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Published August 26, 2008 | Supplemental Material
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Sacrificial Synthesis of Hydroxy-Functionalized ROMP Polymers: An Efficiency Study


We present here a ^1H NMR spectroscopy study of the kinetics of the ROMP macroinitiation of poly(exo-N-phenyl-2,3-norbornene dicarboximide) with various dioxepine derivatives and Grubbs first generation ruthenium initiators. We have recently demonstrated that this so-called "sacrificial block copolymer" approach yields hydroxy-functionalized ROMP polymers with high end-group functionality. This study shows that the substituents on the dioxepine are important for functionalization efficiency, in the order phenyl > isopropyl > methyl. Addition of triphenylphosphine to the ruthenium carbene initiator resulted in lower k_i/k_p (rate of initiation/rate of propagation) values for the macroinitiation than in the absence of triphenylphosphine. We demonstrate that the value of k_i/k_p for macroinitiations can be estimated for new sacrificial monomers by analyzing one or two functionalization reactions. This provides an easy tool for the rapid screening and evaluation of new sacrificial monomers.

Additional Information

© 2008 American Chemical Society. Received May 16, 2008; Revised Manuscript Received June 25, 2008. The authors thank Margarete Deptolla and Ines Wollmer for enduring laboratory assistance as well as Materia, Inc., for generous catalyst support. S.H. thanks the POLYMAT Graduate School of Excellence (University of Mainz) for funding. A.F.M.K. thanks the Deutsche Forschungsgemeinschaft (DFG) for financial support.

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