Carbocationic Polymerization*This chapter has already been published in: Matyjaszewski, K., Müller, A. H. E., Controlled and Living Polymerizations, 2009. Copyright Wiley‐VCH Verlag GmbH & Co. KGaA. Reproduced with kind permission of the authors.

Abstract

The sections in this article are Introduction Mechanistic and Kinetic Details of Living Cationic Polymerization Living Cationic Polymerization Monomers and Initiating Systems Additives in Living Cationic Polymerization Living Cationic Polymerization: Isobutylene ( IB ) β‐Pinene Styrene ( St ) p ‐Methylstyrene ( p ‐ Me St ) p ‐Chlorostyrene ( p ‐ Cl St ) 2,4,6‐Trimethylstyrene ( TMe St ) p ‐Methoxystyrene ( p ‐ Me OSt ) α‐Methylstyrene (α Me St ) Indene N ‐Vinylcarbazol Vinyl Ethers Functional Polymers by Living Cationic Polymerization Functional Initiator Method Functional Terminator Method Telechelic Polymers Macromonomers Synthesis using a Functional Initiator Synthesis using a Functional Capping Agent Chain‐End Modification Block Copolymers Linear Diblock Copolymers Linear Triblock Copolymers Synthesis using Difunctional Initiators Synthesis Using Coupling Agents Block Copolymers with Nonlinear Architecture Synthesis of A n B n Hetero‐Arm Star‐Block Copolymers Synthesis of AA ′ B , ABB ′, and ABC Asymmetric Star‐Block Copolymers using Furan Derivatives Block Copolymers Prepared by the Combination of Different Polymerization Mechanisms Combination of Cationic and Anionic Polymerization Combination of Living Cationic and Anionic Ring‐Opening Polymerization Combination of Living Cationic and Radical Polymerization Branched and Hyperbranched Polymers Surface Initiated Polymerization — Polymer Brushes Conclusions

Sugar-Derived Cyclic Acetals as Comonomers for Cationic Copolymerization with Vinyl Ethers

“…The dormant–active equilibrium that consists of the reversible activation–deactivation of the carbon–chlorine bonds − is most likely constructed (Scheme A), which is responsible for the controlled/living copolymerization. The carbon–chlorine bond formed from the cyclic acetal-derived carbocation (oxocarbenium ion) is reversibly cleavable under the conditions suited for VE polymerization due to the similarity between the carbocations generated from VEs and cyclic acetals.…”

Metal-Free, Photoinitiated Cationic Terpolymerization of Vinyl Ethers, Oxiranes, and Ketones: Simultaneous Control of Monomer Sequence and Molecular Weight by the Formation of Long-Lived Propagating Species

“…Living polymerization, which proceeds with negligible side reactions, is an effective method for synthesizing polymers with controlled MWs and/or well-defined structures such as block, graft, star, and telechelic polymers. Various methods to achieve living polymerization of various monomers, , including cationic polymerization, − have been developed. Control of the initiation reactions is also important for obtaining polymers with well-defined structures.…”

Polyisobutylene-based glycopolymers as potent inhibitors for in vitro insulin aggregation

“…PIB is a saturated, biostable and biocompatible polymer of isobutylene (IB), 25,26 which finds wide applications in various biomedical fields. 27…”