Anionic polymerization is the classical “living” polymerization: the first discovered (in 1956), and still the most widely practiced. Today, the most common initiators are isomers of butyllithium; in our laboratory, we routinely use anionic polymerization to prepare homopolymers and block copolymers from dienes (butadiene, isoprene), styrenes (styrene, methylstyrene), and alkylmethacrylates (alkyl = methyl, butyl, hexyl, 2-ethylhexyl…). Complex macromolecular architectures such as starblocks can be created by reacting the living ends with a suitable multifunctional coupling agent, such as the chlorosilane shown below, which yields six-arm starblock copolymers.
Supported by the National Science Foundation, Polymers Program, and Materials Research Science and Engineering Center (MRSEC) Program, through the Princeton Center for Complex Materials
Current/Recent Group Members Employing Anionic Polymerization, and Their Project Titles:
Dane Christie PhD *19 – “Influence of Confinement and Interfaces on the Structure and Dynamics of Amorphous Polymers”
Will Mulhearn PhD *18 – “Melt-Miscibility in Block Copolymers Containing Polyethylene”
Adam Burns PhD *17 – “Thermoplastic Elastomers with Composite Crystalline-Glassy Hard Domains via Crystallization from a Single-Phase Melt”
Raleigh Davis PhD *15 – “Shear Alignment of Block Copolymer Thin Films to Produce Well-Ordered Microdomains for Use in Nanofabrication”
Bryan Beckingham PhD *13 – “Mixing Thermodynamics of Block-Random Copolymers”
Ha-Kyung Kwon ‘13 – “Synthesis and Characterization of Polystyrene-block-Poly(2-ethylhexylmethacrylate) Diblock Copolymers”
Brian Michal ‘10 – “Synthesis and Characterization of Polystyrene-Poly(n-hexylmethacrylate) Diblock Copolymers”
Selected Recent Publications:
R.L. Davis, P.M. Chaikin, and R.A. Register, "Cylinder Orientation and Shear-Alignment in Thin Films of Polystyrene-Poly(n-hexylmethacrylate) Diblock Copolymers", Macromolecules, 47, 5277-5285 (2014).
H.-K. Kwon, V.E. Lopez, R.L. Davis, S.Y. Kim, A.B. Burns, and R.A. Register, "Polystyrene-Poly(2-ethylhexylmethacrylate) Block Copolymers: Synthesis, Bulk Phase Behavior, and Thin Film Structure", Polymer, 55, 2059-2067 (2014).
B.S. Beckingham and R.A. Register, "Architecture-Induced Microphase Separation in Nonfrustrated A-B-C Triblock Copolymers", Macromolecules, 46, 3486-3496 (2013).
B.S. Beckingham and R.A. Register, "Synthesis and Phase Behavior of Block-Random Copolymers of Styrene and Hydrogenated Isoprene", Macromolecules, 44, 4313-4319 (2011).