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‐MeSt) p‐Chlorostyrene (p‐ClSt) 2,4,6‐Trimethylstyrene (TMeSt) p‐Methoxystyrene (p‐MeOSt) α‐Methylstyrene (αMeSt) 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 ofAnBnHetero‐Arm Star‐Block Copolymers Synthesis ofAA′B,ABB′, andABCAsymmetric 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