CN110408011B - 一种乙二叉二异喹啉四酮聚合物及其制备方法与应用 - Google Patents
一种乙二叉二异喹啉四酮聚合物及其制备方法与应用 Download PDFInfo
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Abstract
本发明公开了一种乙二叉二异喹啉四酮聚合物及其制备方法与应用。该乙二叉二异喹啉四酮聚合物的结构如式Ⅰ所示,其中,R为C1~C60的直链或支链烷基。本发明还提供了式I所示聚合物的制备方法。本发明的合成路线简单、有效;原料为商业化产品;合成方法具有普适性。以本发明乙二叉二异喹啉四酮聚合物为有机半导体层制备的有机场效应晶体管具有双极性的传输性质,开关比大于103,在有机场效应晶体管器件中有一定的应用前景。
Description
技术领域
本发明属于材料领域,涉及一种乙二叉二异喹啉四酮聚合物及其制备方法与应用。
背景技术
新型聚合物半导体材料是柔性电子学的核心部分。其具有可调控的分子结构,低廉的成本,可用于制备柔性器件等优点,在喷墨打印、卷对卷加工等方面具有很大的优势,成为最近的研究热点之一。合成新型聚合物半导体材料是本领域的重要研究方向。
发明内容
本发明的目的是提供一种乙二叉二异喹啉四酮聚合物及其制备方法与应用。
本发明所提供的乙二叉二异喹啉四酮聚合物,其结构通式如式I所示:
所述式I中,R为C1~C60或C10-C30或C15-C25的直链或支链烷基;具体为2-癸基十四烷基。
π基团为常见的共聚单元,具体可选自如下基团中的任意一种:
n为5-100,具体的,n可为5-60;更具体可为10-30;再具体可为11、22或29。
所述式I所示聚合具体为聚合物PEBIQ-DTE、PEBIQ-FBT或PEBIQ-DTBT;
其中,所述聚合物PEBIQ-DTE的结构式如下:
所述聚合物PEBIQ-FBT的结构式如下:
所述聚合物PEBIQ-DTBT的结构式如下:
本发明提供的制备所述式I所示聚合物的方法,包括如下步骤:
将式V所示化合物也即(4Z,4'Z)-4,4'-(乙烷-1,2-二基)双(7-溴-2-烷基异喹啉-1,3(2H,4H)-二酮)与双甲基锡化合物在催化剂和配体作用下进行聚合反应,反应完毕得到所述式I所示聚合物;
R的定义与前述式I中R的定义相同。
上述方法中,所述双甲基锡化合物选自如下化合物中的任意一种:
(也即3,3’-二氟-5,5’-双(三甲基锡烷基)-2,2’-联噻吩)、(也即(E)-1,2-双(5-(三甲基锡烷基)噻吩-2-基)乙烯)、 (也即4,7-双(4-己基-5-(三甲基锡烷基)噻吩-2-基)苯并[c][1,2,5]噻二唑)、
所述催化剂选自四(三苯基膦)钯、二(三苯基膦)二氯化钯、三(二亚苄基丙酮)二钯和二(二亚苄基丙酮)钯中的至少一种;
所述配体选自三苯基膦、三(邻甲苯基)膦、三(呋喃基)膦和三苯基胂中的至少一种。
所述双甲基锡化合物的投料摩尔份数为0.95~1.05份;
所述式V所示化合物也即(4Z,4'Z)-4,4'-(乙烷-1,2-二基)双(7-溴-2-烷基异喹啉-1,3(2H,4H)-二酮)的投料摩尔份数为0.95~1.05份;
所述催化剂的投料摩尔份数为0.01~0.10份;
所述配体的投料摩尔份数为0.04~0.40份;
所述双甲基锡化合物、式V所示(4Z,4'Z)-4,4'-(乙烷-1,2-二基)双(7-溴-2-烷基异喹啉-1,3(2H,4H)-二酮)、催化剂和配体的投料摩尔用量比具体为1.0:1.0:0.05:0.40;
所述聚合反应步骤中,温度为100~140℃,具体为130℃;
时间为24小时~96小时;
所述聚合反应在溶剂中进行;
所述溶剂具体选自甲苯、氯苯和四氢呋喃中的至少一种。
另外,上述方法中作为起始原料的式V所示化合物也属于本发明的保护范围。
所述式V中,R的定义与式I中R的定义相同。具体可为2-癸基十四烷基。
上述式V所示化合物可按照如下步骤制备而得:所有起始原料均为商业品。
1)5-溴-2-羧甲基苯甲酸在乙酸酐作用下于甲苯溶液中反应,反应完毕得到式VI所示的7-溴异苯并吡喃-1,3-二酮;
2)将步骤1)所得式VI所示7-溴异苯并吡喃-1,3-二酮与2-癸基十四-1-胺在甲苯/乙酸溶液中反应,反应完毕后得到式VII所示的7-溴-2-烷基异喹啉-1,3(2H,4H)-二酮;
3)将步骤2)所得式VII所示7-溴-2-烷基异喹啉-1,3(2H,4H)-二酮和乙二醛水溶液(40%)在酸催化下反应,反应完毕后得到式V所示的(4Z,4'Z)-4,4'-(乙烷-1,2-二亚基)双(7-溴-2-(2-烷基)异喹啉-1,3(2H,4H)-二酮);
上述方法的步骤1)中,所述5-溴-2-羧甲基苯甲酸与乙酸酐的投料摩尔用量比为1:1.0~2.0,优选1:1.5;反应步骤中,温度为110~120℃,时间为4~8小时;
所述步骤2)中,所述7-溴异苯并吡喃-1,3-二酮和2-癸基十四-1-胺的投料摩尔用量比为1:0.9~1.5,优选1:1.1;反应步骤中,反应的温度为110~120℃,时间为4~8小时;
所述步骤3)中,所述酸为乙酸、丙酸、三氟乙酸、三氟甲磺酸、盐酸、硫酸中的至少一种;所述7-溴-2-(2-癸基十四烷基)异喹啉-1,3(2H,4H)-二酮和乙二醛水溶液(40%)的投料摩尔用量比为1:0.4~0.6,优选1:0.5;反应步骤中,温度为90~120℃,时间为8~24小时;
上述步骤1)至步骤3)所述反应均在溶剂中进行。所述步骤1)中,所述溶剂为甲苯;所述步骤2)中,所述溶剂选自甲苯和乙酸中的至少一种;所述步骤3)中,所述溶剂选自甲苯和二甲苯中的至少一种。
上述方法的合成路线如图5所示。
上述本发明提供的式I所示化合物在制备聚合物场效应晶体管中的应用及以该化合物为半导体层的聚合物场效应晶体管,也属于本发明的保护范围。
聚合物半导体材料的设计要求分子具有一定的溶解性。本发明通过在共轭骨架上引入酰亚胺基团,实现了可控的能级结构、较好的溶解性和加工性能。该聚合物分子还具有高度对称的结构,有利于形成较好的分子间堆积,有利于载流子在分子间的传输。
本发明的优点在于:
1、原料为商业化产品,可以推广到含各种不同长度取代基的乙二叉二异喹啉四酮聚合物的合成;
2、乙二叉二异喹啉四酮单体具有中心对称性和高度的平面性,有利于聚合物分子的自组装;
3、乙二叉二异喹啉四酮聚合物分子具有较低的能级和带隙,有望应用于包括有机光伏器件等其他光电器件中;
4.以本发明乙二叉二异喹啉四酮聚合物为半导体层制备的有机场效应晶体管制备工艺简单,性能优良,在有机场效应晶体管中有良好的应用前景。
附图说明
图1为以本发明提供的乙二叉二异喹啉四酮聚合物的紫外可见吸收光谱图。
图2为以本发明提供的乙二叉二异喹啉四酮聚合物的循环伏安曲线图。
图3为以本发明提供的乙二叉二异喹啉四酮聚合物场效应晶体管的结构示意图。
图4为以本发明提供的乙二叉二异喹啉四酮聚合物为半导体层的聚合物场效应晶体管的输出特性曲线图和转移特性曲线图。
图5为本发明提供的制备式I所示化合物的合成路线。
具体实施方式
下面结合具体实施例对本发明作进一步阐述,但本发明并不限于以下实施例。所述方法如无特别说明均为常规方法。所述原材料如无特别说明均能从公开商业途径获得。
实施例1、聚合物PEBIQ-DTE
1)7-溴异苯并吡喃-1,3-二酮的合成
向5-溴-2-羧甲基苯甲酸(8.00g,30.9mmol)的甲苯(150mL)溶液中加入乙酸酐(4.5mL,47mmol)。将该悬浮液回流5小时,然后蒸发有机溶剂。将残余物用乙醚洗涤,得到灰白色酸酐7-溴异苯并吡喃-1,3-二酮(6.60g,产率91.2%)。该物质溶解性一般,直接用于下一步实验。
2)7-溴-2-(2-癸基十四烷基)异喹啉-1,3(2H,4H)-二酮的合成
将7-溴异苯并吡喃-1,3-二酮(6.60g,27.4mmol)加入到甲苯(30mL),乙酸(15mL)和2-癸基十四烷-1-胺(10.6g,30.0mmol)的混合液中。将混合物在氮气保护下回流6小时。冷却至室温后,加入水。用碳酸氢钠水溶液洗涤有机层,并用无水硫酸钠干燥。减压除去溶剂后得到的粗产物用二氯甲烷/石油醚(1:3)作为洗脱液进行柱层析,得到无色油状物,在环境条件下逐渐固化(12.7g,产率:73.5%)。结构表征数据如下:
质谱:HRMS(MALDI-TOF):[M+H]+calcd for C33H55BrNO2,576.341069;found,576.341029.。
核磁氢谱和碳谱:1H NMR(300MHz,CDCl3,δ):8.32(d,J=2.2Hz,2H),7.67(dd,J=8.1,2.0Hz,2H),7.15(d,J=8.2Hz,2H),3.96(s,4H),3.89(d,J=7.2Hz,4H),1.90–1.75(m,2H),1.23(m,40H),0.87(t,J=6.5Hz,12H).13C NMR(75MHz,CDCl3,δ):169.55,163.94,136.40,132.79,131.97,128.71,127.23,121.62,44.40,36.38,36.05,31.93,31.57,30.02,29.70,29.66,29.65,29.62,29.37,29.36,26.37,22.70,14.13.
3)N,N’-二(2-癸基十四烷基)-6,6-二溴-7,7-二乙二叉二异喹啉四酮(即EBIQ-2Br)的合成
将7-溴-2-(2-癸基十四烷基)异喹啉-1,3(2H,4H)-二酮(3.15g,5.46mmol)和乙二醛(水溶液,40%w/w,0.396g,2.73mmol)在甲苯(10mL)和乙酸(5mL)中的混合物加热至110℃,反应12小时。原料反应完后,将混合物倒入水中并用乙酸乙酯萃取。用盐水洗涤有机层,然后用无水硫酸钠干燥。减压除去溶剂,粗产物用甲苯/石油醚(1:2)作为洗脱液进行柱层析分离,得到橙色固体1.54g,产率:48.0%。
结构表征数据如下:
质谱:[M+H]+calcd for C68H107Br2N2O4,1175.65771;found,1175.65572。
核磁氢谱和碳谱:1H NMR(300MHz,CDCl3,δ):9.12(s,2H),8.40(d,J=2.0Hz,2H),7.86(d,J=8.7Hz,2H),7.80(dd,J=8.7,2.0Hz,2H),4.01(d,J=7.3Hz,4H),2.05–1.80(m,2H),1.23(m,40H),0.87(t,J=6.5Hz,12H).13C NMR(75MHz,CDCl3,δ):164.14,162.83,137.06,136.81,132.80,132.16,128.50,126.16,125.21,124.34,44.76,36.44,31.93,31.59,30.08,29.72,29.70,29.67,29.65,29.37,26.37,22.70,14.13.
4)聚合物PEBIQ-DTE的合成
将(E)-1,2-双(5-(三甲基锡烷基)噻吩-2-基)乙烯(103.6mg,0.2mmol)、N,N’-二(2-癸基十四烷基)-6,6-二溴-7,7-二乙二叉二异喹啉四酮(235.1mg,0.2mmol)、催化剂三(二亚苄基丙酮)二钯(9.0mg,0.01mmol)、配体三(邻甲苯基)膦(24.6mg,0.08mmol)和氯苯(8mL)加入到反应瓶中,在氩气中进行三次冷冻-抽气-解冻循环除氧,然后将反应混合物加热到130℃进行聚合反应72h。冷却后,加入200毫升盐酸的甲醇溶液(5%),室温下搅拌1h,过滤。得到的聚合物装入索氏提取器抽提。先用甲醇、丙酮、正己烷抽提至无色,除去小分子和催化剂,再用三氯甲烷提取得到最终产物223.6mg,产率92.7%。
结构表征数据如下:
分子量:GPC:Mn=34.8kg mol-1,PDI=2.87,n=29。
核磁氢谱:1H NMR(300MHz,CDCl3,δ):9.17(br,2H),7.9–6.0(br,12H),4.04(br,4H),1.90–0.80(m,94H).
由上可知,该化合物结构正确,为式I所示化合物PEBIQ-DTE,结构式如下所示:
实施例2、聚合物PDBIQ-FBT的合成
1)聚合物PEBIQ-FBT
将3,3’-二氟-5,5’-双(三甲基锡基)-2,2’-联噻吩(105.6mg,0.2mmol)、N,N’-二(2-癸基十四烷基)-6,6-二溴-7,7-二乙二叉二异喹啉四酮(235.1mg,0.2mmol)、催化剂三(二亚苄基丙酮)二钯(9.0mg,0.01mmol)、配体三(邻甲苯基)膦(24.6mg,0.08mmol)和氯苯(8mL)加入到反应瓶中,在氩气中进行三次冷冻-抽气-解冻循环除氧,然后将反应混合物加热到130℃进行聚合反应72h。冷却后,加入200毫升盐酸的甲醇溶液(5%),室温下搅拌1h,过滤。得到的聚合物装入索氏提取器抽提。先用甲醇、丙酮、正己烷抽提至无色,除去小分子和催化剂,再用三氯甲烷提取得到最终产物227.1mg,产率93.4%。
结构表征数据如下:
分子量:GPC:Mn=26.9kg mol-1,PDI=3.61,n=22。
核磁氢谱:1H NMR(300MHz,CDCl3,δ):9.18(br,2H),8.46(m,2H),8.01(m,2H),7.86(m,2H),7.50(br,2H),4.04(br,4H),1.90–0.80(m,94H).
由上可知,该化合物结构正确,为式I所示化合物PEBIQ-FBT,结构式如下所示:
实施例2、聚合物PDBIQ-DTBT的合成
1)聚合物PEBIQ-DTBT
将4,7-双(4-己基-5-(三甲基锡烷基)噻吩-2-基)苯并[c][1,2,5]噻二唑(158.9mg,0.2mmol)、N,N’-二(2-癸基十四烷基)-6,6-二溴-7,7-二乙二叉二异喹啉四酮(235.1mg,0.2mmol)、催化剂三(二亚苄基丙酮)二钯(9.0mg,0.01mmol)、配体三(邻甲苯基)膦(24.6mg,0.08mmol)和氯苯(8mL)加入到反应瓶中,在氩气中进行三次冷冻-抽气-解冻循环除氧,然后将反应混合物加热到130℃进行聚合反应72h。冷却后,加入200毫升盐酸的甲醇溶液(5%),室温下搅拌1h,过滤。得到的聚合物装入索氏提取器抽提。先用甲醇、丙酮、正己烷抽提至无色,除去小分子和催化剂,再用三氯甲烷提取得到最终产物255.2mg,产率86.1%。
结构表征数据如下:
分子量:GPC:Mn=17.0kg mol-1,PDI=2.85,n=11。
核磁氢谱:1H NMR(300MHz,CDCl3,δ):9.23(br,2H),8.46(m,2H),8.06–7.50(m,8H),4.06(br,4H),2.82(br,4H)1.90–0.80(m,116H).
由上可知,该化合物结构正确,为式I所示化合物PEBIQ-DTBT,结构式如下所示:
实施例4、聚合物PEBIQ-DTE,PEBIQ-FBT和PEBIQ-DTBT的光谱性能和场效应晶体管性能
1)聚合物PEBIQ-DTE,PEBIQ-FBT和PEBIQ-DTBT的光谱和电化学性能
图1为聚合物PEBIQ-DTE,PEBIQ-FBT和PEBIQ-DTBT在溶液和薄膜中的紫外可见吸收光谱。
由图1可知,聚合物PEBIQ-DTE,PEBIQ-FBT和PEBIQ-DTBT的光学带隙分别为1.60,1.62和1.67eV。三个聚合物分子均具有比较强的双带型吸收峰。薄膜与溶液态吸收光谱的最大吸收边带差别不大,但因聚集性不同,最大吸收峰产生一定的红移或者蓝移。
图2为聚合物PEBIQ-DTE,PEBIQ-FBT和PEBIQ-DTBT薄膜的循环伏安曲线。用CHI660c电化学工作站测定,并采用传统的三电极结构。测试在乙腈溶液中进行。这三个聚合物都具有一定的氧化还原能力。根据循环伏安曲线,可推算出聚合物PEBIQ-DTE,PEBIQ-FBT和PEBIQ-DTBT的HOMO能级分别为-5.59,-5.85和-5.70eV,LUMO能级为-3.66,-3.75和-3.68eV。
2)聚合物PADTDI-BT和PADTDI-FBT的场效应晶体管性能
图3为有机场效应晶体管的结构示意图,如图所示,采用康宁玻璃作为衬底,700纳米厚的PMMA作为绝缘层,金为源电极和漏电极,铝为栅电极。源漏电极通过蒸镀制备,基底在丙酮、二次水、乙醇中超声清洗后与用氮气枪吹干表面并真空下烘干。实施例1~实施例3所得的聚合物为半导体层。将该聚合物溶于邻二氯苯中通过甩膜的方法在基底上形成薄膜,厚度为40nm,并在热台上退火5分钟。再将60mg/mL的PMMA溶液旋涂制备介电层。最后,将金属铝蒸镀到介电层上,制备栅电极。在室温下用通过Keithley 4200 SCS半导体测试仪测量了所制备的场效应器件的电性质。
决定OFET的性能的两个关键参数是:载流子的迁移率(μ)和器件的开关比(Ion/Ioff)。迁移率是指:在单位电场下,载流子的平均漂移速度(单位是cm2V-1s-1),它反映了在电场下空穴或电子在半导体中的迁移能力。开关比定义为:晶体管在“开”状态和“关”状态下的电流之比,它反映了器件开关性能的优劣。对于一个高性能的场效应晶体管,其迁移率和开关比应尽可能的高。
图4为基于四个乙二叉二异喹啉四酮聚合物分子所制备的场效应晶体管的转移特性曲线和输出特性曲线。四个聚合物场效应晶体管显示了很好的线性区和饱和区,说明基于乙二叉二异喹啉四酮的OFET器件具有很好的场效应调控性能。
载流子迁移率可由方程计算得出:
IDS=(W/2L)Ciμ(VG–VT)2(饱和区,VDS=VG–VT)
其中,IDS为漏极电流,μ为载流子迁移率,VG为栅极电压,VT为阈值电压,W为沟道宽度(W=8000微米),L为沟道长度(L=85微米),Ci为绝缘体电容(单位面积电容(PMMA相对介电常数3.5,厚度700nm)。利用(IDS,sat)1/2对VG作图,并作线性回归,可由此回归线的斜率推算出载流子迁移率(μ),由回归线与X轴的截点求得VT。
迁移率可以根据公式从转移曲线的斜率计算得出,上述各例中制备的聚合物场效应晶体管的器件性能如表1所示。
表1、聚合物场效应晶体管的器件性能
实验结果表明乙二叉二异喹啉四酮聚合物是优良的聚合物半导体材料。本发明并不限于所报道的这几个材料,改变不同的取代基可以得到一系列的聚合物,且本发明给出的合成方法简单、有效,对于研究双极性聚合物半导体材料的结构与性能的关系帮助巨大,对进一步设计和制备高性能的材料有着指导意义。
Claims (13)
2.根据权利要求1所述的聚合物,其特征在于:所述式I中,R为C10-C60的直链或支链烷基。
3.根据权利要求2所述的聚合物,其特征在于:所述R为C10-C30的直链或支链烷基。
4.根据权利要3所述的聚合物,其特征在于:所述R为C15-C25的直链或支链烷基。
5.根据权利要4所述的聚合物,其特征在于:所述R为2-癸基十四烷基或4-癸基十四烷基。
8.根据权利要求6或7所述的方法,其特征在于:所述双甲基锡化合物的投料摩尔份数为0.95~1.05份;
所述式V所示化合物的投料摩尔份数为0.95~1.05份;
所述催化剂的投料摩尔份数为0.01~0.10份;
所述配体的投料摩尔份数为0.04~0.40份。
9.根据权利要求6或7所述的方法,其特征在于:所述聚合反应步骤中,温度为100~140℃;
时间为24小时~96小时。
10.根据权利要求6或7所述的方法,其特征在于:所述聚合反应在溶剂中进行;
所述溶剂选自甲苯、氯苯和四氢呋喃中的至少一种。
11.权利要求1-5任一所述式I所示聚合物在制备有机场效应晶体管中的应用。
12.一种有机场效应晶体管,其特征在于:所述有机场效应晶体管中,构成半导体层的材料为权利要求1-5任一所述式I所示聚合物。
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