Microwave assisted synthesis of high molecular weight polyvinylsilazane via RAFT process

Polymerization of hex-1-ene and propene initiated by several methylalumoxane-activated diimine complexes was critically investigated. Effect of bulkiness of ortho aryl diimine substituents on extent of transfer reactions was examined. All of the complexes allowed us to prepare poly(hex-1-ene) with a very narrow molar mass distribution, molar mass being controlled by stoichiometry in a broad range of reaction conditions. Poly(hex-1-ene)s with molar mass between 15 and 220 kg mol−1 and dispersity (Mw/Mn) between 1.01 and 1.20 were prepared by varying the catalyst, temperature and monomer concentration. Livingness of hex-1-ene polymerization was demonstrated for the first time for nickel complex bearing ethyl ortho aryl substituents by reinitiation of chain growth upon addition of a new portion of monomer. Complexes with ortho methyl substituents did not allow complete reinitiation of chain growth and despite its good control over molar mass cannot be classified as a living polymerization catalyst. Chain branching can effectively be controlled by the choice of the ligand structure due to the chain-walking mechanism. Transfer reactions were more pronounced in propene polymerization. Polypropylene with narrow molar mass distribution could not be prepared using complexes with methyl substituents.