Novel Polyimide Architectures:
Towards Membranes with
Tunable Transport Properties
PhD Candidate: Zeljka Madzarevic
Section: Novel Aerospace Materials
Supervisor: Theo Dingemans
Promoter: Theo Dingemans
Start date: 01-10-2011
Cooperations: MST group, UTwente
Membrane technology has proven to be a highly energy efficient technology for the separation of CO2 form natural gas in industrial applications.
Polyimides are attractive materials for gas separation owing to their excellent gas separation (high selectivity for gas pairs such as CO2/CH4) and
physical properties, such as high thermal stability, high chemical resistance, and mechanical strength. 
Polyetherimide (PEI) films with ODPA dianhydride moiety (P1-ODPA) have shown high selectivities in experiments at elevated pressures with a
50/50% CO2/CH4 feed gas mixture. Therefore a series of PEIs with slightly different moieties has been designed to be tested and compared to give
more information on the effects of molecular structure on their gas separation properties.
This is a homologous series, which will enable us to
investigate the role of polymer backbone composition
on gas transport behaviour The poly(amic acid)s were
prepared from dianhydride and diamine monomers in NMP
(10 or 15 wt.% solids) at room temperature,
filtered and thermally imidized
Average Molecular Weight Table
Thermal analysis results:
DSC and TGA
5% weight loss (oC)d
Compared to a polystyrene standard. b Tg is reported at the inflection point, by DSC (second heat). c Tm is reported as the peak temperature.
e T is not visible in the DSC scan, to be determined by DMTA.
CO2 Permeability of P1 based membranes
The mixed gas
of P1-ODPA II
50/50 CO2/CH4 feed
composition at 40 bar
Selectivity of P1 based membranes
 Cecopierigomez, M. et al. On the limits of gas separation in CO2/CH4, N2/CH4 and CO2/N2 binary mixtures using polyimide membranes. Journal of Membrane Science 293, 53-65 (2007).
 Xiao, Y.T. et al. The strategies of molecular architecture and modification of polyimide-based membranes for CO2 removal from natural gas — A review. Progress in Polymer Science 34, 561-580 (2009).
 Simons, K. et al. CO2 sorption and transport behavior of ODPA-based polyetherimide polymer films. Polymer 51, 3907-3917 (2010).