DOI: 10.1002/marc.202300675 ISSN: 1022-1336

Block Copolymers of Polyolefins with Polyacrylates: Analyzing And Improving The Blocking Efficiencies Using Milrad/ATRP Approach

Khidong Kim, Dee Nguyen, Jacobo Strong, Sajjad Dadashi‐Silab, Mingkang Sun, Huong Dau, Anthony Keyes, Rongguan Yin, Eva Harth, Krzysztof Matyjaszewski
  • Materials Chemistry
  • Polymers and Plastics
  • Organic Chemistry


Despite their industrial ubiquity, polyolefin‐polyacrylate block copolymers (BCPs) are challenging to synthesize due to the distinct polymerization pathways necessary for respective blocks. This study utilized MILRad, metal‐organic insertion light‐initiated radical polymerization, to synthesize polyolefin‐b‐poly(methyl acrylate) copolymer by combining palladium‐catalyzed[1] insertion‐coordination polymerization and atom transfer radical polymerization (ATRP). Brookhart‐type Pd complexes used for the living polymerization of olefins were homolytically cleaved by blue‐light irradiation, generating polyolefin‐based macroradicals, which were trapped with functional nitroxide derivatives forming ATRP macroinitiators. ATRP in the presence of Cu(0), i.e., supplemental activators and reducing agents (SARA ATRP), was used to polymerize methyl acrylate. An increase in the functionalization efficiency of up to 71% was demonstrated in this study by modifying the light source and optimizing the radical trapping condition. Regardless of the radical trapping efficiency, essentially quantitative chain extension of PO‐Br macroinitiator with acrylates was consistently demonstrated, indicating successful second block formation.

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