Synthesis of High-Molecular-Weight Multifunctional Glycerol Polyhydroxyurethanes PHUs.

Glycerol carbonate acrylate is a 5-membered cyclic carbonate synthesized from glycerol that is used as a chemical coupling agent and has proven highly suitable for use in the synthesis of multifunctional polyhydroxyurethanes (PHUs). The multifunctionality of the structure of PHUs is determined by the density of the carbon-amine groups generated by the Aza-Michael reaction and that of the urethane groups and adjacent primary and secondary hydroxyl groups generated by aminolysis. Glycerol carbonate acrylate is polymerized with polyfunctional mono-, di-, tri, and tetra-amines, by type-AB polyaddition, either in bulk or in solution, through stepwise or one-pot reaction strategies in the absence of added catalysts.

Core-shell nanoreactors for efficient aqueous biphasic catalysis.

Water-borne phosphine-functionalized core-cross-linked micelles (CCM) consisting of a hydrophobic core and a hydrophilic shell were obtained as stable latexes by reversible addition-fragmentation chain transfer (RAFT) in water in a one-pot, three-step process. Initial homogeneous aqueous-phase copolymerization of methacrylic acid (MAA) and poly(ethylene oxide) methyl ether methacrylate (PEOMA) is followed by copolymerization of styrene (S) and 4-diphenylphosphinostyrene (DPPS), yielding P(MAA-co-PEOMA)-b-P(S-co-DPPS) amphiphilic block copolymer micelles (M) by polymerization-induced self-assembly (PISA), and final micellar cross-linking with a mixture of S and diethylene glycol dimethacrylate. The CCM were characterized by dynamic light scattering and NMR spectroscopy to evaluate size, dispersity, stability, and the swelling ability of various organic substrates.

Preparation of phosphine-functionalized polystyrene stars by metal catalyzed controlled radical copolymerization and their application to hydroformylation catalysis.

Well defined star copolymers have been prepared by copper-catalyzed atom transfer radical copolymerization of styrene and styryldiphenylphosphine starting from a modified Boltorn™ H30 multifunctional initiator. These polymers and an analogue obtained by debromination of the arm ends with nBu3SnH have been used in combination with [Rh(acac)(CO)2] for the homogeneous phase hydroformylation of 1-octene.