Amphiphilic Molecular Brushes with Regular Polydimethylsiloxane Backbone and Poly-2-isopropyl-2-oxazoline Side Chains. 2. Self-Organization in Aqueous Solutions on Heating.

The behavior of amphiphilic molecular brushes in aqueous solutions on heating was studied by light scattering and turbidimetry. The main chain of the graft copolymers was polydimethylsiloxane, and the side chains were thermosensitive poly-2-isopropyl-2-oxazoline. The studied samples differed in the length of the grafted chains (polymerization degrees were 14 and 30) and, accordingly, in the molar fraction of the hydrophobic backbone. The grafting density of both samples was 0.6. At low temperatures, macromolecules and aggregates, which formed due to the interaction of main chains, were observed in solutions. At moderate temperatures, heating solutions of the sample with short side chains led to aggregation due to dehydration of poly-2-isopropyl-2-oxazoline and the formation of intermolecular hydrogen bonds. In the case of the brush with long grafted chains, dehydration caused the formation of intramolecular hydrogen bonds and the compaction of molecules and aggregates. The lower critical solution temperature for solutions of the sample with long side chains was higher than LCST for the sample with short side chains. It was shown that the molar fraction of the hydrophobic component and the intramolecular density are the important factors determining the LCST behavior of amphiphilic molecular brushes in aqueous solutions.