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Home  >  Journal list  >  Polymer Journal  >  Vol.22  No.8 (1990)  >  pp.649-659

Polymer Journal
<<Previous article Vol.22  No.8 (1990)   pp.649 - 659 Next article>>

Cyclopolymerization XVII. Anionic Cyclopolymerization Tendency of N-Methyldiacrylamide and N-Substituted Dimethacrylamides

Toshiyuki Kodaira1), Hiromi Tanahashi1) and Kazunori Hara1)
1) Department of Industrial Chemistry, Faculty of Engineering, Fukui University

ABSTRACT:  Anionic cyclopolymerizabilities of N-methyldiacrylamide (MDA), N-propyldimethacrylamide (PDMA), and N-methyldimethacrylamide (MDMA) were studied. MDA initiated by tert-butylmagnesium chloride at −78°C yields polymers which consists almost exclusively of 5-membered ring as repeating unit, even though the nature of solvents employed are varied widely. This indicates that MDA has strong tendency toward head-to-head and tail-to-tail additions even in anionic polymerization. NMR spectroscopic studies showed that conjugation between C=C and C=O double bonds of MDA is as effective as that of acrylic esters. Favorable conformation of MDA for the 5-membered ring formation and higher electron density of propagating anion (-CH2-\bar{C}H-CO-) in spite of the fact that its acryloyl groups have conjugative nature are regarded as possible reasons for the unusual addition behavior. Attempted anionic polymerizations of PDMA and MDMA were unsuccessful. NMR spectroscopic studies revealed that conjugation between olefin and C=O double bonds in these monomers is ineffective owing to the twisted conformation between the two double bonds. This unconjugative nature of the methacryloyl groups of PDMA and MDMA is considered to be responsible for their lower polymerizability in the anionic polymerization.


Keyword:
Anionic Cyclopolymerization/ 5-Membered Ring/ Head-to-Head Addition/ Tail-to-Tail Addition/ 1H NMR/ 13C NMR/ N-Methyldiacrylamide/ Dimethacrylamide Derivatives/ Acrylamide Derivatives/ Methacrylamide Derivatives

Published online: April 06, 2005
© Copyright, 2005 by The Society of Polymer Science, Japan

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