CN106957411A - 一种吲哚‑吡咯共聚物及其制备方法 - Google Patents

一种吲哚‑吡咯共聚物及其制备方法 Download PDF

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CN106957411A
CN106957411A CN201710279930.9A CN201710279930A CN106957411A CN 106957411 A CN106957411 A CN 106957411A CN 201710279930 A CN201710279930 A CN 201710279930A CN 106957411 A CN106957411 A CN 106957411A
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copolymer
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蔡志江
宋现友
张青
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Tianjin Polytechnic University
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Abstract

本发明公开一种吲哚‑吡咯共聚物及其制备方法，属于高分子材料领域。该方法包括以下过程：首先将反应器抽真空，用干燥的纯氮气冲洗，保证无残余空气和水份；再在保持恒温情况下加入已用氮气脱过气的溶剂；然后在搅拌、氮气保护条件下，加入引发剂；再在恒压滴定漏斗中加入脱气吡咯和脱气的吲哚，将这两种单体并行滴加入到烧瓶中；滴加完毕后，恒温搅拌下反应；最后经过滤、洗涤、真空干燥后得到吲哚‑吡咯共聚物。本发明制备方法过程简单，所制备的吲哚‑吡咯共聚物转化率约为80～97％，导电率在0.15～3S/cm。

Description

一种吲哚-吡咯共聚物及其制备方法
技术领域
本发明属于高分子材料领域，涉及一种新型共聚物的制备方法，更具体地说，是涉及一种以吲哚和吡咯为单体的新型共聚物及其制备方法。
背景技术
1977年A.J.Heeger，A.G.MacDita rmid和白川英树(H.Shirakawa)发现，聚乙炔薄膜经电子受体(I，AsF5，等)掺杂后电导率增加了9个数量级，从10-6S/cm增加到103S/cm。这一发现打破了有机聚合物都是绝缘体的传统观念，开创了导电聚合物的研究领域，诱发了世界范围内导电聚合韧的研究热潮。大量的研究表明，各种共轭聚合物经掺杂后都能变为具有不同导电性能的导电聚合物，具有代表性的共轭聚合物有聚乙炔、聚吡咯、聚苯胺、聚噻吩、聚对苯撑乙烯、聚对苯等。
目前，对导电聚合物研究比较多是：聚苯胺和聚吡咯，对其聚合方法、电化学性能进行了深入的研究，并将其应用到了各种领域，如：日本的精工电子公司和桥石公司联合研制的3伏钮扣式聚苯胺电池已在日本市场销售，德国的BASF公司研制的聚吡咯二次电池也在欧洲市场出现，日本关西电子和住友电气合作试制出高输出大容量的锂-聚合物二次电池。与普通的铅蓄电池相比，这种二次电池具有能量密度高、转换效率高和便于管理等特点。然而，在这些芳香化合物类的导电聚合物中，对聚吲哚及其衍生物的研究却很少，虽然聚吲哚既具有类似聚吡咯的环状结构，有具有聚苯胺中的N-H键。最早对聚吲哚进行研究报道的是Tourillon和Garnier，他们通过阳极氧化吲哚单体合成聚吲哚，并发现它有非常优异的电化学性能；后来，Waltman系统的研究了用电化学方法合成聚吲哚及其衍生物；随后人们又研究了吲哚聚合的聚合机理及聚吲哚的物理化学性能，并研究了将这种聚合物应用于传感器中。
发明内容
本发明的目的是以吲哚和吡咯为单体，通过化学聚合作用得到吲哚-吡咯的共聚物，使其兼具有聚吲哚和聚苯胺的优点，成为一种新型的导电高分子材料。
本发明采用下述技术方案实现。一种吲哚-吡咯共聚物及其制备方法，该方法首先将反应器抽真空，用干燥的纯氮气冲洗，保证无残余空气和水份；再在保持恒温情况下加入已用氮气脱过气的溶剂；然后在搅拌、氮气保护条件下，加入引发剂；再在恒压滴定漏斗中加入脱气吡咯和脱气的吲哚，将这两种单体并行滴加入到烧瓶中；滴加完毕后，恒温搅拌下反应；最后经过滤、洗涤、真空干燥后得到吲哚-吡咯共聚物，转化率约为80～97％，该吲哚-吡咯共聚物的导电率在0.15～3S/cm。该方法其特征在于包括以下过程：
(1)将反应器抽真空，用干燥的纯氮气反复冲洗3次，保证无残余空气和水份；溶剂、吲哚单体和吡咯单体采用真空过滤，然后氮气脱气后密封备用；
(2)将反应器保持恒温30～60℃，加入溶剂100～200ml，恒温3h；
(3)在搅拌、氮气保护条件下，加入溶有1.5～5g无水氯化铁和(或)3～15g过硫酸铵的去离子水50ml；
(4)在搅拌、氮气保护条件下，采用恒压滴定漏斗将10～30ml苯胺和10～30ml吲哚单体并行滴加入反应器中，滴加速度在0.1～5ml/min；
(5)滴加结束后，反应器恒温30～60℃，搅拌下反应5～24h；
(6)反应结束后，经真空过滤、去离子水洗涤、真空干燥后得到吲哚-吡咯共聚物，转化率约为80～97％，电导率约为0.15～3S/cm。
本发明制备方法过程简单，所制备的吲哚-吡咯共聚物具有较高的转化率和电导率。
具体实施方式
实施例1：
将反应器抽真空，用干燥的纯氮气反复冲洗3次，保证无残余空气和水份；氯仿、吲哚单体和吡咯单体采用真空过滤，然后氮气脱气后密封备用；将反应器保持恒温30℃，加入氯仿200ml，恒温3h；在搅拌、氮气保护条件下，加入溶有1.5g无水氯化铁和3g过硫酸铵的去离子水50ml；在搅拌、氮气保护条件下，采用恒压滴定漏斗将30ml苯胺和30ml吲哚单体并行滴加入反应器中，滴加速度在5ml/min；滴加结束后，反应器恒温30℃，搅拌下反应5h；反应结束后，经真空过滤、去离子水洗涤、真空干燥后得到吲哚-吡咯共聚物，转化率约为80％，电导率约为0.15S/cm。
实施例2：
将反应器抽真空，用干燥的纯氮气反复冲洗3次，保证无残余空气和水份；四氢呋喃、吲哚单体和吡咯单体采用真空过滤，然后氮气脱气后密封备用；将反应器保持恒温40℃，加入四氢呋喃180ml，恒温3h；在搅拌、氮气保护条件下，加入溶有2.5g无水氯化铁和7g过硫酸铵的去离子水50ml；在搅拌、氮气保护条件下，采用恒压滴定漏斗将25ml苯胺和20ml吲哚单体并行滴加入反应器中，滴加速度在3ml/min；滴加结束后，反应器恒温40℃，搅拌下反应8h；反应结束后，经真空过滤、去离子水洗涤、真空干燥后得到吲哚-吡咯共聚物，转化率约为85％，电导率约为0.35S/cm。
实施例3：
将反应器抽真空，用干燥的纯氮气反复冲洗3次，保证无残余空气和水份；乙腈、吲哚单体和吡咯单体采用真空过滤，然后氮气脱气后密封备用；将反应器保持恒温60℃，加入乙腈100ml，恒温3h；在搅拌、氮气保护条件下，加入溶有15g过硫酸铵的去离子水50ml；在搅拌、氮气保护条件下，采用恒压滴定漏斗将10ml苯胺和10ml吲哚单体并行滴加入反应器中，滴加速度在0.1ml/min；滴加结束后，反应器恒温60℃，搅拌下反应24h；反应结束后，经真空过滤、去离子水洗涤、真空干燥后得到吲哚-吡咯共聚物，转化率约为97％，电导率约为3S/cm。
实施例4：
将反应器抽真空，用干燥的纯氮气反复冲洗3次，保证无残余空气和水份；六氟异丙醇、吲哚单体和吡咯单体采用真空过滤，然后氮气脱气后密封备用；将反应器保持恒温50℃，加入六氟异丙醇150ml，恒温3h；在搅拌、氮气保护条件下，加入溶有5g无水氯化铁和5g过硫酸铵的去离子水50ml；在搅拌、氮气保护条件下，采用恒压滴定漏斗将15ml苯胺和15ml吲哚单体并行滴加入反应器中，滴加速度在0.5ml/min；滴加结束后，反应器恒温50℃，搅拌下反应12h；反应结束后，经真空过滤、去离子水洗涤、真空干燥后得到吲哚-吡咯共聚物，转化率约为90％，电导率约为1.5S/cm。

Claims (3)

1.一种吲哚-吡咯共聚物，其特征为，它由吲哚单体和吡咯单体在溶剂中通过引发剂反应生成的共聚物。
2.一种吲哚-吡咯共聚物的制备方法，其特征是它包括下列步骤：
(1)将反应器抽真空，用干燥的纯氮气反复冲洗3次，保证无残余空气和水份；溶剂、吲哚单体和吡咯单体采用真空过滤，然后氮气脱气后密封备用；
(2)将反应器保持恒温30～60℃，加入溶剂100～200ml，恒温3h；
(3)在搅拌、氮气保护条件下，加入溶有1.5～5g无水氯化铁和(或)3～15g过硫酸铵的去离子水50ml；
(4)在搅拌、氮气保护条件下，采用恒压滴定漏斗将10～30ml苯胺和10～30ml吲哚单体并行滴加入反应器中，滴加速度在0.1～5ml/min；
(5)滴加结束后，反应器恒温30～60℃，搅拌下反应5～24h；
(6)反应结束后，经真空过滤、去离子水洗涤、真空干燥后得到吲哚-吡咯共聚物，转化率约为80～97％，电导率约为0.15～3S/cm。
3.根据权利要求2所述的一种吲哚-吡咯共聚物的制备方法，其特征是：所述的溶剂可以是氯仿、四氢呋喃、乙腈、六氟异丙醇中的一种。
CN201710279930.9A 2017-04-21 2017-04-21 一种吲哚‑吡咯共聚物及其制备方法 Pending CN106957411A (zh)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101177483A (zh) * 2006-11-06 2008-05-14 天津科技大学 一种制备吲哚-苯胺共聚物的方法
CN104053689A (zh) * 2011-12-09 2014-09-17 南洋理工大学 聚(偏氟乙烯)系聚合物和至少一种类型的导电聚合物的接枝共聚物，以及形成该接枝共聚物的方法
CN104350625A (zh) * 2012-06-06 2015-02-11 沙特基础工业公司 铁电装置、相互连接件、及其制造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101177483A (zh) * 2006-11-06 2008-05-14 天津科技大学 一种制备吲哚-苯胺共聚物的方法
CN104053689A (zh) * 2011-12-09 2014-09-17 南洋理工大学 聚(偏氟乙烯)系聚合物和至少一种类型的导电聚合物的接枝共聚物，以及形成该接枝共聚物的方法
CN104350625A (zh) * 2012-06-06 2015-02-11 沙特基础工业公司 铁电装置、相互连接件、及其制造方法

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