Preparation of partly hydrophobized, crosslinked polyacrylamide particles by terpolymerization of acrylamide/ N,N-methylenebisacrylamide/styrene in inverse microemulsion

Free-radical polymerization of a termonomer system comprising acrylamide (AAm) N,N′-methylenebisacrylamide (MBAAm) and styrene (S) initiated by water-soluble ammonium peroxodisulphate (APS) or by toluene-soluble dibenzoyl peroxide (DBP) in inverse microemulsion (toluene/ S/AOT//water//AAm/MBAAm), leads to the formation of partly hydrophobized crosslinked polymer particles of tailored chemical composition, degree of crosslinking and polymer particle size. Styrene strongly decreases the rate of terpolymerization, while the presence of MBAAm has almost no effect on the polymerization rates observed. This conclusion is valid for both APS and DBP initiators. Increase of the S/T mass ratio (T is toluene) in inverse microemulsion leads to an increase of polymer particle diameter from about 20 nm to about 50 nm attributed to toluene swelling of the styrene-rich structural moieties of AAm-co-S copolymer located on the surface of polymer particles. Polymerization kinetics measurements pointed to the important role of exiting water soluble AAm and MBAAm monomer radicals generated by thermal decomposition of APS in water pools of inverse micelles for initiation of polymerization reactions of sparingly water-soluble S monomer in the oil-phase of the inverse microemulsion. It was shown that the polymerization and copolymerization reactions of S in the presence of AAm and/or MBAAm are effectively initiated by water-soluble APS and also by oil-soluble DBP initiators. During dialysis the polymerized single-phase water/oil Winsor IV inverse microemulsion gradually converts itself into a two-phase oil/water Winsor I dispersion system with volume fraction of aqueous phase Φ_aw≈0.950. The water phase contains water swelled, crosslinked polymer particles of diameters 80-300 nm. During dialysis, toluene and the sodium salt of bis(2-ethyl hexyl)sulphosuccinic acid (AOT) partition between the oil phase of the dialysed dispersion system and the water dialysate. After evaporation of water from the dialysed inverse microemulsion, solid, dried, crosslinked polymer particles in the form of a transparent film, almost uncontaminated by AOT surfactant, were obtained.