Synthesis and characterization of dual responsive graft copolymers composed of casein and poly(N-isopropylacrylamide)

A series of novel temperature-and pH-responsive water-soluble graft copolymers, casein-g-poly(N-isopropylacrylamide)(PNIPAAm), were prepared via a direct graft copolymerization of N-Isopropylacrylamide (NIPAAm) from casein. The polymerization was induced by tert-butyl hydroperoxide (TBHP) in water at general condition. Chemical structures of the graft copolymers were characterized by Fourier transform infrared spectra (FTIR), Thermo gravimetric analysis (TGA) and differential scanning calorimetry (DSC). The effect elements on graft copolymerization, such as concentration of initiator, reaction time, reaction temperature and ratio of NIPAAm to casein were investigated in terms of NIPAAm conversion, grafting percentage (GP) and grafting efficiency (GE), respectively. The graft copolymers are stimuli-sensitive with respect to both temperature and pH in aqueous solutions. It could self-assembly into core-shell particles in aqueous solution with collapsed PNIPAAm as core as well as inverse core-hair particles with expanded casein as core on changing temperature or pH, as indicated by transmission electron microscopy (TEM).