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In order to prepare polyurethane–polysiloxane block copolymers, α,ω-hydroxyalkyl polysiloxanes with methacrylate side chain and α,ω-bis(2-methyl-3-hydroxypropyl)polymethyl(2-methyl-methylpropanoate) siloxanes, were synthesized and characterized in this study. The syntheses process included hydroxyl protection, hydrosilylation, deprotection, and ring-opening equilibrium reactions. The intermediates and target products were characterized by Fourier transform infrared spectroscopy and  1 H nuclear magnetic resonance methods. The characterization results showed that each step was successfully carried out in all the cases. Then the waterborne polyurethane–polysiloxane block copolymers were prepared via step-growth polymerization. The properties of the block copolymer films were characterized by thermal gravimetric analysis, differential scanning calorimetry, and dynamic thermomechanical analysis methods in detail. The experimental results showed that the block introduction of hydroxyalkyl polysiloxane could reduce the water absorption of waterborne polyurethane from 62 to 11%, and significantly improve the water resistance of polyurethane. With the introduction of polysiloxane, the tensile strength decreased and the elongation at break increased. At the same time, with the increase of the polysiloxane content, the glass transition temperature of the soft segment decreased to −56.4°C and the thermal decomposition temperature increased to 300°C. The results revealed that the introduction of polysiloxane could effectively improve the comprehensive performance of polyurethane–polysiloxane block copolymer films.

Synthesis and characterization of polyurethane–polysiloxane block copolymers modified by α,ω-hydroxyalkyl polysiloxanes with methacrylate side chain