期刊
EUROPEAN POLYMER JOURNAL
卷 49, 期 12, 页码 4130-4140出版社
PERGAMON-ELSEVIER SCIENCE LTD
DOI: 10.1016/j.eurpolymj.2013.09.019
关键词
Stereospecific polymerization; Trans-polybutadiene; Styrene-butadiene copolymer; Rare earths; Microstructure; NMR
The combination of a neodymium borohydride, Nd(BH4)(3)(THF)(3) (1) or Cp *Nd(BH4)(2)(THF)(x) (2), with (MgBuEt)-Bu-n (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)1, 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. (C) 2013 Elsevier Ltd. All rights reserved.
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