CN110218300A - 含吡咯并吡咯烷酮和芴构筑单元的荧光共轭高分子、制备方法及应用 - Google Patents

含吡咯并吡咯烷酮和芴构筑单元的荧光共轭高分子、制备方法及应用 Download PDF

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CN110218300A
CN110218300A CN201910556828.8A CN201910556828A CN110218300A CN 110218300 A CN110218300 A CN 110218300A CN 201910556828 A CN201910556828 A CN 201910556828A CN 110218300 A CN110218300 A CN 110218300A
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范丽娟
吴应忠
马荣梁
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Abstract

本发明公开了吡咯并吡咯烷酮和芴两种构筑单元荧光共轭高分子、制备方法及应用。将吡咯并吡咯烷酮（DPP）结构的单体与芴结构的单体2,7‑二溴‑9,9‑二辛基芴，1,4‑苯二硼酸通过Suzuki偶联共聚的方法，得到一种荧光共轭高分子。按本发明技术方案，可通过调节吡咯并吡咯烷酮（DPP）结构的单体与2,7‑二溴‑9,9‑二辛基芴单体的比例，合成的一系列共轭高分子，在三氯甲烷溶剂中聚合物具有不同的荧光发射波长，荧光颜色的变化范围从橙黄色‑黄色‑紫色‑蓝色，实现了对聚合物荧光颜色的控制和调节。

Description

含吡咯并吡咯烷酮和芴构筑单元的荧光共轭高分子、制备方 法及应用
技术领域
本发明涉及一种荧光共轭高分子、制备方法及其应用，属于荧光高分子材料技术领域。
背景技术
共轭高分子作为一种发光的材料，其在光电领域、传感领域和生物成像等方面有着广泛的应用（参见文献：Chem. Rev. 2009, 109, 897-1091; Chem. Rev. 2000, 100,2537-2574; Coordin. Chem. Rev. 2009, 253, 410-422; Adv. Sci. 2017, 4,1600481），而共轭高分子荧光颜色的调节极大拓宽了在这些领域的具体应用。近年来，关于共轭高分子荧光颜色调节的方法的报导也有很多，主要涉及到的荧光颜色调节的方法包括：物理共混法、共聚法、改变取代基法和控制共轭长度法等（参见文献：ACS Appl. Mater.Interfaces 2015, 7, 26709-26715; J. Phys. Chem. B 2006, 110, 14148-14154; J.Am. Chem. Soc. 2013, 135, 1148−1154; Macromolecules 2016, 49, 4102-4114）。在共聚法中，已有文献报导了用氟硼二吡咯与芴和苯并噻唑的结构共聚调节荧光颜色（ACSNano 2013, 7, 376-384），但将吡咯并吡咯烷酮（DPP）与芴的结构共聚用来调节共轭高分子的荧光颜色还未见报导。
发明内容
本发明的目的在于提供一种新型结构的含吡咯并吡咯烷酮（DPP）和芴构筑单元的荧光共轭高分子及其制备方法，并得到一系列具有不同荧光发射波长的共轭高分子，以实现对共轭高分子荧光颜色的可调节。
实现本发明目的的技术方案是提供一种含吡咯并吡咯烷酮和芴构筑单元的荧光共轭高分子，它的结构式为：
；
其中，X为重复单元，X= 0～0.5。
本发明技术方案还提供一种含吡咯并吡咯烷酮和芴构筑单元的荧光共轭高分子的制备方法，按物质的量计，将1份单体M1与单体M2的混合物，1份单体M3， 0.007～0.010份四（三苯基膦）钯，20～25份碳酸钠，560～600份去离子水和380～420份四氢呋喃混合搅拌，在氩气保护、温度为55～65℃的条件下反应；
所述单体M1的结构式为
；
所述单体M2的结构式为
；
所述单体M3的结构式为
；
反应结束后，经纯化除去杂质、干燥，得到一种含吡咯并吡咯烷酮和芴构筑单元的荧光共轭高分子。
本发明所述1份单体M1与单体M2的混合物中，单体M1与单体M2的份数分别为下列组合中的一种：1份与0份，0.5份与0.5份，0.2份与0.8份，0.1份与0.9份，0.02份与0.98份，0份与1份。
本发明提供的含吡咯并吡咯烷酮和芴构筑单元的荧光共轭高分子的应用，按上述制备方法，改变单体M1与单体M2的比例，用于制备一系列含吡咯并吡咯烷酮和芴构筑单元的荧光共轭高分子，在三氯甲烷溶剂中，它们具有不同的荧光发射波长。
本发明的原理是：吡咯并吡咯烷酮（DPP）的结构是良好的橙黄色荧光的发色团，而芴的结构是优异的蓝色荧光的发色团，它们都具有自己独立的荧光发射，在聚合物中具有各自发色团的荧光颜色复合。本发明利用Suzuki 偶联共聚的方法，将吡咯并吡咯烷酮（DPP）和芴的构筑单元引入到共轭主链结构中，通过调节这两种结构的发色团在聚合物中的比例，合成一系列的共轭聚合物，从而实现对共轭高分子荧光颜色的调节。
与现有的技术相比，本发明的有益效果在于：
1.本发明提供了含吡咯并吡咯烷酮（DPP）和芴构筑单元的荧光共轭高分子的制备方法，合成步骤简单。
2.本发明合成了一系列的共轭聚合物，其荧光颜色的变化范围是橙黄色-黄色-紫色-蓝色之间，实现了荧光颜色的调节。
附图说明
图1是本发明实施例1中提供的含吡咯并吡咯烷酮（DPP）和芴构筑单元的荧光共轭高分子（P1～P6）的合成路线图；
图2是本发明实施例制备的共轭高分子（P1～P6）的核磁谱图；
图3是本发明实施例制备的共轭高分子（P1～P6）的红外谱图；
图4是本发明实施例制备的共轭高分子（P1～P6）的紫外吸收归一化谱图；
图5是本发明实施例制备的共轭高分子（P1～P6）的荧光发射归一化谱图；
图6是本发明实施例制备的共轭高分子（P1～P6）固体状态下在自然光和紫外光（365nm）下的数码照片；
图7是本发明实施例制备的共轭高分子（P1～P6）溶于三氯甲烷在自然光和紫外光（365nm）下的数码照片。
具体实施方式
下面结合附图和实施例对本发明技术方案作进一步的阐述
实施例1
本实施例提供含吡咯并吡咯烷酮（DPP）和芴构筑单元的荧光共轭高分子及其制备方法。
在本实施例中，M1的合成可参见文献（Chem. Commun. 2009, 39, 5859-5861），并作了条件的优化。M2为2,7-二溴-9,9-二辛基芴，M3为1,4-苯二硼酸。
单体M1的结构式为
；
单体M2的结构式为
；
单体M3的结构式为
。
参见附图1，它是本实施例含吡咯并吡咯烷酮（DPP）和芴构筑单元的荧光共轭高分子的（P1～P6）的合成路线图。
附图1中聚合物P1的制备：在氩气保护下，将单体M1（0.335 g, 0.5 mmol）、单体M3（0.083 g, 0.5 mmol）和四（三苯基膦）钯（0.004 g, 0.0035 mmol）依次加入到50 mL的双颈烧瓶中，再加入5 mL浓度为2 M的碳酸钠水溶液和15 mL的四氢呋喃溶液，升温至65 ℃，回流搅拌48 h。反应结束后，冷却至室温，加入20 mL的三氯甲烷和40 mL去离子水进行萃取，有机相用无水硫酸镁干燥，经抽滤，旋蒸除去溶剂后得到粗产物，在氯仿/丙酮中重结晶，将产物放入真空干燥箱中干燥，得到红褐色固体。产量：0.271 g，产率：88.1%。1H NMR(400 MHz, CDCl3, δ): 7.78-7.36(m, 12H), 3.81(t, 4H), 1.54(m, 4H), 1.16(m,20H), 0.82(t, 6H). Calcd (%): C, 81.78; H, 8.50; N, 4.54; found: C, 79.85; H,8.21; N, 3.96.
附图1中聚合物P2的制备:在氩气保护下，将单体M1（0.167 g, 0.25 mmol）、单体M2（0.137 g, 0.25 mmol）、单体M3（0.083 g, 0.5 mmol）和四（三苯基膦）钯（0.004 g,0.0035 mmol）依次加入到50 mL的双颈烧瓶中，再加入5 mL浓度为2 M的碳酸钠水溶液和15mL的四氢呋喃溶液，升温至65℃，回流搅拌48 h。反应结束后，冷却至室温，加入20 mL的三氯甲烷和40 mL去离子水进行萃取，有机相用无水硫酸镁干燥，经抽滤，旋蒸除去溶剂后得到粗产物，在氯仿/丙酮中重结晶，将产物放入真空干燥箱中干燥，得到深红色固体。产量：0.262 g，产率：94.2%。1H NMR(400 MHz, CDCl3, δ): 7.96-7.43(m, 22H), 3.84(t, 4H),2.06(t, 4H), 1.55(m, 8H), 1.22-1.10(m, 40H), 0.81(t, 12H). Calcd (%) :C,82.04 ; H, 9.07; N, 2.52; found: C, 82.55; H, 8.08; N, 2.65.
附图1中聚合物P3的制备：在氩气保护下，将单体M1（0.067 g, 0.1 mmol）、单体M2（0.219 g, 0.4 mmol）、单体M3（0.083 g, 0.5 mmol）和四（三苯基膦）钯（0.004 g, 0.0035mmol）依次加入到50 mL的双颈烧瓶中，再加入5 mL浓度为2 M的碳酸钠水溶液和15 mL的四氢呋喃溶液，升温至65 ℃，回流搅拌48 h。反应结束后，冷却至室温，加入20 mL的三氯甲烷和40 mL去离子水进行萃取，有机相用无水硫酸镁干燥，经抽滤，旋蒸除去溶剂后得到粗产物，在氯仿/丙酮中重结晶，将产物放入真空干燥箱中干燥，得到深红色固体。产量：0.256g，产率：98.5%。1H NMR(400 MHz, CDCl3, δ): 7.96-7.42(m, 22H), 3.85(t, 4H), 2.08(t, 4H), 1.54(m, 8H), 1.12-1.10(m, 40H), 0.81(t, 12H). Calcd (%) :C, 87.82;H, 9.72; N, 1.07; found: C, 84.85; H, 8.35; N,1.50.
附图1中聚合物P4的制备：在氩气保护下，将单体M1（0.034 g, 0.05 mmol）、单体M2（0.247 g, 0.45 mmol）、单体M3（0.083 g, 0.5 mmol）和四（三苯基膦）钯（0.004 g,0.0035 mmol）依次加入到50 mL的双颈烧瓶中，再加入5 mL浓度为2 M的碳酸钠水溶液和15mL的四氢呋喃溶液，升温至65 ℃，回流搅拌48 h。反应结束后，冷却至室温，加入20 mL的三氯甲烷和40 mL去离子水进行萃取，有机相用无水硫酸镁干燥，经抽滤，旋蒸除去溶剂后得到粗产物，在氯仿/丙酮中重结晶，将产物放入真空干燥箱中干燥，得到红色固体。产量：0.218 g，产率：87.3%。1H NMR(400 MHz, CDCl3, δ): 7.82-7.48(m, 22H), 3.87(t, 4H),2.08(t, 4H), 1.55(m, 8H), 1.12(m, 40H), 0.82(t, 12H). Calcd (%) :C, 88.89; H,9.90; N, 0.55; found: C, 87.86; H, 8.43; N, 0.40.
附图1中聚合物P5的制备：在氩气保护下，将单体M1（0.007 g, 0.01 mmol）、单体M2（0.269 g, 0.49 mmol）、单体M3（0.083 g, 0.5 mmol）和四（三苯基膦）钯（0.004 g,0.0035 mmol）依次加入到50 mL的双颈烧瓶中，再加入5 mL浓度为2 M的碳酸钠水溶液和15mL的四氢呋喃溶液，升温至65 ℃，回流搅拌48 h。反应结束后，冷却至室温，加入20 mL的三氯甲烷和40 mL去离子水进行萃取，有机相用无水硫酸镁干燥，经抽滤，旋蒸除去溶剂后得到粗产物，在氯仿/丙酮中重结晶，将产物放入真空干燥箱中干燥，得到橙红色固体。产量：0.212 g，产率：85.5%。1H NMR(400 MHz, CDCl3, δ): 7.82-7.49(m, 22H), 2.08(t, 4H),1.56(m, 8H), 1.12(m, 40H), 0.81(t, 12H). Calcd (%) :C, 89.53; H, 10.00; N,0.01; found: C, 84.86; H, 8.64; N, 0.00.
附图1中聚合物P6的制备：在氩气保护下，将单体M2（0.274 g, 0.5 mmol）、单体M3（0.083 g, 0.5 mmol）和四（三苯基膦）钯（0.004 g, 0.0035 mmol）依次加入到50 mL的双颈烧瓶中，再加入5 mL浓度为2 M的碳酸钠水溶液和15 mL的四氢呋喃溶液，升温至65℃，回流搅拌48 h。反应结束后，冷却至室温，加入20 mL的三氯甲烷和40 mL去离子水进行萃取，有机相用无水硫酸镁干燥，经抽滤，旋蒸除去溶剂后得到粗产物，在氯仿/丙酮中重结晶，将产物放入真空干燥箱中干燥，得到灰色固体。产量：0.232 g，产率：93.9%。1H NMR(400 MHz,CDCl3, δ): 7.96-7.43(m, 10H), 2.06(t,4H), 1.58(m, 4H), 1.10(m, 20H), 0.81(t,6H). Calcd (%): C, 89.81; H, 10.19; found: C, 86.72; H, 8.86.
参见附图2，它是本实施例提供的聚合物（P1～P6）的核磁谱图（溶剂为CDCl3），由图2可以看出，P1～P6的结构与合成路线图中所示结构是一致的。
参见附图3，它是本实施例提供的聚合物（P1～P6）的红外谱图，由图3进一步证实了P1～P6的结构与合成路线图中所示结构完全一致。
实施例2
本实施例提供对含吡咯并吡咯烷酮（DPP）和芴构筑单元的荧光共轭高分子荧光颜色调节的方法。
参见附图4，它是按实施例1制备方法得到的一系列聚合物（P1～P6）的紫外吸收的归一化谱图。
参见附图5，它是按实施例1制备方法得到的一系列聚合物（P1～P6）的荧光发射的归一化谱图。
参见附图6，它是按实施例1制备方法得到的一系列聚合物（P1～P6）的固体粉末，用相机拍照记录聚合物（P1～P6）的固体粉末在自然光和紫外光（365 nm）下的荧光颜色。
参见附图7，它是按实施例1制备方法得到的聚合物（P1～P6）溶于三氯甲烷溶剂中，聚合物的浓度为1×10-4 M（按重复单元计算）。用相机拍照记录聚合物（P1～P6）溶液状态在自然光和紫外光（365 nm）下的荧光颜色。
由本实施例提供的检测结果可以看出，本发明通过调节吡咯并吡咯烷酮（DPP）和芴这两种结构的发色团在聚合物中的比例，合成了一系列的共轭聚合物，其荧光颜色可在橙黄色-黄色-紫色-蓝色范围之间变化，实现了对共轭高分子荧光颜色的调节。

Claims (4)

1.一种含吡咯并吡咯烷酮和芴构筑单元的荧光共轭高分子，其特征在于它的结构式为：
；
其中，X为重复单元，X= 0～0.5。
2.一种含吡咯并吡咯烷酮和芴构筑单元的荧光共轭高分子的制备方法，其特征在于：按物质的量计，将1份单体M1与单体M2的混合物，1份单体M3， 0.007～0.010份四（三苯基膦）钯，20～25份碳酸钠，560～600份去离子水和380～420份四氢呋喃混合搅拌，在氩气保护、温度为55～65℃的条件下反应；
所述单体M1的结构式为
；
所述单体M2的结构式为
；
所述单体M3的结构式为
；
反应结束后，经纯化除去杂质、干燥，得到一种含吡咯并吡咯烷酮和芴构筑单元的荧光共轭高分子。
3.根据权利要求2所述的一种含吡咯并吡咯烷酮和芴构筑单元的荧光共轭高分子的制备方法，其特征在于：所述1份单体M1与单体M2的混合物中，单体M1与单体M2的份数分别为下列组合中的一种：1份与0份，0.5份与0.5份，0.2份与0.8份，0.1份与0.9份，0.02份与0.98份，0份与1份。
4.含吡咯并吡咯烷酮和芴构筑单元的荧光共轭高分子的应用，其特征在于：按权利要求2或3所述的制备方法，改变单体M1与单体M2的比例，用于制备一系列含吡咯并吡咯烷酮和芴构筑单元的荧光共轭高分子，在三氯甲烷溶剂中，它们具有不同的荧光发射波长。
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