CN104045651A - 一种侧链含双季铵盐基团环戊并二噻吩及其共轭聚电解质的制备方法 - Google Patents

一种侧链含双季铵盐基团环戊并二噻吩及其共轭聚电解质的制备方法 Download PDF

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CN104045651A
CN104045651A CN201410184616.9A CN201410184616A CN104045651A CN 104045651 A CN104045651 A CN 104045651A CN 201410184616 A CN201410184616 A CN 201410184616A CN 104045651 A CN104045651 A CN 104045651A
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郭文娟
朱祥伟
裴梅山
丁峰
刘俊芝
王小超
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Abstract

本发明是一种侧链含双季铵盐基团环戊并二噻吩及其共轭聚电解质的制备方法。该合成方法以4H-环戊并[2,1-B:3,4-B']二噻吩为起始原料，经过与二溴丙烷反应溴化，与二甲胺反应后胺基化，以及与溴甲烷反应后季铵盐化制得一种具有水溶性的环戊并二噻吩衍生物，并用三氯化铁引发其发生聚合反应。产品纯度96%以上。本发明具有反应步骤简便易操作，原料易得，生产成本低，产品收率高和纯度高等优点。

Description

一种侧链含双季铵盐基团环戊并二噻吩及其共轭聚电解质的制备方法
技术领域
一种侧链含双季铵盐基团环戊并二噻吩及其共轭聚电解质的制备方法。该合成方法以4H-环戊并[2,1-B:3,4-B']二噻吩为起始原料，依次经过与二溴丙烷溴化反应，与二甲胺胺基化反应，以及与溴甲烷季铵盐化反应制备具有优良水溶性的环戊并二噻吩衍生物单体，并用三氯化铁引发该单体的聚合反应。 
背景技术
目前水溶性共轭聚电解质由于其将传统共轭聚合物的优异光电性质以及聚电解质的优良水溶性结合为一体，已经在新一代光电器件材料及化学生物荧光传感器的制备中获得大量的应用。该类化合物低毒环保，且由于侧链带有亲水性离子基团而具有良好的水溶性，在光电材料加工、生物检测等应用领域可操作性强，展现了比传统的导电聚合物更好的实用价值。目前应用较为广泛的水溶性共轭聚电解质按其聚合物共轭骨架分类主要有聚芴类、聚噻吩类、聚苯胺类等，而环戊并二噻吩类共轭聚电解质的合成及应用尚处于空白期。 
环戊并二噻吩及其衍生物是一种新兴的有机光电材料。由于此类有机化合物的分子稠环结构对称，平面性良好，具有较低的能隙，该类化合物作为噻吩的一类衍生物，在有机太阳能电池、有机薄膜晶体管、有机发光二极管和导电聚合物等方面展现了重要的应用价值。 
目前广泛应用的环戊并二噻吩及其改性后的衍生物主要是非水溶性的，包括环戊并[2,1-B:3,4-B']二噻吩-4-酮及结构类似物，4位上接枝烷基侧链的环戊并[2,1-B:3,4-B']二噻吩及其结构类似物，以上几类化合物由于其水溶性较差，限制了该类光电化合物在生物检测方面的应用。水溶性环戊并二噻吩类共轭聚电解质由于其稠环骨架的平面对称性好，共轭程度高，在溶液中可以消除由于主链旋转带来的不利影响，因而显示出了较好的应用价值。 
发明内容
本发明的目的是合成水溶性环戊并二噻吩单体4,4'-双(3-三甲基溴化铵基丙基)-4H-环戊并[2,1-B:3,4-B']二噻吩并引发其聚合，实现水溶性环戊并二噻吩共轭聚电解质的制备及应用。 
本发明的特征是：以4H-环戊并[2,1-B:3,4-B']二噻吩为起始原料，经过与二溴丙烷反应溴化，与二甲胺反应后胺基化，以及与溴甲烷反应后季铵盐化制得4,4'-双(3-三甲基溴化铵基丙基)-4H-环戊并[2,1-B:3,4-B']二噻吩，并通过化学氧化法以三氯化铁为引发剂聚合单体合成目标聚合物聚[4,4'-双(3-三甲基氯化铵基丙基)-4H-环戊并[2,1-B:3,4-B']二噻吩]。 
该合成方法的主要内容叙述如下：4,4'-双(3-溴丙基)-4H-环戊并[2,1-B:3,4-B']二噻吩（1）的合成：以碘化钾作为催化剂，氮气氛围下4H-环戊并[2,1-B:3,4-B']二噻吩、二溴丙烷在含有氢氧化钾的二甲基亚砜溶液中于暗室下搅拌发生取代反应。投料摩尔比为：4H-环戊并[2,1-B:3,4-B']二噻吩：二溴丙烷：氢氧化钾：碘化钾=1:2.5:5:0.06，反应温度为25℃，反应时间为12~14 h，用正己烷为展开剂柱层析得淡黄色油状产物。 
4,4'-双(3-二甲胺基丙基)-4H-环戊并[2,1-B:3,4-B']二噻吩（2）的合成：氮气氛围下4,4'-双(3-溴丙基)-4H-环戊并[2,1-B:3,4-B']二噻吩、二甲胺在甲醇溶液中进行胺基化反应。投料摩尔比为：4,4'-双(3-溴丙基)-4H-环戊并[2,1-B:3,4-B']二噻吩：二甲胺=1:2.3，反应温度为25℃，反应时间为48~72 h，用正己烷：乙酸乙酯：甲醇：三乙胺 = 30:6:5:1的溶液为展开剂柱层析得淡黄色油状产物。 
4,4'-双(3-三甲基溴化铵基丙基)-4H-环戊并[2,1-B:3,4-B']二噻吩（3）的合成：氮气氛围下4,4'-双(3-二甲胺基丙基)-4H-环戊并[2,1-B:3,4-B']二噻吩、溴甲烷在乙腈溶液中进行季铵化反应。投料摩尔比为：4,4'-双(3-二甲胺基丙基)-4H-环戊并[2,1-B:3,4-B']二噻吩：溴甲烷=1:8。反应温度为25℃，反应时间为48~72 h，从乙腈溶液中析出白色针状产物。 
聚[4,4'-双(3-三甲基氯化铵基丙基)-4H-环戊并[2,1-B:3,4-B']二噻吩]（4）的合成：氮气保护下以三氯化铁作为引发剂在无水氯仿中引发单体4,4'-双(3-三甲基溴化铵基丙基)-4H-环戊并[2,1-B:3,4-B']二噻吩聚合。投料摩尔比为：4,4'-双(3-三甲基溴化铵基丙基)-4H-环戊并[2,1-B:3,4-B']二噻吩：三氯化铁=1:5，反应温度为5℃，反应时间为12~24 h。反应结束后产物去掺杂，以四丁基氯化铵进行离子交换，索式抽提除去小分子后得到紫黑色粉末。 
本发明与现有技术相比，具有以下优点： 
（1）本发明的合成路线在常温下进行，无需加热等处理，降低了反应的难度，从而在一定程度上能提高目标化合物的收率，缩减了反应成本。
（2）合成路线中的各步反应易操作，各步反应产品易分离提纯且收率高。 
（3）本发明的合成路线中所用到的原料易得，生产成本低。 
附图说明
图1是聚[4,4'-双(3-三甲基氯化铵基丙基)-4H-环戊并[2,1-B:3,4-B']二噻吩]的合成路线图。 
实施方式：
为了易于进一步理解本发明，下列实施例阐述了更特定的细节。
实施例1 
4,4'-双(3-溴丙基)-4H-环戊并[2,1-B:3,4-B']二噻吩（1）的合成
将0.2g 4H-环戊并[2,1-B:3,4-B']二噻吩、0.68g二溴丙烷以及6mg的碘化钾溶于3mL的二甲基亚砜溶液， 于氮气保护下将以上混合液缓慢滴加至3mL含0.25g氢氧化钾的二甲基亚砜溶液中，将反应装置于暗室下搅拌反应14小时。加入30mL蒸馏水淬灭反应，用二氯甲烷溶液萃取产物，并用饱和氯化钠溶液洗涤产品2到3次，用分液漏斗分液，取上层***溶液用无水硫酸镁干燥、过滤，旋蒸浓缩溶液后用正己烷为展开剂柱层析得淡黄色油状产物4,4'-双(3-溴丙基)-4H-环戊并[2,1-B:3,4-B']二噻吩（534mg，产率：53%）。
4,4'-双(3-二甲胺基丙基)-4H-环戊并[2,1-B:3,4-B']二噻吩（2）的合成 
配制浓度为12mol/L的二甲胺甲醇溶液，将4,4'-双(3-溴丙基)-4H-环戊并[2,1-B:3,4-B']二噻吩（534mg）旋蒸去除溶剂后并真空干燥，加入5mL二甲胺甲醇溶液，超声30分钟后于常温下反应24h。反应结束后旋蒸除去溶剂，加入氯仿萃取产物，并用质量分数为5%的碳酸氢钠溶液洗涤产品2到3次，用分液漏斗分液，取上层黄色溶液用无水硫酸镁干燥、过滤，旋蒸浓缩溶液后用正己烷：乙酸乙酯：甲醇：三乙胺=30:6:5:1的溶液为展开剂柱层析得淡黄色油状产物。以等体积的正己烷和乙酸乙酯溶液洗涤产物，干燥旋蒸得到淡黄色产品4,4'-双(3-二甲胺基丙基)-4H-环戊并[2,1-B:3,4-B']二噻吩（338mg, 76%）。
4,4'-双(3-三甲基溴化铵基丙基)-4H-环戊并[2,1-B:3,4-B']二噻吩（3）的合成 
配制浓度为4mol/L的溴甲烷乙腈溶液，将4,4'-双(3-二甲胺基丙基)-4H-环戊并[2,1-B:3,4-B']二噻吩（338 mg）旋蒸去除溶剂后并真空干燥，加入4mL配制的溴甲烷乙腈溶液，常温下搅拌反应24h后，溶液中析出白色针状结晶，旋蒸去除溶剂后，用正己烷洗涤产品3次，干燥过滤得到白色固体状产品 (443 mg, 85%)。
聚[4,4'-双(3-三甲基氯化铵基丙基)-4H-环戊并[2,1-B:3,4-B']二噻吩]（4）的合成 
单体4,4'-双(3-三甲基溴化铵基丙基)-4H-环戊并[2,1-B:3,4-B']二噻吩（400 mg）超声分散于无水氯仿中，迅速加入660mg无水三氯化铁，氮气氛围下于温度5℃下引发聚合24h，反应结束后加少量甲醇淬灭反应，将反应物滤出，取滤渣加水合肼/甲醇溶液溶解，加入四丁基氯化铵进行离子交换四次以去除溴离子，以丙酮/甲醇溶液索式提取除去低分子聚合物，最终得到紫黑色粉末聚合物(169mg, 42%)。

Claims (6)

1.一种侧链含双季铵盐基团环戊并二噻吩及其共轭聚电解质的制备方法。
2.该合成方法以4H-环戊并[2,1-B:3,4-B']二噻吩为起始原料，经过与二溴丙烷反应溴化，与二甲胺反应后胺基化，以及与溴甲烷反应后季铵盐化制备具有良好水溶性的环戊并二噻吩衍生物，并用三氯化铁引发其聚合。
3.如权利要求1中所述的溴化反应是以碘化钾作为催化剂，氮气氛围下4H-环戊并[2,1-B:3,4-B']二噻吩、二溴丙烷在含有氢氧化钾的二甲基亚砜溶液中于暗室下进行反应。
4.如权利要求1中所述的胺基化反应是在氮气氛围下4,4'-双(3-溴丙基)-4H-环戊并[2,1-B:3,4-B']二噻吩、二甲胺在甲醇溶液中进行反应。
5.如权利要求2中所述的季铵盐化反应是在氮气氛围下4,4'-双(3-二甲胺基丙基)-4H-环戊并[2,1-B:3,4-B']二噻吩、溴甲烷在乙腈溶液中进行季铵化反应。
6.如权利要求2中所述的聚合反应是利用三氯化铁将制备的单体4,4'-双(3-三甲基溴化铵基丙基)-4H-环戊并[2,1-B:3,4-B']二噻吩在无水氯仿中引发聚合反应，后经产物去掺杂，利用四丁基氯化铵进行离子交换，索式抽提后处理制得。
CN201410184616.9A 2014-05-05 2014-05-05 一种侧链含双季铵盐基团环戊并二噻吩及其共轭聚电解质的制备方法 Expired - Fee Related CN104045651B (zh)

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