142 Advances in Polymer Science Editorial Board: A. Abe. A.-C ...

Synthesis of Branched Polymers by Cationic Polymerization
Bernadette Charleux 1 , Rudolf Faust 2
1 Laboratoire de chimie macromoléculaire, Université Pierre et Marie Curie, T44, E1,
4, Place Jussieu F-75252 Paris cedex 05, France E-mail: charleux@ccr.jussieu.fr
2 University of Massachusetts, Lowell Chemistry Department, 1 University Ave. Lowell, MA
01854, USA E-mail: Rudolf_Faust@uml.edu
The synthesis of branched polymers by cationic polymerization of vinyl monomers is reviewed.
This includes star, graft, and hyperbranched (co)polymers. The description is essentially
focused on the synthetic approach and characterization results are provided as a
proof of the structure. When available, specific properties of the materials are also given.
Keywords. Cationic polymerization, Living cationic polymerization, Branched polymers,
Star polymers, Graft polymers, Hyperbranched polymers, Microgel core, (Multi)functional
initiator, (Multi)functional coupling agent, Grafting from, Grafting onto, Macromonomer
List of Symbols and Abbreviations . . . . . . . . . . . . . . . . . . . . . . . 3
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2 Multi-Arm Star (co)Polymers . . . . . . . . . . . . . . . . . . . . . 4
2.1 Synthesis Using a Difunctional Monomer as a Linker
(Cross-Linked Core) . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.1.1 A n -Type Star Homopolymers . . . . . . . . . . . . . . . . . . . . . . 6
2.1.1.1 Poly(vinyl ethers) n . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.1.1.2 Poly(alkoxystyrenes) n . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.1.1.3 Poly(isobutylene) n . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2.1.2 (AB) n-Type Star Block Copolymers . . . . . . . . . . . . . . . . . 13
2.1.2.1 Poly(vinyl ether-b-vinyl ether) n . . . . . . . . . . . . . . . . . . . . 13
2.1.2.2 Poly(isobutylene-b-styrene) n . . . . . . . . . . . . . . . . . . . . . 14
2.1.3 A n-Type Star Polymers with a Functionalized Core:
Poly(vinyl ether) n . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
2.1.4 A nB n-Type Star Copolymers:
Poly(vinyl ether) n-Star-Poly(vinyl ether) n . . . . . . . . . . . . . . 15
2.2 Synthesis Using a Multifunctional Initiator . . . . . . . . . . . . . 17
2.2.1 A n-Type Star Homopolymers . . . . . . . . . . . . . . . . . . . . . 17
2.2.1.1 Poly(vinyl ethers) n . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
2.2.1.2 Poly(p-methoxystyrene) n . . . . . . . . . . . . . . . . . . . . . . . 19
2.2.1.3 Poly(styrene) n . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
2.2.1.4 Poly(isobutylene) n . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
2.2.2 (AB) n -Type Star Block Copolymers . . . . . . . . . . . . . . . . . 25
2.2.2.1 Poly(vinyl ether-b-vinyl ether) n . . . . . . . . . . . . . . . . . . . . 25
2.2.2.2 Poly(isobutylene-b-styrene) n . . . . . . . . . . . . . . . . . . . . . 28
Advances in Polymer Science, Vol.142
© Springer-Verlag Berlin Heidelberg 1999