Description of raw and processed data accompanying "Tough Polycyclooctene Nanoporous Membranes from Etchable Block Copolymers" by Brenden D. Hoehn, Elizabeth A. Kellstedt, and Marc A. Hillmyer* *Corresponding author (e-mail: hillmyer@umn.edu) Suggested Dataset Citation: Hoehn, Brenden D; Kellstedt, Elizabeth A; Hillmyer, Marc A. (2023). Supporting data for Tough Polycyclooctene Nanoporous Membranes from Etchable Block Copolymers. Retrieved from the Data Repository for the University of Minnesota, https://doi.org/10.13020/xpma-vn76. Organization of raw data: Based on the test performed, raw and processed data related to this publication is provided in individual folders. Raw data are organized in folders entitled "Raw_TESTING METHOD". Processed data are organized in folders entitled "Worked_TESTING METHOD". A folder called "Figures" contains .tif files for all images included in the publication (including supplemental info). ChemDraw structures are included in the main folder in both Chemdraw file format and as a .tif file. A directory of the file structure is can be found a the bottom of this README. Software required: Microsoft Excel or an alternative program that can read .csv files is the only software required to analyze most raw data, with several exceptions. Raw nitrogen sorption data should be analyzed using ASiQwin software. Raw NMR data should be analyzed using MestReNova. Raw SAXS and WAXS data can be processed using various image processing programs (i.e. Datasqueeze). Several plots found in the worked data folders must be opened using Origin. Acronyms defined: PCOE - polycyclooctene PLA - polylactide LCL - PLA-block-PCOE-block-PLA DSC - differential scanning calorimetry IR - infrared spectroscopy NMR - nuclear magnetic resonance SEC - size exclusion chromatography SEM - scanning electron microscopy SAXS - small angle X-ray scattering WAXS - wide-angle X-ray scattering Data collection methodology (copied from main text and supplemental info): Nuclear magnetic resonance (NMR) was performed on either an AX-400 Bruker Avance III HD 400 MHz or HD-500 Bruker Avance III HD 500 MHz spectrometer. Samples were dissolved in CDCl3 and run at 298 Kelvin with relaxation delays between 10–12 seconds. Chemical shifts reported are relative to residual solvent peaks. Fourier-transform infrared (FT-IR) spectroscopy was performed using a Bruker Alpha-P ATR FT-IR spectrometer with a diamond crystal. Data was averaged over 64 scans collected using transmittance mode. Monomer conversion was determined using proton nuclear magnetic resonance (1H NMR) spectroscopy, where the integration of unreacted COE (m, δ = 5.55 ppm) was compared to the alkene signal present in each repeat unit (m, δ = 5.40 ppm). Assuming two hydroxyl groups per chain, end-group analysis was performed on purified PCOE samples to determine the number average molar mass (Mn). To identify samples, the Mn in kg/mol is included in brackets after the name (e.g., PCOE [49] has an Mn of 49 kg/mol). The integration of the protons on the methylene groups adjacent to terminal hydroxyl groups (q at δ = 3.66 ppm) was compared to the alkene signal in the repeat unit. The lactide conversion percentage was determined by comparing the integration of the PLA block methine proton (m, δ = 5.10–5.25 ppm) to residual D,L-lactide (q, δ = 4.77 ppm). The mass fraction of the PLA block (w_PLA) was determined by comparing the integration of the PCOE alkene protons to the PLA methine proton. Notation for triblock copolymer samples includes the molar mass of each block in kg/mol in brackets, e.g., LCL [24-49-24] comprises PLA end blocks of 24 kg/mol and a PCOE midblock of 49 kg/mol. The total molar mass of the triblock copolymer is determined by summing the molar masses of the end and midblocks. The PLA volume fraciton (f_PLA) was determined by dividing the PLA mass fraction by the density of PLA (density of 1.25 g/mL). Size exclusion chromatography (SEC) measurements were performed using an Agilent Infinity 1260 series HPLC system, using THF as the eluent at 25 °C with a 1 mL/min flow rate. The instrument was equipped with a Styragel HR column, a HELEOS II (Wyatt Technology) multi-angle light scattering detector, and an Optilab T-rEX refractive index detector (Wyatt Technology). Samples were prepared by dissolving 3-5 mg polymer sample in THF, then passing it through a 0.2 μm syringe filter. Weight average molar masses (Mw) were determined using light scattering and dispersities (Đ) were determined using differential refractive index. Previous studies report that the dn/dc values for hydroxyl telechelic PCOE and PLA in THF are 0.11 mL/g and 0.049 mL/g respectively. Weighted average dn/dc values were calculated for the LCL triblock copolymers, approximately 0.08 mL/g for all triblock copolymers in this study. Differential scanning calorimetry (DSC) was used to analyze PCOE and LCL polymer samples using a Discovery Series DSC 2500 (TA Instruments) differential scanning calorimeter. 2−8 mg of dried polymer sample were placed in Tzero aluminum pans that were hermetically sealed under air. Samples were heated to 120 °C, cooled down to -85 °C, and heated once more to 120 °C. The heating/cooling rate was 10 °C/min. Data was analyzed using Trios Software provided by TA Instruments. Small-angle X-ray scattering (SAXS) was performed at the DuPont-Northwestern-Dow Collaborative Access Team (DND-CAT) research center 5-ID-D beamline of the Advanced Photon Source at Argonne National Laboratory. Samples were sealed in DSC pans under nitrogen. A variable temperature SAXS analysis of a solvent cast, non-annealed LCL film was performed by taking an initial measurement at 25 °C, then heating the sample to 80 °C and annealing for 20 min. The sample was then cooled to 40 °C and allowed to anneal for 30 min before cooling back to 25 °C. A room-temperature SAXS analysis of nanoporous PCOE was also performed. PLA etched membranes were analyzed using scanning electron microscopy (SEM), using a Hitachi SU8230 Field Emission Gun under high vacuum with an acceleration voltage of 5 kV and current of 5 μA detecting secondary scattered electrons. Surface images were obtained by mounting membranes flat on the sample stage. Samples were prepared for cross-sectional imaging by immersing methanol-infused membranes in liquid nitrogen for 3 minutes, fracturing the membrane, drying under vacuum, and mounting vertically on the sample stage. All samples were sputter coated with 2 nm of platinum to avoid charge buildup. Nominal pore sizes were determined using ImageJ software to manually measure pores from cryo-fractured membranes, with 4 nm added to reported values to account for platinum deposition. Uniaxial tensile testing was performed to determine the stress–strain behavior and determine the toughness of the membranes. Triblock films were prepared from LCL [25-51-25] by melt pressing and solvent casting. After films were prepared, dog bone samples were prepared via die cutting and etched using the etching conditions described above. The tensile bars were 25 mm long, 3 mm wide in gauge region, and 0.1 mm thick. Tensile results are reported for n > 5 tensile bars tested. Tensile testing was performed by Shimadzu AGS-X 500N tensile tester with the accompanying Trapezium software. Contact angle measurements were performed by placing a single droplet (100 μL) of deionized water onto the membrane surface. A horizontal camera was used to obtain an image of the droplet and calculate the water contact angle. Water flux measurements were performed by placing pre-wet membranes in a cross-flow system with a flow rate of 300 mL/min at a pressure of 0.07 bar (10 psig). Gas flux measurements were performed by passing air through dry membranes at a pressure of 0.28 bar (4 psig). Flux results are reported as a mean followed by the range for n > 3 membranes in brackets (i.e., mean [minimum–maximum]) in units of L*m^2/hr/bar. Directory of files: | Chemdraw_scheme1_single.cdx | Chemdraw_scheme1_single.tif | README.txt | +---Figures | Figure_1.tif | Figure_2.tif | Figure_3.tif | Figure_4.tif | Figure_5.tif | Figure_6.tif | Figure_7.tif | Figure_8.tif | Figure_S1.tif | Figure_S10.tif | Figure_S11.tif | Figure_S2.tif | Figure_S3.tif | Figure_S4.tif | Figure_S5.tif | Figure_S6.tif | Figure_S7.tif | Figure_S8.tif | Figure_S9.tif | Figure_TOC.tif | scheme1_single.tif | Table_1.tif | +---Raw_Contact angle | LCL [25-51-25]_control_no plasma treatment_side image.bmp | LCL [25-51-25]_O2 plasma treatment_aged 20 minutes_side image.bmp | LCL [25-51-25]_O2 plasma treatment_aged 3 days_side image.bmp | LCL [25-51-25]_O2 plasma treatment_aged 5 days_side image.bmp | +---Raw_DSC | LCL [26-50-26].csv | LCL [26-50-26]_melt pressed_etched.xls | LCL [26-50-26]_solvent cast_annealed_etched.xls | LCL [26-50-26]_solvent cast_etched-2.xls | PCOE [50].csv | +---Raw_Flux | Air Flux_LCL [25-51-25]_plasma etched and no plasma.xlsx | Water flux_LCL [25-51-25]_no plasma 1.xlsx | Water flux_LCL [25-51-25]_no plasma 2.xlsx | Water flux_LCL [25-51-25]_no plasma 3.xlsx | Water flux_LCL [25-51-25]_plasma etched 1.xlsx | Water flux_LCL [25-51-25]_plasma etched 2.xlsx | Water flux_LCL [25-51-25]_plasma etched 3.xlsx | +---Raw_IR | LCL [26-50-26]_bottom.dpt | LCL [26-50-26]_Etched-bottom.dpt | LCL [26-50-26]_Etched-top.dpt | LCL [26-50-26]_top.dpt | +---Raw_Nitrogen Sorption | iq_phisy_st1_2023_08_17_15_56_08_LCL [25-51-25]_plasma etched.qps | iq_phisy_st2_2023_08_17_15_56_08_LCL [25-51-25]_no plasma.qps | +---Raw_NMR | +---LCL [25-49-25]_etched membrane | | \---10 | | | acqu | | | acqus | | | audita.txt | | | fid | | | format.temp | | | prosol_History | | | pulseprogram | | | scon2 | | | shimvalues | | | specpar | | | uxnmr.info | | | uxnmr.par | | | vtc_pid_settings | | | | | \---pdata | | \---1 | | outd | | proc | | procs | | title | | | +---LCL [25-49-25]_raw data | | \---10 | | | acqu | | | acqus | | | audita.txt | | | fid | | | format.temp | | | fq1list | | | precom.output | | | prosol_History | | | pulseprogram | | | scon2 | | | shimvalues | | | specpar | | | stanprogram23101 | | | uxnmr.info | | | uxnmr.par | | | vtc_pid_settings | | | | | \---pdata | | \---1 | | outd | | proc | | procs | | title | | | \---PCOE [49]_raw data | \---10 | | acqu | | acqus | | audita.txt | | fid | | format.temp | | prosol_History | | pulseprogram | | scon2 | | shimvalues | | specpar | | uxnmr.info | | uxnmr.par | | vtc_pid_settings | | | \---pdata | \---1 | outd | proc | procs | title | +---Raw_SAXS-WAXS | SAXS_LCL [26-55-26]_25C as cast.tif | SAXS_LCL [26-55-26]_25C_after heat-cool.tif | SAXS_LCL [26-55-26]_40C.tif | SAXS_LCL [26-55-26]_80C.tif | SAXS_LCL [28-49-28]_membrane_room temp.tif | WAXS_LCL [26-55-26]_25C as cast.tif | WAXS_LCL [26-55-26]_25C_after heat-cool.tif | WAXS_LCL [26-55-26]_40C.tif | WAXS_LCL [26-55-26]_80C.tif | +---Raw_SEC | LCL [26-50-26]_raw data.csv | LCL [26-50-26]_summary.pdf | PCOE [50]_raw data.csv | PCOE [50]_summary.pdf | +---Raw_SEM | LCL [24-49-24]_15k.tif | LCL [24-49-24]_15k_crack.tif | LCL [25-49-25]_18k.tif | LCL [25-51-25]_cross section_Plasma_8k.tif | LCL [25-51-25]_cross section_skin no plasma_8k.tif | LCL [25-51-25]_SC_ann_hydrolyzed_Plasma 30W_0 sec_18k.tif | LCL [25-51-25]_SC_ann_hydrolyzed_Plasma 30W_10 sec_25k.tif | LCL [25-51-25]_SC_ann_hydrolyzed_Plasma 30W_120 sec_25k.tif | LCL [25-51-25]_SC_ann_hydrolyzed_Plasma 30W_15 sec_25k.tif | LCL [25-51-25]_SC_ann_hydrolyzed_Plasma 30W_180 sec_25k.tif | LCL [25-51-25]_SC_ann_hydrolyzed_Plasma 30W_240 sec_25k.tif | LCL [25-51-25]_SC_ann_hydrolyzed_Plasma 30W_30 sec_25k.tif | LCL [25-51-25]_SC_ann_hydrolyzed_Plasma 30W_300 sec_25k.tif | LCL [25-51-25]_SC_ann_hydrolyzed_Plasma 30W_5 sec_25k.tif | LCL [25-51-25]_SC_ann_hydrolyzed_Plasma 30W_60 sec_25k.tif | LCL [25-51-25]_SC_ann_hydrolyzed_Plasma 30W_600 sec_15k.tif | LCL [25-51-25]_SC_ann_hydrolyzed_Plasma 38W_600 sec_25k.tif | LCL [26-50-26]_20k.tif | LCL [26-55-26]_8k.tif | LCL [28-49-28]_35k.tif | LCL [49-110-49]_22k.tif | +---Raw_Tensile | LCL [25-51-25] _Melt Pressed_NOT etched_stress-strain.csv | LCL [25-51-25]_Melt Pressed_ETCHED_stress-strain.csv | LCL [25-51-25]_solvent cast_annealed_ETCHED_stress-strain.csv | LCL [25-51-25]_solvent cast_annealed_NOT ETCHED_stress-strain.csv | LCL [25-51-25]_solvent cast_NOT annealed_ETCHED_stress-strain.csv | LCL [25-51-25]_solvent cast_NOT annealed_NOT etched_stress-strain.csv | +---Worked_Contact angle | LCL[25-51-25] membrane_control-no plasma treatment.csv | LCL[25-51-25] membrane_O2 plasma treated_30W_60 sec_aged 20 minute in air_0 ms and 1008 ms corrected.csv | LCL[25-51-25] membrane_O2 plasma treated_30W_60 sec_aged 3 days in air_0 ms and 1008 ms corrected.csv | LCL[25-51-25] membrane_O2 plasma treated_30W_60 sec_aged 5 days in air_0 ms and 1008 ms corrected.csv | +---Worked_DSC | LCL [26-50-26]_Etched triblock with different processing history_1st heat.opju | PCOE [50] and LCL [26-50-26].opju | +---Worked_Flux | Water flux_LCL [25-51-25]_plasma etched and no plasma.opju | +---Worked_IR | LCL [26-50-26]_triblock and etched membrane.opju | +---Worked_Nitrogen Sorption | LCL [25-51-25]_plasma etched and no plasma.opju | LCL [25-51-25]_plasma etched and no plasma.xlsx | +---Worked_NMR | PCOE [49] midblock_LCL [25-49-25] triblock_and etched membrane.mnova | +---Worked_SAXS-WAXS | LCL [26-55-26]_VT_SAXS_WAXS.opju | SAXS_LCL [26-55-26]_25C as cast.txt | SAXS_LCL [26-55-26]_25C_after heat-cool.txt | SAXS_LCL [26-55-26]_40C.txt | SAXS_LCL [26-55-26]_80C.txt | SAXS_LCL [28-49-28]_membrane_room temp.txt | WAXS_LCL [26-55-26]_25C as cast.txt | WAXS_LCL [26-55-26]_25C_after heat-cool.txt | WAXS_LCL [26-55-26]_40C.txt | WAXS_LCL [26-55-26]_80C.txt | +---Worked_SEC | PCOE [50] and LCL [26-50-26].opju | +---Worked_SEM | SEM pore size averages for PLA etched membranes.xlsx | SEM pore sizes for plasma treating membranes.xlsx | SEM pore sizes_LCL [25-51-25]_annealed and non annealed.xlsx | \---Worked_Tensile LCL [25-51-25]_ann_NOT ETCHED_summary.xlsx LCL [25-51-25]_Melt Pressed_ETCHED_summary.xlsx LCL [25-51-25]_Melt Pressed_NOT etched_summary.xlsx LCL [25-51-25]_solvent cast_annealed_ETCHED_summary.xlsx LCL [25-51-25]_solvent cast_annealed_NOT ETCHED_summary.xlsx LCL [25-51-25]_solvent cast_NOT annealed_ETCHED_summary.xlsx LCL [25-51-25]_solvent cast_NOT annealed_NOT etched_summary.xlsx LCL [25-51-25]_under different processing conditions.opju Tensile testing statistics for different processing conditions.xlsx End of README