Enhancing CO2 Transport Across the PEG/PPG-Based Crosslinked Rubbery Polymer Membranes with a Sterically Bulky Carbazole-Based ROMP Comonomer.

A series of poly(ethylene glycol)-block-poly(propylene glycol) (PEG/PPG)- and 5,6-di(9H-carbazol-9-yl)isoindoline-1,3-dione (2CZPImide)-based crosslinked rubbery polymer membranes, denoted as PEG/PPG-2CZPImide (x:y), are prepared from the norbornene-functionalized PEG/PPG oligomer (NB-PEG/PPG-NB) and 2-(bicyclo[2.2.1]hept-5-en-2-ylmethyl)-5,6-di(9H-carbazol-9-yl)isoindoline-1,3-dione (2CZPImide-NB) via ring-opening metathesis polymerization (ROMP). The molar ratio (x:y) of the NB-PEG/PPG-NB (x) to 2CZPImide-NB (y) monomers is varied from 10:1 to 6:1. X-ray diffraction (XRD), scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS), and pure gas permeability studies reveal that the comonomer 2CZPImide-NB successfully increases the d-spacing among the crystalline PEG/PPG segments, hence enhancing the diffusivity of gases through the membranes. The synthesized membranes exhibit good CO2 separation performance, with CO2 permeabilities ranging from 311.1 to 418.1 Barrer and CO2/N2 and CO2/CH4 selectivities of 39.4-52.0 and 13.4-16.0, respectively, approaching the 2008 Robeson upper bound. Moreover, PEG/PPG-2CZPImide (6:1), displaying optimal CO2 permeability and CO2/N2 and CO2/CH4 selectivities, shows long-term stability against physical aging and plasticization resistance up to 20 days and 10 atm, respectively.

Developing Mixed Matrix Membranes with Good CO2 Separation Performance Based on PEG-Modified UiO-66 MOF and 6FDA-Durene Polyimide.

The use of mixed matrix membranes (MMMs) comprising metal-organic frameworks (MOFs) for the separation of CO2 from flue gas has gained recognition as an effective strategy for enhancing gas separation efficiency. When incorporating porous materials like MOFs into a polymeric matrix to create MMMs, the combined characteristics of each constituent typically manifest. Nevertheless, the inadequate dispersion of an inorganic MOF filler within an organic polymer matrix can compromise the compatibility between the filler and matrix. In this context, the aspiration is to develop an MMM that not only exhibits optimal interfacial compatibility between the polymer and filler but also delivers superior gas separation performance, specifically in the efficient extraction of CO2 from flue gas. In this study, we introduce a modification technique involving the grafting of poly(ethylene glycol) diglycidyl ether (PEGDE) onto a UiO-66-NH2 MOF filler (referred to as PEG-MOF), aimed at enhancing its compatibility with the 6FDA-durene matrix. Moreover, the inherent CO2-philic nature of PEGDE is anticipated to enhance the selectivity of CO2 over N2 and CH4. The resultant MMM, incorporating 10 wt% of PEG-MOF loading, exhibits a CO2 permeability of 1671.00 Barrer and a CO2/CH4 selectivity of 22.40. Notably, these values surpass the upper bound reported by Robeson in 2008.