Graft polymerization of vinyl monomers from initiating groups introduced onto polymethylsiloxane-coated titanium dioxide modified with alcoholic hydroxyl groups

The grafting of vinyl polymers onto the surface of polymethylsiloxane-coated titanium dioxide modified with alcoholic hydroxyl groups (Ti/Si–R–OH) were investigated. The introduction of azo and trichloroacetyl groups onto the surface of Ti/Si–R–OH was achieved by the reaction of the surface alcoholic hydroxyl groups with 4,4′-azobis(4-cyanopentanoic acid) and trichloroacetyl isocyanate, respectively. The radical polymerizations of vinyl monomers were successfully initiated by the azo groups introduced onto the surface and by the system consisting of Mo(CO)₆ and Ti/Si–R–COCCl₃. During the polymerization, the corresponding polymers were effectively grafted onto the titanium dioxide surface through propagation from surface radicals formed by the decomposition of azo groups and by the reaction of Mo(CO)₆ with trichloroacetyl groups on the surface. The percentage of grafting and grafting efficiency in the graft polymerization initiated by the system consisting of Ti/Si–R–COCCl₃ and Mo(CO)₆ were much larger than those initiated by azo groups. The polymer-grafted titanium dioxide was found to produce a stable colloidal dispersion in good solvents for the grafted polymer. The dispersibility of poly(N,N-diethylacrylamide)-grafted titanium dioxide in water was controlled by temperature. In addition, the wettability of the surface of titanium dioxide to water was readily controlled by grafting of hydrophilic or hydrophobic polymers.