Fast copper catalyzed living radical polymerization of acrylonitrile utilizing a high concentration of radical initiator

• Published in: Journal of polymer science. Part A, Polymer chemistry Polymer chemistry, 2012-05, Vol.50 (10), p.1933-1940
• Main Authors: Liu, Xiao-hui, Wang, Jin, Yang, Jian-shi, An, Shu-lin, Ren, Yuan-lin, Yu, Yun-hai, Chen, Peng
• Format: Article
• Language: English
• Subjects: acrylonitrile; Acrylonitriles; Applied sciences; Catalysts; Chain reactions; Chains (polymeric); Exact sciences and technology; initiator; Initiators; living polymerization; molecular weight distribution; Monomers; Organic polymers; Physicochemistry of polymers; Polymerization; Preparation, kinetics, thermodynamics, mechanism and catalysts; radical polymerization; Radicals
• ISSN: 0887-624X; 1099-0518
• DOI: 10.1002/pola.25967

This article first reports a fast and controlled living radical polymerization (LRP) of acrylonitrile, evidenced by 81.3% monomer conversion within 40 min and well‐defined the polymers with a narrow polydispersity index (PDI) range of 1.14−1.38. This was achieved by utilizing azobis(isobutyronitrile) as radical initiator with a high concentration up to 190 mM and CuBr2 as catalyst with a very low concentration down to 50 ppm. The polymerization displayed typical LRP characteristics, including pseudo first‐order kinetics of polymerization, the linear increase of number‐average molecular weights (MWs), low PDI values. The influence of various experimental components, radical initiator concentration, catalyst concentration, and reaction temperature, on the polymerization reaction and MW as well as PDI has been investigated in detail. 1H NMR and gel permeation chromatography analyses as well as chain extension reaction confirmed the very high chain‐end functionality of the resultant polymer. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 A fast and controlled LRP of acrylonitrile, evidenced by 81.3% monomer conversion within 40 min and well‐defined polymers with polydispersity indices in the range of 1.14−1.38, is reported. This was achieved by utilizing AIBN as radical initiator with a high concentration up to 190 mM and CuBr2 as catalyst with a low concentration down to 50 ppm. The polymerization displayed typical living radical polymerization characteristics, including pseudo first‐order polymerization kinetics, linear increase of molecular weight, and low PDI value. 1H NMR and GPC analyses as well as chain extension reaction confirmed high chain‐end functionality of polyacrylonitrile.