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Novel Polyimide Architectures: Towards Membranes with Tunable Transport Properties PhD Candidate: Zeljka Madzarevic Department: ASM Section: Novel Aerospace Materials Supervisor: Theo Dingemans Promoter: Theo Dingemans Start date: 01-10-2011 Funding: DPI Cooperations: MST group, UTwente Aerospace Engineering [1] 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). [2] Xiao, Y.T. et al. The strategies of molecular architecture and modification of polyimide-based membranes for CO 2 removal from natural gas — A review. Progress in Polymer Science 34, 561-580 (2009). [3] Simons, K. et al. CO 2 sorption and transport behavior of ODPA-based polyetherimide polymer films. Polymer 51, 3907-3917 (2010). Membrane technology has proven to be a highly energy efficient technology for the separation of CO 2 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 CO 2 /CH 4 ) and physical properties, such as high thermal stability, high chemical resistance, and mechanical strength. [1] Polyetherimide (PEI) films with ODPA dianhydride moiety (P1-ODPA) have shown high selectivities in experiments at elevated pressures with a 50/50% CO 2 /CH 4 feed gas mixture. [3] 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. The mixed gas permeation behaviour of P1-ODPA II membrane, using 50/50 CO 2 /CH 4 feed composition at 40 bar GPC results: Average Molecular Weight Table Thermal analysis results: DSC and TGA 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 para ortho meta P1 M1 O1 PMDA BTDA ODPA BPDA Selectivity of P1 based membranes Solution-diffusion mechanism Feed Permeate Retentate CO 2 Permeability of P1 based membranes a Compared to a polystyrene standard. b T g is reported at the inflection point, by DSC (second heat). c T m is reported as the peak temperature. d Degradation temperature. e T g is not visible in the DSC scan, to be determined by DMTA. Polymer MnaMna MwaMwa PDI=M w /M n P1-ODPA52,93098,6191.86 P1-BPDA102,261191,3691.87 P1-BTDA108,700211,7001.95 P1-PMDA108,500154,5001.43 M1-ODPA63,100151,5002.40 M1-BPDA58,700153,4002.62 M1-BTDA86,900168,8001.94 M1-PMDA69,300174,1002.51 O1-ODPA29,90053,9001.81 O1-BPDA27,80083,2002.99 O1-BTDA41,70091,0002.18 O1-PMDA45,800148,0073.24 PolymerT g ( o C) b T m ( o C) c 5% weight loss ( o C) d P1-ODPA 247.6 514.8 P1-BPDA 271.6457.2535.7 P1-BTDA 285.7 508.9 P1-PMDA -e-e 533.4 M1-ODPA 220.7 529.5 M1-BPDA 231.9393.7536.7 M1-BTDA 237.7341.8510.5 M1-PMDA -e-e 539.8 O1-ODPA 216.7 500.6 O1-BPDA 247.8 538.8 O1-BTDA 238.8 529.4 O1-PMDA -e-e 509.3
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