CN107118332A - 含4，4‑联吡啶侧链的聚合物 - Google Patents

含4，4‑联吡啶侧链的聚合物 Download PDF

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CN107118332A
CN107118332A CN201710174833.3A CN201710174833A CN107118332A CN 107118332 A CN107118332 A CN 107118332A CN 201710174833 A CN201710174833 A CN 201710174833A CN 107118332 A CN107118332 A CN 107118332A
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bipyridyl
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CN107118332B (zh
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杨成
刘冉
伍晚花
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    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
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    • C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
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Abstract

本发明为含4，4‑联吡啶侧链的聚合物，公开了一种由结构单元A和结构单元B构成的聚合物，其中，R表示C1‑C20的烷基。本发明提供了一类全新结构的聚合物，可以用于光电材料的制备。

Description

含4，4-联吡啶侧链的聚合物
技术领域
本发明涉及聚合物，具体涉及一种含4，4-联吡啶侧链的聚合物。
背景技术
大多数的共轭聚合物(CPs)活性材料在强极性溶剂中不溶解，而水溶性CPs则可溶解于强极性溶剂，因此，使用水溶性CPs可以很好地实现多层器件结构，这对于进一步提升有机高分子光电器件的性能具有重要的意义。
发明内容
本发明提供了一种由下述结构单元A和结构单元B构成的聚合物：
其中，R表示C1-C20的烷基。
进一步地，所述聚合物的分子量为140000～860000。
进一步地，R表示C1-C12的烷基，优选C1-C6的烷基。
进一步地，R表示甲基、正丙基、正丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基、正十一烷基或正十二烷基。
本发明还提供了一种制备前述聚合物的方法，
以下述式(1-a)化合物和式(1-b)化合物为原料，反应制备得到目标聚合物：
其中，X为Cl、Br或I。
进一步地，式(1-a)化合物与式(1-b)化合物的摩尔比为1:1～1:20。
进一步地，所述反应的溶剂为DMF。
进一步地，所述反应的温度为80℃～120℃。
进一步地，所述反应的温度为80℃～90℃。
本发明还提供了前述聚合物在制备光电材料上的用途。
本发明提供了的全新结构的聚合物，可以用于光电材料的制备。
本发明提供的新的合成共轭聚合物的方法，该方法相对于传统合成方法来说反应条件更简单(无需除氧和加入催化剂)，产率高，同时可以控制侧链上的长度，控制产物在水或醇中的溶解性，具有很好的可溶液加工的特点。
显然，根据本发明的上述内容，按照本领域的普通技术知识和惯用手段，在不脱离本发明上述基本技术思想前提下，还可以做出其它多种形式的修改、替换或变更。
以下通过实施例形式的具体实施方式，对本发明的上述内容再作进一步的详细说明。但不应将此理解为本发明上述主题的范围仅限于以下的实例。凡基于本发明上述内容所实现的技术均属于本发明的范围。
附图说明
图1为实施例1中本发明关键原料单取代联吡啶的核磁氢谱。
图2-3为实施例2中本发明聚合物的核磁氢谱。
图4-14为实施例2中本发明聚合物的红外图谱。
图15为对照紫精的循环伏安图。
图16-20为本发明聚合物的循环伏安图。
图21-26为本发明聚合物的DLS结果。
具体实施方式
氧化铟锡导电玻璃(ITO)
poly(3-hexylthiophene)(P3HT)聚3-己噻吩
[6,6]-phenyl-C61-butyric acid methyl ester(PCBM)
[6,6]-苯基-C61-丁酸甲酯
实施例1本发明关键原料单取代联吡啶的制备
取一定量的4,4-联吡啶用DMF在磁力搅拌下溶解，待溶解完全后，加入RBr(RI)，期间用TLC检测反应，(展开剂用丙醇：乙酸乙酯(EA)：水＝7:7:5，并加入几滴氨水)至单取代产物不再增多，二取代产物量变多时，终止反应，减压蒸馏出其中的DMF，用对应的溶剂溶解，膜过滤后，用C18反相硅胶柱进行分离，收集单取代产物，结果如表1所示，核磁氢谱如图1所示。
当R基增加到庚烷后，随着碳链的增长，水对产物的溶解能力越来越弱，需加入一定量的乙醇进行助溶。
表1
(注：---表示室温，未加热)
实施例2本发明聚合物的制备
按照表2中条件，以R基的单取代4,4-联吡啶和溴丙炔为原料，制备得到本发明的聚合物，聚合物的重均分子量(Mw)约为140000-860000。
表2
实验步骤具体为：取一定量的单取代原料，用DMF在磁力搅拌下溶解，待溶解完全后，加入溴丙炔，控制温度在80～120℃，期间用TLC检测反应，(展开剂用丙醇：乙酸乙酯(EA)：水＝7:7:5，并加入几滴氨水)至原料点消失时，反应至体系颜色不发生变化时终止反应，加入大量的乙酸乙酯，有黑色沉淀生成，抽滤后，得到黑色固体。
核磁氢谱如图2-3所示，红外图谱如图4-14所示。
实施例3本发明聚合物的循环伏安曲线(CV)
溶液配制：
用0.1mol/L的KCl溶液配制5mmol/L的铁氰化钾K3[Fe(CN)6]水溶液作为电极打磨校正液，用来矫正对工作电极的打磨程度。
用0.1mol/L的KCl溶液配制0.02mg/mL配制研究对象的水溶液。将打磨好的电极测试电极打磨校正液，直至△Ep≦0.08,则认为打磨完毕，电极方可使用。
对照紫精(purpurine)和本发明聚合物P01、P03、P04、P05和P06的结果如图15-20所示。
由图可以看出，合成的聚合物较紫精更加稳定，且图中的氧化还原电位为该聚合物制作电池材料提供了数据支持。
实施例4本发明聚合物作为OPV(organic photovoltaic)器件材料的性能
器件制作实验
器件结构：ITO/样品(6nm)/P3HT:PCBM(200nm)/MoO3(5nm)/Al(100nm)
实验步骤：ITO准备：依次用洗洁精加去污粉，丙酮，异丙醇清洗；旋涂样品前对ITO玻璃片紫外处理20min。
旋涂：在ITO上旋涂样品，120℃退火20min，转移至手套箱；旋涂P3HT:PCBM(1:1)活性层溶液，800rpm，28s；慢干2h；110℃退火10min；擦去多余活性层后转移至蒸镀舱待蒸镀。
蒸镀：真空度达到1.0×10-5mbar时，依次蒸镀MoO3(速率5nm)，Al(速率100nm)。器件活性层面积：0.04cm2。
测试结果如表3所示。
表3
PCE(power conversion efficiency)光电转换效率 VOC(V)open circuitvoltage开路电压
JSC(mA/cm2)short circuit current density短路电流 FF(fill factor)填充因子
FF的定义公式为FF＝Jm Vm/JSC VOC(Jm和Vm分别表示输出功率最大时的电流和电压)
实施例5对本发明聚合物分子量的预估
对聚合物分子量的预估：将聚合物分散溶剂中0.025mg/mL，(1-7溶剂为水，8-12溶剂为乙醇)进行动态光散射测量，DLS结果如图21-26所示，根据所示的结果可以估计聚合物的颗粒大小约为100nm-600nm之间，则可以预算出聚合物的聚合度约为500-3000，分子量大约为140,000-860,000(14万-86万)。

Claims (10)

1.一种由下述结构单元A和结构单元B构成的聚合物：
其中，R表示C1-C20的烷基。
2.根据权利要求1所述的聚合物，其特征在于：所述聚合物的分子量为140000～860000。
3.根据权利要求1或2所述的聚合物，其特征在于：R表示C1-C12的烷基，优选C1-C6的烷基。
4.根据权利要求3所述的聚合物，其特征在于：R表示甲基、正丙基、正丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基、正十一烷基或正十二烷基。
5.一种制备权利要求1～4任一项所述聚合物的方法，其特征在于：
以下述式(1-a)化合物和式(1-b)化合物为原料，反应制备得到目标聚合物：
其中，X为Cl、Br或I。
6.根据权利要求5所述的方法，其特征在于：式(1-a)化合物与式(1-b)化合物的摩尔比为1:1～1:20。
7.根据权利要求5或6所述的方法，其特征在于；所述反应的溶剂为DMF。
8.根据权利要求5～7任一项所述的方法，其特征在于：所述反应的温度为80℃～120℃。
9.根据权利要求8所述的方法，其特征在于：所述反应的温度为80℃～90℃。
10.权利要求1～4任一项所述聚合物在制备光电材料上的用途。
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EP3588634A1 (de) 2018-06-27 2020-01-01 Evonik Operations GmbH Verbessertes organisches elektrodenmaterial
WO2020126200A1 (en) 2018-12-17 2020-06-25 Evonik Operations Gmbh Solid electrolyte for organic batteries
WO2020182327A1 (en) 2019-03-14 2020-09-17 Evonik Operations Gmbh Process for producing a shaped organic charge storage unit
EP4016663A1 (de) 2020-12-17 2022-06-22 Evonik Operations GmbH Elektrodenmaterial für den druck von polymerbatterien

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3588634A1 (de) 2018-06-27 2020-01-01 Evonik Operations GmbH Verbessertes organisches elektrodenmaterial
WO2020002032A1 (en) 2018-06-27 2020-01-02 Evonik Operations Gmbh Improved organic electrode material
WO2020126200A1 (en) 2018-12-17 2020-06-25 Evonik Operations Gmbh Solid electrolyte for organic batteries
WO2020182327A1 (en) 2019-03-14 2020-09-17 Evonik Operations Gmbh Process for producing a shaped organic charge storage unit
EP4016663A1 (de) 2020-12-17 2022-06-22 Evonik Operations GmbH Elektrodenmaterial für den druck von polymerbatterien
WO2022128859A1 (de) 2020-12-17 2022-06-23 Evonik Operations Gmbh Neues elektrodenmaterial für den druck von polymerbatterien

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