This readme.txt file was generated on 2024-07-16 by Michaela R. Pfau-Cloud Recommended citation for the data: Pfau-Cloud, Michaela R.; Batiste, Derek C.; Kim, Hee Joong; Ellison, Christopher J.; Hillmyer, Marc A. (2024). Supporting data for Alkyl Substituted Polycaprolactone Poly(Urethane-Urea)s as Mechanically-Competitive and Chemically-Recyclable Materials. Retrieved from the Data Repository for the University of Minnesota. ------------------- GENERAL INFORMATION ------------------- Title of Dataset: Supporting Data for Alkyl Substituted Polycaprolactone Poly(Urethane-Urea)s as Mechanically-Competitive and Chemically-Recyclable Materials. Author Information: Principal Investigator Contact Information Name: Marc A. Hillmyer Institution: University of Minnesota Address: Department of Chemistry, 207 Pleasant St SE, Minneapolis, MN 55455 Email: hillmyer@umn.edu Associate or Co-investigator Contact Information Name: Michaela R. Pfau-Cloud Institution: University of Minnesota Address: Department of Chemistry, 207 Pleasant St SE, Minneapolis, MN 55455 Email: pfau0019@umn.edu Associate or Co-investigator Contact Information Name: Derek C. Batiste Institution: University of Minnesota Address: Department of Chemistry, 207 Pleasant St SE, Minneapolis, MN 55455 Email: bati0016@umn.edu Associate or Co-investigator Contact Information Name: Hee Joong Kim Institution: University of Minnesota Address: Department of Chemical Engineering and Materials Science, 421 Washington Ave SE, Minneapolis, MN 55455 Email: kim00244@umn.edu Associate or Co-investigator Contact Information Name: Christopher J. Ellison Institution: University of Minnesota Address: Department of Chemical Engineering and Materials Science, 421 Washington Ave SE, Minneapolis, MN 55455 Email: cellison@umn.edu Date of data collection March 2021-August 2023 Geographic location of data collection: University of Minnesota (Minneapolis, MN) Brookhaven National Laboratory (Upton, NY) University of Georgia- New Materials Institute Analytical Services (Athens, GA) ioKinetic, LLC (Salem, NH) Information about funding sources that supported the collection of the data: Department of Energy Bio-Optimized Technologies to keep Thermoplastics out of Landfills and the Environment, DE-EE0002245. National Science Foundation Center for Sustainable Polymers, CHE-1901635. Contract for x-ray scattering beamline time at Brookhaven National Laboratory, DE-SC0012704. -------------------------- SHARING/ACCESS INFORMATION -------------------------- 1. Licenses/restrictions placed on the data:CC0 2. Links to publications that cite or use the data: 3. Was data derived from another source? No If yes, list source(s): 4. Terms of Use: Data Repository for the U of Minnesota (DRUM) By using these files, users agree to the Terms of Use. https://conservancy.umn.edu/pages/policies/#drum-terms-of-use --------------------- DATA & FILE OVERVIEW --------------------- Purpose Statement: This document describes raw data in the manuscript "Alkyl Substituted Polycaprolactone Poly(Urethane-Urea)s as Mechanically-Competitive and Chemically-Recyclable Materials" General Notes: The data is organized into five main folders corresponding to sections in the associated manuscript with titles given to reflect the contents. A ChemDraw file and corresponding image file are included for the scheme in the manuscript as a .cdxml and .tif file respectively. All raw data was converted and compiled into .xlsx Excel files for simplicity. Several raw images were also included of experimental set-ups as .jpg files. Acronyms Defined: 4MCL- 4-methylcaprolactone 4PrCL- 4-propylcaprolactone P4MCL- poly(4-methylcaprolactone) PMCL- poly(methylcaprolactone) P4PrCL- poly(4-propylcaprolactone_ PCL- polycaprolactone TPUU- thermoplastic poly(urethane-urea) HS- hard segment TPU- thermoplastic polyurethane 1,4BDO- 1,4-butanediol SnOct2- stannous octoate DMP- dimethyl phosphate DPP- diphenyl phosphate HCl- hydrochloric acid Mn- number average molar mass Me- molar mass of entanglement Tc- ceiling temperature TTS- time-temperature superposition WLF- Williams-Landel-Ferry NMR- proton nuclear magnetic resonance spectroscopy GC- gas chromatography MS- mass spectroscopy IR- infrared spectroscopy SEC- size exclusion chromatography TGA- thermal gravimetric analysis DSC- differential scanning calorimetry DMTA- dynamic mechanical thermal analysis SAXS- small angle x-ray scattering WAXS- wide angle x-ray scattering Polyol naming conventions are as followed: polymer identity-molar mass-functionality For example the "P4MCL-5k-diol" is a 5 kg/mol poly(4-methylcaprolactone) with two hydroxyl groups TPUU naming conventions are as follows: polyol-molar mass of polyol-hard segment weight % For example the "P4MCL-5k-29HS" is a TPUU prepared with a 5 kg/mol P4MCL polyol with 29% by weight hard segment content -------------------------- METHODOLOGICAL INFORMATION -------------------------- Data collection methodology (copied from the manuscript supporting info document): Proton nuclear magnetic resonance (1H NMR) spectra were collected on a Bruker Avance III 500 spectrometer operating at 500 MHz. Chemical shifts were referenced to tetramethylsilane as an internal standard. Attenuated total reflectance, Fourier transform infrared (ATR-FTIR) spectroscopy was performed on a Bruker Alpha Platinum or Thermo Scientific Nicolet iS50 with a single reflection diamond ATR head. Spectra were obtained from 400 to 4000 cm-1 using a minimum of 16 scans. Differential scanning calorimetry (DSC) was performed on a TA Instruments Q-1000. Experiments were performed with hermetically sealed aluminum pans. The Tg was estimated as the midpoint of the thermal transition in the curve of the second heating ramp at 10 °C/min for the prepolymers and 20 °C/min for the TPUUs, which was calculated using the Trios software. Thermogravimetric analysis (TGA) was performed on a TA Instruments Q500 Analyzer at 10 °C min-1 to 550 °C under nitrogen atmosphere. Mass-average molar mass (Mw), number-average molar mass (Mn), and molar mass dispersity (Ð) of the P4MCL, PMCL, P4PrCL, and PCL telechelic diols was measured using an Agilent 1100 series liquid chromatography instrument equipped with three Phenomenex Phenogel-5 columns aligned in series with THF as the mobile phase (1.0 mL/min, 25 °C). A Wyatt Technology DAWN DSP MALLS detector and a Wyatt optlab EX RI detector were used to collect the chromatograms. Mw, Mn, and Ð of the prepared TPUUs was measured using a Tosoh EcoSEC HLC-8420GPC equipped with two TSKgel GMHHR-M columns with hexafluoroispropanol (HFIP) as the mobile phase (0.35 mL/min, 40 °C). A Tosoh RI detector was used to collect the chromatograms and were analyzed using a universal calibration curve prepared with poly(methyl methacrylate) standards. Tensile testing was performed on a Shimadzu Autograph AGS-X series instrument. Uniaxial extension and hysteresis experiments were performed at room temperature with dog bone-shaped specimens [ca. 0.5 mm (T) x 1.5 mm (W) x 12 mm (G)]. Pneumatic grips equipped with a small piece of sandpaper were used with a grip pressure ~100 psi. The test speed for all experiments was set to a strain rate of 50 mm min-1. Data was analyzed using Trapezium software. The extension to break tests were performed with at least 5 replicates per sample and the values reported are averages and standard deviations for each set. The Young’s modulus was calculated by taking the slope of the stress-strain curve from 0-5% strain. For hysteresis testing, one dog bone specimen from each sample was subjected to cyclical loading (50% strain) and unloading for 10 cycles. The hysteresis energy loss per cycle was calculated by subtracting the area of the unloading curve from that of the loading curve, whereas the tensile set per cycle was determined from the residual strain present when the unloading cycle reached zero stress. Dynamic mechanical thermal analysis (DMTA) was performed using a TA Instruments RSA-G2 analyzer with dog bone-shaped specimens [ca. 0.5 mm (T) x 1.5 mm (W) x 12 mm (G)] in a tensile geometry. Liquid nitrogen was used to cool the sample to –90 °C and the axial force was continuously adjusted to 10.00 N (sensitivity 2.0 N) while the sample was cooling. After equilibration, the axial force was adjusted to 2.00 N of tension (sensitivity 0.20 N) to ensure no buckling of the sample. The proportional force mode was set to force tracking to maintain an axial force that was at least 100% greater than the dynamic oscillatory force. The strain adjust was set to 30% with minimum and maximum strain values of 0.05% and 10% and minimum and maximum forces of 0.01 N and 0.2 N, respectively; these settings prevented the sample from going outside the specified strain range. The sample was then heated from –90 °C at a rate of 5 °C min-1 with an angular frequency of 6.28 rad s-1 (1 Hz). To determine an appropriate oscillatory strain setting, an oscillatory amplitude test was performed to determine an oscillating strain in the linear regime of the storage modulus (E’) and producing an oscillatory force between 10-50 g. The Tg was determined using the maximum value in the loss modulus (E”). Synchrotron X-ray scattering data were acquired from the 11-BM Complex Materials Scattering endstation at the National Synchrotron Light Source-II (NSLS-II; Brookhaven, NY) using a photon wavelength of λ = 0.7293 Å (17 keV beam energy) and DECTRIS Pilatus area detectors (2M for SAXS, 800K for WAXS). The 2D detector images were either directly analyzed or azimuthally integrated to produce 1D patterns of intensity I(q) versus scattering wavevector magnitude q = |q| = 4πλ-1 sin(θ/2). Static room temperature images were collected from film samples mounted upright on Kapton tape using three-second exposures. Gas chromatography-mass spectroscopy (GC-MS) was performed on pure and recycled monomers using an Agilent 6890N Network GC system equipped with a 7683 series injector autosampler and an Agilent 5975 MS detector equipped with an HP-5 column (0.25 μm film thickness, 30 m long, 0.32 mm inner diameter). The method used an initial setpoint of 50 °C followed by a 20 °C/min ramp to 320 °C. Dynamic mechanical analysis frequency sweeps of P4PrCL (Mn = 128 kg/mol) using shear rheology was performed at various temperatures within the linear viscoelastic regime in order to determine molar mass of entanglement (Me). Horizontal shift factors (aT) were determined by aligning the loss tangent curves and were applied to each frequency sweep to generate a master time-temperature superposition curve. The fit of the time-temperature superposition curve was evaluated by fitting the horizontal shift factors to the Williams-Landel-Ferry (WLF) equation. The master curve was then used to determine the plateau modulus (GN) defined as the point where the loss tangent (tan δ) was at a minimum and Me was calculated using the following equation: M_e=ρRT/G_N where ρ is the polymer density, R is us the universal gas constant, and T is the reference temperature. The density of the P4PrCL polymer was determined using a Metler-Toledo density kit attached to an XP/XS analytical balance. The following equation was used to determine the polymer density: ρ=A/(A-B) (ρ_0-ρ_L )+ ρ_L where A is the weight of the polymer in air, B is the weight of the polymer in the auxillary liquid, ρ0 is the density of the auxillary liquid, and ρL is the air density (0.0012 g/mL). DI water was used as the auxillary liquid and the temperature was determined to be 22.6 °C; a density table indicated ρ0 = 0.99766 g/mL. The polymer was manually balled up into small beads and measurements were taken ten times to determine an average P4PrCL density (ρ = 1.005 ± 0.008 g/mL). People involved with sample collection, processing, analysis and/or submission: Michaela R. Pfau-Cloud Derek C. Batiste Hee Joong Kim ----------------------------------------- DATA TREE ----------------------------------------- | Scheme1.cdxml | Scheme1.tif +---RAW_P4PrCL_Kinetics_and_Me | Kinetics_Summary.xlsx | Kinetics_SnOct2_130C_NMR.xlsx | Kinetics_SnOct2_180C_10k_NMR.xlsx | Kinetics_SnOct2_180C_100k_NMR.xlsx | Kinetics_SnOct2_180C_100k_SEC.xlsx | Kinetics_DMP_5k_NMR.xlsx | Kinetics_DMP_10k_NMR.xlsx | Kinetics_DPP_NMR.xlsx | Kinetics_HCl_NMR.xlsx | Molar_mass_of_entanglement_TTS_WLF.xlsx | P4PrCL_polymer_density_pycnometer.xlsx | High_Mn_P4PrCL_for_Me_SEC_NMR | +---RAW_Polyol_Characterization | Polyol_NMR.xlsx | Polyol_SEC.xlsx | Polyol_TGA.xlsx | Polyol_DSC.xls +---RAW_TPUU_Characterization | TPUU_Reaction_Conditions_ExcessH2O_Solvent_SEC_DSC.xlsx | TPUU_IR.xlsx | TPUU_SEC.xlsx | TPUU_TGA.xlsx | TPUU_DSC.xlsx | TPUU_DMTA.xlsx | TPUU_SAXS.xlsx | TPUU_WAXS.xlsx | Polyol-1k-28HS_Tensile_Prop.xlsx | Polyol-1k-45HS_Tensile_Prop.xlsx | Polyol-2k-18HS_Tensile_Prop.xlsx | Polyol-2k-31HS_Tensile_Prop.xlsx | Polyol-5k-29HS_Tensile_Prop.xlsx | Elastollan_Tensile_Prop.xlsx | Polyol-1k-28HS_Hysteresis.xlsx | Polyol-1k-45HS_Hysteresis.xlsx | Polyol-2k-18HS_Hysteresis.xlsx | Polyol-2k-31HS_Hysteresis.xlsx | Polyol-5k-29HS_Hysteresis.xlsx | Elastollan_Hysteresis.xlsx | Comparison_to_14BDO_TPU_IR_SEC_Tensile.xlsx | P4MCL-2k-31HS_TPUU.jpg | P4MCL_2k-22HS_14BDO_TPU.jpg | Proof_of_concept_P4MCL_PU_thermoset_DMTA_Tensile.xlsx +---RAW_Chemical_Recycling | Composting_Study.xlsx | Catalyst_Screening_TGA.xlsx | Reactive_Distillation_SnOct2_Vigreux.jpg | Reactive_Distillation_SnOct2_Vigreux_heat_tape.jpg | TPUU_film_scraps.jpg | Recovered_monomer.jpg | Short_path_reactive_distillation.jpg | Chemical_recycling_summary_yield_data.xlsx | Synthesized_versus_recycled_monomer_NMR.xlsx | Synthesized_versus_recycled_monomer_GC.xlsx | Recycled_monomers_MS.xlsx | Repolymerized_TPUUs_SEC.xlsx | Repolymerized_TPUUs_tensile.xlsx | Repolymerized_TPUUs_hysteresis.xlsx +---RAW_Thermodynamics | P4MCL_Heat_of_Combustion_Report.pdf | P4PrCL_Heat_of_Combustion_Report.pdf | ioKinetic_calorimetry_testing.xlsx | Monomer_density_gravimetric_analysis.xlsx | Vant_Hoff_Analysis_4MCL_NMR.xlsx | Vant_Hoff_Analysis_4PrCL_NMR.xlsx | Tc_summary_Vant_Hoff_analysis.xlsx