Gas Transport in Polymers Prepared via Metathesis Copolymerization of exo-N-Phenyl-7-oxanorbornene-5,6-dicarboximide and Norbornene

Abstract

This work reports the synthesis of exo-N-phenyl-7-oxanorbornene-5,6-dicarboximide and its ring-opening metathesis copolymerization with norbornene to yield poly(exo-N-phenyl-7-oxanorbornene-5,6-dicarboximide-co-norbornene), with molar ratio 50/50. The glass transition temperature of the copolymer is 125°C. Permeation and sorption processes of different gases (hydrogen, nitrogen, oxygen, carbon monoxide, carbon dioxide, methane, ethylene, and ethane) were measured in membranes prepared by casting from solutions of the copolymer in chloroform. The Langmuir capacity of the gases is relatively small due to the nearness of the glass transition temperature of the polymer to the working temperature. The solution of the most condensable gases in the continuous phase of the membrane is apparently described by the Flory-Huggins theory of polymer-diluent mixtures. In general, the membranes exhibit a reasonably high separation coefficient of hydrogen with respect to ethane, ethylene, nitrogen, and methane. The value of R(O 2/N2) at room temperature lies in the vicinity of 5.

Gas Sorption in New Fluorine Containing Polynorbornenes with Imide Side Chain Groups

“…17,18 We have already reported gas transport results in polynorbornenes containing imide groups in their structure. 5,19 Permeation data in membranes prepared from these polymers show an enhancement of the selectivity, though the permeability remains low. The information at hand suggests that the presence of fluorine atoms in the structure of membranes of polynorbornenes enhances gas permeability across them.…”

Simulations of gas transport in membranes based on polynorbornenes functionalized with substituted imide side groups

“…These polymers can be prepared via ring-opening metathesis polymerization (ROMP) of bicycloolefins, the latter being synthesized by [4 + 2] cycloaddition of olefins to cyclopentadiene or to its derivatives. Tlenkopatchev et al [54][55][56][57] took advantage of the facile functionalization of norbornene monomers and high reactivity in ring-opening metathesis polymerization to extend gas transport studies to membranes cast from polynorbornenes functionalized with substituted imide side groups. Thus new high Tg polymers have been obtained by ring-opening metathesis polymerization of exo,endo-N-(1-R)-norbornene-5,6-dicarboximide using well-defined vinylidene ruthenium catalysts, where R can be phenyl, cyclohexyl, adamantyl groups, etc.…”

“…Thus new high Tg polymers have been obtained by ring-opening metathesis polymerization of exo,endo-N-(1-R)-norbornene-5,6-dicarboximide using well-defined vinylidene ruthenium catalysts, where R can be phenyl, cyclohexyl, adamantyl groups, etc. The gas transport characteristics of membranes prepared from homopolymers or copolymers with different R groups anchored to the imide group of the comonomers have been reported [54][55][56][57].…”

Polynorbornene Dicarboximides with Cyclic Pendant Groups: Synthesis and Gas Transport Properties

“…[7,8] The gas transport of polynorbornenes with lateral imide groups has been tested. [9][10][11] Membranes prepared from poly(N-cycloalkyl-(N-phenyl) norbornene-dicarboximide) exhibit a rather high permselectivity for the separation of hydrogen from nitrogen, carbon monoxide, methane, and ethylene. [9][10][11] These materials show good physical and mechanical properties, and they are soluble in common organic solvents, a fact that allows the preparation of thin polymer membranes that can be used for gas separation.…”

“…[9][10][11] Membranes prepared from poly(N-cycloalkyl-(N-phenyl) norbornene-dicarboximide) exhibit a rather high permselectivity for the separation of hydrogen from nitrogen, carbon monoxide, methane, and ethylene. [9][10][11] These materials show good physical and mechanical properties, and they are soluble in common organic solvents, a fact that allows the preparation of thin polymer membranes that can be used for gas separation. [12,13] The polynorbornenes are obtained via ring opening metathesis polymerization, ROMP, using Grubbs ruthenium alkylidenes of a new generation.…”