Heterogenization Strategies for Nickel Catalyzed Synthesis of Polyolefins and Composites

Conspectus Polyolefin is one of the most common synthetic polymers. However, most polyolefins are nonpolar materials, which leads to poor compatibility with polar materials, thus limiting their application in some fields. Polar functionalized polyolefins can lead to significantly improved dyeability, adhesiveness and compatibility with polar fillers, and can realize customized properties of polyolefin materials. Transition-metal-catalyzed coordination copolymerization of olefin and polar functionalized comonomers represents a direct and potentially economic route to synthesize polar-functionalized polyolefin materials, which has attracted great attention in recent decades. Literally hundreds of nickel and palladium catalysts have been synthesized and investigated in olefin-polar monomer copolymerization to achieve high copolymerization efficiency by tuning the molecular structures of the catalysts. In particular, earth-abundant and low-cost nickel-based catalysts hold great potential for industrial applications. However, most research efforts focus on homogeneous copolymerization catalysts, while the industrially preferred heterogeneous systems have remained largely unexplored. With the objective of bridging this gap, our group has recently developed a series of heterogenization strategies for the synthesis of high-performance heterogeneous nickel catalysts taking advantage of hydrogen bond anchoring, ionic anchoring, coanchoring, cocatalyst, and ionic cluster formation. These strategies involve known or easily accessible catalysts, can be easily adapted to various catalytic systems, and can lead to simultaneous enhancement in all copolymerization parameters such as thermal stability, activity, comonomer incorporation ratio, and copolymer molecular weight versus the homogeneous counterparts. In addition, the performance of the catalysts can be tuned by changing the type of the support, thereby facilitating the discovery of high-performance heterogeneous nickel catalysts. Most importantly, great product morphology control can be achieved. This is desirable for industrial polymerization processes because it avoids reactor fouling and results in significant improvements in the safety and operational efficiency of the polymerization processes. Finally, these heterogenization strategies give access to high-performance polyolefin materials (polar-functionalized polyolefins, polar-functionalized polyolefin in-reactor blends and polyolefin-based functional composites) with custom-made properties. Compared with melt blending, polyolefin composites obtained by heterogeneous catalytic in situ polymerization have better material properties. By using functional fillers, customized polyolefin composites with high performance can be prepared in situ. These polyolefin-based materials have potential applications in many fields, such as electrical and thermal conductivity, photodegradation, flame retardancy, barrier, etc. It is expected that the continuous research on the copolymerization mechanism/catalysts, heterogenizatioin strategies and material properties of polar functionalized polyolefins and their composites will eventually achieve commercialization of nickel-catalyzed production of polyolefins and composites.