本文已被：浏览 866次 下载 649次
投稿时间：2017-02-28
投稿时间：2017-02-28
中文摘要: 通过还原4，7-二溴-2，1，3-苯并噻二唑制备2，5-二溴邻苯二胺，并分别与1，10-邻菲罗啉-5，6-二酮、苊醌、菲醌和联苯甲酰缩合反应，制备了4种单喹喔啉衍生物（M1、M2、M3、M4）。在二乙酸钯（Pd（CH3COO）2）和配体三环己基膦的催化下，通过Suzuki反应将2，7-二（4，4，5，5-四甲基-1，3，2-二氧杂硼酸烷）-9，9-二辛基芴（M5）分别与M1、M2、M3、M4交替共聚制得4种聚合物（P1、P2、P3、P4）。通过FT-IR和1H-NMR等测试方法表征所有单体及聚合物的结构。通过UV-Vis光谱和荧光光谱探讨了4种聚合物在CHCl3溶液中本征态的光谱性能，以及相应聚合物的CHCl3溶液被低浓度三氟乙酸（TFA）质子化时的光学性能。结果显示，4种聚合物对低浓度TFA有良好的敏感性。聚合物P1与2.17×10-7 mol/L的TFA作用时，P1的CHCl3溶液明显变色。聚合物P2~P4的CHCl3溶液与4.32×10-3 mol/L的TFA作用时，溶液颜色发生变化，与此同时在UV-Vis光谱上500~800 nm处出现新的吸收带。同时，4种交替共聚物的CHCl3溶液具有较好的荧光性能，当溶液中加入低浓度的TFA时，即在4种聚合物的CHCl3溶液中分别加入7.0×10-10、1.73×10-6、7.5×10-7 mol/L和4.0×10-6 mol/L的TFA时，其荧光发射强度明显减弱。
Abstract:2,5-Dibromo-o-pheneylenedimanine was obtained by the reduction of 4,7-dibromo-2,1,3-benzothiadiazole,and four monoquinoxaline type monomers (M1, M2, M3, M4) were prepared by the reaction of 2,5-dibromo-o-pheneylenedimanine with 5,6-dione-1,10-phenanthroline, phenanthrenequinone, acenaphthenequinone and benzyl, respectively. Using palladium diacetate (Pd(CH3COO)2) and ligand tricyclohexylphosphine as catalyst, four donor-acceptor-donor (D-A-D) type polymers (P1, P2, P3, P4) were prepared by Suzuki coupling alternative copolymerization of 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9-dioctylfluorene (M5) with four monoquinoxaline type monomers, respectively. All monomers and polymers were characterized by FT-IR and 1H-NMR spectra. The optical properties of polymers solution in CHCl3, at neutral state and when different concentrations of trifluoracetic acid (TFA) was added to the solution, were investigated by UV-Vis and fluorescence spectrometer. The UV-Vis spectra results showed that four D-A-D type polymers had good sensitivity to low concentration of TFA, wherein polymer P1 was sensitive to 2.17×10-7 mol/L of TFA and polymers P2-P4 were sensitive to 4.32×10-3 mol/L of TFA. Polymer P1 had better sensitivity to low concentration of TFA than P2-P4, due to the existence of two pyridine rings in quinoxaline unit of polymer P1. The colors of polymers CHCl3 solution changed significantly after acidified by TFA, a red shift of absorption bands (UV-Vis spectra of polymers P1-P3) followed, and new wide absorption bands on the UV-Vis spectra of P2-P4 appeared. The fluorescence spectra of P1-P4 solution in CHCl3 were remarkably sensitive to low concentration of TFA, wherein P1 solution (11.0 μg/L) was sensitive to 7.0×10-10 mol/L of TFA and P2-P4 (32.0, 28.0, 10.0 μg/L) solution were sensitive to 1.73×10-6, 7.5×10-7 mol/L and 4.0×10-6 mol/L of TFA, respectively. The fluorescence spectra intensity of all four polymers decreased to very small value when corresponding concentration of TFA was added to the polymer solution.
keywords: quinoxaline dioctyflourene alternative copolymerization acidichromic properties fluorescence properties
文章编号： 中图分类号：O06 文献标志码：
基金项目:国家自然科学基金（21662034，21164011）；新疆大学博士启动基金项目（BS150226）
| 作者 | 单位 | |
| 麦麦提依明·马合木提 | 新疆大学化学化工学院, 功能高分子重点实验室, 乌鲁木齐 830046 | |
| 司马义·努尔拉 | 新疆大学化学化工学院, 功能高分子重点实验室, 乌鲁木齐 830046 | |
| 吐尼莎古丽·阿吾提 | 新疆大学化学化工学院, 功能高分子重点实验室, 乌鲁木齐 830046 | Tunsagul2010@sohu.com |
引用本文：
麦麦提依明·马合木提,司马义·努尔拉,吐尼莎古丽·阿吾提.喹喔啉与二辛基芴交替共聚物的合成及其酸致变色性能[J].功能高分子学报,2017,30(4):429-436.
Mamtimin MAHMUD,Ismayil NURULLA,Tunsagul AWUT.Synthesis and Acidichromic Properties of Copolymers of Quinoxaline and Dioctylflourene[J].Journal of Functional Polymers,2017,30(4):429-436.
麦麦提依明·马合木提,司马义·努尔拉,吐尼莎古丽·阿吾提.喹喔啉与二辛基芴交替共聚物的合成及其酸致变色性能[J].功能高分子学报,2017,30(4):429-436.
Mamtimin MAHMUD,Ismayil NURULLA,Tunsagul AWUT.Synthesis and Acidichromic Properties of Copolymers of Quinoxaline and Dioctylflourene[J].Journal of Functional Polymers,2017,30(4):429-436.
