Xiao Yu, Dai Xiying, Wang Kui, Zhou Guangyuan
State Key Laboratory of Advanced Power Transmission Technology, Global Energy Interconnection Research Institute, No.18 Binhe Avenue, Changping District, Beijing, 102209, P. R. China.
Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry (CIAC), Chinese Academy of Sciences (CAS), No. 5625 Renmin Rd., Changchun, Jilin, 130022, P. R. China.
ChemistryOpen. 2020 Nov 12;9(11):1173-1180. doi: 10.1002/open.202000290. eCollection 2020 Nov.
In this work, different types of polyethylene (linear, spiral nanofibers and microspheres) were obtained via confined polymerization by a PPM-supported Ziegler-Natta catalyst. Firstly, the Ziegler-Natta catalyst was chemical bonded inside the porous polymer microspheres (PPMs) supports with different pore diameter and supports size through chemical reaction. Then slightly and highly confined polymerization occurred in the PPM-supported Ziegler-Natta catalysts. SEM results illustrated that the slightly confined polymerization was easy to obtain linear and spiral nanofibers, and the nanofibers were observed in polyethylene catalyzed by PPMs-1#/cat and PPMs-2#/cat with low pore diameter (about 23 nm). Furthermore, the highly confined polymerization produced polyethylene microspheres, which obtained through other PPM-supported Ziegler-Natta catalysts with high pore diameter. In addition, high second melting point (: up to 143.3 °C) is a unique property of the polyethylene obtained by the PPM-supported Ziegler-Natta catalyst after removing the residue through physical treatment. The high was ascribed to low surface free energy (), which was owing to the entanglement of polyethylene polymerized in the PPMs supports with interconnected multi-modal pore structure.
在这项工作中,通过由PPM负载的齐格勒-纳塔催化剂进行受限聚合获得了不同类型的聚乙烯(线性、螺旋纳米纤维和微球)。首先,通过化学反应将齐格勒-纳塔催化剂化学键合在具有不同孔径和载体尺寸的多孔聚合物微球(PPMs)载体内部。然后在PPM负载的齐格勒-纳塔催化剂中发生轻度和高度受限聚合。扫描电子显微镜(SEM)结果表明,轻度受限聚合易于获得线性和螺旋纳米纤维,并且在由低孔径(约23 nm)的PPMs-1#/cat和PPMs-2#/cat催化的聚乙烯中观察到了纳米纤维。此外,高度受限聚合产生了聚乙烯微球,其通过其他具有高孔径的PPM负载的齐格勒-纳塔催化剂获得。另外,通过物理处理去除残余物后,由PPM负载的齐格勒-纳塔催化剂获得的聚乙烯具有独特的高第二熔点(高达143.3 °C)。高熔点归因于低表面自由能(),这是由于在具有相互连接的多峰孔结构的PPMs载体中聚合的聚乙烯的缠结所致。