【作者】 王迪；

【导师】 黄定海；

【作者基本信息】 天津大学 ， 材料学， 2014， 硕士

【摘要】 红外光谱的特征吸收峰对分子链的结构参数变化敏感，可以用来研究高分子体系的玻璃化转变行为。聚苯乙烯大分子具有复杂的构型和构象，增加了红外光谱图解释的困难，因此借助小分子模型进行辅助研究。本课题主要探索了聚苯乙烯(PS)的简化模型即苯乙烯二聚体的制备方法，即通过伍兹偶联反应(Wurtz Coupling Reaction)和熊田偶联反应(Kumada CouplingReaction)合成苯乙烯的二聚体，通过减压蒸馏和柱色谱进行分离提纯，以质谱仪(MS)和核磁谱仪(NMR)对产物进行表征，用气相色谱仪(GC)研究产率。通过伍兹偶联反应合成具有对称结构的1,4-二苯基丁烷。采用Mn/CuCl2和Zn/CuCl2/KOH/苯这两种不同的催化体系，改变反应时间以及反应温度，以气相色谱的检测表征产率，对比实验可行性和催化效果。实验结果表明，以Mn/CuCl2为催化体系，以β-溴苯乙烷为原料，反应温度25oC，持续16小时的反应产率高，成本低，可以作为合成结构对称的PS模型小分子的优选反应条件。通过对比PS和1,4-二苯基丁烷的红外光谱，验证了模型小分子辅助研究的可行性。通过对1,4-二苯基丁烷变温红外的检测发现，结晶熔融后，1384cm-1与1377cm-1处的谱峰发生融合，1873cm-1、728cm-1处的谱峰强度变弱。通过熊田偶联反应，以1,3-二溴丁烷和格氏试剂苯基溴化镁作为底物合成具有不对称结构的1,3-二苯基丁烷。采用Fe(acac)3/TMEDA/HMTA和FeCl3/TMEDA两种不同的催化体系，以气相色谱的检测研究产率，对比实验可行性和催化效果。结果表明，以Fe(acac)3/TMEDA/HMTA为催化体系时产率较高，成本较低，实验后处理简单,为合成结构不对称的PS模型小分子的优选催化体系。更多还原

【Abstract】 In order to investigate the change of polymer structure, Fourier Transforminfrared spectroscopy(FTIR) is widely applied for its high sensitivity. It can also beused to study the glass transition behavior of the polymer system. The configurationand conformation of polystyrene (PS) are very complex and hard to be confirmed, soa simplified model of polystyrene, especially styrene dimer is needed for auxiliarystudy.In this paper, styrene dimer was generated via Wurtz coupling reaction andKumada coupling reaction and then the product was extracted by vacuum distillationand column chromatography. The structures and properties were characterized viaMass Spectrometry (MS), Gas Chromatography (GC) and Nuclear MagneticResonance (NMR).1,4-diphenylbutane was successfully synthesized by Wurtz coupling reactionwith two different catalytic systems. We changed the time and temperature, andanalyzed the effect and GC yield. When the reaction time and temperature was16hours and25℃, the results showed that the product with β-bromine ethyl benzeneacted as raw material had the highest GC yield. FTIR was used to verify the productand the assignments of infrared peaks were analyzed. It was confirmed that1,4-diphenylbutane can be used as PS model molecule. We also found several changesof1,4-diphenylbutane at various temperatures by analyzing its infrared spectra.1,3-diphenylbutane was successfully synthesized by Kumada cross couplingreaction. We also compared the effect and GC yield of experiments using twodifferent catalytic systems. Two different catalytic systems were used in theexperiment and the results suggested that the experiment withFe(acac)3/TMEDA/HMTA performed better.更多还原