NAMS 2002 Workshop - ICOM 2008

Gas Separation II – 5
Tuesday July 15, 4:30 PM-5:00 PM, Kaua’i
Addition-Type Polynorbornene with Si(CH3)3 Side Groups: Detailed Study
of Gas Permeation and Thermodynamic Properties
L. Starannikova, Institute of Petrochemical Synthesis, Russia - Luda@ips.ac.ru
M. Pilipenko, Institute of Petrochemical Synthesis, Russia - Luda@ips.ac.ru
N. Belov, Institute of Petrochemical Synthesis, Russia - belovna@gmail.ru
Y. Yampolskii (Speaker), Institute of Petrochemical Synthesis, Russia - Yampol@ips.ac.ru
M. Gringolts, Institute of Petrochemical Synthesis, Russia - gringol@ips.ac.ru
E. Finkelshtein, Institute of Petrochemical Synthesis, Russia - fin@ips.ac.ru
Polymerization of norbornene bearing Si(CH3)3 groups in the 5 position with the
opening of double bonds results in creation of a novel high free volume, highly
permeable polymer addition type poly(trimethylsilyl norbornene) (PTMSN). By
accurate selection of the ratios catalyst/co-catalyst and monomer/catalyst the
samples with increased molecular mass (about 400,000) and good film forming
properties can be obtained. Transport parameters of PTMSN were measured
using the gas chromatographic and mass spectrometric methods for different
gases (H2, He, O2, N2, CO2, CH4, C2H6, C3H8, n-C4H10). Temperature
dependence of the permeability coefficients (P) indicated that low activation
energies of permeation (EP) and diffusion (ED) are characteristic for PTMSN. In
some cases (CO2, C2H6) negative EP values were observed. Thermodynamics of
vapor sorption in this polymer was studied using the inverse gas chromatography
method. It was shown that PTMSN is characterized by very large solubility
coefficients S similar to those of poly(trimethylsilyl propyne) (PTMSP). The
comparison of the P, D, and S values of these highly permeable polymers
showed that the greater permeability of PTMSP is determined by the larger D
values. Application of different approaches for the determination of the size of
microcavities in PTMSN indicated that this polymer is characterized by large size
of microcavity (800- 1200 Angstroms 3 ). Possible applications of this novel
polymer as a material for gas separation membranes will be considered.