Synthesis of Mono-Functional Olefin Metathesis Polymers

• Applicant: Professor Dr. Andreas Kilbinger
• Subject Area: Preparatory and Physical Chemistry of Polymers
• Term: from 2007 to 2011
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 47263954

• Final Report Year: 2013

Final Report Abstract

A decade ago ROMP, particularly using ruthenium carbene initiators, used to be a polymerisation method for which very few end-functionalization methods were available. This is no longer the case thanks to the initial DFG funding of this project which was later on continued to be funded by the SNF. Synthetic procedures are in place today that allow the polymer end-functionalisation for all commonly used carbene complexes based on ruthenium, tungsten and molybdenum. From a practical and application focused point of view both ends of a polymer chain are equally useful. From a mechanistic point of view the functionalisation of the polymer chain end using the reactivity of the propagating carbene complex is much more readily achieved than functionalisation of the focal group. Nonetheless, functional initiation is an attractive way to ensure complete end (start) functionalisation which has received comparatively little attention so far. Reliable methods for the functional derivatisation of commercial carbene catalysts will allow not only the synthesis of mono-telechelic polymers with high degrees of end-functionalisation but also polymerisation from surfaces or solid supports and open up more synthetic pathways to hetero-telechelic polymers.

Publications

• "A "Click" Approach to ROMP Block Copolymers"
. J. Polym. Sci. A 2008, 46, 2913

  Hilf, S.; Hanik, N.; Kilbinger, A.F.M.

  
• "End-capping ROMP Polymers with Vinyl Lactones"
. J. Am. Chem. Soc. 2008, 130, 11040

  Hilf, S.; Grubbs, R.H.; Kilbinger A.F.M.

  
• “Sacrificial Synthesis of Hydroxy-functionalized ROMP polymers – An efficiency study"
. Macromolecules 2008, 41, 6006
  Hilf, S.; Grubbs, R.H., Kilbinger, A.F.M.

  
• "Functional Endgroups for ROMP Polymers”
. Nature Chemistry 2009, 1, 537

  Hilf, S.; Kilbinger, A.F.M.

  
• "Long-chain Branched ROMP Polymers"
. J. Polym. Sci. A 2009, 47, 6932

  Hilf, S.; Wurm, F.; Kilbinger, A.F.M.

  
• "Sacrificial Synthesis of Hydroxy-Telechelic Metathesis Polymers via Multiblock-copolymers"
. Macromolecules 2009, 42, 1099
  Hilf, S.; Kilbinger, A.F.M.

  
• "Thiol-functionalized ROMP polymers via Sacrificial Synthesis"
. Macromolecules 2009, 42, 4127

  Hilf, S.; Kilbinger, A.F.M.

  
• "The Synthesis of End-Functional Ring-Opening Metathesis Polymers"
. Functional Polymers by Post-Polymerization Modification
. Wiley-VCH, Weinheim 2012, p. 157-177

  Kilbinger, A.F.M.

  
• "Narrowly distributed homotelechelic polymers in 30 minutes: Using fast in-situ pre-functionalized ROMP initiators"
. J. Polym. Sci. A. 2013, 51, 4183
  Hanik, N.; Kilbinger, A.F.M.