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T. Ueda et al. / Polymer 52 (2011) 3570e3579
2.5. Alkaline hydrolysis of ester groups of the polymers: typical
procedure
2H, eCH ¼ CHe), 7.04 (d, J ¼ 18.8 Hz, 2H, eCH ¼ CHe), 7.36e7.64
(m, 20H, Ar). IR (cmꢀ1, KBr): 3423, 2977, 1747, 1718, 1591, 1245, 1163,
999, 780, 700.
Aqueous NaOH (1 M, 0.17 mL) was added to a solution of (E)-
(Z)-Poly(1p-Si1) (run 10 in Table 1) 1H NMR (400 MHz, CDCl3):
poly(1p-Si1) (40 mg, 54
m
mol) in THF (1.25 mL) dropwise at 0 ꢂC, and
d 0.30e0.45 [br, 12H, eSi(CH3)2e], 1.44 [s, 9H, e(CH3)3], 3.73 (s, 3H,
then the resulting mixture was stirred at 50 ꢂC for 12 h. The reaction
mixture was poured into 0.5 M aqueous citric acid (100 mL) to
precipitate a polymer. It was separated by filtration using a membrane
filter (ADVANTEC H100A047A) and dried under reduced pressure.
eCO2CH3), 4.12 (s, 3H, eOCH3), 5.25 (s, 1H, eNHCHe), 5.63 (s, 1H,
eNHCOe), 6.05 [d, J ¼ 14.8 Hz, 2H, eCH ¼ CHe, (Z)-vinyl protons],
6.62 [d, J ¼ 19.0 Hz, 2H, eCH ¼ CHe, (E)-vinyl protons], 6.92 [d,
J ¼ 19.0 Hz, 2H, eCH ¼ CHe, (E)-vinyl protons], 7.23e7.59 [m, 16H,
Ar and (Z)-vinyl protons]. IR (cmꢀ1, KBr): 3432, 2957, 1746, 1719,
1602, 1507, 1250, 1162, 1132, 816.
2.6. Spectroscopic data of the polymers
(E)-Poly(1p-Si1)-hydrolyzed 1H NMR (400 MHz, DMSO-d6):
(E)-Poly(1p-Si1) (run 1 in Table 1) 1H NMR (400 MHz, CDCl3):
d
0.22e0.41 [br, 12H, eSi(CH3)2e], 1.37 [s, 9H, e(CH3)3], 4.05 (s, 3H,
eOCH3), 5.14 (s, 1H, eNHCHe), 6.68e6.82 (m, 2H, eCH ¼ CHe),
d
0.30e0.45 [br, 12H, eSi(CH3)2e], 1.44 [s, 9H, e(CH3)3], 3.75 (s, 3H,
6.87e7.09 (m, 2H, eCH ¼ CHe), 7.22e7.55 (m, 14H, Ar). IR (cmꢀ1
,
eCO2CH3), 4.14 (s, 3H, eOCH3), 5.26 (s, 1H, eNHCHe), 5.63 (s, 1H,
eNHCOe), 6.61 [d, J ¼ 18.8 Hz, 2H, eCH ¼ CHe], 6.92 [d, J ¼ 18.8 Hz,
2H, eCH ¼ CHe], 7.45e7.63 (m,14H, Ar). IR (cmꢀ1, KBr): 3423, 2954,
1750, 1718, 1602, 1507, 1250, 1162, 1134, 818.
KBr): 3423, 2955, 1719, 1602, 1507, 1249, 1161, 1133, 817.
(E)-Poly(1p-Si2)-hydrolyzed 1H NMR (400 MHz, DMSO-d6):
d
1.40 [s, 9H, e(CH3)3], 4.10 (s, 3H, eOCH3), 5.16 (s, 1H, eNHCHe),
(E)-Poly(1p-Si2) (run 4 in Table 1) 1H NMR (400 MHz, CDCl3):
1.44 [s, 9H, e(CH3)3], 3.75 (s, 3H, eCO2CH3), 4.15 (s, 3H, eOCH3),
6.94e6.96 (m, 2H, eCH ¼ CHe), 7.09e7.13 (m, 2H, eCH ¼ CHe),
7.42e7.70 (m, 20H, Ar). IR (cmꢀ1, KBr): 3422, 2976, 1718, 1600, 1507,
1243, 1159, 1111, 996, 795, 699.
d
5.26 (s, 1H, eNHCHe), 5.64 (s, 1H, eNHCOe), 6.88 (d, J ¼ 19.0 Hz,
2H, eCH ¼ CHe), 7.01 (d, J ¼ 19.0 Hz, 2H, eCH ¼ CHe), 7.17e7.63
(m, 20H, Ar). IR (cmꢀ1, KBr): 3423, 2975, 1746, 1718, 1599, 1509,
1244, 1161, 1111, 997, 797, 700.
(E)-Poly(1m-Si1)-hydrolyzed 1H NMR (400 MHz, DMSO-d6):
d
1.35 [s, 9H, e(CH3)3], 4.05 (s, 3H, eOCH3), 5.16 (s, 1H, eNHCHe),
6.72e6.82 (m, 2H, eCH ¼ CH-), 6.82e7.08 (m, 2H, eCH ¼ CHe),
7.08e7.87 (m, 20H, Ar). IR (cmꢀ1, KBr): 3423, 2955, 1719,1592, 1475,
1249, 1161, 1133, 987, 845, 780.
(E)-Poly(1m-Si1) (run 5 in Table 1) 1H NMR (400 MHz, CDCl3):
0.29e0.45 [br, 12H, eSi(CH3)2e], 1.43 [s, 9H, e(CH3)3], 3.74 (s, 3H,
d
(E)-Poly(1m-Si2)-hydrolyzed 1H NMR (400 MHz, DMSO-d6):
eCO2CH3), 4.14 (s, 3H, eOCH3), 5.26 (s, 1H, eNHCHe), 5.62 (s, 1H,
eNHCOe), 6.04 [d, J ¼ 14.8 Hz, 2H, eCH ¼ CHe, (Z)-vinyl protons],
6.61 [d, J ¼ 19.2 Hz, 2H, eCH ¼ CH-e (E)-vinyl protons], 6.91 [d,
J ¼ 19.2 Hz, 2H, eCH ¼ CHe, (E)-vinyl protons], 7.19e7.62 (m, 14H,
Ar). IR (cmꢀ1, KBr): 3423, 2953, 1749, 1719, 1591, 1477, 1249, 1161,
1132, 987, 843, 782.
d
1.35 [s, 9H, e(CH3)3], 4.07 (s, 3H, eOCH3), 5.16 (s, 1H, eNHCHe),
6.93e6.99 (m, 2H, eCH ¼ CHe), 7.03e7.15 (m, 2H, eCH ¼ CHe),
7.42e7.82 (m, 20H, Ar). IR (cmꢀ1, KBr): 3422, 2977, 1718, 1591, 1477,
1246, 1161, 998, 778, 700.
(Z)-Poly(1p-Si1)-hydrolyzed 1H NMR (400 MHz, DMSO-d6):
(E)-Poly(1m-Si2) (run 6 in Table 1) 1H NMR (400 MHz, CDCl3):
d
0.23e0.42 [br, 12H, eSi(CH3)2e], 1.38 [s, 9H, e(CH3)3], 4.04 (s, 3H,
eOCH3), 5.28 (s, 1H, eNHCHe), 6.06e6.13 [m, 2H, eCH ¼ CHe, (Z)-
d
1.42 [s, 9H, e(CH3)3], 3.73 (s, 3H, eCO2CH3), 4.13 (s, 3H, eOCH3),
vinyl protons], 6.62e6.86 [m, 2H, eCH ¼ CHe, (E)-vinyl protons],
5.25 (s, 1H, eNHCHe), 5.62 (s, 1H, eNHCOe), 6.93 (d, J ¼ 18.8 Hz,
Fig. 3. UVevis spectra of (E)- and (Z)-model compounds predicted by the DFT (B3LYP/6-31G*) calculation.