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Functionalized initiators for group transfer and metal‐free anionic polymerization for the synthesis of macromonomers: overview and new results
Author(s) -
Bandermann Friedhelm,
Beckelmann Dirk,
Broska Dirk,
Fieberg Andreas,
Roloff Thorsten,
Wolters Dieter
Publication year - 1995
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/macp.1995.021960720
Subject(s) - polymer chemistry , chemistry , polymerization , anionic addition polymerization , macromonomer , acrylate , chain transfer , living free radical polymerization , ring opening polymerization , monomer , end group , radical polymerization , organic chemistry , polymer
Vinylphenyloxy‐ and allyloxy‐substituted silyl ketene acetals are presented as new functionalized initiators for group transfer polymerization (GTP). All initiators initiated GTP of butyl acrylate in tetrahydrofuran with tetrabutylammonium cyanide as catalyst to yield butyl acrylate macromonomers with number‐average molecular weights somewhat lower than those calculated for an ideal living polymerization and with polydispersities of about 1,8–2,6. For the metal‐free anionic polymerization, functionalized initiators were obtained introducing allyloxy and vinylbenzyl groups into tetrabutylammonium diethyl malonate. Both compounds initiated a very rapid polymerization of butyl acrylate in tetrahydrofuran with high monomer conversion. The number‐average molecular weights of the macromonomers, produced in a semi‐batch procedure, reached nearly theoretical values, the polydispersities were about 1,2. In all macromonomers the functionality with respect to terminal vinyl and allyl groups was near one, so that they can be used with other monomers to form graft copolymers, e. g., in a free‐radical polymerization.