Closed-System One-Pot Block Copolymerization by Temperature-Modulated Monomer Segregation.
A biphasic one-pot polymerization method enables the preparation of block copolymers from monomers with similar and competitive reactivities without the addition of external materials. AB diblock copolymers were prepared by encapsulating a frozen solution of monomer B on the bottom of a reaction vessel, while the solution polymerization of monomer A was conducted in a liquid layer above. Physical separation between the solid and liquid phases permitted only homopolymerization of monomer A until heating above the melting point of the lower phase, which released monomer B, allowing the addition of the second block to occur. The triggered release of monomer B allowed for chain extension without additional deoxygenation steps or exogenous monomer addition. A method for the closed (i.e., without addition of external reagents) one-pot synthesis of block copolymers with conventional glassware using straightforward experimental techniques has thus been developed.
George & Joesphine Bulter Polymer Research Laboratory, Center for Macromolecular Science & Engineering, Department of Chemistry, University of Florida, 11700, Gainesville, FL, 32611-7200, USA.
R Nicholas
RN
Carmean
George & Joesphine Bulter Polymer Research Laboratory, Center for Macromolecular Science & Engineering, Department of Chemistry, University of Florida, 11700, Gainesville, FL, 32611-7200, USA.
C Adrian
CA
Figg
George & Joesphine Bulter Polymer Research Laboratory, Center for Macromolecular Science & Engineering, Department of Chemistry, University of Florida, 11700, Gainesville, FL, 32611-7200, USA.
Troy E
TE
Becker
George & Joesphine Bulter Polymer Research Laboratory, Center for Macromolecular Science & Engineering, Department of Chemistry, University of Florida, 11700, Gainesville, FL, 32611-7200, USA. Sumerlin@chem.ufl.edu.
Brent S
BS
Sumerlin
RAFT polymerization; block copolymers; photopolymerization; radical polymerization