Polyelectrolyte complexes of binary and ternary systems containing poly(sodium styrene sulfonate), poly(sodium styrene sulfonate), poly(sodium phosphate), and poly(N‐ethyl‐4‐vinylpyridinium bromide)

Polyelectrolyte complexes (PECs) were prepared by precipitation upon mixing solutions of poly(N‐ethyl‐4‐vinylpyridinium bromide), PVPE, and poly(sodium styrene sulfonate), PSS, and/or poly(sodium phosphate), PP. The chemical composition of the PECs was determined as a function of the initial polyelectrolyte (PE) concentration ratio. With binary systems water‐insoluble PECs being 1:1 stoichiometrically composed were formed in the case of the system PP/PVPE at ϕPP = [PP]0/ = 0.8 to 4.0. In the case of the system PSS / PVPE, water‐insoluble PECs were formed at all ϕPSS = [PVPE]0 ratios. Up to ϕPSS = 1.0 the PEC composition was stoichiometric. At ϕPSS = 1.0–8.0 non‐stoichiometric PECs containing surplus PSS were formed. With ternary systems, water‐insoluble PECs were formed regardless of the initial PE concentration ratio. The PEC composition was stoichiometric up to ϕPSS = 1.0, but preferntial binding of PSS became increasingly important with rising ϕPSS. At ϕPSS 2.5, PP was totally replaced by PSS and non‐stoichiometric PECs containing surplus PSS were formed.