Addition Homo- and Copolymerizations of Dicyclopentadiene and 5-n-Hexylnorbornene in the Presence of Pd-N-Heterocyclic Carbene Complexes

Herein for the first time addition homopolymerization of dicyclopentadiene (DCPD) and its copolymerization with 5-n-hexylnorbornene in the presence of different Pd-N-heterocyclic carbene complexes activated by a borate (Na+[B(3,5-(CF3)(2)C6H5)(4)](-) (NaBARF)) or methylaluminoxane (MAO) are investigated. It is found that systems based on Pd-N-heterocyclic carbene complex in combination with NaBARF or MAO are effective catalysts and a Pd-N-heterocyclic carbene complex/NaBARF system allows for the addition polymerization of these monomers in air. The influence of the N-heterocyclic carbene structure, the nature of cocatalyst, and solvent on the catalyst activity of a system based on Pd-N-heterocyclic carbene complex are determined. The properties of the obtained addition polydicyclopentadiene (poly(DCPD)) such as thermal stability, solid-state structure, and porosity are studied. The synthesized poly(DCPD) possesses Brunauer, Emmett, and Teller surface area as high as 155 m(2) g(-1) and so addition polymerization of DCPD can be considered as a single-step and convenient way to synthesize of porous polymers from a norbornene derivative.