Aqueous Polyketone Latices Prepared with Water-Insoluble Palladium(II) Catalysts

Alternating copolymerization of carbon monoxide with ethylene or 1-olefins in aqueous emulsion by water-insoluble palladium(II) complexes is reported. Latices of aliphatic polyketones (1-olefin/CO copolymers and ethylene/undec-10-enoic acid/CO terpolymers), prepared by catalytic polym- erization, are described for the first time. An in situ catalyst system ({R2P(CH2)3PR2}Pd(OAc)2)/ strong acid (R ) Ph or (CH2)13CH3) or well-defined complexes ({Ph2P(CH2)3PPh2}PdMe(NCCH3)) + Y - (Y- ) (B{3,5-(F3C)2C6H3}4)- or SbF6 -) were used in the form of a solution of the palladium(II) complex in miniemulsion droplets of a hydrocarbon dispersed in the continuous aqueous phase. Catalyst activities of up to 5 10 3 TO h -1 slightly exceed those of nonaqueous polymerizations in methanol with the same catalysts. Polymer molecular weights (GPC vs PMMA standards) are typically Mw 2 10 5 (ethylene copolymers) respectively Mw 2 10 4 (1-olefin copolymers) with Mw/Mn 2-4. The 1-olefin copolymers exhibit glass transition temperatures of Tg )+ 10 to -55 °C, which is in the range desirable for latex applications.