Controlled radical polymerization of 4-vinylimidazole

Michael H. Allen, Sean T. Hemp, Adam E. Smith, Timothy E. Long

Research output: Contribution to journalArticlepeer-review

61 Scopus citations


We report the unprecedented controlled radical polymerization of 4-vinylimidazole (4VIM). Reversible addition-fragmentation chain transfer (RAFT) of 4VIM in glacial acetic acid afforded homopolymers with well-defined molecular weights and narrow polydispersity indices (PDIs). The polymerizations in acetic acid mediated with 4-cyano-4-(ethylsulfanylthiocarbonylsulfanyl) pentanoic acid (CEP) displayed linear pseudo-first-order kinetics and linear molecular weight growth with monomer conversion. Systematic variation of numerous polymerization parameters included solvent composition, initiator concentration, monomer concentration, and the calculated degree of polymerization. Aqueous size exclusion chromatography (SEC) confirmed linear molecular weight growth to number-average molecular weights (M n) of 65000 g/mol with low PDIs (<1.20). Subsequent monomer addition confirmed the presence of the trithiocarbonate functionality at the chain ends, which provided further evidence of controlled polymerization conditions. Polymerizations in traditional aqueous RAFT solvents (acidic buffers) failed to achieve controlled molecular weight growth. Effectively controlling 4VIM homopolymerizations enables the design of amphoteric block copolymers for emerging applications including nucleic acid delivery and electroactive membranes.

Original languageEnglish (US)
Pages (from-to)3669-3676
Number of pages8
Issue number9
StatePublished - May 8 2012
Externally publishedYes

ASJC Scopus subject areas

  • Organic Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry
  • Materials Chemistry


Dive into the research topics of 'Controlled radical polymerization of 4-vinylimidazole'. Together they form a unique fingerprint.

Cite this