Characteristics of polymer - supported ruthenium complex catalyst; preparation of the support and isomerization over the catalyst

Abstract

Preparation of macroporous styrene-divinylbenzene(St-DVB) copolymer was studied in terms of phase separation and characteristics of phosphinated St-DVB copolymer containing $RuCl_2(PPh_3)_3$ was investigated through 1-hexene isomerization. In Chapter II, macroporous St-DVB copolymer was prepared and studied in terms of phase separation which may be affected by initial volume fraction of monomers, type of pore-forming agent, and crosslinking density. Modeling equations considering such factors were established assuming thermodynamic equilibrium in every step of crosslinking reaction and network isotropy. The change of chemical potential by mixing and deformation of network were expressed in terms of Flory-Huggins semiempirical equation. St-DVB copolymer was prepared by suspension copolymerization. Properties of copolymer such as surface area and swelling ratio were measured at different conversion of monomers by varying the factors considered in modeling equations. The copolymer properties were changed sharply at a certain point of conversion presumably due to phase separation. The conversion at which phase separation is considered to occur was correlated with initial volume fraction of monomers, type of pore-forming agents and crosslinking density, and then the results were compared with those obtained by modeling. In Chapter III were obtained the characteristics of phosphinated copolymer containing $RuCl_2(PPh_3)_3$ through olefin isomerization reaction. Chloromethylated copolymer was prepared in macroporous type by direct copolymerization of chloromethylstyrene and DVB. The chlorine content in the copolymer could be controlled rather easily. The chloromethylated beads were phosphinated and then the ruthenium complex was anchored onto the phosphinated copolymer to give catalysts. Phosphination and anchoring reactions were characterized by FTIR and NMR studies, respectively. Anchoring stoichiometry was obtained by elemental analysis and varied with crosslinking...