Polynorbornenes are ideal materials for systematic structure–property investigations designed to correlate gas-transport properties to polymer structure. The modular nature of norbornene-based systems provides a facile route towards the synthesis of diverse polymeric materials. Though many valuable correlations between gas-permeability and polynorbornene structure have been summarized in a prior review (2017), many of these efforts focused heavily on the design of materials with high permeabilities. More recently, the design of next-generation polynorbornene membranes has shifted toward the development of materials that are highly selective for multiple targeted gas separations. Since 2017, tremendous progress has been realized in the preparation of stable and highly selective polynorbornenes for membrane-based gas separations. Examples include polynorbornene derivatives that exhibit very high selectivity for CO₂/N₂ and light hydrocarbon (e.g., C₃₊/C₁) separations, some of which exhibit gas separation performances that approach or exceed the 2008 upper bound. Herein, we summarize prior findings, present recent developments in the field of advanced polynorbornene membrane materials for targeted gas separations, and provide an outlook for the future of this field of research.

The ability to control polymerizations via external stimuli has become a burgeoning field of research. Herein, we will demonstrate that polyethylene microstructure may be tailored via a redox-active olefin polymerization catalyst in conjunction with a photoreductant and visible light irradiation. The changes in polyethylene branching content are confirmed via¹H NMR analysis, gel permeation chromatography, and quantitative ¹³C NMR spectroscopy.