含烷基噻吩与三嗪π-共轭聚合物的合成及性能

Synthesis and Properties of π-Conjugated Polymers Comprising Alkyl Thiophene and Triazine Unit

以二价镍配合物(Ni(dppp)Cl2)作为催化剂,2-二异丙基氨基-4,6-二氯均三嗪分别与3-丁基-2,5-二溴噻吩格氏(Grignard)试剂、3-辛基2,5-二溴噻吩格氏试剂、3-十二烷基-2,5-二溴噻吩格氏试剂交替共聚合成了3种含2-二异丙基氨基均三嗪的聚合物P1,P2和P3。并经傅里叶变换红外光谱、氢核磁共振谱、紫外-可见光谱、荧光光谱、循环伏安、X射线粉末衍射和凝胶渗透色谱等测试手段对其进行了表征,对聚合物P1在CHCl3溶液中的酸致变色行为进行了研究。结果表明,得到的聚合物在甲苯、氯仿、四氢呋喃(THF)等有机溶剂中溶解性好,3种聚合物的紫外-可见最大吸收波长在372 nm处出现,在CHCl3溶液中聚合物P1,P2,P3最大发射峰分别位于478 nm,549 nm和523 nm。聚合物均在-1.8~0 V出现n-掺杂峰。通过X射线衍射测试聚合物均有一定结晶性但结晶性较差。

π-Conjugated polymers containing 2-diisopropylamino-s-triazine as P1,P2 and P3 were prepared between2-diisopropylamino-4,6-dichloro-s-triazine and 3-butyl-2,5-dibromothiophene Grignard reagent,3-octyl-2,5-dibromothiophene Grignard reagent and 3-dodecyl-2,5-dibromothiophe-ne Grignard reagent by Grignard reaction using Ni( dppp)Cl2as catalyst,respectively. The structures of polymers were performed by Fourier translation infrared spectroscopy( FTIR),1H-nuclear magnetic resonance(1H-NMR),ultraviolet and visible spectrophotometry( UV-vis),fluorescence spectroscopy( PL),gel permeation chromatography( GPC),cyclic voltammogram( CV) and X-ray diffraction analysis( XRD) and acidichromic property of polymer P1 in CHCl3 was studied. The results show that all polymers are soluble in common organic solvent such as tetrahydrofuran( THF),CHCl3,toluene and the maximum absorption peaks of polymers appear at 372 nm. The maximum emission peaks of P1,P2 and P3 appear at 478 nm,549 nm and 523 nm in CHCl3 solution respectively. All polymers have n-doped peaks in the regions from 0 V to- 1. 8 V. XRD patterns show that all three polymers have a little crystallinity.