A novel series membranes based on non-linear all-aromatic polyimides (PIs) was investigated with the aim to understand how the PI backbone geometry and local electrostatics govern gas transport and the ability to separate CO₂/CH₄ mixtures. Non-linear 3-ring aromatic diamines, with exocyclic bond angles varying between 120 and 134°, enable the design of high Tg (>276 °C) PIs. A polar 1,3,4-oxadiazole diamine (ODD) (μ = 3D) monomer and a non-polar m-terphenyl diamine (TPD) reference monomer were synthesized and coupled with 3 dianhydrides, i.e. ODPA, ODDA, and 6FDA. In 6FDA-based membranes CO₂ permeabilities (P_CO2) are the highest of the series. The 6FDA-ODD membrane shows excellent membrane performance with high P_CO2 values at all feed pressures. Up to 12 bar (6 bar CO₂) none of the membranes reached their plasticization pressure. The non-linear backbone geometry promotes CO₂ permeability, whereas the presence of an electrostatic dipole moment associated with the 1,3,4-oxadiazole heterocycle governs CO₂/CH₄ separation selectivity.

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A homologous series of 12 all-aromatic PEI membranes was investigated with the aim to understand how subtle changes in the PEI main-chain affect the carbon dioxide/methane (CO2/CH4) gas separation performance. The 3-ring diamines selected for this study are either para-, meta- or ortho-aryloxy substituted with respect to the central benzene ring, i.e. 1,4-bis(4-aminophenoxy)benzene (P1), 1,3-bis(4-aminophenoxy)benzene (M1) and 1,2-bis(4-aminophenoxy)benzene (O1). Doing so changes the backbone geometry from a more linear to a more kinked conformation. In addition, four dianhydrides were selected with the aim to tailor the segmental mobility and hence the free volume of the PEIs, i.e. pyromellitic dianhydride (PMDA), 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA), 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA) and 3,3′,4,4′-oxydiphthalic dianhydride (ODPA). We have investigated how subtle changes in these prototypical PEIs affect membrane critical performance criteria such as CO2 permeability, CO2/CH4 selectivity and ability to withstand high operating pressures. In ODPA-based membranes the CO2 permeability decreases in the order P1 > O1 > M1 and remains steady throughout measurements with mixed feed pressures up to 40 bar, however, the selectivity decreases for ODPA-O1 and ODPA-M1. For high-pressure applications, the OPDA-P1 membrane is a good candidate with a selectivity of 48, permeability of CO2 of 0.74 Barrer and ability to resist plasticization up to 40 bar of total pressure (16 bar of CO2 partial pressure). Alternatively, for applications up to 10 bar of total mixed feed (5 bar of CO2 partial pressure), BPDA-O1 is a promising candidate because this membrane displays a high selectivity of 70 and permeability of 1.3 Barrer.@en

The reaction kinetics and structure property relationships of isomeric tri-aromatic ether-linked amines based on the structure bis (aminophenoxy) benzene, cured with diglycidyl ether of bisphenol F (BisF) are investigated in this study. Reaction kinetics are explored using rheological and calorimetric measurements, whereas structure property relationships are determined from their flexural properties, dynamic mechanical properties (DMTA), and thermogravimetric analysis (TGA). A BisF network cured with 4,4 diamino diphenyl sulphone (44 DDS) is used as a benchmark to represent a commercially available high-performance resin system. Varying the substitution of the ether linkages on the aromatic groups from ortho, meta to para was found to have a significant impact on reactivity and network properties after cure. The variations are explained in terms of inductive and resonance effects primarily acting on the outer aromatic rings. Interestingly, however, these same effects acting on the central aromatic ring also impact upon reactivity despite their proximity from the amines. Mechanical and thermal properties are explained by changes in the short-range molecular mobility within the network architecture such as phenylene rotations or π flips and are experimentally validated from the breadth and position of the subambient γ relaxations.@en

In order to characterize the free volume of a homologous series all-aromatic poly(ether imide) (PEI) membranes, two positron annihilation techniques were utilized: positron annihilation lifetime spectroscopy (PALS) and Doppler broadening (DB) of annihilation radiation. First, DB, which is a fast and convenient method, indicated differences in free volume of all PEIs investigated, whereas PALS experiments gave more quantitative information, with respect to the size and distribution of the voids. DB results show that S, W pairs for this PEI-series tend to group according to their dianhydride moiety, meaning that, in this series, dianhydrides govern the differences in the S parameter, indicating more free volume with increasing S value. The semicrystalline PEI samples exhibit the lowest S parameter, while the amorphous samples based on 3,3′,4,4′-oxydiphthalic dianhydride (ODPA) all lie on the higher S side of the S-W plot. With the 1,4-bis(4-aminophenoxy)benzene (P1)-based PEI (ODPA-P1) standing out with the highest S parameter. The same could be confirmed and quantified by PALS, where ODPA-P1 is the only membrane in this series with its free volume described by both smaller and larger free-volume elements. The larger voids in ODPA-P1 can be characterized as having a radius (R) of 3.3 Å, which is 5 times larger than the lowest measured free-volume content in this series observed for 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA) and 1,3-bis(4-aminophenoxy)benzene (M1)-based PEI (BPDA-M1), which has voids with a radius of R ≈ 0.7 Å. When comparing results obtained by DB and PALS, a very good correlation is observed between the S parameter (determined by DB) and the free-volume content (quantified by PALS).@en

Efficient and cost-effective technologies that will enable separation and capture of CO2 are needed. The development of high-performance all-aromatic poly(ether)imide (P(E)I) membranes is attractive as they offer a large degree of design freedom and they are cheap to operate. However, the molecular design rules towards P(E)I membranes that exhibit high selectivity and high permeability with no or little CO2 plasticization are still largely unknown. The main objective of the research presented in this thesis is to understand the structure-property relationships of all-aromatic polyimide- and polyetherimidebased gas separation (CO2/CH4) membranes. In particular, the role of backbone design and how this affects the free volume and gas separation performance of the final membranes.@en