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Near‐ and supercritical fluid solvents for living anionic polymerizations
Author(s) -
Desimone J.M.,
Maury E.E.,
Lemert R.M.,
Combes J. R.
Publication year - 1993
Publication title -
makromolekulare chemie. macromolecular symposia
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.257
H-Index - 76
eISSN - 1521-3900
pISSN - 0258-0322
DOI - 10.1002/masy.19930670120
Subject(s) - supercritical fluid , cyclohexane , solubility , chemistry , isobutane , anionic addition polymerization , hildebrand solubility parameter , solvent , polymer chemistry , polymerization , solvatochromism , organic chemistry , polymer , catalysis
Near‐ and supercritical fluids are investigated as solvents for anionic polymerizations of 1,3‐dienes. Solvent strength (solubility parameter) of mixtures of light hydrocarbons containing cyclohexane is shown to be adjustable using solvatochromic probe methods. The results indicate that these mixtures have solubility parameter values that are lower than conventional liquid solvents and represent a regime of solvent strength that has remained unexplored for ionic polymerizations. The anionic initiator 3‐methyl‐1,1‐diphenyl‐pentyllithium (MDPPL) was shown to be soluble in supercritical ethane and that its ultraviolet/visible absorption maximum was sensitive to systematic density changes of the supercritical fluid induced by pressure profiling. These results were extended to the anionic polymerization of isoprene in butane/cyclohexane mixtures.