CN107522848B - 一种聚喹吖啶酮类化合物及其制备方法与应用 - Google Patents

一种聚喹吖啶酮类化合物及其制备方法与应用 Download PDF

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CN107522848B
CN107522848B CN201710579831.2A CN201710579831A CN107522848B CN 107522848 B CN107522848 B CN 107522848B CN 201710579831 A CN201710579831 A CN 201710579831A CN 107522848 B CN107522848 B CN 107522848B
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贾建洪
叶孙斌
李益珠
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Zhejiang University of Technology ZJUT
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Abstract

本发明涉及一种聚喹吖啶酮类化合物及其制备方法与应用，其化学结构式如下式I：
Figure DDA0001351942840000011
式Ⅰ中：R为氧、二氰亚甲基等吸电子基团，n＝15～60。本发明在喹吖啶酮两端引入合适的给电子基团，在母环上引入强吸电子基团，从而形成分子内电子能高效传输的推‑拉型体系，使得材料的三阶非线性光学性能大大提高。这类化合物光学性能优异、稳定性好，可用作有机荧光材料。

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一种聚喹吖啶酮类化合物及其制备方法与应用
(一)技术领域
本发明属于功能材料领域，具体涉及一种聚喹吖啶酮类化合物及其制备方法与在荧光材料中的应用。
(二)背景技术
在过去的几十年里,有机电子学作为一个新兴领域迅猛发展,为科学技术的进步作出了巨大的贡献。有机材料被广泛应用在有机电子学中,取得了卓越的成效。作为使用在电子器件中最基本的组分,有机光电材料更是备受瞩目。
聚喹吖啶酮衍生物因具有较好的载流子迁移率，优良的化学稳定性、热稳定性，且紫外吸收范围宽，荧光量子产率高，使其在有机发光二极管(OLEDs)，有机场效应晶体管(OFETs)以及有机太阳能电池(OSCs)等众多领域有着较大的潜在应用价值。
共轭型聚合物非线性光学材料由于π电子的离域化，电荷易于移动，大多具有大的三阶非线性极化率和超快的光学响应时间。π共轭聚合物具有良好的光电学性质以及机械性能和加工性，有希望用于制造如化学传感器、光泵塑性激光、光发散二极管和光电芯片等器件。迄今，科研人员曾以苯并噻二唑、芴、酞菁等为主要主体材料合成了许多性能优异的三阶非线性光学材料，然而其中可实用化的屈指可数。如能在喹吖啶酮两端引入合适的给电子基团，在母环上引入强吸电子基团，使之形成分子内电子能高效传输的推-拉型体系，可大大提高材料的三阶非线性光学性能。
(二)发明内容
本发明针对现有技术存在的缺陷，提供一种聚喹吖啶酮新类化合物及其制备方法与在荧光材料中的应用。根据有机三阶非线性光学材料的分子结构特征，设计了以喹吖啶酮为环兼电子受体的有机功能色素，得到了一类在D-A型高分子聚喹吖啶酮型光学材料。这类化合物光学性能优异、稳定性好，可用作有机荧光材料。
本发明采用的技术方案是：
本发明提供一类D-A型高分子聚喹吖啶酮型，所述的D-A型高分子聚喹吖啶酮型光学材料的结构式如式Ⅰ所示：
Figure BDA0001351942820000021
式Ⅰ中：R为氧、二氰亚甲基等吸电子基团，n＝15～60。
发明的第二个目的是提供一种合成上述D-A型喹吖啶酮三阶非线性光学材料(如式Ⅰ所示化合物)的方法，所述合成方法包括如下步骤：
(1)Suzuki偶联反应
Figure BDA0001351942820000022
在碱A和催化剂A的存在下，将化合物Ⅱ加入联硼酸频那醇酯，并在气体A的保护下注入溶剂A，在60～100℃下反应8～14h得到化合物III。
(2)聚合物的合成
Figure BDA0001351942820000023
Figure BDA0001351942820000031
式Ⅳ中：X＝Br，Cl，I等卤素。
在碱B，钯催化剂B，相转移催化剂的条件下，在化合物III中加入化合物Ⅳ，其结构如式Ⅳ所示，用气体B保护，注入蒸馏水在室温下搅拌10～30min后再注入溶剂B，混合物在80～120℃下回流1～3d后停止反应得到聚合物Ⅰ。
作为优选，步骤(1)中催化剂A为[1,1'-双(二苯基膦基)二茂铁]二氯化钯，所述碱A是指碳酸钾、碳酸钙、碳酸钠、碳酸氢钠、醋酸钠、醋酸钾，所述化合物Ⅱ、催化剂A与碱A的摩尔比为1:0.1～0.7:2～4，所述化合物Ⅱ与联硼酸频那醇酯的摩尔比为1:1～3，气体A为惰性气体如氮气，氩气，氖气。
作为优选，步骤(2)中钯催化剂B为四(三苯基膦)钯，相转移催化剂为三辛基甲基氯化铵，所述碱B为碳酸钾、碳酸钙、碳酸钠、碳酸氢钠、醋酸钠、醋酸钾，溶剂B为甲苯、三氯乙烷、异丙醇、四氯乙烷、苯，化合物III、催化剂B、碱B、溶剂B的摩尔比为1:1～3:0.05～0.15:200～500，化合物III、三辛基甲基氯化铵与化合物Ⅳ的摩尔比为：1:0.3～0.8:0.5～1.5，气体B为惰性气体如氮气，氩气，氖气。
(三)本发明的有益效果：
本发明通过烷基化修饰的喹吖啶酮使喹吖啶酮表现出一定的三阶非线性光学性能。在喹吖啶酮两端引入合适的给电子基团，在母环上引入强吸电子基团，从而形成分子内电子能高效传输的推-拉型体系，使得材料的三阶非线性光学性能大大提高。将小分子化合物通过上述反应生成聚合物，得到的聚合物具有小分子喹吖啶酮衍生物的优异光电化学性能、稳定性和三阶非线性光学性能。
(四)说明书附图
图1聚喹吖啶酮衍生物Ⅰ-1和Ⅰ-2的紫外-可见吸收光谱图。
图2聚喹吖啶酮衍生物Ⅰ-1和Ⅰ-2的荧光光谱图
图3聚喹吖啶酮衍生物Ⅰ-1和Ⅰ-2的TGA曲线。
(五)具体实施方式
下面结合具体实施例对本发明进行进一步描述，但本发明的保护范围并不仅限于此：
实施例1
(1)Suzuki偶联
将化合物Ⅱ-1(0.804g,1mmol)，联硼酸频那醇酯(0.638g,2.5mmol)，乙酸钾(0.245g,2.5mmol)，[1,1'-双(二苯基膦基)二茂铁]二氯化钯PdCl2(dppf)(0.211g,0.3mmol)置于25mL Schlenk管中，利用氮气置换3次，并在氮气保护下注入10mL1,4-二氧六环作为溶剂。反应物于80℃下反应12h后停止，待化合物冷却至室温，缓慢转移至40mL饱和食盐水中，过滤，滤饼用去离子水洗涤，通过重结晶提纯(乙酸乙酯/石油醚＝10:1)，得到化合物III-2(0.781g,85％)。
Figure BDA0001351942820000041
(2)聚合物的合成
将化合物III-1(0.451g,0.5mmol)，化合物Ⅳ-1(0.344g,0.5mmol)，碳酸钾(0.138g,1.0mmol)，四(三苯基膦)钯(0.058g,0.05mmol)，三辛基甲基氯化铵(0.101g,0.25mmol)置于100mL三颈烧瓶中，利用氮气置换3次，并在氮气保护下注入10mL蒸馏水于室温下搅拌15min后再注入20mL甲苯，混合物于100℃下回流反应3d后停止反应。待反应液冷却至室温后，加入30mL乙醇待固体完全析出后，过滤，滤饼依次用乙醇，乙酸乙酯洗涤。通过重结晶(二氯甲烷/甲醇＝3:1)提纯，得到化合物Ⅰ-1(0.575g,57.5％)。
Figure BDA0001351942820000051
实施例2
(1)Suzuki偶联
将化合物Ⅱ-2(0.717g,1mmol)，联硼酸频那醇酯(0.638g,2.5mmol)，乙酸钠(0.250g,2.5mmol)，[1,1'-双(二苯基膦基)二茂铁]二氯化钯PdCl2(dppf)(0.211g,0.3mmol)置于25mL Schlenk管中，利用氩气置换3次，并在氮气保护下注入10mL1,4-二氧六环作为溶剂。反应物于80℃下反应12h后停止，待化合物冷却至室温，缓慢转移至40mL饱和食盐水中，过滤，滤饼用去离子水洗涤，通过重结晶提纯(乙酸乙酯/石油醚＝10:1)，得到化合物III-2(0.781g,85％)。
Figure BDA0001351942820000052
(2)聚合物的合成
将化合物III-1(0.451g,0.5mmol)，化合物Ⅳ-2(0.299g,0.5mmol)，碳酸钠(0.138g,1.0mmol)，四(三苯基膦)钯(0.058g,0.05mmol)，三辛基甲基氯化铵(0.101g,0.25mmol)置于100mL三颈烧瓶中，利用氮气置换3次，并在氮气保护下注入10mL蒸馏水于室温搅拌15min后再注入20mL甲苯，混合物于100℃下回流反应3d后停止反应。待反应液冷却至室温后，加入30mL乙醇待固体完全析出后，过滤，滤饼依次用乙醇，乙酸乙酯洗涤。通过重结晶(二氯甲烷/甲醇＝3:1)提纯，得到化合物Ⅰ-1(0.575g,57.5％)。
Figure BDA0001351942820000061
实施例3
(1)Suzuki偶联
将化合物Ⅱ-3(0.900g,1mmol)，联硼酸频那醇酯(0.638g,2.5mmol)，碳酸钾(0.345g,2.5mmol)，[1,1'-双(二苯基膦基)二茂铁]二氯化钯PdCl2(dppf)(0.211g,0.3mmol)置于25mL Schlenk管中，利用氩气置换3次，并在氮气保护下注入10mL1,4-二氧六环作为溶剂。反应物于80℃下反应12h后停止，待化合物冷却至室温，缓慢转移至40mL饱和食盐水中，过滤，滤饼用去离子水洗涤，通过重结晶提纯(乙酸乙酯/石油醚＝10:1)，得到化合物III-2(0.781g,85％)。
Figure BDA0001351942820000062
(2)聚合物的合成
将化合物III-1(0.451g,0.5mmol)，化合物Ⅳ-3(0.390g,0.5mmol)，碳酸钠(0.138g,1.0mmol)，四(三苯基膦)钯(0.05 8g,0.05mmol)，三辛基甲基氯化铵(0.101g,0.25mmol)置于100mL三颈烧瓶中，利用氩气置换3次，并在氩气保护下注入10mL蒸馏水于室温搅拌15min后再注入20mL二甲苯，混合物于100℃下回流反应3d后停止反应。待反应液冷却至室温后，加入30mL乙醇待固体完全析出后，过滤，滤饼依次用乙醇，乙酸乙酯洗涤。通过重结晶(二氯甲烷/甲醇＝3:1)提纯，得到化合物Ⅰ-1(0.517g,51.7％)
Figure BDA0001351942820000063
实施例4
(1)Suzuki偶联
将化合物Ⅱ-4(0.902g,1mmol)，联硼酸频那醇酯(0.638g,2.5mmol)，乙酸钾(0.245g,2.5mmol)，[1,1'-双(二苯基膦基)二茂铁]二氯化钯PdCl2(dppf)(0.211g,0.3mmol)置于25mL Schlenk管中，利用氮气置换3次，并在氮气保护下注入10mL 1,4-二氧六环作为溶剂。反应物于80℃下反应12h后停止反应，待化合物冷却至室温，缓慢转移至40mL饱和食盐水中，过滤，滤饼用去离子水洗涤，通过重结晶提纯(乙酸乙酯/石油醚＝10:1)，得到化合物III-2(0.871g,86％)。
Figure BDA0001351942820000071
(2)聚合物的合成
将化合物III-2(0.506g,0.5mmol)，化合物Ⅳ-1(0.344g,0.5mmol)，碳酸钾(0.138g,1.0mmol)，四(三苯基膦)钯(0.058g,0.05mmol)，三辛基甲基氯化铵(0.101g,0.25mmol)置于100mL三颈烧瓶中，利用氮气置换3次，并在氮气保护下注入10mL蒸馏水于室温搅拌15min后再注入20mL甲苯。混合物于100℃下回流反应3d后停止反应。待反应液冷却至室温后，加入30mL乙醇待固体完全析出后，过滤，滤饼依次用乙醇，乙酸乙酯洗涤。通过重结晶(二氯甲烷/甲醇＝3:1)提纯，得到化合物Ⅰ-2(0.546g,54.6％)。
Figure BDA0001351942820000072
实施例5
(1)Suzuki偶联
将化合物Ⅱ-5(0.814g,1mmol)，联硼酸频那醇酯(0.638g,2.5mmol)，乙酸钾(0.245g,2.5mmol)，[1,1'-双(二苯基膦基)二茂铁]二氯化钯PdCl2(dppf)(0.211g,0.3mmol)置于25mL Schlenk管中，利用氮气置换3次，并在氮气保护下注入10mL 1,4-二氧六环作为溶剂。反应物于80℃下反应12h后停止反应，待化合物冷却至室温，缓慢转移至40mL饱和食盐水中，过滤，滤饼用去离子水洗涤，通过重结晶提纯(乙酸乙酯/石油醚＝10:1)，得到化合物III-2(0.871g,86％)。
Figure BDA0001351942820000081
(2)聚合物的合成
将化合物III-2(0.506g,0.5mmol)化合物Ⅳ-2(0.299g,0.5mmol)，碳酸钾(0.138g,1.0mmol)，四(三苯基膦)钯(0.058g,0.05mmol)，三辛基甲基氯化铵(0.101g,0.25mmol)置于100mL三颈烧瓶中，利用氮气置换3次，并在氮气保护下注入10mL蒸馏水于室温搅拌15min后再注入20mL二甲苯。混合物于100℃下回流反应3d后停止反应。待反应液冷却至室温后，加入30mL乙醇待固体完全析出后，过滤，滤饼依次用乙醇，乙酸乙酯洗涤。通过重结晶(二氯甲烷/甲醇＝3:1)提纯，得到化合物Ⅰ-2(0.518g,51.75％)。
Figure BDA0001351942820000091
实施例6
(1)Suzuki偶联
将化合物Ⅱ-6(0.996g,1mmol)，联硼酸频那醇酯(0.638g,2.5mmol)，乙酸钾(0.245g,2.5mmol)，[1,1'-双(二苯基膦基)二茂铁]二氯化钯PdCl2(dppf)(0.211g,0.3mmol)置于25mL Schlenk管中，利用氮气置换3次，并在氮气保护下注入10mL 1,4-二氧六环作为溶剂。反应物于80℃下反应12h后停止反应，待化合物冷却至室温，缓慢转移至40mL饱和食盐水中，过滤，滤饼用去离子水洗涤，通过重结晶提纯(乙酸乙酯/石油醚＝10:1)，得到化合物III-2(0.871g,86％)。
Figure BDA0001351942820000092
(2)聚合物的合成
将化合物III-2(0.506g,0.5mmol)，化合物Ⅳ-3(0.390g,0.5mmol)，碳酸钾(0.138g,1.0mmol)，四(三苯基膦)钯(0.058g,0.05mmol)，三辛基甲基氯化铵(0.101g,0.25mmol)置于100mL三颈烧瓶中，利用氮气置换3次，并在氮气保护下注入10mL蒸馏水于室温搅拌15min后再注入20mL甲苯。混合物于100℃下回流反应3d后停止反应。待反应液冷却至室温后，加入30mL乙醇待固体完全析出后，过滤，滤饼依次用乙醇，乙酸乙酯洗涤。通过重结晶(二氯甲烷/甲醇＝3:1)提纯，得到化合物Ⅰ-2(0.575g,57.5％)。
Figure BDA0001351942820000101
实施例7
聚喹吖啶酮衍生物Ⅰ-1和Ⅰ-2的紫外-可见吸收光谱图如图1所示，将化合物配成浓度为浓度为0.15g/L的溶液，溶剂为二氯甲烷，使用的仪器是Shimadzu UV-1800分光光度计。聚喹吖啶酮衍生物Ⅰ-1和Ⅰ-2的荧光光谱图见图2：将化合物配成浓度为0.15g/L的溶液，溶剂为二氯甲烷，使用的仪器是Shimadzu RF-6000 PC光谱仪。
表1聚喹吖啶酮衍生物Ⅰ-1和Ⅰ-2的光物理性能参数、
Figure BDA0001351942820000102
λabs表示吸收波长；、λem表示发射波长；λonset表示吸收波长阈值；
Figure BDA0001351942820000103
表示光能带隙；ΦPL表示荧光量子产率.
聚喹吖啶酮衍生物Ⅰ-1和Ⅰ-2在溶液中具有较宽的吸收带，其最大吸收波长分别是567nm和536nm。此外，聚合物Ⅰ-1和Ⅰ-2能显示出较强的橙色荧光，荧光量子产率分别为0.64和0.20，是一类很好的光学材料。聚合物Ⅰ-1和Ⅰ-2的能带隙分别为2.081eV和2.109eV，有利于电子的分子内转移，是一类很有潜力的非线性光学材料。
实施例8
聚喹吖啶酮衍生物Ⅰ-1和Ⅰ-2的热稳定性是在氮气条件下利用热重分析(TGA)测定的，测试结果如图3所示。两个聚合物具有较高的热分解温度，能满足三阶非线性光学材料器件化的要求热分解温度(Td失重5％)>100℃。其中，聚合物Ⅰ-1的热分解温度高达402℃。
实施例9
经过Z-扫描测试，聚合物Ⅰ-1和Ⅰ-2具有优异的三阶非线性光学性能。聚合物Ⅰ-1和Ⅰ-2的三阶非线性极化率χ(3)分别为9.820×10-12esu和13.723×10-12esu，分子二阶超极化率γ分别为4.412×10-33esu和6.219×10-33esu。综合各测试结果，聚合物Ⅰ-1和Ⅰ-2具有良好的热稳定，较大的吸收波长，显著的三阶非线性光学性能，在非线性光学器件的应用中具有很好的潜力。

Claims (4)

1.一种聚喹吖啶酮型化合物在三阶非线性光学材料中的应用，其特征在于，所述聚喹吖啶酮型化合物为式I-1或I-2之一：
Figure DEST_PATH_IMAGE002
式中：n＝15～60。
2.根据权利要求1所述的应用，其特征在于，聚喹吖啶酮型化合物的制备方法包括以下步骤：
(1)Suzuki偶联反应
Figure DEST_PATH_IMAGE004
在碱A和催化剂A的存在下，将化合物Ⅱ加入联硼酸频那醇酯，并在惰性气体A的保护下注入溶剂A，在60～100℃下反应8～14h得到化合物III；
(2)聚合物的合成
Figure DEST_PATH_IMAGE006
式中：R选自氧、二氰亚甲基，式Ⅳ中：X选自Br、Cl、I；
在碱B、钯催化剂B、相转移催化剂的条件下，将化合物III加入化合物Ⅳ，其结构如式Ⅳ所示，在惰性气体B保护下，注入蒸馏水在室温下搅拌10～30min后再注入溶剂B，混合物在80～120℃下回流1～3d后停止反应得到聚合物Ⅰ。
3.如权利要求2所述的应用，其特征在于，步骤(1)中催化剂A为[1,1'-双(二苯基膦基)二茂铁]二氯化钯，所述碱A是指碳酸钾、碳酸钙、碳酸钠、碳酸氢钠、醋酸钠、醋酸钾，所述化合物Ⅱ、催化剂A与碱A的摩尔比为1:0.1～0.7:2～4，所述化合物Ⅱ与联硼酸频那醇酯的摩尔比为1:1～3，气体A选自氮气、氩气、氖气，溶剂A为1,4-二氧六环。
4.如权利要求2所述的应用，其特征在于，步骤(2)中钯催化剂B为四(三苯基膦)钯，相转移催化剂为三辛基甲基氯化铵，所述碱B为碳酸钾、碳酸钙、碳酸钠、碳酸氢钠、醋酸钠、醋酸钾，溶剂B为甲苯、三氯乙烷、异丙醇、四氯乙烷、二甲苯，化合物III、催化剂B、碱B、溶剂B的摩尔比为1:1～3:0.05～0.15:200～500，化合物III、三辛基甲基氯化铵与化合物Ⅳ的摩尔比为：1:0.3～0.8:0.5～1.5，气体B选自氮气、氩气、氖气。
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