慢滴加正丁基锂(21.87mL,52.5mmol)，继续搅拌15分钟，在15分钟内滴加噻吩-3-甲醛(5.88g，52.5mmol)的THF(75mL)溶液，冷却至-78℃下搅拌2小时。再次滴加(21.87mL，52.5mmol)n-LiBu完毕后，升至室温搅拌过夜反应。停止反应后将反应液倒入200mL水中。用二氯甲烷萃取，合并的有机相用硫酸镁干燥，旋干溶剂，粗产物过硅胶柱(为淋洗液,二氯甲烷：石油醚＝1：2)，最后用乙醇重结晶得到黄色固体，化合物3(4.7g,46％)。1HNMR(400MHz,CDCl3)δ7.74(d,J＝1.8Hz,1H),7.71(d,J＝5.0Hz,1H),7.65(d,J＝5.0Hz,1H),6.97(d,J＝1.8Hz,1H).
d)N2保护下，将化合物3(1.632g,8mmol)的5mLTHF溶液加入到2-异辛基噻吩(3.92g,20mmol)中。0℃下逐滴加入9mLn-LiBu,完毕后，升至50℃回流搅拌1.5h，冷却至室温，将10％稀盐酸(25.6mL)的SnCl2-2H2O(14.5g,64mmol)加入反应物中，继续反应1.5h。停止反应后将混合物倒入水中，二氯甲烷萃取，有机相水洗2次，无水硫酸镁干燥，旋干溶剂，粗产物过硅胶柱(石油醚为淋洗液)，得淡黄色液体4(1.85g,41％)，即噻吩并[2,3-f]苯并呋喃化合物。1HNMR(400MHz,CDCl3)δ7.92(d,J＝5.7Hz,1H),7.78(d,J＝2.3Hz,1H),7.51(t,J＝5.3Hz,1H),7.49–7.44(m,2H),7.22(d,J＝2.3Hz,1H),6.92(dd,J＝7.7,4.7Hz,2H),2.93–2.84(m,4H),1.71(dd,J＝11.9,5.9Hz,2H),1.53–1.27(m,16H),1.04–0.87(m,12H).
e)将化合物4(1.126g,2mmol)放置在100mL的圆底三口烧瓶中，氮气保护下，用注射器加入无水四氢呋喃50mL，冷却至-78℃，再缓慢滴加n-LiBu(3mL,7mmol)，然后继续搅拌1个小时，移至室温锂化1小时，再冷却至-78℃下，一次性加入三甲基氯化锡(8mL,8mmol)，完毕后，室温反应过夜。反应混合物倒入冰水中，乙醚萃取，有机相水洗2次，无水硫酸镁干燥，旋干溶剂，粗产物为黄色油状液体，低温冷冻后，粗产物变为黄色固体，用异丙醇60℃重结晶得到淡黄色针状晶体M1(1.4g,产率80％)。1HNMR(400MHz,CDCl3):δ:7.99(d,J＝15.2Hz,1H),7.55-7.50(m,1H),7.48(t,J＝3.6Hz,1H),7.35-7.30(m,1H),6.92(dt,J＝16.3,8.2Hz,2H),2.90(dd,J＝11.0,6.7Hz,4H),1.72(dd,J＝12.0,6.0Hz,2H),1.55-1.21(m,16H),1.07-0.85(m,12H),0.57-0.35(m,18H).
f)采用Stille反应制备聚合物(PTBFDTBT)：氮气保护下，将M1(0.1550g,0.174mmol)和5,6-二辛氧基-4,7-二噻吩基-苯并噻二唑二溴(0.1246g,0.174mmol)加入到10mL无水甲苯与2mLN,N-二甲基甲酰胺(DMF)中，再加入Pd(PPh3)4(10mg)，110℃下搅拌反应24小时后，冷却至室温，倒入100mL甲醇中沉析，过滤，于索氏提取器中依次用甲醇、正己烷、氯仿抽提，回收氯仿溶液，旋干多余溶剂，再加入少量氯仿使之溶解后倒入离心管中，加入甲醇使之层析出来，高速离心后倒掉上层清夜，反复几次，得到目标聚合物PTBFDTBT(158mg,81％yield).GPC(THF):Mn＝42.7kDa；Mw＝141.9kDa；PDI＝3.31.Anal.Calcdfor(C64H78N2O3S6)n(％):C,69.19；H,7.39；N,2.44；O,4.19；S,16.79.Found(％):C,64.62；H,7.51；N,2.65；O,4.19；S,16.79.
实施例2
噻吩并[2,3-f]苯并呋喃化合物的合成方法如实施例1。
采用Stille反应制备聚合物(PTBFDTBTz)：氮气保护下，将M1(0.134g,0.151mmol)和N-辛基-4,7-二噻吩基-苯并三唑二溴(0.0838g,0.151g)加入到10mL无水甲苯和2毫升DMF中，再加入Pd(PPh3)4(10mg)，110℃下搅拌反应24小时后，冷却至室温，倒入100mL甲醇中沉析，过滤，于索氏提取器中依次用甲醇、正己烷、氯仿抽提，回收氯仿溶液，旋干多余溶剂，再加入少量氯仿使之溶解后倒入离心管中，加入甲醇使之层析出来，高速离心后倒掉上层清夜，反复几次，得到目标聚合物PTBFDTBTz(91mg,62％)。Mn＝2.8kDa；Mw＝21.88kDa；PDI＝7.8。Anal.Calcdfor(C58H69N3OS5)n(％):C,70.76；H,7.06；N,4.27；O,1.63；S,16.28.Found(％):C,70.71；H,7.03；N,4.29O,1.69；S,16.28..
实施例3
噻吩并[2,3-f]苯并呋喃聚合物的合成方法如实施例1。
采用Stille反应制备聚合物(PTBFDTBO)：氮气保护下，将M1(0.1359g,0.153mmol)和5,6-二辛氧基-4,7-二噻吩基-苯并噁二唑二溴(0.1068g,0.153mmol)加入到10mL无水甲苯2毫升DMF中，再加入Pd(PPh3)4(10mg)，110℃下搅拌反应24小时后，冷却至室温，倒入100mL甲醇中沉析，过滤，于索氏提取器中依次用甲醇、正己烷、氯仿抽提，回收氯仿溶液，旋干多余溶剂，再加入少量氯仿使之溶解后倒入离心管中，加入甲醇使之层析出来，高速离心后倒掉上层清夜，反复几次，得到目标聚合物PTBFDTBO(89mg,产率52％)。Mn＝524.1kDa；Mw＝1011.5kDa；PDI＝1.9。Anal.Calcdfor(C66H84N2O4S5)n(％):C,70.17；H,7.49；N,2.48；O,5.66；S,14.19.Found(％):C,70.18；H,7.43；N,2.29；O,5.66；S,14.44.
实施例4
噻吩并[2,3-f]苯并呋喃聚合物的合成方法如实施例1。
采用Stille反应制备聚合物(PTBFFBT)：氮气保护下，将M1(174.6g,0.2mmol)和4,7-二(5-溴-4-十二烷基噻吩)-5-氟苯并噻二唑(163.7mg,0.2mmol)加入到10mL无水甲苯2毫升DMF中，再加入Pd(PPh3)4(15mg,0.013mmol)，110℃下搅拌反应24小时后，冷却至室温，倒入100mL甲醇中沉析，过滤，于索氏提取器中依次用甲醇、正己烷、氯仿抽提，回收氯仿溶液，旋干多余溶剂，再加入少量氯仿使之溶解后倒入离心管中，加入甲醇使之层析出来，高速离心后倒掉上层清夜，反复几次，得到目标暗绿色固体(158mg,yield:63％).GPC(THF):Mn＝12.0kDa；Mw＝25.8kDa；PDI＝2.14.Anal.Calcdfor(C72H93N2OS6)n(％):C,72.37；H,7.84；N,2.34；O,1.34；S,16.10.Found(％):C,73.10；H,7.89；N,2.44.
实施例5
实施例1～4的聚合物的性能测试：
1、热稳定性分析：
聚合物的热学性能对于器件的制备与使用非常重要。PTBFDTBT聚合物的热失重分析结果(见图1)表明，该聚合物的5％热分解温度在318℃，这表明该聚合物具有良好的热稳定性,而且其热稳定性完全满足其在光电器件方面的应用。实施例2和例3制得的PTBFDTBTz和PTBFDTBO聚合物材料的热失重分析如图8。实施例4制得的PTBFFBT聚合物材料的热失重分析图如图14。
2、光学性能：
本发明采用紫外-可见吸收光谱法考察了PTBFDTBT的光学性能，测量其在溶液状态和薄膜状态下的光学特性，该聚合物吸收光谱如图2所示。图2可以看出该聚合物吸收光谱较宽，尤其是其膜的最大吸收峰在608nm有一个较好的吸收。同时，可以看到TBF基聚合物的能隙较低，而且吸收光谱较宽。这种能隙的降低应该归因于噻吩并[2,3-f]苯并呋喃引入D-A聚合物中，形成了电荷转移态，从而带隙降低，达到了更好的吸光效果。该化合物的薄膜吸收和该化合物的溶液吸收相比，其吸收宽度变宽，吸收位置明显红移。该在可见光区有着宽吸收的窄带隙聚合物在聚合物太阳能电池的制备中有着广阔的应用前景。实施例2和例3制得的PTBFDTBTz和PTBFDTBO聚合物材料的紫外-可见光吸收光谱图如图9。实施例4制得的PTBFFBT聚合物材料的紫外-可见光吸收光谱图如图15。
3、电化学性能：
图3为TPTBFDTBT薄膜的循环伏安图。将PTBFDTBT的三氯甲烷溶液涂在铂电极上，以Ag/AgCl为参比电极，等晾干成膜后置于六氟磷酸四丁基胺乙腈溶液中测量。从图3中得到PTBFDTBT起始氧化电位为：0.80V，可以从氧化曲线部分看出该聚合物材料有较低的HOMO能级，而没有测试出聚合物的还原部分，所以LUMO能级依照光学带隙与HOMO能级计算得到。低的HOMO能级表明这类聚合物材料有良好的空气稳定性，非常适合制备太阳能电池器件。实施例2和例3制得的PTBFDTBTz和PTBFDTBO聚合物材料的电化学分析图如图10所示。实施例4制得的PTBFFBT聚合物材料的电化学分析图如图16所示。
表1.聚TBF衍生物材料PTBFDTBT的光学与电化学结果
4、空穴迁移率：
本发明设计这种两维共轭聚合物是为了拓宽有机分子的光吸收、降低带隙、提高有机半导体材料的空穴迁移率。以十八烷基三氯硅烷(OTS)修饰的SiO2为绝缘层，高掺杂的硅为栅极，Au膜为源漏电极。制备了有机场效应晶体管(OFET)。采用顶电极式结构，在空气中测试了PTBFDTBT的空穴迁移率，迁移率示意图见附图4PTBFDTBT的空穴迁移率达到了2×10-3cm2·V-1·s-1。实施例2和例3制得的PTBFDTBTz和PTBFDTBO光伏性能测试图如图11。制得的PTBFFBT聚合物材料的空穴迁移率图如图17。
5、溶解性能：
PTBFDTBT、PTBFDTBTz、PTBFDTBO和PTBFFBT聚合物在二氯甲烷，三氯甲烷，四氢呋喃，甲苯等常用溶剂中溶解良好。
6、聚合物太阳能电池性能
以实施例1制得的聚合物材料(PTBFDTBT)制备太阳能电池器件。
器件结构为ITO/PEDOT:PSS/PTBFDTBT:PC71BM/Ca/Al。
5mg的PTBFDTBT与10mg的PC71BM混合，加入0.5mL邻二氯苯溶解，通过旋涂方式在经PEDOT:PSS修饰过的导电玻璃上制备出一层约80nm厚的薄膜，作为活性层，然后通过真空蒸镀的方式用铝在活性层上制备金属电极。其器件性能表现为：
短路电流＝13.51mA/cm2；开路电压＝0.78V；填充因子＝61％；
模拟太阳光(A.M.1.5，100mW/cm2)下的能量转换效率＝6.42％。
(a)、光伏性能(太阳能电池性能)：
从表2可知所有基于PTBFDTBT与PC71BM共混的器件中，最高的能量转化效率为6.42％，开路电压为0.78V，短路电流为13.51mA/cm2,填充因子为61％，PTBFDTBT的光伏性能如图5所示，表明该聚合物有优异的光伏性能。太阳能电池的转换效率可以通过优化器件和提高聚合物的分子量得到进一步提升。图6中可以看出聚合物具有较宽的光谱响应和EQE效率，同时也印证了聚TBF衍生物材料PTBFDTBT的高效率。实施例2和例3制得的PTBFDTBTz和PTBFDTBO光伏性能测试图如图11。实施例4制得的PTBFFBT光伏性能测试图如图18；PTBFFBT的外量子转换效率如图19。
表2.聚TBF衍生物材料PTBFDTBT的光伏性能结果
表3.聚TBF衍生物材料PTBFFBT的光伏性能结果
(b)、形貌：
光伏活性层的形貌也是获得高能量转换效率的重要因素，用原子力显微镜测试了聚合物与PCBM共混膜的形貌，如图7所示，结果表明光伏活性层具有很好的纳米级相分离，聚合物给体与PCBM受体间形成了互穿网络结构，这样有利于电荷的分离与收集，提高器件的光电流和填充因子。图12为实施例2制备的PTBFDTBTz聚合物与PCBM共混膜活性层的形貌图。图13为本发明实施例3PTBFDTBO聚合物与PCBM共混膜活性层的形貌图。图20为PTBFFBT与PCBM共混膜活性层的形貌图。

Claims (5)

1.具有噻吩并[2,3-f]苯并呋喃化合物单元结构的聚合物，其特征在于，具有式2、式3、式4或式5所示结构：所述的噻吩并[2,3-f]苯并呋喃化合物具有式1所示结构：
其中，n为10～25。
2.权利要求1所述具有噻吩并[2,3-f]苯并呋喃化合物单元结构的聚合物的应用，其特征在于，作为光伏层给体材料应用于制备聚合物太阳能电池。
3.如权利要求2所述的应用，其特征在于，将所述的具有噻吩并[2,3-f]苯并呋喃化合物单元结构的聚合物与电子受体物质混合后，溶于溶剂，再涂覆在导电玻璃上制成聚合物薄膜，进一步在薄膜上制备金属电极，即制得聚合物太阳能电池器件。
4.如权利要求3所述的应用，其特征在于，所述电子受体物质为富勒烯C60或含C60基团的化合物、富勒烯C70或含C70基团的化合物。
5.如权利要求3所述的应用，所述的溶剂为邻二氯苯、三氯甲烷、四氢呋喃中一种或几种。
CN201410171994.3A 2014-04-25 2014-04-25 噻吩并[2,3-f]苯并呋喃化合物及其聚合物和聚合物的应用 Expired - Fee Related CN103936760B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410171994.3A CN103936760B (zh) 2014-04-25 2014-04-25 噻吩并[2,3-f]苯并呋喃化合物及其聚合物和聚合物的应用

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410171994.3A CN103936760B (zh) 2014-04-25 2014-04-25 噻吩并[2,3-f]苯并呋喃化合物及其聚合物和聚合物的应用

Publications (2)

Publication Number Publication Date
CN103936760A CN103936760A (zh) 2014-07-23
CN103936760B true CN103936760B (zh) 2016-01-13

Family

ID=51184667

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410171994.3A Expired - Fee Related CN103936760B (zh) 2014-04-25 2014-04-25 噻吩并[2,3-f]苯并呋喃化合物及其聚合物和聚合物的应用

Country Status (1)

Country Link
CN (1) CN103936760B (zh)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016089002A (ja) * 2014-10-31 2016-05-23 出光興産株式会社 ベンゾフラノチオフェン骨格を有するモノマー及びポリマー、及びそのポリマーを用いた有機薄膜太陽電池材料
CN105753851B (zh) * 2016-03-23 2018-09-14 中南大学 四氟化苯并喹喔啉化合物与四氟化苯并喹喔啉基聚合物及其制备方法和应用
CN109776766B (zh) * 2018-12-24 2021-03-19 河南大学 一种噻吩[3, 4-f]异苯并呋喃-4,8-二酮基聚合物、其制备方法及应用
CN111848930B (zh) * 2020-07-30 2021-07-13 清华大学 可溶性聚苯并呋喃及其制备方法与在合成5-取代苯并呋喃的应用

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
5,6-Bis(decyloxy)-2,1,3-benzooxadiazole-Based Polymers with Different Electron Donors for Bulk-Heterojunction Solar Cells;Ping Ding et al.;《The Journal of Physical Chemistry C》;20110712;第115卷;第16211-16219页 *
Variation of the SideChainBranch Position Leads to Vastly ImprovedMolecularWeight and OPV Performance in 4,8-dialkoxybenzo[1,2-b:4,5-b]dithiophene/ 2,1,3-benzothiadiazole Copolymers;Robert C. Coffin，et al.;《Journal of Nanotechnology》;20111231;第2011卷;第1-10页 *
苯并稠杂环类聚合物太阳能电池材料的性能研究;刘波;《中国博士学位论文全文数据库 工程科技II辑》;20140215;第2014卷(第2期);C042-50 *

Also Published As

Publication number Publication date
CN103936760A (zh) 2014-07-23

Similar Documents

Publication Publication Date Title
Zhang et al. Copolymers from benzodithiophene and benzotriazole: synthesis and photovoltaic applications
CN106905306B (zh) 六氟代喹喔啉化合物和六氟代喹喔啉类共聚物及应用
Huo et al. Benzodifuran-alt-thienothiophene based low band gap copolymers: substituent effects on their molecular energy levels and photovoltaic properties
CN104045657B (zh) 五元杂环衍生物桥联的苝二酰亚胺二聚体、其制备方法及其在有机光伏器件中的应用
CN104086752A (zh) 苯并二噻吩类聚合物、其制备方法、包括其的半导体组合物及应用其的太阳能电池
Hou et al. Synthesis and photovoltaic properties of the copolymers of 2-methoxy-5-(2′-ethylhexyloxy)-1, 4-phenylene vinylene and 2, 5-thienylene-vinylene
CN105753851B (zh) 四氟化苯并喹喔啉化合物与四氟化苯并喹喔啉基聚合物及其制备方法和应用
EP2586810A1 (en) Conjugated polymer based on benzodithiophene and thienopyrazine, preparation method and uses thereof
CN113527641B (zh) 一类基于酯基侧链取代喹喔啉衍生物的聚合物材料及应用
KR20140010156A (ko) 반도체 폴리머
CN103936760B (zh) 噻吩并[2,3-f]苯并呋喃化合物及其聚合物和聚合物的应用
CN111808126B (zh) 一种A-π-D-π-A型的BODIPY小分子光伏材料及其制备方法和应用
JP2016501294A (ja) チエノ［３，４−ｂ］チオフェンユニットを含有するベンゾジチオフェン系共重合体、製造方法、及びその使用方法
Medlej et al. Effect of spacer insertion in a commonly used dithienosilole/benzothiadiazole-based low band gap copolymer for polymer solar cells
EP2927259B1 (en) Benzodithiophene based copolymer containing thiophene pyrroledione units and preparing method and applications thereof
JP6096313B2 (ja) ピリジノ［２，１，３］チアジアゾールユニットを含有するベンゾジチオフェン系共重合体、製造方法、及び、その使用方法
Chen et al. A Novel Thiophene Derivative‐based Conjugated Polymer for Polymer Solar Cells with High Open‐circuit Voltage
Pola et al. Synthesis of fluorinated benzotriazole (BTZ)-and benzodithiophene (BDT)-based low-bandgap conjugated polymers for solar cell applications
Gao et al. Efficient polymer solar cells based on poly (thieno [2, 3-f] benzofuran-co-thienopyrroledione) with a high open circuit voltage exceeding 1 V
Yu et al. Structure-performance correlation of indacenodithiophene-based narrow band-gap polymers with pendant diketopyrrolopyrrole units
CN106700039B (zh) 氟代吡啶[3,4-b]吡嗪化合物及氟代吡啶[3,4-b]吡嗪基共聚物材料和应用
Fan et al. Benzodithiophene-based two-dimensional polymers with extended conjugated thienyltriphenylamine substituents for high-efficiency polymer solar cells
CN111039961A (zh) 基于5, 6-双氟苯并噻二唑单元的齐聚物光伏供体材料的制备及应用
Fu et al. Synthesis and characterization of new electron-withdrawing moiety thieno [2, 3-c] pyrrole-4, 6-dione-based molecules for small molecule solar cells
Li et al. A comparative study of diketopyrrolopyrrole and isoindigo based polymers for organic photovoltaic applications

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
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20160113

Termination date: 20170425

CF01 Termination of patent right due to non-payment of annual fee