Polymerization of 1,3-Conjugated Dienes with Rare-Earth Metal Precursors

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This chapter surveys the publications except patents related to cis-1,4-, trans-1,4-, 3,4-regio-, and stereoselective polymerizations of 1,3-conjugated dienes with rare-earth metal-based catalytic systems during the past decade from 1999 to 2009. The concerned catalyst systems are classified into the conventional Ziegler- Natta catalysts, the modified Ziegler-Natta catalysts, and the single-site cationic systems composed of lanthanocene and noncyclopentadienyl precursors, respec- tively. For the conventional Ziegler-Natta catalysts of the most promising indus- try applicable recipe, the multicomponents based on lanthanide carboxylate or phosphate or alkoxide precursors, research works concern mainly about optimiz- ing the catalyst preparation and polymerization techniques. Special emphases are put on the factors that influence the catalyst homogeneority, catalytic activity and efficiency, as well as cis-1,4-selectivity. Meanwhile, tailor-made lanthanide ary- loxide and amide complexes are designed and fully characterized to mimic the conventional Ziegler-Natta catalysts, anticipated to elucidate the key processes, alkylation and cationization, for generating the active species. Regarding to the single-site catalytic systems generally comprising well-defined complexes contain- ing lanthanide-carbon bonds, investigations cover their versatile catalytic activity and efficiency, and the distinguished regio- and stereoselectivity for both poly- merization of dienes and copolymerization of dienes with alkenes. The correla- tion between the sterics and electronics of ligands and the molecular structures of the complexes and their catalytic performances are highlighted. The isolation of the probable active species in these polymerization processes from the stoichiomet- ric reactions of the precursors with activators will be presented.