Simple Trends in the Methylene and α-Substituent Regions of NMR Spectra of Vinyl Polymers

Chemical shift trends in the methylene and α substituent regions of 13C NMR spectra of vinyl polymers have been analyzed in terms of a three‐state rotational isomeric states (RIS) model and the γ‐gauche effect. In this framework, it has been demonstrated that the three sequencing rules observed for...

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Bibliographic Details
Published in:Macromolecular chemistry and physics 2004-07, Vol.205 (10), p.1327-1337
Main Authors: Monaco, Guglielmo, Viglione, Rosario G.
Format: Article
Language:English
Subjects:
Applied sciences
conformational analysis
Exact sciences and technology
NMR
Organic polymers
peak assignment
Physicochemistry of polymers
Properties and characterization
Structure, morphology and analysis
tacticity
vinyl polymers
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Summary:Chemical shift trends in the methylene and α substituent regions of 13C NMR spectra of vinyl polymers have been analyzed in terms of a three‐state rotational isomeric states (RIS) model and the γ‐gauche effect. In this framework, it has been demonstrated that the three sequencing rules observed for poly(propylene) can also be expected to work for many other vinyl polymers. The first two rules, justified in terms of the conformational perturbability of stereosequences, turn out to be respected by a considerable number of NMR spectra. On the other hand, the same spectral data are in substantial disagreement with the third rule. An explanation is proposed for this breakdown. Sketches of the three conformations expected for rotation on the two prochiral bonds flanking the methine carbon of a vinyl polymer.
ISSN:1022-1352
1521-3935
DOI:10.1002/macp.200400073