Copolymerization of Vinyl Chloride and Sulfur Dioxide. III. Evaluation of the Copolymerization Mechanism

Cais R.E., Hill D.J.T. and O'Donnell J.H. (1982) Copolymerization of Vinyl Chloride and Sulfur Dioxide. III. Evaluation of the Copolymerization Mechanism. Journal of Macromolecular Science: Part A - Chemistry, 17 9: 1437-1467. doi:10.1080/00222338208074408


Author Cais R.E.
Hill D.J.T.
O'Donnell J.H.
Title Copolymerization of Vinyl Chloride and Sulfur Dioxide. III. Evaluation of the Copolymerization Mechanism
Journal name Journal of Macromolecular Science: Part A - Chemistry
ISSN 0022-233X
Publication date 1982-01-01
Sub-type Article (original research)
DOI 10.1080/00222338208074408
Open Access Status Not yet assessed
Volume 17
Issue 9
Start page 1437
End page 1467
Total pages 31
Subject 1600 Chemistry
2507 Polymers and Plastics
2505 Materials Chemistry
2503 Ceramics and Composites
2200 Engineering
Abstract The mechanism of copolymerization of vinyl chloride (V) with sulfur dioxide (S) to form a variable composition polysulfone with average V:S molar ratio n ≥ 1 is examined. The copolymerization deviates from Lewis-Mayo behavior above -78° C. Alternative models for propagation involving (1) penultimate and pen-penultimate unit effects, (2) complex participation, and (3) depropagation are considered quantitatively by comparison of calculated and experimental copolymer/comonomer composition relationships and comonomer sequence distributions. Our theoretical modeling of the copolymerization shows that it is difficult to discriminate convincingly between alternative mechanisms. The penultimate and pen-penultimate effect models can account for the copolymer compositions, but not for the dilution effects which were observed provided the diluent is truly inert. The complex participation model can account for experimental behavior from -78 to -18°C by the assumption of addition of SV complexes, but it becomes rapidly less satisfactory at higher temperatures. Depropagation is the only model which can account for the compositions and dilution effects above 0°C. Progressive depropagation, with increasing temperature, of chains ending in the triad sequences “SVS”, “VVS”, and “VSV” can explain the observed behavior over the entire comonomer composition and temperature range, but involvement of comonomer complexes in the propagation reactions is highly likely below 0°C.
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status Unknown

Document type: Journal Article
Sub-type: Article (original research)
Collection: Scopus Import - Archived
 
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