Complex formation in the model three‐component system, including polymer‐polymer complex of poly(styrene‐alt‐maleic acid) (PSMA) and poly(ethylene oxide) (PEO), and also silica sol (SiO2) in aqueous solution as a function of molecular weight of PEO and the order of component mixing, were investigated. The degree of binding of PSMA links with PEO and SiO2 as well as the Gibbs energy of formation of the polymer‐polymer complex and polymer‐colloid complexes were defined. It was shown that the main factor of stabilization of the structure is hydrogen bonds. The conditions of three‐component polymer‐colloid system are practically independent of the order of component mixing. The spontaneous formation of polymer‐colloid complexes between chemically complementary polymers and small dispersed particles is considered as the main reason for the abnormally high binding ability of colloid particles to the polymer‐polymer complex.
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