Supporting Information for: Generation of Living Species Using Perfluoroalkylsulfonic Acids in Concurrent Cationic Vinyl-Addition and Ring-Opening Copolymerization via Crossover Reactions Daisuke Hotta, Arihiro Kanazawa*, and Sadahito Aoshima* Department of Macromolecular Science, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan. Contents: Figure S1. 1 H NMR spectra of poly(ipve-co-ibo)s obtained by SnCl 4, TfOH, and B(C 6 F 5 ) 3 Figure S2. MWD curves of the polymers obtained by B(C 6 F 5 ) 3 and Ph 3 C + PF 6 Figure S3. 1 H and 19 F NMR spectra of the poly(ipve-co-ibo) obtained by Ph 3 C + PF 6 Figure S4. Time conversion plots for the copolymerization of IPVE and IBO by TfOH in dichloromethane and MWD curves of the obtained polymers Figure S5. Relative concentrations of IPVE to IBO under various conditions Figure S6. 13 C and DEPT 135 NMR spectra of poly(ipve-co-ibo), 3-buten-1-ol, a product obtained by the homopolymerization of IBO, and IPVE homopolymer Figure S7. 1 H NMR spectra of polymers obtained using 3-buten-1-ol as a quencher Scheme S1. A possible mechanism of the incorporation of a quencher fragment into the VE-derived end Figure S8. The ratios of isomerization of IBO to IBA in the polymerization using various initiators or catalysts, the ratios of the isomerization of IBO to IBA using TfOH or C 4 F 9 SO 3 H as an initiator under various polymerization conditions, and M n values of the polymers produced in the presence or absence of purposely-added IBA Figure S9. MWD curves of the products obtained by the copolymerization of cyclohexyl VE and IBO; IPVE and (+)-limonene oxide; and IPVE and styrene oxide Figure S10. Time conversion plots for the copolymerization of IPVE and IBO using perfluoroalkylsulfonic acids as initiators in dichloromethane at 78 ºC, M n values, and MWD curves of the obtained polymers Figure S11. MWD curves of polymers produced in dichloromethane/hexane (1/9 v/v) at 95 ºC
Figure S1. 1 H NMR spectra of poly(ipve-co-ibo)s obtained by (A) SnCl 4 (entry 14 in Table 1), (B) TfOH (the same spectrum to that shown in Figure 3A), and (C) B(C 6 F 5 ) 3 (entry 10 in Table 1). For the assignment: Beckwith, A. L. J.; Bowry, V. W. J. Org. Chem. 1988, 53, 1632 1641. Figure S2. MWD curves of the polymers obtained by (A) B(C 6 F 5 ) 3 and (B) Ph 3 C + PF 6 (black: original polymers, purple: products obtained by acid hydrolysis; the data correspond to those listed in Table 1); see Table 1 for the polymerization conditions; * monomer conversion values calculated from 1 H NMR and gravimetry.
Figure S3. (A) 1 H and (B) 19 F (470.62 MHz) NMR spectra of the poly(ipve-co-ibo) obtained by Ph 3 C + PF 6 (entry 13 in Table 1). For the assignment: Chaabouni, M. M. Baklouti, A. Synth. Commun. 1989, 19, 2683 2689. * Decomposition products of the initiator: Peaks at 82.9ppm (d, 978 Hz) and 83.2 (d, 985 Hz) were assigned to dialkyl monofluorophosphates derived from PF 6 (reference: Wagner, R.; Korth, M.; Streipert, B.; Kasnatscheew, J.; Gallus, D. R.; Brox, S.; Amerller, M.; Cekic-Laskovic, I.; Winter, M. ACS Appl. Mater. Interfaces 2016, 8, 30871 30878). A peak at 128.0ppm (s) was assigned to Ph 3 CF (reference: Habibi, M. H.; Mallouk, T. E. J. Fluorine Chem. 1991, 51, 291 294).
Figure S4. (A) Time conversion plots for the copolymerization of IPVE (blue) and IBO (red) by TfOH in dichloromethane and (B) MWD curves of the obtained polymers (black: original polymers, purple: products obtained by acid hydrolysis; the same samples to those of entries 1 and 2 in Table 1); polymerization conditions: [IPVE] 0 = 0.75 M, [IBO] 0 = 0.22 M, [TfOH] 0 = 5.0 mm, in dichloromethane at 78 ºC; * monomer conversion values calculated from 1 H NMR and gravimetry. NOTE for Monomer Units per Block The hydrolysis products of the copolymers obtained in dichloromethane at higher monomer conversion values had larger MWs than those obtained at lower monomer conversion values, which indicates that the IPVE units per block increased as the polymerization proceeded. This behavior most likely stemmed from the change in the instantaneous monomer concentrations. Indeed, the [VE]/[IBO] ratio increased along with the increase of monomer conversion values in dichloromethane as shown in Figure S5. The frequent occurrence of isomerization reaction of IBO to IBA in dichloromethane is likely partly responsible for the fast consumption of IBO. Figure S5. Relative concentrations of IPVE to IBO under various conditions. See Figures S4 and 7 for the polymerization conditions.
Figure S6. 13 C and DEPT 135 NMR spectra of (A) poly(ipve-co-ibo) (the same sample to that shown in the middle of Figure 2B), (B) 3-buten-1-ol, (C) a product obtained by the homopolymerization of IBO [obtained by B(C 6 F 5 ) 3 ], and (d) IPVE homopolymer [obtained by B(C 6 F 5 ) 3 ] recorded in CDCl 3 at 30 ºC; spectra (C) and (D) are the same data to those reported in reference 8; * solvent.
Figure S7. 1 H NMR spectra of polymers obtained using 3-buten-1-ol as a quencher: (A) poly(ipve-co-ibo) obtained by TfOH (the same spectrum to that shown in Figure 3A), (B) poly(ipve) (the spectrum reported in our previous study [reference 48]), (C) poly(ipve-co-ibo) obtained by Ph 3 C + B(C 6 F 5 ) 4 (entry 12 in Table 1), (D) poly(ipve-co-ibo) obtained by B(C 6 F 5 ) 3 (entry 10 in Table 1), and (E) 3-buten-1-ol. Scheme S1. A possible mechanism of the incorporation of a quencher fragment into the VE-derived end.
Figure S8. (A) The ratios of isomerization of IBO to IBA in the polymerization using various initiators or catalysts (the data correspond to entries 2, 8, and 11 13 in Table 1). The ratios of the isomerization of IBO to IBA were based on the originally charged amount of IBO. (B) The ratios of the isomerization of IBO to IBA using TfOH or C 4 F 9 SO 3 H as an initiator under various polymerization conditions (the conditions correspond to those of Figures 7 and 8). (C) M n values of the polymers produced in the presence or absence of purposely-added IBA; polymerization conditions: [IPVE] 0 = 0.75 M, [IBO] 0 = 0.22 M, [IBA] 0 = 0, 22, 66, 220, or 1000 mm, in CH 2 Cl 2 at 78 ºC. NOTE for the Isomerization of IBO to IBA The isomerization of epoxides to aldehydes were reported to occur via acid catalysis (references 49 and 50). In Figure S8A, the possibility of the isomerization at the propagating end (R = polymer chain) is also shown as well as the catalysis by TfOH (R = H). In addition, the counteranion (OTf etc.) may also be responsible for the isomerization because IBA was not generated in the reactions using Ph 3 CB(C 6 F 5 ) 4 and B(C 6 F 5 ) 3 (Figure S8B). Moreover, the generated amount of IBA was larger in dichloromethane than in dichloromethane/hexane (1/9) (Figure S8C), which corresponds to the lower incorporated ratios of IBO into the copolymers in the polymerization in dichloromethane.
Figure S9. MWD curves of the copolymerization products (black) and their acid hydrolysis products (purple): Copolymerization of (A) cyclohexyl VE and IBO; (B) IPVE and (+)-limonene oxide; and (C) IPVE and styrene oxide; polymerization conditions: [VE] 0 = 0.75 M, [oxirane] 0 = 0.22 (for A and C) or 0.21 M (for B), [TfOH] 0 = 5.0 mm, in dichloromethane at 78 ºC. Note for Figure S9: The reaction conditions for the copolymerization shown in Figure S9 have not been optimized yet. We have not conducted the detailed investigation of the copolymerization of VEs and oxiranes other than IPVE and IBO. We need to examine the copolymerization using not only TfOH but also B(C 6 F 5 ) 3 for understanding the behavior of the oxiranes that generate a tertiary carbocation [e.g. (+)-limonene oxide] with a ring structure or an aromatic ring-adjacent carbocation (styrene oxide).
Figure S10. (A) Time conversion plots for the copolymerization of IPVE and IBO using perfluoroalkylsulfonic acids as initiators (green: TfOH, purple: C 4 F 9 SO 3 H, black: C 8 F 17 SO 3 H) in dichloromethane at 78 ºC; see entries 1 and 2 in Table 1 and entries 3, 4, 9, and 10 in Table 2 for the polymerization conditions. (B) M n values and (C), (D) MWD curves (black: original polymers; purple: products obtained by acid hydrolysis) of the obtained polymers (entries 3, 4, 9, and 10 in Table 2); * monomer conversion values calculated from gravimetry and 1 H NMR of the product. Figure S11. MWD curves (black: original polymers; purple: products obtained by acid hydrolysis) of polymers produced in dichloromethane/hexane (1/9 v/v) at 95 ºC; see Figure 8 for the polymerization conditions; * monomer conversion values calculated from gravimetry and 1 H NMR of the product.