The heterogenization of homogeneous metal complexes on solid supports presents an efficient strategy for bridging homogeneous catalysts with industrially-preferred heterogeneous catalysts; however, a series of drawbacks restrict their implementation in olefin polymerization, particularly for copolymerization with polar comonomers. In this contribution, we report an ionic anchoring strategy that is highly versatile, generally applicable to different systems, and enables strong catalyst-support interactions while tolerating various polar functional groups. In addition to greatly enhanced polymerization properties, the supported catalysts achieved higher comonomer incorporation than their unsupported counterparts. This strategy enabled efficient polymerization at high temperatures at large scale and great control over product morphology, and the facile synthesis of polyolefin composites. More importantly, the dispersion of different fillers in the polyolefin matrix produced great material properties even at low composite loadings. It is expected that this strategy will find applications in different catalytic systems and the synthesis of advanced engineering materials.

Since polar groups can poison the metal centers in catalysts, the incorporation of polar comonomers usually comes at the expense of catalytic activity and polymer molecular weight. In this contribution, we demonstrate polar bimodal polyethylene as a potential solution to this trade-off. The more-polar/more-branched low-molecular-weight fraction provides polarity and processability, while the less-polar/less-branched high-molecular-weight fraction provides mechanical and melt properties. To achieve high miscibility between these two fractions, three synthetic routes are investigated: mixtures of homogeneous catalysts, separately supported heterogeneous catalysts, and a co-anchoring strategy (CAS) to heterogenize different homogeneous catalysts on one solid support. The CAS route is the only viable strategy for the synthesis of polar bimodal polyethylene with good molecular level entanglement and minimal phase separation. This produces polyolefin materials with excellent mechanical properties, surface/dyeing properties, gas barrier properties, as well as extrudability and 3D-printability.

Phosphine and pyridine groups have been widely employed in various olefin polymerization catalysts. In this contribution, these two moieties are connected using different bridges, and the properties of their corresponding palladium and nickel complexes are investigated. A series of CH2, NH and O bridged phosphine‐pyridine ligands (2‐(diarylphosphino)methyl‐pyridine, 2‐(diarylphosphino)amino‐pyridine, 2‐diarylphosphinito‐pyridine) are synthesized and characterized. For the CH2 bridged ligand, the introduction of a C6F5 substituent leads to the generation of a mixture of diastereomers, which can be separated by column chromatography. Starting with these five phosphine‐pyridine ligands, the corresponding palladium and nickel complexes are prepared and characterized. The bridging moiety (CH2, NH and O), the substituents on the bridge, and the ligand orientations significantly influence the properties of the metal complexes in ethylene oligomerization and cooligomerization reactions. For the palladium complexes, ethylene oligomerization and cooligomerization with some polar comonomers (methyl acrylate, butyl vinyl ether, vinyltrimethoxysilane, allyl acetate and allyl choride) can be realized. For the nickel complexes, ethylene oligomerization followed by Friedel‐Crafts addition of the resulting oligomers to toluene solvent leads to the formation of branched alkylated aromatic materials.

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