WO2011113194A1 - 环戊二烯二噻吩-喹喔啉共聚物、其制备方法和应用 - Google Patents

环戊二烯二噻吩-喹喔啉共聚物、其制备方法和应用 Download PDF

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WO2011113194A1
WO2011113194A1 PCT/CN2010/071053 CN2010071053W WO2011113194A1 WO 2011113194 A1 WO2011113194 A1 WO 2011113194A1 CN 2010071053 W CN2010071053 W CN 2010071053W WO 2011113194 A1 WO2011113194 A1 WO 2011113194A1
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quinoxaline
cyclopentadiene
organic
group
compound
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PCT/CN2010/071053
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English (en)
French (fr)
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周明杰
黄杰
许二建
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海洋王照明科技股份有限公司
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Priority to JP2012555277A priority Critical patent/JP5746226B2/ja
Priority to PCT/CN2010/071053 priority patent/WO2011113194A1/zh
Priority to US13/582,763 priority patent/US20120329982A1/en
Priority to EP10847663.1A priority patent/EP2548909A4/en
Priority to CN201080061233.2A priority patent/CN102725331B/zh
Publication of WO2011113194A1 publication Critical patent/WO2011113194A1/zh

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Definitions

  • the invention belongs to the technical field of organic compound synthesis, and in particular relates to a cyclopentadiene dithio. a quinoxaline copolymer, a process for its preparation and an application.
  • the energy conversion efficiency of PCPDTBT and PCBM blends has reached 6.5%, but it is still much lower than the conversion efficiency of inorganic solar cells.
  • the main constraints to performance improvement are: relatively low carrier mobility of organic semiconductor devices, the optical response of the device does not match the solar radiation spectrum, and the red region of high photon flux is not effectively utilized and carriers are Electrode collection efficiency is low. In order to make polymer solar cells practical applications, it is still the primary task in this research field to develop new materials and greatly improve their energy conversion efficiency.
  • a cyclopentadiene dithio is provided.
  • a quinolinated conjugated polymer having good solubility, carrier mobility, and strong chemical and structural modification.
  • Embodiments of the present invention further provide a cyclopentadienyldithiophene-quinoxaline conjugated polymer in a polymer solar cell, an organic electroluminescence, an organic field effect transistor, an organic optical storage, an organic nonlinear material, or/and an organic Applications in the field of lasers.
  • x+y l, 0.5 ⁇ 1, ⁇ is a positive integer less than 100, is an alkyl group of ( ⁇ 0 2 );
  • R 2 , R 3 , R4 , R 5 are the same or different groups
  • the group is a hydrogen atom, a CH ⁇ o alkyl group or an alkoxy group, an alkyl group-containing group, an alkylpyrrol group-containing group, and an alkylbenzene group-containing group.
  • the heteroconjugate was subjected to a stille coupling reaction to obtain the cyclopentadienyldithiophene-quinoxaline conjugated polymer.
  • cyclopentadienyldithiophene-quinoxaline conjugated polymer is in the field of polymer solar cells, organic electroluminescence, organic field effect transistors, organic optical storage, organic nonlinear materials or/and organic lasers.
  • the polymer contains structural units of cyclopentadiene dithiophene or a derivative thereof, and the two thiophene rings in the structural unit are on the same plane, which effectively prolongs the conjugate property of the polymer and reduces the energy of the polymer. Gap, and this coplanar structure makes it easier to transfer carriers between the two main chains, thereby increasing carrier mobility;
  • the polymer contains a quinoxaline unit such that the polymer has high electron transport properties, High glass transition temperature, excellent electrochemical reduction properties; and quinoxaline unit as an excellent acceptor unit with strong electron-withdrawing ability, thus making the polymer of the invention also have strong chemical and structural modification , the electron-donating group and the electron-accepting group can be introduced by a simple method to adjust the electron-withdrawing property;
  • the cyclopentadienyldithiophene-quinoxaline conjugated polymer effectively improves the solubility of the material by introducing a long alkyl chain, improves the processing performance, and expands the application in the field of polymer solar cells. Scope; temperature can react to produce the target product, therefore, the preparation process is simple, easy to operate and control, suitable for industrial production; light, organic field effect transistor, organic light storage, organic nonlinear material or/and organic laser field In the process of high temperature treatment, the order and regularity of the arrangement between the groups and the molecular segments in the material can be effectively increased, so that the transport rate and efficiency of carrier mobility are improved, and thus effective.
  • the ground has improved the photoelectric conversion efficiency of the device.
  • Figure 1 is a poly(4,4-dioctyl-cyclopentadiene (2, lb: 3,4-b,) dithiophene-2,3-bis(phenyl)quinoxaline) using an embodiment of the present invention.
  • Figure 3 is a poly(4,4-dioctyl-cyclopentadienyl (2,lb:3,4-b,)dithiophene-2,3-bis(phenyl)quinoxaline) using an embodiment of the present invention.
  • the present invention provides a cyclopentadienyldithiophene-quinoxaline conjugated polymer, which has the following formula
  • x+y l, 0.5 ⁇ 1, n is a positive integer less than 100, is an alkyl group of CH ⁇ o; and R 2 , R 3 , R 4 , R 5 are the same or different groups,
  • the group is an alkyl group or alkoxy group of 11, CH ⁇ o, an alkyl group containing an alkyl group, an alkylpyrrol group-containing group, and an alkylbenzene group-containing group.
  • the above-mentioned structural formula of the alkyl group-containing group is preferably a group represented by the following (A), wherein R 7 and R 8 are selected from an alkyl group of CH ⁇ o, and the unsubstituted site on the alkane-containing ring may also be used. Arbitrarily replaced,
  • the structural formula of the alkyl-containing pyrrole group is preferably the following (B), wherein R 9 is d
  • the structural formula of the alkyl-containing benzene ring group is preferably the following (C), wherein. Is an alkyl group of CH ⁇ o, and R 1Q may be at any position in the unsubstituted position of the benzene ring.
  • the polymer of the embodiment of the invention contains a structural unit of cyclopentadiene dithiophene or a derivative thereof, and the two thiophene rings in the structural unit are on the same plane, which effectively prolongs the conjugate property of the polymer and reduces the polymerization.
  • the energy gap of the object, and this coplanar structure makes it easier to transfer carriers between the two main chains, thereby increasing carrier mobility, for example, cyclopentadiene (2, lb: 3, 4) -b,)
  • carrier mobility for example, cyclopentadiene (2, lb: 3, 4) -b,
  • PCPDTBT benzothiadiazole
  • the unoptimized carrier mobility of the copolymer of dithiophene and benzothiadiazole (PCPDTBT) has reached 2X 10- 2 cm 1 ⁇ " 1 and therefore contains cyclopentadiene dithiophene Structural units, such as polymers containing cyclopentadiene (2, lb: 3, 4-b,) dithiophene structural units, have important applications in organic solar cells.
  • the polymer of the embodiment of the present invention further contains a quinoxaline unit, so that the polymer of the present invention has high electron transport properties, high glass transition temperature, excellent electrochemical reduction property, and quinoxaline unit as one
  • the excellent acceptor unit of strong electron-withdrawing ability thus making the polymer of the invention also have strong chemical and structural modification, and the electron-donating group and the electron-accepting group can be introduced by a simple method to adjust the electron-withdrawing property. Expanded its wide application in the field of organic optoelectronic materials.
  • the cyclopentadienyldithiophene-quinoxaline conjugated polymer introduces a long alkyl or alkoxy chain, such as an alkyl or alkane of Cl CH ⁇ o
  • the oxy group effectively improves the solubility of the material, improves the processing performance, and expands the application range in the field of polymer solar cells.
  • Step i adding a diketone compound and an o-phenylenediamine compound to an organic solvent to obtain a dibromo compound of a quinoxaline heteroaryl ring;
  • Step ii the above-mentioned quinoxaline heteroaryl ring dibromo compound and 4,4-dialkyl-2,6-bistridecyltin-cyclopentadiene (2, lb: 3, 4-b, ) Dithiophene.
  • the compound is subjected to a stille coupling reaction to obtain the cyclopentadiene dithio.
  • step i The preparation of the above-mentioned dibromo compound of the quinoxaline heteroaryl ring (ie, step i) is carried out by adding a diketone compound to an o-phenylenediamine compound in a molar ratio of 1:0.1 to 10, and adding the organic solvent at 20 ° C. The reaction was carried out at 120 ° C for 1 to 24 h.
  • the minimum amount of the organic solvent should ensure the dissolution of the reaction, and the amount of the organic solvent can be flexibly adjusted according to actual production under the premise of ensuring the minimum dosage, and the organic solvent is preferably acetic acid, m-nonylphenol, decyl alcohol, ethanol or butanol. Etc., most preferred is acetic acid.
  • the above stille coupling reaction (ie, step ii) is 4,4-dialkyl-2,6-bistridecyltin-cyclopentadiene (2, lb: 3, 4-b,) dithiophene, 4 , di-dialkyl-2,6-dibromo-cyclopentadiene (2,lb:3,4-b,) dithiophene and quinoxaline heteroaryl ring dibromo compound molar ratio 1: 1 ⁇ 100 : 1 Add the organic reaction solvent, and carry out Stille coupling reaction at 50 °C ⁇ 150 °C for 24 ⁇ 72 h.
  • the minimum amount of the organic reaction solvent should ensure the dissolution of the reaction, and the amount of the organic solvent can be flexibly adjusted according to actual production under the premise of ensuring the minimum dosage, and the organic reaction solvent is preferably tetrahydrofuran, ethylene glycol diterpene ether, benzene, hydrazine. At least one of benzene.
  • reaction time The shorter the reaction time of the Stille coupling reaction, the smaller the molecular weight of the copolymer may be, or the polymerization is not at all, but the reaction time is longer to a certain extent, the molecular weight of the copolymer does not increase, tends to be stable, and the reaction time The longer the energy consumption, the higher the production cost, so the reaction time is set to be 24 ⁇ 72 h.
  • the above Stille coupling reaction may also be added with a catalyst to increase the rate and the target of the coupling reaction, and the addition amount thereof is 4,4-dialkyl-2,6-bistridecyltin-cyclopentadiene (2). , lb: 3, 4-b,) dithia. 0.05 to 50% of the moles.
  • the organic palladium catalyst is at least one of Pd 2 (dba) 3 /P(o-Tol) 3 , Pd(PPh 3 ) 4 , Pd(PPh 3 ) 2 Cl 2 ; an organic palladium catalyst and an organophosphine ligand
  • the molar ratio of the mixture is 1:2 ⁇ 20.
  • the preparation of the dibromo compound of the quinoxaline heteroaryl ring and/or the preparation of the cyclopentadienyl dithiophene-quinoxaline conjugated polymer can be carried out under aerobic or anaerobic conditions, preferably under anaerobic conditions.
  • the anaerobic conditions can be carried out by vacuum or by filling with an inert gas, preferably an inert gas, which is an inert gas commonly used in the art, such as nitrogen, argon or the like, preferably nitrogen.
  • reaction temperature can be reacted to obtain the target product, and therefore, the preparation method is simple, easy to handle and control, and is suitable for industrial production.
  • the order and regularity of the arrangement between the groups and the molecular segments in the material can be effectively increased, and the transport speed and efficiency of the carrier mobility are obtained. Improve, effectively improve the photoelectric conversion efficiency of the device.
  • the cyclopentadienyldithiophene-quinoxaline conjugated polymer of the present invention can be used as an active material in an organic photoelectric material, a polymer solar cell, an organic electroluminescence, an organic field effect transistor, an organic optical storage. , organic nonlinear materials or / and applications in the field of organic lasers.
  • Example 1 The invention will now be further described in detail by taking the preparation of a specific polymer as an example.
  • Example 1 The invention will now be further described in detail by taking the preparation of a specific polymer as an example.
  • the mixture was added to a mixed organic reaction solvent of 50 mL of 1:1 ethylene glycol dioxime and tetrahydrofuran, and bubbling for 0.8 h to remove residual oxygen in the reaction environment, and then adding 0.025 mmol of Pd(PPh 3 )4 And continue to bubble for 1 h to remove residual oxygen in the reaction environment, and then heated to 150 ° C for 24 hours.
  • the mixed droplets are first added to the decyl alcohol to be sedimented, suction filtered, washed with decyl alcohol, dried, dissolved with chlorobenzene, and added to an aqueous solution of sodium diethyldithiocarbamate, followed by Heat the mixture to 80.
  • the structure of the solar cell device is shown in Figure 1.
  • the active layer material comprises the poly 4,4-dioctyl-cyclopentadiene (2, lb: 3,4-b') dithiophene-2,3-bis(phenyl)quinoxaline polymer of the present invention.
  • an electron donor material [6,6]phenyl-C 61 -butyrate (PCBM ) is used as an electron acceptor material, that is, the device structure is sequentially a glass layer 11, an ITO layer 12, a PEDOT:PSS layer 13, Copolymer active layer 14 and metal layer 15, wherein ITO is indium tin oxide having a sheet resistance of 10-20 ⁇ / ⁇ , PEDOT is polyethylene dioxythiophene, PSS is polystyrene-cross acid; and ITO layer is coated
  • the glass 11 of 12 is first ultrasonically cleaned, then treated with oxygen-Plasma, then the PEDOT:PSS layer 13 is applied to the ITO layer, and then the poly-4,4-dioctyl-cyclopenta
  • the solar cell device comprises a glass substrate 11, a transparent anode 12, an intermediate auxiliary layer 13, an active layer 14, and a cathode 15 which are sequentially laminated.
  • the intermediate auxiliary layer 13 is made of polyethylene dioxythiophene: polystyrene-sulfonic acid composite material.
  • the active layer 14 comprises an electron donor material and an electron acceptor material, and the electron donor material adopts the above poly 4,4-dioctyl-cyclopentadiene (2, lb: 3, 4- b,) Dithiophene.
  • The-2,3-bis(phenyl)quinoxaline, the electron acceptor material may be [6,6]phenyl-C 61 -butyrate (PCBM for short).
  • the transparent anode 12 may be indium tin oxide (abbreviated as ITO), preferably indium tin oxide having a sheet resistance of 10-20 ⁇ /.
  • the cathode 15 may be an aluminum electrode or a bimetal layer electrode such as Ca/Al or Ba/Al or the like.
  • the glass base layer 11 can be used as the bottom layer.
  • the ITO glass is selected, it is ultrasonically cleaned, treated with oxygen-Plasma, and the intermediate auxiliary layer 13 is coated on the ITO glass, and then the 4,4-dioctyl group is polymerized.
  • Cyclopentadiene (2, lb: 3, 4-b,) dithiophene-2,3-bis(phenyl)quinoxaline and an electron acceptor material are coated on the intermediate auxiliary layer 13 by blending to form
  • the active layer 14 is then deposited on the active layer 14 by vacuum evaporation to obtain the solar cell device described above.
  • the transparent anode 12, the intermediate auxiliary layer 13, the active layer 14, the bimetal layer Ca, and the A1 layer have thicknesses of 160 nm, 40 nm, 150 nm, 20 nm, and 70 nm, respectively.
  • Dithiophene-2,3-bis(phenyl)quinoxaline absorbs light energy and generates excitons that migrate to the interface of the electron donor/acceptor material and transfer electrons to the electron acceptor Materials, such as PCBM, achieve charge separation, thereby forming free carriers, ie free electrons and holes. These free electrons are transferred to the metal cathode along the electron acceptor material and collected by the cathode.
  • the free holes are transferred to the ITO anode along the electron donor material and collected by the anode, thereby forming photocurrent and photovoltage, realizing photoelectric conversion, and external connection.
  • the load When the load is 16, it can be powered.
  • The-2,3-bis(phenyl)quinoxaline can more fully utilize light energy due to its wide spectral response range, in order to obtain higher photoelectric conversion efficiency. Add the power generation capability of solar cell devices.
  • the organic material can also reduce the quality of the solar cell device, and can be fabricated by techniques such as spin coating, which is convenient for mass production.
  • an organic electroluminescent device of -2,3-bis(phenyl)quinoxaline which comprises a glass substrate 21, a transparent anode 22, a light-emitting layer 23, a buffer layer 24, and a cathode 25 which are laminated in this order.
  • the transparent anode 22 may be made of indium tin oxide (abbreviated as ITO), preferably indium tin oxide having a sheet resistance of 10-20 ⁇ /.
  • the light-emitting layer 23 contains the poly 4,4-dioctyl-cyclopentadiene (2,1-b:3,4-b,)dithiophene-2,3-bis(phenyl)quinoxaline in the above embodiment.
  • the buffer layer 24 may be LiF or the like, but is not limited thereto.
  • the cathode 25 may be, but not limited to, metal A1 or Ba or the like, but is not limited thereto.
  • the organic electroluminescent device structure is represented by: ITO/poly 4,4-dioctyl-cyclopentadiene (2,l-b:3,4-b,) dithio.
  • Each layer can be formed by an existing method, and poly 4,4-dioctyl-cyclopentadiene (2, lb: 3, 4-b,) dithiophene-2,3-bis(phenyl)quinoxaline It can be formed on ITO by spin coating technique.
  • the poly 4,4-dioctyl-cyclopentadiene (2, lb: 3,4-b,) dithio in the above examples is used.
  • An organic field effect transistor of -2,3-bis(phenyl)quinoxaline comprising a substrate 31, an insulating layer 32, a modifying layer 33, an organic semiconductor layer 34, and an organic semiconductor layer 34, which are sequentially stacked. Source electrode 35 and drain electrode 36.
  • the substrate 31 may be, but not limited to, a highly doped silicon wafer (Si), and the insulating layer 32 may be, but not limited to, a micro-nano (eg, 450 nm) thick SiO 2 .
  • the organic semiconductor layer 34 employs the poly 4,4-dioctyl-cyclopentadiene (2, lb: 3,4-b,) dithiophene-2,3-bis(phenyl)quinoxaline described above.
  • Both the source electrode 35 and the drain electrode 36 may be, but not limited to, gold.
  • the modifying layer 33 can be, but is not limited to, octadecyltrichlorosilane.
  • the substrate 31, the insulating layer 32, the modifying layer 33, and the source electrode 35 and the drain electrode 36 can be formed by a conventional method.
  • the organic semiconductor layer 34 may be poly 4,4-dioctyl-cyclopentadiene (2, lb: 3, 4-b,) dithiophene-2,3-bis(phenyl)quinidine in the above embodiment. Porphyrin spin-coated on the modified layer 33 On the insulating layer 32.

Description

环戊二烯二噻吩-喹喔啉共聚物、 其制备方法和应用
技术领域
本发明属于有机化合物合成技术领域， 具体的说是涉及一种环戊二烯二噻 。分 -喹喔啉共聚物、 其制备方法和应用。
说
背景技术
利用廉价材料制备低成本、 高效能的太阳能电池一直是光伏领域的研究热 点和难点。 目前用于地面的硅太阳能电池由于生产工艺复杂、 成本高， 使其应 书
用受到限制。 为了降低成本， 拓展应用范围， 长期以来人们一直在寻找新型的 太阳能电池材料。 聚合物太阳能电池因为原料价格低廉、 质量轻、 柔性、 生产 工艺简单、 可用涂布、 印刷等方式大面积制备等优点而备受关注， 如果能够将 其能量转化效率提高到接近商品硅太阳能电池的水平， 其市场前景将是非常巨 大的。 自 1992年 N. S. Sariciftci等报道了共轭聚合物与 C6。之间的光诱导电子 转移现象后， 人们在聚合物太阳能电池方面投入了大量研究， 并取得了飞速的 发展。 目前， 聚合物太阳能电池的研究主要集中于给体、 受体共混体系， 采用 PCPDTBT与 PCBM共混体系的能量转化效率已经达到 6.5%,但是仍比无机太 阳能电池的转换效率低得多， 限制性能提高的主要制约因素有： 有机半导体器 件相对较低的载流子迁移率， 器件的光语响应与太阳辐射光谱不匹配， 高光子 通量的红光区没有被有效利用以及载流子的电极收集效率低等。 为了使聚合物 太阳能电池得到实际的应用， 开发新型的材料， 大幅度提高其能量转换效率仍 是这一研究领域的首要任务。
发明内容
有鉴于此， 提供一种环戊二烯二噻。分-喹喔啉共轭聚合物， 该聚合物具有良 好的溶解性能、 载流子迁移率、 有较强的化学和结构可修饰性。
以及， 一种工艺简单， 易于操作和控制， 适合于工业化生产的环戊二烯二 噻。分 -喹喔啉共轭聚合物制备方法。
本发明实施例进一步提供一种环戊二烯二噻吩 -喹喔啉共轭聚合物在聚合 物太阳能电池、 有机电致发光、 有机场效应晶体管、 有机光存储、 有机非线性 材料或 /和有机激光领域中的应用。
一种环戊二烯 （ I ):
Figure imgf000004_0001
其中， x+y=l , 0.5<χ<1 , η为小于 100的正整数， 为（^〜02。的烷基； R2, R3, R4 , R5为相同或者不同的基团， 该基团为氢原子、 CH^o的烷基或烷氧基、 含 烷基芴基团、 含烷基吡咯基团、 含烷基苯环基团。
以及， 一种环戊二烯二噻吩-喹喔啉共轭聚合物制备方法， 包括如下工艺步 骤：
将二酮类化合物与邻苯二胺类化合物加入有机酸溶液中制得喹喔啉类杂芳 环的二溴代物；
将上述喹喔啉类杂芳环的二溴代物与 4,4-二烷基 -2,6-双三曱基锡-环戊二烯 (2,l-b:3,4-b，)二噻。分化合物、 4,4-二烷基 -2,6-二溴-环戊二烯 (2,l-b:3,4-b，)二噻。分化 合物进行 stille耦合反应， 制得所述环戊二烯二噻吩-喹喔啉共轭聚合物。
进一步， 所述的环戊二烯二噻吩-喹喔啉共轭聚合物在聚合物太阳能电池、 有机电致发光、 有机场效应晶体管、 有机光存储、 有机非线性材料或 /和有机 激光领域中的应用。
上述技术方案具备以下优点：
1. 所述聚合物含有环戊二烯二噻吩或其衍生物结构单元， 该结构单元中的 两个噻吩环在同一个平面上， 有效延长了聚合物的共轭性能， 降低聚合物的能 隙， 且这种共平面结构使得载流子在两个主链之间转移变得更加容易， 从而增 加载流子迁移率；
2. 所述聚合物含有喹喔啉单元， 从而使得聚合物具有高的电子传输性质、 高的玻璃化转变温度、 优异的电化学还原性质； 而且喹喔啉单元作为一种具有 强吸电子能力的优良受体单元， 因而使得本发明聚合物还具有较强的化学和结 构可修饰性， 可以利用简便的方法引入供电子基团和受电子基团， 调节其吸电 子性能；
3. 所述环戊二烯二噻吩-喹喔啉共轭聚合物通过引入长的烷基链， 有效提 高了材料的溶解性能， 改善了加工性能， 扩大了在聚合物太阳能电池等领域的 应用范围； 温度就能发生反应从而制得目标产物， 因此， 制备工艺简单， 易于操作和控制， 适合于工业化生产； 光、 有机场效应晶体管、 有机光存储、 有机非线性材料或 /和有机激光领域的 过程中， 经过高温处理后， 材料中分子内各基团和分子链段间排列的有序性和 规整度能有效增加， 因而载流子迁移率的传输速度和效率得到了提高， 进而有 效地提高了器件的光电转换效率。 附图说明
下面将结合附图及实施例对本发明作进一步说明， 附图中：
图 1是利用本发明实施例的聚 4,4-二辛基-环戊二烯 (2,l-b:3,4-b，)二噻吩 -2,3- 双（苯基）喹喔啉为活性层的聚合物太阳能电池器件的结构示意图；
图 2 是采用本发明实施例的聚 4,4-二辛基-环戊二烯 (2,l-b:3,4-b，)二噻吩 -2,3-双（苯基）喹喔啉的有机电致发光器件的结构示意图；
图 3 是采用本发明实施例的聚 4,4-二辛基-环戊二烯 (2,l-b:3,4-b，)二噻吩 -2,3-双（苯基）喹喔啉的有机场效应晶体管的结构示意图。 本发明的实施方式
为了使本发明要解决的技术问题、 技术方案及有益效果更加清楚明白， 以 下结合实施例， 对本发明进行进一步详细说明。 应当理解， 此处所描述的具体 实施例仅仅用以解释本发明， 并不用于限定本发明。
本发明实施例提供一种环戊二烯二噻吩-喹喔啉共轭聚合物，其通式为下述
( I ):
Figure imgf000006_0001
其中， x+y=l , 0.5<χ<1 , n为小于 100的正整数， 为 CH^o的烷基； R2, R3, R4, R5为相同或者不同的基团， 该基团为11、 CH^o的烷基或烷氧基、 含 烷基芴基团、 含烷基吡咯基团、 含烷基苯环基团。
上述的含烷基芴基团结构通式优选为下述（A )表示的基团,其中， R7、 R8 选自 CH^o的烷基， 该含烷 环上的未取代位还可任意被取代，
Figure imgf000006_0002
所述的含烷基吡咯基团结构通式优选为下述（B ), 其中， R9为 d
烷基， 该含吡咯单元基团中苯环上的未取代位还可任意被取代，
Figure imgf000006_0003
( B );
所述的含烷基苯环基团结构通式优选为下述（C ) , 其中， 。为 CH^o的 烷基， R1Q可以在苯环未取代位的任意位置，
、'
( c )。
本发明实施例的聚合物含有环戊二烯二噻吩或其衍生物结构单元， 结构单 元中的两个噻吩环在同一个平面上， 有效延长了聚合物的共轭性能， 降低聚合 物的能隙， 且这种共平面结构使得载流子在两个主链之间转移变得更加容易， 从而增加载流子迁移率， 比如， 环戊二烯 (2,l-b:3,4-b，)二噻吩与苯并噻二唑的共 聚物（PCPDTBT ) 的未优化的载流子迁移率就已经达到了 2X 10-2 cm 1^"1 , 因此， 含有环戊二烯二噻吩结构单元， 如含有环戊二烯 (2,l-b:3,4-b，)二噻吩结构 单元的聚合物在有机太阳能电池等方面有着重要的应用前景。
本发明实施例的聚合物还含有喹喔啉单元， 从而使得本发明聚合物具有高 的电子传输性质， 高的玻璃化转变温度， 优异的电化学还原性质， 而且喹喔啉 单元作为一种具有强吸电子能力的优良受体单元， 因而使得本发明聚合物还具 有较强的化学和结构可修饰性， 可以利用简便的方法引入供电子基团和受电子 基团， 调节其吸电子性能， 扩展了其在有机光电材料领域中有着广泛的应用。 与此同时， 在本发明一个优选实施例中， 环戊二烯二噻吩-喹喔啉共轭聚合物引 入长的烷基链或烷氧基链， 例如 为 Cl CH^o的烷基或烷氧基， 有效 提高了材料的溶解性能， 改善了加工性能， 扩大了在聚合物太阳能电池等领域 的应用范围。
本发明实施例提供的一种上述环戊二烯二噻吩 -喹喔啉共轭聚合物制备方
Figure imgf000007_0001
该方法具体工艺步骤如下：
步骤 i:将二酮类化合物与邻苯二胺类化合物加入有机溶剂中制得喹喔啉类 杂芳环的二溴代物；
步骤 ii: 将上述喹喔啉类杂芳环的二溴代物与 4,4-二烷基 -2,6-双三曱基锡- 环戊二烯 (2,l-b:3,4-b，)二噻。分化合物、 4,4-二烷基 -2,6-二溴-环戊二烯 (2,l-b:3,4-b，) 二噻。分化合物进行 stille耦合反应， 制得所述环戊二烯二噻。分-喹喔啉共轭聚合 物。
上述的喹喔啉类杂芳环的二溴代物制备（即步骤 i )是将二酮类化合物与邻 苯二胺类化合物按摩尔比 1 ： 0.1〜10加入有机溶剂， 并在 20°C〜120°C下反应 1〜24 h。 其中， 该有机溶剂最低用量应保证反应溶解， 在保证最低用量的前提 下， 可以根据实际生产灵活调整该有机溶剂的用量， 该有机溶剂优选为乙酸、 间曱苯酚、 曱醇、 乙醇或丁醇等， 最优选为乙酸。
上述的 stille耦合反应 (即步骤 ii )是将 4,4-二烷基 -2,6-双三曱基锡-环戊二 烯 (2,l-b:3,4-b，)二噻吩、 4,4-二烷基 -2,6-二溴-环戊二烯 (2,l-b:3,4-b，)二噻吩与喹喔 啉类杂芳环的二溴代物按摩尔比 1 ： 1〜100 ： 1 加入有机反应溶剂中， 并在 50 °C〜 150 °C下进行 Stille耦合反应 24〜72 h。 其中， 该有机反应溶剂最低用量应 保证反应溶解， 在保证最低用量的前提下， 可以根据实际生产灵活调整该有机 溶剂的用量， 有机反应溶剂优选为四氢呋喃、 乙二醇二曱醚、 苯、 曱苯中的至 少一种。 该 Stille耦合反应的反应的时间越短， 共聚物分子量可能就会越小， 或者根本没聚合上， 但反应时间长到一定程度， 共聚物分子量也就不会增加， 趋于稳定了， 反应时间越长， 能耗越大， 导致生产成本越高， 因此反应时间定 为 24〜72 h为宜。
上述的 Stille耦合反应还可以添加有催化剂来提高本耦合反应的速率和目 合物，其添加量是 4,4-二烷基 -2,6-双三曱基锡-环戊二烯 (2,l-b:3,4-b，)二噻。分摩尔 的 0.05 ~ 50%。其中，有机钯催化剂是 Pd2(dba)3/P(o-Tol)3、 Pd(PPh3)4、 Pd(PPh3)2Cl2 中的至少一种； 有机钯催化剂与有机膦配体的混合物按摩尔比为 1:2〜20。
喹喔啉类杂芳环的二溴代物制备和 /或环戊二烯二噻吩 -喹喔啉共轭聚合物 制备反应步骤可以在有氧或无氧的条件下进行， 优选在无氧条件下进行， 无氧 条件可以采用真空或充满惰性气体来实现，优选充满惰性气体来实现无氧条件， 该惰性气体是本技术领域常用的惰性气体， 例如氮气、 氩气等， 优选氮气。 优 选在无氧条件下进行的是分别用来提高两反应步骤的反应产物得率， 因为氧气 是个很活泼的成分， 能与反应物反应， 干扰了反应的顺利进行， 从而降低了各 反应产物得率。 制温度就能发生反应从而制得目标产物， 因此， 制备方法简单， 易于操作和控 制， 适合于工业化生产。
将本发明实施例中的共聚物经过高温处理后， 材料中分子内各基团和分子 链段间排列的有序性和规整度能有效增加， 载流子迁移率的传输速度和效率得 到了提高， 有效地提高了器件的光电转换效率。
由此，本发明实施例的环戊二烯二噻吩-喹喔啉共轭聚合物可作为活性材料 用在有机光电材料、 聚合物太阳能电池、 有机电致发光、 有机场效应晶体管、 有机光存储、 有机非线性材料或 /和有机激光领域中的应用。
现以具体聚合物的制备为例， 对本发明进行进一步详细说明。 实施例 1
聚 4,4-二辛基-环戊二烯 (2,l-b:3,4-b')二噻。分 -2,3-双（苯基）喹喔啉的制备： 氮气保护下，将 3.7 mmol ( 1.0 g )的 3,6-二溴 -邻苯二胺和 1.84 mmol ( 0.39 g )化合物二苯基乙二酮加入到的 20 mL乙酸溶液中。 在 120。C下回流 1小时 后， 将反应液倒入水中， 先用碳酸氢钠中和至中性， 再用氯仿萃取， 饱和食盐 水洗涤， 然后无水硫酸钠干燥后， 旋转蒸发除去溶剂， 粗产品柱层析得白色固 体， 然后用氯仿 /正己烷将前述的白色固体重结晶得到白色固体产物， 即 5,8-二 溴 -2,3-双 (苯基 )喹喔啉化合物， 产率 81%。 MS (EI) m/z: 440(M+)。
在氮气保护下， 将 0.5 mmol ( 0.22 g )的化合物 5,8-二溴 -2,3-双 (苯基 )喹 喔啉、 0.5 mmol ( 0.356 g )的 4,4-二辛基 -2,6-双三曱基锡-环戊二烯 (2,l-b:3,4-b，) 二噻吩、 0.5 mmol 的 4,4-二烷基 -2,6-二溴-环戊二烯 (2,l-b:3,4-b，)二噻。分加入到 30 mL曱苯溶液中， 并鼓泡 0.5 h 除去反应环境中残留的氧气， 然后加入 0.015 mol ( 0.014 g )的 Pd2(dba)3和 0.027 mmol ( 0.0083 g ) P(o-Tol)3, 并继续鼓泡 1 h 除去反应环境中残留的氧气， 然后加热至 50°C回流 72小时。 待反应后， 将 混合液滴先加到曱醇中进行沉降， 抽滤， 曱醇洗涤， 干燥， 再用氯苯溶解， 并 加入到二乙基二硫代氨基曱酸钠的水溶液中， 接着将混合液加热到 80。C搅拌 12小时， 然后将有机相通过氧化铝的柱层析， 氯苯淋洗， 减压除去有机溶剂， 曱醇沉降，抽滤得固体。将所得固体用丙酮索氏提取 72小时， 曱醇沉降，抽滤， 真空泵下抽过夜， 得到固体产物， 产率 53%。 GPC: Mn = 39500, PDI = 2.3。 实施例 2
聚 4,4-二辛基-环戊二烯 (2,l-b:3,4-b')二噻。分 -2,3-双（苯基）喹喔啉的制备： 氮气保护下， 将 0.184mmol ( 0.050 g ) 的 3,6-二溴 -邻苯二胺和 1.84 mmol ( 0.39 g )化合物二苯基乙二酮加入到的 20 mL的按体积比为 1： 1的间曱苯酚、 曱醇混合有机溶剂中。 在 80。C下回流 12小时后， 将反应液倒入水中， 先用碳 酸氢钠中和至中性， 再用氯仿萃取， 饱和食盐水洗涤， 然后无水硫酸钠干燥后， 旋转蒸发除去溶剂， 粗产品柱层析得白色固体， 然后用氯仿 /正己烷将前述的白 色固体重结晶得到白色固体产物， 即 5,8-二溴 -2,3-双（苯基）喹喔啉化合物， 产率 93%。 MS (EI) m/z: 480(M+)。
将 0.5 mmol ( 0.22 g ) 的化合物 5,8-二溴 -2,3-双（苯基 )喹喔啉、 0.5 mmol ( 0.356 g )的 4,4-二辛基 -2,6-双三曱基锡-环戊二烯 (2,l-b:3,4-b，)二噻吩、 50mmol 的 4,4-二烷基 -2,6-二溴-环戊二烯 (2,l-b:3,4-b，)二噻。分加入到按体积比为 50 mL 1： 1乙二醇二曱醚与四氢呋喃的混合有机反应溶剂中， 并鼓泡 0.8h 除去反应环境 中残留的氧气， 然后加入 0.025mmol Pd(PPh3)4 , 并继续鼓泡 1 h 除去反应环境 中残留的氧气， 然后加热至 150°C回流 24小时。 待反应后， 将混合液滴先加到 曱醇中进行沉降， 抽滤， 曱醇洗涤， 干燥， 再用氯苯溶解， 并加入到二乙基二 硫代氨基曱酸钠的水溶液中， 接着将混合液加热到 80。C搅拌 12小时， 然后将 有机相通过氧化铝的柱层析， 氯苯淋洗， 减压除去有机溶剂， 曱醇沉降， 抽滤 得固体。 将所得固体用丙酮索氏提取 72小时， 曱醇沉降， 抽滤， 真空泵下抽过 夜， 得到固体产物， 产率 41%。 GPC: Mn = 39300, PDI = 2.2。 实施例 3
聚 4,4-二辛基-环戊二烯 (2,l-b:3,4-b')二噻。分 -2,3-双（苯基）喹喔啉的制备： 将 18.4mmol ( 4.973 g ) 的 3,6-二溴 -邻苯二胺和 1.84 mmol ( 0.39 g )化合物二 苯基乙二酮加入到 20 mL丁醇溶剂中。 在 20。C下回流 24小时后， 将反应液倒 入水中， 先用碳酸氢钠中和至中性， 再用氯仿萃取， 饱和食盐水洗涤， 然后无 水硫酸钠干燥后， 旋转蒸发除去溶剂， 粗产品柱层析得白色固体， 然后用氯仿 / 正己烷将前述的白色固体重结晶得到白色固体产物， 即 5,8-二溴 -2,3-双 (苯基 ) 喹喔啉化合物， 产率 74%。 MS (EI) m/z: 410(M+)。
在氮气保护下， 将 0.5 mmol ( 0.22 g )的化合物 5,8-二溴 -2,3-双 (苯基 )喹 喔啉、 0.5 mmol ( 0.356 g )的 4,4-二辛基 -2,6-双三曱基锡-环戊二烯 (2,l-b:3,4-b，) 二噻吩、 25mmol 的 4,4-二烷基 -2,6-二溴-环戊二烯 (2,1 -b:3,4-b，)二噻。分加入到按 体积比为 40 mL四氢呋喃的水溶液中， 并鼓泡 0.8h 除去反应环境中残留的氧 气， 然后加入 12.5mmol Pd(PPh3)2Cl2, 并继续鼓泡 1 h 除去反应环境中残留的 氧气， 然后加热至 100°C回流 36小时。 待反应后， 将混合液滴先加到曱醇中进 行沉降， 抽滤， 曱醇洗涤， 干燥， 再用氯苯溶解， 并加入到二乙基二硫代氨基 曱酸钠的水溶液中， 接着将混合液加热到 80。C搅拌 12小时， 然后将有机相通 过氧化铝的柱层析， 氯苯淋洗， 减压除去有机溶剂， 曱醇沉降， 抽滤得固体。 将所得固体用丙酮索氏提取 72小时， 曱醇沉降， 抽滤， 真空泵下抽过夜， 得到 固体产物， 产率 49%。 GPC: Mn = 39470, PDI = 2.3。
应用实施例 4
以聚 4,4-二辛基-环戊二烯 (2,l-b:3,4-b，)二噻。分 -2,3-双（苯基 )喹喔啉作为活 性层的太阳能电池器件中应用：
太阳能电池器件结构如图 1。
活性层材料包含本发明中的聚 4,4-二辛基-环戊二烯 (2,l-b:3,4-b')二噻吩 -2,3-双（苯基）喹喔啉聚合物作为电子给体材料， [6,6]苯基 -C61 -丁酸曱酯（简 称 PCBM )作为电子受体材料， 即器件结构依次为玻璃层 11、 ITO 层 12、 PEDOT:PSS层 13、共聚物活性层 14和金属层 15,其中 ITO是方块电阻为 10-20 Ω/口的氧化铟锡， PEDOT为聚乙烯二氧基噻吩， PSS为聚苯乙烯-横酸； 将涂 有 ITO层 12的玻璃 11先经过超声波清洗后，再用氧 -Plasma处理，接着在 ITO 层上涂上 PEDOT:PSS 层 13 , 然后将本发明中的聚 4,4-二辛基-环戊二烯 (2,l-b:3,4-b，)二噻吩 -2,3-双（苯基）喹喔啉与 PCBM溶解共混后涂覆 PEDOT:PSS 表面上， 构成共聚物活性层 14, 最后采用真空蒸镀技术在活性层上蒸镀金属 A1, 构成金属层 15, 并将该金属层 15作为阴极， 将涂有 ITO层 12作为阳极， 得到含有本实施例聚合物的有机太阳能电池器件。 由于器件经过热处理后， 材 料的化学结构更加规整有序， 提高了载流子的传输速度和效率， 从而提高了器 件的光电转换效率。 应用实施例 5
以聚 4,4-二辛基-环戊二烯 (2,l-b:3,4-b，)二噻。分 -2,3-双（苯基 )喹喔啉作为活 性层在太阳能电池器件中应用：
请参阅图 1 , 采用上述实施例中聚 4,4-二辛基-环戊二烯 (2,l-b:3,4-b，)二噻吩 -2,3-双（苯基）喹喔啉的太阳能电池器件， 其包括依次层叠的玻璃基层 11、 透 明阳极 12、 中间辅助层 13、 活性层 14、 阴极 15, 中间辅助层 13采用聚乙烯二 氧基噻吩： 聚苯乙烯-磺酸复合材料（简称为 PEDOT:PSS ), 活性层 14包括电 子给体材料和电子受体材料， 电子给体材料采用上述聚 4,4-二辛基-环戊二烯 (2,l-b:3,4-b，)二噻。分 -2,3-双（苯基）喹喔啉， 电子受体材料可以是 [6,6]苯基 -C61 - 丁酸曱酯 (简称为 PCBM )。 透明阳极 12可采用氧化铟锡 (简称为 ITO ) , 优 选为方块电阻为 10-20 Ω/ 的氧化铟锡。 阴极 15可采用铝电极或者双金属层电 极，例如 Ca/Al或 Ba/Al等。其中，玻璃基层 11可作为底层，制作时，选取 ITO 玻璃， 并经超声波清洗后， 用氧 -Plasma处理， 在 ITO玻璃上涂覆中间辅助层 13 , 再将聚 4,4-二辛基-环戊二烯 (2,l-b:3,4-b，)二噻吩 -2,3-双（苯基）喹喔啉和电 子受体材料通过共混后涂覆于中间辅助层 13上， 形成活性层 14, 然后再通过 真空蒸镀技术在活性层 14上沉积阴极 15, 获得上述太阳能电池器件。 在一个 优选的实施例中， 透明阳极 12、 中间辅助层 13、 活性层 14、 双金属层 Ca和 A1层的厚度分别为 160 nm、 40 nm、 150 nm、 20 nm、 70 nm。
如图 1所示， 在光照下， 光透过玻璃基层 11和 ITO电极 12, 活性层 14中 的聚 4,4-二辛基-环戊二烯 (2,l-b:3,4-b')二噻吩 -2,3-双（苯基）喹喔啉吸收光能， 并产生激子， 这些激子再迁移到电子给体 /受体材料的界面处， 并将电子转移给 电子受体材料， 如 PCBM, 实现电荷的分离， 从而形成自由的载流子， 即自由 的电子和空穴。 这些自由的电子沿电子受体材料向金属阴极传递并被阴极所收 集， 自由的空穴沿电子给体材料向 ITO阳极传递并被阳极所收集， 从而形成光 电流和光电压， 实现光电转换，外接负载 16时，可对其进行供电。在此过程中， 聚 4,4-二辛基-环戊二烯 (2,l-b:3,4-b，)二噻。分 -2,3-双（苯基 )喹喔啉由于其具有很 宽的光谱响应范围， 能够更充分地利用光能， 以获得更高的光电转换效率， 增 加太阳能电池器件的产电能力。 而且这种有机材料还能减轻太阳能电池器件的 质量， 并通过旋涂等技术即可制作， 便于大批量的制备。
应用实施例 6
以聚 4,4-二辛基-环戊二烯 (2,l-b:3,4-b，)二噻。分 -2,3-双（苯基 )喹喔啉在有机 电致发光器件中应用：
请参阅图 2,显示采用上述实施例中的聚 4,4-二辛基-环戊二烯 (2,l-b:3,4-b，) 二噻。分 -2,3-双（苯基）喹喔啉的有机电致发光器件， 其包括依次层叠设置的玻 璃基层 21、 透明阳极 22、 发光层 23、 緩冲层 24、 阴极 25。 透明阳极 22可采 用氧化铟锡（简称为 ITO ) , 优选为方块电阻为 10-20 Ω/ 的氧化铟锡。 发光层 23 包含上述实施例中的聚 4,4-二辛基-环戊二烯 (2,l-b:3,4-b，)二噻吩 -2,3-双（苯 基）喹喔啉。 緩冲层 24可采用 LiF等， 但不限于此。 阴极 25可以是但不限于 金属 A1或 Ba等， 但不限于此。 因而， 在一个具体实施例中， 有机电致发光器 件结构表示为： ITO/聚 4,4-二辛基-环戊二烯 (2,l-b:3,4-b，)二噻。分 -2,3-双（苯基 ) 喹喔啉 /LiF/Al。 各层可采用现有方法形成， 而聚 4,4-二辛基-环戊二烯 (2,l-b:3,4-b，)二噻吩 -2,3-双（苯基）喹喔啉可通过旋涂技术形成于 ITO上。
应用实施例 7
以聚 4,4-二辛基-环戊二烯 (2,l-b:3,4-b，)二噻。分 -2,3-双（苯基 )喹喔啉在有机 场效应晶体管中应用：
请参阅图 3 ,显示采用上述实施例中的聚 4,4-二辛基-环戊二烯 (2,l-b:3,4-b，) 二噻。分 -2,3-双（苯基）喹喔啉的有机场效应晶体管， 其包括依次层叠设置的衬 底 31、 绝缘层 32、 修饰层 33、 有机半导体层 34以及设于有机半导体层 34上 的源电极 35和漏电极 36。 其中， 衬底 31可以是但不限于高掺杂的硅片 （Si ) , 绝缘层 32可以是但不限于微纳米（如 450 nm )厚的 Si02。 有机半导体层 34采 用上述描述的聚 4,4-二辛基-环戊二烯 (2,l-b:3,4-b，)二噻吩 -2,3-双（苯基）喹喔啉。 源电极 35和漏电极 36均可采用但不限于金。修饰层 33可以是但不限于十八烷 基三氯硅烷。 衬底 31、 绝缘层 32、 修饰层 33以及源电极 35和漏电极 36都可 采用现有的方法形成。有机半导体层 34可以是将上述实施例中的聚 4,4-二辛基 -环戊二烯 (2,l-b:3,4-b，)二噻吩 -2,3-双（苯基）喹喔啉旋涂于由修饰层 33修饰的 绝缘层 32上。
以上所述仅为本发明的较佳实施例而已， 并不用以限制本发明， 凡在本发 明的精神和原则之内所作的任何修改、 等同替换和改进等， 均应包含在本发明 的保护范围之内。

Claims

权 利 要 求 书
1. 一种环戊二 述 ( I ):
Figure imgf000015_0001
其中， x+y=l , 0.5<χ<1 , n为小于 100的正整数， 为（^〜02。的烷基； R2、 R3、 R4、 R5为相同或者不同的基团， 该基团选自 H、 〜C2。的烷基或烷氧基、 含烷基芴基团、 含烷基吡咯基团、 含烷基苯环基团。
2、 根据权利要求 1所述的环戊二烯二噻吩-喹喔啉共轭聚合物， 其特征在 于：
所述的含烷基芴基团结构通式为下述（ A ), 其中， R7、 R8选自 CH^o的 烷基，
Figure imgf000015_0002
所述的含烷基吡咯基团结构通式为下述（B ), 其中， R9选自 〜C2Q的烷
Figure imgf000015_0003
所述的含烷基苯环基团结构通式为下述（C ), 其中， 。为 CH^o的烷基,
Figure imgf000015_0004
( c )。
3. 一种环戊二烯二噻。分-喹喔啉共轭聚合物制备方法， 包括如下工艺步骤: 将二酮类化合物与邻苯二胺化合物加入有机溶剂中反应， 制得喹喔啉类杂 芳环的二溴代物； 将所述喹喔啉类杂芳环的二溴代物与 4,4-二烷基 -2,6-双三曱基锡-环戊二烯 (2,l-b:3,4-b，)二噻。分化合物、 4,4-二烷基 -2,6-二溴-环戊二烯 (2,l-b:3,4-b，)二噻。分化 合物进行 stille耦合反应， 制得所述环戊二烯二噻吩-喹喔啉共轭聚合物。
4. 根据权利要求 3 所述的环戊二烯二噻吩-喹喔啉共轭聚合物制备方法， 其特征在于： 所述的喹喔啉类杂芳环的二溴代物制备步骤和 /或 stille耦合反应 制备步骤是在无氧的条件下进行。
5. 根据权利要求 3 所述的环戊二烯二噻吩-喹喔啉共轭聚合物制备方法， 其特征在于： 所述的喹喔啉类杂芳环的二溴代物制备是将二酮类化合物与邻苯 二胺类化合物按摩尔比 1 ： 0.1〜10加入有机溶剂， 然后在 20°C〜120°C下反应 1〜24 h;
所述的有机溶剂为乙酸、 间曱苯酚、 曱醇、 乙醇或丁醇中的至少一种。
6. 根据权利要求 3 所述的环戊二烯二噻吩-喹喔啉共轭聚合物制备方法， 其特征在于： 所述的 stille耦合反应是将 4, 4-二烷基 -2,6-双三曱基锡-环戊二烯 (2,l-b:3,4-b，)二噻吩、 4,4-二烷基 -2,6-二溴-环戊二烯 (2,l-b:3,4-b，)二噻吩与喹喔啉 类杂芳环的二溴代物按摩尔比 1 ： 1〜100 ： 1 加入有机反应溶剂中， 然后在 50°C〜150°C下反应 24〜72 h; 所述的有机反应溶液为四氢呋喃、 乙二醇二曱醚、 苯、 曱苯中的至少一种。
7. 根据权利要求 3 所述的环戊二烯二噻吩-喹喔啉共轭聚合物制备方法， 其特征在于： 所述的 stille耦合反应中还添加有催化剂， 所述的催化剂为有机钯 催化剂或有机钯催化剂与有机膦配体的混合物， 所述的催化剂的添加量是 4,4- 二烷基 -2,6-双三曱基锡-环戊二烯 (2,l-b:3,4-b，)二噻。分摩尔的 0.05 ~ 50%。
8. 根据权利要求 7 所述的环戊二烯二噻吩-喹喔啉共轭聚合物制备方法， 其特征在于： 所述的有机钯催化剂是 Pd2(dba)3/P(o-Tol)3 、 Pd(PPh3)4 或 Pd(PPh3)2Cl2;
9. 根据权利要求 8 所述的环戊二烯二噻吩-喹喔啉共轭聚合物制备方法， 其特征在于： 所述的有机钯催化剂与有机膦配体的混合摩尔配比为 1:2〜20。
10. 根据权利要求 1所述的环戊二烯二噻吩-喹喔啉共轭聚合物在有机光电 材料、 聚合物太阳能电池、 有机电致发光器件、 有机场效应晶体管、 有机光存 储器件、 有机非线性材料或 /和有机激光器件中的应用。
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102827357A (zh) * 2012-08-30 2012-12-19 西安近代化学研究所 双噻吩并环戊二烯-氟代喹喔啉共轭聚合物
JP2015518497A (ja) * 2012-03-16 2015-07-02 メルク パテント ゲーエムベーハー 共役ポリマー
CN114316216A (zh) * 2021-11-17 2022-04-12 厦门华厦学院 基于含二噻吩并喹喔啉母体为中心的对称型聚合物及柔性电致变色器件
CN115594828A (zh) * 2022-09-30 2023-01-13 武汉工程大学（Cn） 一种卤代环戊二噻吩聚合物及其制备方法和在光伏器件中的应用

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102770476B (zh) * 2010-05-18 2014-02-05 海洋王照明科技股份有限公司 一种含喹喔啉单元卟啉共聚物及其制备方法和应用
CN104744676B (zh) * 2015-03-30 2017-04-05 华南理工大学 含7H–吡咯并[3,4–g]喹喔啉–6,8–二酮的共轭聚合物及应用
GB2554422A (en) * 2016-09-27 2018-04-04 Sumitomo Chemical Co Organic microcavity photodetectors with narrow and tunable spectral response
CN109081917B (zh) * 2018-10-10 2020-11-10 上海交通大学 一种二维聚苯环桥接吡咯及其制备方法
CN113831511B (zh) * 2021-09-08 2022-09-27 南方科技大学 一种含有二噻吩[3，2-f：2’，3’-h]喹喔啉的聚合物及其制备方法与应用
CN114874418B (zh) * 2022-04-24 2023-12-19 广东聚石科技研究有限公司 基于三氟甲基取代喹喔啉的共轭聚合物及其制备方法和应用
CN115286644B (zh) * 2022-08-12 2023-09-01 电子科技大学 含[1,2,5]噻二唑[3,4-g]喹喔啉结构的有机光电小分子及其制备方法和应用
CN116425769B (zh) * 2023-04-18 2024-04-05 天津大学 一种含二甲胺侧链的醌式小分子及其制备方法和在太阳能电池器件中的应用

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1663981A (zh) * 2003-12-08 2005-09-07 三星电子株式会社 主链中含有喹喔啉环的用于有机薄膜晶体管的有机半导体聚合物

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101069519B1 (ko) * 2004-07-08 2011-09-30 삼성전자주식회사 올리고티오펜과 ｎ-형 방향족 화합물을 주쇄에 교호로 포함하는 유기 반도체 고분자
US7781673B2 (en) * 2005-07-14 2010-08-24 Konarka Technologies, Inc. Polymers with low band gaps and high charge mobility
US20080262183A1 (en) * 2007-04-17 2008-10-23 Lutz Uwe Lehmann Dithienopyrrole-containing copolymers
JP5190784B2 (ja) * 2008-08-08 2013-04-24 株式会社リコー 重合体
JP5723784B2 (ja) * 2008-12-18 2015-05-27 アイメックＩｍｅｃ 有機電子デバイスに使用する有機層の結晶性ナノファイバ含有率を制御する方法
JP5664200B2 (ja) * 2009-12-16 2015-02-04 東レ株式会社 共役系重合体、これを用いた電子供与性有機材料、光起電力素子用材料および光起電力素子
WO2011112701A1 (en) * 2010-03-09 2011-09-15 Konarka Technologies, Inc. Photovoltaic module containing buffer layer
JP5634530B2 (ja) * 2010-03-15 2014-12-03 ▲海▼洋王照明科技股▲ふん▼有限公司 有機太陽電池及びその製造方法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1663981A (zh) * 2003-12-08 2005-09-07 三星电子株式会社 主链中含有喹喔啉环的用于有机薄膜晶体管的有机半导体聚合物

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
ARGIRI TSAMI: "Two Novel Cyclopentadithiophene-Based Alternating Copolymers as Potential Donor Components for High-Efficiency Bulk-Heterojunction-Type Solar", CELLS. CHEM. MATER., vol. 20, no. 12, 2008, pages 4045 - 4050, XP002541043 *
LIEVEN DE CREMER: "Chiroptical Properties of Cyclopentadithiophene-Based Conjugated Polymers", MACROMOLECULES, vol. 41, no. 3, 2008, pages 591 - 598, XP008166521 *
See also references of EP2548909A4 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015518497A (ja) * 2012-03-16 2015-07-02 メルク パテント ゲーエムベーハー 共役ポリマー
JP2017137496A (ja) * 2012-03-16 2017-08-10 メルク パテント ゲーエムベーハー 共役ポリマー
JP2018016810A (ja) * 2012-03-16 2018-02-01 メルク パテント ゲーエムベーハー 共役ポリマー
CN102827357A (zh) * 2012-08-30 2012-12-19 西安近代化学研究所 双噻吩并环戊二烯-氟代喹喔啉共轭聚合物
CN114316216A (zh) * 2021-11-17 2022-04-12 厦门华厦学院 基于含二噻吩并喹喔啉母体为中心的对称型聚合物及柔性电致变色器件
CN115594828A (zh) * 2022-09-30 2023-01-13 武汉工程大学（Cn） 一种卤代环戊二噻吩聚合物及其制备方法和在光伏器件中的应用

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