Toward an Efficient Process for the Cu(0)-Mediated Synthesis and Chain Extension of Poly(methyl acrylate) Macroinitiator Using PMDETA as Ligand

摘要

Me_6TREN (tris2-(dimethylamino)ethylamine) is commonly used in Cu(0)-mediated polymerization of acrylates due to its ability to promote high reaction rates while maintaining excellent control of chain growth.However, its cost presents a significant barrier to commercialization.Thus,the use of PMDETA (N,N,N',N'',N''-pentamethyldiethylenetriamine),a ligand that is significantly less expensive than Me_6TREN but is known to reduce the polymerization rate as well as control,is explored.The continuous production of low molecular weight (MW) poly(methyl acrylate) using PMDETA ligand in a copper tubular reactor is demonstrated,with conversions >70 achieved with a residence time of 32 min at 70 °C.The resulting macroinitiator solution can be stored and chain extended with methyl acrylate (MA) to high conversion in a semibatch reactor using either PMDETA or Me_6TREN as additional ligand,increasing the versatility of a newly developed process to efficiently produce block copolymers using either ligand,or a combination of the two.First results suggest that the two-step process can also be used to chain extend the macroinitiator with methacrylates,thus extending the range of materials that can be produced.