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Living Anionic Polymerization of Monomers with Functional Groups, 15. Anionic Polymerization and Reaction of Styrene and 1,1‐Diphenylethylene Derivatives Substituted with Alkoxymethyl Groups
Author(s) -
Hirao Akira,
Negishi Yumi,
Hayashi Mayumi,
Sako Kanjiro,
Ryu Sang Woog,
Loykulnant Surapich,
Matsuo Akira,
Sugiyama Kenji
Publication year - 2001
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 - 10.1002/1521-3935(20011201)202:18<3590::aid-macp3590>3.0.co;2-0
Subject(s) - polymerization , anionic addition polymerization , chemistry , polymer chemistry , living anionic polymerization , styrene , monomer , living polymerization , ionic polymerization , polymer , copolymer , radical polymerization , organic chemistry
Anionic polymerizations of ortho ‐, meta ‐, and para ‐substituted styrene derivatives with alkoxymethyl groups have been studied. It was found that their polymerization behaviors were significantly affected by the substituted position of the alkoxymethyl group. The meta ‐ and ortho ‐substituted styrenes successfully underwent living anionic polymerization in THF at –78°C with the initiators having K + as a counter cation such as cumylpotassium and oligo( α ‐methylstyryl)potassium, and potassium napthalenide. On the other hand, no appreciable polymerization of the para ‐substituted styrenes occurred under the identical conditions. The similar positional effect was also observed in the reactions of polystyryllithium with o,o‐ , m,m‐ , and p,p ‐disubstituted 1,1‐diphenylethylene (DPE) derivatives with methoxymethyl groups. Instead of the expected 1 : 1 addition products, undesirable high molecular weight polymers were formed especially using p,p ‐disubstituted DPE. In order to account for such anomalous polymerization and reaction behaviors of the para ‐substituted styrene and DPE derivatives, we postulated the reaction pathway based on the anion‐mediated rearrangement followed by a 1,6‐elimination reaction to produce very reactive p ‐xylylene and/or biradical intermediates that were coupled to each other. This postulated reaction pathway was discussed throughout the results of the stoichiometric reactions of sec ‐BuLi with p ‐methoxymethylstyrene and 1‐(4‐methoxymethylphenyl)‐1‐phenylethylene.