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X. Liang et al. / Polymer 51 (2010) 3693e3705
(aromatic CeC]O), 140.43 (aromatic CeCH]CH2), 144.26e144.37
(aromatic CeOeC]O), 156.70 (aromatic CeO CH2CH2OCH3),
164.54e165.31 (C]O). Elemental Analysis: Found (Calc.): C 68.21
(68.28); H 5.62 (5.73). MS (EI): Mþ ¼ 492.
115.24 (aromatic C ortho to eOCH2CH2), 118.31 (eCH]CH2), 122.18
(aromatic C ortho to eOeC]O) 128.52 (aromatic C ortho to eCH]
CH2 and eC]O), 128.91 (aromatic C para to eCH]CH2), 130.81
(aromatic C meta to eCH]CH2 and ortho to eC]O), 131.80 (eCH]
CH2), 133.03e134.52 (aromatic CeC]O), 140.37 (aromatic CeCH]
CH2), 144.10e144.20 (aromatic CeOeC]O), 156.62 (aromatic CeO
CH2CH2OCH3), 164.42e165.19 (C]O). Elemental Analysis: Found
(Calc.): C 62.18 (63.48); H. 6.86 (6.93) MS (EI): Mþ ¼ 756.
2.5.2. 2,5-Bis{4-[methoxydis(oxyethylene)phenyl]oxycarbonyl}
styrene (2EOPCS)
The synthetic procedure was the same as that for 1EOPCS except
that 4-methoxybis(oxyethylene)phenol was used instead of
4-methoxyethoxyphenol. 1H NMR (
d, CDCl3, ppm): 8.44e8.43
(d,1H, AreH), 8.22e8.16 (m, 2H, AreH), 7.58e7.51 (q, 1H, eCH]
CH2), 7.16e7.14 (q, 4H, AreH), 6.99e6.97 (q, 4H, AreH), 5.86e5.82
(d, 1H, eCH]CH2), 5.50e5.47 (d, 1H, eCH]CH2), 4.18e4.15 (m, 4H,
AreOCH2eCH2Oe), 4.00e3.87 (m, 4H, AreOCH2eCH2Oe),
3.57e3.73 (m, 4H, AreOCH2eCH2OeCH2eCH2Oe), 3.60e3.59 (m,
4H, AreOCH2eCH2OeCH2eCH2Oe), 3.40 (s, 6H, -OCH3). 13C NMR
2.6. Polymerization
Polymers were obtained either by conventional solution
radical polymerization or by atom transfer radical polymerization
(ATRP). A typical polymerization procedure by conventional
solution radical polymerization is summarized as the following.
(d
, CDCl3, ppm): 59.18e59.23 (-OCH3), 67.78 (AreOCH2e), 69.62
(AreOCH2CH2Oe), 70.66 (eOCH2CH2OCH3), 71.84
About 1EOPCS (0.4 g, 0.8 mol), 40 mL of 0.05M BPO chlorobenzene
(eOCH2CH2OCH3), 115.27 (aromatic C ortho to eOCH2CH2OCH3),
118.42 (eCH]CH2), 122.29 (aromatic C meta to eOCH2CH2OCH3),
128.62 (aromatic C ortho to eCH]CH2 and eC]O), 129.00
(aromatic C para to eCH]CH2), 130.91 (aromatic C meta to eCH]
CH2 and ortho to eC]O), 131.91 (eCH]CH2), 133.14e134.64
(aromatic CeC]O), 140.43 (aromatic CeCH]CH2), 144.26e144.37
(aromatic CeOeC]O), 156.70 (aromatic CeO CH2CH2OCH3),
164.54e165.31 (C]O). Elemental Analysis: Found (Calc.): C 66.12
(66.19); H 6.16 (6.25). MS (EI): Mþ ¼ 580.
solution, and 2 mL of chlorobenzene were transferred into
a polymerization tube. After three freezeepumpethaw cycles,
the tube was sealed under vacuum. Polymerization was carried
out at 60 ꢀC for 24 h. The tube was then opened and the reaction
mixture was diluted with 10 ml THF. After evaporation of the
solvent, the products were purified using column chromatog-
raphy with dichloromethane as the eluent in order to remove
unreacted monomers. Polymers were obtained by precipitation
in methanol followed by drying under vacuum at room temper-
ature for 24 h.
2.5.3. 2,5-Bis{4-[methoxytris(oxyethylene)phenyl]oxycarbonyl}
styrene (3EOPCS)
A typical polymerization procedure by ATRP is summarized as
the following. 1EOPCS (0.25 g, 0.5 mmol), BEB (1.85 mg, 0.1 mmol),
PMDETA (1.73 mg, 0.1 mmol), and chlorobenzene (4 g) were added
sequentially into a reaction tube containing a magnetic stir bar. The
reaction mixture was purged with nitrogen and was subjected to
two freezeethaw cycles to remove any dissolved oxygen. Then CuBr
(1.44 mg, 0.1 mmol) was added into the reaction tube. After another
two freezeethaw cycles, the tube was sealed under vacuum. Poly-
merization was carried out at 90 ꢀC for 24 h. After the polymeri-
zation was terminated by immersing the tube into cold water, the
tube was broken. The polymerization mixture was then diluted
with 20 mL THF, and was passed through an Al2O3 column to
remove the copper complex. The solution was concentrated by
rotary evaporation and purified by silica gel column chromatog-
raphy with dichloromethane as the eluent. The solution was
precipitated using methanol. The precipitate was dried under
vacuum. The molecular weight and polydispersity of the polymer
were measured by GPC with PS standards.
The synthetic procedure was the same as that for 1EOPCS except
that 4-methoxytris(oxyethylene)phenol was used instead of
4-methoxyethoxyphenol. 1H NMR (
d, CDCl3, ppm): 8.45e8.44
(d,1H, AreH), 8.22e8.17 (m, 2H, AreH), 7.59e7.52 (q, 1H, eCH]
CH2), 7.16e7.14 (q, 4H, AreH), 6.99e6.96 (q, 4H, AreH), 5.85e5.82
(d, 1H, eCH]CH2), 5.51e5.47 (d, 1H, eCH]CH2), 4.20e4.17 (m, 4H,
AreOCH2eCH2Oe), 3.91e3.90 (m, 4H, AreOCH2eCH2Oe),
3.78e3.56 (m, 12H, AreOCH2CH2eOCH2CH2OCH2CH2e), 3.58e3.56
(m, 4H, AreOCH2CH2OCH2CH2OCH2CH2e), 3.40 (s, 6H, OCH3). 13C
NMR (d, CDCl3, ppm): 58.66 (OCH3), 67.22 (AreOCH2CH2Oe), 69.47
(AreOCH2CH2Oe),
70.22e70.51 (ArOCH2CH2OCH2CH2OCH2
-
CH2OCH3), 71.56 (eOCH2CH2OCH3), 115.03 (aromatic C ortho to
eOCH2CH2), 118.48 (eCH]CH2), 122.04 (aromatic C ortho to
eOeC]O), 128.67 (aromatic C ortho to eCH]CH2 and eC]O),
129.04 (aromatic C para to eCH]CH2), 130.91 (aromatic C meta to
eCH]CH2 and ortho to eC]O),132.01 (eCH]CH2), 133.14e134.64
(aromatic CeC]O), 140.43 (aromatic CeCH]CH2), 144.24e144.39
(aromatic CeOeC]O), 156.70 (aromatic CeO CH2CH2OCH3),
164.64e165.51 (C]O). Elemental Analysis: Found (Calc.): C 63.48
(63.52); H 6.93 (6.90). MS (EI): Mþ ¼ 648.
Table 1
Polymerization results of PnEOPCS.
Mn (ꢁ104 g/mol)
PDIa
Liquid Crystallinityb
a
2.5.4. 2,5-Bis{4-[methoxytetra(oxyethylene)phenyl]oxycarbonyl}
styrene (4EOPCS)
Sample
P1EOPCS-1
P1EOPCS-2
P1EOPCS-3
P1EOPCS-4
P1EOPCS-5
P1EOPCS-6
P2EOPCS-1
P2EOPCS-2
P3EOPCS-1
P3EOPCS-2
P4EOPCS-1
P4EOPCS-2
2.69
3.08
4.44
4.47
5.89
11.4
2.0
10.1
2.45
12.7
4.1
1.32
1.27
1.27
1.24
1.24
1.65
1.18
1.50
1.20
1.65
1.60
1.99
No
No
The synthetic procedure was the same as that for 1EOPCS except
that 4-methoxytetra(oxyethylene)phenol was used instead of
Yes
Yes
Yes
Yes
No
Yes
No
Yes
No
4-methoxyethoxyphenol. 1H NMR (
d, CDCl3, ppm): 8.43e8.42
(d,1H, AreH), 8.22e8.17 (m, 2H, AreH), 7.55e7.49 (q, 1H, eCH]
CH2), 7.16e7.14 (q, 4H, AreH), 6.99e6.96 (q, 4H, AreH), 5.86e5.80
(d, 1H, eCH]CH2), 5.50e5.46 (d, 1H, eCH]CH2), 4.17e4.15 (m, 4H,
AreOCH2eCH2Oe), 3.89e3.87 (m, 4H, AreOCH2eCH2Oe),
3.75e3.61 (m, 20H, AreOCH2CH2eOCH2CH2OCH2CH2 OCH2CH2e),
3.58e3.56 (m, 4H, AreOCH2CH2OCH2CH2OCH2CH2e), 3.35 (s, 6H,
9.7
Yes
OCH3). 13C NMR
(d
,
CDCl3, ppm): 58.90 (OCH3), 67.43
a
Molecular weights and polydispersity were measured by GPC, using terahy-
drofuran as an eluent at 35 ꢀC and monodisperse polystyrene as the standard.
(AreOCH2CH2Oe), 67.78 (AreOCH2CH2Oe), 69.57.39e70.73
(ArOCH2CH2O(CH2CH2)2OCH2CH2OCH3), 71.81 (eOCH2CH2OCH3),
b
Determined from PLM.