Supporting Information for
Ring-opening Polymerization of Six-membered Cyclic Carbonates
Initiated by Ethanol Amine Derivatives and Their Application to
Protonated or Quaternary Ammonium Salt-functionalized
Polycarbonate Films
Hiroyuki Matsukizono, Takeshi Endo
Molecular Engineering Institute, Kinki University,
11-6 Kayanomori, Iizuka, Fukuoka, 820-8555, Japan
Correspondence to: T. Endo (E-mail: tendo@moleng.fuk.kindai.ac.jp)
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Synthesis of star-shaped, telechelic or linear polycarbonates
Synthesis of star-shaped polycarbonates N-pNPGC3
Star-shaped polycarbonate N-pNPGC3 was synthesized by the same procedures as N2-pNPGC4. A
THF solution of NPGC with N-(OH)3 (I) and DBU (1 mL, [M]0 = 4.0 M, [M]0/[I]0/[DBU] = 40/1/2) was
stirred at ambient temperature for 8 h under nitrogen atmosphere. After an addition of acetic acid,
the solution was added to methanol (200 mL) and the mixture was kept at 4 °C for several hours.
Resulting precipitates were collected and washed with methanol and then dried under reduced
pressure. The star-shaped polycarbonate N-pNPGC3 was obtained as white powders. Yield: 419 mg.
At 5.0 mol% of N-(OH)3, N-pNPGC3 was similarly obtained. Yield: 128 mg. Details are listed in Entry
2 and 3 in Table 1.
Synthesis of telechelic polycarbonate N-pNPGC2
Telechelic polycarbonate N-pNPGC2 was synthesized according to the same procedure as N2pNPGC4. A THF solution of NPGC with N-(OH)2 (I) and DBU (1 mL, [M]0 = 4.0 M, [M]0/[I]0/[DBU] =
40/1/2) was stirred at ambient temperature for 8 h under nitrogen atmosphere. After an addition of
acetic acid, the solution was added to methanol (200 mL) and the mixture was kept at 4 °C for several
hours. Resulting precipitates were collected and washed with methanol and then dried under
reduced pressure. The telechelic polycarbonate N-pNPGC2 was obtained as white powders. Yield:
395 mg. At 5.0 mol% of N-(OH)2, N-pNPGC2 was similarly obtained. Yield: 228 mg. Details are listed
in Entry 4 and 5 in Table 1.
Synthesis of linear polycarbonate N-pNPGC
Linear polycarbonate N-pNPGC was synthesized according to the same procedure as N2-pNPGC4.
A THF solution of NPGC with N-OH (I) and DBU (1 mL, [M]0 = 4.0 M, [M]0/[I]0/[DBU] = 20/1/1) was
stirred at ambient temperature for 8 h under nitrogen atmosphere. After an addition of acetic acid,
the solution was added to methanol (200 mL) and the mixture was kept at 4 °C for several hours.
Resulting precipitates were collected and washed with methanol and then dried under reduced
pressure. The linear polycarbonate N-pNPGC was obtained as white powders. Yield: 342 mg. At 10
mol% of N-OH, N-pNPGC was similarly obtained. Yield: 32 mg. Details are listed in Entry 6-8 in Table
1.
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FIGURE S1 1H NMR spectrum of a THF solution of NPGC ([M]0 = 4.0 M) containing 2.5 mol% of N2-(OH)4 and
5.0 mol% of DBU after reaction at ambient temperature for 8 h.
FIGURE S2 Characterization of the ROP of NPGC initiated by 2.5 mol% of triethanol amine (N-(OH)3) at
ambient temperature. a) Reaction equation. b) ln([M]/[M]0) versus reaction time plot. c) Mn versus conversion
plot. Dotted line: theoretical line of Mn. ln([M]/[M]0), Conversion and Mn were calculated by 1H NMR
spectroscopy.
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FIGURE S3 Top: 1H NMR spectrum of a THF solution of NPGC ([M]0 = 4.0 M) containing 2.5 mol% of N-(OH)3
and 5.0 mol% of DBU after reaction at r. t. for 9 h. Bottom: 1H NMR spectrum of N-pNPGC3 after purification
by precipitation from methanol. Inset: Magnified spectrum.
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FIGURE S4 Top: 1H NMR spectrum of a THF solution of NPGC ([M]0 = 4.0 M) containing 5.0 mol% of N-(OH)3
and 5.0 mol% of DBU after reaction at ambient temperature for 8 h. Bottom: 1H NMR spectrum of N-pNPGC3
after purification by precipitation from methanol. Inset: Magnified spectrum.
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FIGURE S5 Characterization of the ROP of NPGC initiated by a) 2.5 or b) 5.0 mol% of N-(OH)2 at ambient
temperature. Left) ln([M]/[M]0) versus reaction time plot. Right) Mn versus conversion plot. Dotted line:
theoretical line of Mn. ln([M]/[M]0), Conversion and Mn were calculated by 1H NMR spectroscopy.
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FIGURE S6 Top: 1H NMR spectrum of a THF solution of NPGC ([M]0 = 4.0 M) containing 2.5 mol% of N-(OH)2
and 5.0 mol% of DBU after reaction at ambient temperature for 8 h. Bottom: 1H NMR spectrum of N-pNPGC2
after purification by precipitation from methanol. Inset: Magnified spectrum.
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FIGURE S7 Top: 1H NMR spectrum of a THF solution of NPGC ([M]0 = 4.0 M) containing 5.0 mol% of N-(OH)2
and 5.0 mol% of DBU after reaction at ambient temperature for 8 h. Bottom: 1H NMR spectrum of N-pNPGC2
after purification by precipitation from methanol. Inset: Magnified spectrum.
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FIGURE S8 Characterization of the ROP of NPGC initiated by a) 5.0 or b) 10 mol% of N-OH at ambient
temperature. Left: ln([M]/[M]0) versus reaction time plot. Right: Mn versus conversion plot. Dotted line:
theoretical line of Mn. ln([M]/[M]0), Conversion and Mn were calculated by 1H NMR spectroscopy.
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FIGURE S9 Top: 1H NMR spectrum of a THF solution of NPGC ([M]0 = 4.0 M) containing 2.5 mol% of N-OH and
5.0 mol% of DBU after reaction at ambient temperature for 8 h. Bottom: 1H NMR spectrum of N-pNPGC after
purification by precipitation from methanol. Inset: Magnified spectrum.
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FIGURE S10 Top: 1H NMR spectrum of a THF solution of NPGC ([M]0 = 4.0 M) containing 5.0 mol% of N-OH
and 5.0 mol% of DBU after reaction at ambient temperature for 8 h. Bottom: 1H NMR spectrum of N-pNPGC
after purification by precipitation from methanol. Inset: Magnified spectrum.
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FIGURE S11 Top: 1H NMR spectrum of a THF solution of NPGC ([M]0 = 4.0 M) containing 10 mol% of N-OH and
10 mol% of DBU after reaction at ambient temperature for 8 h. Bottom: 1H NMR spectrum of N-pNPGC after
purification by precipitation from methanol. Inset: Magnified spectrum.
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FIGURE S12 MALDI-TOF mass spectrum of N-pNPGC. The attribution of each fragment is also depicted.
Figure S13 Possible mechanism of the inhibition of the chain extension reaction by N,N-dimethylamino
ethanol residues through the electrostatic interaction.
FIGURE S14 TGA profiles of star-shaped, telechelic or linear polycarbonates bearing tertiary amine groups
after purification. a) Red) N2-pNPGC4 (Entry 5 in Table 1). Blue) N-pNPGC3 (Entry 6). Green) N-pNPGC2 (Entry
7). Orange) N-pNPGC (Entry 8). b) Polycarbonates synthesized by the ROP of NPGC initiated with different
amounts of ethanol amine derivatives at 50 °C for 18 h. The amounts of Initiators were 5/4 for N2-(OH)4, 5/3
for N-(OH)3, 5/2 for N-(OH)2 or 5 mol% for N-OH. Red) N2-pNPGC4 (degree of polymerization (n) = 24). Blue)
N-pNPGC3 (n = 21). Green) N-pNPGC2 (n = 25). Orange) N-pNPGC (n = 20).
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FIGURE S15 1H NMR spectrum of partially-networked polycarbonate PNP-A in CDCl3 with 0.03 v/v% of TMS.
After purification by precipitation from methanol.
FIGURE S16 1H NMR spectrum of partially-networked polycarbonate PNP-B in CDCl3 with 0.03 v/v% of TMS.
After purification by precipitation with methanol.
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FIGURE S17 1H NMR spectrum of partially-networked polycarbonate PNP-C in CDCl3 with 0.03 v/v% of TMS.
After purification by precipitation with methanol.
FIGURE S18 1H NMR spectrum of partially-networked polycarbonate PNP-D in CDCl3 with 0.03 v/v% of TMS.
After purification by precipitation with methanol.
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FIGURE S19 TGA profiles of tertiary amine-modified polycarbonate films. Solid line: Film A. Dashed line: Film
B. Dotted line: Film C. Dotted and dashed line: Film D.
FIGURE S20 TGA profile of networked polycarbonate films prepared without using ethanol amine analogues
as initiators. The film was prepared by the ROP of THF solution ([M]0 = 1.25 M) containing NPGC (70 mol%
with respect to total monomers), DTMPC (30 mol% with respect to total monomers) and DBU (5 mol% with
respect to total monomers) at 60 °C for 12 h.
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FIGURE S21 a) Protonation of tertiary amine-modified polycarbonate films with p-toluenesulfonic acids (pTolSO3H). b, c) UV/vis-absorption spectra of b) Film A or c) Film B before/after the reaction with p-TolSO3H.
Dashed lines: Before protonation. Solid lines: After protonation.
Figure S22 1H NMR spectra of a) BnBr-N-OH, b) N-pNPGC and c) BnBr-N-pNPGC in DMSO-d6. BnBr-N-pNPGC
was synthesized from the stirring of N-pNPGC in methanolic solution of BnBr at ambient temperature
overnight.
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Figure S23 FT-IR spectra of PAS- or QAS-functionalized polycarbonate films before (red) or after an immersion
in PBS buffers (10 mM, pH 7.4) (blue) at ambient temperature for one week. These films were measured by
ATR method. Peaks at ca. 3400 cm-1 are ascribed to the stretching vibrations of adsorbed water molecules
and/or terminal hydroxyl groups of networked polycarbonate films.
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