Study of the Propagation Center in the Anionic Polymerization of (Meth)acrylic Monomers:  NMR and MNDO Study of the Complexes of Di-tert-butyl 2-Lithio-2,4,4-trimethylglutarate and of the Living Poly(tert-butyl methacrylate) Oligomers with Lithium Chloride

Interactions of living oligomers of tert-butyl methacrylate (tBuMA) with a Li counterion and of the model living dimer di-tert-butyl 2-lithio-2,4,4-trimethylglutarate (A) with LiCl (B) were studied in tetrahydrofuran-d8 (THF-d8) solution by 7Li, 6Li, 1H, and 13C, 1D and 2D, NMR spectroscopy. Di-tert-butyl 2-lithio-2,4,4-trimethylglutarate is shown to form a 1:1 complex with lithium chloride in THF. 1H, 7Li NMR results suggest that a rapid equilibrium between free LiCl and the mixed complex takes place when the molar ratio LiCl:lithiated dimer is higher than 1. From 13C relaxation times, a dimeric aggregation (i.e. A2B2) of the complex is deduced, in full accord with MNDO calculations. Preliminary results are presented for living tBuMA oligomers prepared by initiation with diphenylhexyllithium in the presence of various amounts of lithium chloride. Fast-acquired 13C NMR spectra of the living ends were recorded using 13C-enriched monomer added at the end of the polymerization. Their structure is shown to be affected by the amount of LiCl added and to correspond to an equilibrium between free lithium chloride and a complexed end group. A higher excess of LiCl apparently does not change the nature of the complexed living end. The oligomers exhibit marked self-termination in THF at 273 K. Finally, a correlation of the structure of the living chain ends with the macromolecular parameters of the resulting polymer is attempted.