Journal of Materials Science and Engineering with Advanced TechnologyAuthor's: JOEL VARGAS, ARLETTE A. SANTIAGO, JAVIER CRUZ-GÓMEZ, JORGE A. CRUZ-MORALES, MIKHAIL A. TLENKOPATCHEV, MARÃA I. LORÃA-BASTARRACHEA, JOSÉ LUIS SANTIAGO-GARCÃA and MANUEL AGUILAR-VEGA
Pages: [107] - [133]
Received Date: March 12, 2012
Submitted by:
The N-2,2,6,6-tetramethylpiperidyl-norbornene-5,6-dicarboximide
(2a), N-4-hydroxy-phenyl-norbornene-5,6-dicarboximide
(2b), and N-pentafluorophenyl-norbornene- 5,6
-dicarboximide (2c) mixtures of exo and endo
monomers were synthesized and polymerized via ring opening metathesis
polymerization (ROMP) using bis(tricyclohexylphosphine) benzylidene
ruthenium (IV) dichloride (I) and tricyclohexylphosphine
[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene]
[benzylidene] ruthenium dichloride (II) to produce the
corresponding polynorbornene dicarboximides PTMPiNDI,
PHPhNDI, and PPFPhNDI, respectively. The transport of
five gases He, 
and 
across membranes prepared from these
polynorbornenes were determined at 35°C by using a constant volume
permeation cell. Gas permeability, diffusion, and solubility
coefficients of PTMPiNDI classify it as a low permeability
polymer for oxygen and carbon dioxide with possibilities of use in
packaging applications. It was also found that gas permeation is lower
in PTMPiNDI due to a lower fractional free volume (FFV), which
difficulties the diffusion through it as compared to PHPhNDI
and PPFPhNDI that present more open structures. The
permeability coefficients for all gases in the fluorine-containing
PPFPhNDI membrane are much more larger than those in the
non-fluorinated PHPhNDI and PTMPiNDI membranes. The
sorption process and not the diffusive step is responsible for this
increase in the permeability of the PPFPhNDI membrane. A
molecular dynamics simulation of each polynorbornene was performed to
estimate the density value. The results are in good agreement with the
experimentally measured densities and allow to corroborate FFV
determinations.
gas permeation, polynorbornene dicarboximide, ring-opening metathesis polymerization.
