Multicyclic Polystyrenes: Synthesis and Topology-Property Relationships

This book focuses on the systematic synthesis and characterization of multicyclic polystyrenes, a class of topologically complex polymers containing multiple cyclic units within a single macromolecule. Its purpose is to clarify how multicyclic topology governs polymer conformation, thermal properties, and bulk-state structures independently of chemical composition.

The book presents a versatile synthetic platform based on the cyclopolymerization of α,Ï-dinorbornenyl-functionalized polystyrene macromonomers using the Grubbs catalyst. This approach enables the preparation of well-defined multicyclic polystyrenes with independently controllable ring number and ring size, as well as polystyrene-containing multicyclic copolymers. Through comparisons with corresponding linear and graft analogues, the book examines how multicyclic topology affects glass-transition temperature, thermal stability, intrinsic viscosity, hydrodynamic dimensions, and bulk-state conformation. It also describes the synthesis of deuterated multicyclic polystyrenes and their application to small-angle neutron scattering studies, providing insight into topology-dependent structures in neat bulk materials and polymer blends.

Readers will gain practical synthetic strategies as well as fundamental design principles for controlling polymer properties through molecular topology. This topic is timely because polymer architecture offers an increasingly important route to advanced materials without changing chemical composition, supporting the rational design of functional and sustainable polymeric materials.