Effect of Counter Anions on Kinetics and Stereoregularity for the Strong Brønsted Acid-Promoted Group Transfer Polymerization of N,N-Dimethylacrylamide

• Published in: Macromolecular chemistry and physics Vol. 213; no. 15; pp. 1604 - 1611
• Main Authors: Fuchise, Keita, Chen, Yougen, Takada, Kenji, Satoh, Toshifumi, Kakuchi, Toyoji
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 14.08.2012; WILEY‐VCH Verlag; Wiley
• Subjects: Applied sciences; Exact sciences and technology; group transfer polymerization; kinetics; monomer activated mechanism; Organic polymers; Physicochemistry of polymers; Polymerization; Preparation, kinetics, thermodynamics, mechanism and catalysts; propagation rate constants (kp); strong Brønsted acid; propagation rate constants (k; Organic siloxane; ); Experimental study; strong Brønsted acid; Acrylamide derivative polymer; Chemical reaction kinetics; Solution polymerization; Group transfer polymerization; Brönsted acid; monomer activated mechanism; Counter ion; Stereospecificity; Fluorine Organic compounds; Rate constant; kinetics; Activation energy; Reaction propagation; Comparative study
• ISSN: 1022-1352; 1521-3935
• DOI: 10.1002/macp.201200146

The strong Brønsted acid‐promoted group transfer polymerization (GTP) of N,N‐dimethylacrylamide (DMAA) using trifluoromethanesulfonimide (Tf2NH) and 2,3,4,5,6‐pentafluorophenyl‐1,1‐bis(trifluoromethanesulfonyl)methane (Tf2CHC6F5) was carried out to quantitatively evaluate the effect of the counter anions for the employed acid on the kinetics and the stereoregularity of the polymerization. The equilibrium constant for the monomer activation (K) and the rate constant for the propagation reaction (kp) were determined from the integrated rate equation derived from the presumed polymerization mechanism. Both of the constants for the polymerization using Tf2CHC6F5 were higher than those for Tf2NH. The activation parameters for the syndiotactic propagation were determined from the Fordham plot. The strong Brønsted acid‐promoted group transfer polymerization of N,N‐dimethylacrylamide is carried out to quantitatively evaluate the effect of the counter anions for the employed acids on the kinetics and the stereoregularity of the polymerization. The equilibrium constant for the monomer activation and the rate constant for the propagation reaction are determined. The activation parameters for the stereospecific propagation are determined from the Fordham plot.