Hyuk-Joon Jung, Hootan Roshandel, Michael J. Pung, Kieran Pearson, Kilmer Bennewitz, Qijia Zhou, Takeo Iwase, Parisa Mehrkhodavandi, Paula L. Diaconescu. “Direct access to poly(amino ester)s with main-chain H-bonding motifs.” ChemRxiv (). https://doi.org/10.26434/chemrxiv.15007541/v1

The main paper refers to supporting information, but no separate supporting information file was found among the files available from the ChemRxiv record

Poly(PO-alt-NCAH)
Solubility Readily soluble in chloroform, dichloromethane, tetrahydrofuran, and dimethylformamide
¹H NMR (400 MHz, CDCl₃, 25 °C), monomer ratio 1:1
¹H NMR (400 MHz, CDCl₃, 25 °C), regioregularity 90.3 %
¹³C NMR {¹H} (125 MHz, CDCl₃, 25 °C), poly(propylene oxide) signals Not observed
¹³C NMR {¹H} (125 MHz, CDCl₃, 25 °C), ester-linkage peak 168 ppm
DOSY (500 MHz, CDCl₃, 25 °C) All proton species diffused at the same rate
¹H–¹H COSY (500 MHz, CDCl₃, 25 °C) Correlations between the nitrogen-bound proton and the epoxide-unit methylene protons
¹H–¹³C HSQC, amine-proton and carbon cross peaks Not observed
ATR-IR (solid-state, 25 °C), N–H stretching 3354 cm⁻¹
ATR-IR (solid-state, 25 °C), N–H bending 1539 cm⁻¹
ATR-IR (solid-state, 25 °C), C–N stretching 1675 cm⁻¹
ATR-IR (solid-state, 25 °C), C=O stretching range 1630–1740 cm⁻¹
ATR-IR (solid-state, 25 °C), free C=O 1708 cm⁻¹
ATR-IR (solid-state, 25 °C), H-bound C=O 1676 cm⁻¹
ATR-IR (solid-state, 25 °C), H-bound C=O groups 95 %
ATR-IR (solid-state, 25 °C), C–O stretching 1128 cm⁻¹
MALDI-TOF-MS Alkoxy and NCA-derived chain-end groups observed
TGA, Td,5 % 326 °C
DSC, second-heating Tg 89.8 °C
Main, pp. 3–5, 7, 9
Crude reaction mixture from polymerization at 80 °C
¹H NMR, poly(PO-alt-NCAH):propylene carbonate ratio 1:1
Main, p. 3
Crude reaction mixture from polymerization at room temperature
¹H NMR, poly(PO-alt-NCAH):propylene carbonate ratio 1:1
Main, p. 3
Poly(PO-alt-NCAH) in wet CDCl₃
DOSY Polymer-bound water diffused together with the polymer; free water diffused at a different rate
¹H NMR (600 MHz, CDCl₃), new peak at 5 °C 5.81 ppm, polymer-bound water
¹H NMR (600 MHz, CDCl₃), 5.81 ppm peak at 25 °C Broadened
¹H NMR (600 MHz, CDCl₃), 5.81 ppm peak at 45 °C Unobservable
¹H NMR (600 MHz, CDCl₃), amine peak at 5 °C 8.08 ppm
¹H NMR (600 MHz, CDCl₃), 8.08 ppm peak at 45 °C Unobservable
Main, p. 4
Poly(PO-alt-NCAH) with water
NOESY Exchange cross-peaks between amine protons and polymer-bound water
¹H NMR after D₂O addition Amine and water resonances disappeared
Main, p. 5
Protonated poly(PO-alt-NCAH) in DMSO-d₆
¹H NMR, original amine resonance 7.87 ppm, disappeared
¹H NMR, new broad resonance Centered at 4.65 ppm
¹H NMR after D₂O addition Broad resonance disappeared and a sharp HOD signal appeared
Main, p. 5
Poly(PO-alt-NCAH)-co-poly(PO-alt-PA)
¹H NMR, poly(amino ester):polyester composition ratio 1:1
¹³C NMR {¹H} Additional peaks adjacent to the typical carbonyl peak of the poly(amino ester) segment
DOSY Single copolymer species
ATR-IR, C=O stretching range 1630–1780 cm⁻¹
ATR-IR, free C=O of poly(PO-alt-PA) units 1722 cm⁻¹
ATR-IR, free C=O of poly(PO-alt-NCAH) units 1708 cm⁻¹
ATR-IR, H-bound C=O of poly(PO-alt-NCAH) units 1676 cm⁻¹
TGA, degradation profile Single-step
DSC, median Tg 74.7 °C
Main, pp. 5–6, 9
Poly(AGE-alt-NCAH)
SEC in THF, Mn 4.3 kDa
SEC in THF, dispersity 1.18
TGA, Td,5 % 315 °C
DSC, second-heating Tg 24.8 °C
Main, pp. 3–4, 8–9
Poly(ECH-alt-NCAH)
¹H NMR, regioregularity 87.2 %
SEC in THF, Mn 2.9 kDa
SEC in THF, dispersity 1.17
TGA, Td,5 % 206 °C
DSC, second-heating Tg 86.4 °C
Main, pp. 3–4, 6, 8–9
Poly(SO-alt-NCAH)
SEC in THF, Mn 5.4 kDa
SEC in THF, dispersity 1.07
TGA, Td,5 % 262 °C
DSC, second-heating Tg 80.0 °C
Main, pp. 3–4, 8–9
Poly(CHO-alt-NCAH)
SEC in THF, Mn 4.6 kDa
SEC in THF, dispersity 1.19
TGA, Td,5 % 284 °C
DSC, second-heating Tg 144.7 °C
Main, pp. 3–4, 8–9
Poly(PEGDE-alt-NCAH)
Solubility Water soluble
¹H NMR One PEGDE epoxide group opened; the remaining epoxide and cyclic carbonate were retained as pendant functionalities
DOSY Single polymer species
ATR-IR, N–H 3362 cm⁻¹
ATR-IR, C–O–C 1087 cm⁻¹
SEC in THF, Mn 4.3 kDa
SEC in THF, dispersity 1.24
TGA, Td,5 % 272 °C
DSC, second-heating Tg −39.1 °C
Main, pp. 3–4, 6, 8–9
Poly(PO-alt-FNCAH)
SEC in THF, Mn 4.8 kDa
SEC in THF, dispersity 1.18
TGA, Td,5 % 299 °C
DSC, second-heating Tg 90.8 °C
Main, pp. 3–4, 9
Poly(amino ester)s
TGA, degradation profile Single-step
DSC, melting transitions from −50 to 250 °C Not observed
PXRD, distinct diffraction peaks Not observed
Main, pp. 8–9
Poly(PO-alt-PA)
DSC, Tg 59.0 °C
Main, p. 9
Crude mixture from poly(PO-alt-NCAH) degradation with 1 M aqueous NaOH after reflux for 48 h
Crude ¹H NMR, broad polymer peaks Not observed
Crude ¹H NMR, new sharp aromatic signals 6.36–7.78 ppm
Crude ¹H NMR, new sharp methyl signal 1.12 ppm