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This paper describes the preparation of spheroidal polystyrene core and polyglycidol-rich microparticles by stretching the relevant core-shell microspheres embedded into the poly(vinyl alcohol) film. The requirements for the preparation of the defect-free core-shell spheroids were determined. The rearrangement of the microparticle interfacial layer accompanying the conversion of the microspheres into microspheroids is described.

Linear and hyperbranched polyglycidol (LPGL and HPGL) with average molecular weight of a few thousands were studied in water and surfactant solutions. The employed surfactants are hexaethyleneglycol mono n -dodecyl ether (C 12 E 6 ), cetyl trimethyl ammonium bromide (CTAB) and sodium dodecyl sulfate (SDS). The working methods are surface tension, steady-state fluorescence, dynamic light scattering (DLS), electrokinetic potential and FTIR spectroscopy. The linear polyglycidols are weakly associative species, unlike the hyperbranched one which is more hydrophilic and harder associates. The linear polymers most efficiently interact with the anionic surfactant, followed by cationic and most weakly with the nonionic. The hydrodynamic diameters of the investigated polyglycidols depend on their structure and molecular weight. In the presence of SDS, the hydrodynamic diameters vary with surfactant concentration. The study reveals the solubilization of fluorescent probes (pyrene, naphthalene) inside the polyglycidol aggregates. Unlike the LPGL, the presence of cavities in HPGL macromolecule offers supplementary “pockets” for solubilization.

In the batch emulsion copolymerization of styrene and α- tert -butoxy-ω-vinylbenzyl-polyglycidol macromonomer, carried out at macromonomer concentrations exceeding the critical micelle concentration ( c mc ), particles are formed by a two-step coagulative nucleation mechanism. This mechanism leaves its mark on morphology of particle interface, rate of polymerization and on molecular weight distribution of the obtained polymer. AFM studies revealed that the interface of particles is composed of objects with dimensions close to dimensions of the primary particles. Compartmentalization of styrene in the macromonomer micelles leads to the higher initial rate of styrene conversion than in the similar macromonomer free homopolymerization of styrene. The initial polymerization in the monomer-swollen macromonomer micelles, similar to the microemulsion polymerization, is responsible for the formation of the highest molecular weight component. In the mature particles there are two different polymerization loci: the interfacial layer and the core. This leads to bimodal molecular weight distribution of the formed polymer.

Emulsion copolymerization of hydrophilic α - tert -butoxy- ω -vinylbenzyl-polyglycidol macromonomer with styrene yields core–shell microspheres and a water-soluble copolymer fraction. This copolymer has a higher content of hydrophilic polyglycidol attested by 1 H NMR. Further information is acquired by labeling the copolymer with 5-(4,6-dichlorotriazinyl)aminofluorescein (DTAF) and making absorption and fluorescence studies. The acquired data on aqueous solution of labeled copolymer without (L) and with micelles of dodecyltrimethylammonium chloride (LD), sodium dodecylsulfate (LS) and hexaethyleneglycol mono n -dodecyl ether (LE) reveal that the dianionic and anionic tautomers of the DTAF-label are apparent and concordant with the recorded spectrophotometric p K a values. The emission intensities, quantum yields and lifetimes obey the sequence LE LS L LD . They are along with the increasingly deprotonated forms of the fluorophore and unveil that the micelle-label interactions depend on the surfactant.