"Clickable" polymers via a combination of RAFT polymerization and isocyanate chemistry

John Moraes, Thomas Maschmeyer, Sébastien Perrier

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27 Citations (Scopus)


We describe a facile, one-pot, two-step polymerization towards synthesizing block co-polymers bearing reactive isocyanate functional groups. Reversible addition fragmentation chain transfer (RAFT) polymerization is used to mediate the co-polymerization of isocyanate-bearing monomers dimethyl meta-isopropenyl benzyl isocyanate (TMI) and 2-isocyanatoethyl methacrylate (ICEMA) with styrene and methyl methacrylate (MMA), respectively. ICEMA was incorporated into the polymer at a faster rate than TMI and its unhindered isocyanate group was found to be more reactive than the hindered isocyanate group of TMI. Both the TMI/styrene and the MMA/ICEMA systems maintain the reactivity of the isocyanate functionality, which was exploited by attaching representative hydroxyl-bearing small and large molecules as well as solid substrates to the block co-polymers. Thus, we demonstrate the versatility of the block co-polymer system as a basis for forming branched polymers or as grafts for a solid substrate. 

Original languageEnglish
Pages (from-to)2771-2782
Number of pages12
JournalJournal of Polymer Science, Part A: Polymer Chemistry
Issue number13
Publication statusPublished - 1 Jul 2011
Externally publishedYes


  • click chemistry
  • diblock copolymers
  • functionalization of polymers
  • isocyanates
  • reversible addition fragmentation chain transfer

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