High-speed organocatalytic polymerization of a renewable methylene butyrolactone by a phosphazene superbase

The organic phosphazene superbase, 1-tert-butyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamino) phosphoranylid-enamino]-2 lambda(5),4 lambda(5)-catenadi(phosphazene) (t-Bu-P-4), is found to directly initiate highspeed polymerization of the biomass-derived renewable gamma-methyl-alpha-methylene-gamma-butyrolactone (MMBL), in contrast to other polymerization systems using t-Bu-P-4 which typically require addition of an organic acid or a nucleophile as a co-initiating component. This MMBL polymerization by t-Bu-P-4 alone is extremely rapid; even with a low t-Bu-P-4 loading of 0.1 mol% or 0.02 mol%, quantitative monomer conversion is achieved in 20 s or 1 min, respectively, affording medium to high molecular weight PMMBL bioplastics in a catalytic fashion. The combined experimental and theoretical/computational studies have yielded mechanisms of chain initiation through abstraction of a proton from a monomer by t-Bu-P-4, essentially barrier-less chain propagation through rapid conjugate addition of the enolate anion stabilized by the nano-size cation [t-Bu-P4H](+) to the monomer, and chain termination through chain transfer to the monomer which generates a saturated termination chain end and the [t-Bu-P4H](+)-stabilized anionic active species that starts a new chain.