| Chiral HPLC (ChiralPak OD-H, 150 × 4.6 mm, 30 °C) | tR = 6.81 min, peak area = 12044, 49.18 % of total area; tR = 8.31 min, peak area = 12443, 50.82 % of total area |
|---|---|
| Chiral HPLC chromatogram | Image data were not transcribed |
William Ramos, Nick M. Legaux, Brandon M. Hosford, Hanlin M. Wang, Elizabeth A. Murphy, Alicia C. Huggett, Frank A. Leibfarth, Jessica R. Lamb. “Accessing block copolymers with independently modulated tacticities using sequential cationic-anionic polymerization of vinyl ethers and thiiranes.” ChemRxiv (). https://doi.org/10.26434/chemrxiv.15007792/v1
| Identifier | (S)-POPS |
|---|---|
| ¹H NMR (500 MHz, CDCl₃) | δ 7.32 (m, 2H), 7.00 (m, 1H), 6.94 (m, 2H), 4.23 (ddd, J = 10.2, 5.5, 0.7 Hz, 1H), 3.92 (dd, J = 10.2, 7.1 Hz, 1H), 3.29 (ddt, J = 7.0, 6.2, 5.4 Hz, 1H), 2.62 (dt, J = 6.2, 1.1 Hz, 1H), 2.34 (dd, J = 5.3, 1.4 Hz, 1H) |
| ¹H NMR spectrum (500 MHz, CDCl₃) | Image data were not transcribed |
| Chiral HPLC (ChiralPak OD-H, iPrOH:hexanes = 10:90, 0.8 mL min⁻¹, λ = 250 nm) | tR = 6.81 min; tS = 8.17 min; e.r. = 99:1 |
| Chiral HPLC (ChiralPak OD-H, 150 × 4.6 mm, 30 °C) | tR = 6.81 min, peak area = 0, 0 % of total area; tR = 8.17 min, peak area = 16268, 100 % of total area |
| Chiral HPLC chromatogram | Image data were not transcribed |
| Identifier | (S)-PS |
|---|---|
| ¹H NMR (500 MHz, CDCl₃) | δ 2.92 (pseudo-h, J ≈ 5.8 Hz, 1H), 2.51 (dd, J = 6.3, 0.9 Hz, 1H), 2.12 (dd, J = 5.7, 0.8 Hz, 1H), 1.52 (d, J = 5.8 Hz, 3H) |
| ¹H NMR spectrum (500 MHz, CDCl₃) | Image data were not transcribed |
| Size-exclusion chromatography (DMF, 0.025 M LiBr, PMMA calibration), batch 1 | Mn = 3.38 kDa; Mw = 4.49 kDa; Đ = 1.33 |
|---|---|
| Size-exclusion chromatography (DMF, 0.025 M LiBr, PMMA calibration), batch 2 | Mn = 4.30 kDa; Mw = 5.59 kDa; Đ = 1.31 |
| Size-exclusion chromatography traces | Image data were not transcribed |
| ¹H NMR spectrum (500 MHz, CDCl₃) | Image data were not transcribed |
| Size-exclusion chromatography (DMF, 0.025 M LiBr, PMMA calibration) | Mn = 8.33 kDa; Đ = 1.39 |
|---|---|
| Size-exclusion chromatography trace (DMF, 0.025 M LiBr) | Image data were not transcribed |
| ¹³C NMR (126 MHz, 20 mg sample, 4096 scans, 1 s delay), tacticity | 54 % m; methine-carbon peaks at δ 46.8, [46.7, 46.6], and 46.5 corresponding to mm, [mr + rm], and rr triads, respectively |
| ¹³C NMR spectrum, methine-carbon region | Image data were not transcribed |
| Thermogravimetric analysis (10 °C min⁻¹, N₂), extrapolated onset temperature | To = 284 °C |
| Differential scanning calorimetry (10 °C min⁻¹, N₂, second heat) | Tg = 11 °C |
| Size-exclusion chromatography (DMF, 0.025 M LiBr, PMMA calibration) | Mn = 8.06 kDa; Đ = 1.56 |
|---|---|
| Size-exclusion chromatography trace (DMF, 0.025 M LiBr) | Image data were not transcribed |
| ¹³C NMR (126 MHz, 20 mg sample, 4096 scans, 1 s delay), tacticity | >99 % m; only the methine-carbon peak corresponding to the mm triad was observed |
| ¹³C NMR spectrum, methine-carbon region | Image data were not transcribed |
| Thermogravimetric analysis (10 °C min⁻¹, N₂), extrapolated onset temperature | To = 312 °C |
| Differential scanning calorimetry (10 °C min⁻¹, N₂) | Tg = 16 °C, second heat; Tm = 131 °C, first heat |
| Thermogravimetric analysis and differential scanning calorimetry, thermograms | Image data were not transcribed |
| Size-exclusion chromatography (THF, polystyrene calibration) | Mn = 15.7 kDa; Đ = 1.29 |
|---|---|
| Size-exclusion chromatography trace (Waters THF) | Image data were not transcribed |
| ¹³C NMR (126 MHz, 20 mg sample, 4096 scans, 1 s delay), tacticity | 42 % m; multiple methine peaks were observed; the reported % m is approximate because the methine peaks overlap |
| ¹³C NMR spectra, methine-carbon region and peak deconvolution | Image data were not transcribed |
| Thermogravimetric analysis (10 °C min⁻¹, N₂), extrapolated onset temperature | To = 296 °C |
| Differential scanning calorimetry (10 °C min⁻¹, N₂, second heat) | Tg = −40 °C |
| Thermogravimetric analysis and differential scanning calorimetry, thermograms | Image data were not transcribed |
| Size-exclusion chromatography (THF, polystyrene calibration) | Mn = 14.6 kDa; Đ = 1.20 |
|---|---|
| Size-exclusion chromatography trace (DMF, 0.025 M LiBr) | Image data were not transcribed |
| ¹³C NMR (126 MHz, 20 mg sample, 4096 scans, 1 s delay), tacticity | 93 % m; one major methine peak was observed; the reported % m is approximate because the methine peaks overlap |
| ¹³C NMR spectra, methine-carbon region and peak deconvolution | Image data were not transcribed |
| Thermogravimetric analysis (10 °C min⁻¹, N₂), extrapolated onset temperature | To = 308 °C |
| Differential scanning calorimetry (10 °C min⁻¹, N₂, second heat) | Tg = −39 °C |
| Thermogravimetric analysis and differential scanning calorimetry, thermograms | Image data were not transcribed |
| Size-exclusion chromatography (THF, polystyrene calibration) | Mn = 14.2 kDa; Mw = 18.0 kDa; Đ = 1.27 |
|---|---|
| Size-exclusion chromatography trace (Waters THF) | Image data were not transcribed |
| Thermogravimetric analysis (10 °C min⁻¹, N₂), extrapolated onset temperature | To = 387 °C |
| Differential scanning calorimetry (10 °C min⁻¹, N₂, second heat) | Tg = −16 °C |
| Thermogravimetric analysis and differential scanning calorimetry, thermograms | Image data were not transcribed |
| Differential scanning calorimetry, artefact | Instrument impurity observed at ~50 °C |
| Thermogravimetric analysis (10 °C min⁻¹, N₂), extrapolated onset temperature | To = 383 °C |
|---|---|
| Differential scanning calorimetry (10 °C min⁻¹, N₂, second heat) | Tg = −12 °C; Tm = 131, 142 °C |
| Thermogravimetric analysis and differential scanning calorimetry, thermograms | Image data were not transcribed |
| Differential scanning calorimetry, artefact | Instrument impurity observed at ~50 °C |
| Thermogravimetric analysis (10 °C min⁻¹, N₂), extrapolated onset temperatures | First To = 119 °C; second To = 317 °C |
|---|---|
| Differential scanning calorimetry (10 °C min⁻¹, N₂, second heat) | Tg = 13 °C |
| Thermogravimetric analysis, thermogram | Image data were not transcribed |
| Size-exclusion chromatography (DMF, 0.025 M LiBr, PMMA calibration) | Mn = 10.1 kDa; Đ = 1.38 |
|---|---|
| Size-exclusion chromatography traces (DMF, 0.025 M LiBr) | Image data were not transcribed |
| Small-angle X-ray scattering | Most samples were disordered; lamellar morphology was observed at 50–70 mol % p(EVE), hexagonally packed cylinders at 46–47 mol % p(EVE), and some samples were poorly ordered with unknown morphologies |
| Automated chromatography composition and mass-recovery graph | Image data were not transcribed |
| Small-angle X-ray scattering analysis | Image data were not transcribed |
| Size-exclusion chromatography (DMF, 0.025 M LiBr, PMMA calibration) | Mn = 11.3 kDa; Đ = 1.42 |
|---|---|
| Size-exclusion chromatography traces (DMF, 0.025 M LiBr) | Image data were not transcribed |
| ¹H NMR spectrum (500 MHz, CDCl₃) | Image data were not transcribed |
| Thermogravimetric analysis (10 °C min⁻¹, N₂), extrapolated onset temperatures | To = 290, 382 °C |
| Differential scanning calorimetry (10 °C min⁻¹, N₂) | Tg = −32, 20 °C, second heat; Tm = 118 °C, first heat |
| Thermogravimetric analysis (10 °C min⁻¹, N₂), extrapolated onset temperatures | First To = 271 °C; second To = 373 °C |
|---|---|
| Thermogravimetric analysis and differential scanning calorimetry, thermograms | Image data were not transcribed |
| Differential scanning calorimetry, artefact | Instrument impurity observed at ~50 °C |
| Size-exclusion chromatography (THF, polystyrene calibration) | Mn = 16.2 kDa; Đ = 1.41 |
|---|---|
| Size-exclusion chromatography traces (Waters THF) | Image data were not transcribed |
| Thermogravimetric analysis (10 °C min⁻¹, N₂), extrapolated onset temperatures | To = 284, 441 °C |
| Differential scanning calorimetry (10 °C min⁻¹, N₂, second heat) | Tg = −30, −5 °C; Tm = 151 °C |
| Thermogravimetric analysis and differential scanning calorimetry, thermograms | Image data were not transcribed |
| Differential scanning calorimetry, artefact | Instrument impurity observed at ~50 °C |
| Thermogravimetric analysis (10 °C min⁻¹, N₂), extrapolated onset temperatures | First To = 290 °C; second To = 382 °C |
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| Size-exclusion chromatography (THF, polystyrene calibration) | Mn = 23.2 kDa; Đ = 1.41 |
|---|---|
| Size-exclusion chromatography traces (Waters THF) | Image data were not transcribed |
| ¹H NMR spectrum (500 MHz, CDCl₃) | Image data were not transcribed |
| Thermogravimetric analysis (10 °C min⁻¹, N₂), extrapolated onset temperatures | To = 295, 398 °C |
| Differential scanning calorimetry (10 °C min⁻¹, N₂, second heat) | Tg = −40, −18 °C |
| Thermogravimetric analysis and differential scanning calorimetry, thermograms | Image data were not transcribed |
| Small-angle X-ray scattering (70 °C annealing, 18 h) | Hexagonally packed cylinders were observed for fractions containing 58–63 mol % p(IBVE) |
| Thermogravimetric analysis (10 °C min⁻¹, N₂), extrapolated onset temperatures | First To = 284 °C; second To = 441 °C |
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| Size-exclusion chromatography (THF, polystyrene calibration) | Mn = 22.5 kDa; Đ = 1.40 |
|---|---|
| Size-exclusion chromatography traces (Waters THF) | Image data were not transcribed |
| ¹H NMR spectrum (500 MHz, CDCl₃) | Image data were not transcribed |
| Thermogravimetric analysis (10 °C min⁻¹, N₂), extrapolated onset temperatures | To = 298, 397 °C |
| Differential scanning calorimetry (10 °C min⁻¹, N₂, second heat) | Tg = −38, −14 °C |
| Thermogravimetric analysis and differential scanning calorimetry, thermograms | Image data were not transcribed |
| Small-angle X-ray scattering (70 °C annealing, 18 h) | Hexagonally packed cylinders were observed for fractions containing 56–77 mol % p(IBVE) |
| Thermogravimetric analysis (10 °C min⁻¹, N₂), extrapolated onset temperatures | First To = 295 °C; second To = 398 °C |
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| Size-exclusion chromatography (THF, polystyrene calibration) | Mn = 41.3 kDa; Đ = 1.29 |
|---|---|
| Size-exclusion chromatography traces (Waters THF) | Image data were not transcribed |
| ¹H NMR spectrum (500 MHz, CDCl₃) | Image data were not transcribed |
| Thermogravimetric analysis (10 °C min⁻¹, N₂), extrapolated onset temperatures | To = 298, 388 °C |
| Differential scanning calorimetry (10 °C min⁻¹, N₂, second heat) | Tg = −39, −17 °C; Tm = 141 °C |
| Thermogravimetric analysis and differential scanning calorimetry, thermograms | Image data were not transcribed |
| Differential scanning calorimetry, artefact | Instrument impurity observed at ~50 °C |
| Thermogravimetric analysis (10 °C min⁻¹, N₂), extrapolated onset temperatures | First To = 298 °C; second To = 397 °C |
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| Size-exclusion chromatography (THF, polystyrene calibration) | Mn = 43.7 kDa; Đ = 1.36 |
|---|---|
| Size-exclusion chromatography traces (Waters THF) | Image data were not transcribed |
| ¹H NMR spectrum (500 MHz, CDCl₃) | Image data were not transcribed |
| Thermogravimetric analysis (10 °C min⁻¹, N₂), extrapolated onset temperatures | To = 294, 406 °C |
| Differential scanning calorimetry (10 °C min⁻¹, N₂, second heat) | Tg = −38, −17 °C; Tm = 138 °C |
| Thermogravimetric analysis and differential scanning calorimetry, thermograms | Image data were not transcribed |
| Thermogravimetric analysis (10 °C min⁻¹, N₂), extrapolated onset temperatures | First To = 298 °C; second To = 388 °C |
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| Automated chromatography, child-polymer composition for the a-p(IBVE)-containing block copolymers | 32–100 mol % vinyl-ether block; the 100 mol % pVE fraction indicated that a portion of the p(IBVE) homopolymer did not chain extend |
|---|---|
| Automated chromatography, child-polymer composition for the iso-p(IBVE)-containing block copolymers | 24–68 mol % vinyl-ether block |
| Automated chromatography composition and mass-recovery graphs | Image data were not transcribed |
| Small-angle X-ray scattering analyses of the a-p(IBVE) block copolymers | Image data were not transcribed |
| Differential scanning calorimetry thermograms | Image data were not transcribed |