Research > Organocatalytic Polymerization

Polymers derived from renewable resources are intriguing targets to replace conventional olefin-based polymers.  In collaboration with Jim Hedrick of IBM Research Laboratories, we have pioneered the application of organocatalysis to polymer chemistry as a new and versatile strategy for Green Polymer Chemistry.  Several new families of organic catalysts have been discovered which rival or exceed metal-based alternatives  for polyester synthesis, both in terms of activity and selectivity.  Organocatalytic approaches to ring-opening, anionic, zwitterionic, group transfer, and condensation polymerization techniques.  Fundamental mechanistic and theoretical investigations have provided new scientific insights on the diversity of mechanistic pathways for organocatalytic polymerization reactions and the opportunities that these new insights have created for the synthesis of well-defined macromolecular architectures. Significant achievements of this team include organocatalytic strategies for the synthesis of polyesters, polycarbonates, polysiloxanes, and polyacrylates; chemical recycling of polyesters, the use of metal-free polymers to template inorganic nanostructures for microelectronics applications, the development of new synthetic strategies for the synthesis of high molecular weight cyclic polyesters, and the generation of new families of biocompatible polymers for medical applications.

Selected Publications

186.  Kiesewetter, M. K.; Shin, E. J.; Hedrick, J. L.; Waymouth. R. M. "Organocatalysis: Opportunities and Challenges for Polymer Synthesis" Macromolecules, 2010, 43, 2093-2107.  

187.  Kamber, N. E.; Tsujii, Y.; Keets, K.; Pratt, R. C.; Nyce, G. W.; Waymouth, R. M.; Hedrick, J. L. "Chemical Recycling of Poly(ethylene terephthalate) (PET) Bottles using N-heterocyclic Carbenes from Ionic Liquids"  J. Chem. Educ., 2010, 87, 519-521.

181.  Trantow, B. M.; Cooley, C. B.; Nederberg, F.; Kiesewetter, M. K.; Hedrick, J. L.; Waymouth, R. M.; Wender, P. A. "Oligocarbonate Molecular Transporters: Oligomerization Based Syntheses and Cell Penetrating Studies"  J. Am. Chem. Soc., 2009, 131, 16401-16403.

177.  Jeong, W.; Shin, E. J.; Culkin, D. A.; Hedrick, J. L.; Waymouth, R. M. "Zwitterionic Polymerization:  A Kinetic Strategy for the Controlled Synthesis of Cyclic Polylactide" J. Am. Chem. Soc., 2009, 131(13), 4884-4891.

167.  Chuma, A.; Horn, H. W.; Swope, W. C.; Pratt, R. C.; Zhang, L.; Lohmeijer, B. G. G.; Wade, C. G.; Waymouth, R. M.; Hedrick, J. L.; Rice, J. E. "The Reaction Mechanism for the Organocatalytic Ring-Opening Polymerization of L-Lactide Using a Guanidine-Based Catalyst: Hydrogen-Bonded or Covalently Bound?" J. Am. Chem. Soc., 2008, 6794-6754.

133.  Dove, A. P.; Pratt, R. C.; Lohmeijer, B. G. G.; Waymouth, R. M.; Hedrick, J. L. “Thiourea-based Bifunctional Organocatalysts: Supramolecular Recognition for Living Polymerization” J. Am. Chem. Soc., 2005, 127, 13798-13799.