CN113754868B - 基于噻吩与苯并噻二唑的共轭聚合物及其制备方法 - Google Patents
基于噻吩与苯并噻二唑的共轭聚合物及其制备方法 Download PDFInfo
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- CN113754868B CN113754868B CN202111008316.1A CN202111008316A CN113754868B CN 113754868 B CN113754868 B CN 113754868B CN 202111008316 A CN202111008316 A CN 202111008316A CN 113754868 B CN113754868 B CN 113754868B
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- Prior art keywords
- thiophene
- conjugated polymer
- benzothiadiazole
- polymer based
- monomer
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- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229920000547 conjugated polymer Polymers 0.000 title claims abstract description 27
- 229930192474 thiophene Natural products 0.000 title claims abstract description 20
- FNQJDLTXOVEEFB-UHFFFAOYSA-N 1,2,3-benzothiadiazole Chemical compound C1=CC=C2SN=NC2=C1 FNQJDLTXOVEEFB-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 239000005964 Acibenzolar-S-methyl Substances 0.000 title claims abstract description 19
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
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- IEPCZQNAYOMNIG-UHFFFAOYSA-N C=C.CCCC[Sn](CCCC)CCCC Chemical group C=C.CCCC[Sn](CCCC)CCCC IEPCZQNAYOMNIG-UHFFFAOYSA-N 0.000 claims description 4
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- ARYHTUPFQTUBBG-UHFFFAOYSA-N thiophen-2-ylboronic acid Chemical compound OB(O)C1=CC=CS1 ARYHTUPFQTUBBG-UHFFFAOYSA-N 0.000 claims description 3
- IIOSDXGZLBPOHD-UHFFFAOYSA-N tris(2-methoxyphenyl)phosphane Chemical compound COC1=CC=CC=C1P(C=1C(=CC=CC=1)OC)C1=CC=CC=C1OC IIOSDXGZLBPOHD-UHFFFAOYSA-N 0.000 claims description 3
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- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
本发明涉及基于噻吩与苯并噻二唑的共轭聚合物及其制备方法。本发明中的基于噻吩与苯并噻二唑的共轭聚合物具有在可见‑近红外区宽而强的吸收，且柔性侧链可为材料提供良好的溶解度，因此该材料可溶液加工。所以本发明作为半导体活性层给体材料在有机场效应晶体管器件中有潜在的应用前景。本发明中基于噻吩与苯并噻二唑的共轭聚合物通过直接芳基化聚合而成。该方法不需要有机金属官能团的单体的制备，这有助于更高的原子经济，该方法还具有合成步骤少、避免有毒物质对人体和环境的危害等优点。本发明所涉及聚合方法符合环保、经济的绿色化学原则。
Description
技术领域
本发明涉及一种在可见-近红外区有强吸收的给体聚合物及其制备方法，属于有机场效应晶体管给体材料领域。
背景技术
有机场效应晶体管(Organic field-effect transistor,OFET)是一种利用有机半导体组成具有从传感器到电路或数据存储的应用的功能装置。有机场效应晶体管具有优异的机械柔性、重量轻、可低温沉积、较低的制造成本和大面积印刷等优点。尽管相对于传统的晶体管，有机场效应晶体管的电荷载流子迁移率较低，但其具有高的环境敏感性、选择性以及机械柔韧性，目前已经探索了有机场效应晶体管应用于各种传感器中，例如：气体传感器、湿度传感器、热传感器、化学传感器以及生物传感器等。
共轭聚合物是有机场效应晶体管的重要组成部分。这些共轭聚合物的聚合方法大都采用传统的芳基-芳基交叉耦合形成C-C键，比如Stille偶联，Suzuki偶联等。传统的偶联的方法可以合成大部分的聚合物，然而在合成过程中需要使用有机金属试剂，偶联同时会产生等化学计量的金属副产物。这些有机金属试剂的合成成本昂贵，且其本身和反应所得的副产物通常是具有毒性，会对人体以及环境造成伤害。近年来，直接芳基化引起了大家的重视，该方法在聚合过程中无需使用有机金属试剂，是替代传统偶联方法优异的选择。直接芳基化缩聚具有合成步骤更简化、无有机金属试剂参与反应、所得聚合物缺陷更少等优点。本发明采用直接芳基化缩聚符合环保、原子经济性的绿色化学原则。
发明内容
本发明的目的是提供一种通过直接芳基化缩聚合成的p-型共轭聚合物给体材料，得到一种基于噻吩与苯并噻二唑的共轭聚合物的制备方法。该聚合物采用直接芳基化合成，具有合成步骤简化，原料成本低，制备过程绿色环保等优点。本发明的聚合物可溶液处理，在可见光区域具有宽而强的光吸收，在有机场效应晶体管给体材料方面有很大的应用潜力。
本发明的目的是通过以下的技术方案实现的：
第一方面，本发明涉及基于噻吩与苯并噻二唑的共轭聚合物，所述共轭聚合物的结构式如式(Ⅰ)所示：
第二方面，本发明涉及基于噻吩与苯并噻二唑的共轭聚合物的制备方法，包括如下步骤：
(1)按摩尔量份数，将1份单体M1，1份单体M2，0.02-0.05份催化剂三(二亚苄基丙酮)二钯，0.1份三(2-甲氧基苯基)膦,3份碳酸钾，1.2份新戊酸，溶于邻二甲苯或2-甲基四氢呋喃中；在氩气气氛下，加热聚合后，经过索氏提取进行提纯，真空干燥获得黑色的基于噻吩与苯并噻二唑的共轭聚合物P。所述加热具体为：80℃下反应1～26小时；所述索氏提取依次采用的溶剂为甲醇、石油醚和氯仿。
所述单体M1的结构式如式(Ⅱ)所示：
所述单体M2(4,7-二溴-2,1,3-苯并噻二唑)的结构式如式(Ⅲ)所示：
(2)步骤(1)中所述的单体M1制备步骤如下:
a、按摩尔量份数，将1份4,7-二溴-5-硝基苯并[c][1,2,5]噻二唑与1.1份2-噻吩硼酸以及2M碳酸钾水溶液和0.005份催化剂加到有机溶剂，以70℃反应24小时；反应结束后，经硅胶柱提纯干燥后得到中间化合物A，其结构式如下：
b、按摩尔量份数，将1份中间化合物A与3份三苯基膦加到有机溶剂氯苯中，140℃反应17小时；反应结束后，经硅胶柱提纯干燥后得到粗产物；将粗产物与1.4份溴化烃以及0.3份碘化钾和1.7份碳酸钾加到有机溶剂N,N-二甲基甲酰胺中，以80℃反应17小时；反应结束后，经硅胶柱提纯干燥后得到单体前置体B，其结构式如下：
c、按摩尔量份数，将2.1份单体前置体B溶于有机溶剂中，与1份三丁基锡乙烯化合物C和0.19份的催化剂以115℃反应24小时，反应结束后，经硅胶柱提纯干燥后得到单体M1。
所述三丁基锡乙烯化合物C(反式-1,2-双(三丁基锡)乙烯)具有如下结构：
所述步骤a有机溶剂为四氢呋喃，催化剂为四(三苯基膦)钯，4,7-二溴-5-硝基苯并[c][1,2,5]噻二唑的合成参考专利：CN109879870A基于苯并噻二唑新型功能材料的合成及其应用；步骤b有机溶剂分别为氯苯和N,N-二甲基甲酰胺，溴化烃为C1-C30溴化烷烃；所述步骤c有机溶剂为甲苯，催化剂为四(三苯基膦)钯。
4,7-二溴-5-硝基苯并[c][1,2,5]噻二唑的具体结构如下：
本发明的显著优点
(1)本发明合成的p-型基于噻吩与苯并噻二唑的共轭聚合物的聚合方法是直接芳基化缩聚，该方法不需要使用有机金属官能团的单体，这有助于更高的原子经济，是一种绿色环保且经济的聚合方法。
(2)本发明所用到的原料均易获得且价格低，且合成工艺简单成熟，整体而言，合成成本低。
(3)本发明所制备的共轭聚合物，主链具有刚性平面的大π共轭结构，侧链为可增加聚合物柔性的烷基结构，使聚合物具有可溶液加工处理，使其具有作为有机场效应晶体管器件的潜力。
(4)本发明的聚合物具有较大的光吸收范围，良好的化学稳定性与热稳定性。
附图说明
图1为本发明实施例1中聚合物P的合成路线图。
图2为本发明实施例1中的单体M1核磁共振氢谱。
图3为本发明实施例1中的单体M1核磁共振碳谱。
图4为本发明实施例1中的聚合物P核磁共振氢谱。
图5为本发明实施例2中的聚合物P凝胶渗透色谱GPC(四氢呋喃为洗脱剂)。
图6为本发明实施例2中聚合物P紫外可见光谱。
图7为本发明实施例2中聚合物P的CV曲线图。
图8为本发明实施例2中聚合物P热重曲线图。
具体实施方式
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对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。
实施例1、基于噻吩与苯并噻二唑的共轭聚合物的制备
本实施例提供1种基于噻吩与苯并噻二唑的共轭聚合物，其合成路线参见图1。
1.1、单体M1的制备
单体M1的制备具体包括以下步骤：
(a)中间化合物A的合成
中间化合物A的结构式为
在氩气气氛下，将4,7-二溴-5-硝基苯并[c][1,2,5]噻二唑(5mmol)，2-噻吩硼酸(5.5mmol)和四氢呋喃(15mL)加入耐压管中，液下鼓泡20min后，加入2M碳酸钾水溶液(10mL)与四(三苯基膦)钯(0.025mmol)，液上除氧，封口。在70℃下反应24小时后，用水与二氯甲烷萃取，无水硫酸镁干燥，通过旋转蒸发去除溶剂后，将残余物通过硅胶柱色谱纯化(洗脱剂为二氯甲烷：石油醚＝1:2，体积比)，真空干燥后得到橙色固体中间化合物A(产率为20.6％)。
其中，4,7-二溴-5-硝基苯并[c][1,2,5]噻二唑的合成参考专利：CN109879870A基于苯并噻二唑新型功能材料的合成及其应用。
(b)单体前置体B的合成
单体前置体B的结构式为
在氩气气氛下，将中间化合物A(11.4mmol,)和氯苯(40mL)加入耐压管，液下鼓泡20min后，加入三苯基膦(36.4mmol)，液上除氧，封口。在140℃下反应17小时，待反应物冷却至室温后，旋转蒸发去除溶剂后，通过硅胶柱色谱提纯(洗脱剂为石油醚：乙酸乙酯＝4:1，体积比)，得到粗产物。将所得粗产物，1-溴-2-癸基十四烷(16.1mmol)和N,N-二甲基甲酰胺(40mL)加入耐压管中，液下鼓泡20min后，加入碳酸钾(19.3mmol)和碘化钾(3.4mmol)，液上除氧，封口。在80℃下反应17小时，待反应物冷却至室温后，用二氯甲烷进行萃取，所得有机相用水进行洗涤，收集有机相，用无水硫酸镁干燥。通过旋转蒸发去除溶剂后，将残余物通过硅胶柱色谱纯化(洗脱剂为二氯甲烷：石油醚＝2:3，体积比)，真空干燥后得到橙色油状物单体前置体B(产率为41.6％)。
(c)单体M1的合成
单体M1的结构式为
在氩气气氛下，将单体前置体B(1.19mmol),反式-1,2-双(三丁基锡)乙烯(0.57mmol)和甲苯(30ml)加入双口瓶并鼓泡30min后，加入四(三苯基膦)钯(0.11mmol)，液上除氧10min，封管。在115℃下反应24小时，待反应物冷却至室温后，用乙酸乙酯进行萃取，所得有机相用水进行洗涤，收集有机相，用无水硫酸钠干燥。通过旋转蒸发去除溶剂后，将残余物通过硅胶柱色谱纯化(洗脱剂为乙酸乙酯：石油醚＝1:30，体积比)，真空干燥后得到红色固体单体M1(产率为86.0％)。
1.2、聚合物P的合成
聚合物P的结构式为
本发明对共轭聚合物的反应条件进行了多次优化，首先是对聚合所使用的溶剂进行优化，选择了邻二甲苯、2-甲基四氢呋喃等作为溶剂。此外，还对催化剂的量进行优化。最终优化结果如下：
在氩气氛围下，向耐压管中加入单体M1(0.1mmol)，单体M2(0.1mmol)，碳酸钾(0.3mmol)，特戊酸(0.12mmol)和除氧的邻二甲苯(0.4mL)，待搅拌溶解后加入三(二亚苄基丙酮)二钯(0.005mmol)和三(2-甲氧基苯基)膦(0.01mmol)，液上除氧10min，封管。在80℃下反应2小时，待反应物冷却至室温，加入甲醇后减压过滤得粗产物。将粗产物依次用甲醇，石油醚和氯仿进行索氏提取，收集氯仿提取片段，减压去除溶剂，加入甲醇得到沉淀，过滤后真空干燥得到目标聚合物P(97.9％)。
实施例2、聚合物P的凝胶渗透色谱、紫外吸收光谱、电化学性质和热稳定性2.1、聚合物P的凝胶渗透色谱
图5给出了聚合物P的凝胶渗透色谱GPC测得的数均分子量为6179，重均分子量为51856，分布系数PDI为5.01。
2.2、聚合物P的紫外吸收光谱
图6给出了聚合物P在氯苯溶液和薄膜时的的紫外吸收光谱，可看到聚合物有两个吸收峰，它的薄膜的最大吸收峰位置在648nm左右，溶液的最大吸收峰位置在662nm左右，其紫外可见光吸收范围较广，说明聚合物P具有一定有机场效应晶体管的应用潜力。聚合物薄膜的起始吸收波长(λonsetfilm)为804nm，由此可计算出Egfilm＝1.54eV(Egfilm＝1240/λonsetfilm eV)，说明该聚合物是一个窄带隙聚合物。
2.3、聚合物P的电化学性质
以铂片为工作电极，铂丝为对电极，Ag/AgNO3电极为参比电极，0.1M的四丁基六氟磷酸铵乙腈溶液为电解质，二茂铁为标定物，扫描速度为60mV/s，在铂片上对聚合物进行了测试。图7给出了测试所得到的聚合物的电化学曲线。根据公式可计算其能级与能隙：EHOMO＝﹣(Eox onset+4.71)eV，ELUMO＝﹣(Ere onset+4.71)eV，Eg＝ELUMO－EHOMO，其中Eox onset是起始氧化电势，Ere onset是起始还原电势。
由图7可知，聚合物的Ere onset和Eox onset分别为-1.16V和0.40V。根据给出的公式可分别计算出，聚合物的HOMO能级和LUMO能级分别为-5.11eV和-3.55eV，能隙为1.56eV。从其能级的角度看其可以作为给体材料。
2.4、聚合物P的热稳定性
图8给出聚合物P的热分解温度为407℃，说明其具有良好的热稳定性。
2.5、聚合物P的溶解性
聚合物P室温下在氯仿、氯苯等溶剂中具有较好的溶解性，为其可溶液处理提供了保证。
以上所述仅为本发明的较佳实施例，凡依本发明申请专利范围所做的均等变化与修饰，皆应属本发明的涵盖范围。
Claims (6)
1.基于噻吩与苯并噻二唑的共轭聚合物，其特征在于，所述共轭聚合物的结构式如式(Ⅰ)所示：
2.一种制备如权利要求1所述的基于噻吩与苯并噻二唑的共轭聚合物的方法，其特征在于，包括如下步骤：
按摩尔量份数，将1份单体M1，1份单体M2，0.02-0.05份催化剂三(二亚苄基丙酮)二钯，0.1份三(2-甲氧基苯基)膦，3份碳酸钾，1.2份新戊酸，溶于无水邻二甲苯或2-甲基四氢呋喃中；在氩气气氛下加热聚合后，经过索氏提取进行提纯，真空干燥获得黑色的基于噻吩与苯并噻二唑的共轭聚合物；
所述单体M1的结构式如式(Ⅱ)所示：
所述单体M2的结构式如式(Ⅲ)所示：
3.根据权利要求2所述的基于噻吩与苯并噻二唑的共轭聚合物的制备方法，其特征在于，所述单体M1具体制备步骤为：
a、按摩尔量份数，将1份4,7-二溴-5-硝基苯并[c][1,2,5]噻二唑与1.1份2-噻吩硼酸以及2M碳酸钾水溶液和0.005份催化剂加到有机溶剂，以70℃反应24小时；反应结束后，经硅胶柱提纯干燥后得到中间化合物A，其结构式如下：
(A)
b、按摩尔量份数，将1份中间化合物A与3份三苯基膦加到有机溶剂氯苯中，140℃反应17小时；反应结束后，经硅胶柱提纯干燥后得到粗产物；将粗产物与1.4份溴化烃以及0.3份碘化钾和1.7份碳酸钾加到有机溶剂N,N-二甲基甲酰胺中，以80℃反应17小时；反应结束后，经硅胶柱提纯干燥后得到单体前置体B，其结构式如下：
(B)
c、按摩尔量份数，将2.1份单体前置体B溶于有机溶剂中，与1份三丁基锡乙烯化合物C和0.19份的催化剂以115℃反应24小时，反应结束后，经硅胶柱提纯干燥后得到单体M1；
所述三丁基锡乙烯化合物C具有如下结构：
4.根据权利要求3所述的基于噻吩与苯并噻二唑的共轭聚合物的制备方法，其特征在于，步骤a有机溶剂为四氢呋喃，催化剂为四(三苯基膦)钯；步骤b溴化烃为C1-C30溴化烷烃；所述步骤c有机溶剂为甲苯，催化剂为四(三苯基膦)钯。
5.根据权利要求2所述的基于噻吩与苯并噻二唑的共轭聚合物的制备方法，其特征在于，所述加热具体为：80℃下反应1～26小时；所述索氏提取依次采用的溶剂为甲醇、石油醚和氯仿。
6.根据权利要求1所述的基于噻吩与苯并噻二唑的共轭聚合物的应用，其特征在于，所述基于噻吩与苯并噻二唑的共轭聚合物作为半导体活性层给体材料在有机场效应晶体管器件中的应用。
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