Cycloolefin Copolymers by Early and Late Transition Metal Catalysts

The complex [Pd(κ 2 ‐ P,O ‐{2‐(2‐MeOC 6 H 4 ) 2 P}C 6 H 4 SO 3 )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(κ 2 ‐ N,O ‐{2,6‐F 2 C 6 H 3 N = C(Me)C(H) = C(CF 3 )O}) 2 Cl 2 ] ( 2 ) is evaluated as catalyst for living E‐ co ‐N copolymerization upon activation with dried methylaluminoxane between 25 and 90 °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 °C. Block copolymers are synthesized and fully characterized.