Synthesis and Morphology of High-Molecular-Weight Polyisobutylene-Polystyrene Block Copolymers Containing Dynamic Covalent Bonds.

Incorporating dynamic covalent bonds into block copolymers provides useful molecular level information during mechanical testing, but it is currently unknown how the incorporation of these units affects the resultant polymer morphology. High-molecular-weight polyisobutylene-b-polystyrene block copolymers containing an anthracene/maleimide dynamic covalent bond are synthesized through a combination of postpolymerization modification, reversible addition-fragmentation chain-transfer polymerization, and Diels-Alder coupling. The bulk morphologies with and without dynamic covalent bond are characterized by atomic force microscopy  and small-angle X-ray scattering, which reveal a strong dependence on annealing time and casting solvent.

Direct Chain End Functionalization of Living Polyisobutylene Using Phenoxyalkyl (Meth)acrylates.

Phenoxyalkyl acrylates and methacrylates were studied as quenching (capping) agents for living carbocationic polymerization of isobutylene (IB) at -70 °C in 40/60 (v/v) hexane/methyl chloride, catalyzed by TiCl. Quenching reactions were carried out by reactivation by TiCl of preformed difunctional -chloride-terminated polyisobutylene (PIB) or by a one-step method in which IB polymerization and quenching were conducted sequentially in the same reactor. Chain-end concentrations ranged from 0.