Influence of hydrophilic block length on the aggregation properties of polyglycidol-polystyrene-polyglycidol copolymers

Amphiphilic triblock copolymers, polyglycidol-polystyrene-polyglycidol (PGL-PS-PGL), were synthesised via anionic polymerization starting from the synthesis of a polystyrene macroinitiator with 60 styrene units in the block terminated by ethylene oxide. Poly(ethoxyethyl glycidyl ether) blocks of different lengths were created on both sides of the macroinitiator. By removing the ethoxyethyl blocking groups, PGL-PS-PGL copolymers containing polyglycidol blocks with DP 11, 23, 44 and 63 were received. Their structures were determined by NMR and FTIR. The hydrophilicity of PLG-PS-PGL films was studied upon exposure to water vapour. To perform the copolymers' aggregation in water, the samples were dialysed from DMF into water. The critical concentration of their micellisation (CMC) was determined by measuring the absorbance of the 1,6-diphenylhexa-1,3,5-triene (DPH) probe and the intensity of light scattered by the copolymers' solution as a function of concentration. CMC values increased with increasing the number of hydrophilic glycidol units in the copolymer chain. The sizes of aggregates formed slightly above the critical concentration were measured by dynamic light scattering (DLS), and particles were imaged by cryo-TEM. Cryo-TEM pictures showed the presence of regular micelles in copolymer dispersions. For copolymers with shorter PGL chains aggregated partices were detected. Moreover, cryo-TEM demonstrated that the copolymers with a polyglycidol block of DP = 63 formed regular spherical micelles that formed 2D ordered organisation on the surface. X-ray measurements showed the formation of a partially crystallised PS core in the micelle's interior. The aggregates of all copolymers were stable. Their sizes did not change after one year of storage. The particles did not disassociate even after diluting their dispersions to a concentration 10 times lower than the critical concentration. Aggregation of precisely synthesised polyglycidol-polystyrene-polyglycidol copolymers is presented. The relationship of CMC vs. composition of copolymers has been shown. π-stacking between benzene rings in micelles cores has been observed.