Cited by 64Advanced Polymer Synthesis and CharacterizationPolymer Synthesis and Characterizationbiodegradable polymer synthesis and properties

The macroester ⇄ macroion equilibrium in the cationic polymerization of THF observed directly by 300 MHz1 H NMR

Matyjaszewski, Krzysztof, Penczek, Stanisłw·1974·Journal of Polymer Science: Polymer Chemistry Edition

Abstract

Abstract Two isomeric forms of active chain ends were observed simultaneously in the living cationic polymerization of tetrahydrofuran (THF) initiated with derivatives of trifluoromethanesulphonic acid (CF3SO2OH). These forms are magnified image the macroion and the macroester. Concentrations of both species were determined in the polymerization of THF conducted in CCl4, CH2Cl2, and CH3NO2, by using 300 MHz 1H NMR spectroscopy. In CCl4 the macroester form dominates (96%), and in CH3NO2 only 8% of macroester could be detected. In CH2Cl2 both species coexist in comparable concentrations ([macroion]:[macroester] = 1:3). The present direct measurements are in agreement with our previous determination of the proportions of macroester and macroions based on kinetics data. Therefore, this also confirms our earlier conclusion, that if an equilibrium between the macroions and macroester is involved in the polymerization of THF, the chain growth proceeds almost exclusively on the macroions.

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Crossref · 10.1002/pol.1974.170120905

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  • Trialkyl oxonium ions react with cyclic acetals, ethers, sulfides and amines.

    “Typical examples are the reactions of trialkyl oxonium ions with cyclic acetals [38], ethers [52], or sulfides [53] as well as with amines [54].”

    From Ring-Opening Polymerization—An Introductory Review (2013) · cites this paper as [52]

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Authors
Matyjaszewski, K., & Penczek, S.
Affiliations
Centrum Badań Molekularnych i Makromolekularnych Polskiej Akademii Nauk (PL)
Venue
Journal of Polymer Science: Polymer Chemistry Edition
Publisher
Wiley
Published
1974-09
Volume
12
Issue
9
Pages
1905-1912
ISSN
  • 0360-6376 (ISSN-L)
  • 1542-9369
OpenAlex
W2134158187
Cited by
63
References
11
Citations by year
2023: 1 · 2018: 1 · 2017: 3 · 2016: 1 · 2015: 1 · 2013: 1 · 2012: 2
FWCI
7.10
Type
journal article
Language
en
Open access
closed
Locations
Journal of Polymer Science Polymer Chemistry Edition (publishedVersion)
Topics
  • Physical Sciences › Chemistry › Organic Chemistry › Advanced Polymer Synthesis and Characterization
  • Physical Sciences › Materials Science › Polymers and Plastics › Polymer Synthesis and Characterization
  • Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
Keywords
living cationic polymerization, tetrahydrofuran, trifluoromethanesulfonic acid, macroions, chain growth mechanism, solvent effects, 1H NMR

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