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Mechanism of anionic polymerization of (meth)acrylates in the presence of aluminium alkyls, 2. Kinetic investigations with methyl methacrylate in toluene
Author(s) -
Schlaad Helmut,
Müller Axel H. E.
Publication year - 1995
Publication title -
macromolecular rapid communications
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.348
H-Index - 154
eISSN - 1521-3927
pISSN - 1022-1336
DOI - 10.1002/marc.1995.030160601
Subject(s) - methyl methacrylate , toluene , aluminium , polymerization , polymer chemistry , kinetic energy , mechanism (biology) , anionic addition polymerization , reaction mechanism , methacrylate , chemistry , materials science , polymer , organic chemistry , catalysis , philosophy , physics , epistemology , quantum mechanics
The kinetics of the polymerization of methyl methacrylate initiated by lithium alkyls ( tert ‐butyllithium or ethyl α‐lithiobutyrate) was investigated in the presence of aluminium alkyls (triethylaluminium or triisobutylaluminium) in toluene at −78°C. The rate of polymerization decreases considerably once the living dimer is formed. This suggests that the aluminate end‐group coordinates with the penultimate ester group of the polymer chain, thus decreasing reactivity. The results are at variance with an activated monomer mechanism.