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首页> 外文学位 >Theoretical prediction and spectroscopic characterization of novel norbornene and norbornadiene polymer structures.
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Theoretical prediction and spectroscopic characterization of novel norbornene and norbornadiene polymer structures.

机译：新型降冰片烯和降冰片二烯聚合物结构的理论预测和光谱表征。

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摘要

This thesis describes efforts in theoretical prediction of the macrostructures of poly(norbornadienes) and poly(norbornenes). In contrast to existing synthetic helical polymers such as poly(isocyanides) and poly(methacrylates), the helical parameters of norbornene and norbornadiene polymers may be tunable by judicious choice of substituents. Computer modelling surveys were carried out to qualitatively compare effects from tacticity, steric bulk, pi-stacking and hydrogen-bonding on polymer topology. Models capable of pi-stacking and hydrogen-bonding displayed interactions between substituents on neighbouring repeat units. These modelling studies suggest that helical turns will collapse to form and enforce a tube-like structure.; Polymers of functionalized norbornenes and norbornadienes were produced using different achiral and racemic catalysts. Microstructural characterization was conducted by 1H, 1H-1H COSY and 13C{lcub}1H{rcub} NMR spectroscopy. The tacticities of poly(norbornadienes) agreed well with literature reported values of the catalyst used. However, all three poly(norbornenes) had the same tacticity. Macrostructural characterization was accomplished by GPC, LS, polarimetry and CD spectroscopy. All polymers had a spherical conformation in solution. Polymers made of optically active monomers were optically active whereas polymers made of non-optically active monomers were not.
机译：本文介绍了聚降冰片二烯和聚降冰片烯的宏观结构的理论预测工作。与现有的合成螺旋聚合物如聚（异氰酸酯）和聚（甲基丙烯酸酯）相反，降冰片烯和降冰片二烯聚合物的螺旋参数可通过明智地选择取代基来调节。进行了计算机建模调查，以定性比较策略性，空间体积，π堆积和氢键对聚合物拓扑的影响。能够pi堆积和氢键的模型显示了相邻重复单元上取代基之间的相互作用。这些建模研究表明，螺旋线匝将塌陷以形成并增强管状结构。使用不同的非手性和外消旋催化剂可生产功能化降冰片烯和降冰片二烯的聚合物。通过1H，1H-1H COZY和13C {lcub} 1H {rcub} NMR光谱进行微观结构表征。聚降冰片二烯的策略与文献报道的所用催化剂的值非常吻合。但是，所有三个聚降冰片烯具有相同的立构规整度。宏观结构表征是通过GPC，LS，极化法和CD光谱法完成的。所有聚合物在溶液中均具有球形构象。由光学活性单体制成的聚合物具有光学活性，而由非光学活性单体制成的聚合物则没有。

著录项

  • 作者

    Mainville-Dale, Rachel M. E.;

  • 作者单位

    University of Ottawa (Canada).;

  • 授予单位 University of Ottawa (Canada).;
  • 学科 Chemistry Polymer.
  • 学位 M.Sc.
  • 年度 2002
  • 页码 141 p.
  • 总页数 141
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类 高分子化学（高聚物）;
  • 关键词

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