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Towards the control of the reactivity in high temperature bulk anionic polymerization of styrene, 1. Influence of n,s ‐dibutylmagnesium on the reactivity of polystyryllithium species
Author(s) -
Desbois Philippe,
Fontanille Michel,
Deffieux Alain,
Warzelhan Volker,
Lätsch Stephan,
Schade Christian
Publication year - 1999
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/(sici)1521-3935(19990301)200:3<621::aid-macp621>3.0.co;2-k
Subject(s) - reactivity (psychology) , chemistry , polymerization , molar mass , polymer chemistry , styrene , cyclohexane , polystyrene , anionic addition polymerization , emulsion polymerization , stoichiometry , living polymerization , organic chemistry , copolymer , radical polymerization , polymer , medicine , alternative medicine , pathology
The influence of n,s ‐dibutylmagnesium on the kinetics of styrene polymerization initiated by s ‐butyllithium was investigated in cyclohexane at 50°C. The presence of n,s ‐dibutylmagnesium, in molar ratios ranging from 0 to 20 with respect to polystyryllithium, leads to a drastic and continuous reduction of the reactivity of the propagating species. The living character of the polymerization, especially the control of the molar mass is preserved over the entire range studied. The experimental molar masses are in agreement with the formation of one polystyrene chain per lithium and 0.5 to 0.8 chains per magnesium atom, indicating that both alkyllithium and dialkylmagnesium species are involved in the polymerization process through the formation of “ate” complexes. The UV‐visible study of the PSLi/ n,s ‐dibutylmagnesium systems shows that several types of “ate” complexes with different stoichiometry are formed depending on the proportion of the two metal derivatives.