WO2011160302A1 - 基于苯唑二噻吩和噻吩并吡嗪的共轭聚合物及其制备方法和应用 - Google Patents

基于苯唑二噻吩和噻吩并吡嗪的共轭聚合物及其制备方法和应用 Download PDF

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WO2011160302A1
WO2011160302A1 PCT/CN2010/074454 CN2010074454W WO2011160302A1 WO 2011160302 A1 WO2011160302 A1 WO 2011160302A1 CN 2010074454 W CN2010074454 W CN 2010074454W WO 2011160302 A1 WO2011160302 A1 WO 2011160302A1
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conjugated polymer
layer
organic
compound
added
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PCT/CN2010/074454
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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 PCT/CN2010/074454 priority Critical patent/WO2011160302A1/zh
Priority to CN201080066878.5A priority patent/CN102906151B/zh
Priority to JP2013515661A priority patent/JP5638695B2/ja
Priority to EP10853445.4A priority patent/EP2586810A4/en
Priority to US13/704,687 priority patent/US20130102746A1/en
Publication of WO2011160302A1 publication Critical patent/WO2011160302A1/zh

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Definitions

  • the invention relates to the field of optoelectronics, in particular to a benzodiazepine based. And thiophene.
  • Polymer solar cells are attracting attention because of their low raw material price, light weight, flexibility, simple production process, large-area preparation by coating, printing, etc., if their energy conversion efficiency can be improved to close to commercial silicon solar cells. At the level, its market prospects will be very large. Since NS Sariciftci et al. in 1992 (N. S Sariciftci, L. Smilowitz, AJ Heeger, et al. Science, 1992, 258, 1474) reported light-induced electron transfer between a conjugated polymer and C60, People have invested a lot of research in polymer solar cells and have achieved rapid development.
  • the research of traditional polymer solar cells is mainly focused on donor and acceptor blends.
  • the energy conversion efficiency of PTB7 and PC71BM blends has reached 7.4% (Y. Liang et al., Adv. Mater.; DOI: 10.1002). /adma.200903528 ), but still much less efficient than inorganic solar cells.
  • the main limiting factors for limiting performance improvement are: relatively low carrier mobility of organic semiconductor devices, spectral response of the device does not match solar radiation spectrum, red light region of high photon flux is not effectively utilized, and carrier Electrode collection efficiency is low.
  • a conjugated polymer based on benzodiazepine and thienopyrazine having the general formula:
  • n is an integer from 1 to 100;
  • R 2 is an alkyl group of CH ⁇ o;
  • the fragrant group is any one of the following structural formulas:
  • R 5 is an alkyl group of Cr ⁇ ds or an alkoxy group of Cr ⁇ ds
  • R 6 , R 7 , and R 8 are a C 15 -alkyl group
  • Method for preparing the object including the following steps
  • n is an integer from 1 to 100;
  • R 2 is an alkyl group of ( ⁇ 0 2 .
  • R 3 and R 4 are hydrogen, an alkyl group of ( ⁇ 0 2 , an alkoxy group or an aromatic group of CH ⁇ .
  • step S11 compound C is obtained by the following steps:
  • the solvent is one or more selected from the group consisting of decyl alcohol, ethanol and ethyl acetate; wherein the weak base is one or two selected from the group consisting of triethylamine and sodium carbonate;
  • the organic solvent is one or more selected from the group consisting of tetrahydrofuran, ethylene glycol dioxime ether, benzene, chlorobenzene or toluene; the reaction temperature is 60 to 130 ° C, and the reaction time is 24 ⁇ 72 hours; the catalyst is added in an amount of 0.05 to 50% by mole of the compound A; the catalyst is an organic palladium or a mixture of an organic palladium and an organophosphine ligand; and a mixture of an organic palladium and an organophosphine ligand, an organic palladium and an organic phosphine
  • the molar ratio of the body is 1: 2 ⁇ 1: 20; the organic palladium is Pd 2 (dba) 3 , Pd(PPh 3 ) 4 or Pd(PPh 3 ) 2 Cl 2 ; the organic phosphine ligand is P (o-Tol) 3 ; The molar ratio of the organic palladium
  • the method for preparing a conjugated polymer further comprises a purification process after the conjugated polymer is obtained, and the specific steps are as follows:
  • the conjugated polymer is added dropwise to decyl alcohol, subjected to sedimentation treatment, and then suction filtration, decyl alcohol washing, and drying to obtain a conjugated polymer-containing colloid;
  • a solar cell device prepared by using the above conjugated polymer, comprising a substrate, a conductive layer deposited on one surface of the substrate as an anode, and a modified poly 3,4-Asia coated on the conductive layer Ethylenedioxythiophene: a polystyrene sulfonic acid layer, an active layer coated on the surface of poly 3,4-ethylenedioxythiophene: polystyrenesulfonic acid layer, and a metal disposed on the surface of the active layer as a cathode
  • the aluminum layer; the active layer is made of a mixture, including an electron donor material and an electron acceptor material; the electron acceptor material is [6,6]phenyl-C 61 -butyrate butyrate, and the electron donor material contains the above-mentioned benzene-based
  • a conjugated polymer comprising a substrate, a conductive layer deposited on one surface of the substrate as an anode, and a modified poly 3,4-Asi
  • An organic electroluminescent device prepared by the above conjugated polymer, comprising a substrate, a conductive layer deposited on one surface of the substrate as an anode, a light-emitting layer coated on the conductive layer, and vacuum-evaporated in the light-emitting layer a buffer layer made of LiF on the layer, and a metal aluminum layer as a cathode provided on the buffer layer, and the light-emitting layer material contains the above-mentioned conjugated polymer based on benzodiazepine and thienopyrazine.
  • An organic field effect transistor prepared by the above conjugated polymer the structure of which comprises: a doped silicon wafer, a Si0 2 insulating layer, an octadecyltrichlorosilane layer for modifying the Si0 2 insulating layer, coated on ten
  • the organic semiconductor layer on the octadecyltrichlorosilane layer is provided at a source electrode and a drain electrode which are disposed on the organic semiconductor layer, and the organic semiconductor layer material contains the above conjugated polymer based on benzodiazepine and thienopyrazine.
  • Oxazole dithiophene has a rigid crystal structure in which two thiophene rings in the structural unit are on the same plane. This structure can effectively extend the conjugate properties of the polymer and reduce the bandwidth of the polymer. Moreover, this coplanar structure makes it easier to transfer carriers between the two main chains, thereby increasing carrier mobility.
  • Thienopyrazine is a receptor unit having an excellent planar structure, containing a five-membered ring and a six-membered ring skeleton, and has intramolecular charge transfer properties and excellent electrochemical reduction properties.
  • the conjugated polymer based on benzoxyldithiophene and thienopyrazine combines the advantages of two units, has high carrier mobility and excellent electrochemical reduction properties, and has high photoelectric conversion efficiency.
  • FIG. 1 is a schematic structural view of an embodiment of a solar cell device
  • FIG. 2 is a schematic structural view of an embodiment of an organic electroluminescent device
  • FIG. 3 is a schematic structural view of an embodiment of an organic field effect transistor. ⁇ detailed description ⁇
  • the object of the present invention is to provide a conjugated polymer based on benzodiazepine and thienopyrazine and a preparation method thereof, and to point out the application of the conjugated polymer material in the field of optoelectronics.
  • a conjugated polymer based on benzodiazepine and thienopyrazine having the general formula:
  • n is an integer from 1 to 100;
  • R 2 is an alkyl group of CH ⁇ o;
  • R 5 is an alkyl group of Cr ⁇ ds or an alkoxy group of Cr ⁇ ds
  • R 6 , R 7 , and R 8 are a C 15 -alkyl group
  • a conjugate polymerization based on benzoxyldithiophene and thienopyrazine Prepared by the following method: Step one
  • the solvent is one or more selected from the group consisting of decyl alcohol, ethanol and ethyl acetate; wherein the weak base is one or two selected from the group consisting of triethylamine and sodium carbonate;
  • Compound F was added to a mixture of chloroform and acetic acid at 0 to 70 ° C, and then n-bromosuccinyl group was added for 48 hours to obtain a compound C of the following formula:
  • n is an integer from 1 to 100;
  • R 2 is an alkyl group of ( ⁇ 0 2 .
  • R 3 and R 4 are selected from hydrogen and ⁇ C 2 .
  • R 5 is an alkyl group of Cr ⁇ ds or an alkoxy group of Cr ⁇ ds
  • R 6 , R 7 and R 8 are an alkyl group of ⁇ C 15 ;
  • the organic solvent is one or more selected from the group consisting of tetrahydrofuran, ethylene glycol dioxime ether, benzene, chlorobenzene or toluene; the reaction temperature is 60 to 130 ° C, and the reaction time is 24 to 72 hours;
  • the molar ratio of the compound A is 0.05 to 50%;
  • the catalyst is an organic palladium or a mixture of an organic palladium and an organophosphine ligand; and the mixture of the organic palladium and the organophosphine ligand has a molar ratio of the organic palladium to the organophosphine ligand: 2 ⁇ 1: 20; organic palladium is Pd 2 (dba) 3 , Pd(PPh 3 ) 4 or Pd(PPh 3 ) 2 Cl 2 ; organic phosphine ligand is P(o-Tol) 3 ; organic palladium and organophosphine In the mixture of ligands, the molar
  • the obtained conjugated polymer is added dropwise to decyl alcohol, subjected to sedimentation treatment, followed by suction filtration, decyl alcohol washing, and drying to obtain a colloid containing a conjugated polymer ruthenium;
  • the colloid containing the conjugated polymer is dissolved in toluene, and the toluene solution is added to the aqueous solution of sodium diethyldithiocarbamate, heated and stirred at 80 to 100 ° C, and passed through the alumina column. After chromatography, the conjugated polymer P is separated, and the chlorobenzene is rinsed, and the organic solvent is removed under reduced pressure;
  • step A Repeat step A at least once, and finally extract the separated conjugated polymer with acetone Soxhlet to obtain a conjugated polymer solid.
  • the mixture was heated under reflux for 3 days to obtain a conjugated polymer solution.
  • the conjugated polymer solution was added dropwise to methanol to carry out sedimentation treatment, followed by suction filtration and drying to obtain a colloid containing a conjugated polymer.
  • the colloid containing the conjugated polymer is dissolved in toluene, and the solution of the toluene is added to an aqueous solution of sodium diethyldithioaminosulfonium S. sodium, heated and stirred at 90 ° C, and subjected to alumina column chromatography.
  • the conjugated polymer was separated, and the chlorobenzene was rinsed, and then the organic solvent was removed under reduced pressure.
  • the obtained conjugated polymer was added to a decyl alcohol to carry out sedimentation, followed by suction filtration, decyl alcohol washing, and drying, and then sorbing the conjugated polymer with acetone to obtain a conjugated polymer solid of 0.23 g, a yield of 66%.
  • the colloid of the yoke polymer is dissolved in toluene, and the toluene solution is added to an aqueous solution of sodium diethyldithiocarbamate, heated and stirred at 90 ° C, and subjected to alumina column chromatography to separate the conjugate.
  • the polymer, chlorobenzene was rinsed, and the organic solvent was removed under reduced pressure.
  • the obtained conjugated polymer was added to decyl alcohol to carry out sedimentation, followed by suction filtration, decyl alcohol washing, and drying, and the conjugated polymer was Soxhlet extracted with acetone to obtain 0.21 g of a conjugated polymer solid in a yield of 51%.
  • the benzene solution is added to an aqueous solution of sodium diethyldithiocarbamate, heated and stirred at 90 ° C, and then subjected to alumina column chromatography to separate the conjugated polymer, chlorobenzene After washing, the organic solvent was removed under reduced pressure.
  • the colloid containing the conjugated polymer is dissolved in In toluene, the toluene solution is added to an aqueous solution of sodium diethyldithiocarbamate, heated and stirred at 90 ° C, and then subjected to alumina column chromatography to separate the conjugated polymer, and the chlorobenzene is rinsed. The organic solvent was removed under reduced pressure.
  • the obtained conjugated polymer was added to a decyl alcohol to carry out sedimentation, followed by suction filtration, decyl alcohol washing, and after drying, the conjugated polymer was Soxhlet extracted with acetone to obtain 0.29 g of a conjugated polymer solid in a yield of 66%.
  • the colloid containing the conjugated polymer is dissolved in toluene, and the toluene solution is added to an aqueous solution of sodium diethyldithiocarbamate, heated and stirred at 80 ° C, and separated by alumina column chromatography.
  • the conjugated polymer was eluted, and the organic solvent was removed under reduced pressure after washing with chlorobenzene. Will get together
  • the conjugated polymer was added to decyl alcohol for sedimentation, followed by suction filtration, decyl alcohol washing, and after drying, the conjugated polymer was Soxhlet extracted with acetone to obtain 0.33 g of a conjugated polymer solid in a yield of 62%.
  • the conjugated polymer was eluted, and the organic solvent was removed under reduced pressure after washing with chlorobenzene.
  • the obtained conjugated polymer was added to a decyl alcohol to carry out sedimentation, followed by suction filtration, decyl alcohol washing, and drying, and then sorbing the conjugated polymer with acetone to obtain a conjugated polymer solid of 0.17 g in a yield of 48%.
  • the colloid containing the conjugated polymer is dissolved in toluene, and the toluene solution is added to an aqueous solution of sodium diethyldithiocarbamate, heated and stirred at 100 ° C, and separated by alumina column chromatography.
  • the conjugated polymer was eluted, and the organic solvent was removed under reduced pressure after washing with chlorobenzene.
  • the obtained conjugated polymer was added to a decyl alcohol to carry out sedimentation, followed by suction filtration, decyl alcohol washing, and drying, and then sorbing the conjugated polymer with acetone to obtain a conjugated polymer solid of 0.41 g, a yield of 62%.
  • the colloid containing the conjugated polymer is dissolved in toluene, and the toluene solution is added to an aqueous solution of sodium diethyldithiocarbamate, heated and stirred at 100 ° C, and separated by alumina column chromatography.
  • the conjugated polymer was eluted, and the organic solvent was removed under reduced pressure after washing with chlorobenzene.
  • the separated conjugated polymer was added to decyl alcohol to carry out sedimentation, followed by suction filtration, decyl alcohol washing, and after drying, the conjugated polymer was Soxhlet extracted with acetone to obtain 0.41 g of a conjugated polymer solid in a yield of 53%.
  • the reaction was heated under reflux at 80 ° C for 72 hours to obtain a conjugated polymer solution.
  • the conjugated polymer solution was added dropwise to methanol to carry out sedimentation treatment, followed by suction filtration and drying to obtain a colloid containing a conjugated polymer.
  • the colloid containing the conjugated polymer is dissolved in toluene, and the toluene solution is added to an aqueous solution of sodium diethyldithiocarbamate, heated and stirred at 80 ° C, and separated by alumina column chromatography.
  • the conjugated polymer was eluted, and the organic solvent was removed under reduced pressure after washing with chlorobenzene.
  • the obtained conjugated polymer was added to decyl alcohol to carry out sedimentation, followed by suction filtration, decyl alcohol washing, and drying, and then sorbing the conjugated polymer with acetone to obtain 0.23 g of a conjugated polymer solid in a yield of 60%.
  • the colloid containing the conjugated polymer is dissolved in toluene, and the toluene solution is added to an aqueous solution of sodium diethyldithiocarbamate, heated and stirred at 80 ° C, and separated by alumina column chromatography.
  • the conjugated polymer was eluted, and the organic solvent was removed under reduced pressure after washing with chlorobenzene.
  • the separated conjugated polymer was added to decyl alcohol to carry out sedimentation, followed by suction filtration, decyl alcohol washing, and after drying, the conjugated polymer was Soxhlet extracted with acetone to obtain 0.27 g of a conjugated polymer solid, and the yield was 64%.
  • Molecular weight GPS, THF, R.
  • bismuth glass indium tin oxide glass
  • yttrium indium tin oxide
  • the structure of the solar cell device is: glass / ITO / PEDOT: PSS / active layer / A1; wherein the active layer is made of a mixture comprising [6,6] phenyl-C 61 -butyrate butyrate Electron donor material and An electron acceptor material based on a conjugated polymer of benzodiazepine and thienopyrazine; ITO is indium tin oxide having a sheet resistance of 10-20 ⁇ / ⁇ ? £00 is poly 3,4-ethylenedioxythiophene and PSS is polystyrenesulfonic acid.
  • the manufacturing process of the solar cell device is as follows:
  • the active layer material comprises an electron donor material based on [6,6]phenyl-C 61 -butyrate butyrate and based on
  • the conjugated polymer of benzodiazepine and thienopyrazine is an electron acceptor material of the material;
  • Metal aluminum was vacuum-deposited on the surface of the active layer to form a metal aluminum layer as a cathode to obtain the organic solar cell device.
  • the thickness of the metal aluminum layer is 170 nm, respectively. In other embodiments, the thickness of the metal aluminum layer may also be 30 nm, 130 nm, or 60 nm.
  • the ITO conductive layer is used as an anode, and the solar cell is subjected to a sealing condition of 110 degrees Celsius for 4 hours, and then cooled to room temperature. After annealing, the device can effectively increase the order among the groups and molecular segments in the molecule. Sex and regularity, improve the transmission speed and efficiency of carrier mobility, and thus improve the photoelectric conversion efficiency.
  • ITO glass indium tin oxide glass
  • ITO indium tin oxide
  • the structure of the organic electroluminescent device is: glass / ITO / luminescent layer / buffer layer / A1; wherein, the luminescent layer is a conjugated polymer based on benzodiazepine and thienopyrazine; the buffer layer is made of LiF ITO is indium tin oxide having a sheet resistance of 10-20 ⁇ / ⁇ , PEDOT is poly 3,4-ethylenedioxythiophene, and PSS is polystyrene.
  • the manufacturing process of the organic electroluminescent device is as follows:
  • a conjugated polymer based on benzodiazepine and thienopyrazine is coated on the surface of the ITO to form a light-emitting layer;
  • the thickness of the metal aluminum layer is 170 nm, respectively. In other embodiments, the thickness of the metal aluminum layer may also be 30 nm, 130 nm, and 60 nm. In this embodiment, the ITO conductive layer serves as an anode.
  • Example 7
  • An organic field effect transistor has a structure as shown in Figure 3.
  • a highly doped silicon wafer is used as the substrate.
  • the structure of the organic field effect transistor is: Si/Si0 2 /OTS/organic semiconductor layer/source electrode (S) and drain electrode (D); wherein, Si0 2 has a thickness of 450 nm for insulation; OTS is octadecane a trichlorosilane; the organic semiconductor layer is a conjugated polymer based on benzodiazepine and thienopyrazine; the source electrode (S) and the drain electrode (D) are made of metal gold, and in other embodiments, the source The electrode (S) and the drain electrode (D) can also be made of copper.
  • a source electrode and a drain electrode made of a metal gold are provided on the organic semiconductor layer to obtain the organic field effect transistor.

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Description

基于苯唑二噻吩和噻吩并吡嗪的共轭聚合物及其制备方法和应用
【技术领域】
本发明涉及光电领域, 尤其涉及一种基于苯唑二噻。分和噻。分并吡嗪的共轭 聚合物及其制备方法和应用。
【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。 传统的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等在 SCIENCE ( N. S Sariciftci, L. Smilowitz, A. J. Heeger, et al. Science, 1992, 258, 1474 )上报道共轭聚合物与 C60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。
传统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 PTB7 与 PC71BM共混体系的能量转化效率已经达到 7.4%( Y. Liang et al., Adv. Mater.; DOI: 10.1002/adma.200903528 ), 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, 器件的光谱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】
基于此, 有必要提供一种光电转换效率高的基于苯唑二噻吩和噻吩并吡嗪 的共轭聚合物。 此外, 还有必要提供一种该光电转换效率高的基于苯唑二噻吩和噻吩并吡 嗪的共轭聚合物制备方法, 并指出该共轭聚合物在光电领域的应用。
一种基于苯唑二噻吩和噻吩并吡嗪的共轭聚合物, 通式如下:
Figure imgf000004_0001
其中, x+y=2, 0<y<l , n为 1 ~ 100的整数; R2为 CH^o的烷基; R: 为氢、 CH^o的烷基、 CH^o的烷氧基或芳香基团。
优选的, 香基团为如下结构式中的任一种:
Figure imgf000004_0002
其中, R5为 Cr^ds的烷基或 Cr^ds的烷氧基, R6、 R7、 R8为 〜C15的烷 一种基于苯唑二噻吩和噻吩并吡嗪的共轭聚合物的制备方法, 包括如下步
Sll、 分别提供如下结构式表示的化合物 A、 B、 C :
Figure imgf000004_0003
S12、 在无水无氧环境下, 有机溶剂和催化剂存在条件下, 将化合物 、 B、 C混合, 按如下反应方程式进行 Stille偶合反应:
Figure imgf000005_0001
Stille反应
Figure imgf000005_0002
其中, m=i+j, 0<i<m; 得到如下结构式表示的共轭聚合物:
Figure imgf000005_0003
其中, x+y=2, 0<y<l, n为 1 ~ 100的整数;
Ri、 R2为(^〜02。的烷基;
R3、 R4为氢、 (^〜02。的烷基、 CH^。的烷氧基或芳香基团
上述芳香 如下结构式中的任一种:
Figure imgf000005_0004
其中, R5为 Cr^ds的烷基或 Cr^ds的烷氧基, R6、 R7、 R8为 〜C15的烷 优选的, 步骤 S11中, 化合物 C由如下步骤制得:
分别提供结构式如下的化合物 D和 E:
D:
Figure imgf000005_0005
在 0~78°C下, 按化合物 D与化合物 E摩尔比满足 1: 0.1 - 1: 10将两者混 合溶解在溶剂中, 按化合物摩尔数的 2~50倍加入弱碱后反应 1 ~24小时, 得 到结构式如下的化合物 F:
3
Figure imgf000006_0001
其中, 所述溶剂为选自曱醇、 乙醇和乙酸乙酯中的一种或几种; 其中, 所 述弱碱为选自三乙胺和碳酸钠中的一种或两种;
在 0 ~ 70 °C下,将化合物 F加入到氯仿和乙酸的混合液中,再加入 n-溴代丁 二酰 ~ 48小时后得到结构式如下的化合物 C:
Figure imgf000006_0002
优选的, 步骤 S 12 中, 有机溶剂为选自四氢呋喃、 乙二醇二曱醚、 苯、 氯 苯或曱苯中的一种或几种; 反应温度为 60〜130 °C , 反应时间为 24〜72小时; 催 化剂加入量为化合物 A摩尔数的 0.05 ~ 50%; 催化剂为有机钯或有机钯和有机 膦配体的混合物; 有机钯和有机膦配体的混合物中, 有机钯和有机膦配体的摩 尔比范围为 1 : 2〜1: 20; 有机钯为 Pd2(dba)3、 Pd(PPh3)4或 Pd(PPh3)2Cl2; 有机 膦配体为 P(o-Tol)3; 有机钯和有机膦配体的混合物中, 有机钯和有机膦配体的 摩尔比范围为 1 : 2〜1: 20。
在优选的实施例中, 共轭聚合物的制备方法还包括得到所述共轭聚合物后 的纯化过程, 具体步骤如下:
513、 将所述共轭聚合物滴加到曱醇中, 进行沉降处理, 然后抽滤, 曱醇洗 涤, 干燥, 得到含共轭聚合物的胶体;
514、 将含共轭聚合物的胶体溶解于曱苯中, 并将该曱苯溶液加入到二乙基 二硫代氨基曱酸钠的水溶液中, 80 ~ 100 °C加热搅拌后过氧化铝柱层析, 分离出 共轭聚合物, 氯苯淋洗后减压除去有机溶剂;
515、 重复步骤 S 13至少一次, 并用丙酮索氏提取步骤 S 14中分离出来的共 轭聚合物, 得到共轭聚合物固体。 一种采用上述共轭聚合物制备的太阳能电池器件, 包括衬底, 沉积在衬底 一个表面上的、作为阳极的导电层,涂覆在导电层上的起修饰作用的聚 3,4-亚乙 二氧基噻吩: 聚苯乙烯磺酸层, 涂覆在聚 3,4-亚乙二氧基噻吩: 聚苯乙烯磺酸层 表面的活性层, 以及设置在活性层表面、 作为阴极的金属铝层; 活性层的材质 为混合物, 包括电子给体材料和电子受体材料; 电子受体材料为 [6,6]苯基 -C61 - 丁酸曱酯, 电子给体材料含上述基于苯唑二噻吩和噻吩并吡嗪的共轭聚合物。
一种上述共轭聚合物制备的有机电致发光器件, 包括衬底, 沉积在衬底的 一个表面上的、 作为阳极的导电层, 涂覆在导电层上的发光层, 真空蒸镀在发 光层上的以 LiF 为材质的緩冲层, 以及设置在緩冲层上的、 作为阴极的金属铝 层, 发光层材料含上述基于苯唑二噻吩和噻吩并吡嗪的共轭聚合物。
一种上述共轭聚合物制备的有机场效应晶体管, 其结构依次包括: 掺杂硅 片, Si02绝缘层, 用于修饰 Si02绝缘层的十八烷基三氯硅烷层, 涂覆在十八烷 基三氯硅烷层上的有机半导体层, 间隔设置在有机半导体层上的源电极和漏电 极, 有机半导体层材料含上述基于苯唑二噻吩和噻吩并吡嗪的共轭聚合物。
苯唑二噻吩具有刚性的晶体结构——它的结构单元中的两个噻吩环在同一 个平面上。 这种结构可以有效延长聚合物的共轭性能, 降低聚合物的带宽。 并 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, 从而增加了 载流子迁移率。
噻吩并吡嗪是一种具有优良的平面结构, 含有一个五元环和六元环骨架的 受体单元, 并且具有分子内电荷转移性质, 优异的电化学还原性质。
该基于苯唑二噻吩和噻吩并吡嗪的共轭聚合物集合了两个单元的优势, 具 有较高的载流子迁移率和优异的电化学还原性质, 光电转换效率高。
【附图说明】
图 1为太阳能电池器件一实施例的结构示意图;
图 2为有机电致发光器件一实施例的结构示意图;
图 3为有机场效应晶体管一实施例的结构示意图。 【具体实施方式】
本发明的目的在于提供一种基于苯唑二噻吩和噻吩并吡嗪的共轭聚合物及 其制备方法, 并指出了该共轭聚合物材料在光电领域的应用。
一种基于苯唑二噻吩和噻吩并吡嗪的共轭聚合物, 通式如下:
Figure imgf000008_0001
其中, x+y=2, 0<y<l, n为 1 ~ 100的整数; R2为 CH^o的烷基; R: 为选自氢、 o的烷基、 CH^o的烷氧基或是下述结构单元中的一种:
Figure imgf000008_0002
其中, R5为 Cr^ds的烷基或 Cr^ds的烷氧基, R6、 R7、 R8为 〜C15的烷 一种基于苯唑二噻吩和噻吩并吡嗪的共轭聚合物, 由下述方法制备: 步骤一
分别提供结构式如下的化合物 D和 E:
0、 ,0
D: R3 R2; E:
Figure imgf000008_0003
在 0~78°C下, 按化合物 D与化合物 E摩尔比满足 1: 0.1 - 1: 10将两者混 合溶解在溶剂中, 按化合物摩尔数的 2~50倍加入弱碱后反应 1 ~24小时, 得 到结构式如下的化合物 F:
3
Figure imgf000008_0004
其中, 所述溶剂为选自曱醇、 乙醇和乙酸乙酯中的一种或几种; 其中, 所 述弱碱为选自三乙胺和碳酸钠中的一种或两种; 在 0 ~ 70°C下,将化合物 F加入到氯仿和乙酸的混合液中,再加入 n-溴代丁 二酰 ~ 48小时后得到结构式如下的化合物 C:
Figure imgf000009_0001
步骤二
分别提供如下结构式表示的化合物 A、 B、 C :
A:
Figure imgf000009_0002
在无水无氧环境下, 有机溶剂和催化剂存在条件下, 将化合物 、 B、 C混 合, 按如下反应方程式进行 Stille偶合反应:
Figure imgf000009_0003
Stille反应
Figure imgf000009_0004
其中, m=i+j , 0<i<m; 得到如下结构式表示的共轭聚合物:
Figure imgf000009_0005
其中, x+y=2, 0<y<l , n为 1 ~ 100的整数;
Ri、 R2为(^〜02。的烷基;
R3、 R4为选自氢、 〜C2。的烷基、 CH^o的烷氧基或芳香基团
上述芳香基团为如下结构式中的任一种:
Figure imgf000010_0001
其中, R5为 Cr^ds的烷基或 Cr^ds的烷氧基, R6、 R7、 R8为 〜C15的烷 基;
有机溶剂为选自四氢呋喃、 乙二醇二曱醚、 苯、 氯苯或曱苯中的一种或几 种; 反应温度为 60〜130°C , 反应时间为 24〜72小时; 催化剂加入量为化合物 A 摩尔数的 0.05 ~ 50%;催化剂为有机钯或有机钯和有机膦配体的混合物;有机钯 和有机膦配体的混合物中, 有机钯和有机膦配体的摩尔比范围为 1 : 2〜1: 20; 有机钯为 Pd2(dba)3、 Pd(PPh3)4或 Pd(PPh3)2Cl2; 有机膦配体为 P(o-Tol)3; 有机钯 和有机膦配体的混合物中, 有机钯和有机膦配体的摩尔比范围为 1 : 2〜1: 20。
步骤三
Α、 将得到的上述共轭聚合物滴加到曱醇中, 进行沉降处理, 然后抽滤, 曱 醇洗涤, 干燥, 得到含共轭聚合物 Ρ的胶体;
Β、 将含共轭聚合物的胶体溶解于曱苯中, 并将该曱苯溶液加入到二乙基二 硫代氨基曱酸钠的水溶液中, 80 ~ 100°C加热搅拌后过氧化铝柱层析, 分离出共 轭聚合物 P, 氯苯淋洗后减压除去有机溶剂;
C、 重复步骤 A至少一次, 最后用丙酮索氏提取分离出的共轭聚合物, 得到 共轭聚合物固体。
下面结合具体实施例对本发明公开的共轭聚合物及其制备方法和应用作进 一步的说明。 实施例 1
本实施例公开了 4,5-二烷基取代苯唑 [2,1 -b:3,4-b']二噻吩 -2,3-双苯基-噻吩并 [3,4-b]吡嗪类共轭聚合物, 结构式如下:
Figure imgf000011_0001
上述聚合物的制备过程如下:
一、 结构式如下的化合物的制备
Figure imgf000011_0002
以化合物 2,3- 苯基-噻吩并 [3,4-b]吡嗪的制备为例予以说明, 制备过程如
Figure imgf000011_0003
将 3,4-二胺基噻吩.氯化氢(1.0 g, 5.34 mmol)加入到化合物二苯基乙二酮 (1.12 g, 5.34 mmol)的无水乙醇 (100 mL)溶液中,避光条件下加入三乙胺( 1.15 g , 11 mmol )后搅拌过夜。 旋转蒸发除去溶剂后柱层析(二氯曱烷作为淋洗剂 )得 到针状固体 1.1 g , 产率 69%。 MS (EI) m/z: 288.4(M+)。
二、 结构式如下的化合物的制备
Figure imgf000012_0001
以化合物 5,7-二溴 2,3-双苯基-噻吩并 [3,4-b]吡嗪的制备为例予以说明,制备 过程如下:
将 NBS ( 0.72 g, 4 mmol )加入到含有化合物 2,3-双苯基-噻吩并 [3,4-b]吡 嗪 (0.49g, 1.7 mmol) 的 氯仿 /乙酸( v/v=l/l, 10 mL ) 的溶液中, 搅拌过夜。 将 反应液加入饱和碳酸钠溶液中, 氯仿萃取后用水洗涤, 再用无水硫酸钠干燥。 旋去溶剂, 柱层析得固体 0.42 g, 产率 55%。 MS (EI) m/z: 446 (M+)。;
三、 结构式如下的化合物的制备
Figure imgf000012_0002
按照 Macromolecules 2008, 41, 5688公开的方法制备得到了相应的产物。 以 制备 2,7-双三曱基锡 -4,5-二辛基苯唑 [2,l-b:3,4-b,]二噻吩为例予以说明:
Figure imgf000012_0003
-78 °C下将 t-BuLi(5.3 mL, 1.4 mol/L, 7.5 mmol)滴加到 4,5-二辛基苯唑
[2,l-b:3,4-b,]二噻。分 (1.03 g, 2.5)的四氢呋喃溶液( 100 mL )中, 混合液緩慢恢复 到室温后搅拌 0.5 h,再然后冷却至 -78°C ,将三曱基氯化锡(7.5 mmol, 7.5 mL ) 滴加到上述溶液中。 緩慢恢复室温, 搅拌过夜。 将上述反应液用水淬灭, 旋转 蒸发除去四氢呋喃, 再用氯仿 /水萃取, 水洗涤后无水硫酸钠干燥。 除去有机相 得到 1.1 g棕色固体, 产率 54%。 MS (MALDI) m/z: 617(M+)。
四、 基于苯唑二噻吩和噻吩并吡嗪的共轭聚合物的制备
P! ( 4,5-二辛基苯唑 [2, 1 -b: 3 ,4-b,]二噻。分 -2,3 -双苯基-噻吩并 [3 ,4-b]吡嗪类共轭 合物)
Figure imgf000013_0001
P.
在氮气保护下, 往含有化合物 5,7-二溴 2,3-双苯基-噻吩并 [3 ,4-b]吡嗪( 0.22 g, 0.5 mmol), 2,7-双三曱基锡 -4,5-二辛基苯唑 [2,l-b:3,4-b,]二噻吩 (0.37 g, 0.5 mmol)的氯苯( 20 mL )溶液中鼓泡 0.5 h 除去残留的氧气,然后加入 Pd2(dba)3 ( 0. 014 g, 0.015 mol )和 P(o-Tol)3 ( 0.0083 g, 0.027 mmol ), 再鼓泡 1 h 除去残留的 氧气。 加热回流 3 天, 得到共轭聚合物溶液。 将所述共轭聚合物溶液滴加到曱 醇中, 进行沉降处理, 然后抽滤、 干燥, 得到含共轭聚合物的胶体。 将含共轭 聚合物的胶体溶解于曱苯中, 并将该曱苯溶液加入到二乙基二硫代氨基曱 S炱钠 的水溶液中, 90°C加热搅拌后过氧化铝柱层析, 分离出共轭聚合物, 氯苯淋洗 后减压除去有机溶剂。 将得到的共轭聚合物加入到曱醇中进行沉降, 然后抽滤、 曱醇洗涤, 干燥后用丙酮索氏提取共轭聚合物, 得到共轭聚合物固体 0.23 g, 产 率 66 %。 Molecular weight ( GPC, THF, R. I): n = 43 , 500, M Mn = 2.1。
P2 ( 4,5-二辛基苯唑 [2, 1 -b: 3 ,4-b,]二噻。分 -2,3 -双苯基-噻吩并 [3 ,4-b]吡嗪类共轭 聚合物 的制备
Figure imgf000013_0002
在氮气保护下,往含有化合物 5,7-二溴 2,3-双苯基-噻吩并 [3 ,4-b]吡嗪( 0.022 g, 0.05 mmol), 2,7-二溴 -4,5-二辛基苯唑 [2,l-b:3,4-b,]二噻吩( 0.26 g, 0.45 mmol ) 和 2,7-双三曱基锡 -4,5-二辛基苯唑 [2,l-b:3,4-b,]二噻。分 (0.37 g, 0.5 mmol)的氯苯 ( 20 mL )溶液中鼓泡 0.5 h, 除去残留的氧气。 然后加入 Pd2(dba)3 ( 0.014 g, 0.015 mol )和 P(o-Tol)3 ( 0.0083 g, 0.027 mmol ),鼓泡 1 h 除去残留的氧气。 60 °C 下加热回流反应 72小时, 得到共轭聚合物溶液。 将所述共轭聚合物溶液滴加到 曱醇中, 进行沉降处理, 然后抽滤、 干燥, 得到含共轭聚合物的胶体。 将含共 轭聚合物的胶体溶解于曱苯中, 并将该曱苯溶液加入到二乙基二硫代氨基曱酸 钠的水溶液中, 90°C加热搅拌后过氧化铝柱层析, 分离出共轭聚合物, 氯苯淋 洗后减压除去有机溶剂。 将得到的共轭聚合物加入到曱醇中进行沉降, 然后抽 滤、 曱醇洗涤, 干燥后用丙酮索氏提取共轭聚合物,得到共轭聚合物固体 0.21g, 产率 51 %。 Molecular weight ( GPC, THF, R. I): Mn = 62,000, M Mn = 1.9。
P3 ( 4-曱基 -5-正十二烷基苯唑 [2,l-b:3,4-b,]二噻吩 -2,3-双苯基-噻吩并 [3,4-b] 吡嗪
Figure imgf000014_0001
P3
在氮气保护下,往含有化合物 5,7-二溴 -2-(4-正二十烷基苯基) 3-(4-正二十烷 氧基苯基 )噻吩并 [3,4-b]吡嗪( 0.51 g, 0.5 mmol)、 2,7-双三曱基锡 -4-曱基 -5-正二 十烷基苯唑 [2,l-b:3,4-b']二噻吩 (0.41 g, 0.5 mmol)的氯苯( 20 mL )溶液中鼓泡 0.5 h ,除去残留的氧气。然后加入 Pd2(dba)3 ( 0. 014 g, 0.015 mol P(o-Tol)3( 0.0083 g, 0.027 mmol ), 鼓泡 1 h 除去残留的氧气。 60°C下加热回流反应 72小时, 得到 共轭聚合物溶液。 将所述共轭聚合物溶液滴加到曱醇中, 进行沉降处理, 然后 抽滤、 干燥, 得到含共轭聚合物的胶体。 将含共轭聚合物的胶体溶解于曱苯中, 并将该曱苯溶液加入到二乙基二硫代氨基曱酸钠的水溶液中, 90 °C加热搅拌后 过氧化铝柱层析, 分离出共轭聚合物, 氯苯淋洗后减压除去有机溶剂。 得到的 共轭聚合物加入到曱醇中进行沉降, 然后抽滤、 曱醇洗涤, 干燥后用丙酮索氏 提取共轭聚合物,得到共轭聚合物固体 0.43 g,产率 64 %。 Molecular weight ( GPC, THF, R. I): Ma = 82,000, M Ma = 2.1。
P4 ( 4,5-二辛基苯唑 [2, 1 -b: 3 ,4-b,]二噻。分 -2,3 -双苯基-噻吩并 [3 ,4-b]吡嗪类共轭 聚合物) 的制备
Figure imgf000015_0001
4
在氮气保护下,往含有化合物 5,7-二溴 -2-(4-正丁基苯基) 3-(4-正丁氧基苯基 ) 噻吩并 [3,4-b]吡嗪( 0.29 g, 0.5 mmol)、 2,7-双三曱基锡 -4,5-二辛基苯唑 [2,l-b:3,4-b,]二噻。分 (0.37 g, 0.5 mmol)的氯苯( 20 mL )溶液中鼓泡 0.5 h, 除去 残留的氧气。然后加入 Pd2(dba)3 ( 0. 014 g, 0.015 mol P(o-Tol)3( 0.0083 g, 0.027 mmol ), 鼓泡 l h 除去残留的氧气。 60°C下加热回流反应 72小时, 得到共轭聚 合物溶液。 将所述共轭聚合物溶液滴加到曱醇中, 进行沉降处理, 然后抽滤、 干燥, 得到含共轭聚合物的胶体。 将含共轭聚合物的胶体溶解于曱苯中, 并将 该曱苯溶液加入到二乙基二硫代氨基曱酸钠的水溶液中, 90°C加热搅拌后过氧 化铝柱层析, 分离出共轭聚合物, 氯苯淋洗后减压除去有机溶剂。 将得到的共 轭聚合物加入到曱醇中进行沉降, 然后抽滤、 曱醇洗涤, 干燥后用丙酮索氏提 取共轭聚合物,得到共轭聚合物固体 0.26 g,产率 61 %。 Molecular weight ( GPC, THF, R. I): Mn = 37,400, M Mn = 1.7。 实施例 2
本实施例公开了 4,5-二辛基苯唑 [2,l-b:3,4-b,]二噻吩 -2-苯基 -3咔唑基噻吩并 [3,4-b]吡嗪类共轭聚合物,
Figure imgf000015_0002
上述聚合物的制备过程如下: 一
Figure imgf000016_0001
以制备 5,7-二溴 -2-(3- (氮己基咔唑)基) -3-苯基-噻吩并 [3 ,4-b]吡嗪为例予以说 明, 制备过程
Figure imgf000016_0002
将 NBS ( 0.43 g, 2.4 mmol )加入到含有化合物 2-(3- (氮己基咔唑)基) -3-苯 基-噻吩并 [3,4-b]吡嗪 (0.50g, 1.1 mmol) 的 氯仿 /乙酸( v/v=l/l, 20 mL ) 的溶液 中, 搅拌过夜。 将反应液加入到饱和碳酸钠溶液中, 氯仿萃取后用水洗涤, 再 用无水石 史钠干燥。 旋去溶剂后柱层析得固体 0.55 g, 产率 81%。 MS (MALDI) m/z: 619 (M+)。
二、 基于苯唑二噻吩和噻吩并吡嗪的共轭聚合物的制备
P5 ( 4,5-二辛基苯唑 [2,l-b:3,4-b,]二噻吩 -2-(3- (氮烷基咔唑)基) -3-苯基-噻吩并 [3,4-b]吡嗪类共轭聚合物) 的制备
Figure imgf000016_0003
p 在氮气保护下,往含有化合物 5,7-二溴 2-(3- (氮己基咔唑)基) -3-苯基-噻吩并 [3,4-b]吡嗪( 0.31 g, 0.5 mmol), 2,7-双三曱基锡 -4,5-二辛基苯唑 [2,l-b:3,4-b,]二噻 。分 (0.37 g, 0.5 mmol)的氯苯 ( 20 mL )溶液中鼓泡 0.5 h, 除去残留的氧气。 然后 加入 Pd2(dba)3 ( 0.014 g, 0.015 mol )和 P(o-Tol)3 ( 0.0083 g, 0.027 mmol ), 鼓泡
1 h 除去残留的氧气。 80°C下加热回流反应 24小时, 得到共轭聚合物溶液。 将 所述共轭聚合物溶液滴加到曱醇中, 进行沉降处理, 然后抽滤、 干燥, 得到含 共轭聚合物的胶体。 将含共轭聚合物的胶体溶解于曱苯中, 并将该曱苯溶液加 入到二乙基二硫代氨基曱酸钠的水溶液中, 80°C加热搅拌后过氧化铝柱层析, 分离出共轭聚合物, 氯苯淋洗后减压除去有机溶剂。 将得到的共轭聚合物加入 到曱醇中进行沉降, 然后抽滤、 曱醇洗涤, 干燥后用丙酮索氏提取共轭聚合物, 得到共轭聚合物固体 0.29g,产率 66 %。 Molecular weight ( GPC, THF, R. I): Mn = 37,000, / = 2.3。
P6 ( 4,5-二辛基苯唑 [2,l-b:3,4-b,]二噻吩 -2-(3- (氮烷基咔唑)基) -3-苯基-噻吩并 [3,4-b]
Figure imgf000017_0001
6
在氮气保护下, 往含有化合物 5,7-二溴 2-(3- (氮正二十烷基咔唑)基) -3-苯基 -噻吩并 [3,4-b]吡嗪( 0.41 g, 0.5 mmol), ( 0.41 g, 0.5 mmol), 2,7-双三曱基锡 -4,5-二 辛基苯唑 [2,l-b:3,4-b,]二噻。分 (0.37 g, 0.5 mmol)的氯苯( 20 mL )溶液中鼓泡 0.5 h, 除去残留的氧气。然后加入 Pd2(dba)3 ( 0.014 g, 0.015 mol )和 P(o-Tol)3 ( 0.0083 g, 0.027 mmol ), 鼓泡 1 h 除去残留的氧气。 80°C下加热回流反应 24小时, 得到共 轭聚合物溶液。 将所述共轭聚合物溶液滴加到曱醇中进行沉降处理, 然后抽滤、 干燥, 得到含共轭聚合物的胶体。 将含共轭聚合物的胶体溶解于曱苯中, 并将 该曱苯溶液加入到二乙基二硫代氨基曱酸钠的水溶液中, 80°C加热搅拌后过氧 化铝柱层析, 分离出共轭聚合物, 氯苯淋洗后减压除去有机溶剂。 将得到的共 轭聚合物加入到曱醇中进行沉降, 然后抽滤、 曱醇洗涤, 干燥后用丙酮索氏提 取共轭聚合物,得到共轭聚合物固体 0.33 g,产率 62 %。 Molecular weight ( GPC, THF, R. I): n = 23,000, M Ma = 2.1。
P7 ( 4,5-二辛基苯唑 [2,l-b:3,4-b,]二噻吩 -2-(3- (氮烷基咔唑)基) -3-苯基-噻吩并 [3,4-b]吡
Figure imgf000018_0001
p
在氮气保护下,往含有化合物 5,7-二溴 2-(3- (氮正丁基咔唑)基) -3-苯基 -噻吩 并 [3,4-b]吡嗪( 0.29 g, 0.5 mmol)、 2,7-双三曱基锡 -4,5-二辛基苯唑 [2,l-b:3,4-b,]二 噻。分 (0.37 g, 0.5 mmol)的氯苯( 20 mL )溶液中鼓泡 0.5 h, 除去残留的氧气。 然 后加入 Pd2(dba)3 ( 0.014 g, 0.015 mol )和 P(o-Tol)3 ( 0.0083 g, 0.027 mmol ), 鼓泡
1 h 除去残留的氧气。 80°C下加热回流反应 24小时, 将混合液滴加到曱醇中沉 降, 抽滤后曱醇洗涤、 干燥, 最后用氯苯溶解, 得到共轭聚合物溶液。 将所述 共轭聚合物溶液滴加到曱醇中, 进行沉降处理, 然后抽滤、 干燥, 得到含共轭 聚合物的胶体。 将含共轭聚合物的胶体溶解于曱苯中, 并将该曱苯溶液加入到 二乙基二硫代氨基曱酸钠的水溶液中, 80°C加热搅拌后过氧化铝柱层析, 分离 出共轭聚合物, 氯苯淋洗后减压除去有机溶剂。 将得到的共轭聚合物加入到曱 醇中进行沉降, 然后抽滤、 曱醇洗涤, 干燥后用丙酮索氏提取共轭聚合物, 得 到共轭聚合物固体 0.17 g, 产率 48 %。 Molecular weight ( GPC, THF, R. I): = 17000, w/ n = 2.10 实施例 3
本实施例公开了 4,5-二辛基苯唑 [2,l-b:3,4-b']二噻吩 -2,3-双((2-(9,9-二取代 芴)基)噻吩并 [3,4-b]吡嗪类聚合物
Figure imgf000019_0001
Figure imgf000019_0002
以制备 5,7-二溴 -2,3-双 (2-(9,9-二辛基芴)基)噻吩并 [3,4-b]吡嗪为例予以说 明, 具体操
Figure imgf000019_0003
将 NBS ( 0.25 g, 1.4 mmol )加入到含有化合物 2-(3- (氮己基咔唑)基) -3-苯 基-噻吩并 [3,4-b]吡嗪 (0.55 g, 0.6 mmol) 的 氯仿 /乙酸( v/v=l/l, 20 mL )的溶液 中, 搅拌过夜。 将反应液饱和碳酸钠溶液中, 氯仿萃取后水洗涤, 在用无水硫 酸钠干燥。 旋去溶剂, 柱层析得固体 0.43 g, 产率 66%。 MS (MALDI) m/z: 1071
(M+)。
二、 基于苯唑二噻吩和噻吩并吡嗪的共轭聚合物的制备
P8 ( 4,5-二辛基苯唑 [2,l-b:3,4-b']二噻吩 -2,3-双 (2-(9,9-二烷基芴)基)噻吩并 [3,4-b]吡 的制备:
Figure imgf000020_0001
P8
在氮气保护下, 往含有化合物 5,7-二溴 -2,3-双 (2-(9,9-二辛基芴)基)噻吩并 [3,4-b]吡嗪( 0.54 g, 0.5 mmol)、 2,7-双三曱基锡 -4,5-二辛基苯唑 [2,l-b:3,4-b,]二噻 。分 (0.31 g, 0.5 mmol)的曱苯( 30 mL )溶液中鼓泡 0.5 h, 除去残留的氧气。 然后 加入 Pd2(dba)3 ( 0. 0.14 g, 0.015 mol )和 P(o-Tol)3 ( 0.0083 g, 0.027 mmol ), 鼓泡 l h 除去残留的氧气。 130°C下加热回流反应 48小时, 得到共轭聚合物溶液。 将 所述共轭聚合物溶液滴加到曱醇中, 进行沉降处理, 然后抽滤、 干燥, 得到含 共轭聚合物的胶体。 将含共轭聚合物的胶体溶解于曱苯中, 并将该曱苯溶液加 入到二乙基二硫代氨基曱酸钠的水溶液中, 100°C加热搅拌后过氧化铝柱层析, 分离出共轭聚合物, 氯苯淋洗后减压除去有机溶剂。 将得到的共轭聚合物加入 到曱醇中进行沉降, 然后抽滤、 曱醇洗涤, 干燥后用丙酮索氏提取共轭聚合物, 得到共轭聚合物固体 0.41 g,产率 62 %。 Molecular weight ( GPC, THF, R. I): Ma = 92, 500, w/ n = 2. K
P9 ( 4,5-二辛基苯唑 [2,l-b:3,4-b']二噻吩 -2,3-双 (2-(9,9-二烷基芴)基)噻吩并 [3,4-b]吡 的制备
Figure imgf000020_0002
9
在氮气保护下, 往含有化合物 5,7-二溴 2-(2-(9,9-二辛基芴)基) -3-(2-(9,9-二 正二十烷基芴)基)-噻吩并 [3,4-b]吡嗪(0.65 g, 0.5 mmol)、 2,7-双三曱基锡 -4,5-二 辛基苯唑 [2,l-b:3,4-b,]二噻。分 (0.37 g, 0.5 mmol)的曱苯( 30 mL )溶液中鼓泡 0.5 h, 除去残留的氧气。 然后加入 Pd2(dba)3 ( 0.014 g, 0.015 mol )和 P(o-Tol)3 ( 0.0083 g, 0.027 mmol ), 鼓泡 1 h 除去残留的氧气。 130°C下加热回流反应 48小时, 得 到共轭聚合物溶液。 将所述共轭聚合物溶液滴加到曱醇中, 进行沉降处理, 然 后抽滤、 干燥, 得到含共轭聚合物的胶体。 将含共轭聚合物的胶体溶解于曱苯 中, 并将该曱苯溶液加入到二乙基二硫代氨基曱酸钠的水溶液中, 100°C加热搅 拌后过氧化铝柱层析, 分离出共轭聚合物, 氯苯淋洗后减压除去有机溶剂。 将 分离出的共轭聚合物加入到曱醇中进行沉降, 然后抽滤、 曱醇洗涤, 干燥后用 丙酮索氏提取共轭聚合物, 得到共轭聚合物固体 0.41g, 产率 53 %。 Molecular weight ( GPC, THF, R. I): Mn = 11,300, M Mn = 2.3。 实施例 4
本实施例公开了 4,5-二辛基苯唑 [2,l-b:3,4-b,]二噻吩 -2,3-二烷基噻吩并 [3,4-b] 吡嗪类共轭聚合物, 结构式如下
Figure imgf000021_0001
上述聚合物的制备过程如下:
一、 结构式如下的化合物的制备
Figure imgf000021_0002
Br Br Br g Br
以制备 5,7-二溴 -2,3-二辛基噻吩并 [3,4-b]吡嗪的制备为例予以说明; 制备过 程如下:
Figure imgf000021_0003
将 3, 4-二胺基噻吩 ·氯化氢( 1.0 g, 5.34 mmol)加入到化合物 1,2-二辛基乙二 酮 ( 1.66 g, 5.87 mmol ) 乙醇溶液( 50 mL ) 中, 搅拌过夜。 停止反应后旋转蒸 发除去溶剂, 柱层析得到产物 1.2 g, 产率 62%。 MS (EI) m/z:360 (M+)
二、 以 5,7-二溴 -2,3-二辛基噻吩并 [3,4-b]吡嗪二溴代物的制备
7
Figure imgf000022_0001
将 NBS ( 0.72 g, 4 mmol )加入到含有化合物 2,3-双苯基-噻吩并 [3,4-b]吡 嗪 (0.49g, 1.7 mmol) 的 氯仿 /乙酸( v/v=l/l, 10 mL ) 的溶液中, 搅拌过夜。 将 反应液加入到饱和碳酸钠溶液中, 氯仿萃取后水洗涤, 再用无水硫酸钠干燥。 旋去溶剂, 柱层析得固体 0.42 g, 产率 55%。 MS (EI) m/z: 446 (M+)„
三、 基于苯唑二噻吩和噻吩并吡嗪的共轭聚合物的制备
p10 ( 4,5-二辛基苯唑 [2,l-b:3,4-b,]二噻吩 -2,3-二烷基噻吩并 [3,4-b]吡嗪类共轭 1合) 的制备:
Figure imgf000022_0002
在氮气保护下, 往含有化合物 5,7-二溴 2,3-二辛基-噻吩并 [3,4-b]吡嗪( 0.26 g, 0.5 mmol) , 2,7-双三曱基锡 -4,5-二辛基苯唑 [2,l-b:3,4-b,]二噻吩 (0.37 g, 0.5 mmol)的曱苯(30 mL )溶液中鼓泡 0.5 h, 除去残留的氧气。 然后加入 Pd2(dba)3 ( 0.014 g, 0.015 mol )和 P(o-Tol)3 ( 0.0083 g, 0.027 mmol ), 鼓泡 1 h 除去残留的 氧气。 80°C下加热回流反应 72小时, 得到共轭聚合物溶液。 将所述共轭聚合物 溶液滴加到曱醇中, 进行沉降处理, 然后抽滤、 干燥, 得到含共轭聚合物的胶 体。 将含共轭聚合物的胶体溶解于曱苯中, 并将该曱苯溶液加入到二乙基二硫 代氨基曱酸钠的水溶液中, 80°C加热搅拌后过氧化铝柱层析, 分离出共轭聚合 物, 氯苯淋洗后减压除去有机溶剂。 将得到的共轭聚合物加入到曱醇中进行沉 降, 然后抽滤、 曱醇洗涤, 干燥后用丙酮索氏提取共轭聚合物, 得到共轭聚合 物固体 0.23g, 产率 60%。 Molecular weight ( GPC, THF, R. I): Mn = 74,900, M Mn = 1.9。
pu ( 4,5-二辛基苯唑 [2,l-b:3,4-b,]二噻吩 -2,3-二烷基噻吩并 [3,4-b]吡嗪类共轭 聚合物 的制备
Figure imgf000023_0001
在氮气保护下, 往含有化合物 5,7-二溴 2-曱基 -3正二十烷基-噻吩并 [3,4-b] 吡嗪( 0.29 g, 0.5 mmol)、 2,7-双三曱基锡 -4,5-二辛基苯唑 [2,l-b:3,4-b,]二噻吩 (0.37 g, 0.5 mmol)的曱苯 ( 30 mL )溶液中鼓泡 0.5 h, 除去残留的氧气。 然后加入 Pd2(dba)3 ( 0. 0.14 g, 0.015 mol )和 P(o-Tol)3 ( 0.0083 g, 0.027 mmol ),鼓泡 1 h 除 去残留的氧气。 80°C下加热回流反应 72小时, 得到共轭聚合物溶液。 将所述共 轭聚合物溶液滴加到曱醇中, 进行沉降处理, 然后抽滤、 干燥, 得到含共轭聚 合物的胶体。 将含共轭聚合物的胶体溶解于曱苯中, 并将该曱苯溶液加入到二 乙基二硫代氨基曱酸钠的水溶液中, 80°C加热搅拌后过氧化铝柱层析, 分离出 共轭聚合物, 氯苯淋洗后减压除去有机溶剂。 将分离出的共轭聚合物加入到曱 醇中进行沉降, 然后抽滤、 曱醇洗涤, 干燥后用丙酮索氏提取共轭聚合物, 得 到共轭聚合物固体 0.27 g, 产率 64 %。 Molecular weight ( GPC, THF, R. I): = 57,000, w/ n = 2. K 以下实施例是基于苯唑二噻吩和噻吩并吡嗪的共轭聚合物在聚合物太阳能 电池, 有机电致发光器件, 有机场效应晶体管, 有机光存储, 有机非线性材料 和有机激光材料等领域中的应用。
实施例 5
一种太阳能电池器件, 其结构如图 1。 本实施例中采用 ΙΤΟ玻璃(铟锡氧化 物玻璃), 即玻璃作为衬底, ΙΤΟ (铟锡氧化物)作为导电层。
该太阳能电池器件的结构为: 玻璃 /ITO/PEDOT:PSS/活性层 /A1 ; 其中, 活 性层的材质为混合物,包括以 [6,6]苯基 -C61-丁酸曱酯为材质的电子给体材料和以 基于苯唑二噻吩和噻吩并吡嗪的共轭聚合物为材质的电子受体材料; ITO是方块 电阻为 10-20 Ω/口的氧化铟锡, ?£00丁为聚3,4-亚乙二氧基噻吩, PSS为聚苯 乙烯磺酸。
该太阳能电池器件的制造过程如下:
ITO玻璃经过超声波清洗, 并用氧 -Plasma处理后, 在 ITO表面涂上一层起 修饰作用的 PEDOT:PSS层;
在所述 PEDOT:PSS层上采用旋涂技术涂覆一层活性层,该活性层的材质包 括以 [6,6]苯基 -C61-丁酸曱酯为材质的电子给体材料和基于苯唑二噻吩和噻吩并 吡嗪的共轭聚合物为材质的电子受体材料;
在所述活性层的表面真空蒸镀金属铝, 形成作为阴极的金属铝层, 得到所 述有机太阳能电池器件。 本实施例中, 金属铝层的厚度分别为 170 nm, 在其他 的实施例中, 金属铝层的厚度还可以为 30 nm、 130 nm, 60 nm。
在本实施例中, ITO导电层作为阳极,该太阳能电池经过 110摄氏度密闭条 件下 4 小时, 再降到室温, 器件经过退火后能有效增加分子内各基团和分子链 段间排列的有序性和规整度, 提高载流子迁移率的传输速度和效率, 进而提高 光电转换效率。 实施例 6
一种有机电致发光器件, 结构如图 2所示。 本实施例中采用 ITO玻璃(铟 锡氧化物玻璃), 即玻璃作为衬底, ITO (铟锡氧化物)作为导电层。
该有机电致发光器件的结构为: 玻璃 /ITO/发光层 /緩冲层 /A1; 其中, 发光层 采用基于苯唑二噻吩和噻吩并吡嗪的共轭聚合物; 緩冲层材质为 LiF; ITO是方 块电阻为 10-20 Ω/口的氧化铟锡, PEDOT为聚 3,4-亚乙二氧基噻吩, PSS为聚 苯乙烯横酸。
该有机电致发光器件的制造过程如下:
ITO玻璃经过超声波清洗, 并用氧 -Plasma处理后, 在 ITO表面涂上一层基 于苯唑二噻吩和噻吩并吡嗪的共轭聚合物形成发光层;
在所述发光上真空蒸镀 LiF形成绥冲层; 在所述緩冲层的表面真空蒸镀金属铝, 形成作为阴极的金属铝层, 得到所 述有机电致发光器件。 本实施例中, 金属铝层的厚度分别为 170 nm, 在其他的 实施例中, 金属铝层的厚度还可以为 30 nm、 130 nm, 60 nm。 在本实施例中, ITO导电层作为阳极。 实施例 7
一种有机场效应晶体管, 结构如图 3 所示。 本实施例中采用高掺杂的硅片 作为衬底。
该有机场效应晶体管的结构为: Si/Si02/OTS/有机半导体层 /源电极( S )和 漏电极(D ); 其中, Si02厚度为 450nm, 起到绝缘作用; OTS为十八烷基三氯 硅烷; 有机半导体层材质为基于苯唑二噻吩和噻吩并吡嗪的共轭聚合物; 源电 极( S )和漏电极( D )采用金属金制作, 在其他的实施例中, 源电极( S )和漏 电极(D ) 也可以采用铜制作。
该有机场效应晶体管的制造过程如下:
清洗掺杂硅衬底, 沉积具有绝缘作用的 Si02层;
在所述 Si02绝缘层上涂覆 OTS, 形成 OTS层;
在所述 OTS层上涂覆一层基于苯唑二噻吩和噻吩并吡嗪的共轭聚合物, 形 成有机半导体层;
在所述有机半导体层上设置金属金材质的源电极和漏电极, 得到所述有机 场效应晶体管。
但并不能因此而理解为对本发明专利范围的限制。 应当指出的是, 对于本领域 的普通技术人员来说, 在不脱离本发明构思的前提下, 还可以做出若干变形和 改进, 这些都属于本发明的保护范围。 因此, 本发明专利的保护范围应以所附 权利要求为准。

Claims

权利要求书
1、 一种基于苯唑二噻 , 通式如下:
Figure imgf000026_0001
其中, x+y=2, 0<y<l , n为 1 ~ 100的整数;
Ri、 R2为(^〜02。的烷基;
R3、 R4为氢、 Cr^ 。的烷基、 CH^。的烷氧基或芳香基团。
2、 如权利要求 1所述的共轭聚合物, 其特征在于, 所述芳香基团为如下结 构式中的任一
Figure imgf000026_0002
其中, R5为 Cr^ds的烷基或 Cr^ds的烷氧基, R6、 R7、 R8为 Cr^ds的烷 基。
3、 一种基于苯唑二噻吩和噻吩并吡嗪的共轭聚合物的制备方法, 其特征在 于, 包括如下步骤:
Sll、 分别提供如下结构式表示的化合物 A、 B、 C :
Figure imgf000026_0003
S12、 在无水无氧环境下, 有机溶剂和催化剂存在条件下, 将化合物 、 B、 C混合, 按如下反应方程式进行 Stille偶合反应:
Figure imgf000027_0001
Figure imgf000027_0002
其中, m=i+j , 0<i<m; 得到如下结构式表示的共轭聚合物:
Figure imgf000027_0003
其中, x+y=2, 0<y<l , n为 1 ~ 100的整数;
Ri、 R2为(^〜02。的烷基;
R3、 R4为氢、 (^〜02。的烷基、 CH^。的烷氧基或芳香基团。
4、 如权利要求 3所述的制备方法, 其特征在于, 所述芳香基团为如下结构 式中的任一种:
Figure imgf000027_0004
其中, R5为 CH^的烷基或 CH^的烷氧基, R6、 R7、 R8为 〜C15的烷 基。
5、 如权利要求 3所述的制备方法, 其特征在于, 步骤 S11中, 所述化合物 C由如下步骤制得:
分别提供结构式如 D和 E:
Figure imgf000027_0005
在 0 ~ 78 °C下, 按化合物 D与化合物 E摩尔比满足 1 : 0.1 - 1 : 10将两者混 合溶解在溶剂中, 按化合物摩尔数 D的 2 ~ 50倍加入弱碱后反应 1 ~ 24小时, 得到结构式如下的化合物 F:
Figure imgf000028_0001
其中, 所述溶剂为选自曱醇、 乙醇和乙酸乙酯中的一种或几种; 所述弱碱 为选自三乙胺和碳酸钠中的一种或两种;
在 0 ~ 70 °C下,将化合物 F加入到氯仿和乙酸的混合液中,再加入 n-溴代丁 二酰亚 反应 1 ~ 48小时后得到结构式如下的化合物 C:
Figure imgf000028_0002
6、 如权利要求 3所述的制备方法, 其特征在于, 步骤 S 12中, 所述有机溶 剂为选自四氢呋喃、 乙二醇二曱醚、 苯、 氯苯或曱苯中的一种或几种;
反应温度为 60〜130 °C , 反应时间为 24〜72小时;
所述催化剂加入量为化合物 A摩尔数的 0.05 ~ 50%;
所述催化剂为有机钯或有机钯和有机膦配体的混合物;
所述有机钯为 Pd2(dba)3、 Pd(PPh3)4或 Pd(PPh3)2Cl2;
所述有机膦配体为 P(o-Tol)3;
所述有机钯和有机膦配体的混合物中, 有机钯和有机膦配体的摩尔比范围 为 1 : 2〜1: 20。
7、 如权利要求 3所述的共轭聚合物的制备方法, 其特征在于, 还包括得到 所述共轭聚合物后的纯化过程, 具体步骤如下:
513、 将所述共轭聚合物滴加到曱醇中, 进行沉降处理, 然后抽滤, 曱醇洗 涤, 干燥, 得到含共轭聚合物的胶体;
514、 将含共轭聚合物的胶体溶解于曱苯中, 并将该曱苯溶液加入到二乙基 二硫代氨基曱酸钠的水溶液中, 80 ~ 100°C加热搅拌后过氧化铝柱层析, 分离出 共轭聚合物, 氯苯淋洗后减压除去有机溶剂;
S15、 重复步骤 S13至少一次, 并用丙酮索氏提取步骤 S14中分离出来的共 轭聚合物, 得到共轭聚合物固体。
8、 一种权利要求 1所述共轭聚合物制备的太阳能电池器件, 包括衬底, 沉 积在所述衬底一个表面上的、 作为阳极的导电层, 涂覆在所述导电层上的起修 饰作用的聚 3,4-亚乙二氧基噻吩: 聚苯乙婦横 S史层, 涂覆在所述聚 3,4-亚乙二氧 基噻吩: 聚苯乙烯磺酸层表面的活性层, 以及设置在所述活性层表面、 作为阴 极的金属铝层; 所述活性层的材质为混合物, 包括电子给体材料和电子受体材 料; 所述电子受体材料为 [6,6]苯基 -C61 -丁酸曱酯, 其特征在于, 所述电子给体材 料含权利要求 1所述的基于苯唑二噻吩和噻吩并吡嗪的共轭聚合物。
9、 一种权利要求 1所述共轭聚合物制备的有机电致发光器件, 包括衬底, 沉积在所述衬底的一个表面上的、 作为阳极的导电层, 涂覆在所述导电层上的 发光层, 真空蒸镀在所述发光层上的以 LiF 为材质的緩冲层, 以及设置在所述 緩冲层上的、 作为阴极的金属铝层, 其特征在于, 所述发光层材料含权利要求 1 所述的基于苯唑二噻吩和噻吩并吡嗪的共轭聚合物。
10、 一种权利要求 1 所述聚合物制备的有机场效应晶体管, 其结构依次包 括: 掺杂硅片, Si02绝缘层, 用于修饰所述 Si02绝缘层的十八烷基三氯硅烷层, 涂覆在所述十八烷基三氯硅烷层上的有机半导体层, 间隔设置在所述有机半导 体层上的源电极和漏电极, 其特征在于, 所述有机半导体层材料含权利要求 1 所述的基于苯唑二噻吩和噻吩并吡嗪的共轭聚合物。
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EP2586810A1 (en) 2013-05-01
JP2013537564A (ja) 2013-10-03
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