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The Mechanism of Diene Polymerisation by Organolanthanide Catalysts Deduced from Microwave Experiments
Author(s) -
Zinck Philippe,
BarbierBaudry Denise,
Loupy André
Publication year - 2005
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.200400434
Subject(s) - isoprene , polymerization , diene , monomer , catalysis , chemistry , selectivity , alkylation , photochemistry , polymer chemistry , reaction mechanism , microwave , reactivity (psychology) , microwave irradiation , copolymer , polymer , organic chemistry , medicine , natural rubber , physics , alternative medicine , pathology , quantum mechanics
Summary: Isoprene polymerisation performed under microwave irradiation with [Nd(BH 4 ) 3 (THF) 3 ]/Mg(Bu) 2 and [Nd(BH 4 ) 3 (THF) 3 ]/Al(Et) 3 showed an enhancement in reactivity, with selectivity being only slightly modified. An explanation of the observed effect is proposed based on our current knowledge of the catalytic mechanism and by considering the alkylated complex as an ion pair. An analogy is proposed with the pseudoanionic polymerisation of oxygenated monomers. Finally, depolymerisation is observed under microwave irradiation at high temperature.Postulated mechanism for the polymerisation of isoprene with [Nd(BH 4 ) 3 (THF) 3 ]/Mg(Bu) 2 .