Modifications of addition poly(5-vinyl-2-norbornene) and gas-transport properties of the obtained polymers

• Published in: Reactive & functional polymers 2020-04, Vol.149, p.104513, Article 104513
• Main Authors: Wozniak, Alyona I., Bermesheva, Evgeniya V., Andreyanov, Fedor A., Borisov, Ilya L., Zarezin, Danil P., Bakhtin, Danila S., Gavrilova, Natalia N., Ilyasov, Igor R., Nechaev, Mikhail S., Asachenko, Andrey F., Topchiy, Maxim A., Volkov, Alexey V., Finkelshtein, Eugene Sh, Ren, Xiang-Kui, Bermeshev, Maxim V.
• Format: Article
• Language: English
• Subjects: Addition polymerization; Carbon dioxide; CO2/N2-membrane; Diazomethane; Epoxidation; Gas permeability; Gas separation; Gas transport; Hydrogenation; Micro- and mesoporous materials; Norbornenes; Permeability; Polymerization; Polymers; Post-polymerization reactions; Selectivity; Transport properties
• ISSN: 1381-5148; 1873-166X
• DOI: 10.1016/j.reactfunctpolym.2020.104513

Herein four modified polymers were prepared from readily available addition poly(5-vinyl-2-norbornene) (PVNB) and their gas-transport properties were studied in detail. Hydrogenation, epoxidation, cyclopropanation and thiol-en reactions were chosen for the modifications of PVNB. Hydrogenation of PVNB was performed using p-toluenesulfonyl hydrazide. Epoxidation of PVNB was realized employing m-chloroperoxybenzoic acid. Cyclopropanation of PVNB was carried out using diazomethane in the presence of a Pd-catalyst. For thiol-en reaction, thioacetic acid was applied as the source of a thiol and AIBN as an initiator. All listed modifications were performed in high yields (≥80%) without the destruction of polymer main chains. The degree of functionalizations was up to 99%. The influence of these modifications on the properties of the resulting polymers was evaluated. Cyclopropanation and hydrogenation of PVNB led to an enhancement of gas permeability with minimal decrease in selectivity, while epoxidation or thioacetylation gave a substantial increase in CO2/N2 selectivity with decrease in permeability. The modified polymers with polar side-groups exhibited attractive selectivities for CO2/N2, CO2/CH4 and H2/N2 gas separations. [Display omitted] •Various functionalizations of addition poly(5-vinyl-2-norbornene) were performed.•The modifications were carried out in high yields without destruction of main chains.•Structure-property study of polynorbornenes for membrane gas separations.•Cyclopropanation and hydrogenation increase permeability with minimal decrease in selectivity.•Epoxidation or thioacetylation gave a substantial increase in CO2/N2 selectivity with decrease in permeability.