CN113698381A - 一种芴基小分子半导体受体材料及其制备方法 - Google Patents
一种芴基小分子半导体受体材料及其制备方法 Download PDFInfo
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- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 title claims abstract description 14
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- -1 fluorenyl small molecule Chemical class 0.000 claims description 38
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical group N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 18
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- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/24—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
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- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
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Abstract
本发明属于有机太阳能电池受体材料技术领域,具体涉及一种芴基小分子半导体受体材料及其制备方法。在无机催化剂条件下将具有活性亚甲基的化合物与醛采用机械球磨方式进行Knoevenagel缩合反应,反应结束后,经提纯、真空干燥获得芴基小分子半导体,其在可见‑近红外区有宽而强的吸收,且柔性侧链为材料提供良好的溶解度,可溶液加工,作为半导体活性层受体材料在有机太阳能电池中有潜在的应用前景。本发明避免使用有害、高毒性的催化剂,减少有机溶剂的使用,符合环保、经济的绿色化学原则。
Description
技术领域
本发明属于有机太阳能电池受体材料技术领域,具体涉及一种芴基小分子半导体受体材料及其制备方法。
背景技术
上世纪九十年代,Paul Anastas和John Warner提出了今天仍在使用的绿色化学的12条原则,这些原则依赖于在化学过程和分析中尽量减少或不使用有毒溶剂,以及不产生废物。这些原则提出了从产品规划到其合成、加工、分析和使用后目的地的环保行动。(DOI:10.1016/j.jsps.2018.07.011,Evolution of green chemistry and itsmultidimensional impacts:A review和DOI:10.1039/C8GC00482J,The GreenChemisTREE:20years after taking root with the 12principles),自此绿色化学得以迅速发展,也开发出了一系列的绿色合成技术:例如超声合成技术(DOI:/10.3390/ph13020023,Ultrasound for Drug Synthesis:A Green Approach)、微波合成技术(DOI:10.3233/MGC-200956,A new rapid synthesis of potassium borates by microwaveirradiation)、无溶剂条件下的机械研磨(10.1134/s0036023621030116,Role of Mixingand Milling in Mechanochemical Synthesis)等。
机械化学(Mechanochemistry,也叫做机械力化学),是研究在利用机械力诱发物质化学性质发生变化的一门交叉学科。其起源于19世纪末,在1891年,德国学者Ostwald首次提出了机械化学新概念,随后Careey Lee报道了贵金属及汞的卤化物在研磨后会分解为卤素与金属。但是机械化学技术一直没有获得应有的重视,直到1962年Peters等报道了机械化学促进碳酸盐分解等机械化学反应的研究,同时将机械化学这一概念引入化学反应中,机械化学才逐渐引起了学术界的注意。不过由于溶剂反应在有机合成中的普遍应用,机械化学只是作为一种辅助手段一直发展得不愠不火。二十世纪末时机械化学作为一种新兴的绿色合成方法逐步应用于各种类型的共价有机合成反应中。而随着制造业的蓬勃发展,越来越多的机械化学设备被开发出来,与溶液反应相比,机械化学固态反应的优势也渐渐凸显。
机械研磨合成技术是机械化学各研究领域中起步最晚的,但却是这门新兴学科中应用最广泛的一种技术。它是利用固态的反应物在研磨(主要为机械球磨)过程中剪切、撞击产生的压力和温度,引发局部的、非均相的反应的方法。另外,机械研磨法除了促进纯固态合成,还可以促进有一定液态物质参与或者辅助的准固态合成(DOI:10.1002/cssc.201700873/Mechanochemical Ring-Opening Polymerization of Lactide:Liquid-Assisted Grinding for the Green Synthesis of Poly(lactic acid)with HighMolecular Weight)。
与传统溶液反应相比,机械研磨技术作为新兴的技术有着众多的优点:1)从根本上解决由溶剂造成的环境污染、安全隐患、资源浪费等问题;2)使得有些溶剂难以溶解的原料可以进行反应;3)分离效率可以得到优化;4)反应时间大幅度缩减等。
太阳能电池发展的初衷是应对环境与能源问题,机械力化学是在绿色化学的提出下应运而生,这两个领域在近数十年的发展过程中已经取得了很大的进步,而将有机太阳能电池中的有机分子合成与机械力化学两个领域结合运用却还没有被报道,而本发明就是将这两个领域结合在一起,将机械力化学应用在有机太阳能电池的有机合成中,使得有机太阳能电池的制造过程更加地绿色环保。
发明内容
本发明的目的在于提供一种芴基小分子半导体受体材料及其制备方法,改善现有有机太阳能电池领域所涉及的诺文葛尔缩合对环境不利的影响,是一种低成本、环境友好、易于工业化生产的新方法。
为实现上述目的,本发明采用的技术方案为:
一种芴基小分子半导体的结构式如式(Ⅰ-Ⅳ)所示:
其中R为C1-C30烷基链。
一种合成芴基小分子半导体的方法,包括如下步骤:
(1)按摩尔量份数,将单体M1,单体M2或单体M3或单体M4或单体M5,催化剂醋酸铵或醋酸钠或碳酸氢铵按照一定比例加入到球磨罐中,并加入不同规格的不锈钢磨球后封闭球磨罐;
(2)将球磨罐装在行星式球磨机上,然后以一定的转速球磨,反应一定时间,期间使用薄层色谱进行监控反应进程;
(3)反应结束后,经过有机溶剂溶解、萃取、柱层析以及重结晶进行提纯,真空干燥获得芴基小分子半导体。
步骤(1)中,单体M1的结构式如式(Ⅴ)所示:
单体M1和与其进行诺文葛尔缩合的单体M2或单体M3或单体M4或单体M5摩尔量份数比1:3-3.5。
单体M1与催化反应的催化剂醋酸铵或醋酸钠或碳酸氢铵摩尔量份数比1:12-24。
不锈钢磨球的直径3-11毫米。
通过2,7-二溴芴与溴代烷烃反应得到中间化合物A;从中间化合物A到单体M1具体的合成过程是按摩尔量份数,将1份中间化合物A、3份2-噻吩甲醛、1.51份碳酸钾、0.31份三甲基乙酸、0.08份配体、0.04份催化剂加到有机溶剂中,120℃反应24小时,反应结束后,经硅胶柱提纯干燥后得到单体M1;溴代烷烃为C1-C30溴代烷烃;单体M2或单体M3或单体M4或单体M5,催化剂醋酸铵或醋酸钠或碳酸氢铵,以及2,7-二溴芴与溴代烷烃,2-噻吩甲醛均是购买而来,不需合成。
所述中间化合物A具有如下结构:
步骤(2)中,球磨转速为540-900转/分钟,球磨时间为150-370分钟。
如果反应原料的活性不高,则需要高温辅助球磨,具体操作为,反应中断时将球磨罐敞口放置在真空干燥箱中,80℃抽真空1小时。
步骤(3)中,有机溶剂是乙酸乙酯或者二氯甲烷等一些对于产物有良好溶解性的溶剂,萃取使用的水或者饱和食盐水,柱层析使用的硅胶是二氧化硅、使用的洗脱剂为石油醚和二氯甲烷的混合溶剂,重结晶使用的溶剂为甲醇。
制得的芴基小分子半导体作为受体材料在有机太阳能电池中的应用。
本发明的有益效果在于:
(1)本发明是利用行星式球磨机的机械力作用合成芴基小分子半导体,同时将溶剂法常用的催化剂哌啶换成对环境更加友好的无机催化剂,该方法不需要使用有机溶剂进行溶解,另外大幅缩减了反应的时间,有助于更高的原子经济、节约能耗,是一种绿色环保且经济的合成方法。
(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)本发明所制备的芴基小分子半导体,侧链为可增加柔性的烷基结构,使小分子具有可溶液加工处理,同时具有较大的光吸收范围,良好的化学稳定性与热稳定性,使其具有作为有机太阳能电池受体材料的潜力。
附图说明
图1为本发明实施例1-4中芴基小分子半导体(Ⅰ-Ⅳ)的合成路线图。
图2为本发明实施例1中芴基小分子半导体(Ⅰ)的紫外可见光谱。
图3为本发明实施例1中芴基小分子半导体(Ⅰ)的循环伏安曲线图。
图4为本发明实施例2中芴基小分子半导体(Ⅱ)的紫外可见光谱。
图5为本发明实施例2中芴基小分子半导体(Ⅱ)的循环伏安曲线图。
图6为本发明实施例3中芴基小分子半导体(Ⅲ)的紫外可见光谱。
图7为本发明实施例3中芴基小分子半导体(Ⅲ)的循环伏安曲线图。
图8为本发明实施例4中芴基小分子半导体(Ⅳ)的紫外可见光谱。
图9为本发明实施例4中芴基小分子半导体(Ⅳ)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。
实施例1-实施例4中所述的单体M1制备首先是参考文献(DOI:10.1007/s00289-018-2401-3,Photophysical properties of new fluorene-based conjugated polymerscontaining polyphenylene-substituted dendronized core),通过2,7-二溴芴与1-溴己烷反应得到中间化合物A;
从中间中间化合物A到单体M1具体的合成过程为:在氩气保护下,将中间化合物A(0.55mmol)、碳酸钾(0.83mmol)、三甲基乙酸(0.17mmol)、2-噻吩甲醛(1.65mmol)、甲苯(5mL)加至厚壁反应瓶中,充分除氧后加入配体三环己基膦氟硼酸盐(0.044mmol)、醋酸钯(0.022mmol),于120℃反应24小时,反应结束后用二氯甲烷产物,用水进行萃取,无水硫酸镁干燥,旋蒸除去溶剂后使用石油醚与二氯甲烷(7:13,体积比)进行柱层析,得到黄色固体(产率为73.44%)。
单体M2或单体M3或单体M4或单体M5,催化剂醋酸铵或醋酸钠或碳酸氢铵,以及2,7-二溴芴与1-溴己烷,2-噻吩甲醛均是购买而来,不需合成。
实施例1.芴基小分子半导体(Ⅰ)的合成
本实施例提供一种合成芴基小分子半导体(Ⅰ)的方法,其合成路线参见图1。
本实施例中,芴基小分子半导体(Ⅰ)的结构式为
本发明对芴基小分子半导体(Ⅰ)的机械合成条件进行了多次优化,首先是对机械进行的诺文葛尔缩合所使用无机催化剂进行探寻,选择了醋酸铵、醋酸钠或碳酸氢铵等作为催化剂。此外,还对行星式球磨机进行机械力化学的反应参数(包括不锈钢磨球的大小和个数、行星式球磨机的转速)进行优化。最终优化结果如下:
使用行星式球磨机弗卡斯F-P400E进行反应,磨球选用直径约为6毫米的不锈钢磨球,个数为50个,占球磨罐体积的20~30%,球磨转速为720转/分钟,反应以醋酸铵作为催化剂。将单体M1(0.2mmol)、单体M2(0.45mmol)、醋酸铵(1.2mmol)加至球磨罐中,整个反应过程使用薄层色谱跟踪监测。在40分钟、80分钟各补加0.6mmol醋酸铵,在60分钟时补充了0.15mmol单体M2,球磨至160分钟结束反应。使用乙酸乙酯溶解产物再使用饱和食盐水进行萃取,无水硫酸钠进行干燥,旋蒸除去溶剂后使用柱层析和重结晶提纯得到黑色固体(60.4%)。1H NMR(600MHz,CDCl3,ppm):δ8.93(s,2H),8.73(d,J=7.7Hz,2H),7.99(d,J=6.9Hz,2H),7.92(d,J=3.9Hz,2H),7.87(d,J=7.9Hz,2H),7.80(dd,J=16.3,8.3Hz,8H),7.62(d,J=3.9Hz,2H),2.13(m,4H),1.11(m,J=7.2Hz,6H),1.05(m,4H),0.75(m,J=7.1Hz,6H),0.66(t,6H).
实施例2.芴基小分子半导体(Ⅱ)的合成
本实施例提供一种合成芴基小分子半导体(Ⅱ)的方法,其合成路线参见图1。
本实施例中,芴基小分子半导体(Ⅱ)的结构式为
本发明对芴基小分子半导体(Ⅱ)的机械合成条件主要参照实施例1,并加以优化,结果如下:
使用行星式球磨机弗卡斯F-P400E进行反应,磨球选用直径约为6毫米的不锈钢磨球,个数为50个,占球磨罐体积的20~30%,球磨转速为720转/分钟,反应以醋酸铵作为催化剂。将单体M1(0.2mmol)、单体M3(0.6mmol)、醋酸铵(1.2mmol)加至球磨罐中,整个反应过程使用薄层色谱跟踪监测。在40分钟、80分钟各补加0.6mmol醋酸铵,球磨至160分钟结束反应。使用乙酸乙酯溶解产物再使用饱和食盐水进行萃取,无水硫酸钠进行干燥,旋蒸除去溶剂后使用柱层析和重结晶提纯得到红色固体(50.9%)。1H NMR(600MHz,CDCl3,ppm):δ8.01(m,8H),7.85-7.74(m,10H),7.57(d,J=4.1Hz,2H),2.11(m,4H),1.15-1.00(m,12H),0.75(t,J=7.2Hz,6H),0.66(m,4H).
实施例3.芴基小分子半导体(Ⅲ)的合成
本实施例提供一种合成芴基小分子半导体(Ⅲ)的方法,其合成路线参见图1。
本实施例中,芴基小分子半导体(Ⅲ)的结构式为
本发明对芴基小分子半导体(Ⅲ)的机械合成条件主要参照实施例1,并加以优化,结果如下:
使用行星式球磨机弗卡斯F-P400E进行反应,磨球选用直径约为6毫米的不锈钢磨球,个数为50个,占球磨罐体积的20~30%,球磨转速为720转/分钟,反应以醋酸铵作为催化剂。将单体M1(0.2mmol)、单体M4(0.6mmol)、醋酸铵(1.2mmol)加至球磨罐中,整个反应过程使用薄层色谱跟踪监测。在40分钟、80分钟各补加0.6mmol醋酸铵,球磨至160分钟结束反应。使用乙酸乙酯溶解产物再使用饱和食盐水进行萃取,无水硫酸钠进行干燥,旋蒸除去溶剂后使用柱层析和重结晶提纯得到红色固体(86.2%)。1H NMR(600MHz,CDCl3,ppm):δ7.83(s,2H),7.80(d,J=7.9Hz,2H),7.76-7.73(m,4H),7.64(d,J=1.8Hz,2H),7.54(d,J=4.1Hz,2H),2.09-2.07(m,4H),1.13-1.00(m,12H),0.75(t,J=7.2Hz,6H),0.66-0.60(m,4H).
实施例4.芴基小分子半导体(Ⅳ)的合成
本实施例提供一种合成芴基小分子半导体(Ⅵ)的方法,其合成路线参见图1。
本实施例中,芴基小分子半导体(Ⅳ)的结构式为
本发明对芴基小分子半导体(Ⅳ)的机械合成条件主要参照实施例1,并加以优化,结果如下:
使用行星式球磨机弗卡斯F-P400E进行反应,磨球选用直径约为6毫米的不锈钢磨球,个数为50个,占球磨罐体积的20~30%,球磨转速为720转/分钟,反应以醋酸铵作为催化剂。将单体M1(0.2mmol)、单体M5(0.6mmol)、醋酸铵(1.2mmol)加至球磨罐中,整个反应过程使用薄层色谱跟踪监测。此反应的活性不高,使用高温辅助球磨,反应中断时将球磨罐敞口放置在真空干燥箱中,80℃抽真空1小时。在40分钟、80分钟、120分钟时抽真空保温1小时各补加1.2mmol醋酸铵,球磨至160分钟结束反应。使用乙酸乙酯溶解产物再使用饱和食盐水进行萃取,无水硫酸钠进行干燥,旋蒸除去溶剂后使用柱层析和重结晶提纯得到酒红色固体(31.0%)。1H NMR(600MHz,CDCl3,ppm):δ7.89(s,2H),7.75(d,J=8.0Hz,2H),7.68(d,J=7.7Hz,2H),7.61(s,2H),7.49(d,J=3.9Hz,2H),7.44(d,J=4.0Hz,2H),4.29-4.14(m,4H),2.11-2.03(m,4H),1.31(t,J=7.2Hz,6H),1.15-0.99(m,8H),0.75(m,8H),0.67(m,6H).
根据图2、图4、图6、图8四种芴基小分子半导体的紫外可见光谱可知,四种芴基小分子半导体(Ⅰ-Ⅳ)的溶液的最大吸收峰、薄膜的最大吸收波长和溶液的起始吸收波长、薄膜的起始吸收波长分别为:(Ⅰ)579nm,637nm,634nm,763nm,1.63eV;(Ⅱ)511nm,529nm,572nm,617nm,2.01eV;(Ⅲ)475nm,491nm,532nm,575nm,2.16eV;(Ⅳ)490nm,490nm,557nm,616nm,2.01eV。从这些数据来看,这四种芴基小分子半导体紫外可见光吸收范围较广,说明这四种小分子具有作为有机太阳能电池受体材料的潜力。
根据图3、图5、图7、图9四种芴基小分子半导体的循环伏安曲线图可知,四种芴基小分子半导体(Ⅰ-Ⅳ)的第一起始氧化电位、第一起始还原电位、HOMO能级、LUMO能级分别为:(Ⅰ)1.00V,-0.80V,-5.71eV,-3.91eV;(Ⅱ)1.14V,-1.04V,-5.85eV,-3.67;(Ⅲ)1.08V,-1.18V,-5.79eV,-3.53eV;(Ⅳ)0.94V,1.05V,-5.65V,-3.66eV。从能级的角度看四种芴基小分子半导体可以作为受体材料。
以上所述的实施例只是本发明的较佳方案,并非对本发明作任何形式上的限制,在不超出权利要求所记载的技术方案的前提下还有其它的变体及改型。
Claims (7)
4.根据权利要求2所述的方法,其特征在于:单体M1与单体N1的摩尔份数比为1:3-3.5。
5.根据权利要求2所述的方法,其特征在于:单体M1与催化剂的摩尔份数比为1:12-24。
6.根据权利要求2所述的方法,其特征在于:球磨转速为540-900转/分钟,球磨时间为150-370分钟,使用的不锈钢磨球的直径为3-11毫米。
7.一种如权利要求1所述的芴基小分子半导体或如权利要求2所述的方法制得的芴基小分子半导体作为受体材料在有机太阳能电池中的应用。
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