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Issue 7, 2019
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Group 4 permethylindenyl complexes for the polymerisation of L-, D- and rac-lactide monomers

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Abstract

A series of well-defined group 4 permethylindenyl complexes have been prepared and fully characterised by NMR spectroscopy and X-ray crystallography. Me2SB(Cp,I*)ZrCl2 ({(η5-C9Me6)Me2Si(η5-C5H4)}ZrCl2; 1), Me2SB(CpMe,I*)ZrCl2 ({(η5-C9Me6)Me2Si(η5-C5H3Me)}ZrCl2; 2), Me2SB(Cp,I*)HfCl2 (3) and Z-Me2SB(Cp,I*)ZrCl(O-2,6-Me-C6H3) (4) were investigated as initiators for the ring-opening polymerisation (ROP) of L-, D- and rac-lactide monomers in the presence of benzyl alcohol. 1–4 displayed second order dependence on monomer concentration and produced isotactic and heterotactic (Pr = 0.81) polylactides for the polymerisation of L-, D- and rac-lactide respectively. The effects of temperature, catalyst concentration, co-initiator concentration, solvent and scale were studied. At 80 °C, with two equivalents of benzyl alcohol, 4 was the most active initiator for the ROP of L-, D- and rac-lactide (kobs = 6.39, 6.38 and 5.89 M−1 h−1 respectively). The polylactides were characterised by NMR spectroscopy, GPC and MALDI-TOF mass spectrometry.

Graphical abstract: Group 4 permethylindenyl complexes for the polymerisation of l-, d- and rac-lactide monomers

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Publication details

The article was received on 18 Dec 2018, accepted on 23 Jan 2019 and first published on 24 Jan 2019


Article type: Paper
DOI: 10.1039/C8DT04986F
Dalton Trans., 2019,48, 2510-2520

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    Group 4 permethylindenyl complexes for the polymerisation of L-, D- and rac-lactide monomers

    J. V. Lamb, J. Buffet, J. E. Matley, C. M. R. Wright, Z. R. Turner and D. O'Hare, Dalton Trans., 2019, 48, 2510
    DOI: 10.1039/C8DT04986F

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