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Living polymerization of [ o ‐(trifluoromethyl)phenyl]acetylene by a new catalyst system, MoOCl 4 –Et 3 Al–EtOH (1 : 1 : 4)
Author(s) -
Kaneshiro Hisayasu,
Hayano Shigetaka,
Masuda Toshio
Publication year - 1999
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/(sici)1521-3935(19990101)200:1<113::aid-macp113>3.0.co;2-3
Subject(s) - anisole , polymerization , chemistry , molar mass distribution , polymer chemistry , osmometer , trifluoromethyl , acetylene , vapor pressure osmometry , polymer , solution polymerization , catalysis , gel permeation chromatography , anionic addition polymerization , organic chemistry , vapor pressure , alkyl
A new MoOCl 4 ‐based living polymerization catalyst, MoOCl 4 –Et 3 Al–EtOH (mole ratio 1 : 1 : 4)/anisole, has been developed. Polymerization of [ o ‐(trifluoromethyl)phenyl]acetylene by this catalyst in anisole at 30°C yielded a polymer having very narrow molecular weight distribution ( M w / M n = 1,02), a four‐fold excess of ethanol over MoOCl 4 was necessary to attain narrow molecular weight distributions. Multistage polymerization experiments clearly showed the living nature of the polymerization, which was maintained in the temperature range of 0 to 30°C. The absolute number‐average molecular weight of the polymer measured by vapor pressure osmometry could be correlated with the number‐average molecular weight measured by gel permeation chromatography as follows: M n (VPO) = 1,48 × M n (GPC). The propagation rate constant ( k p ) at 30°C is 1,5 mol·L –1 ·s –1 .