The Synthesis And Functionalization Of Three-Dimensionally Ordered Macroporous Poly (Vinyl Aromatic Hydrocarbon)

In order to fabricate the three-dimensionally ordered macroporous(3DOM) polymer which is not only excellently resistant to water and other chemical agents, but also easy to functionalization. silica colloidal crystal templates with varied average sphere diameter (110nm-1100nm) were firstly synthesized by Stober-Fink-Hohn approach.By means of these silica templates with average diameter of 548, 340, 214, 114nm. respectively, 3DOM syndioatactic polystyrene(sPS), poly(p-methylstyrene) and styrene/p-methylstyrene syndiotactic copolymer were prepared using (dbm)2Ti(OPh)2/MAO catalytic system respectively. The resulting materials, bulk sample, polymer/silica composites and 3D0M polymer were characterized. Compared the properties of the bulk sample with composite and 3D0M materials, the impact of confined polymerization in the rigid silica template on the resulting polymer were investigated. The experiments indicated that the confined polymerization affected many properties of 3DOM polymers, such as melting temperature(Tm), glass transition temperature(Tg), crystalline form, crystallinity, conformation, molecular weight and molecular weight distribution. The effects were related with the category of polymer and the average diameter of silica templates. As for the results, no reports have been involved.In addition, using the silica template supported with methylaluminoxane(MAO)/metallocene catalystic system, 3DOM polyethylene(PE) was fabricated. The characterization results indicated that PE/SiO2 composite exhibited the lower Tm than that of bulk and 3 DOM PE, which was different from other polymers. The new way to prepare 3DOM polymer and the related results have few reported.To broad the scope of application of 3DOM polymer, the further experiment was designed to introduced the functional group (chloromethyl and dimethylamine group) onto the surface of 3DOM sPS. Thus the functionalized surface used in the catalytic field can be expected. In addition, the experimental results indicated that the functionalization reaction occurred at para-position of sPS and not destroyed the crystal area.