La. Pessan et al., GAS-TRANSPORT PROPERTIES OF POLYMERS BASED ON SPIROBIINDANE BISPHENOL, Journal of polymer science. Part B, Polymer physics, 33(3), 1995, pp. 487-494
Transport properties of pure gases in polycarbonates, polyesters, and
polyetherimides based on 6,6'-dihydroxy-3,3,3',3'-tetramethyl-1,1'-spi
ro biindane (SBI) and bisphenol-A (BPA) are compared at 35 degrees C.
The SBI monomer contains two spiro-linked five-membered rings which ar
e fused to the phenyl rings at the meta and para positions to the hydr
oxyl groups. This molecular structure gives SBI-based polymers with hi
gher fractional free volume (FFV) and lower intramolecular motions as
compared to the BPA-based analogs. The inhibition of chain packing due
to the SBI moiety yields polymers with much higher permeabilities for
all the gases studied, despite the hinderance of mobility associated
with the SBI structure. Simultaneous increase in selectivity was also
observed for some gas pairs. Oxygen permeabilities up to 5.9-fold high
er with increases of up to 13% in O-2/N-2 selectivities were observed
for a polyester based on SBI as compared to its analog based on BPA. H
igher permeabilities of up to 4.3-fold for He and up to 4.8-fold for C
O2 were observed due to the substitution of SBI for BPA. Not surprisin
gly, lower values of He/CH4 and CO2/CH4 selectivities were obtained fo
r the more open SBI-containing polymers. The changes in fractional fre
e volume and inhibition of small-scale mobility for some materials cau
sed by the SBI moiety were measured and used in the interpretation of
the gas transport properties. The individual contributions of diffusiv
ity and solubility to the overall transport behavior of the polymers a
re discussed and correlated to the structural alterations caused by th
e SBI substitution for BPA monomer. (C) 1995 John Wiley & Sons, Inc.