Copolymerization of vinyl chloride with sulphur dioxide—I molecular association between vinyl chloride and sulphur dioxide |
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Authors: | R.E. Cais,J.H. O Donnell |
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Affiliation: | Chemistry Department, University of Queensland, Brisbane 4067. Australia |
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Abstract: | The formation of VC-SO2 and VC-(SO2)2 complexes in liquid mixtures of vinyl chloride (VC) and sulphur dioxide has been shown by (a) the freezing point composition diagram and (b) chemical shifts in the PMR spectrum of VC over the complete composition range. It is postulated that SO2 can associate with the CC bond and the Cl atom. These complexes may be involved in the copolymerization and influence the composition and stereochemistry of the product. PMR spectra of VC-SO2-ethane(E) mixtures with [SO2] ? [E] ? [VC] gave Kv = 2·0 ± 0·5, 1·5 ± 0·1 and 1·1 ± 0·3 at 232·6, 272·6 and 301·3 K with ΔHf0Hf = ?6·6 ± 1·4 kJ mol?1 for the VC -(SO2)2 complex. The chemical shift of the trans β-proton was twice that of the other two protons. indicating that SO2 adopts an asymmetric orientation to the double bond. |
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Keywords: | To whom correspondence should be addressed. |
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