Metallocene-Catalyzed Polymerization in Nonaqueous Fluorous Emulsion

• Published in: Macromolecular chemistry and physics Vol. 208; no. 13; pp. 1362 - 1369
• Main Authors: Nenov, Svetlin, Clark Jr, Christopher G., Klapper, Markus, Müllen, Klaus
• Format: Journal Article Conference Proceeding
• Language: English
• Published: Weinheim WILEY-VCH Verlag 03.07.2007; WILEY‐VCH Verlag; Wiley
• Subjects: Applied sciences; emulsion polymerization; Exact sciences and technology; metallocene catalysts; non-aqueous; Organic polymers; perfluorinated; Physicochemistry of polymers; Polymerization; polyolefins; Preparation, kinetics, thermodynamics, mechanism and catalysts; Fluorine containing copolymer; perfluorinated; Nanoparticle; Emulsifying power; Surfactant polymer; Complex catalyst polymerization; Styrene derivative copolymer; nonaqueous; Etherification; Metallocene; metallocene catalysts; Emulsion polymerization; Olefin polymer; Chloro complex; Polyethylene; Non ionic surfactant; Propylene polymer; Zirconium complex; Experimental study; Styrene(hydroxy) polymer; Random copolymer; Chemical modification; polyolefins; Preparation; Nonaqueous media; Catalyst activity
• ISSN: 1022-1352; 1521-3935
• DOI: 10.1002/macp.200700050

A nonaqueous organic‐in‐fluorous emulsion applicable for polymerization using water‐sensitive catalysts is presented. With statistical biphasic copolymers based on poly(4‐hydroxystyrene) containing fluorinated and nonfluorinated alkyl side chains, emulsions of hydrocarbons dispersed in perfluorocarbons were stabilized. The addition of metallocenes, activated by methylalumoxane (MAO), enabled the polymerization of olefins inside this highly hydrophobic system. High molecular weight polyolefin nanoparticles ($\overline M _{\rm n}$ up to 450 000) of polyethylene and poly(propylene) were synthesized without supporting the catalyst and without reactor fouling. In this diffusion‐controlled process, the sizes of the particles were controlled by the reaction time and the ratio of the emulsifier to solvents.