One-step preparation of flower-like poly(styrene-co-zwitterionic ionic liquid) microspheres with hierarchical structures for supported acidic heterogeneous catalysts

By using a one-step copolymerization of styrene (St) and 3-(1-vinyllimidazolium-3-yl)propane-1-sulfonate (VIPS), a kind of poly(St-co-VIPS) microsphere, with a hierarchical structure composed of nanospheres or nanoparticles with diameters in the range of 70–90 nm arranged on its surface and that look like a flower, has been simply prepared in the presence of polyvinyl pyrrolidone (PVP) in an aqueous alcohol system. A formation mechanism of the flower-like poly(St-co-VIPS) microspheres is proposed by investigating the influence of reaction conditions on its morphologies and observing its growth process with time. Because of the existence of zwitterionic liquid functional groups, flower-like poly(St-co-VIPS)-acid microspheres, a novel kind of heterogeneous catalyst, were successfully prepared by immobilizing heteropoly acids and H2SO4 on the flower-like poly(St-co-VIPS) microspheres, and the heterogeneous catalysts showed better catalytic activities for esterifications, acetalizations and transesterifications than with H2SO4 as the catalyst. Especially, the heterogeneous catalysts presented excellent catalytic efficiency for the acetalization of benzaldehyde and 1,2-propanediol, which could successfully reach 96.2%. Furthermore, the crosslinked flower-like poly(DVB-co-VIPS)–H2SO4 microspheres prepared under the same conditions where only St was replaced by divinyl benzene (DVB) have better reusability than that of the flower-like poly(St-co-VIPS)–H2SO4 with poor solvent resistance, and could be reused four times without significant loss of the catalytic activity, indicating that they could act as excellent recyclable heterogeneous catalysts for the synthesis of acetals and have potential application in industry.