title: Organocatalytic ring opening polymerization of trimethylene carbonate.
abstract: A variety of organocatalysts has been surveyed in the ring opening polymerization of trimethylene carbonate. Excellent control was found for several of these catalysts yielding well-defined polycarbonates with molecular weights up to 50,000 g mol(-1), polydispersities below 1.08, and high end-group fidelity. Melt or bulk polymerization was accomplished without loss of control of molecular weight or polydispersity, and random ester-carbonate bulk polymerizations were also demonstrated. Furthermore, by combining disparate polymerization techniques using bifunctional initiators, the mild polymerization conditions allow for the preparation of new block copolymers. Hydrogen-bond activation of monomer and initiator/propagating species is proposed as the underlying mechanism, which can be tuned to mitigate adverse side reactions.
authors.affiliation: IBM Almaden Research Center, 650 Harry Road, San Jose, California 95120, USA.
authors.forename: Fredrik
authors.initials: F
authors.lastname: Nederberg
authors.forename: Bas G G
authors.initials: BG
authors.lastname: Lohmeijer
authors.forename: Frank
authors.initials: F
authors.lastname: Leibfarth
authors.forename: Russell C
authors.initials: RC
authors.lastname: Pratt
authors.forename: Jeongsoo
authors.initials: J
authors.lastname: Choi
authors.forename: Andrew P
authors.initials: AP
authors.lastname: Dove
authors.forename: Robert M
authors.initials: RM
authors.lastname: Waymouth
authors.forename: James L
authors.initials: JL
authors.lastname: Hedrick
mesh_terms: D001671:Biochemistry / Q000379:methods*; D002384:Catalysis; D002623:Chemistry Techniques, Analytical / Q000379:methods; D004146:Dioxanes / Q000737:chemistry*; D006860:Hydrogen Bonding; D046911:Macromolecular Substances; D009682:Magnetic Resonance Spectroscopy; D008956:Models, Chemical; D008968:Molecular Conformation; D011108:Polymers / Q000737:chemistry; D013696:Temperature; D013997:Time Factors
chemical_list: D004146:Dioxanes; D046911:Macromolecular Substances; D011108:Polymers; C443643:trimethylene carbonate