Cobalt and nickel complexes （la-ld and 2a-2d, respectively） supported by 2-imidate-pyridine ligands were synthesized and used for 1,3-butadiene polymerization. The complexes were characterized by IR and element analysis, and complex la was further characterized by single-crystal X-ray diffraction. The solid state structure of complex la displayed a distorted tetrahedral geometry. Upon activation with ethylaluminum sesquichloride （EASC）, all the complexes showed high activities toward 1,3-butadiene polymerization. The cobalt complexes produced polymers with high cis-1,4 contents and high molecular weights, while the nickel complexes displayed low cis-l,4 selectivity and the resulting polymers had low molecular weights. The catalytic activities of the complexes highly depended on the ligand structure. With the increment of polymerization temperature, the cis-1,4 content and the molecular weight of the resulting polymer decreased.
The polymerization of 1,3-butadiene was examined by using a novel halogen-free neodymium m-nitrobenzenesulfonate （Nd（3-NBSOa）3·donors）/alkylaluminum binary catalyst system. The catalyst showed fairly high activity and controllable selectivity. The microstructure of the resultant polymer was adjustable by variation of electron donor and/or the alkylaluminum. ^13C-NMR and thermal analysis demonstrate that the produced polybutadienes have stereo-block chain structures of cis-1,4 and trans-1,4 segments with adjustable Tm and To. The neodymium sulfonate-based catalyst is believed to be significant in regulating the chain structure of polydienes and in exploring 1,3-diene polymerization mechanism.
