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solution for 24 h separated and dried with Na2SO4. The solu-
tion was filtered and the organic solvent was evaporated in
vacuo to obtain the crude product as a colorless oil. Ten mil-
ligram of 2,6-di-tert-butyl-4-methylphenol were added and
the product was subjected a fractionated destillation under
vacuum to yield 34.97 g (0.2 mol) of the desired product in
highest purity and 37% yield. bp 55 8C (4.5 mmHg). dH (300
MHz; CDCl3) 6.49 (m, 1H, CH2@CH), 6.19 (m, 1H, CH2@CH),
5.90 (m, 1H, CH2@CH), 4.48 (t, 2H, 3J 6.2, CH2CH2Br), and
g mol21, Ð 5 1.19. Anal. calcd for C503H824O317S48: C, 44.81;
H, 6.16; S, 11.41; Br, 0. Found: C, 43.87; H, 6.17; S, 10.81; Br,
0.89.
P5
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1H NMR (300 MHz; D2O, d ppm) 4.44 (n H, d, J 9.3, HGal-1),
4.25 (2n H, br s), 3.89 (n H, s), 3.82–3.41 (5n H, m), 3.16–
2.72 (2n H, m), 2.36 (2n H, br s), 2.04–1.00 (2n 1 1 H, m).
SEC (H2O, 0.1 M NaNO3, 0.05% NaN3, pullulan standard):
Mn 5 9,900 g mol21, Mw 5 12,000 g mol21, Ð 5 1.22. Anal.
calcd for C503H824O317S48: C, 44.81; H, 6.16; S, 11.41; Br, 0.
Found: C, 41.88; H, 6.13; S, 11.99; Br, 1.99.
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4.48 (t, 2H, J 6.2, CH2CH2Br).
General Procedure for the Syntheses of PBEA
Homopolymers
P7
CPAETC, BEA, and AIBN were dissolved in dioxane and the
reaction mixture was deoxygenated with Ar for 10 min and
stirred at 65 8C for 4 h. After completion, the solution was
cooled to room temperature, opened to air, and precipitated
in diethyl ether to give PBEA homopolymers P1 to P3.
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1H NMR (300 MHz; D2O, d ppm) 4.49 (n H, d, J 9.7, HGlc-1),
4.24 (2n H, br s), 3.85–3.70 (n H, m), 3.70–3.56 (n H, m),
3.55–3.18 (4n H, m), 3.11–2.70 (2n H, m), 2.37 (2n H, br s),
2.11–1.00 (2n 1 1 H, m). SEC (H2O, 0.1 M NaNO3, 0.05%
NaN3, pullulan standard): Mn 5 17,400 g mol21, Mw 5 21,800
g mol21, Ð 5 1.25. Anal. calcd for C866H1418O548S81: C, 44.84;
H, 6.16; S, 11.20; Br, 0. Found: C, 44.15; H, 6.18; S, 9.48; Br,
2.14.
P1
1H NMR (300 MHz; CDCl3, d ppm) 4.99–4.88 (1 H, m), 4.42
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(2n H, br s), 3.57 (2n H, br s), 3.40 (2 H, t, J 7.4), 2.49 (2n
H, br s), 2.05 (2n H, br s), 1.94–1.50 (2n 1 1 H, m), 1.48–
1.41 (3 H, m), 0.95 (3 H, t, 3J 7.3). SEC (DMAc 1 0.21 wt %
P8
LiCl, PS standard): Mn 5 8,800 g mol21, Mw 5 9,600 g mol21
Ð 5 1.10.
,
1H NMR (300 MHz; D2O, d ppm) 4.44 (n H, d, J 8.9, HGal-1),
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4.24 (2n H, br s), 3.90 (n H, s), 3.83–3.41 (5n H, m), 3.17–
2.71 (2n H, m), 2.38 (2n H, br s), 2.04–0.99 (2n 1 1 H, m).
SEC (H2O, 0.1 M NaNO3, 0.05% NaN3, pullulan standard):
Mn 5 16,400 g mol21, Mw 5 21,000 g mol21, Ð 5 1.28. Anal.
calcd for C866H1418O548S81: C, 44.84; H, 6.16; S, 11.20; Br, 0.
Found: C, 43.28; H, 6.18; S, 9.31; Br, 3.09.
P2
1H NMR (300 MHz; CDCl3, d ppm) 4.98–4.88 (1 H, m), 4.43
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(2n H, br s), 3.57 (2n H, br s), 3.39 (2 H, t, J 7.2), 2.47 (2n
H, br s), 2.15–1.97 (2n H, br s), 1.90–1.39 (2n H, m), 0.96
(3 H, t, 3J 7.4). SEC (DMAc 1 0.21 wt % LiCl, PS standard):
Mn 5 11,200 g mol21, Mw 5 13,500 g mol21, Ð 5 1.21.
P10
1H NMR (300 MHz; D2O, d ppm) 4.49 (n H, d, J 9.7, HGlc-1),
3
P3
4.24 (2n H, br s), 3.86–3.69 (n H, m), 3.69–3.55 (n H, m),
3.55–3.17 (4n H, m), 3.08–2.71 (2n H, m), 2.36 (2n H, br s),
2.06–1.00 (2n 1 1 H, m). SEC (H2O, 0.1 M NaNO3, 0.05%
NaN3, pullulan standard): Mn 5 23,300 g mol21, Mw 5 29,300
g mol21, Ð 5 1.26. Anal. calcd for C1273H2084O807S118: C,
44.86; H, 6.16; S, 11.10; Br, 0. Found: C, 43.53; H, 6.20; S,
10.20; Br, 1.54.
1H NMR (300 MHz; CDCl3, d ppm) 4.98–4.88 (1 H, m), 4.42
3
(2n H, br s), 3.57 (2n H, br s), 3.38 (2 H, t, J 6.4), 2.47 (2n
H, br s), 2.14–1.96 (2n H, m), 1.92–1.39 (2n H, m), 0.95
(3 H, t, 3J 7.3). SEC (DMAc 1 0.21 wt % LiCl, PS standard):
Mn 5 18,000 g mol21, Mw 5 20,000 g mol21, Ð 5 1.11.
General Procedure for the Postpolymerization
Modification with Glc and Gal
P11
One hundred milligram of the precursor polymer was dis-
solved in 1 mL DMSO and a solution of the desired carbohy-
drate (DPꢀ1.1 equiv.) in 1 mL DMSO was added. The solution
was deoxygenated with Ar for 30 min and 1 equiv. (based
on the carbohydrate) dry triethylamine was added dropwise.
The reaction mixture was stirred at room temperature for
one day and dialyzed against water for one week (CE,
MWCO: 3.5 kDa). The dialyzed solution was freeze-dried to
obtain the desired polymer.
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1H NMR (300 MHz; D2O, d ppm) 4.44 (n H, d, J 9.1, HGal-1),
4.24 (2n H, br s), 3.89 (n H, s), 3.83–3.41 (5n H, m), 3.22–
2.72 (2n H, m), 2.37 (2n H, br s), 2.09–1.00 (2n 1 1 H, m).
SEC (H2O, 0.1 M NaNO3, 0.05% NaN3, pullulan standard):
Mn 5 23,300 g mol21, Mw 5 29,900 g mol21, Ð 5 1.28. Anal.
calcd for C1273H2084O807S118: C, 44.86; H, 6.16; S, 11.10; Br,
0. Found: C, 41.73; H, 6.05; S, 10.58; Br, 2.52.
General Procedure for the Postpolymerization
Modification with Man
P4
1H NMR (300 MHz; D2O, d ppm) 4.49 (n H, d, J 9.8, HGlc-1),
3
One hundred milligram of the precursor polymer was dis-
solved in 1 mL DMSO and a solution of Man-SNa (DPꢀ1.1
equiv.) in 0.5 mL H2O was added. The solution was deoxygen-
ated with Ar for 30 min, stirred at room temperature for one
day and dialyzed against water for one week (CE, MWCO: 3.5
4.24 (2n H, br s), 3.85–3.69 (n H, m), 3.69–3.55 (n H, m),
3.47–3.17 (4n H, m), 3.07–2.74 (2n H, m), 2.33 (2n H, br s),
2.03–1.00 (2n 1 1 H, m). SEC (H2O, 0.1 M NaNO3, 0.05%
NaN3, pullulan standard): Mn 5 10,000 g mol21, Mw 5 11,800
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JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY 2017, 00, 000–000
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