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Synthesis and Fourier transform Raman spectroscopic study of diene‐terminated polystyrene oligomers
Author(s) -
Ward N. J.,
Edwards H. G. M.,
Johnson A. F.
Publication year - 2005
Publication title -
journal of raman spectroscopy
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.748
H-Index - 110
eISSN - 1097-4555
pISSN - 0377-0486
DOI - 10.1002/jrs.1274
Subject(s) - diene , raman spectroscopy , polystyrene , isoprene , polymer , cyclohexane , wavenumber , chemistry , double bond , polymerization , polymer chemistry , materials science , photochemistry , analytical chemistry (journal) , copolymer , organic chemistry , optics , natural rubber , physics
Polystyrene oligomers capped with a known number of butadiene or isoprene units were synthesized by ‘living’ anionic polymerization in cyclohexane. The FT‐Raman spectra of these compounds show small but significant differences in ν(CC) wavenumber position depending on whether just a single unit or several units of the diene are present at the chain end. However, if the butadiene experiments are repeated under polar‐modified conditions, so that 1,2‐ rather than 1,4‐addition takes place, the ν(CC) Raman band position is found to be independent of the number of ‘out‐of‐chain’ vinyl double bonds which are present. This conclusion is explained in terms of the mass change on diene addition to the polymer chains. Application of the method for the quantitation of polymer chain‐end diene termination is proposed. Copyright © 2004 John Wiley & Sons, Ltd.