CN113881019A - 一种基于2-吲哚酮的聚合物给体材料及其制备方法 - Google Patents
一种基于2-吲哚酮的聚合物给体材料及其制备方法 Download PDFInfo
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- QNLOWBMKUIXCOW-UHFFFAOYSA-N indol-2-one Chemical compound C1=CC=CC2=NC(=O)C=C21 QNLOWBMKUIXCOW-UHFFFAOYSA-N 0.000 title claims abstract description 33
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Abstract
Description
技术领域
本发明属于有机合成领域,具体涉及一种基于2-吲哚酮的聚合物给体材料及其制备方法。
背景技术
有机共轭聚合物是一类重要的半导体材料,具有良好的光电和热力学性能,使它们成为制造下一代电子产品的最佳候选材料,影响这类材料如可加工性等多种性能参数易于通过合成设计来调控。然而就目前情况来看,典型的合成方法主要采用过渡金属催化的交叉偶联反应,如在Pd催化剂存在的条件下,将二溴单体和有机锡试剂之间进行缩聚的Stille反应,或是涉及有机硼试剂间的Suzuki反应。这些方法不仅需要使用昂贵且不可持续的催化剂,氯代的高沸点有机溶剂,同时有机硼试剂、有机锡试剂等这类有机金属试剂的合成过程比较繁琐,加之有机金属试剂稳定性较差、不易提纯,导致这类单体合成成本较高,且不易宏量制备。此外,这类反应在聚合过程中还会生成大量毒性较大的副产物,这些缺点大大制约了这些有前途的材料的环境可持续性。
上述传统合成方法的缺点可以通过直接杂芳基化缩合反应(DHAP)避免。由于直接芳基化是通过芳基化合物的sp2C-H键功能化来形成不饱和C-C键的成键新方法,因此使用直接芳基化缩聚不需要有机金属单体,故而不会形成金属副产物。因此,该方法由于具有合成策略简单,单体合成步骤少,无需去除源自有机金属试剂的副产物等诸多先天优势,有利于π共轭聚合物的合成,更适用于有机光电器件制造的实际应用。
2-吲哚酮骨架结构是一类重要的有机结构块,它们广泛地存在于天然产物和药物分子之中,是生物医药等领域关键的中间体。因此,发展一种高效绿色的合成方法来制备基于2-吲哚酮单元的共轭聚合物具有重大意义。
发明内容
本发明目的在于提供一种操作简单,避免使用昂贵、高毒化学试剂的2-吲哚酮基共轭聚合物的合成方法。该聚合物采用直接碳氢活化合成,原料简单易得,合成简便,制备过程绿色环保,适用大规模生产。
本发明的目的是通过以下的技术方案实现的:
第一方面,所述基于2-吲哚酮的聚合物给体材料,其结构式如下所示:
其中,R为C1-C30烷基链,n≥1。
第二方面,所述基于2-吲哚酮的聚合物给体材料的合成方法,采用绿色环保的碳氢活化聚合。具体包括如下步骤:
按摩尔量份数,以1份的单体M为标准,将其与1.2份的新戊酸、3份的碳酸钾、0.01份的催化剂三(二亚苄基丙酮)二钯和0.04份的膦配体三(2-甲氧基苯基)膦,溶于无水甲苯有机溶剂中;整个体系在无水和无氧气氛下进行,90℃下反应19-24小时至胶状。经过索氏提取进行提纯,真空干燥获得有金属光泽的基于2-吲哚酮单元的聚合物给体材料。所述的单体M如下图所示:
其中,R为C1-C30烷基链。
所述的单体M第一种制备方法对应的具体制备步骤如下:
步骤S1按摩尔量份数,以1份含溴吲哚酮化合物A为标准,将其与1.05份噻吩甲醛化合物B和吡啶(5mL)依次加入到有机溶剂中并升温至回流温度进行反应;反应结束后,经硅胶柱提纯干燥后得到单体M;
所述含溴吲哚酮物质A具有如下结构:
其中,R为C1-C30烷基链。
(A)
所述噻吩甲醛化合物B具有如下结构:
(B)
所述步骤S1有机溶剂为甲醇,反应温度为70-80℃,反应时间为20-24小时。反应结束后,采用柱层析将产物分离纯化,所述柱层析的洗脱液为石油醚和二氯甲烷的混合溶剂。
含溴吲哚酮化合物A的合成参考文献:Luo,X.;Tran,D.T.;Sun,H.;Mi,T.;Kadlubowski,N.M.;Zhao,Y.;Zhao,K.;Mei,J.,Bis-Isoindigos:New Electron-DeficientBuilding Blocks for Constructing Conjugated Polymers with Extended ElectronDelocalization.Asian Journal of Organic Chemistry 2018,7,2248-2253。
噻吩甲醛化合物B的合成参考文献:Grisorio,R.;De Marco,L.;Allegretta,G.;Giannuzzi,R.;Suranna,G.P.;Manca,M.;Mastrorilli,P.;Gigli,G.,AnchoringStability and Photovoltaic Properties ofNew D(-Π-a)2Dyes for Dye-SensitizedSolar CellApplications.Dyes andPigments 2013,98,221-231。
所述的单体M第二种制备方法对应的具体制备步骤如下:
步骤SS1按摩尔量份数,以1份噻吩甲醛化合物B为标准,将其与1.1份含溴吲哚酮化合物C和哌啶5mL依次加入到有机溶剂中,升温至回流温度进行反应;反应结束后,所得固体用不同的有机溶剂依次洗涤,干燥后得到中间体D;所述含溴吲哚酮化合物C具有如下结构:
(C)
所述中间体D具有如下结构:
(D)
步骤SS2按摩尔量份数,以1份中间体D为标准,将其与5份碳酸钾和3份碘化烃依次加入到有机溶剂中并升温进行反应;反应结束后,经硅胶柱提纯干燥后得到单体M;
所述步骤SS1中反应时的有机溶剂为甲醇,反应结束后处理的不同有机溶剂依次为水、甲醇、乙酸乙酯。回流反应温度为70-80℃,反应时间为20-24小时。
所述步骤SS2的有机溶剂为N,N-二甲基甲酰胺,反应时间为先120℃反应1小时,再缓慢降温至80℃,碘化烃逐渐滴加完毕后再以80℃温度反应20-24小时。反应结束后,采用柱层析将产物分离纯化,所述柱层析的洗脱液为石油醚和二氯甲烷的混合溶剂。
含溴吲哚酮化合物C的合成参考文献:Maes,V.;Pirotte,G.;Brebels,J.;Verstappen,P.;Lutsen,L.;Vanderzande,D.;Maes,W.,Synthesis Ofn,N’-Dialkyl-6,6’-Dibromoisoindigo Derivatives by Continuous Flow.Journal of Flow Chemistry2015,5,201-209。
本发明的显著优点
(1)本发明合成的基于2-吲哚酮单元聚合物所采取的聚合方法是碳氢活化,该方法与目前普遍采用的过渡金属催化的交叉偶联缩聚相比,由于不需要合成高纯度有机金属试剂,符合绿色化学的理念,在共轭聚合物的合成方面具有先天优势。
(2)本发明所采用的原料均廉价易得,制备工艺简单成熟,合成成本低,且反应产率相对较高。
(3)反应的底物适用性比较广,能够高效合成各种功能基取代的2-吲哚酮衍生物。
(4)本发明的半导体聚合物,其侧链为可增强聚合物柔性的烷基结构,使聚合物具有可溶液加工处理,有利于作为太阳能电池或晶体管器件的应用。
附图说明
图1为本发明实施例3中聚合物的两条合成路线图。
图2为本发明实施例3中聚合物的核磁共振氢谱。
图3为本发明实施例3中聚合物的紫外吸收光谱。
图4为本发明实施例3中聚合物的循环伏安曲线图。
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。以下实施例旨在说明本发明而不是对本发明的进一步限定。
实施例1、基于2-吲哚酮单元单体的第一种合成方法
将6-溴-1-(2-辛基十二烷基)吲哚啉-2-酮(0.4926g,1mmol)、2,2’-联噻吩-5-甲醛(0.204g,1.05mmol)和干燥甲醇(60mL)加入到100mL的耐压管中。用氩气液面下脱气20分钟后以一秒一滴的滴加速度缓慢逐滴滴加吡啶(5mL)。再用氩气液面上除氧10分钟后将所得溶液体系升温至75℃搅拌回流反应24小时。冷却至室温后,通过TLC监测确认反应结束。残留物用硅胶柱色谱提纯,用石油醚/二氯甲烷(v/v,2/1)作为洗脱剂,除去溶剂后得到橙红色油状M(0.2854g,42.7%)。
实施例2、基于2-吲哚酮单元单体的第二种合成方法
a、中间体D的合成:
在氩气保护下,将6-溴-吲哚(2.3326g,11mmol),2,2’-联噻吩-5-甲醛(1.9427g,10mmol)和干燥甲醇(30mL)加入到250mL的双颈烧瓶中。用氩气液面下脱气20分钟后以一秒一滴的滴加速度向双颈烧瓶中缓慢滴加哌啶(2.5mL)。再用氩气液面上除氧10分钟后将所得溶液体系升温至75℃回流反应24小时。通过TLC监测确认反应结束,并将体系冷却至室温。将粗产物减压过滤,所得固体用水、甲醇、乙酸乙酯多次洗涤后直接收集得到中间体D(3.5544g,91.5%)。
b、单体M的合成:
在氩气保护下,将中间体D(0.7766g,2mmol),碳酸钾(1.3821g,10mmol)和N,N-二甲基甲酰胺(80mL)依次加入到250mL双颈烧瓶中。用氩气液面下脱气20分钟后用氩气液面上除氧10分钟,并将体系升温至120℃先反应1小时。待温度降至80℃后,再以一秒一滴的滴加速度缓慢滴加1-碘-2-辛基十二烷(2.4507g,6mmol)于反应瓶中,并以80℃温度继续反应24小时。溶液冷却至室温,通过TLC监测确认反应结束。残留物用二氯甲烷和水萃取三次后稀盐酸和饱和食盐水各洗涤一次。收集到的有机层用无水硫酸镁干燥并减压过滤。粗产物用硅胶柱色谱提纯,用二氯甲烷/石油醚(v/v,2/1)作为洗脱剂,除去溶剂后得到橙红色油状M(0.9992g,74.7%)。
单体M的核磁氢谱数据具体如下:1H NMR(400MHz,氘代氯仿)δ6.95(d,J=1.6Hz,1H),7.03–7.09(m,1H),7.16(dd,J=8.0,1.6Hz,1H),7.21(d,J=4.0Hz,1H),7.32(dd,J=11.0,6.5Hz,2H),7.40(d,J=3.6Hz,1H),7.61(d,J=3.0Hz,2H).
单体M的核磁碳谱数据具体如下:13C NMR(101MHz,氘代氯仿)δ14.26,14.27,22.81,22.83,26.55,26.79,29.45,29.49,29.68,29.72,29.77,29.79,30.06,30.13,31.23,31.66,32.03,32.06,36.32,37.35,44.67,66.80,111.90,119.61,119.75,121.71,123.05,123.93,124.38,125.36,126.14,128.34,128.56,136.58,137.17,138.90,142.91,145.89,161.51,166.65.
实施例1和实施例2的主要差别在于连接烷基链的先后问题。与实施例2相比,实施例1的合成步骤虽然只有一步,但所得产率相对较低。相反,实施例2中第一步6-溴-吲哚和噻吩甲醛化合物反应的后处理简单,无需经硅胶柱层析提纯,因此较优选实施例2的两步法。
实施例3、聚合物的合成
优化后的聚合条件如下:
将单体M(0.2007g,0.3mmol)、新戊酸(0.0368g,0.36mmol)、碳酸钾(0.1244g,0.9mmol)以及1mL无水甲苯投入到耐压管中,进行鼓泡除氧,最后加入催化剂三(二亚苄基丙酮)二钯(0.0027g,0.003mmol)和膦配体三(2-甲氧基苯基)膦(0.0042g,0.012mmol),90℃加热反应19小时至接近胶状,将反应液冷却到室温,加入甲醇沉淀,减压过滤出固体后依次用甲醇、石油醚、氯仿索氏提取。收集氯仿溶液,减压除去溶剂后再用甲醇沉淀得有金属光泽的黑色共轭聚合物,聚合物的氯仿片段产率为75%。
聚合物的核磁氢谱数据具体如下:1H NMR(400MHz,氘代氯仿)δ0.81–0.91(m,2H),1.24(d,J=10.8Hz,1H),1.27(s,6H),1.33(s,2H),7.06(s,1H).
实施例4、聚合物的紫外-可见吸收光谱
图3给出了聚合物在氯苯溶液和通过旋涂在载玻片上形成固态薄膜后的紫外吸收光谱。从图中不难看出,无论是在溶液中还是薄膜状态下该聚合物材料均显示出强而宽的吸收响应,并且由于聚合状态下聚合物链的聚集而发生明显红移(>20nm),其吸收范围明显更宽。该聚合物薄膜的起始吸收(λonset film)为775nm,根据公式Eg film=1240/λonset film eV计算可得Eg film=1.6eV。
实施例5、聚合物的电化学性质
聚合物的电化学性能是通过循环伏安法来测定(如图4)。采用盈思便携式电化学工作站,测试条件为:工作电极为铂碳电极、铂丝电极为对电极、饱和甘汞电极为参比电极,以0.1mol/L的四丁基六氟磷酸铵(Bu4NPF6)为电解质,乙腈为溶剂,扫描速度为60mV/s。最高占有分子轨道能级(HOMO)和最低未占有分子轨道能级(LUMO)由起始氧化电位(Eox on)和起始还原电位(Ered on)通过相应公式计算:EHOMO/LUMO=-e(Eox/red on+4.71)(eV),得出聚合物的HOMO能级为-5.35eV,LUMO能级为-3.5eV。相应地,由公式Eg CV=ELUMO-EHOMO计算得到聚合物的电化学带隙(Eg CV)为1.85eV。
综上可知,本发明涉及的2-吲哚酮基共轭聚合物的合成方法,采用6溴吲唑为原料,采用一步或两步合成2-吲哚酮基共轭聚合物,为2-吲哚酮基共轭聚合物的合成提供了新的思路和路线。其中,后上烷基链的两步法所得收率更高。此外,我们采用直接芳基化聚合,从而避免了常规技术中繁琐的反应操作,以及昂贵、高毒、高危试剂的使用,是一种符合绿色化学原则的合成方法。另外,该合成方法所用原料及辅料价廉易得、反应条件温和、操作简便,因而整个合成过程可控性强、后处理简单、适合大规模化生产。
上述对实施例的描述是为了便于该技术领域的普通技术人员能理解和使用本发明。熟悉本领域技术人员显然可以容易的对这些实施例做出各种修改,并把在此说明的一般原理应用到其他实施例中,而不必经过创造性的劳动。因此,本发明不限于上述实施例。本领域技术人员根据本发明的原理,不脱离本发明的范畴所做出的改进和修改都应该在本发明的保护范围之内。
Claims (10)
4.根据权利要求3所述的基于2-吲哚酮的聚合物给体材料的制备方法,其特征在于,碳氢活化聚合的反应具体为:90℃下反应至胶状,反应时间为19-24小时。
6.根据权利要求5所述的基于2-吲哚酮的聚合物给体材料的制备方法,其特征在于,有机溶剂为甲醇;所述回流反应温度为70-80℃,反应时间为20-24小时;反应结束后,采用柱层析将产物分离纯化,所述柱层析的洗脱液为石油醚和二氯甲烷的混合溶剂。
8.根据权利要求7所述的基于2-吲哚酮的聚合物给体材料的制备方法,其特征在于,所述步骤(1)中反应时的有机溶剂为甲醇,反应结束后处理的不同有机溶剂依次为水、甲醇、乙酸乙酯;回流反应温度为70-80℃,反应时间为20-24小时。
9.根据权利要求7所述的基于2-吲哚酮的聚合物给体材料的制备方法,其特征在于,所述步骤(2)的有机溶剂为N,N-二甲基甲酰胺,反应时间为先120℃反应1小时,再缓慢降温至80℃,碘化烃逐渐滴加完毕后再以80℃温度反应20-24小时;反应结束后,采用柱层析将产物分离纯化,所述柱层析的洗脱液为石油醚和二氯甲烷的混合溶剂。
10.如权利要求1所述的基于2-吲哚酮的聚合物给体材料在有机太阳能电池上的应用。
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Citations (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103467711A (zh) * | 2013-08-27 | 2013-12-25 | 上海交通大学 | 连二噻吩羟吲哚基的半导体聚合物及其制备、用途 |
US20140371409A1 (en) * | 2011-10-20 | 2014-12-18 | Universite Laval | Preparation of high molecular weight polymers by direct arylation and heteroarylation |
US20150105520A1 (en) * | 2013-10-15 | 2015-04-16 | The Board of Trustees of the Leland Stanford Junior Uninersity | Conjugated polymer-based apparatuses, articles and compounds |
CN104927030A (zh) * | 2015-06-09 | 2015-09-23 | 中国科学院化学研究所 | 吲哚-2-酮类聚合物及其制备方法与应用 |
CN105367561A (zh) * | 2015-11-19 | 2016-03-02 | 上海交通大学 | 一种吲哚衍生物及其共轭聚合物的制备和用途 |
CN105418896A (zh) * | 2015-12-02 | 2016-03-23 | 上海交通大学 | 吲哚与吩类化合物的共轭聚合物的制备方法 |
CN105418897A (zh) * | 2015-12-02 | 2016-03-23 | 上海交通大学 | 吲哚与吩类化合物的共轭聚合物及其制备方法和用途 |
CN105482082A (zh) * | 2014-09-19 | 2016-04-13 | 中国科学院苏州纳米技术与纳米仿生研究所 | 结构规整聚噻吩及其合成方法 |
CN106589326A (zh) * | 2016-12-05 | 2017-04-26 | 中国科学院化学研究所 | 二氟连二噻吩类聚合物及其制备方法与其在场效应晶体管中的应用 |
CN106750196A (zh) * | 2017-01-06 | 2017-05-31 | 天津大学 | 基于异靛蓝衍生物的电子传输型聚合物及有机场效应晶体管 |
CN108727567A (zh) * | 2018-05-03 | 2018-11-02 | 上海交通大学 | 引入重原子硒的异靛蓝衍生物共轭聚合物的制备及用途 |
CN108948329A (zh) * | 2018-06-12 | 2018-12-07 | 合肥工业大学 | 一种超低能级的共轭聚合物半导体材料及其制备方法 |
FR3069541A1 (fr) * | 2017-07-28 | 2019-02-01 | Centre National De La Recherche Scientifique | Molecule polymere comprenant des motifs pyrrolopyrrole et spirobifluorene notamment pour cellule photovoltaique et procede de preparation |
CN110028654A (zh) * | 2019-04-26 | 2019-07-19 | 南京邮电大学 | 基于萘酰亚胺-硒吩衍生物的有机n型半导体聚合物材料及其制备方法与应用 |
CN110283304A (zh) * | 2019-06-12 | 2019-09-27 | 南京邮电大学 | 一种二噻吩并苯二酰亚胺基共轭聚合物及其制备方法与应用 |
CN111961030A (zh) * | 2020-07-31 | 2020-11-20 | 天津大学 | 四氯代联噻吩、聚合物及合成方法和有机薄膜晶体管应用 |
CN112062938A (zh) * | 2020-09-14 | 2020-12-11 | 福州大学 | 基于吲哚酮与萘二酰亚胺单元的共轭聚合物及其制备方法 |
-
2021
- 2021-10-18 CN CN202111207774.8A patent/CN113881019A/zh active Pending
Patent Citations (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20140371409A1 (en) * | 2011-10-20 | 2014-12-18 | Universite Laval | Preparation of high molecular weight polymers by direct arylation and heteroarylation |
CN103467711A (zh) * | 2013-08-27 | 2013-12-25 | 上海交通大学 | 连二噻吩羟吲哚基的半导体聚合物及其制备、用途 |
US20150105520A1 (en) * | 2013-10-15 | 2015-04-16 | The Board of Trustees of the Leland Stanford Junior Uninersity | Conjugated polymer-based apparatuses, articles and compounds |
CN105482082A (zh) * | 2014-09-19 | 2016-04-13 | 中国科学院苏州纳米技术与纳米仿生研究所 | 结构规整聚噻吩及其合成方法 |
CN104927030A (zh) * | 2015-06-09 | 2015-09-23 | 中国科学院化学研究所 | 吲哚-2-酮类聚合物及其制备方法与应用 |
CN105367561A (zh) * | 2015-11-19 | 2016-03-02 | 上海交通大学 | 一种吲哚衍生物及其共轭聚合物的制备和用途 |
CN105418896A (zh) * | 2015-12-02 | 2016-03-23 | 上海交通大学 | 吲哚与吩类化合物的共轭聚合物的制备方法 |
CN105418897A (zh) * | 2015-12-02 | 2016-03-23 | 上海交通大学 | 吲哚与吩类化合物的共轭聚合物及其制备方法和用途 |
CN106589326A (zh) * | 2016-12-05 | 2017-04-26 | 中国科学院化学研究所 | 二氟连二噻吩类聚合物及其制备方法与其在场效应晶体管中的应用 |
CN106750196A (zh) * | 2017-01-06 | 2017-05-31 | 天津大学 | 基于异靛蓝衍生物的电子传输型聚合物及有机场效应晶体管 |
FR3069541A1 (fr) * | 2017-07-28 | 2019-02-01 | Centre National De La Recherche Scientifique | Molecule polymere comprenant des motifs pyrrolopyrrole et spirobifluorene notamment pour cellule photovoltaique et procede de preparation |
CN108727567A (zh) * | 2018-05-03 | 2018-11-02 | 上海交通大学 | 引入重原子硒的异靛蓝衍生物共轭聚合物的制备及用途 |
CN108948329A (zh) * | 2018-06-12 | 2018-12-07 | 合肥工业大学 | 一种超低能级的共轭聚合物半导体材料及其制备方法 |
CN110028654A (zh) * | 2019-04-26 | 2019-07-19 | 南京邮电大学 | 基于萘酰亚胺-硒吩衍生物的有机n型半导体聚合物材料及其制备方法与应用 |
CN110283304A (zh) * | 2019-06-12 | 2019-09-27 | 南京邮电大学 | 一种二噻吩并苯二酰亚胺基共轭聚合物及其制备方法与应用 |
CN111961030A (zh) * | 2020-07-31 | 2020-11-20 | 天津大学 | 四氯代联噻吩、聚合物及合成方法和有机薄膜晶体管应用 |
CN112062938A (zh) * | 2020-09-14 | 2020-12-11 | 福州大学 | 基于吲哚酮与萘二酰亚胺单元的共轭聚合物及其制备方法 |
Non-Patent Citations (4)
Title |
---|
DONG ZHAO: "Cyano substituted (Z)-(thienylmethylene)-2-indolone as a new building block for near-IR absorbing polymers", 《DYES AND PIGMENTS》 * |
FRANÇOIS GRENIER: "Electroactive and Photoactive Poly[Isoindigo-alt-EDOT] Synthesized Using Direct (Hetero)Arylation Polymerization in Batch and in Continuous Flow", 《CHEM. MATER.》 * |
WEI YANG: "Thienylmethylene Oxindole Based Conjugated Polymers via Direct Arylation Polymerization and Their Electrochromic Properties", 《CHINESE J. POLYM. SCI.》 * |
ZHIFENG DENG: "Centrosymmetric Thiophenemethyleneoxindole-Based Donor–Acceptor Copolymers for Organic Field-Effect Transistors", 《MACROMOL. RAPID COMMUN.》 * |
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