Well-defined Magnesium and Aluminum Initiators

The use of single-site initiators for the polymerization of acrylates is attractive, since steric protection of the metal center should eliminate the unwanted side reactions described above, allowing living polymerization systems to be developed. Further, stereocontrol may be achievable by appropriate ligand selection. 

The rate of polymerization may be dramatically accelerated upon addition of a bulky Lewis acid. For example, addition of (184) to a sample of living PMMA generated by irradiation of (181)/MMA causes an increase in polymerization rate by a factor of 45,000.444 The dualcomponent systems (181)/(184), and (181)/(185), have been used to prepare monodisperse, ultra-high-molecular-weight samples of PMMA (Mn 106, Mw/Mn= 1.2).445 

The thiolate species (182) and (183) do not require photo excitation in order to initiate polymerization (182) consumes 200 equivalents MMA in 18 h at 35 °C (Mn = 22,000, Mn(calc) = 20,000, Mw/ Mn= 1.12) 446 The propagating species is again believed to be an enolate.447 Propagation is accelerated upon addition of (185), with 100 equivalents of MMA requiring just 90 seconds for full conversion. The steric bulk of the Lewis acid prevents scrambling of the propagating enolate between the two aluminum centers.448 Hence, for aluminum diphenolates, ortho substitution is essential, whilst smaller Lewis acids such as Me3Al may only be used successfully at low temperatures, e.g., —40 °C. 

Complexes (181)-(183) may also be used to polymerize acrylates449 and methacrylonitrile450 in a living manner, although (181) again requires photoinitiation. Acrylates such as BuA polymerize faster than methacrylates. The rate of propagation of methacrylonitrile is much slower than methacrylates, although in the presence of (185), 100 equivalents are consumed within 3 hours. 

The well-defined single-site magnesium enolate initiator (187) initiates the living polymerization of MMA at -30 °C.452 Mw/Mn values are typically 1.07-1.11, and Mn increases linearly both with 

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