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Porous organic polymers (POPs) have proven to be an efficient support in the olefin polymerization catalyst field. In this paper, nano TiO 2 beads were used to modulate the pore structure, bulk density, and surface morphology and flowability of the prepared POPs. With the incorporation of the hydrophilic nano TiO 2 beads, the prepared TiO 2 /POP supports obtained reasonable specific surface area (100-300 m 2 /g) and higher bulk density (0.26-0.35 g/mL) and flowability than the pure POP supports. The results show that bulk density of the prepared TiO 2 /POP particles increased when adding an increased amount of TiO 2 , and when 37.5% TiO 2 (weight percent to the total comonomers divinylbenzene (DVB) and 2-hydroxyethyl methacrylate (HEMA)) and 3:1 DVB/HEMA (molar ratio) were added, highly flowable TiO 2 /POP composites (POP-6 and POP-7) were obtained. With the modulation of the nano TiO 2 template during the support synthesis, the prepared POP-7 particles successfully achieved a normal distribution with a narrow particle size distribution (PSD) of 0.717 and average particle size of 24.1 m, a specific surface area (SSA) of 279 m 2 /g, and relatively high bulk density of 0.30 g/mL. Furthermore, all the prepared TiO 2 /POP supports obtained higher ethylene polymerization activity than silica gel-supported commercial metallocene catalyst. The immobilized (n-BuCp) 2 ZrCl 2 /MAO@POP-7 catalyst exhibited the highest ethylene polymerization activity of 4794 kg PE/mol Zr.bar.h and productivity of 389 g PE/g cat, more than twice that of the commercial counterpart. Even higher catalyst productivity (3197 g PE/g cat) and bulk density of the produced PE (0.36 g/mL) could be obtained in higher ethylene partial pressure at 80 ∘C for 2 h, and the prepared TiO 2 /POP catalyst shows no obvious Zr + active sites decay during the ethylene polymerization.

Highly Flowable Nano TiO2/Porous Organic Polymer (POP) Supports for Efficient Metallocene Catalysts