Article Dans Une Revue Journal of Polymer Science Part A: Polymer Chemistry Année : 2010

Reversible coordinative chain transfer polymerization of styrene by rare earth borohydrides, chlorides/dialkylmagnesium systems

Résumé

The ability of various rare earth borohydride and chloride complexes/n-butylethylmagnesium systems to operate styrene chain transfer polymerization in mild conditions has been assessed. Thirteen precatalysts have been considered: the rare earth trisborohydrides Ln(BH4)3(THF)x (x = 3, Ln = Nd (1), La (2), Sm (3), x = 2, Ln = Y (4), Sc (5)), the rare earth chlorides LnCl3(THF)x (x = 3, Ln = Nd (6), La (7), Sm (8), Y (9), x = 2, Ln = Sc (10)), the mixed La(BH4)2Cl(THF)2.6 (11) and the half-lanthanidocenes Cp*Ln(BH4)2(THF)2 (Ln = Nd (12), La (13)). Six systems were found to be active precatalysts for the polymerization of styrene. 1, 2, and 11 led to an efficient transmetalation of the growing polystyrene chain with the simultaneous occurrence of βH elimination, whereas 7, 12, and 13 led to catalyzed chain growth behavior. It is noteworthy that the catalyzed chain growth obtained with 12 and 13 occurs with significant stereoselectivity.

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hal-02269380 , version 1 (08-04-2026)

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Philippe Zinck, Andreia Valente, Fanny Bonnet, Ana Violante, André Mortreux, et al.. Reversible coordinative chain transfer polymerization of styrene by rare earth borohydrides, chlorides/dialkylmagnesium systems. Journal of Polymer Science Part A: Polymer Chemistry, 2010, 48 (4), pp.802-814. ⟨10.1002/pola.23828⟩. ⟨hal-02269380⟩
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