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Living Anionic Polymerization of Functionalized Monomers, 2. Anionic Polymerization of p ‐Alkenylstyrene Derivatives
Author(s) -
Hirao Akira,
Kubota Shin,
Sueyoshi Takayuki,
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(20010401)202:7<1044::aid-macp1044>3.0.co;2-t
Subject(s) - polymer chemistry , anionic addition polymerization , styrene , propenyl , chemistry , copolymer , monomer , polymerization , methyl methacrylate , living anionic polymerization , living polymerization , molar mass distribution , polymer , radical polymerization , organic chemistry
A study has been carried out on the anionic polymerization of eight p ‐alkenylstyrene derivatives. The monomers used are p ‐(2‐propenyl)styrene ( 1 ), p ‐(2‐propenyl)‐α‐methylstyrene ( 2 ), p ‐(2‐butenyl)styrene ( 3 ), p ‐(2‐butenyl)‐α‐methylstyrene ( 4 ), p ‐(2‐methyl‐2‐propenyl)styrene ( 5 ), p ‐(2‐methyl‐2‐propenyl)‐α‐methylstyrene ( 6 ), 8‐( p ‐vinylphenyl)‐1‐octene ( 7 ), and 2‐methyl‐7‐( p ‐vinylphenyl)‐1‐heptene ( 8 ). The anionic polymerizations of 1 – 4 were accompanied by competitive side reactions presumably due to the proton abstraction from their allyl groups. Furthermore, significant degrees of the propagating chain‐end carbanions derived from 1 , 3 , and 4 were deactivated in THF at –78°C after 1–2 h. In contrast, the polymerizations of 5 – 8 proceed in a living manner in THF at –78°C to afford polymers with predictable molecular weights and narrow molecular weight distributions. Novel well‐defined block copolymers of 5 – 8 with styrene or 2‐hydroxyethyl methacrylate were successfully prepared.