Synthesis and Gas Permeability of Chemically Cross-Linked Polynorbornene Dicarboximides Bearing Fluorinated Moieties

This work reports on the synthesis of a novel bifunctional norbornene dicarboximide monomer (HFDA) based on 4,4′-(hexafluoroisopropylidene)bis(p-phenyleneoxy)dianiline and its application as a cross-linking agent in the ring-opening metathesis polymerization (ROMP) with N-3-trifluoromethylphenyl-exo,endo-norbornene-5,6-dicarboximide (mCF ) employing the Grubbs 2nd generation catalyst (I) and cis-1,4-diacetoxy-2-butene as a chain transfer agent (CTA) to yield a series of soluble nonlinear highly branched chains polymers with increasing degree of cross-linking. A comparative study of gas transport in membranes based on these cross-linked polynorbornene dicarboximides is performed and the gases studied are hydrogen, oxygen, nitrogen, carbon dioxide, methane, ethylene, and propylene. It is found that cross-linking increases the gas permeability, leads to the highest separation factor reported to date for the H /C H mixture in this kind of polymers, and also enhances the CO plasticization resistance up to 14 atm upstream pressure. The chemical cross-linking approach employed in this research is an effective tool to enhance gas transport properties for dense polynorbornene dicarboximide membranes.The authors thank CONACyT for the generous support with contract 239947. Financial support from DGAPA-UNAM PAPIIT through projects IA101817, IA101317, and MAT2016-81001-P from the Ministerio de Economía y Competitividad (MINECO) is gratefully acknowledged. The authors are grateful to Gerardo Cedillo Valverde, Karla Eriseth Reyes Morales, Adriana Tejeda Cruz, and Eliezer Hernández Mecinas for their assistance in NMR, thermal properties, X-ray diffraction measurements, and mechanical properties, respectively.Peer Reviewe