Facile Access to Chain Length Dependent Termination Rate Coefficients via Reversible Addition-Fragmentation Chain Transfer (RAFT) Polymerization: Influence of the RAFT Agent Structure

Feldermann, A., Stenzel, M. H., Davis, T. P., Vana, P., & Barner-Kowollik, C. (2004) Facile Access to Chain Length Dependent Termination Rate Coefficients via Reversible Addition-Fragmentation Chain Transfer (RAFT) Polymerization: Influence of the RAFT Agent Structure. Macromolecules, 37(7).

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Abstract

A recently developed methodology for determining chain length dependent termination rate coefficients, 〈kt i,i〉, via reversible addition-fragmentation chain transfer (RAFT) polymerizations has been extended and validated for 1-phenylethyl phenyldithioacetate (PEPDA) and 3-benzylsulfanylthiocarbo-nylsulfanylpropionic acid (BSPA) mediated styrene (bulk) free radical polymerizations at 80°C. While the use of cumyl phenyldithioacetate (CPDA) enables a highly precise mapping of the chain length dependence of the termination rate coefficient, employment of PEPDA and BSPA leads to considerable information loss for short chain lengths (i < 10). Careful simulations demonstrate that such behavior is caused by a substantial decrease in the initial transfer effectiveness of the RAFT agents when going from CPDA to BSPA, leading to hybrid behavior between conventional and living free radical polymerization. The observed hybrid behavior is quantifiable via (overall) transfer rate coefficients for the individual RAFT agents in the preequilibrium step [CPDA (ktr,R = 5.0 × 105 L mol-1 s-1), PEPDA (ktr,R = 2.0 × 10 5 L mol-1 s-1), and BSPA (ktr,R = 1.0 × 104 L mol-1 s-1) at 80°C]. The underlying structural cause is the change from a tertiary (CPDA), via a secondary (PEPDA), to a primary (BSPA) leaving group in the initial RAFT agent. Further, the presented simulations open an efficient pathway for approximating overall preequilibrium transfer rate coefficients for the employed RAFT agents.

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ID Code: 99086
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :48
Export Date: 5 September 2016
CODEN: MAMOB
Correspondence Address: Barner-Kowollik, C.; Ctr. for Adv. Macromolecular Design, Sch. of Chem. Eng./Indust. Chemistry, University of New South Wales, Sydney, NSW 2033, Australia
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Keywords: Approximation theory, Computer simulation, Fourier transform infrared spectroscopy, Molecular structure, Monte Carlo methods, Reaction kinetics, Rate coefficients, Reversible addition fragmentation chain transfer (RAFT, Free radical polymerization
DOI: 10.1021/ma0358428
ISSN: 00249297
Divisions: Current > Schools > School of Chemistry, Physics & Mechanical Engineering
Current > Institutes > Institute for Future Environments
Current > QUT Faculties and Divisions > Science & Engineering Faculty
Deposited On: 22 Sep 2016 04:50
Last Modified: 22 Sep 2016 04:50

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