The cationic polymerization of cyclohexyl vinyl ether (CHVE) initiated
by alpha-halogeno ethers in the presence of a Lewis acid activator ha
s been investigated first. In conditions leading to a living polymeriz
ation of alkyl vinyl ethers (ethyl, isobutyl, etc.), an extremely fast
polymerization, accompanied by chain transfer reactions, is observed
with CHVE. In fact, we have shown that the polymerization of this mono
mer may be directly initiated by the HI and HCl adducts of CHVE, in th
e absence of any electrophilic activator. However, even in these condi
tions, the polymerization cannot be controlled. A ''living'' polymeriz
ation of CHVE was finally obtained by addition of ammonium salts (NBu4
X; X = Cl, Br, I) to the systems free of electrophilic activators. The
added salts stabilize the alpha-halogeno ether chain ends and reduce
the overall reactivity. Using this procedure, we have synthesized poly
(CHVE)s with M(n)'sBAR ranging from 6 . 10(3) to 4 . 10(4) g . mol-1 (
in good agreement with the predicted values assuming the formation of
one polymer chain per initiator molecule) and narrow molecular weight
distributions (M(w)BAR/M(n)BAR < 1,2). Though most of poly(alkyl vinyl
ether)s exhibit glass transition temperatures far below 0-degrees-C,
the glass transition temperature of the poly(CHVE) is close to + 50-de
grees-C, indicating that this monomer can be used as a precursor to ri
gid poly(vinyl ether) blocks.