Organocatalytic ring opening polymerization of trimethylene carbonate.
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.
Nederberg
Fredrik
F
IBM Almaden Research Center, 650 Harry Road, San Jose, California 95120, USA.
Lohmeijer
Bas G G
BG
Leibfarth
Frank
F
Pratt
Russell C
RC
Choi
Jeongsoo
J
Dove
Andrew P
AP
Waymouth
Robert M
RM
Hedrick
James L
JL
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
D004146:Dioxanes; D046911:Macromolecular Substances; D011108:Polymers; C443643:trimethylene carbonate