Fabrication,polymerization And Function Of Supramonomers

Supramolecular polymers are polymeric arrays whose monomers are held by high directional and reversible noncovalent interactions.Various supramolecular polymers with different structures and functions were designed and constructed since 1990.In the meantime,it remains to be a great challenge for controllable supramolecular polymerization.To this end,we have proposed the supramonomer strategy.Supramonomers are bifunctional monomers fabricated on the basis of noncovalent interactions,but can undergo traditional covalent polymerization,showing great potential for realizing controllable supramolecular polymerization.Supramolecular polymeric materials with specific topological structures are of dynamic properties,such as reversibility,stimuli-responsiveness,adaptive ability,and self-healing property.It is of significant importance to develop facile methods for the construction of supramolecular polymeric materials with desirable structures and functions.Illustrated by supramolecular microgel and supramolecular hydrogel,we explored and demonstrated the feasibility and advantages of the supramonomer strategy towards supramolecular polymeric materials.This thesis is focused on the fabrication,polymerization and function of supramonomers.By designing supramonomers with different functions,we constructed supramolecular polymers at molecular level,and expanded to microscopic level and macroscopic level to fabricate supramolecular polymeric materials.The work includes three parts as follows:(1)Supramolecular polymers through covalent polymerization and noncovalent polymerization from supramonomers are constructed,respectively.On the basis of host-guest interactions,bifunctional supramonomers with two thiol groups are designed to undergo thiol-ene click polymerization to form supramolecular polymers.Moreover,based on two orthogonal host-guest interactions,we have realized the fabrication of multi-responsive supramolecular polymers through noncovalent polymerization from supramonomers.(2)Supramolecular microgels based on the polymerization of supramonomers are constructed for the first time.Cross-linkable supramonomers are designed as supramolecular cross-linkers to undergo radical precipitation polymerization to form supramolecular microgels.As demonstrated,the supramolecular microgels not only show temperature-responsive properties similar to conventional PNIPAm-based microgels but also exhibit stimuli-responsive and degradable properties benefiting from the dynamic nature of supramonomers.(3)Supramolecular hydrogels based on the polymerization of supramonomers are constructed.Polymerizable supramonomers are designed as supramolecular cross-linkers to undergo radical polymerization to form supramolecular hydrogels.As demonstrated,the biocompatible supramolecular hydrogels with desirable mechanical properties are able to dissolve quickly under certain chemical stimuli,representing a promising candidate as easy-removable wound dressing materials.