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 [{R2P (CH2)-) 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.

Half‐Life Extension with Pharmaceutical Formulations: Nanoparticles by the Miniemulsion Process

“…The cationic polymerization permits the formation of poly -p -methoxystyrene particles [50,51] , the catalytic polymerization enables the synthesis of polyolefi n [52,53] or polyketone particles [54] , the ring opening metathesis polymerization leads to polynorbonene nanoparticles [55,56] , and the step -growth acyclic diene metathesis ( ADMET ) polymerization to oligo(phenylene vinylenes) particles [57] . The polyaddition in miniemulsion permits the formation of polyepoxides [58] or polyurethane particles [59,60] .…”

From polymeric particles to multifunctional nanocapsules for biomedical applications using the miniemulsion process

“…Therefore, other types of polymerizations can also be carried out in miniemulsion: the anionic polymerization in nonaqueous miniemulsions leads to polyamide nanoparticles, 21 and in aqueous phase, polybutylcyanoacrylate (PBCA) nanoparticles can be synthesized. 22 The cationic polymerization allows the formation of poly-p-methoxystyreneparticles, 23,24 the catalytic polymerization enables the synthesis of polyolefine 25,26 or polyketone particles, 27 the ring-opening metathesis polymerization leads to polynorbonene nanoparticles, 28,29 and the step-growth acylic diene metathesis (ADMET) polymerization to oligo(phenylene vinylenes) particles. 30 The polyaddition in miniemulsion allows the formation of polyepoxides 31 or polyurethanes (PUs) particles.…”

Catalytic Polymerization and Post Polymerization Catalysis Fifty Years After the Discovery of Ziegler's Catalysts

“…These nanodroplets provide a very high degree of dispersion of the catalyst precursor at the beginning of the polymerization, which enables the formation of stable polyolefin latexes. This technology was applied to catalytic copolymerization of ethylene with polar and non-polar 1-olefins in emulsion [305] and the formation of novel aqueous polyketone emulsions [306] prepared by means of aqueous catalytic strictly alternating copolymerization of ethylene and other 1-olefins with CO. This new field of aqueous catalytic polymerization and manufacturing of emulsions based upon olefin feedstocks and single site catalyst technology is progressing very rapidly and is expanding the frontiers of polyolefin technology.…”