Atom Transfer Radical Polymerization of Methacrylic Acid: A Won Challenge

J Am Chem Soc. 2016 Jun 15;138(23):7216-9. doi: 10.1021/jacs.6b01935. Epub 2016 May 31.

Abstract

Polymerization of acidic monomers is one of the biggest challenges for atom transfer radical polymerization (ATRP). An intramolecular cyclization reaction leading to the loss of the C-X chain-end functionality was found to be the main reason for the partial termination of the growing polymer chains. Three approaches were used to overcome this problem: using Cl as the chain-end halogen, lowering the pH (to 0.9), and increasing polymerization rate. Methacrylic acid (MAA) was polymerized by both electrochemically mediated ATRP and supplemental activator and reducing agent ATRP up to high conversion (>90%), in t ≤ 4 h at 25 °C, using inexpensive and nontoxic reagents (NaCl, diluted HCl, water). Control over molecular weight (MW) dispersity was satisfactory, and MWs were in agreement with theoretical values. The "livingness" of the process was confirmed by an electrochemical switch, used to repeatedly and periodically deactivate/reactivate growing chains.

Publication types

  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.