Processes of making catalyst compositions are provided. In an exemplary embodiment, the processes include modifying an organoaluminum compound with a modifier that decreases the initial reducing strength of the organoaluminum compound, where the modifier can be an ether, an anhydride, an amine, an amide, a silicate, a silyl ether, a siloxane, an ester, a carbonate, a urea, a carbamate, a sulfoxide, a sulfone, a phosphoramide, or a combination thereof. The processes further include adding a transition metal complex to the mixture of the organoaluminum compound and the modifier; and obtaining a catalyst composition including the organoaluminum compound and the transition metal complex.

Processes of making catalyst compositions are provided. In an exemplary embodiment, the processes include modifying an organoaluminum compound with a modifier that decreases the initial reducing strength of the organoaluminum compound, where the modifier can be an ether, an anhydride, an amine, an amide, a silicate, a silyl ether, a siloxane, an ester, a carbonate, a urea, a carbamate, a sulfoxide, a sulfone, a phosphoramide, or a combination thereof. The processes further include adding a transition metal complex to the mixture of the organoaluminum compound and the modifier; and obtaining a catalyst composition including the organoaluminum compound and the transition metal complex.

A series of ligands with site specific electron donating substituents that form a catalyst complex with a transition metal and are suitable for catalysis of atom transfer radical reactions, including ATRP are described. Faster catalysis rates were observed allowing for low catalyst concentrations and linear increases in molecular weight with monomer conversion, and narrow molecular weight distributions. Cyclic voltammetry revealed that increasing the strength and number of conjugated electron donating groups resulted in more stable complexes and larger ATRP equilibrium constants.

The present invention relates to a catalyst composition for cyclic olefin polymerization, and a method for preparing a cyclic olefin-based oligomer or a cyclic olefin-based polymer by using same, and, more specifically, to: a catalyst composition for cyclic olefin polymerization, the composition forming catalytically active species inside and outside the same reaction system during polymerization of cyclic olefin-based monomers, thereby enabling an oligomer or a polymer to be prepared from the cyclic olefin-based monomers; and a method for preparing a cyclic olefin-based oligomer or a cyclic olefin-based polymer by using same.