Supporting Information for Radical Induced Oxidation Agents—A Kinetic Study CHANGXI LI, 1,2 JUNPO HE*, 1,2 YANWU ZHOU, of 1,2 RAFT YUANKAI GU, 1,2 YULIANG YANG 1,2 1 Key Laboratory of Molecular Engineering of Polymers at Fudan University, Ministry of Education, Shanghai 200433, China 2 Department of Macromolecular Science, Fudan University, Shanghai 200433, China Corresponding author: Junpo He; Email: jphe@fudan.edu.cn The characterization results of RAFT agents 1. 1-Phenylethyl dithiobenzoate (PEDB) H NMR: δ (ppm): 1.81 (d, 3H, CH-CH3), 5.26 (q, 1H, CH-CH3), 7.95 (d, 2H, o-ArH of dithiobenzoate), 7.50(dd, 1H, p-ArH of dithiobenzoate), 7.25-7.45 (m, 7H, ArH), FT-IR: ν (cm-1) = 1225 and 1042 (C=S). UV-vis max (cyclohexane) : 298 and 500 nm. GC-MS (EI): m/e = 258. Purity by HPLC = 99.2%. 1 2. Cumyl Dithiobenzoate (CDB) H NMR: δ (ppm): 2.00 (s, 6H, CH3-C-CH3), 7.85 (d, 2H, o-ArH of dithiobenzoate), 7.46 (dd, 1H, p-ArH of dithiobenzoate), 7.55 (d, 2H, o-ArH), 7.22 (dd, 1H, p-ArH), 7.31-7.39 (m, 4H, ArH). FT-IR: ν (cm-1) = 1218 and 1042 (C=S). UV-vis max (cyclohexane): 299 and 444 nm. GC-MS (EI): m/e = 272. Purity by HPLC = 99.0%. 1 3. 2-Cyanoprop-2-yl Dithiobenzoate(CyDB) H NMR: δ (ppm): 1.95 (s, 6H, CH3-C-CH3), 7.92 (d, 2H, o-ArH of dithiobenzoate), 7.56(dd, 1H, p-ArH of dithiobenzoate), 7.40 (dd, 2H, m-ArH of dithiobenzoate). FT-IR: ν (cm-1) = 1229 and 1047 (C=S); ν (cm-1) = 2231(CN). UV-vis max (cyclohexane): 296 and 529 nm. GC-MS (EI): m/e = 221. Purity by HPLC = 98.8%. 1 4. Benzyl Dithiobenzoate (BDB) H NMR: δ (ppm): 4.6 (s, 2H, CH2-Ph), 8.00 (d, 2H, o-ArH of dithiobenzoate), 7.53 (dd, 1H, p-ArH of dithiobenzoate), 7.25-7.45 (m, 7H, ArH). FT-IR: ν (cm-1) = 1226 1 and 1044 (C=S). UV-vis max (cyclohexane): 302 and 504 nm. GC-MS (EI): m/e = 244. Purity by HPLC = 99.4%. 5. 1-Phenylethyl phenyldithioacetate(BDES) H NMR: δ (ppm): 1.68 (d, 3H, CH-CH3), 5.05 (q, 1H, CH-CH3), 4.26 (s, 2H, CH2-ph), 7.17-7.35 (m, 10H, ArH). FT-IR: ν (cm-1) = 1219 and 1037 (C=S). UV-vis max (cyclohexane): 308nm. GC-MS (EI): m/e = 272. Purity by HPLC = 99.0%. 1 6. Dibenzyl Trithiocarbonate (DBTTC) H NMR: δ (ppm): 4.62 (s, 4H, CH2-Ph), 7.26-7.36 (m, 20H, ArH). FT-IR: ν (cm-1) = 1223 and 1063 (C=S). UV-vis max (cyclohexane): 307nm. GC-MS (EI): m/e = 290. Purity by HPLC = 99.5%. 1 7. O-ethyl-S-Cumyl Xanthate(EtoCDB) H NMR: δ (ppm): 1.82(s, 6H, CH3-C-CH3), 4.38(q, 3H, CH3-CH2), 1.06(t, 2H, CH3-CH2), 7.52 (d, 1H, o-ArH), 7.31 (dd, 2H, p-ArH), 7.22(dd, 2H, m-ArH). FT-IR: ν (cm-1) = 1238 and 1042 (C=S). UV-vis max (cyclohexane): 286 nm. Purity by HPLC = 98.6%. 1 Figure S1. HPLC diagrams detected at 254 nm for PEDB in tert-butyl benzene at 100 C for 16 h in the presence of air. Figure S2. HPLC diagrams detected at 254 nm of purified PEBT by thin layer chromatography. Figure S3. HPLC diagrams detected at 300 nm for the reaction of AIBN and PEDB at 80 C in benzene solution in the nitrogen atmosphere. Feed: AIBN: PEDB = 10:1 (molar ratio). Figure S4. HPLC diagrams monitoring the reaction of PEDB and PEET in cyclohexane at 90 C in the nitrogen atmosphere. Feed: PEDB : PEET = 1:4 (molar ratio). (a) (b) Figure S5. (a) UV-Vis spectrometric monitoring and (b) GC-MS spectra for the reaction of PEDB (0.026 g, 0.1 mmol) and AIBN (0.032 g, 0.2 mmol) in benzene at 60 C in the presence of air (The arrow directs the reaction time of 0, 0.25, 0.5, 1, 2, 4, 6, 8h). (a) (b) Figure S6. (a) UV-Vis spectrometric monitoring and (b) GC-MS spectra for the reaction of CDB (0.027 g, 0.1 mmol) and AIBN (0.032 g, 0.2 mmol) in benzene at 60 C in the presence of air (The arrow directs the reaction time of 0, 0.5, 1, 2, 3, 4h). (a) (b) Figure S7. (a) UV-Vis spectrometric monitoring and (b) GC-MS spectra for the reaction of: BDB (0.024 g, 0.1 mmol) and AIBN (0.032 g, 0.2 mmol) in benzene at 60 C in the presence of air (The arrow directs the reaction time of 0, 0.5, 1, 2, 3, 4, 6, 8h). (a) (b) Figure S8. (a) UV-Vis spectrometric monitoring and (b) GC-MS spectra for the reaction of: CyDB (0.024 g, 0.1 mmol) and AIBN (0.032 g, 0.2 mmol) in benzene at 60 C in the presence of air (The arrow directs the reaction time of 0, 0.5, 1, 2, 3h). (a) (b) Figure S9. (a) UV-Vis spectrometric monitoring and (b) GC-MS spectra for the reaction of: MADB (0.024 g, 0.1 mmol) and AIBN (0.032 g, 0.2 mmol) in benzene at 60 C in the presence of air (The arrow directs the reaction time of 0, 0.25, 0.5, 0.75, 1, 2, 4, 6, 8h). (a) (b) Figure S10. (a) UV-Vis spectrometric monitoring and (b) GC-MS spectra for the reaction of: BDES(0.027 g, 0.1 mmol) and AIBN (0.032 g, 0.2 mmol) in benzene at 60 C in the presence of air (The arrow directs the reaction time of 0, 0.5, 1, 2, 3, 4, 8, 10h). (a) (b) Figure S11. (a) UV-Vis spectrometric monitoring and (b) GC-MS spectra for the reaction of : DBTTC(0.029 g, 0.1 mmol) and AIBN (0.032 g, 0.2 mmol) in benzene at 60 C in the presence of air (The arrow directs the reaction time of 0, 1, 2, 4, 8, 12, 16, 20, 28 , 38h). (a) (b) Figure S12. (a) UV-Vis spectrometric monitoring and (b) GC-MS spectra for the reaction of : EtoCDB (0.024 g, 0.1 mmol) and AIBN (0.032 g, 0.2 mmol) in benzene at 60 C in the presence of air (The arrow directs the reaction time of 0, 1, 2, 4, 8, 16, 24, 32, 46h). Figure S13. GC-MS spectra of AIBN in figure S5-S11. Figure S14. HPLC diagrams detected at 254 nm for the cyclohexyl benzothioate (CHBT) isolated by TLC. Figure S15. GC-MS spectra of the cyclohexyl benzothioate (CHBT). Figure S16. 1HNMR spectrum of the cyclohexyl benzothioate (CHBT). (The signals with star and open symbol are from water and solvent, cyclohexane). 3.0 before reation after reaction Absorbance 2.5 2.0 1.5 15 16 17 18 19 20 21 22 23 24 25 Elution time / min 1.0 0.5 0.0 270 300 330 360 390 420 450 (nm) Figure S17. UV-Vis spectrometry and GPC diagrams detected by 410 RI detector (the inset) monitoring the heating of PS-RAFT (0.228 g, 0.1mmol) and AIBN (0.065 g, 0.4 mmol) in benzene in the presence of air. Solid line: before the reaction; Red line: after heating at 60 C for 4 h. Feed: PS-RAFT: AIBN = 1:4 (molar ratio).