Polysiloxanes, polymers and copolymers of various topologies having hydrophilic HO-QAS groups [HO(CH2)(2)]Me2+N(CH2)(3)- and [HO(CH2)(3)]Me2+N(CH2)(3)- at silicon atoms, are obtained by quaternization of corresponding hydroxyalkyldimethylamine by 3-chloropropyl or 3-bromopropyl groups attached to polysiloxane chains. Highly hydrophilic linear all-siloxane copolymers of various structures bearing the HO-QAS groups are generated. It was demonstrated by fluorescence spectroscopy using pyrene as static probe that the diblock copolymer of hydrophilic [HO(CH2)(2)]Me2+N(CH2)(3)SiMeO and hydrophobic Me2SiO forms micelle structure in water solution. The ability for the association of the macromolecules evidently depends upon the temperature. It was also shown that a segmental copolymer having a lower content of the hydrophilic functional units (19%), although itself insoluble in water was able to absorb over 1000 wt% of water. (C) 2004 Elsevier B.V. All rights reserved.