Macromonomers were obtained by cationic polymerization of propylene ox
ide and epichlorohydrin proceeding by the activated monomer mechanism
with hydroxyethyl acrylate as initiator. Up to DPn similar to 15 for p
ropylene oxide and DPn similar to 20 for epichlorohydrin, polymerizati
on proceeds as a living process, giving with quantitative yields macro
monomers with functionality equal to one, controlled molecular weight
and narrow molecular weight distribution ((M) over bar(w)/(M) over bar
(n) < 1.2) free of side products. In the higher molecular weight regio
n, side reactions become increasingly noticeable. Propylene oxide macr
omonomers undergo radical homopolymerization. Homopolymerization of ma
cromonomer with (M) over bar(n) = 8 x 10(2) gives graft copolymers wit
h (M) over bar(n) up to 7.2 x 10(3). In copolymerization with styrene,
completely soluble graft copolymers with (M) over bar(n) similar to 2
x 10(4) were obtained. Radical copolymerization of epichlorohydrin ma
cromonomers with styrene gives initially soluble products with (M) ove
r bar(n) similar to 6 x 10(4) which are converted in the later stages
into insoluble gels, apparently due to the chain transfer to chloromet
hyl groups of the polyepichlorohydrin chains.