Polyethylene-poly(methyl acrylate) Block Copolymers from PACE-SARA ATRP: Utilizing Polyolefin Active Ester Exchange-Based Macroinitiators in Atom Transfer Radical Polymerization

Accessing a facile pathway to prepare polyolefin-polar block copolymers with low dispersity and high control remains a challenge due to the distinct polymerization pathways of the composing blocks. This study utilized the polyolefin active ester exchange, the PACE approach, as a viable solution. The PACE approach, using palladium-catalyst-based coordination-insertion polymerization, was combined with SARA ATRP (supplemental activator/reducing agent atom transfer radical polymerization). A single-chain-end active ester functionalized polyethylene (PE) was produced from an α-diimine Pd(II) hexafluoroisopropyl ester chelate complex, which facilitated a living polymerization of ethylene. Transesterification with 2-hydroxyethyl α-bromoisobutyrate (HOBIB) or 2-hydroxyethyl α-bromoisobutyramide (HOBIBA) formed α-bromoisobutyrate or α-bromoisobutyramide chain-end-functionalized polyethylene. The approach resulted in controlled synthesis of polymers with low dispersity (Đ), high initiation efficiency, and high reproducibility. Both the amide-linked and ester-linked macroinitiators showed >90% initiation efficiency and Đ values of block copolymers as low as 1.05. This work demonstrated a successful combination of two living polymerization techniques, an insertion and controlled radical polymerization, unified in PACE-SARA ATRP, offering access to polyolefin-containing block copolymers with chemically distinct structures.