Supplementary Material
Synthesis of Block and End-Functionalized Polyesters
by Triflimide-Catalyzed Ring-Opening Polymerization
of ε-Caprolactone, 1,5-Dioxepan-2-one, and racLactide
Kosuke Makiguchi, Seiya Kikuchi, Toshifumi Satoh, and Toyoji Kakuchi*
Graduate School of Chemical Sciences and Engineering, Faculty of Engineering, Hokkaido
University, Sapporo, 060-8628, Japan
Correspondence to Toyoji Kakuchi (kakuchi@poly-bm.eng.hokudai.ac.jp)
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Figure S1. 1H NMR spectrum of the obtained PCL (Table 1, run 1) in CDCl3 and the chemical
structure.
Figure S2. 1H NMR spectrum of the obtained PDXO (Table 1, run 3) in CDCl3 and the chemical
structure.
2
Figure S3. 1H NMR spectrum of the obtained PLA (Table 1, run 6) in CDCl3 and the chemical
structure.
Figure S4. SEC traces of the obtained PCL detected by refractive index (RI) and ultra violet (UV)
detectors (solvent, DMF containing 0.01 mol∙L-1 LiCl; flow rate, 0.4 mL∙min-1).
3
Figure S5. SEC traces of the obtained PDXO (Table 1, run 3) detected by refractive index (RI) and
ultra violet (UV) detectors (solvent, DMF containing 0.01 mol∙L-1 LiCl; flow rate, 0.4 mL∙min-1).
Figure S6. SEC traces of the obtained PLA (Table 1, run 6) detected by refractive index (RI) and
ultra violet (UV) detectors (solvent, DMF containing 0.01 mol∙L-1 LiCl; flow rate, 0.4 mL∙min-1).
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Figure S7. (a) MALDI-TOF MS spectrum of the obtained PDXO in reflector mode (Table 1, run 3),
(b) expanded spectrum, and (c) calculated molecular weight.
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Figure S8. (a) MALDI-TOF MS spectrum of the obtained PLA in reflector mode (Table 1, run 6),
(b) expanded spectrum, and (c) calculated molecular weight.
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Figure S9. 13C NMR spectra of the carbonyl carbon signals of (a) ε-CL, (b) a 1:1 mixture of ε-CL
and HNTf2, (c) DXO, (d) a 1:1 mixture of DXO and HNTf2, (e) rac-LA, and (f) a 1:1 mixture of racLA and HNTf2 in CDCl3.
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Figure S10. SEC traces of first PCL sequence (solid line; Mn,NMR 5,670, Mw/Mn 1.14) and
postpolymerization (dashed line; Mn,NMR 11,000, Mw/Mn 1.19) (eluent, CHCl3, flow rate, 0.8
mL·min-1).
Figure S11. IR spectra of PCL-N3 (black line) and PCL-b-PLA (red line).
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Table S1. Synthesis of End-functionalized Polymers by the HNTf2-catalyzed ROP of Cyclic Monomers using Various Functional Initiators a
monomer Funcional Initiator
[M]0
run
[HNTf2]0/[PPA]0 Time (h) Conv. (%) b Mn,theo. (g mol-1) c Mn,NMR (g mol-1)b
Mw/Mn d
(M)
(FI)
(mol L-1)
1
δ-VL
AHA
3
0.1
2
92.0
4,700
4,700
1.12
2
δ-VL
HEMI
3
0.1
2
91.0
4,700
6,300
1.11
3
δ-VL
HEA
3
0.1
2
94.9
4,850
5,130
1.17
4
δ-VL
HEMA
3
0.1
2
92.4
4,760
4,950
1.18
5
ε-CL
AHA
3
0.1
7
96.5
5,650
5,750
1.15
6
ε-CL
HEMI
3
0.1
7
98.0
5,740
5,760
1.17
7
ε-CL
HEA
3
0.1
7
98.5
5,720
5,740
1.19
8
ε-CL
HEMA
3
0.1
7
98.3
5,740
5,910
1.16
9
DXO
AHA
3
0.1
7
96.7
5,760
5,830
1.17
10
DXO
HEMI
3
0.1
7
97.5
5,800
5,780
1.19
11
DXO
HEA
3
0.1
7
97.5
5,790
5,770
1.17
12
DXO
HEMA
3
0.1
7
97.9
5,790
5,980
1.16
13
rac-LA
AHA
1
3.0
385
80.8
5,970
n.d.e
1.94 f
14
rac-LA
HEMI
1
3.0
385
90.6
6,670
7,040
1.19
15
rac-LA
HEA
1
3.0
385
98.1
6,940
7,170
1.24
16
rac-LA
HEMA
1
3.0
385
97.7
6,910
7,170
1.22
a
Temperature, room temp.; solvent, CH2Cl2; [M]0/[FI]0, 50. b Determined by 1H NMR in CDCl3 c Calculated from ([M]0/[FI]0) × conv. × (M.W.
of monomer) + (M. W. of FI). d Determined by SEC in CHCl3 using PSt standards. e Not determined. f Azido was degraded as indicated by IR and
MALDI-TOF MS.
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