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Effect of temperature, solvent, Lewis acid and additives on the polymerization of tert ‐butyl vinyl ether using Lewis acid‐induced N ‐methyleneamines as cationic initiators
Author(s) -
Leasure Joshua G,
Brinkman Chelsea E,
Tillman Eric S,
Monk Ian W,
Cohen Nicole A
Publication year - 2010
Publication title -
polymer international
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.592
H-Index - 105
eISSN - 1097-0126
pISSN - 0959-8103
DOI - 10.1002/pi.2742
Subject(s) - lewis acids and bases , cationic polymerization , chemistry , polymer chemistry , dichloromethane , living cationic polymerization , polymerization , vinyl ether , solvent , polymer , ether , vinyl chloride , organic chemistry , ring opening polymerization , catalysis , monomer , copolymer
N ‐Methyleneamines, formed by treating 1,3,5‐trimethylhexahydro‐1,3,5‐triazines with Lewis acids, have been shown to be capable initiators in the cationic polymerization of tert ‐butyl vinyl ether, yielding polymers with amine functionality at the chain ends. Previous work was limited to titanium(IV) chloride (TiCl 4 ) as the Lewis acid in dichloromethane solvent at 0 °C (with resulting polymers possessing relatively broad polydispersity index (PDI) values near 2), while this contribution details the effect of reaction parameters on the polymeric products; specifically, the role of temperature, solvent, Lewis acid and additives. Ultimately, performing the polymerization at −78 °C in dichloromethane with TiCl 4 as the Lewis acid and tetra‐ n ‐butylammonium chloride ( n Bu 4 NCl) as the additive afforded the best control over the system, with polymers formed possessing low PDI values (<1.2). Dramatic changes in number‐average molecular weight and PDI were observed in polymers formed by initiating systems of Lewis acid‐induced N ‐methyleneamines, with temperature, solvent, Lewis acid and additives all playing a role. By varying single parameters, optimization of the system was achieved. Copyright © 2009 Society of Chemical Industry