TY - JOUR
T1 - Understanding the Topology of the Polymer of Intrinsic Microporosity PIM-1
T2 - Cyclics, Tadpoles, and Network Structures and Their Impact on Membrane Performance
AU - Foster, Andrew
AU - Tamaddondar, Marzieh
AU - Luque-Alled, José
AU - Harrison, Wayne
AU - Li, Ze
AU - Gorgojo, Patricia
AU - Budd, Peter
PY - 2020/1/7
Y1 - 2020/1/7
N2 - The synthesis of PIM-1 is reported from step growth polymerizations of 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spirobisindane (TTSBI) with the commercially cheaper monomer, tetrachloroterephthalonitrile (TCTPN). Nitrogen purged polymerizations (100 - 160 C) were quenched after a monitored increase in viscosity. A combination of multiple detector SEC, NMR, MALDI TOF, DLS and elemental analysis was used to elucidate significant structural differences (cyclic, branched, tadpole, extended and network topologies) in the polymers produced under different conditions. A significant proportion of the apparent surface area (up to 200 m2 g-1) associated with PIM-1 can be attributable to whether its contorted polymer chains in fact link to form cyclic or other non-linear structures. Membranes cast from solutions of polymer samples containing higher branching and network content exhibited higher gas pair selectivities (CO2 / CH4 and CO2 / N2), above the Robeson 2008 upper bound. A toolbox approach to the characterization and production of topologically different PIM-1 samples has been developed which can be used to tune membrane performance for gas separation and other applications.
AB - The synthesis of PIM-1 is reported from step growth polymerizations of 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spirobisindane (TTSBI) with the commercially cheaper monomer, tetrachloroterephthalonitrile (TCTPN). Nitrogen purged polymerizations (100 - 160 C) were quenched after a monitored increase in viscosity. A combination of multiple detector SEC, NMR, MALDI TOF, DLS and elemental analysis was used to elucidate significant structural differences (cyclic, branched, tadpole, extended and network topologies) in the polymers produced under different conditions. A significant proportion of the apparent surface area (up to 200 m2 g-1) associated with PIM-1 can be attributable to whether its contorted polymer chains in fact link to form cyclic or other non-linear structures. Membranes cast from solutions of polymer samples containing higher branching and network content exhibited higher gas pair selectivities (CO2 / CH4 and CO2 / N2), above the Robeson 2008 upper bound. A toolbox approach to the characterization and production of topologically different PIM-1 samples has been developed which can be used to tune membrane performance for gas separation and other applications.
KW - polymers of intrinsic microporosity
KW - cyclic polymers
KW - tadpole polymers
KW - polymer topology
KW - gas separation membranes
KW - thin film composites
UR - http://www.scopus.com/inward/record.url?scp=85078401055&partnerID=8YFLogxK
U2 - 10.1021/acs.macromol.9b02185
DO - 10.1021/acs.macromol.9b02185
M3 - Article
SN - 0024-9297
VL - 53
SP - 569
EP - 583
JO - Macromolecules
JF - Macromolecules
ER -