Supporting information : 6FDA-polyimide thin-film composite hollow fiber membranes for hydrofluorocarbons and CO2 separations

TABLE OF CONTENTS S1 Materials and methods S1 S1.1 Materials S1 Table S1. Physical properties of F-gas R-32, R-134a, R-125 and R-1234yf, and the mixtures R-410A, R-454B and R-407C used in this work (𝑀: molar mass; 𝑃𝐶: critical pressure; 𝑇𝐶: critical temperature; 𝑉𝐶: critical volume; 𝑃𝑣: vapor pressure; GWP: global warming potential). S2 S1.2 Methods S4 S1.3 Synthesis of polyimides S5 S1.4 Gas permeability measurements S6 Fig. S1. Schematic representation of the continuous permeation setup. MFC- mass flow controller, MFG- mass flow gauge, PC- pressure controller. S6 S2 Characterization of polyimide membranes S7 S2.1 Nuclear magnetic resonance (NMR) S7 Fig. S2. 1H NMR of 6FDA-6FpDA polyimide in CDCl3. S7 Fig. S3. 19F NMR of 6FDA-6FpDA polyimide in CDCl3. S7 Fig. S4. 1H NMR of 6FDA-TMPD polyimide in CDCl3. S8 Fig. S5. 19F NMR of 6FDA-TMPD polyimide in CDCl3. S8 Fig. S6. 1H NMR of 6FDA-durene polyimide in CDCl3. S9 Fig. S7. 19F NMR of 6FDA-durene polyimide in DMSO-d6. S9 S2.2 Fourier-transform infrared spectroscopy -Attenuated total reflection (FTIR- ATR) S10 Fig. S8. FTIR of polyimide thick membranes. S10 S2.3 Morphology properties of polyimides S10 S2.3.1 Wide Angle X-ray Scattering (WAXS) S10 Fig. S9. WAXS of polyimide thick membranes. S11 S2.4 Thermal characterization S11 S2.4.1 Thermogravimetric analysis (TGA) S11 Fig. S10. TGA in N2 atmosphere of polyimide thick membranes. S12 S2.4.2 Differential scanning calorimetry (DSC) S12 Fig. S11. DSC of polyimide thick membranes. *𝑇𝑔 of 6FDA-durene film could not be detected in the range of measurements of the apparatus (<380 °C). S13 Table S2. Density, viscosity, FFV, and thermal properties. S14 S2.5 Mechanical properties of polyimide thick membranes S14 Table S3. Mechanical properties of polyimide thick membranes. S14 S3 Characterization of HF S14 Table S4. Physical properties PP hollow fibers support S14 Fig. S12. PP hollow fiber pore diameter distribution. S15 Fig. S13. Tailoring the influence of 6FDA-TMPD concentration in the polymer solution and the number of coating layers on the R-410A separation performance at 1.3 bar and 30 °C. S15 S4 Experimental results S16 S4.1 6FDA-based thick flat membranes S16 Table S5. Mixed-gas permeability data of (R-410A R-32/R-125, 69.7:30.3 vol%) through 6FDA-based thick flat membranes at 3 bar and 30 °C. S16 Table S6. Single gas permeability (𝑃) of R-125, R-1234yf, R-134a, and R-32 through 6FDA-TMPD thick flat membrane at 1.3 bar and 30 °C. S16 Table S7. Guggenheim, Anderson and de Boer (GAB) model parameters of R-32, R-134a, R-125 and R-1234yf in 6FDA-TMPD at 30 °C. S16 Fig. S14. Sorption isotherms of CO2, CH4 and N2 in 6FDA-TMPD at 30 °C. The dashed lines represent the dual mode-sorption (DMS) model results. S17 S4.2 6FDA-TMPD HF-TFCMs mixed-gas separation performance S17 Table S8. Mixed-gas permeance and CO2 separation factor data of CO2/CH4 (50:50 vol%) and CO2/N2 (15:85 vol%) through 6FDA-TMPD HF-TFCMs at 1.3 bar and 30 °C. S17 Table S9. Mixed-gas permeance and R-32 separation factor data of R-410A (R- 32/R-125, 69.7:30.3 vol%), R-454B (R-32/R-1234yf 82.9:17.1 vol%) and R-407C (R-32/R-134a/R-125 38.2:43.8:18 vol%) through 6FDA-TMPD HF-TFCMs at 1.3 bar and 30 °C. S18 Table S10. Mixed-gas permeance and R-32 separation factor data of R-410A (R- 32/R-125, 69.7:30.3 vol%) as a function of R-410A feed pressure through 6FDA- TMPD HF-TFCMs at 30 °C. S18 S5 Reference