Article

Stannous(II) trifluoromethane sulfonate: a versatile catalyst for the controlled ring-opening polymerization of lactides: Formation of stereoregular surfaces from polylactide “brushes”

  1. Michael Möller1,
  2. Fredric Nederberg1,
  3. Lisa S. Lim1,
  4. Rikard Kånge1,
  5. Craig J. Hawker1,
  6. James L. Hedrick1,*,
  7. Yuedong Gu2,
  8. Rahul Shah2,
  9. Nicholas L. Abbott2

Article first published online: 31 AUG 2001

DOI: 10.1002/pola.10003

Issue

Journal of Polymer Science Part A: Polymer Chemistry

Journal of Polymer Science Part A: Polymer Chemistry

Volume 39, Issue 20, pages 3529–3538, 15 October 2001

Additional Information

How to Cite

Möller, M., Nederberg, F., Lim, L. S., Kånge, R., Hawker, C. J., Hedrick, J. L., Gu, Y., Shah, R. and Abbott, N. L. (2001), Stannous(II) trifluoromethane sulfonate: a versatile catalyst for the controlled ring-opening polymerization of lactides: Formation of stereoregular surfaces from polylactide “brushes”. Journal of Polymer Science Part A: Polymer Chemistry, 39: 3529–3538. doi: 10.1002/pola.10003

Author Information

  1. 1

    Center for Polymeric Interfaces and Macromolecular Assemblies, IBM Almaden Research Center, 650 Harry Road, San Jose, California 95120

  2. 2

    Department of Chemical Engineering, University of Wisconsin, 1415 Engineering Drive, Madison, Wisconsin 53706

*Center for Polymeric Interfaces and Macromolecular Assemblies, IBM Almaden Research Center, 650 Harry Road, San Jose, California 95120

Publication History

  1. Issue published online: 31 AUG 2001
  2. Article first published online: 31 AUG 2001
  3. Manuscript Accepted: 26 JUL 2001
  4. Manuscript Received: 16 JUL 2001

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Keywords:

  • ring-opening polymerization;
  • polylactide;
  • organometallic catalysts;
  • surfaces;
  • nanolayers

Graphical Abstract

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A general method for the controlled synthesis of polylactide in solution and from solid supports is presented. The evaluation of stannous(II) trifluoromethane sulfonate [Sn(OTf)2] and scandium(III) trifluoromethane sulfonate [Sc(OTf)3] as catalysts for the ring-opening polymerization of L-, D-, and L,D-lactide permits mild, low-temperature, yet highly selective conditions to be developed for the preparation of polylactide brushes attached to gold surfaces.

Abstract

A general method for the controlled synthesis of polylactide in solution and from solid supports is presented. The evaluation of stannous(II) trifluoromethane sulfonate [Sn(OTf)2] and scandium(III) trifluoromethane sulfonate [Sc(OTf)3] as catalysts for the ring-opening polymerization (ROP) of L-, D-, and L,D-lactide is described as a route to polylactide using mild and highly selective conditions. These triflate catalysts must be used in conjunction with a nucleophilic compound such as an alcohol that is the actual initiating species via the active metal alkoxide species. Consistent with this process, 1H NMR analysis revealed that the α-chain-end bears the ester from the initiating alcohol, and upon hydrolysis of the active metal alkoxide chain end, a ω-hydroxyl chain end was clearly detected. Polymers of predictable molecular weights and narrow polydispersities were obtained in high yields in accordance with a controlled polymerization process. The addition of base either as a solvent or additive significantly enhanced the polymerization rate with minimal loss to the polymerization control. The ROP of lactide isomers from an initiator, HO(CH2CH2O)3(CH2)11SH, self-assembled onto a gold surface using Sn(OTf)2 produced polylactide brushes under living conditions and provides the opportunity to prepare stereoregular or chiral surfaces by polymerization of enantiomerically pure monomers. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3529–3538, 2001

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