Effect of Counter Anions on Kinetics and Stereoregularity for the Strong Brønsted Acid-Promoted Group Transfer Polymerization of N,N-Dimethylacrylamide
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 a...
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Published in | Macromolecular chemistry and physics Vol. 213; no. 15; pp. 1604 - 1611 |
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Main Authors | , , , , |
Format | Journal Article |
Language | English |
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Weinheim
WILEY-VCH Verlag
14.08.2012
WILEY‐VCH Verlag Wiley |
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Abstract | 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. |
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AbstractList | Abstract
The strong Brønsted acid‐promoted group transfer polymerization (GTP) of
N
,
N
‐dimethylacrylamide (DMAA) using trifluoromethanesulfonimide (Tf
2
NH) and 2,3,4,5,6‐pentafluorophenyl‐1,1‐bis(trifluoromethanesulfonyl)methane (Tf
2
CHC
6
F
5
) 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 (
k
p
) were determined from the integrated rate equation derived from the presumed polymerization mechanism. Both of the constants for the polymerization using Tf
2
CHC
6
F
5
were higher than those for Tf
2
NH. The activation parameters for the syndiotactic propagation were determined from the Fordham plot. 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. |
Author | Satoh, Toshifumi Takada, Kenji Fuchise, Keita Kakuchi, Toyoji Chen, Yougen |
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Keywords | 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 |
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Snippet | The strong Brønsted acid‐promoted group transfer polymerization (GTP) of N,N‐dimethylacrylamide (DMAA) using trifluoromethanesulfonimide (Tf2NH) and... Abstract The strong Brønsted acid‐promoted group transfer polymerization (GTP) of N , N ‐dimethylacrylamide (DMAA) using trifluoromethanesulfonimide (Tf 2 NH)... |
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SubjectTerms | 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 |
Title | Effect of Counter Anions on Kinetics and Stereoregularity for the Strong Brønsted Acid-Promoted Group Transfer Polymerization of N,N-Dimethylacrylamide |
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