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.