Metathesis-type poly-exo-tricyclononenes with fluoroorganic side substituents: Synthesis and gas-transport properties

• Published in: Polymer (Guilford) Vol. 153; pp. 626 - 636
• Main Authors: Karpov, G.O., Bermeshev, M.V., Borisov, I.L., Sterlin, S.R., Tyutyunov, A.A., Yevlampieva, N.P., Bulgakov, B.A., Volkov, V.V., Finkelshtein, E. Sh
• Format: Journal Article
• Language: English
• Published: Kidlington Elsevier Ltd 26.09.2018; Elsevier BV
• Subjects: Carbon dioxide; Chemical synthesis; Cycloaddition; Diffusion; Gas separation; Gases; High performance polymer membranes; Membrane gas separation; Metathesis; Molecular weight; Monomers; Permeability; Polymers; Polynorbornene; Polytricyclononene; Transport properties; Tricyclononene; Membrane gas separation; High performance polymer membranes; Tricyclononene; Polynorbornene; Metathesis; Polytricyclononene
• ISSN: 0032-3861; 1873-2291
• DOI: 10.1016/j.polymer.2018.08.055

The synthesis and gas-transport properties of new metathesis-type polynorbornenes bearing fluoroorganic side groups are reported. The necessary monomers, fluorosubstituted exo-norbornene derivatives (exo-tricyclononenes), were obtained using one-step method based on stereo- and regioselective [2 + 2+2]-cycloaddition of quadricyclane and fluoroalkenes. A set of high molecular weight polymers with different side groups were prepared from the synthesized F-substituted exo-tricyclononenes over the 1-st generation Grubbs catalyst. Permeability and diffusion coefficients of various gases (He, H2, O2, N2, CO2, CH4) in these poly-exo-tricyclononenes were determined for the first time and new relationships between polymer structure and gas permeability were established. Metathesis poly-exo-tricyclononene bearing four CF3-groups in each monomer unit displayed the highest gas permeability for the tested gases among metathesis polynorbornenes with F-organic substituents reported so far. [Display omitted] •Novel highly reactive fluoro-containing exo-tricyclononenes were synthesized via [2 + 2+2]-cycloaddition reaction.•A group of new metathesis polytricyclononenes bearing side fluoroorganic-substituents was prepared.•The obtained polymers possessed both the chemical and thermal stability.•The synthesized metathesis polytricyclononenes with fluorooganic-substituents exhibited the improved gas permeability.•New structure-property relationships for polynorbornenes were established.