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Home  >  Journal list  >  Polymer Journal  >  Vol.19  No.10 (1987)  >  pp.1183-1190

Polymer Journal
<<Previous article Vol.19  No.10 (1987)   pp.1183 - 1190 Next article>>

Synthesis, Methanolysis, and Asymmetric Polymerization of meta- and para-substituted Triphenylmethyl Methacrylates

Yoshio Okamoto1), Eiji Yashima1), Motoshi Ishikura1) and Koichi Hatada1)
1) Department of Chemistry, Faculty of Engineering Science, Osaka University

ABSTRACT:  Five novel meta- and para-substituted triphenylmethyl methacrylates, diphenyl-m-fluorophenylmethyl methacrylate (m-F1TrMA), m-chlorophenyldiphenylmethyl methacrylate (m-Cl1TrMA), tris(m-chlorophenyl)methyl methacrylate (m-Cl3TrMA), tris(p-chlorophenyl)methyl methacrylate(p-Cl3TrMA), and tris(m-tolyl)methyl methacrylate (m-Me3TrMA), were synthesized: Their solvolysis rates were measured in CDCl3-CD3OD (1:1) by 1H NMR spectroscopy at 35°C. The rates were greatly affected by the substituents. Chlorine and fluorine substituents decreased the rates of the methanolysis and the methyl group accelerated it. These methacrylates were polymerized with chiral anionic initiators, such as (+)-(2S,3S)- or (−)-(2R,3R)-dimethoxy-1,4-bis(dimethylamino)butane (DDB)-N,N′-diphenylethylenediamine monolithium amide (DPEDA-Li) and (−)-sparteine-fluorenyllithium (Sp-FlLi) complexes in toluene at −78°C. DDB-DPEDA-Li complex was more reactive than the Sp-FlLi complex and gave quantitatively optically active, isotactic polymers with one-handed helicity except for p-Cl3TrMA. p-Cl3TrMA did not form a high polymer probably because of the bulkiness of the ester group. The CD spectra of the optically active polymers were different from each other. The copolymerization of p-Cl3TrMA with TrMA by (+)-DDB-DPEDA-Li complex gave a low-molecular-weight copolymer of low optical activity which decreased slowly with time probably because of uncoiling of the helix.


Keyword:
Asymmetric Polymerization/ Anionic Polymerization/ Triphenylmethyl Methacrylate/ Triphenylmethyl Methacrylate Derivatives/ Solvolysis/ (−)-Sparteine/ 2,3-Dimethoxy-1,4-bis(dimethylamino)butane/ Optically Active Polymer/ Helix/ Optical Resolution

Published online: April 08, 2005
© Copyright, 2005 by The Society of Polymer Science, Japan

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