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 X_c,DSC = 72.9 % and linear crystallinity X_c,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.

建立理想的聚乙烯上部结构是开发高附加值产品的重要主题之一，这将为社会和可持续发展带来潜在利益。晶序是增强聚合物材料机械性能的普遍存在的上层结构。在这项工作中，聚苯乙烯共聚物（c -PS）通过苯乙烯和对-氯甲基苯乙烯的湿法浸渍过程掺入二氧化硅的孔中，然后进行原位自由基共聚。茂金属催化剂进一步固定在负载的二氧化硅上。这个合并的c事实证明，-PS被涂在二氧化硅孔壁的表面上，而不是阻塞颗粒间通道。孔内c -PS的溶胀行为通过脉冲场梯度NMR（PFG-NMR）和热孔隙率法（TPM-DSC）进行，其中由于c -PS之间的溶度参数匹配，因此在甲苯中显示出溶胀行为和甲苯。根据限制在孔中的c -PS的溶胀行为，形成了分隔，阻碍了链重叠的形成并增加了新生聚合物的结晶度。结果，具有高结晶度（即，本体结晶度X _c，DSC  = 72.9％和线性结晶度）的新生聚乙烯X _c，WAXD  ＝ 90.5％）被合成。在70°C下有相当大的活​​性（即3.8×10 ⁶ g PE·（molZr·h）^-1）。最后，基于c -PS的溶胀行为研究了新生聚乙烯的颗粒形态。