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

Abstract

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 polymerization, are described for the first time. An in situ catalyst system [{R 2 P(CH 2 ) 3 PR 2 }Pd(OAc) 2 ]/ strong acid (R = Ph or (CH 2 ) 13 CH 3 ) or well-defined complexes [{Ph 2 P(CH 2 ) 3 PPh 2 }PdMe(NCCH 3 )] + Y - (Y - = [B{3,5-(F 3 C) 2 C 6 H 3 } 4 ] - or SbF 6 - ) 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 M w 2 × 10 5 (ethylene copolymers) respectively M w 2 × 10 4 (1-olefin copolymers) with M w / M n 2−4. The 1-olefin copolymers exhibit glass transition temperatures of T g = +10 to −55 °C, which is in the range desirable for latex applications.