CN116462846A - 一种具有聚集诱导荧光增强效应的聚酰亚胺前体溶液和聚酰亚胺的制备方法 - Google Patents
一种具有聚集诱导荧光增强效应的聚酰亚胺前体溶液和聚酰亚胺的制备方法 Download PDFInfo
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Abstract
本发明公开了一种具有聚集诱导荧光增强效应的聚酰亚胺前体溶液和聚酰亚胺的制备方法，涉及聚酰亚胺前体溶液和聚酰亚胺。本发明中，本发明通过引入具有聚集诱导荧光增强效应的荧光染料到聚酰亚胺前体溶液和聚酰亚胺中，其中，聚集导致发光增强(AIE)效应基元的引入，使得有机染料分子在聚集状态条件下，其发光效率得到显著提升，使得该类材料具有良好的力学性能、热稳定性同时，实现其在光致发光材料领域如发光二极管、彩色面板等领域的应用，为构筑具有良好光致发光性能的聚酰亚胺材料提供一种有效策略。
Description
技术领域
本发明涉及一种聚酰亚胺前体溶液和聚酰亚胺，具体是一种具有聚集诱导荧光增强效应的聚酰亚胺前体溶液和聚酰亚胺的制备方法。
背景技术
电致发光(Electroluminescence，EL)是指在一定的电场作用下，被相应的电能所激发而产生的发光现象，它是一种将电能直接转变成光能的过程。Lossew首先在1923年发现了电致发光现象，其从发光材料的角度可将电致发光分为无机电致发光和有机电致发光。无机电致发光早在二十世纪三十年代就开始研究，六十年代初期，美国通用电气公司就将无机半导体材料GaAsP引入可以商业化的发光器件中，使无机电致发光有了质的发展。然而，但仍然有许多缺陷，如发光品种少，特别是蓝光材料稀少；效率仍比不上普通的白炽灯(普通的白炽灯将电能转化为光能的效率可达15lmW)；TFEL的驱动电压太高，响应速度慢等等，这些都阻碍了无机EL器件在彩色平板显示器中的应用。
有机电致发光材料是上世纪六十年代开始研究，并在八十年代取得突破性进展。1987年，柯达公司的CWTang(邓青云)等【8】用8-羟基喹啉铝(Alq；)的无定型薄膜实现了高亮度、高效率、低驱动电压的有机小分子双层结构电致发光器件，驱动电压仅10V，效率1.5lm/W，而亮度高达1000cd/m，在氩气气氛中器件的寿命为100h。1990年，剑桥大学卡文迪许实验室JHBurroughes等[1】首次用简单的旋转涂膜方法将聚苯撑乙烯(PPV)预聚体制成薄膜，在真空干燥下转化成PPV薄膜，成功地实现了聚合物的电致发光，从而开辟了发光器件的一个新领域一一聚合物电致发光器件。聚合物用于电致发光有以下特点:(1)可通过旋涂、浸涂、浇铸、LB膜、自组装和喷墨打印等技术制成大面积薄膜；(2)具有良好的电、热稳定性；(3)共轭聚合物电子结构、发光颜色可在合成过程中进行化学调节:(4)聚合物本身电导率虽很低，但由于膜很薄(10-100nm)，工作电压仍很低。目前这一领域的研究相当活跃。
聚酰亚胺(polyimidePI)是指主链上含有酰亚胺环的一类聚合物。聚酰亚胺具有突出的综合性能，如耐高温、耐低温、优良的机械性能和介电性能等。聚酰亚胺在合成上具有多种途径，根据各种应用目的选择不同的二元酐或二元胺，可合成出品种繁多，形式多样的聚酰亚胺。聚酰亚胺薄膜有两个特点:一，PI的分子链沿与膜表面平行的方向取向，从而使其具有各向异性；二，PI体系内存在电荷转移配合物，使其具有某些特殊的光学或电学性质。由于PI的合成的多样性和PI的易修饰性，从PI的上述两个特点出发，通过分子设计把具有一定功能的官能团引入PI主链或侧链中，使聚酰亚胺在电致发光光伏(photovoltaic，PV)材料、非线性光学(non-linear optical NLO)材料、光折变(photorefractive,PR)材料、波导(waveguide)材料、显示取向膜材料、液晶显示的相位差补偿膜材料、和光敏(photosensitivepolyimide)材料等领域获得了新的应用。在有机EL发光领域，聚酰亚胺类材料一般作为发光材料、空穴传输材料和基质材料等。
为了把小分子有机染料的高光量子效率和聚酰亚胺的优良热稳定性结合起来，研究者通过对有机染料进行修饰，合成出具有光学活性的荧光二胺或二酐(绝大部分为二胺)，然后对于不溶性聚酰亚胺可由二酐和二胺在极性溶剂(如DMF.DMAC或NMP)中先进行低温缩聚，获得可溶的聚酰胺酸前驱体，在ITO玻璃上成膜后逐步加热至300C左右脱水转变为聚酰亚胺；对于可溶性聚酰亚胺，可在高沸点溶剂(如间甲酚)中，200℃和惰性气流(带走生成的水)下直接脱水制备聚酰亚胺，聚合物在甲醇中沉淀出来。聚酰亚胺可溶解到氯仿、环己酮等低沸点溶剂直接旋涂成膜。目前常用的有机染料分子主要是一些稠环芳烃结构，如蒽、芘、萘、苝等衍生物。而上述有机染料分子在聚集状态条件下发光会发生淬灭(聚集导致发光猝灭)，因此限制了其应用价值。因此，将具有聚集导致发光增强(AIE)效应的有机染料分子引入到聚酰亚胺体系中，是一种有效的解决方案。
虽然，将含有聚集导致发光增强(AIE)效应的有机染料分子如氰基二苯乙烯类分子引入聚酰亚胺体系已有专利报道，但是在该专利中，其主要是作为吸光基元并应用于光热材料中。其作为光致发光材料并未见报道。
发明内容
本发明的目的在于提供一种具有聚集诱导荧光增强效应的聚酰亚胺前体溶液和聚酰亚胺的制备方法，通过将含有聚集导致发光增强(AIE)效应的有机染料分子衍生化引入反应活性基团氨基，与酸酐反应构筑具有良好发光性能的聚酰亚胺前体溶液和聚酰亚胺；其中，所述的有机染料分子百分含量为本发明的特点在于，聚集导致发光增强(AIE)效应基元的引入，使得有机染料分子在聚集状态条件下，其发光效率得到显著提升，从而，在该类材料具有良好的力学性能、热稳定性同时，实现其在光致发光材料领域如发光二极管、彩色面板等领域的应用，以解决上述背景技术中提出的问题
为实现上述目的，本发明提供如下技术方案：
一种具有聚集诱导荧光增强效应的聚酰亚胺前体溶液和聚酰亚胺的制备方法，包括化学式(1)与下化学式(2)，所述聚酰亚胺前体，有以下化学式(1)表示的重复单元，聚酰亚胺，有以下化学式(2)表示的重复单元。
作为本发明进一步的方案：所述聚酰亚胺前体与聚酰亚胺，有以下化学式(1)和化学式(2)中，A1和A2基团为(3)中的一种或两种。
作为本发明再进一步的方案：所述聚酰亚胺前体与聚酰亚胺，有以下化学式(1)和化学式(2)中，B1基团为(4)中的一种或两种。
作为本发明再进一步的方案：所述聚酰亚胺前体与聚酰亚胺，有以下化学式(1)和化学式(2)中，B2基团为(5)中的一种或两种。
作为本发明再进一步的方案：所述聚酰亚胺，包含化学式(6)表示的结构，其中A1和A2基团以及B1和B2基团如上述定义，n，m是1至1000的整数。
与现有技术相比，本发明的有益效果是：发明通过引入具有聚集诱导荧光增强效应的荧光染料到聚酰亚胺前体溶液和聚酰亚胺中；其中，聚集导致发光增强(AIE)效应基元的引入，使得有机染料分子在聚集状态条件下，其发光效率得到显著提升，使得该类材料具有良好的力学性能、热稳定性同时，实现其在光致发光材料领域如发光二极管、彩色面板等领域的应用。
附图说明
图1为一种具有聚集诱导荧光增强效应的聚酰亚胺前体溶液和聚酰亚胺的制备方法的结构示意图。
图2为一种具有聚集诱导荧光增强效应的聚酰亚胺前体溶液和聚酰亚胺的制备方法中单体的核磁谱图。
图3为一种具有聚集诱导荧光增强效应的聚酰亚胺前体溶液和聚酰亚胺的制备方法中聚酰亚胺前体溶液示意图。
图4为一种具有聚集诱导荧光增强效应的聚酰亚胺前体溶液和聚酰亚胺的制备方法中聚酰亚胺示意图。
图5为一种具有聚集诱导荧光增强效应的聚酰亚胺前体溶液和聚酰亚胺的制备方法中聚酰亚胺薄膜tgc示意图。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
本发明实施例1中，一种具有聚集诱导荧光增强效应的聚酰亚胺前体溶液和聚酰亚胺的制备方法，其结构如下所示：
制备方法如下：
原料：均苯四甲酸二酐(PDM)，(Z)-2,3-双(4-氨基苯基)-2-丁烯二腈，4,4'-二氨基二苯基甲烷，N-甲基吡咯烷酮(NMP)。
在放有机械搅拌的史莱克聚合管中加入二酐单体均苯四甲酸二酐(PDMA)2.18g(0.0lmol)，再加入25mlNMP，在搅拌条件下加入(Z)-2,3-双(4-氨基苯基)-2-丁烯二腈0.260g(0.00lmol)，4,4'-二氨基二苯基甲烷1.78g(0.009mol)，经过抽真空鼓氮气过程，在0℃条件下反应10h，产生一个透明淡黄色粘稠液体，即聚酰亚胺前体溶液，如图3所示。
亚胺化制备聚酰亚胺薄，其结构如下所示：
将上述聚酰亚胺前体溶液均匀涂抹到玻璃衬底上，在空气中进行热亚胺化，按如下程序升温：加热到60℃维持然后继续加热到100℃维持/>160℃维持lh，200℃维持lh，250℃维持lh，得到聚酰亚胺薄膜，如图4、图5所示。
本发明实施例2中，一种具有聚集导致发光增强荧光染料基元的聚酰亚胺前体溶液，其结构如下所示：
制备方法如下：
原料：均苯四甲酸二酐(PDM)，(2Z，2’Z)-2，2’-(1，4-苯二亚甲基)双(4-氨基苯乙腈)，4,4'-二氨基二苯基甲烷，N-甲基吡咯烷酮(NMP)。
在放有机械搅拌的史莱克聚合管中加入二酐单体均苯四甲酸二酐(PDMA)2.18g(0.0lmol)，再加入25ml NMP，在搅拌条件下加入(2Z，2’Z)-2，2’-(1，4-苯二亚甲基)双(4-氨基苯乙腈)0.362g(0.00lmol)，4,4'-二氨基二苯基甲烷1.78g(0.009mol)，经过抽真空鼓氮气过程，在0℃条件下反应10h，产生一个透明淡黄色粘稠液体，即聚酰亚胺前体溶液。
亚胺化制备聚酰亚胺薄，其结构如下图所示：
将上述聚酰亚胺前体溶液均匀涂抹到玻璃衬底上，在空气中进行热亚胺化，按如下程序升温：加热到60℃维持然后继续加热到100℃维持/>160℃维持lh，200℃维持lh，250℃维持lh，得到聚酰亚胺薄膜。
本发明的工作原理是：将含有聚集导致发光增强(AIE)效应的有机染料分子衍生化引入反应活性基团氨基，与酸酐反应构筑具有良好发光性能的聚酰亚胺前体溶液和聚酰亚胺；其中，所述的有机染料分子百分含量为本发明的特点在于，聚集导致发光增强(AIE)效应基元的引入，使得有机染料分子在聚集状态条件下，其发光效率得到显著提升。
尽管参照前述实施例对本发明进行了详细的说明，对于本领域的技术人员来说，其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
Claims (5)
1.一种具有聚集诱导荧光增强效应的聚酰亚胺前体溶液和聚酰亚胺的制备方法，包括化学式(1)与下化学式(2)，其特征在于：所述聚酰亚胺前体，有以下化学式(1)表示的重复单元，聚酰亚胺，有以下化学式(2)表示的重复单元。
2.根据权利要求1所述的一种具有聚集诱导荧光增强效应的聚酰亚胺前体溶液和聚酰亚胺的制备方法，其特征在于：所述聚酰亚胺前体与聚酰亚胺，有以下化学式(1)和化学式(2)中，A1和A2基团为(3)中的一种或两种。
3.根据权利要求1所述的一种具有聚集诱导荧光增强效应的聚酰亚胺前体溶液和聚酰亚胺的制备方法，其特征在于：所述聚酰亚胺前体与聚酰亚胺，有以下化学式(1)和化学式(2)中，B1基团为(4)中的一种或两种。
4.根据权利要求1所述的一种具有聚集诱导荧光增强效应的聚酰亚胺前体溶液和聚酰亚胺的制备方法，其特征在于：所述聚酰亚胺前体与聚酰亚胺，有以下化学式(1)和化学式(2)中，B2基团为(5)中的一种或两种。
5.根据权利要求1所述的一种具有聚集诱导荧光增强效应的聚酰亚胺前体溶液和聚酰亚胺的制备方法，其特征在于：所述聚酰亚胺，包含化学式(6)表示的结构，其中A1和A2基团以及B1和B2基团如上述定义，n，m是1至1000的整数。
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