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Polymerization of 1,3-Butadiene with Catalysts Based on Cobalt Dichloride Complexes with Aminophosphines: Switching the Regioselectivity by Varying the MAO/Co Molar Ratio

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Abstract

Several novel cobalt dichloride complexes with amino-phosphine bidentate ligands were synthesized and characterized. For some of them single crystals were obtained and their molecular structure was determined by X-ray diffraction method. All the complexes were then used in combination with MAO for the polymerization of 1,3-butadiene, obtaining polymers with different structures (i.e., predominantly 1,2 or cis-1,4) mainly depending on the type of ligand and on the MAO/Co molar ratio. The behavior of these novel catalysts was compared with that exhibited, in the polymerization of the same monomer, by the systems CoCl2(PR3)2-MAO and CoCl2(PRPh2)2-MAO (R = alkyl or cycloalkyl group), and by the systems based on cobalt dichloride complexes with various bi- and tridentate ligands (e.g., diphosphines, bis-imines, pyridyl-imines, bis-iminopyridines). The comparison between the different systems allowed us to make some clarity about the actual and effective role played by the various types of ligands in the polymerization of conjugated dienes with catalytic systems CoCl2(L)-MAO, in which L = mono-, bi-, or tri-dentate ligand.

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Acknowledgments

We thank Mrs. Fulvia Greco and Mr. Daniele Piovani for their assistance in NMR and GPC analyses of the polymers, respectively. A.F. thanks Pietro Colombo for support in X-ray data collection.

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Authors and Affiliations

  1. CNR-Istituto di Scienze e Tecnologie Molecolari “Giulio Natta” (SCITEC), via A. Corti 12, 20133, Milano, Italy

    Giovanni Ricci

  2. Viale Giovanni XXIII 34, I-28100, Novara, NO, Italy

    Anna Sommazzi

  3. Via Galvani 7, I-26866, Sant’Angelo Lodigiano, LO, Italy

    Francesco Masi

  4. CNR-Istituto di Scienze e Tecnologie Molecolari “Giulio Natta” (SCITEC), via C. Golgi 19, 20133, Milano, Italy

    Alessandra Forni

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Correspondence to Giovanni Ricci.

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Polymerization of 1,3-Butadiene with Catalysts Based on Cobalt Dichloride Complexes with Aminophosphines: Switching the Regioselectivity by Varying the MAO/Co Molar Ratio

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Ricci, G., Sommazzi, A., Masi, F. et al. Polymerization of 1,3-Butadiene with Catalysts Based on Cobalt Dichloride Complexes with Aminophosphines: Switching the Regioselectivity by Varying the MAO/Co Molar Ratio. Chin J Polym Sci 42, 501–510 (2024). https://doi.org/10.1007/s10118-023-3060-x

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