Living coordination polymerization of end-allenyloxy poly(ethylene glycol)macromonomer by a pi-allylnickel catalyst

The living coordination polymerization of end-allenyloxy poly(ethylene oxid e)s (2A-2C) was carried out by [(eta(3)-allyl)NiOCOCF3](2) (1) in the prese nce of PPh3 to produce narrowly dispersed polyallenes bearing poly(ethylene oxide) side chains. for instance, the polymerization of 2B ((M) over bar(n ) = 590, [2]/[1] = 100) proceeded smoothly to give a polymer ((M) over bar( n) = 39 800, (M) over bar(w)/(M) over bar(n) = 1.13) in high yield. The mol ecular weight of poly(2) could be controlled by the ratio of 2 to 1 and by the molecular weight of 2. The block copolymers of 2B with various alkoxyal lenes (3A-3C) or with 1-phenylethyl isonitrile (3D) were also obtained by t he two-stage copolymerization process i.e., the polymerization of 2, follow ed by that of 3A-3D). The resulting block copolymers were found to serve as polymeric surfactants in the polymer blend systems of PSt and PMMA.