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Tailored crystalline order of nascent polyethylene from metallocene supported on confined polystyrene

Wu, Yanjie; Yang, Huaqin; Li, Wei; Mattea, Carlos; Stapf, Siegfried; Zhang, Letian; Ye, Chunlin; Ye, Xiaofeng

Catalysis Today, 2019,



Building the desirable superstructure of polyethylene is one of the important topics for developing high value-added products, which brings potential benefits for society and sustainable development. Crystalline order is the ubiquitous superstructure for enhancing mechanical properties of polymeric materials. In this work, polystyrene copolymers (c-PS) are incorporated into pores of silica through the wet-impregnation procedure of styrene and p-chloromethyl styrene followed by the in-situ free-radical copolymerization. Metallocene catalyst is further immobilized on supported silica. This incorporated c-PS is proved to be coated on the surface of silica pore walls rather than blocking the interparticle channels. The swelling behavior of c-PS inside the pores are performed by pulsed field gradient NMR (PFG-NMR) and thermoporosimetry (TPM-DSC), where a swelling behavior is shown in the toluene owing to the matched solubility parameters between the c-PS and toluene. According to the swelling behavior of c-PS confined in the pores, a compartmentalization is created hindering the formation of chain overlaps and increasing the crystallinity order of nascent polymers. As a result, the nascent polyethylene with a high crystallinity (i.e., bulk crystallinity Xc,DSC?=?72.9 % and linear crystallinity Xc,WAXD?=?90.5 %) is synthesized. There is a considerable activity (i.e., 3.8?×?106 g PE·(molZr·h)?1) at 70?°C. Finally, the particle morphology of the nascent polyethylene is investigated based on the swelling behavior of c-PS.

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