Synthesis of monodisperse crosslinked polystyrene microspheres

Monodisperse crosslinked polystyrene （CPS） particles were prepared through the normal emulsion polymerization method by adding crosslinker--divinylbenzene （DVB） into the reaction system after polystyrene （PS） particles grew to -80% of the final size. When the amount of crosslinker DVB added was less than 6.17 wt% based on styrene, the prepared CPS particles were spherical and uniform and the size of the CPS particles could be predicted through the normal emulsion method. The glass transition temperature （Tg） of the prepared CPS particles was higher than that of un-crosslinked PS particles and, the more crosslinker that was added, the higher the Tg of CPS Particles. The prepared CPS particles had strong resistance to organic solvents.

Synthesis of crosslinked polystyrene particles by seeded batch polymerization with monomer absorption

A highly crosslinked, monodispersed polystyrene（PS） particle was prepared by a seeded batch dispersion polymerization with a monomer absorption method. Prior to polymerization, 1,9 lam monodispersed PS seed particles were treated under an optimum condition of monomer absorption. The effects of divinylbenzebe（DVB） concentration and polymerization temperature were examined for styrene（in PS seed）/styrene（in the second stage） mass ratio of 1：1 in the medium range of EtOH/water mass ratio of 100/0-80/20 and 2.3 μm uniform crosslinked PS particles containing 15%-20% （mass fraction） DVB were prepared at 60-70 ℃. The results show that monomer absorption before the second stage of polymerization is more effective to prepare highly crosslinked monodispersed PS particles.

FLUORESCENCE STUDIES ON MORPHOLOGICAL CHANGE OF ST/DVB CROSSLINKED GELS DURING CHLOROMETHYLATION

The morphological change of St/DVB crosslinked gels during chloromethylation wasstudied by fluorescence spectroscopy using St/DVB crosslinked and hypercrosslinked gels as controlsamples. It has been found that with increase of chlorine content, the excimer emission band (~325nm)approaches to vanish, while the intensity of multi-ring aggregate emission band (~420nm) quicklyreaches a maximum, and then decreases sharply accompanied by appearance ofa new broad bandcentred at ca 488nm which roughly coincides with the typical emission band of hypercrossllinkedSt/DVB gels. Mearwhile, the result of IR measurement suggests that methylene bridge between phenylrings forms and increases with chloromethylation process. These results are explained in terms ofaside reaction of post-crosslinking, which densifies the loosely crosslinked networks and undoes thedensely entangled microgel nuclei. As a result, the morphology of the crosslinked gels becom es morehomogeneous with chloromethylation.

POLYMER-SUPPORTED GRIGNARD REAGENT AND ITS USE IN THE FUNCTIONALIZATION OF POLYMER

Polymeric Grignard Reagent (PGR) based on the chloromethylated poly(ST-co-DVB) resinhas been prepared by means of anthracene-magnesium complex in THF (Anth-Mg-THF), andpolymer matrix with long polymethylene spacer was synthesized via the coupling reaction betweenPGR and α, ω-dibromoalkanes. Based on the studies of factors affecting the coupling, such ascatalyst,reaction time,the length of spacer etc.,this paper offers the optimal reaction conditionsand three typical experiment procedures. The mechanism for the formation and coupling reactionof PGR are also discussed.

Chelating Properties of Salicylhydroxamic Acid-functionalized Polystyrene Resins and Its Application to Efficient Removal of Heavy Metal Ions from Aqueous Solutions

Salicylhydroxamic acid（SHA） was covalently bound onto crosslinked polystyrene spheres（CPSs） via the Friedel-Crafts alkylation reaction between chloromethylated CPSs and SHA in the presence of SnCI4 as the Lewis acid catalyst. The resulted SHA-CPSs possessed very strong chelating ability for heavy metal ions. In particular, the saturated adsorption amount of SHA-CPSs for Cu2＋ ions could reach as high as 34.2 mg/g at 318 K. The chelating capability of SHA-CPSs towards heavy metal ions was pH and temperature dependent. SHA-CPSs also showed se- lective metal coordination with the chelating capacity decreasing in the order of Cu2＋ 〉Zn2＋〉〉Pb2＋. The adsorption isotherms conformed well to the Langmuir model, and the adsorption process was found to be entropy-driven and endothermic. Besides, SHA-CPSs possessed the excellent reusability.

Immobilization of Transition-metal Hydroxamates on Polystyrene Resins： Effective Biomimetic Heterogeneous Catalysts for Aerobic Oxidation of Ethylbenzene

Salicylhydroxamic acid（SHA） was covalently grafted onto chloromethylated crosslinked polystyrene spheres（CMCPS） by the Friedel-Crafts alkylation reaction. The amount of SHA on CPS was found to be mainly dependent on the amount of Lewis acid（SnCl4） used and the reaction temperature. Under optimized conditions, the amount of SHA attached to CPS could reach up to 0.43 g/g CPS. Transition metal ions[Co（II）, Cu（II）, Fe（III） or Mn（II）] were then introduced into the resulting SHA-functionalized microspheres（SHA/CPS） through SHA-metal ion chelation. The obtained microspheres MSHA/CPS were explored as biomimetic catalysts for the aerobic oxidation of ethylbenzene（EB） to ethylbenzene hydroperoxide（EBHP）. Among the four supported metal catalysts, FeSHA/CPS showed the highest catalytic activity and good reusability, indicating its great potential as an effective heterogeneous catalyst for the aerobic oxidation of hydrocarbons under mild conditions.