通过四重氢键杂化络合物介导的自组装形成可混溶的超分子聚合物共混物。

Formation of a miscible supramolecular polymer blend through self-assembly mediated by a quadruply hydrogen-bonded heterocomplex.

作者信息

Park Taiho, Zimmerman Steven C

机构信息

Department of Chemistry, Roger Adams Laboratory, 600 S. Mathews Avenue, University of Illinois, Urbana, Illinois 61801, USA.

出版信息

J Am Chem Soc. 2006 Sep 6;128(35):11582-90. doi: 10.1021/ja0631854.

DOI:10.1021/ja0631854

PMID:16939282

Abstract

A supramolecular network polymer consisting of a pair of immiscible polymers, poly(butyl)methacrylate (PBMA) and polystyrene (PS), is described. A urea of guanosine (1, UG) and 2,7-diamido-1,8-naphthyridine (2, DAN), which form an exceptionally strong quadruply hydrogen-bonding complex, are displayed at 1-10 mol % along the main backbone of PBMA and PS, respectively. (1)H NMR studies show heterocomplexation between UG and DAN exclusively. This high-fidelity, high-affinity supramolecular connection of two different polymer coils at the molecular level produces a polymer blend. Blends containing different weight ratios of the polymers and mole percent of the recognition units were characterized by AFM and DSC experiments with no isolated domains observed and a single glass-transition temperature (T(g)). The T(g) is tunable by varying the weight ratio of the polymers in the blend. In addition, viscosity measurements, size-exclusion chromatography (SEC), and dynamic light-scattering (DLS) studies demonstrate the formation of a supramolecular network structure.

摘要

本文描述了一种由一对互不相溶的聚合物——聚甲基丙烯酸丁酯（PBMA）和聚苯乙烯（PS）组成的超分子网络聚合物。鸟苷脲（1，UG）和2,7-二氨基-1,8-萘啶（2，DAN）形成一种异常强的四重氢键复合物，它们分别以1 - 10摩尔%沿着PBMA和PS的主链分布。核磁共振氢谱（¹H NMR）研究表明UG和DAN之间仅存在异质络合。这种在分子水平上两种不同聚合物链的高保真、高亲和力超分子连接产生了一种聚合物共混物。通过原子力显微镜（AFM）和差示扫描量热法（DSC）实验对含有不同重量比聚合物和不同摩尔百分比识别单元的共混物进行了表征，未观察到孤立的区域，且只有一个玻璃化转变温度（T(g)）。通过改变共混物中聚合物的重量比可以调节T(g)。此外，粘度测量、尺寸排阻色谱法（SEC）和动态光散射（DLS）研究表明形成了超分子网络结构。