Synthesis and aggregate formation of poly(styrenesulfonate)-b-poly(ethylene glycol)-b-poly(styrenesulfonate) triblock copolymers in aqueous solution induced by binding with aluminum ions

Summary  Well-defined water-soluble poly(styrenesulfonate)-b-poly(ethylene glycol)-b- poly(styrenesulfonate) (PSS-b-PEG-b-PSS) triblock copolymers with narrow molecular weight distribution (1.29 < M_w/M_n < 1.36) were synthesized in aqueous solution at 70 ^oC via reversible addition-fragmentation chain transfer (RAFT) polymerization. The complex formed by the PSS-b-PEG-b-PSS triblock copolymer coordinated with aluminum ion was investigated with turbidimetry, dynamic light scattering (DSL), zeta-potential, and transmission electron microscopy (TEM). The aggregation formation was based on the neutralization of the SO₃^- groups in the PSS blocks with Al³⁺ ions. The appearance, size and stability of the PSS-b-PEG-b-PSS/Al³⁺ aggregates were controlled by varying the PSS block length and degree of neutralization (DN). At DN = 0.33, where the PSS-b-PEG-b-PSS copolymer was completely neutralized with Al³⁺, the aggregate size increased with increasing PSS block length. The transition from the shrinking coil of small size to the interchain aggregates of large size was found at DN of about 0.33.