High norbornene incorporation in ethylene-norbornene copolymerization with a bis(α-alkyloxoimine) titanium-MAO catalyst

Abstract

A novel bis(-alkyloxoimine) titanium(IV) complex was synthesized and used as a catalyst precursor to catalyze homo-and copolymerization of ethylene and norbornene. The titanium complex activated with methylalumoxane exhibits good activities for the homopolymerizations of ethylene and norbornene under high temperature to produce high-molecular-weight linear polyethylene and vinyl-type polynorbornene, respectively. Ethylene-norbornene copolymers with high molecular weight can also be produced by this catalyst. The incorporation of norbornene from 0 to 76 mol% in the copolymers can be controlled by varying the charged norbornene. 13 C NMR analyses show that the microstructures of the ethylene-norbornene copolymers with low norbornene incorporation are predominantly alternated and isolated norbornene units, while those with high norbornene incorporation are random polymers containing long norbornene sequences.

Performance of a Bis(imine)Pyridine Iron Catalyst System in Ethylene/Norbornene Copolymerization with Zinc Diethyl

“…The catalytic activity was strongly influenced by the reaction temperature, i.e., at 30 °C the lowest activity reported was 3.66 kg/mol.h and at 70 °C the highest activity was 8.90 Kg/mol.h . Besides this, the same influence of polymerization temperature has been observed in other works in the literature dealing with ethylene‐norbornene polymerization, like using a half‐metallocene Ti complex cocatalyzed by modified methylaluminoxane (MMAO), or using the catalytic system bis(α‐alkoxyimine)titanium/MAO, as well as for systems using metallocenes with C 2 or C s symmetry …”

Copolymerization of styrene and norbornene with β‐diketiminato nickel/methylaluminoxane catalytic system

“…Copolymerization of norbornene and ethylene by metallocene and early transition metal (group IV) catalytic systems has been reported . In general, these group IV catalytic systems show very low activity for norbornene copolymerization, and produce alternative or random ethylene/norbornene copolymers with low norbornene incorporation.…”

Kinetics, Mechanism and Theoretical Studies of Norbornene-Ethylene Alternating Copolymerization Catalyzed by Organopalladium(II) Complexes Bearing Hemilabile α-Amino–pyridine

“…Cyclic olefin copolymers (COC) have demonstrated wide-range applications in the industries of coating, packaging, medical equipment, etc. [ 1 , 2 , 3 , 4 , 5 , 6 ], because of their high T g , high transparency, low dielectric constants, and good biocompatibility and processability [ 7 , 8 , 9 , 10 , 11 , 12 , 13 , 14 , 15 , 16 ]. These physical properties are usually controlled by the compositions and the microstructures of the monomers, resulting from the design of the catalysts [ 17 , 18 , 19 , 20 , 21 , 22 , 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 , 31 , 32 , 33 , 34 , 35 , 36 ].…”