Trans-stereospecific polymerization of butadiene and random copolymerization with styrene using borohydrido neodymium/magnesium dialkyl catalysts

Abstract : The combination of a neodymium borohydride, Nd(BH4)3(THF)3 (1) or Cp*Nd(BH4)2(THF)x (2), with MgnBuEt (BEM), affords an efficient and highly selective (up to 96.7% 1,4-trans) catalyst for butadiene polymerization. In the presence of excesses of Mg co-catalyst, polymer chain transfer takes place between neodymium and magnesium, and significant amounts of 1,2-units are observed. When considered for butadiene-styrene statistical copolymerization, the catalytic system based on 2 showed a good ability to produce poly[(1,4-trans-butadiene)-co-styrene)], with strong impact of the Mg/Nd ratio on the yield and on the copolymer microstructure, including the percentage of inserted styrene (up to 16.9 mol%). Whatever the co-monomers concentration the polybutadiene backbone remained 1,4-trans. The precise microstructure of the polymers and copolymers was thoroughly analyzed by means of high resolution NMR spectroscopy (900 MHz) and MALDI-ToF spectrometry.
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Submitted on : Wednesday, March 5, 2014 - 2:53:26 PM
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Aude Ventura, Thomas Chenal, Marc Bria, Fanny Bonnet, Philippe Zinck, et al.. Trans-stereospecific polymerization of butadiene and random copolymerization with styrene using borohydrido neodymium/magnesium dialkyl catalysts. European Polymer Journal, Elsevier, 2013, 49 (12), pp.4130-4140. ⟨10.1016/j.eurpolymj.2013.09.019⟩. ⟨hal-00950265⟩

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