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Issue 6, 2012
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New insights on Ni-based catalysts for stereospecific polymerization of butadiene

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Abstract

A new class of nickel catalysts for stereospecific polymerization of butadiene Ni(COD)2/[X][B(C6F5)4] (X = CPh3 or HNMe2Ph) was investigated and compared to the conventional ternary system Ni(O2CC7H15)2/BF3·OEt2/AlEt3. Both families of catalysts showed high activity and stereospecificity but catalysts based on the relatively non-coordinating anion B(C6F5)4 displayed lower molar masses. The combinations of Ni(O2CR)2 with AlEt3/[CPh3][B(C6F5)4] and of Ni(COD)2 with BF3·OEt2, [CPh3][B(C6F5)4]/BF3·OEt2 and AlEt3/BF3·OEt2 were also implemented. The polymerization tests using the resulting catalysts demonstrated that in the case of the industrial catalyst Ni(O2CR)2/BF3·OEt2/AlEt3, the formation of the active species is based on the reduction of Ni(O2CR)2 in the presence of AlEt3 followed by the re-oxidation of nickel(0) to nickel(II) by butadiene leading to the bis(allyl) complex Ni(C12H18). A cationic active species is finally obtained by the activation of Ni(C12H18) with a fluorinated compound formed by the reaction of BF3·OEt2 with AlEt3.

Graphical abstract: New insights on Ni-based catalysts for stereospecific polymerization of butadiene

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Publication details

The article was received on 07 Feb 2012, accepted on 16 Mar 2012 and first published on 12 Apr 2012


Article type: Paper
DOI: 10.1039/C2PY20063E
Citation: Polym. Chem., 2012,3, 1490-1494
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    New insights on Ni-based catalysts for stereospecific polymerization of butadiene

    F. Vaultier, V. Monteil, R. Spitz, J. Thuilliez and C. Boisson, Polym. Chem., 2012, 3, 1490
    DOI: 10.1039/C2PY20063E

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