三苯胺-螺硅芴共聚物的合成  

Synthesis of A Triphenylamine-Spirosilabifluorene Alternating Copolymer

作　　者：肖海波[1] 冷冰[1] 田禾[1] 

机构地区：[1]华东理工大学精细化工研究所和教育部结构可控先进功能材料及其制备重点实验室,上海200237

出　　处：《应用化学》2006年第2期140-143,共4页Chinese Journal of Applied Chemistry

基　　金：国家自然科学基金资助课题

摘　　要：通过钯盐催化的Suzuk i偶联反应,将2,2′-二溴螺硅芴与三苯胺二硼酸共聚得三苯胺-螺硅芴聚合物。其中2,2′-二溴螺硅芴是以邻二溴苯为原料,经2步偶联,硝化,还原,取代共5步反应制得;三苯胺二硼酸是以三苯胺为原料,经溴化,锂化,再与硼酸三甲酯反应制得。单体和共聚物的结构经核磁共振氢谱、质谱、红外光谱测试技术确证。凝胶渗透色谱法测得共聚物的分子量Mn=7 014,Mw=9 577,分散度1.36。螺硅芴的引入提高了共聚物的溶解性和热稳定性。共聚物的玻璃化转变温度(Tg)为158.22℃。由循环伏安法测得的电化学性质表明,共聚物具有可逆的氧化过程和较低的离子势(-5.47 eV,与三苯胺接近)。A novel triphenylamine-spirosilabifluorene alternating copolymer was synthesized by copolymerization of 2,2＇-dibromo-9,9＇-spiro-9-silabifluorene and triphenylamine diboronic acid via a palladium-catalyzed Suzuki coupling reaction. The dibromo monomer was synthesized in five steps starting from 1, 2- dibromobenzene. Triphenylamine diboronic acid was obtained from triphenylamine in three steps. The structures of the monomers and the copolymer were verified by means of ^1H NMR, MS, and FTIR. The molecular weight of the polymer was determined by gel permeation chromatography （GPC） analysis against polystyrene standards. The polymer has a M. of 7 014, a M, of 9 577, with a polydispersity of 1.36. The introduction of a spiro-structure leads to a high thermal stability（ TE =158.22 ℃ ） and a good solubility of the polymer in common organic solvents. The electrochemical behavior of the polymer was investigated with cyclic voltammetry. The reversible electrochemical oxidation and low ionization potential（ -5.47eV, which is very close to the data reported for triphenylamine） suggest that the polymer might have potential application as a hole transport material for polymer LEDs.

关 键 词：螺硅芴 三苯胺 共聚物 合成 

分 类 号：O634.4[理学—高分子化学]