Synthesis of Poly(ethylene oxide-b-acrylonitrile) Block Copolymers with Higher Polyacrylonitrile Content Using Controlled Radical Polymerization Techniques

c2015 The Korean Fiber Society Abstract: Poly(ethylene oxide-b-acrylonitrile) (PEO-b-PAN) block copolymers were prepared as precursors to mesoporous carbons. Redox-initiated radical polymerization and controlled radical polymerization techniques, such as reversible addition-fragmentation chain transfer (RAFT) and activators regenerated by electron transfer atom-transfer radical polymerization (ARGET ATRP), were successfully applied to prepare PEO-b-PAN block copolymers with high PAN content. Radical polymerization of acrylonitrile (AN) using ceric ion as redox initiator gave block copolymers with PEO:PAN ratio of up to 1:38.4, but their high molecular weight and polydispersity index (PDI) indicated that the structure was not controlled. Therefore, in order to achieve better control on the structure of the PAN block, controlled radical polymerization techniques were used. Poly(ethylene oxide) with trithiocarbonate (PEO-CTA) and bromide (PEO-Br) end groups were synthesized as polymeric chain transfer agent for the RAFT process and as initiator for the ATRP process, respectively. The RAFT process of AN using PEO-CTA gave block copolymers with PAN block length 0.53–3.58 times that of the PEO block. Moreover, ARGET ATRP allowed to prepare block copolymers with a very high molecular weight of 72,000, while maintaining a PDI value as low as 1.20.

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