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Well-defined polymeric materials incorporating strong hydrogen bonding groups.

机译：定义明确的聚合物材料，结合了强大的氢键基团。

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摘要

The field of supramolecular chemistry has drastically grown in recent years, and in particular the development of new strongly hydrogen bonding groups has yielded numerous fundamental and practical advances allowing for the design of materials with unique combinations of macroscopic properties. For polymers whose properties typically are rather insensitive to temperature (other than e.g. when passing through the glass transition), the incorporation of hydrogen bonding groups into their structures can provide a new handle with which to tune their structural, mechanical, and thermal behavior. Limited fundamental studies exist, however, in which the combined effects of the polymer behavior and supramolecular interactions are characterized.;In this work new chemistry has been developed to allow the synthesis of well-defined polymers containing quadruple hydrogen bonding groups which bind either through a complementary or self-complementary interaction. The MHB groups can be incorporated either at the chain end or along the backbone, and through simple blending a number of different architectures can be obtained. In the simplest case, two chemically distinct homopolymers with MHB groups attached at a single chain end were mixed to produce supramolecular copolymers analogous to traditional diblocks. The nature of the hydrogen bonding groups was found to be highly influential in determining the bulk microstructure. In analyzing the phase behavior of such blends, a new polymer system was discovered to display lower critical ordering behavior and its temperature dependent Flory-Huggins c parameter was measured. By randomly incorporating strongly self-complementary MHB groups as side chains rather than end groups, a new class of thermoplastic elastomers was developed which are unentangled and contain no glassy or crystalline domains, yet show dynamical properties in some ways typical of polymer networks. The study of ABA triblock copolymer-like architectures in which the MHB groups are randomly distributed in the end blocks showed that the distribution of these groups along the chain drastically affects the rheological properties and provides a design strategy for best taking advantage of the benefits of such monomers while minimizing their incorporation in the polymers.
机译：近年来，超分子化学领域急剧发展，特别是新的强氢键基团的开发已经产生了许多基础和实际的进展，从而允许设计具有宏观性质的独特组合的材料。对于其性质通常对温度相当不敏感的聚合物（例如，当通过玻璃化转变时除外），将氢键合基团引入其结构中可提供新的处理方法，用以调节其结构，机械和热行为。然而，存在有限的基础研究，其中表征了聚合物行为和超分子相互作用的综合作用。在这项工作中，已经开发出新的化学方法以允许合成定义明确的聚合物，该聚合物包含通过两个氢键结合的四氢键合基团。互补或自我互补的互动。 MHB基团可以在链端或在主链上掺入，并且通过简单的掺混可以获得许多不同的结构。在最简单的情况下，将两种在化学上不同的均聚物（在单链末端带有MHB基团）混合在一起，生成类似于传统二嵌段的超分子共聚物。发现氢键合基团的性质在确定本体微观结构中具有很大的影响。在分析此类共混物的相态行为时，发现了一种新的聚合物体系，该体系显示出较低的临界有序行为，并测量了其温度相关的Flory-Huggins c参数。通过随机掺入强自补体MHB基团作为侧链而不是端基，开发了一种新型的热塑性弹性体，它们无缠结，不包含玻璃或结晶域，但在某些聚合物网络中表现出动态特性。 MABA基团在末端嵌段中随机分布的ABA类三嵌段共聚物样结构的研究表明，这些基团沿链的分布会极大地影响流变性能，并提供了一种设计策略，可最佳地利用此类优点单体同时最小化它们在聚合物中的掺入。

著录项

  • 作者

    Feldman, Kathleen E.;

  • 作者单位

    University of California, Santa Barbara.;

  • 授予单位 University of California, Santa Barbara.;
  • 学科 Chemistry Polymer.;Engineering Materials Science.
  • 学位 Ph.D.
  • 年度 2009
  • 页码 169 p.
  • 总页数 169
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类 高分子化学（高聚物）;工程材料学;
  • 关键词

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