Use of poly(methyl methacrylate) with an unsaturated chain end as a macroinitiator precursor in organocatalyzed living radical block polymerization

Poly(methyl methacrylate) (PMMA) with an unsaturated chain end (PMMA–Y) was transformed into PMMA–iodide (PMMA–I) in situ in the organocatalyzed living radical polymerization of butyl acrylate; the generated PMMA–I acted as a macroinitiator to successfully generate a PMMA–PBA–I block copolymer, where PBA is poly(butyl acrylate). The use of PMMA–Y overcomes the drawback of the direct use of the isolated PMMA–I, i.e. its general lack of long-term stability upon storage, and thus significantly improves the ease of operation. This method is highly suitable for practical use. A quantitative mechanistic study on the transformation of PMMA–Y into PMMA–I was also conducted.