Ionic Liquid-Modified Porous Organic Polymers as Efficient Metallocene Catalyst Supports

Abstract

Porous organic polymers (POPs) are widely used in various areas such as adsorption, separation and catalysis. In the present work, ionic liquid-modified porous organic polymers (IL-POPs) synthesized by dispersion polymerization were applied to immobilize metallocene catalysts for olefin polymerization. The prepared IL-POPs were characterized by Fourier transform infrared spectrometer (FT-IR), nitrogen sorption porosimetry, X-ray photoelectron spectroscopy (XPS), thermal gravimetric analysis (TGA), inductively coupled plasma atomic emission spectrometer (ICP) and scanning electron microscope (SEM) analysis. The IL-POPs obtained pores with surface specific area (SSA) ranging from 16.9 m2/g to 561.8 m2/g, and total pore volume (TPV) ranging from 0.08 cm3/g to 0.71 cm3/g. The supported catalysts Zr/MAO@IL-POPs exhibit great activity (3700 kg PE/mol·Zr·bar·h) in ethylene polymerization, and the GPC-IR results show that the polyethylene has narrow molecular weight distribution (2.2 to 2.8). The DSC results show that the melting point of prepared polyethylene was as high as 138 °C, and the TREF analysis results indicate that they have similar chemical composition distribution with elution temperature at 100.5–100.7 °C.

Porous Organic Polymers-Supported Zeigler-Natta Catalysts for Preparing Highly Isotactic Polypropylene with Broad Molecular Weight Distribution

“…The immobilization procedure of Ziegler–Natta catalysts was similar to our recent work [ 37 ], with some modifications. Using Schlenk techniques, 10 mL CH 3 MgCl (3M in THF solution) were added into a glass reactor containing 2.0 g POP support and 80 mL dry toluene.…”

“…In addition, the POP support with designed functional groups could tune effectively the micro-chemical environment of active sites when interacted with Mg and Ti compounds. A variety of functional monomers containing hydroxyl, chloromethyl, carboxylic acid and amino group, ionic liquid, etc., have been revealed in the synthesis of POP-based polyolefin catalysts [ 35 , 36 , 37 ]. The selected functional monomer(s) would have an important influence in both the particle-forming of POP support and the modulation of the chemical environment of metal active sites, which determines the microstructure of the produced polyolefins.…”

Electrochemical Formation of Ionic Porous Organic Polymers Based on Viologen for Electrochromic Applications

“…[14,15] DOI: 10.1002/marc.202400031 iPOPs are a new class of porous organic polymers in which the structure is connected by ionic and covalent bonds, in which the ionic fragments are not only attached to the pore walls but also embedded in the skeleton. [16,17] The inclusion of ions in iPOPs brings about a remarkable transformation of their structures and properties. The presence of a large number of ions in iPOPs, especially the apparent mutual repulsion of like-charged ions, significantly affects the structure of the polymers and their porosity.…”

Experimental nibble for computational chemists: On the construction and CO2 capture by different zeolite imidazole ester framework‐8 and ionic

“…The third type of PILs is a stable suspension obtained by dispersing advanced porous materials such as MOFs, COFs, MOPs, and zeolites in steric hindrance solvents. These three types have unique characteristics such as permanent pores, solvent‐free volatilization, strong regeneration ability, adjustable viscosity, low melting point, and high stability, which accelerate their development in fields such as CO 2 gas adsorption, separation, catalysis, and extraction [24].…”