First Synthesis of Poly(ethene-c o-1,3-butadiene) with Neodymocene Catalysts

The copolymerization of conjugated dienes and olefins is of particular importance but is considered very difficult because the two classes of monomers behave differently on polymerization catalysts. The most widely studied catalysts are vanadium- or titanium-based. Early studies showed that alternat...

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Bibliographic Details
Published in:Macromolecules 2000-11, Vol.33 (23), p.8521-8523
Main Authors: Barbotin, Fanny, Monteil, Vincent, Llauro, Marie-France, Boisson, Christophe, Spitz, Roger
Format: Article
Language:English
Subjects:
Applied sciences
Chemical Sciences
Copolymerization
Exact sciences and technology
Organic polymers
Physicochemistry of polymers
Preparation, kinetics, thermodynamics, mechanism and catalysts
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Summary:The copolymerization of conjugated dienes and olefins is of particular importance but is considered very difficult because the two classes of monomers behave differently on polymerization catalysts. The most widely studied catalysts are vanadium- or titanium-based. Early studies showed that alternating copolymers have been obtained at very low temperature. At higher temperatures, homogeneous vanadium or heterogeneous titanium systems have been reported to copolymerize dienes and olefins. However, in some recent patents, more efficient catalytic systems for conjugated diene-olefin copolymerization based on ansa-cyclopentadienyl-amido or phenoxy complexes have been reported. We report herein efficient catalysts based on nonbulky neodymocenes which can lead to butadiene-ethylene copolymers with up to 40 mol% of inserted butadiene. Recently, we developed a catalyst based on a neutral base-free neodymocene complex and an equimolar mixture of BuLi/( exp i Bu) sub 2 AlH as alkylating agent. This catalyst led to high and stable activity in ethylene polymerization. In this paper, we studied the ability of such ternary systems to copolymerize ethylene and butadiene. The experimental conditions and results are summarized.
ISSN:0024-9297
1520-5835
DOI:10.1021/ma0012043