WO2013078635A1 - 一种2，7-咔唑与二噻吩基噻唑并噻唑共聚物及其制备方法和包含其的太阳能电池 - Google Patents

一种2，7-咔唑与二噻吩基噻唑并噻唑共聚物及其制备方法和包含其的太阳能电池 Download PDF

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WO2013078635A1
WO2013078635A1 PCT/CN2011/083210 CN2011083210W WO2013078635A1 WO 2013078635 A1 WO2013078635 A1 WO 2013078635A1 CN 2011083210 W CN2011083210 W CN 2011083210W WO 2013078635 A1 WO2013078635 A1 WO 2013078635A1
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thiazole
compound
carbazole
palladium
organic
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French (fr)
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周明杰
王平
张振华
冯小明
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海洋王照明科技股份有限公司
深圳市海洋王照明工程有限公司
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Priority to EP11876538.7A priority Critical patent/EP2787019A4/en
Priority to CN201180073516.3A priority patent/CN103814058A/zh
Priority to JP2014534911A priority patent/JP2015501339A/ja
Priority to PCT/CN2011/083210 priority patent/WO2013078635A1/zh
Priority to US14/348,589 priority patent/US20140224332A1/en
Publication of WO2013078635A1 publication Critical patent/WO2013078635A1/zh

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Definitions

  • the invention belongs to the field of organic solar cell materials, and particularly relates to a 2,7-carbazole and dithia.
  • the present invention provides a 2,7-carbazole and a dithio.
  • the invention also provides a preparation method of the copolymer and a solar cell comprising the copolymer, wherein the raw material used in the preparation method is cheap and easy to obtain, and the synthesis route is simple.
  • the invention provides a 2,7-oxazole and a dithiophene of formula (I). Branched thiazole and thiazole copolymer:
  • R l R 2 are both ⁇ C 2 .
  • the alkyl group, n is an integer from 10 to 100.
  • the same or different as R 2 is selected from CH 3 , C 8 H 17 or C 2 , respectively. H 41 .
  • the invention provides a 2,7-oxazole and a dithio.
  • the preparation method of the base thiazole and thiazole copolymer formula (I) comprises the following steps:
  • R 2 are all alkyl groups of ⁇ C 2Q ;
  • the compound A and the compound B are added to the organic solvent containing the catalyst, and the molar ratio of the compound A to the compound B is 1:1 to 1.2, and the Suzuki coupling reaction is carried out by heating, and the reaction is terminated after the temperature is lowered to room temperature.
  • decyl alcohol was precipitated, extracted by a Soxhlet extractor, and then extracted with decyl alcohol and n-hexane, and then extracted with chloroform until colorless.
  • the chloroform solution was collected and dried to obtain a red powder, and the obtained red color was collected. After the powder is vacuum dried, the copolymer of the formula (I) is obtained.
  • R l R 2 are both ⁇ C 2 .
  • the alkyl group, n is an integer from 10 to 100.
  • the catalyst is a mixture of an inorganic base and an organic palladium, or a mixture of an organic palladium and an organophosphine ligand.
  • the inorganic base is potassium carbonate, sodium carbonate or sodium bicarbonate.
  • the organic palladium is bistriphenylphosphine palladium dichloride, tetrakistriphenylphosphine palladium or trisethylenebenzyl acetone dipalladium, and the molar ratio of the organic palladium to the compound A is 1. : 20 ⁇ 100. In a more preferred embodiment, the molar ratio of the organic palladium to the compound A is from 1:40 to 80.
  • the organophosphine ligand is tri-tert-butylphosphine, tri-p-phenylenephosphine or 2-bicyclohexylphosphino-2,6-dimethoxybiphenyl.
  • the molar ratio of organopalladium to organophosphine ligand in the mixture of organopalladium and organophosphine ligand is from 1:4 to 8.
  • the organic solvent is at least one selected from the group consisting of toluene, anthracene, anthracene-dimercaptoamide, and tetrahydrofuran.
  • the Suzuki coupling reaction has a reaction temperature of from 70 to 130. C, the reaction time is 12 to 96 hours.
  • the Suzuki coupling reaction has a reaction temperature of 90 to 100 ° C and a reaction time of 36 to 72 hours.
  • the present invention provides a solar cell comprising an anode, an active layer and a cathode which are sequentially laminated, and the electron donor material in the active layer is 2,7-carbazole and dithia as described above.
  • a thiazole-thiazole copolymer
  • the present invention provides a 2,7-carbazole and a dithio.
  • the thiazole-thiazole copolymer has a novel structure.
  • 2,7-carbazole and thiazole are polymerized to obtain a polymer having good solubility, excellent film-forming property and high energy conversion efficiency.
  • poly(2,7-carbazole) derivatives were first synthesized by the Leclerc group in 2001. They have good hole transport properties, superior chemical stability and easy modification. Photophysical properties.
  • the energy gap is easily regulated by adjusting different receptor units.
  • Thiazole is a typical electron-deficient unit which contains an electron-withdrawing imine group.
  • the thiazole-thiazolyl group in the copolymer backbone exhibits a high hole mobility and two thiophenes per unit. The partition can reduce the band gap of the copolymer.
  • the invention also provides a process for the preparation of the copolymer and a solar cell comprising the copolymer.
  • the raw materials used in the preparation method are cheap and easy to obtain, and the synthesis route is simple.
  • Figure 1 is a UV-visible poly[2,5-di(3-octyl-2-thiazide)thiazolo[5,4-d]thiazole-co-N-octylcarbazole prepared in Example 1. Absorption spectrum. detailed description
  • the monomer A can be synthesized by a method disclosed in the literature (Journal of Advanced Materials, 2007, 19, 4160.) or commercially available, and the monomer B can be obtained.
  • References (Macromolecules, 2008, 41, 6012.) are published synthetically or commercially available. It should be noted that many modifications and adaptations may be made by those skilled in the art without departing from the principles of the invention, and such modifications and adjustments are also considered to be within the scope of the invention.
  • ⁇ is an integer from 10 to 100,
  • the preparation method is as follows:
  • n is an integer from 10 to 100
  • the preparation method is as follows:
  • the mixed droplets were added to 50 ml of methanol to precipitate. After filtration through a Soxhlet extractor, it was sequentially extracted with decyl alcohol and n-hexane for 24 h each. Then, it was extracted with chloroform as a solvent, and the chloroform solution was collected and dried to obtain a red powder, which was vacuum pumped overnight. Product, yield 55%.
  • n is an integer from 10 to 100
  • the preparation method is as follows:
  • Phenylphosphine palladium (3.73 mg, 0.003 mmol) was added thereto, and then a solution of sodium hydrogencarbonate (3 mL, 2 mol/L) was added to the solution, and then air was exhausted through nitrogen for about 10 minutes, and then stirred at 70 for 96 hours. , performing a Suzuki coupling reaction. After the temperature was lowered to room temperature, the reaction was stopped, and 40 mL of decyl alcohol was precipitated into the flask, which was filtered through a Soxhlet extractor and then extracted with decyl alcohol and n-hexane, respectively, for 24 hours. Then, it was extracted with chloroform as a solvent to a colorlessness. The chloroform solution was collected and dried to give a red solid, which was collected and dried under vacuum at 50 ° C for 24 h to give the product. The yield was 84%.
  • ⁇ is an integer from 10 to 100
  • the preparation method is as follows:
  • UV-visible absorption spectrum of poly[2,5-bis(3-octyl-2-thiazide)thiazolo[5,4-d]thiazole-co-N-octylcarbazole prepared in Example 1 As shown in Figure 1. It can be seen from Fig. 1 that the conjugated polymer has a relatively large absorption between 350 nm and 750 nm, and the maximum absorption peak is around 611 nm.

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Abstract

本发明提供一种式（I）的2，7-咔唑与二噻吩基噻唑并噻唑共聚物及其制备方法和包含其的太阳能电池。该2，7-咔唑与二噻吩基噻唑并噻唑共聚物的结构式如式（I）所示：其中，R1、R2均为C1∼C20的烷基，n为10~100的整数。本发明共聚物结构新颖，溶解性能良好，成膜性能优良，具有较高能量转换效率，可用作太阳能电池材料。本发明还提供了该共聚物的制备方法和包含其的太阳能电池，所述制备方法采用的原材料价廉易得，合成路线简单。

Description

一种 2,7-咔唑与二噻吩基噻唑并噻唑共聚物及其制备方法和包含其的 太阳能电池 技术领域
本发明属于有机太阳能电池材料领域， 具体涉及一种 2,7-咔唑与二噻。分基噻 唑并噻唑共聚物及其制备方法和包含其的太阳能电池。 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。 有机半导体材料以其原料易得、 价格低廉、 工艺简单、 稳定性强、 光 伏效应良好等优点备受关注。 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 C6。之间的光诱导电子转移现象后，有机聚合物太阳能电池逐渐成为研究 的热点。 近年来这方面的研究取得了飞速的发展， 但是有机聚合物太阳能电池 仍比无机太阳能电池的转换效率低得多。 为了使有机聚合物太阳能电池得到实 际的应用， 开发具有较高能量转换效率的新型材料仍是这一领域的首要任务。 发明内容
为解决上述有机聚合物太阳能电池低效率的问题， 本发明提供了一种 2,7-咔 唑与二噻。分基噻唑并噻唑共聚物， 所述共聚物结构新颖， 溶解性能良好， 成膜 性能优良， 具有较高能量转换效率， 可用作太阳能电池材料。 本发明还提供了 该共聚物的制备方法以及包含该共聚物的太阳能电池， 所述制备方法采用的原 材料价廉易得， 合成路线简单。 一方面， 本发明提供了一种式 (I)的 2,7-咔唑与二噻。分基噻唑并噻唑共聚物:
Figure imgf000004_0001
其中， Rl R2均为 ~C2。的烷基， n为 10~ 100的整数。
在优选的实施方案中， 与 R2相同或不同，分别选自 CH3、 C8H17或 C2。H41。 第二方面， 本发明提供了一种 2,7-咔唑与二噻。分基噻唑并噻唑共聚物式 (I) 的制备方法， 包括如下步骤：
(1) 分别提供如下结构式表示的化合物 A和化合物 B,
Figure imgf000004_0002
Ri, R2均为 ~C2Q的烷基;
(2)在无氧环境下， 将化合物 A和化合物 B加入至含有催化剂的有机溶剂 中 , 化合物 A和化合物 B摩尔比为 1:1〜1.2, 加热进行 Suzuki耦合反应， 降至 室温后终止反应， 向所得溶液中加入曱醇沉析， 通过索氏提取器提取之后依次 用曱醇和正己烷抽提， 然后用氯仿抽提至无色， 收集氯仿溶液并旋干， 得到红 色粉末， 收集所得红色粉末真空干燥后即得式 (I)所示共聚物
Figure imgf000004_0003
其中， Rl R2均为 ~C2。的烷基， n为 10~ 100的整数。
在优选的实施方案中， 与 R2相同或不同，分别选自 CH3、 C8H17或 C20H 在优选的实施方案中， 催化剂为无机碱与有机钯的混合物， 或者有机钯与 有机膦配体的混合物。
在优选的实施方案中， 无机碱为碳酸钾、 碳酸钠或碳酸氢钠。
在优选的实施方案中， 有机钯为双三苯基膦二氯化钯、 四三苯基膦钯或者 三二亚苄基丙酮二钯， 所述有机钯与所述化合物 A的摩尔比为 1:20〜100。 在更 优选的实施方案中， 所述有机钯与所述化合物 A的摩尔比为 1 :40〜80。
在优选的实施方案中， 有机膦配体为三叔丁基膦、 三对曱苯基膦或 2-双环 己基磷 -2，， 6，-二曱氧基联苯。
在优选的实施方案中， 有机钯与有机膦配体的混合物中有机钯与有机膦配 体的摩尔比为 1:4〜8。
在优选的实施方案中， 所述有机溶剂选自曱苯、 Ν,Ν-二曱基曱酰胺、 四氢 吹喃中的至少一种。
在优选的实施方案中， Suzuki耦合反应的反应温度为 70 ~ 130。C, 反应时 间为 12 ~ 96小时。
在更优选的实施方案中， Suzuki耦合反应的反应温度为 90 ~ 100°C,反应时 间为 36 ~ 72小时。
第三方面， 本发明提供了一种太阳能电池， 包括依次层叠的阳极、 活性层 和阴极， 活性层中的电子给体材质为如前文所述的 2,7-咔唑与二噻。分基噻唑并噻 唑共聚物。
本发明提供一种 2,7-咔唑与二噻。分基噻唑并噻唑共聚物， 结构新颖， 首次将 2, 7-咔唑与噻唑聚合，得到溶解性能良好、成膜性能优良且具有较高能量转换效 率的聚合物。 聚 (2, 7-咔唑)衍生物作为一种很有前景的共轭聚合物首次被 Leclerc 组于 2001年合成， 它具有良好的空穴传输性能、 优越的化学稳定性以及易修饰 的光物理性质。 通过调整不同的受体单元， 能隙很容易被调控。 噻唑是一个典 型的缺电子单元， 它包含一个吸电子亚胺基团， 共聚物主链中含有噻唑并噻唑 基表现出较高的空穴迁移率， 每个单元增加两个噻。分基可以降低共聚物的带隙。
本发明还提供该共聚物的制备方法以及包含该共聚物的太阳能电池。 所述 制备方法采用的原材料价廉易得， 合成路线简单。 附图说明
图 1为实施例 1制备的聚 [2, 5-二 (3-辛基 -2-噻。分)噻唑并 [5,4-d]噻唑 -co- N- 辛基咔唑]的紫外可见吸收光谱图。 具体实施方式
以下所述是本发明的优选实施方式， 其中单体 A可参照文献（ Journal of Advanced Materials (先进材料）， 2007, 19, 4160. )公开的方法合成或者从市场 上购买得到， 单体 B可参照文献 ( Macromolecules (大分子 ) , 2008, 41, 6012. ) 公开的方法合成或者从市场上购买得到。 应当指出， 对于本技术领域的普通技 术人员来说， 在不脱离本发明原理的前提下， 还可以做出若干改进和调整， 这 些改进和调整也视为在本发明的保护范围内。
实施例 1:
式 (II)的聚 [2, 5-二 (3-辛基 -2-噻。分)噻唑并 [5,4-d]噻唑 -co- N-辛基咔唑]:
Figure imgf000006_0001
η为 10 ~ 100的整数， 其制备方法如下：
其中， 提供如下结构式表示的化合物 A和化合物 B,
Figure imgf000007_0001
氮气保护下， 2, 5-二 (5-溴 -3-辛基 -2-噻。分)噻唑并 [5,4-d]噻唑（257 mg, 0.3 mmol), 2, 7-二硼酸频哪醇酯 -N-辛基咔唑 (159 mg, 0.3 mmol),三二亚苄基丙酮二 钯 (13.75 mg, 0.015mmol), 2-双环己基磷 -2，， 6，-二曱氧基联苯 (42 mg, 0.1 mmol), 溶解在 12 mL曱苯中， 再将碳酸钾 (3 mL, 2mol/L)溶液加入到溶液中， 充分通氮 气排空气约 30 min后， 在 90°C搅拌反应 72 h, 进行 Suzuki耦合反应。 降至室温 后停止反应， 向烧瓶中加入 40 mL曱醇沉析， 通过索氏提取器过滤之后依次用 曱醇和正己烷抽提， 各 24 h。 然后以氯仿为溶剂抽提至无色， 收集氯仿溶液并 旋干得到红色粉末， 收集后在真空下 50°C干燥 24 h后即为产物， 产率为 76%。
测试结果为： 分子量（ GPC, THF, R. I): M„ =55.9kDa, MJMn =2.2。
实施例 2:
式 (III)的聚 [2, 5-二 (3-曱基 -2-噻。分)噻唑并 [5,4-d]噻唑 -CO-N-二十烷基咔唑]:
Figure imgf000008_0001
n为 10 ~ 100的整数，
制备方法如下：
其中， 提供如下结构式表示的化合物 A和化合物 B,
Figure imgf000008_0002
在氮气保护下， 加入 2, 5-二 (5-溴 -3-曱基 -2-噻。分)噻唑并 [5,4-d]噻唑 (98 mg, 0.2mmol)、 2, 7-二硼酸频哪醇酯 -N-二十烷基咔唑 (140 mg, 0.2mmol)和 Ν,Ν-二曱 基曱酰胺溶剂 15ml, 再将碳酸钠 (2 mL, 2mol/L)溶液加入到溶液中， 抽真空除氧 并充入氮气， 然后加入双三苯基膦二氯化钯（ 5 mg, 0.007 mmol ), 加热到 110°C 进行 Suzuki耦合反应 36 h。 冷却至室温后将混合液滴加到 50 ml曱醇中进行沉 降。 通过索氏提取器过滤之后依次用曱醇和正己烷抽提， 各 24 h。 然后以氯仿 为溶剂抽提至无色， 收集氯仿溶液并旋干得到红色粉末， 真空泵下抽过夜得到 产物， 产率 55%。
测试结果为： 分子量（ GPC, THF, R. I): Mn = 44.5kDa, MJMn =2.3。
实施例 3:
式 (IV)的聚 [2, 5-二 (3-二十烷基 -2-噻。分)噻唑并 [5,4-d]噻唑 -co- N-曱基咔唑]:
Figure imgf000009_0001
n为 10 ~ 100的整数，
制备方法如下：
其中， 提供如下结构式表示的化合物 A和化合物 B,
Figure imgf000009_0002
氮气保护下， 2, 5-二 (5-溴 -3-二十烷基 -2-噻。分)噻唑并 [5,4-d]噻唑 (308 mg, 0.3 mmol), 2, 7-二硼酸频哪醇酯 -N-曱基咔唑 (130 mg, 0.3 mmol)以及 15 mL四氢呋 喃分别加入到 50 mL的两口瓶中， 充分通氮气排空气约 20 mm后， 然后将四三 苯基膦钯（3.73 mg, 0.003 mmol )加入其中， 然后再将碳酸氢钠 (3 mL, 2mol/L) 溶液加入到溶液中， 再充分通氮气排空气约 10 min后， 在 70 搅拌反应 96h, 进行 Suzuki耦合反应。 降至室温后停止反应， 向烧瓶中加入 40 mL曱醇沉析， 通过索氏提取器过滤之后依次用曱醇和正己烷抽提， 各 24 h。 然后以氯仿为溶 剂抽提至无色， 收集氯仿溶液并旋干得到红色固体， 收集后在真空下 50°C干燥 24 h后得到产物。 产率为 84%。
测试结果为： 分子量（ GPC, THF, R. I): Mn =68.1 kDa, MJMn =2.1。
实施例 4:
式 (II)的聚 [2, 5-二 (3-辛基 -2-噻。分)噻唑并 [5,4-d]噻唑 -co- N-辛基咔唑]:
Figure imgf000010_0001
(Π) ，
η为 10 ~ 100的整数，
其制备方法如下：
其中， 提供如下结构式表示的化合物 Α和化合物 Β,
A:
Figure imgf000010_0002
, B:
反应方程式为:
Figure imgf000011_0001
氮气保护下， 2, 5-二 (5-溴 -3-辛基 -2-噻。分)噻唑并 [5,4-d]噻唑（257 mg, 0.3 mmol), 2, 7-二硼酸频哪醇酯 -N-辛基咔唑 (159 mg, 0.36 mmol)、 三二亚苄基丙酮 二钯 (13.75 mg, 0.015mmol), 2-双环己基磷 -2，， 6，-二曱氧基联苯（42 mg, 0.10 mmol ), 溶解在 12 mL曱苯中， 再将碳酸钾 (3 mL, 2mol/L)溶液加入到溶液中， 充分通氮气排空气约 30 min后，在 130°C搅拌反应 12 h, 进行 Suzuki耦合反应。 降至室温后停止反应， 向烧瓶中加入 40 mL曱醇沉析， 通过索氏提取器过滤之 后依次用曱醇和正己烷抽提， 各 24 h。 然后以氯仿为溶剂抽提至无色， 收集氯 仿溶液并旋干得到红色粉末， 收集后在真空下 50°C干燥 24 h后即为产物， 产率 为 76%。
测试结果为： 分子量（ GPC, THF, R. I): M„ =55.9kDa, MJMn =2.2。
效果实施例
实施例 1制备的聚 [2, 5-二 (3-辛基 -2-噻。分)噻唑并 [5,4-d]噻唑 -co- N-辛基咔 唑]的紫外可见吸收光谱图如图 1所示。 由图 1可以看出该共轭聚合物在 350nm ~ 750nm之间有较大较宽的吸收， 其中最大吸收峰位于 611 nm左右。

Claims

权 利 要 求
1、 一种 2,7-咔唑与二噻。分基噻唑并噻唑共聚物， 其特征在于， 结构式如式 (I)所示：
Figure imgf000012_0001
其中， R2均为 ~ C2。的烷基， n为 10 ~ 100的整数。
2、 一种 2,7-咔唑与二噻。分基噻唑并噻唑共聚物的制备方法 , 其特征在于 , 包括如下步骤：
( 1 ) 分别提供如下结构式表示的化合物 A和化合物 B,
Figure imgf000012_0002
Ri , R2均为 ~ C2Q的烷基;
( 2 ) 在无氧环境下， 将化合物 A和化合物 B加入至含有催化剂的有机溶 剂中， 化合物 A和化合物 B摩尔比为 1:1〜1.2, 加热进行 Suzuki耦合反应， 降 至室温后终止反应， 向所得溶液中加入曱醇沉析， 通过索氏提取器提取之后依 次用曱醇和正己烷抽提， 然后用氯仿抽提至无色， 收集氯仿溶液并旋干， 得到 红色粉末， 收集所得红色粉末真空干燥后即得式 (I)所示共聚物
Figure imgf000012_0003
其中， R2均为 ~ C2。的烷基， n为 10 ~ 100的整数。
3、 如权利要求 2所述的制备方法， 其特征在于， 步骤（2 ) 中所述催化剂 为无机碱与有机钯的混合物， 或者有机钯与有机膦配体的混合物。
4、 如权利要求 3所述的制备方法， 其特征在于， 所述无机碱为碳酸钾、 碳 酸钠或碳酸氢钠。
5、 如权利要求 3所述的制备方法， 其特征在于， 所述有机钯为双三苯基膦 二氯化钯、四三苯基膦钯或者三二亚苄基丙酮二钯，所述有机钯与所述化合物 A 的摩尔比为 1:20〜謂。
6、 如权利要求 3所述的制备方法， 其特征在于， 所述有机膦配体为三叔丁 基膦、 三对曱苯基膦或 2-双环己基磷 -2，， 6，-二曱氧基联苯。
7、 如权利要求 6所述的制备方法， 其特征在于， 所述有机钯与有机膦配体 的混合物中有机钯与有机膦配体的摩尔比为 1:4〜8。
8、 如权利要求 2 所述的制备方法， 其特征在于， 步骤（2 ) 中所述有机溶 剂选自曱苯、 Ν,Ν-二曱基曱酰胺、 四氢呋喃中的至少一种。
9、 如权利要求 2所述的制备方法， 其特征在于， 所述 Suzuki耦合反应温度 为 70 ~ 130°C, 反应时间为 12 ~ 96 小时。
10、 一种太阳能电池， 包括依次层叠的阳极、 活性层和阴极， 其特征在于， 所述活性层中的电子给体材质为如权利要求 1所述的 2,7-咔唑与二噻。分基噻唑并 噻唑共聚物。
PCT/CN2011/083210 2011-11-30 2011-11-30 一种2，7-咔唑与二噻吩基噻唑并噻唑共聚物及其制备方法和包含其的太阳能电池 WO2013078635A1 (zh)

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