含四苯乙烯单元荧光聚合物的合成与表征

发布时间：2018-05-06 16:10

  本文选题：荧光聚合物 + 聚集诱导发光　； 参考：《河北大学》2017年硕士论文

【摘要】：聚集诱导发光(AIE)材料在溶液状态下有微弱的荧光信号,在聚集状态下荧光显著增强,这与传统生色团的聚集诱导淬灭(ACQ)行为相反。近年来,这类具有AIE特点的发光有机分子已经被引起广泛关注。其中四苯乙烯及其衍生物因其发光性能优良、合成简便、易功能化、AIE效应明显等优点而得到了研究者的青睐。本文合成了6个含四苯乙烯单元化合物、2个含四苯乙烯单元油溶性荧光聚合物和1个含四苯乙烯单元水溶性荧光聚合物,并对其结构和光学性能等进行了表征和测试。以4-羟基二苯甲酮为起始原料合成了两端带有环氧丙氧基的四苯乙烯衍生物1,2-二[4'-(2'',3''-环氧丙氧基)苯基]-1,2-二苯基乙烯(M2)。再以叔丁醇钾为引发剂,M2为单体,通过阴离子开环聚合制备了含四苯乙烯单元的超支化油溶性聚合物(P1)。利用NMR、MALDI-TOF-MS、FTIR、GPC、UV-Vis和PL等对M2和P1的化学结构和光学性能进了表征与测试。结果表明:P1保持了四苯乙烯基的油溶性AIE特性,其溶液状态与聚集状态均发射出蓝绿色荧光;P1在THF/H2O(1/99,V/V)中的荧光强度比其在THF中的增加了6.06倍。主要原因是由于P1的分子链结构约束了苯环的自由旋转,从而成功地解决了AIE分子在溶液状态荧光极低的局限。利用循环伏安法测得P1的HOMO值为-5.55 eV,LUMO值为-2.34 eV。通过MTT法对P1的细胞毒性进行了测试,结果表明:P1在浓度不大于100μg·mL-1情况下对细胞没有毒性。通过TG测试表明P1在氮气中的热失重阶段为340~600℃,表明P1具有较高的热分解温度,具有优良的热稳定性。以4-羟基二苯甲酮和4-溴二苯甲酮为起始原料,通过McMurry偶联反应和Suzuki偶联反应合成两端带有硼酸酯和溴的四苯乙烯衍生物(M4),将M4引入到傒酰亚胺衍生物N,N'-二(3-戊基)-1,7-二溴傒-3,4,9,10-四羧酸二酰亚胺(C1)中,Suzuki偶联反应合成了含四苯乙烯-傒酰亚胺单元的ATRP引发剂(M6)。然后以M6为引发剂,2-(2',3',4',6'-四-O-乙酰基-α-D-吡喃甘露糖基氧基)甲基丙烯酸乙酯(C2)为单体进行ATRP反应制备油溶性聚合物P2;脱除乙酰基后得到含四苯乙烯-傒酰亚胺共轭单元水溶性荧光聚合物P3。利用NMR、MALDI-TOF-MS、GPC、UV-Vis和PL等对化合物M3、M4、M5、M6和聚合物P2、P3的化学结构和光学性能进行表征与测试。其实验结果表明:M3、M4保持了四苯乙烯基所具有的AIE特性,且M4成功地引入到傒酰亚胺衍生物C1中分子中,解决了C1分子的ACQ效应使其具有AIE活性,得到的含四苯乙烯-傒酰亚胺共轭单元化合物M6同样具有AIE效应;通过TTRP反应得到的聚合物P2有较好的油溶性,其数均分子量(Mn)为18000 g/mol,具有AIE特性;P3具有较好的水溶性,其峰位分子量(Mp)为7200 g/mol,在光学细胞成像领域存在一定的潜在应用价值。
[Abstract]:The agglomeration induced luminescence (AIEs) materials have weak fluorescence signals in the solution state and enhanced fluorescence in the aggregation state, which is contrary to the agglomeration induced quenching (ACQ) behavior of the traditional chromophore. In recent years, this kind of luminescent organic molecules with the characteristics of AIE have attracted wide attention. Among them, tetrastyrene and its derivatives have been favored by researchers because of their excellent luminescent properties, simple synthesis, easy functionalization of AIE effect and so on. In this paper, six tetrastyrene unit compounds, two oil-soluble fluorescent polymers containing tetrastyrene unit and one water-soluble fluorescent polymer containing tetrastyrene unit were synthesized, and their structures and optical properties were characterized and tested. A tetrastyrene derivative with epichloropropyl group at both ends was synthesized from 4-hydroxybenzophenone. The hyperbranched oil-soluble polymer (P1N) containing tetrastyrene unit was prepared by anion ring-opening polymerization with potassium tert-butanol as initiator M 2 as monomer. The chemical structures and optical properties of M2 and P1 were characterized and tested by NMR-MALDI-TOF-MST FTIRI GPC-Vis and PL et al. The results show that: P1 maintains the oil-soluble AIE property of tetrastyrene-group, and the luminescence intensity of the blue-green fluorescence P1 in THF / H _ 2O _ 1 / 9 / 9 V / V) is 6.06 times higher than that in THF, both in the solution state and in the aggregation state. The main reason is that the molecular chain structure of P1 restricts the free rotation of benzene ring, which successfully solves the limitation of extremely low fluorescence of AIE molecule in the solution state. By cyclic voltammetry, the HOMO value of P1 is -5.55 EV / L UMO = -2.34 EV. The cytotoxicity of P1 was tested by MTT method. The results showed that no cytotoxicity was found when the concentration of P1 was not more than 100 渭 g mL-1. The TG results show that the thermal weight loss of P1 in nitrogen is 340 鈩，

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