Please use this identifier to cite or link to this item:
https://hdl.handle.net/10356/84596
Title: | Theoretical and Experimental Studies on Elementary Reactions in Living Radical Polymerization via Organic Amine Catalysis | Authors: | Goto, Atsushi Sanada, Shohei Lei, Lin Hori, Kenji |
Keywords: | living radical polymerization transition state quantum calculation |
Issue Date: | 2016 | Source: | Goto, A., Sanada, S., Lei, L., & Hori, K. (2016). Theoretical and Experimental Studies on Elementary Reactions in Living Radical Polymerization via Organic Amine Catalysis. Macromolecules, 49(7), 2511-2517. | Series/Report no.: | Macromolecules | Abstract: | The reaction mechanism of living radical polymerization using organic catalysts, a reversible complexation mediated polymerization (RCMP), was studied using both theoretical calculations and experiments. The studied catalysts are tetramethylguanidine (TMG), triethylamine (TEA), and thiophene. Methyl 2-iodoisobutyrate (MMA-I) was used as the low-molar-mass model of the dormant species (alkyl iodide) of poly(methyl methacrylate) iodide (PMMA-I). For the reaction of MMA-I with TEA to generate MMA• and •I-TEA radicals (activation process), the Gibbs activation free energy for the inner-sphere electron transfer mechanism was calculated to be 39.7 kcal mol–1, while the observed one was 25.1 kcal mol–1. This difference of the energies suggests that the present RCMP proceeds via the outer-sphere electron transfer mechanism, i.e., single-electron transfer (SET) reaction from TEA to MMA-I to generate MMA• and •I-TEA radicals. The mechanism of the deactivation process of MMA• to generate MMA-I was also theoretically studied. For the studied three catalysts, the theoretical results reasonably elucidated the experimentally observed polymerization behaviors. | URI: | https://hdl.handle.net/10356/84596 http://hdl.handle.net/10220/41882 |
ISSN: | 0024-9297 | DOI: | 10.1021/acs.macromol.6b00230 | Schools: | School of Physical and Mathematical Sciences | Rights: | © 2016 American Chemical Society (ACS). This is the author created version of a work that has been peer reviewed and accepted for publication by Macromolecules, American Chemical Society (ACS). It incorporates referee’s comments but changes resulting from the publishing process, such as copyediting, structural formatting, may not be reflected in this document. The published version is available at: [http://dx.doi.org/10.1021/acs.macromol.6b00230]. | Fulltext Permission: | open | Fulltext Availability: | With Fulltext |
Appears in Collections: | SPMS Journal Articles |
Files in This Item:
File | Description | Size | Format | |
---|---|---|---|---|
Theoretical and Experimental Studies on Elementary Reactions.pdf | 486.32 kB | Adobe PDF | View/Open |
SCOPUSTM
Citations
20
27
Updated on Mar 23, 2024
Web of ScienceTM
Citations
10
25
Updated on Oct 28, 2023
Page view(s) 50
511
Updated on Mar 29, 2024
Download(s) 20
177
Updated on Mar 29, 2024
Google ScholarTM
Check
Altmetric
Items in DR-NTU are protected by copyright, with all rights reserved, unless otherwise indicated.