超分子聚合物是指单体单元通过定向的非共价相互作用连接而成的聚合物。尽管超分子聚合物在近年来得到了较大的发展，但是如何实现可控的超分子聚合仍然是巨大的挑战。超分子单体是通过非共价相互作用构筑的可聚合单体。我们基于超分子单体的共价聚合策略，将溶液中不易可控的超分子聚合转移到液-液界面，建立并发展了超分子界面聚合的新方法，实现了超分子聚合物材料的可控制备。另外，如何利用非共价相互作用的动态可逆性构筑功能化的超分子聚合物材料是一个重要的问题。以交联聚合物为例，我们利用超分子单体的动态性，制备了可多次加工成型的交联超分子聚合物材料，希望运用超分子化学的思路去解决传统共价交联聚合物难以回收的问题。本论文以四重氢键构筑的超分子单体为基础，从可控聚合和功能材料两方面出发，构筑了具有特定结构和功能的超分子聚合物材料。论文主要取得了以下三方面的成果：一、提出了不互溶单体的超分子界面聚合的新方法，用以构筑超分子聚合物。基于四重氢键相互作用，我们在有机相构筑了两端带有巯基的油溶性超分子单体，在水相构筑了两端带有马来酰亚胺的水溶性单体。利用巯基与马来酰亚胺的点击反应，两相单体在界面发生共价聚合，进而在水-油界面成功制备了超分子聚合物。通过改变超分子界面聚合的反应条件，能够实现对超分子聚合物性质的有效调控。二、发展了互溶单体的超分子界面聚合，并且探究了超分子界面聚合的独特优势和机理。基于四重氢键相互作用，在有机相构筑两端带有异氰酸酯的油溶性超分子单体。利用异氰酸酯和氨基的反应，分别在溶液和界面构筑超分子聚合物。通过对比，界面聚合制备的超分子聚合物具有更高的分子量和玻璃化转变温度。我们推测导致上述现象的原因如下：一是单体分子的两亲性，使得界面处的浓度更高；二是界面反应速率很快，使得界面聚合受扩散控制，因此两相的单体分子更容易与界面处的聚合物末端反应。三、提出了超分子单体构筑可回收的交联超分子聚合物材料的方法。将低含量的基于四重氢键的超分子单体与共价单体进行共聚制备交联超分子聚脲材料。该材料不仅具有良好的力学性能和耐溶剂性能，同时也具有优异的可重复加工性能，这为可回收的交联聚合物提供了一种新思路，有望应用于其他的交联体系。
Supramolecular polymers are polymeric arrays in which monomers are held through highly directional and reversible noncovalent interactions. Even though significant progress has been made in the field of supramolecular polymers during the past decades, the control of supramolecular polymerization remains a great challenge. To this end, we have transferred the supramolecular polymerization from solutions to water-oil interfaces and developed a new method of supramolecular interfacial polymerization. In addition, it is also significant to construct functional supramolecular polymeric materials with desirable structures and unique properties. Illustrated by cross-linked supramolecular polymeric materials, we have demonstrated the feasibility of incorporating supramonomers into main-chains to resolve the problems of recyclability in cross-linked polymers.In the thesis, based on supramonomers linked by quadruple hydrogen bonds, we have focused on the controllable supramolecular polymerization and functional supramolecular polymeric materials. Three parts are concluded as follows:(1) A controllable method of supramolecular interfacial polymerization to fabricate supramolecular polymeric materials is proposed for the first time. As a proof of the concept, an oil-soluble supramonomer bearing thiol end groups based on quadruple hydrogen bonds and a water-soluble monomer containing maleimide end groups were designed and synthesized, respectively. Supramolecular interfacial polymerization was implemented through a thiol-maleimide click reaction at the interface to obtain supramolecular polymeric films. Moreover, the properties of such supramolecular polymers are well regulated through changing the polymerization conditions.(2) Supramolecular interfacial polymerization of miscible monomers is utilized to construct supramolecular polymers with defined structures and properties. A bifunctional supramonomer containing two isocyanate end groups based on quadruple hydrogen bonds was fabricated in chloroform. By isocyanate-amine reaction, supramolecular polymers were constructed at the oil-water interface. Supramolecular polymers with higher molecular weights are successfully prepared via supramolecular interfacial polymerization than those synthesized through homogeneous solution polymerization. The higher molecular weights are owing to the higher effective concentration of monomers at the interface than in solutions and diffusion-limited characteristic of supramolecular interfacial polymerization. In addition, the properties of supramolecular polymers are well modulated by changing the monomer structures and supramolecular interfacial copolymerization.(3) A new strategy of incorporating supramonomers into main-chains is developed to construct cross-linked supramolecular polymeric materials. In this strategy, low-content supramonomers based on quadruple hydrogen bonds were incorporated into main-chains as chain extenders, rather than in side-chains as transient cross-linking points, to endow the networks with dynamic property and recyclability with little sacrifice of the solvent resistance simultaneously. It is anticipated that the research will provide a facile and general method to construct various cross-linked polymer materials.
