Spectra and GPC Data for Polyhydroxyurethanes Formation from Bis(cyclic carbonate) Monomers in Multicomponent Semi-IPN Hydrogels Fabrication [Dataset]

Spectraand GPC Data for PolyhydroxyurethanesFormationfrom Bis(cycliccarbonate) Monomersin MulticomponentSemi-IPN Hydrogels Fabrication Authors: Ana I. Carbajo-Gordillo, Elena Benito*, Elsa Galbis, Roberto Grosso, Nieves Iglesias, M.-Gracia García-Martín, M.-Violante de-Paz* Email corresponding authors: [email protected]; [email protected]. 1 Dpto. Química Orgánica y Farmacéutica, Facultad de Farmacia, Universidad de Sevilla, 41012-Sevilla, Spain. Authors information Researcher email ORCID Ana -I. CarbajoGordillo [email protected]om 0000-0001-5230-6077 Elena Benito* [email protected] 0000-0002-8796-6873 Elsa Galbis [email protected] 0000-0001-8521-2835 Roberto Grosso r[email protected] 0000-0003-4304-6124 Nieves Iglesias nieves[email protected]om 0000-0003-0201-883X M. -Gracia GarcíaMartín gr[email protected] 0000-0002-7171-5236 M.-Violante de-Paz* [email protected] 0000-0002-6544-4732 2 Dpto. Química Orgánica y Farmacéutica, Facultad de Farmacia, Universidad de Sevilla, 41012-Sevilla, Spain. Index and Keywords Dataset language: English NMR, ATR-FTIR and Mass Spectra of small molecules and monomers: 1. {1-[3,5-bis(trifluoromethyl)phenyl]-3-cyclohexylthiourea} (TU) Pages [6-13] 1H NMR, COSY, 13C NMR, HSQC, ATR-FTIR, ESI-MS 2. 3-(Prop-2-yn-1-ylthio)-propane-1,2-diol (1) Pages [14-20] 1H NMR, COSY, 13C NMR, HSQC, ATR-FTIR, ESI-MS, ESI-HRMS 3. 4-[(Prop-2-yn-1-ylthio)methyl]-1,3-dioxolan-2-one (2) Pages [21-27] 1H NMR, COSY, 13C NMR, HSQC, ATR-FTIR, ESI-MS, ESI-HRMS 4. Five-membered bis(cylic carbonate) (Monomer A) Pages [28-38] 1H NMR, COSY, 13C NMR, HSQC, ATR-FTIR, ESI-HRMS 5. Five-membered bis(cylic carbonate) (Monomer E) Pages [39-45] 1H NMR, COSY, 13C NMR, HSQC, ATR-FTIR, ESI-MS, ESI-HRMS NMR, ATR-FTIR spectra and GPC chromatograms of polymers: 1. PHU A-DETA [monomer A + diethylenetriamine (DETA)] Pages [47-72] 1H NMR, COSY, HSQC, ATR-FTIR, GPC (samples P2, P4-P20) 2. PHU E-DETA [monomer E + diethylenetriamine (DETA)] Pages [73-81] 1H NMR, 13C NMR, ATR-FTIR, GPC (samples P1-P5) 3. PHU E-HMDA [monomer E + hexamethylenediamine (HMDA)] Pages [82-90] 1H NMR, 13C NMR, ATR-FTIR, GPC (samples P1-P5) 3 Keywords: Cyclic carbonates, monomers, polyhydroxyurethanes, PHU, aminolysis, NIPU, non-isocyanate polyurethanes Grant information and Table of contents Funding: the authors received with gratitude financial support from: Ministerio de Ciencia e Innovación - Agencia Estatal de Investigación (MCIN/AEI) Grant Number: PID2020-115916GB-I00; Fondo Europeo de Desarrollo Regional (FEDER), and La Consejería de Economía y Conocimiento (Junta de Andalucía) Grant Number: US-1380587. Table of contents: 1st Part: Monomers and small molecules Pg. 5 2nd Part: Polyhydroxyurethanes Pg 46 4 1st Part: Monomers and small molecules 1. {1-[3,5-bis(trifluoromethyl)phenyl]-3-cyclohexylthiourea} (TU) Pages [6-13] 1H NMR, COSY, 13C NMR, HSQC, ATR-FTIR, ESI-MS 2. 3-(Prop-2-yn-1-ylthio)-propane-1,2-diol (1) Pages [14-20] 1H NMR, COSY, 13C NMR, HSQC, ATR-FTIR, ESI-MS, ESI-HRMS 3. 4-[(Prop-2-yn-1-ylthio)methyl]-1,3-dioxolan-2-one (2) Pages [21-27] 1H NMR, COSY, 13C NMR, HSQC, ATR-FTIR, ESI-MS, ESI-HRMS 4. Five-membered bis(cylic carbonate) (Monomer A) Pages [28-38] 1H NMR, COSY, 13C NMR, HSQC, ATR-FTIR, ESI-HRMS 5. Five-membered bis(cylic carbonate) (Monomer E) Pages [29-45] 1H NMR, COSY, 13C NMR, HSQC, ATR-FTIR, ESI-MS, ESI-HRMS 5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm 1.202 1.228 1.239 1.362 1.372 1.400 1.433 1.444 1.455 1.472 1.482 1.494 1.606 1.618 1.631 1.647 1.679 1.693 1.706 1.725 1.738 2.052 2.063 2.094 2.105 4.190 6.074 7.707 7.761 8.131 {1-[3,5-bis(trifluoromethyl)phenyl]-3-cyclohexylthiourea} (TU) Spectrum 1H-RMN, 300 MHz, CDCl3 1H-NMR (300 MHz, CDCl3, δppm, JHz) δ8.13 (Bs, 1H, Ph-NH-), 7.76 (s, 2H, H-2’, H-6’), 7.71 (s, 1H, H-4’), 6.07 (bs, 1H, -NH-cyclohexyle), 4.19 (bs, 1H, H-1), 2.07 (dd, H-2a, H-6a, 2J2a,2b = 2J6a,6b = 12.4, J2a,3a = J6a,5a 3.3), 1.70-1.10 (m, 8H, H-2b, H-3, H-4, H-5, H-6b). 6 1H-NMR (300 MHz, CDCl3, δppm, JHz) δ 8.13 (Bs, 1H, Ph-NH-), 7.76 (s, 2H, H-2’, H6’), 7.71 (s, 1H, H-4’), 6.07 (bs, 1H, -NHcyclohexyle), 4.19 (bs, 1H, H-1), 2.07 (dd, H-2a, H-6a, 2J2a,2b = 2J6a,6b = 12.4, J2a,3a = J6a,5a 3.3), 1.70-1.10 (m, 8H, H-2b, H-3, H-4, H-5, H-6b). COSY (Bidimensional 1H-1H) {1-[3,5-bis(trifluoromethyl)phenyl]-3-cyclohexylthiourea} (TU) 7 COSY (Bidimensional 1H-1H) {1-[3,5-bis(trifluoromethyl)phenyl]-3-cyclohexylthiourea} (TU) 1H-NMR (300 MHz, CDCl3, δppm, JHz) δ 8.13 (Bs, 1H, Ph-NH-), 7.76 (s, 2H, H-2’, H6’), 7.71 (s, 1H, H-4’), 6.07 (bs, 1H, -NHcyclohexyle), 4.19 (bs, 1H, H-1), 2.07 (dd, H-2a, H-6a, 2J2a,2b = 2J6a,6b = 12.4, J2a,3a = J6a,5a 3.3), 1.70-1.10 (m, 8H, H-2b, H-3, H-4, H-5, H-6b). 8 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm 24.56 25.28 32.37 54.04 119.35 120.94 123.86 124.56 132.89 138.88 179.25 {1-[3,5-bis(trifluoromethyl)phenyl]-3-cyclohexylthiourea} (TU) Spectrum 13C-RMN, 75 MHz, CDCl3 13C-NMR (75 MHz, CDCl3, δ ppm) δ 179.3 (C=S), 138.9 (C-1’), 124.6 (C-2’, C-6’), 123.9 (C-3’, C-5’), 120.9 (-CF3), 119.4 (C-4’), 54.0 (C-1), 32.4 (C-2, C-6), 35.3 (C-4), 24.6 (C-3, C-5). 9 3-(Prop-2-yn-1-ylthio)-propane-1,2-diol (1) Spectrum 13C-RMN, 125 MHz, CDCl3 20 25 30 35 40 45 50 55 60 65 70 75 80 ppm 19.67 35.26 65.38 70.00 71.63 79.77 13C-NMR (CDCl3, 125 MHz) (ppm) 79.7 (C-2’), 71.6 (C-3’), 70.0 (C-2), 65.3 (C-1), 35.4 (C-3), 19.7 (C-1’). 16 3-(Prop-2-yn-1-ylthio)-propane-1,2-diol (1) 13C-NMR (CDCl3, 125 MHz) (ppm) 79.7 (C-2’), 71.6 (C-3’), 70.0 (C-2), 65.3 (C-1), 35.4 (C-3), 19.7 (C-1’). HSQC (Bidimensional 1H-13C) 1H-NMR (CDCl3, 500 MHz) (ppm) 3.933.89 (m, 1H, H-2), 3.79-3.75 (m, 1H, H-1a) 3.62-3.57 (m, 1H, H-1b), 3.33 (dd, 1H, H1’a, J1’a,3’ = 2.7 Hz, 2J1’a,1’b = 17.0 Hz), 3.28 (dd, 1H, H-1’b, J1’b,3’ = 2.5 Hz), 2.91 (dd, 1H, H-3a, J3a,2 = 4.0 Hz, 2J3a,3b = 13.9 Hz), 2.78 (dd, 1H, H-3b, J3b,2 = 8.0 Hz), 2.28 (t, 1H, H3’), 2.12, 1.65 (2 bs, 2H, OH). 17 3-(Prop-2-yn-1-ylthio)-propane-1,2-diol (1) Spectrum ATR-FTIR Wavenumber [cm-1]%T 1 3365.17 80.1709 2 3279.36 75.2066 3 2918.73 90.1671 4 1626.66 94.8913 5 1406.82 83.1675 6 1232.29 84.3515 7 1066.44 63.7818 8 1024.02 57.5546 9 887.095 84.7066 10 668.214 58.7689 18 3-(Prop-2-yn-1-ylthio)-propane-1,2-diol (1) Spectrum ESI-MS 170303_4V59 03/03/17 13:43:07 4V59 PM=146 C6H10O2S 170303_4V59 #54-67 RT: 0.22-0.27 AV: 14 SB: 89 1.05-1.41 NL: 1.51E8 T: FTMS + c ESI Full ms [60.00-900.00] 60 80 100 120 140 160 180 200 220 240 260 280 300 320 m/z 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 Relative Abundance 102.13 169.03 140.14 103.13 283.17 170.03 301.14 166.02 259.04129.04 239.04 277.05141.15 74.10 286.18 101.04 315.16221.0387.03 183.19 111.03 214.99 195.03 67.05 139.06 (M+Na)+= 146+23 = 169 19 3-(Prop-2-yn-1-ylthio)-propane-1,2-diol (1) Spectrum ESI-HRMS 170303_4V59 03/03/17 13:43:07 4V59 PM=146 C6H10O2S 170303_4V59 #65 RT: 0.26 AV: 1SB: 42 0.03-0.07 , 1.25-1.37 NL: 5.30E7 T: FTMS + c ESI Full ms [60.00-900.00] 168.0 168.5 169.0 169.5 170.0 170.5 171.0 171.5 172.0 172.5 173.0 173.5 174.0 174.5 m/z 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 Relative Abundance 169.0291 C6H10 O2Na S= 169.0294 -1.4292 ppm (M+Na)+= 146+23 = 169 20 2.42.62.83.03.23.43.63.84.04.24.44.64.85.0 ppm 1.08 1.08 0.99 2.08 1.09 1.01 1.00 4-[(Prop-2-yn-1-ylthio)methyl]-1,3-dioxolan-2-one (2) Spectrum 1H-RMN, 500 MHz, CDCl3 1H-NMR (CDCl3, 500 MHz)  (ppm) 5.00-4.94 (m, 1H, H-2), 4.59 (t, 1H, H-1a, 2J1a,1b = J1a,2 = 8.4 Hz), 4.32 (dd, 1H, H-1b, J1b,2 = 7.0 Hz), 3.35 (d, 2H, H-4, J4,6 = 2.7 Hz), 3.12 (dd, 1H, H3a, J3a,2 = 4.9 Hz, 2J3a,3b = 14.5 Hz), 2.99 (dd, 1H, H-3b, J3b,2 = 7.0 Hz ), 2.33 (t, 1H, H-6). 21 4-[(Prop-2-yn-1-ylthio)methyl]-1,3-dioxolan-2-one (2) COSY (Bidimensional 1H-1H) 1H-NMR (CDCl3, 500 MHz)  (ppm) 5.00-4.94 (m, 1H, H-2), 4.59 (t, 1H, H-1a, 2J1a,1b = J1a,2 = 8.4 Hz), 4.32 (dd, 1H, H-1b, J1b,2 = 7.0 Hz), 3.35 (d, 2H, H-4, J4,6 = 2.7 Hz), 3.12 (dd, 1H, H3a, J3a,2 = 4.9 Hz, 2J3a,3b = 14.5 Hz), 2.99 (dd, 1H, H-3b, J3b,2 = 7.0 Hz ), 2.33 (t, 1H, H-6). 22 20 30 40 50 60 70 80 90 100 110 120 130 140 150 ppm 20.16 33.91 68.54 72.45 75.31 79.02 154.41 4-[(Prop-2-yn-1-ylthio)methyl]-1,3-dioxolan-2-one (2) Spectrum 13C-RMN, 125 MHz, CDCl3 13C-NMR (CDCl3, 125 MHz)  (ppm) 154.4 (C=O), 79.0 (C5), 75.3 (C-2), 72.5 (C-6), 68.6 (C-1), 33.9 (C-3), 20.2 (C-4). 23 4-[(Prop-2-yn-1-ylthio)methyl]-1,3-dioxolan-2-one (2) HSQC (Bidimensional 1H-13C) 1H-NMR (CDCl3, 500 MHz)  (ppm) 5.00-4.94 (m, 1H, H-2), 4.59 (t, 1H, H-1a, 2J1a,1b = J1a,2 = 8.4 Hz), 4.32 (dd, 1H, H-1b, J1b,2 = 7.0 Hz), 3.35 (d, 2H, H-4, J4,6 = 2.7 Hz), 3.12 (dd, 1H, H3a, J3a,2 = 4.9 Hz, 2J3a,3b = 14.5 Hz), 2.99 (dd, 1H, H-3b, J3b,2 = 7.0 Hz ), 2.33 (t, 1H, H-6). 13C-NMR (CDCl3, 125 MHz)  (ppm) 154.4 (C=O), 79.0 (C5), 75.3 (C-2), 72.5 (C-6), 68.6 (C-1), 33.9 (C3), 20.2 (C-4). 24 4-[(Prop-2-yn-1-ylthio)methyl]-1,3-dioxolan-2-one (2) Spectrum ATR-FTIR 25 Five-membered bis(cylic carbonate) Monomer A COSY (Bidimensional 1H-1H) 1H-NMR (500 MHz, CDCl3)δ(ppm) 7.65 (s, 2H, H-6), 4.92-4.83 (m, 2H, H-2), 4.66 (t, 4H, J7,8 = 6.5 Hz, H-7), 4.53 (t, 2H, 2J1a,1b =J1a,2 = 8.5 Hz, H-1a), 4.21 (dd, 2H, J1b,2= 6.5 Hz, H1b), 3.92 (d, 2H, 2J4a,4b =14.5 Hz, H-4a), 3.89 (d, 2H, H-4b), 3.21 (t, 4H, H-8), 2.95 (dd, 2H, J3a,2= 5.0 Hz, 2J3a,3b =14.0 Hz, H-3a), 2.87 (dd, 2H, J3b,2= 6.5 Hz, H-3b). 32 30 40 50 60 70 80 90 100 110 120 130 140 150 ppm 26.63 34.10 37.85 48.75 68.61 75.56 123.10 144.84 154.68 Five-membered bis(cylic carbonate) Monomer A Spectrum 13C-RMN, 125 MHz, CDCl3 13C-NMR (125 MHz, CDCl3) δ(ppm) 154.6 (C=O), 144.9 (C-5), 123.1 (C-6), 75.5 (C-2), 68.6 (C-1), 48.7 (C-7), 37.9 (C-8), 34.1 (C-3), 26.7 (C-4). 33 Five-membered bis(cylic carbonate) Monomer A HSQC (Bidimensional 1H-13C) 1H-NMR (500 MHz, CDCl3)δ(ppm) 7.65 (s, 2H, H-6), 4.924.83 (m, 2H, H-2), 4.66 (t, 4H, J7,8 = 6.5 Hz, H-7), 4.53 (t, 2H, 2J1a,1b =J1a,2= 8.5 Hz, H-1a), 4.21 (dd, 2H, J1b,2= 6.5 Hz, H1b), 3.92 (d, 2H, 2J4a,4b =14.5 Hz, H-4a), 3.89 (d, 2H, H-4b), 3.21 (t, 4H, H-8), 2.95 (dd, 2H, J3a,2= 5.0 Hz, 2J3a,3b =14.0 Hz, H-3a), 2.87 (dd, 2H, J3b,2= 6.5 Hz, H-3b). 13C-NMR (125 MHz, CDCl3)δ(ppm) 154.6 (C=O), 144.9 (C-5), 123.1 (C-6), 75.5 (C-2), 68.6 (C-1), 48.7 (C-7), 37.9 (C-8), 34.1 (C-3), 26.7 (C-4). 34 Five-membered bis(cylic carbonate) Monomer A HSQC (Bidimensional 1H-13C) 1H-NMR (500 MHz, CDCl3)δ(ppm) 7.65 (s, 2H, H-6), 4.924.83 (m, 2H, H-2), 4.66 (t, 4H, J7,8 = 6.5 Hz, H-7), 4.53 (t, 2H, 2J1a,1b =J1a,2= 8.5 Hz, H-1a), 4.21 (dd, 2H, J1b,2= 6.5 Hz, H1b), 3.92 (d, 2H, 2J4a,4b =14.5 Hz, H-4a), 3.89 (d, 2H, H-4b), 3.21 (t, 4H, H-8), 2.95 (dd, 2H, J3a,2= 5.0 Hz, 2J3a,3b =14.0 Hz, H-3a), 2.87 (dd, 2H, J3b,2= 6.5 Hz, H-3b). 13C-NMR (125 MHz, CDCl3)δ(ppm) 154.6 (C=O), 144.9 (C-5), 123.1 (C-6), 75.5 (C-2), 68.6 (C-1), 48.7 (C-7), 37.9 (C-8), 34.1 (C-3), 26.7 (C-4). 35 Five-membered bis(cylic carbonate) Monomer A HSQC (Bidimensional 1H-13C) 1H-NMR (500 MHz, CDCl3)δ(ppm) 7.65 (s, 2H, H-6), 4.924.83 (m, 2H, H-2), 4.66 (t, 4H, J7,8 = 6.5 Hz, H-7), 4.53 (t, 2H, 2J1a,1b =J1a,2= 8.5 Hz, H-1a), 4.21 (dd, 2H, J1b,2= 6.5 Hz, H1b), 3.92 (d, 2H, 2J4a,4b =14.5 Hz, H-4a), 3.89 (d, 2H, H-4b), 3.21 (t, 4H, H-8), 2.95 (dd, 2H, J3a,2= 5.0 Hz, 2J3a,3b =14.0 Hz, H-3a), 2.87 (dd, 2H, J3b,2= 6.5 Hz, H-3b). 13C-NMR (125 MHz, CDCl3)δ(ppm) 154.6 (C=O), 144.9 (C-5), 123.1 (C-6), 75.5 (C-2), 68.6 (C-1), 48.7 (C-7), 37.9 (C-8), 34.1 (C-3), 26.7 (C-4). 36 PHU MA-DETA (black) and Monomer A (green) Spectra ATR-FTIR 37 Five-membered bis(cylic carbonate) Monomer A Spectrum ESI-HRMS 210219_V2003 02/19/21 14:14:44 V2003 PM=548 C18H24N6O6S4 210219_V2003 #100 RT: 0.49 AV: 1SB: 1 3.00 NL: 9.51E6 T: FTMS + c ESI Full ms [60.00-900.00] 570.0 570.5 571.0 571.5 572.0 572.5 573.0 573.5 574.0 574.5 575.0 575.5 576.0 m/z 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 Relative Abundance 571.0531 C18 H24 O6N6Na S4= 571.0532 -0.2578 ppm 571 = 548 + 23 Mw = 548 38 Five-membered bis(cylic carbonate) Monomer E Spectrum 1H-RMN, 300 MHz, CDCl3 1H-NMR (300 MHz, CDCl3)δ(ppm) 4.99-4.85 (m, 2H, H-2, H-2’), 4.61 (t, 2H, J1a,2 = 8.6 Hz, H-1a, H1’a), 4.20-4.09 (m, 2H, H-1b, H-1’b), 3.85-3.70 (m, 2H, H-7), 3.50 (bs, 1H, O-H), 2.99-2.88 (m, 1H, H5), 2.88-2.63 (m, 6H, H-4, H-4’ and H-6), 2.22-2.06 (m, 2H, H-3a, H-3’a), 2.05-1.90 (m, 2H, H-3b, H3’b). 39 Five-membered bis(cylic carbonate) Monomer E COSY (Bidimensional 1H-1H) 1H-NMR (300 MHz, CDCl3)δ(ppm) 4.99-4.85 (m, 2H, H-2, H-2’), 4.61 (t, 2H, J1a,2 = 8.6 Hz, H1a, H-1’a), 4.20-4.09 (m, 2H, H-1b, H-1’b), 3.85-3.70 (m, 2H, H-7), 3.50 (bs, 1H, O-H), 2.99-2.88 (m, 1H, H-5), 2.88-2.63 (m, 6H, H-4, H-4’ and H-6), 2.22-2.06 (m, 2H, H-3a, H-3’a), 2.05-1.90 (m, 2H, H-3b, H-3’b). 40 Five-membered bis(cylic carbonate) Monomer E Spectrum 13C-RMN, 75 MHz, CDCl3 13C-NMR (75 MHz, CDCl3)δ(ppm) 154.7 (C=O), 75.4 (C-2, C-2’), 69.2 (C-1, C-1’), 63.4 (C-7), 49.0 (C-5), 34.5 (C-3, C-3’), 28.1 and 26.4 (C-4, C-4’ and C-6). 41 3.03.54.04.55.05.56.06.57.07.58.0 ppm 6 73, 12 2 10 8, 11 4 9 1 NH 1H-NMR (500 MHz, CD3OD) δ(ppm) 7.94 (s, 2H, H-6), 7.34-7,11 (m, 2H, N-H urethane), 4.92 (bs, 1H, H-2), 4.68 (t, 4H, J7,8 = 6.5 Hz, H-7), 4.07, 4.02 (2 bs, 4H, H-10), 3.86 (bs, 4H, H-4), 3.77-3.31 (m, 2H, H-9, H-1), 3.24 (bs, 8H, H-8, H-11), 2.85-2.50 (m, 8H, H-3, H-12). Spectrum 1H-RMN, 500 MHz, CD3OD 48 PHU A-DETA 1H-NMR (500 MHz, CD3OD) δ(ppm) 7.94 (s, 2H, H-6), 7.347,11 (m, 2H, N-H urethane), 4.92 (bs, 1H, H-2), 4.68 (t, 4H, J7,8 = 6.5 Hz, H-7), 4.07, 4.02 (2 bs, 4H, H-10), 3.86 (bs, 4H, H-4), 3.77-3.31 (m, 2H, H-9, H-1), 3.24 (bs, 8H, H-8, H-11), 2.85-2.50 (m, 8H, H-3, H-12). COSY (Bidimensional 1H-1H) 49 PHU A-DETA 1H-NMR (500 MHz, CD3OD) δ(ppm) 7.94 (s, 2H, H-6), 7.347,11 (m, 2H, N-H urethane), 4.92 (bs, 1H, H-2), 4.68 (t, 4H, J7,8 = 6.5 Hz, H-7), 4.07, 4.02 (2 bs, 4H, H-10), 3.86 (bs, 4H, H-4), 3.77-3.31 (m, 2H, H-9, H-1), 3.24 (bs, 8H, H-8, H-11), 2.85-2.50 (m, 8H, H-3, H-12). 13C-NMR (125 MHz, CD3OD)δ(ppm) 159.1 (C=O), 143.7 (C5), 125.0 (C-6), 75.6 (C-2), 70.5 (C-9), 68.5 (C-10), 63.6 (C-1), 50.1 (C-7), 41.5 (C-8), 39.0 (C-11), 36.1 (C-12)33.1 (C-3), 27.4 (C-4). HSQC (Bidimensional 1H-13C) 50 PHU A-DETA 1H-NMR (500 MHz, CD3OD) δ(ppm) 7.94 (s, 2H, H-6), 7.347,11 (m, 2H, N-H urethane), 4.92 (bs, 1H, H-2), 4.68 (t, 4H, J7,8 = 6.5 Hz, H-7), 4.07, 4.02 (2 bs, 4H, H-10), 3.86 (bs, 4H, H-4), 3.77-3.31 (m, 2H, H-9, H-1), 3.24 (bs, 8H, H-8, H-11), 2.85-2.50 (m, 8H, H-3, H-12). 13C-NMR (125 MHz, CD3OD)δ(ppm) 159.1 (C=O), 143.7 (C5), 125.0 (C-6), 75.6 (C-2), 70.5 (C-9), 68.5 (C-10), 63.6 (C-1), 50.1 (C-7), 41.5 (C-8), 39.0 (C-11), 36.1 (C-12)33.1 (C-3), 27.4 (C-4). HSQC (Bidimensional 1H-13C) 51 PHU A-DETA 1H-NMR (500 MHz, CD3OD) δ(ppm) 7.94 (s, 2H, H-6), 7.347,11 (m, 2H, N-H urethane), 4.92 (bs, 1H, H-2), 4.68 (t, 4H, J7,8 = 6.5 Hz, H-7), 4.07, 4.02 (2 bs, 4H, H-10), 3.86 (bs, 4H, H-4), 3.77-3.31 (m, 2H, H-9, H-1), 3.24 (bs, 8H, H-8, H-11), 2.85-2.50 (m, 8H, H-3, H-12). 13C-NMR (125 MHz, CD3OD)δ(ppm) 159.1 (C=O), 143.7 (C5), 125.0 (C-6), 75.6 (C-2), 70.5 (C-9), 68.5 (C-10), 63.6 (C-1), 50.1 (C-7), 41.5 (C-8), 39.0 (C-11), 36.1 (C-12)33.1 (C-3), 27.4 (C-4). HSQC (Bidimensional 1H-13C) 52 PHU A-DETA 1H-NMR (500 MHz, CD3OD) δ(ppm) 7.94 (s, 2H, H-6), 7.347,11 (m, 2H, N-H urethane), 4.92 (bs, 1H, H-2), 4.68 (t, 4H, J7,8 = 6.5 Hz, H-7), 4.07, 4.02 (2 bs, 4H, H-10), 3.86 (bs, 4H, H-4), 3.77-3.31 (m, 2H, H-9, H-1), 3.24 (bs, 8H, H-8, H-11), 2.85-2.50 (m, 8H, H-3, H-12). 13C-NMR (125 MHz, CD3OD)δ(ppm) 159.1 (C=O), 143.7 (C5), 125.0 (C-6), 75.6 (C-2), 70.5 (C-9), 68.5 (C-10), 63.6 (C-1), 50.1 (C-7), 41.5 (C-8), 39.0 (C-11), 36.1 (C-12)33.1 (C-3), 27.4 (C-4). HSQC (Bidimensional 1H-13C) 53 PHU A-DETA PHU A-DETA (black) and Monomer A (green) Spectra ATR-FTIR 54 PHU A-DETA GPC ADETA-P2 Injection Peak Mn Mw Mp Mz Ɖ 11 2787 3726 1889 4953 1.337 12 943 961 996 980 1.019 21 2565 3337 1984 4542 1.301 22 975 985 990 996 1.01 (*) Mn = number average molecular weight; Mw = weight average molecular weight; Mp = peak maximum molecular weight; Mz = Z average molecular weight 1 2 system peak Toluene 55 TFE, 50°C, [Monomer]: 165 mM; No catalyst PHU A-DETA GPC ADETA-P4 1 2 system peak Toluene Injection Peak Mn Mw Mp Mz Ɖ 11 2576 3254 1975 4232 1.26 12 979 992 990 1006 1.01 21 2636 3382 1984 1014 1.28 22 987 1000 990 1014 1.01 (*) Mn = number average molecular weight; Mw = weight average molecular weight; Mp = peak maximum molecular weight; Mz = Z average molecular weight 56 DMSO, 50°C, [Monomer]: 165 mM; No catalyst PHU A-DETA GPC ADETA-P5 57 TFE, TU, 25°C, [Monomer]: 165 mM PHU A-DETA GPC ADETA-P12 64 DMSO, DBU, 50°C ; [Monomer]: 165 mM PHU A-DETA GPC ADETA-P13 65 TFE, TU, 25°C, [Monomer]: 1.8 M PHU A-DETA GPC ADETA-P14 66 TFE, TU, 50°C, [Monomer]: 1.8 M PHU A-DETA GPC ADETA-P15 67 DMSO, TU, 25°C, [Monomer]: 1.8 M PHU A-DETA GPC ADETA-P16 68 DMSO, TU, 50°C, [Monomer]: 1.8 M PHU A-DETA GPC ADETA-P17 69 TFE, DBU, 25°C, [Monomer]: 1.8 M PHU A-DETA GPC ADETA-P18 70 TFE, DBU, 50°C, [Monomer]: 1.8 M PHU A-DETA GPC ADETA-P19 71 DMSO, DBU, 25°C, [Monomer]: 1.8 M PHU A-DETA GPC ADETA-P20 72 DMSO, DBU, 50°C, [Monomer]: 1.8 M PHU E-DETA Monomer E + diethylenetriamine (DETA) 73 PHU E-DETA GPC EDETA-P4 80 EtOH, TU, 50°C, [Monomer]: 1.8 M PHU E-DETA GPC EDETA-P5 81 EtOH, DBU, 50°C, [Monomer]: 1.8 M PHU E-HMDA Monomer E + hexamethylenediamine (HMDA) 82 PHU E-HMDA Spectrum 1H-RMN, 500 MHz, DMSO-d6 1H-NMR (500 MHz, DMSO-d6) δ(ppm) 7.11, 7.06 (2 bs, 2H, N-H), 4.97-4.79 (m, 2H, OH), 4.68 (bs, 1H, H-2), 3.97-3.81 (m, 2H, H-9), 3.73 (bs, 1H, H-8), 3.70-3.61 (m, 2H, H-7), 3.60-3.51 (m, 2H, H-1), 3.07-2.96 (m, 4H, H-10), 2.95-2.80 (m, 1H, H-5), 2.79-2.66 (m, 2H, H-6), 2.46-2.58 (m, 4H, H-4, H-4’), 1.95-1.52 (m, 4H, H-3, H-3’), 1.43 (bs, 4H, H-11), 1.29 (bs, 4H, H-12). 83 PHU E-HMDA Spectrum 13C-RMN, 125 MHz, DMSO-d6 13C-NMR (125 MHz, DMSO-d6)δ (ppm) 156.7 (C=O), 73.6 (C-2), 68.1 (C-9), 67.7 (C-8), 63.2 (C-7), 62.7 (C-1), 48.2 (C-5), 40.8 (C-10), 34.5, 31.9 (C-3, C-3’), 34.3 (C-6), 29,7 (C-11), 28.5, 26.7 (C-4, C-4’), 26.3 (C-12). 84 PHU E-HMDA Spectra ATR-FTIR 85 PHU E-HMDA GPC EHMDA-P1 86 DMSO, DBU, 25°C, [Monomer]: 1.8 M GPC EHMDA-P2 PHU E-HMDA 87 DMSO, DBU, 50°C, [Monomer]: 1.8 M GPC EHMDA-P3 PHU E-HMDA 88 DMSO, TU, 50°C, [Monomer]: 1.8 M GPC EHMDA-P4 PHU E-HMDA 89 EtOH, TU, 50°C, [Monomer]: 1.8 M