Cycloolefin Copolymers by Early and Late Transition Metal Catalysts

The complex [Pd(kappa(2)-P,O-{2-(2-MeOC6H4)(2)P}C6H4SO3)Me(dmso)] (1) is investigated for the copolymerization of (E) with norbornene (N) and functionalized N derivatives affording P(E-co-N) in excellent yields. Copolymer molar masses are higher than those of PE and increase with N concentration. In addition, the complex [Ti(kappa(2)-N,O-{2,6-F2C6H3N=C(Me)C(H)=C(CF3)O})(2)Cl-2] (2) is evaluated as catalyst for living E-co-N copolymerization upon activation with dried methylaluminoxane between 25 and 90 degrees C. Copolymerization at different [N]/[E] feed ratios affords stereoirregular alternating high molar mass P(E-co-N) with narrow molar mass distribution. P(E-co-N) living copolymerization is demonstrated by kinetics at 50 degrees C. Block copolymers are synthesized and fully characterized.