1 research outputs found
Polymerization of Hydroxy-Containing Diazoacetates: Synthesis of Hydroxy-Containing “Poly(substituted methylene)s” by Palladium-Mediated Polymerization and Poly(ester–ether)s by Polycondensation through O–H Insertion Reaction
Two types of polymerization of hydroxy-containing
diazoacetates
are described. The polymerization of hydroxy-containing diazoacetates
using palladium complexes proceeded successfully under chain-growth
mechanism even without a protecting group to give C–C main
chain polymers bearing a hydroxy-containing ester substituent on each
carbon of the backbone. The resulting polymers had a slightly branched
structure due to chain transfer reaction with the hydroxy groups,
while the polymers obtained by polymerization of silyl-protected diazoacetates
and subsequent deprotection had a completely linear structure. The
hydroxy-containing polymers with an appropriate hydrophilic/hydrophobic
balance showed a lower critical solution temperature-type phase separation
in an aqueous medium. On the other hand, the polymerization of hydroxy-containing
diazoacetates using InCl<sub>3</sub> as a catalyst proceeded under
step-growth mechanism to give oligomers having a distinct repeating
unit (ester–ether), where a new ether bond was generated through
O–H insertion reaction of diazocarbonyl groups into hydroxy
groups