In their recent published article ‘A lutetium allyl complex that bears a pyridyl-functionalized cyclopentadienyl ligand: dual catalysis on highly syndiospecific and cis-1, 4-selective (co)polymerizations of styrene and butadiene’, CIAC scientists discuss new findings in alkadienes.

“A novel linked-half-sandwich lutetium-bis(allyl) complex [(C(5)Me(4)-C(5)H(4)N)Lu('(3)-C(3)H(5))(2)] (1) attached by a pyridyl-functionalized cyclopentadienyl ligand was synthesized and fully characterized. Complex 1 in combination with [Ph (3) C] [B(C (6) F (5)) (4)] exhibited unprecedented dual catalysis with outstanding activities in highly syndiotactic (rrrr >99%) styrene polymerization and distinguished cis-1, 4-selective (99%) butadiene polymerization, respectively.” JIAN Zhongbao, and co-reseachers describe, “Strikingly, this catalyst system exhibited remarkable activity (396 kg copolymer (mol_Luh)^-1) for the copolymerization of butadiene and styrene. Irrespective of whether the monomers were fed in concurrent mode or sequential addition of butadiene followed by styrene, diblock copolymers were obtained exclusively, which was confirmed by a kinetics investigation of monomer conversion of copolymerization with time.”

In the copolymers, the styrene incorporation rate varied from 4.7 to 85.4 mol%, whereas the polybutadiene (PBD) block was highly cis-1, 4-regulated (95%) and the polystyrene segment remained purely syndiotactic (rrrr>99%). Correspondingly, the copolymers exhibited glass transition temperatures (T_g) around -107℃，and melting points (T_m) around 268℃; typical values for diblock microstructures. Such copolymers cannot be accessed by any other methods known to date. X-ray powder diffraction analysis of these diblock copolymers showed that the crystallizable syndiotactic polystyrene (syn-PS) block was in the toluened δ clathrate form. The AFM micrographs of diblock copolymer showed remarkable phase-separation morphology of the cis-1, 4-PBD block and syn-PS block. This represents the first example of a lutetium-based catalyst showing both high activity and selectivity for the (co)polymerization of styrene and butadiene.

The project is supported by National Natural Science Foundation of China (51073148 and 20934006), The Ministry of Science and Technology of China (2005CB623802 and 2009AA03Z501). The findings have been published in Chem. Eur. J. 2010, 16, 14007 – 14015.