Gas transport properties of a series of highTg polynorbornenes with aliphatic pendant groups

Abstract

A study of gas transport properties of novel polynorbornenes with increasing length of an aliphatic pendant group R (CH3, CH3(CH2)3, CH3(CH2)5, CH3(CH2)9) has been performed. These polymers were synthesized using novel organometallic complex catalysts via an addition polymerization route. This reaction route maintained the bridged norbornene ring structure in the final polymer backbone. Gas permeability and glass transition temperature were found to be higher than those for polynorbornenes prepared by ring‐opening metathesis and reported in the literature. It was shown that for noncondensable gases such as H2 and He the selectivity over N2 decreased when the length of the pendant group increased, but remained relatively stable for the more condensable gases (O2 and CO2). The permeability coefficient is correlated well to the inverse of the fractional free volume of the polymers. The more condensable gases showed a deviation from this correlation for the longest pendant group, probably due to an increase of the solubility effect. This polymer series demonstrated a simultaneous increase in permeability and selectivity, uncommon for polymers. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 797–803, 1998

Structural characteristics and gas permeation properties of polynorbornenes with retained bicyclic structure

“…Recently, Dorkenoo et al [8] investigated the membrane permeabilities of a series of polynorbornenes with aliphatic pendent groups, namely methyl, butyl, hexyl and decyl, obtained by addition polymerisation. The values for O 2 and N 2 permeabilities were found to be quite high and ranged from 19 to 90 Barrer and from 7 to 24 Barrer, respectively.…”

“…This peculiar structural feature suggests many interesting properties. For example, these polynorbornenes exhibit much higher glass transition temperatures than those obtained by the ROMP route: the T g value for the addition type polynorbornenes is above 220ЊC [4,7] while the one for ROMP polynorbornenes is 30ЊC [8]. Additionally, unusual diffusion and barrier properties are observed, which are an important asset in polymer design for gas permeation membranes.…”

Synthesis and Properties of Addition-Type Poly(norbornene)s with Siloxane Substituents

“…[2][3][4][5][6][7][8][9][10][11][12][13] Heitz et al 2,3 investigated the addition-type copolymerizations of norbornene with norbornene carboxylic acid esters, and found that the solubility of the copolymers and the thermal properties, such as glasstransition and decomposition temperatures, were dependent on the content as well as structure of the substituents. Risse et al [4][5][6] came to the same conclusion by studying poly-(norbornene)s containing hydroxyl, carboxylic acid and ester.…”

“…Goodall et al [7][8][9] and Grove et al 10 prepared alkyl-or alkoxysilyl-substituted poly(norbornene)s, which showed improved mechanical toughness and adhesion to common substrate materials. On the other hand, Dorkenoo et al 11 and Finkelshtein et al 12 investigated the homopolymers of norbornene derivatives bearing alkyl or alkylsilyl substituents, and demonstrated that the chain length and the bulkiness of the substituents played a decisive role in the transport properties, such as gas permeability and permselectivity, for the polymeric membranes. These results show that the nature of substituent and the content in the main chain are an important factor for the regulation of the material properties.…”

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

“…A wealth of experimental work has been done focused on gas transport in membranes based on polynorbornenes [43][44][45][46][47][48][49][50][51][52][53]. 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.…”