CN107151312B - 一种茚并芴基共轭聚合物激光增益材料及制备方法与应用 - Google Patents

一种茚并芴基共轭聚合物激光增益材料及制备方法与应用 Download PDF

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CN107151312B
CN107151312B CN201710351035.3A CN201710351035A CN107151312B CN 107151312 B CN107151312 B CN 107151312B CN 201710351035 A CN201710351035 A CN 201710351035A CN 107151312 B CN107151312 B CN 107151312B
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赖文勇
黄维
常驷驹
陆婷婷
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Nanjing Post and Telecommunication University
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Abstract

本发明涉及一种茚并芴基共轭聚合物激光增益材料及制备方法与应用，该材料是以茚并芴芴结构为骨架，选用不同的受体结构进行共聚而得到的梯形嵌段共聚物，其结构通式如下式所示：通式I中，R为C1‑C30的烷基、烷氧基、烷苯基、烷氧基苯基中的一种，A为电子受体结构修饰单元。该材料具有成本低廉、合成简单可控、产率高、溶解性好等优势，同时该类材料具有较好的热稳定性、可逆的氧化还原特性、良好的成膜性能，可以采用简易的溶液成膜方式制备薄膜器件，作为活性发光层在机电致发光器件表现出较高的亮度和优异的发光效率，同时在有机激光器件中表现出较低的激光阈值和较高的增益，是一类有重要应用潜力的发光材料体系。

Description

一种茚并芴基共轭聚合物激光增益材料及制备方法与应用
技术领域
本发明属光电材料和应用技术领域，具体涉及一种共轭聚合物激光增益材料及其制备方法与应用，该材料具有热稳定性优异、成膜性能好，可以作为有机激光增益介质和发光主体，通过简单的溶液加工法制备有机激光器件或有机电致发光器件。
背景技术
有机光电材料是一类具有光电活性的有机材料，通常是富含碳原子、具有大π共轭体系的有机分子。与无机材料相比，有机光电材料可以通过溶液法实现大面积制备和柔性器件制备。此外，有机材料具有多样化的结构组成和宽广的性能调节空间，可以进行分子设计来获得所需要的性能，能够进行自组装等自下而上的器件组装方式来制备纳米器件和分子器件。
由于有机分子较无机材料具有密度小、价格低廉且结构易修饰性强等优势，具有广阔的应用前景。化学家及材料学家正是从设计合成特殊的有机π-共轭体系出发，探索其在光电功能领域内的应用，并以此为反馈指导分子设计。近年来，有机光电材料备受科研者青睐并得到快速的发展。这类材料主要应用于有机电致发光二极管(OLEDs)、有机薄膜晶体管(OTFTs)、有机太阳能电池(OPVs)、有机激光等方面。根据分子量大小和分子结构的不同，有机半导体材料主要分为两类：有机小分子材料、高分子聚合物材料。有机小分子结构明确，能够获得较高的纯度，具有较好的器件性能，但溶液加工性能较差，限制了其在低成本溶液过程制作有机光电器件中的更广泛应用。高分子聚合物因其适于简易的溶液制膜过程，具有成膜性好、热稳定性和无定形性能优异、制备工艺简单等突出优点，而备受关注。
其中梯形聚对苯结构(LPPP)是一类重要的共轭聚合物体系。此类材料具有刚性骨架、大平面结构、优良的电荷传输性能。然而，LPPP结构由于分子间相互作用及共轭单元之间的π-π堆积而存在着低能带发射的现象，这严重降低了该发光材料的色纯性、色稳定性。
为改善LPPP的发光性能，本发明设计了一种共轭聚合物激光增益材料，以梯形芴结构为骨架，选用不同的受体结构进行共聚而得到的梯形嵌段共聚物，通过共聚单体的引入，打断了梯形共轭聚合物的长共轭链，这样既保留了LPPP结构单元的优良的电荷传输性能，又克服了自吸收现象严重的问题，极大改善了此类材料的光电性能，增益系数更是其均聚物3-5倍左右。该材料具有成本低廉、合成简单可控、产率高、溶解性好等优势，同时该类材料具有较好的热稳定性、可逆的氧化还原特性、良好的成膜性能，可以采用简易的溶液成膜方式制备薄膜器件。此外，随着梯形链的延伸，作为活性发光层在机电致发光器件表现出更高的亮度和优异的发光效率，同时在有机激光器件中也表现出更低的激光阈值和更高的增益，是一类有重要应用潜力的发光材料体系。
发明内容
技术问题：本发明的目的是提供一种共轭聚合物激光增益材料及制备方法与应用，解决现有有机发光材料体系稳定性不足、迁移率不高等问题。
技术方案：为解决现有技术问题，本发明采取的技术方案为：
该材料是以梯形芴结构为骨架，选用不同电子受体结构进行共聚而得到的梯形嵌段共聚物，具有如下式I所示的结构通式：
其中，R为C1-C30烷基、烷氧基、烷苯基、烷氧基苯基中的一种；n的取值大于等于5，A选自以下官能团中的一种：
其中，*为连接位置；C为碳原子；O为氧原子；N是氮原子；S是硫原子；F是氟原子。
本发明的一种茚并芴基共轭聚合物激光增益材料的制备方法包括以下步骤：
步骤一：利用对溴茚并芴酮制备化合物1
取对溴茚并芴酮溶于四氯化碳中，加入甲基磺酸，苯酚，60-120℃下搅拌24-60小时，除去四氯化碳和苯酚，再与碳酸钾、柔性链R混合，溶于乙醇溶液中60-100℃下反应8-24小时，待反应结束后经柱色谱纯化得化合物1
步骤二：合成化合物2LF-A在避光且氮气保护下，将四三苯基膦钯催化剂、含官能团A的双硼酸酯、相转移催化剂四丁基溴化铵与化合物1溶于甲苯和碳酸钾水溶液的混合溶液中，80-100℃下反应2-4天，反应结束后经氧化铝柱纯化、甲醇沉降、抽提分别得到化合物2LF-A
其中：
所述步骤一中，合成化合物1时，对溴茚并芴酮：苯酚：柔性链R1：甲基磺酸：碳酸钾＝1:(15-20):(4-20):(0.05-0.1):(2-8)。
所述步骤一中，每摩尔对溴茚并芴酮加入四氯化碳溶剂20-50L，每摩尔对溴茚并芴酮加入乙醇5-15L。
所述步骤二中，合成化合物2LF-A时，化合物1含官能团A的双硼酸酯：相转移催化剂四丁基溴化铵：四三苯基膦钯催化剂＝1:(1-2):(0.3-1):(0.05-0.15),每摩尔化合物1加入甲苯30-50L。
所述甲苯与碳酸钾水溶液体积比为(2-3):1。
本发明的茚并芴基共轭聚合物激光增益材料作为发光介质应用于有机激光器件或有机电致发光器件中。
有益效果：本发明提供了一种共轭聚合物激光增益材料，该材料以茚并芴结构为骨架，选用不同电子受体结构单元，通过Suzuki偶联、傅克酰化/烃化反应、环化反应、聚合反应等一系列过程制备而得到。该材料具有成本低廉、合成简单可控、产率高、溶解性好等优势，同时该类材料具有较好的热稳定性、可逆的氧化还原特性、良好的成膜性能等，可以采用简易的溶液成膜方式制备薄膜器件；可以作为活性发光层在机电致发光器件表现出较高的亮度和优异的发光效率，同时在有机激光器件中表现出较低的激光阈值和较高的增益。
附图说明
图1为化合物1的1H NMR谱图。
图2为化合物1的13C NMR谱图。
图3为共聚物A的溶液态UV/PL光谱。
图4为共聚物A的薄膜态UV/PL光谱。
图5为共聚物A的热重曲线。
图6为共聚物A的ASE输出斜率随激光强度变化图。
图7为共聚物A的光学增益参数随激光能量变化图。
具体实施方式
实施例1：化合物1的合成
第I步：取对溴茚并芴酮(1g,2.27mmol)，苯酚(3.84g,40.82mmol)溶于100mL四氯化碳中，缓慢加入0.7mL甲基磺酸，苯酚，80℃下搅拌42小时，除去四氯化碳和苯酚，再与碳酸钾K2CO3(3.13g,22.7mmol)、7-(溴甲基)-十五烷(4.16g,13.62mmol)混合，溶于50mL乙醇溶液中90℃下反应14小时，反应结束后，用二氯甲烷和水萃取，收集有机相，用无水硫酸镁干燥，抽滤，蒸除溶剂所得固体经色谱柱纯化得到化合物1(3.86g,产率98％)。
实施例2
用实施例1中的化合物1制备嵌段共聚物A。
其中，合成路线分别如下所示：
反应路线图：
共聚物A的合成步骤如下：
在避光且氮气保护下，将化合物1(168mg,0.1mmol)、苯并噻二唑硼酸酯(038.9mg,0.1mmol),四三苯基膦钯Pd(PPh3)4(11.5mg,0.01mmol),相转移催化剂四丁基溴化铵(25mg,0.05mmol)，甲苯溶液(4.5mL),2M K2CO3溶液(1.5mL)加入到15mL反应瓶中，95℃下反应72小时。反应结束后，反应结束后经氧化铝柱纯化、甲醇沉降、抽提分别得到共聚物A。
共聚物A:GPC测得Mn＝15445,PDI＝1.76。
化合物1:1H NMR(400MHz,CDCl3):δ7.65(s,2H),7.49(d,J＝8.1Hz,2H),7.46(d,J＝1.5Hz,2H),7.41(d,J＝8.1Hz,2H),7.13(d,J＝8.8Hz,8H),6.78(d,J＝8.9Hz,8H),3.78(d,J＝5.5Hz,8H),1.73(d,J＝5.5Hz,4H),1.41–1.26(m,96H),0.88(t,J＝6.7Hz,24H).13CNMR(100MHz,CDCl3):δ158.4,154.4,151.7,139.3,138.8,137.0,130.5,129.2,121.5,121.3,117.6,114.3,70.8,64.0,53.4,38.0,31.9,31.4,30.0,29.6,29.3,26.9,22.7,14.1.MALDI-TOF MS(m/z):calcd for C108H156Br2O4；Exact Mass:1675.04,Mol.Wt.:1678.20；Found:1677.88(M+).Anal.Calcd.for C108H156Br2O4：C,77.29；H,9.37；Found:C,77.19；H,9.39.
实施例3
有机激光器件的制备
采用二氯苯做溶剂，发光主体为共聚物A，制备35mg/mL的溶液。石英片经过超声波清洗，采用简单的旋凃方式制备有机激光器件，旋涂条件为1500rpm。其中，共聚物A的PL光谱的发射峰分别为545nm，用不同的受体封端，有利于电子的有效传输。这类共聚物A表现出优异的激光性能，ASE峰位分别在552nm处；FWHM分别为8nm；ASE阈值低至65.84μJ/cm2，最大增益系数为66cm-1，是目前有机黄绿色激光半导体中较好的结果。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的原理下所做的改进和变换，均应为等效的置换方式，都包含在本发明的保护范围内。

Claims (7)

1.一种茚并芴基共轭聚合物激光增益材料，其特征在于，该材料是以梯形芴结构为骨架，选用不同电子受体结构进行共聚而得到的梯形嵌段共聚物，具有如下式I所示的结构通式：
其中，R为n的取值大于等于5，A选自以下官能团中的一种：
其中，*为连接位置；C为碳原子；O为氧原子；N是氮原子；S是硫原子；F是氟原子。
2.一种如权利要求1所述的一种茚并芴基共轭聚合物激光增益材料的制备方法，其特征在于，该制备方法包括以下步骤：
步骤一：利用对溴茚并芴酮制备化合物1取对溴茚并芴酮溶于四氯化碳中，加入甲基磺酸，苯酚，60-120℃下搅拌24-60小时，除去四氯化碳和苯酚，再与碳酸钾、柔性链R混合，溶于乙醇溶液中60-100℃下反应8-24小时，待反应结束后经柱色谱纯化得化合物1
步骤二：合成化合物2LF-A在避光且氮气保护下，将四三苯基膦钯催化剂、含官能团A的双硼酸酯、相转移催化剂四丁基溴化铵与化合物1溶于甲苯和碳酸钾水溶液的混合溶液中，80-100℃下反应2-4天，反应结束后经氧化铝柱纯化、甲醇沉降、抽提分别得到化合物2LF-A
3.根据权利要求2所述的一种茚并芴基共轭聚合物激光增益材料的制备方法，其特征在于：所述步骤一中，合成化合物1时，对溴茚并芴酮：苯酚：柔性链R：甲基磺酸：碳酸钾＝1:(15-20):(4-20):(0.05-0.1):(2-8)。
4.根据权利要求2所述的一种茚并芴基共轭聚合物激光增益材料的制备方法，其特征在于：所述步骤一中，每摩尔对溴茚并芴酮加入四氯化碳溶剂20-50L，每摩尔对溴茚并芴酮加入乙醇5-15L。
5.根据权利要求2所述的一种茚并芴基共轭聚合物激光增益材料的制备方法，其特征在于：
所述步骤二中，合成化合物2LF-A时，化合物1含官能团A的双硼酸酯：相转移催化剂四丁基溴化铵：四三苯基膦钯催化剂＝1:(1-2):(0.3-1):(0.05-0.15),每摩尔化合物1加入甲苯30-50L。
6.根据权利要求2所述的一种茚并芴基共轭聚合物激光增益材料的制备方法，其特征在于：
所述甲苯与碳酸钾水溶液体积比为(2-3):1。
7.一种如权利要求1所述的茚并芴基共轭聚合物激光增益材料的应用，其特征在于，该材料作为发光介质应用于有机激光器件或有机电致发光器件中。
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