Y. Wan et al. / Polymer 53 (2012) 967e975
969
Scheme 1. Synthesis of (4-methoxy)phenylhydroquinone (Me-HQ).
(
12F, m), ꢁ138.5 (8F, m), ꢁ153.5 (8F, m). Anal. Calcd for C45
C, 46.31; H, 1.20; F, 45.45. Found: C, 47.22; H, 1.41; F, 43.64.
FA-APE Me 4. Yield: 93.6%. M /M ¼ 1.78. IR (KBr,
¼ 11257; M
), 1120e1300 (CeF). H NMR (500 MHz, acetone-
(ppm) 7.52 (2H, d, 10 Hz), 7.11 (1H, s), 6.99 (2H, s), 6.97
H
14
F
28
O
5
:
TMS):
s), 7.20 (3H, d, 10 Hz), 6.85 (6H, d, 10 Hz), 5.24 (4H, s). C NMR
(125 MHz, DMSO, TMS): (ppm) 158.4, 153.8, 150.5, 146.2, 144.2,
143.2, 142.6, 141.2, 140.6, 136.3, 135.7, 133.3, 131.2, 126.7, 119.0, 118.7,
d (ppm) 9.65 (3H, s), 7.40 (6H, d, 5 Hz), 7.34 (3H, s), 7.30 (3H,
13
n
w
n
d
ꢁ
1
1
cm ): 3020 (-CH
, TMS):
2H, s), 4.20 (12H, m), 3.84 (3H, s). C NMR (125 MHz, acetone-d
TMS): (ppm) 160.2, 154.0, 150.6, 146.0, 144.0, 143.3, 142.6, 141.3,
40.7,138.5, 135.8, 133.4,130.8, 128.5, 118.7, 118.0, 116.0,114.2,102.9,
01.9, 70.4, 55.1. 19F NMR (470 MHz, CDCl
, CFCl ):
(ppm) ꢁ122.3
3
19
d
(
6
d
116.3, 116.1, 102.7, 102.0, 70.4. F NMR (470 MHz, DMSO, CFCl
(ppm) ꢁ122.5 (12F, m), ꢁ138.5 (16F, m), ꢁ153.4 (16F, m). Anal.
Calcd for C92 11: C, 51.49; H, 1.31, F, 38.99. Found: C, 53.03; H,
1.30; F, 36.22.
PA-AE OH 3. Yield: 94.1%. M
3
):
13
6
,
d
d
28 44
H F O
1
1
(
C
5
3
3
d
n
¼ 11261; M
w
/M
cm ): 3460 (-OH), 1120e1300 (CeF). H NMR (500 MHz, DMSO,
TMS): (ppm) 9.66 (1H, s), 7.40 (2H, d, 5 Hz), 7.34 (1H, s), 7.29 (1H,
d, 5 Hz), 7.20 (1H, s), 6.84 (2H, d, 5 Hz), 5.26 (4H, s). C NMR
125 MHz, DMSO, TMS): (ppm) 158.4, 153.8, 150.5, 146.2, 144.2,
143.8,142.6,141.2,140.6, 138.5,136.3,133.3,131.2,126.7,119.0,118.6,
n
¼ 1.85. IR (KBr,
ꢁ1
1
36F, m), ꢁ138.5 (16F, m), ꢁ153.6 (16F, m). Anal. Calcd for
H
85 22
F
68
O
9
: C, 41.16; H, 0.89; F, 52.14. Found: C, 42.11; H, 1.00; F,
d
13
3.25.
(
d
2
.3.3. Synthesis of highly fluorinated aromatic-aliphatic
1
9
copolyethers containing hydroxyl group (FA-APE OH)
3
116.4, 116.1, 102.7, 102.0, 70.4. F NMR (470 MHz, DMSO, CFCl ):
A typical synthetic procedure for the preparation of FA-APE OH
d
(ppm) ꢁ122.6 (12F, m), ꢁ138.5 (8F, m), ꢁ153.5 (8F, m). Anal. Calcd
1
is as follows.1.0 g FA-APE Me 1 was dissolved into 20 mL CH
2
Cl
2
in
for C44
46.02.
12 28 5
H F O : C, 45.83; H, 1.04, F, 46.18. Found: C, 46.12; H, 1.13; F,
a 100 mL three-neck flask equipped with a magnetic stirrer and
ꢀ
a nitrogen inlet. The solution was cooled down to 0 C (ice bath) and
PA-AE OH 4. Yield: 91.4%. M
n
¼ 11602; M
w
/M
cm ): 3460 (-OH), 1120e1300 (CeF). H NMR (500 MHz, DMSO,
TMS): (ppm) (ppm) 9.66 (1H, s), 7.40 (2H, d, 5 Hz), 7.35 (1H, s),
7.29 (1H, d, 5 Hz), 7.20 (1H, s), 6.84 (2H, d, 5 Hz), 5.26 (12H, s).
NMR (125 MHz, DMSO, TMS): (ppm) 158.4, 153.8, 150.5, 146.2,
144.3, 143.9, 142.6, 141.2, 140.6, 138.5, 136.3, 133.3, 131.2, 126.6,
119.0, 118.6, 116.4, 116.1, 102.6, 102.1, 70.4. F NMR (470 MHz,
DMSO, CFCl ):
(ppm) ꢁ122.4 (36F, m), ꢁ138.5 (16F, m), ꢁ153.6
(16F, m). Anal. Calcd for C84 : C, 40.91; H, 0.81; F, 52.44.
Found: C, 42.14; H, 0.96; F, 53.11.
n
¼ 1.73. IR (KBr,
ꢁ1
1
1
3 2 2
mL BBr dissolved in 10 mL CH Cl was added dropwise. The
reaction mixture was stirred at room temperature under nitrogen
atmosphere for 12 h. Then the mixture was poured into 200 mL
methanol, and the obtained copolyether was filtered and washed
with methanol and deionized water several times. Finally, the
resulting copolymers were dried at room temperature under
vacuum for 48 h.
d
d
13
C
d
19
3
d
Yield: 90.2% M
n
¼ 10736; M
w
/M
n
¼ 2.05. IR (KBr, cmꢁ1): 3460
20 68 9
H F O
1
(
-OH), 1120e1300 (CeF). H NMR (500 MHz, DMSO, TMS): d (ppm)
9
6
.65 (1H, s), 7.40 (2H, d, 8 Hz), 7.33 (1H, s), 7.29 (1H, s), 7.19 (1H, s),
.84 (2H, d, 10 Hz). 13C NMR (125 MHz, DMSO, TMS):
d
(ppm) 158.4,
2.3.4. Synthesis of highly fluorinated aromatic-aliphatic
copolyethers containing epoxy group (FA-APE EP)
153.8, 150.4, 146.2, 144.2, 143.1, 142.6, 141.4, 140.6, 136.3, 135.9,
19
1
(
33.4, 131.2, 126.7, 119.0, 118.7, 116.4, 116.1, 102.8, 102.0. F NMR
470 MHz, DMSO, CFCl ):
: C, 58.06; H,1.61, F, 30.65. Found: C, 58.74;
FA-APE OH (5.10 g, 0.01 mol hydroxyl groups) and epoxy
chloropropane (20 g, 0.216 mol) were added into a 100 mL three-
necked flask equipped with a mechanical stirrer and a water
3
d
(ppm) ꢁ138.2 (4F, m), ꢁ153.4 (4F, m).
Anal. Calcd for C24
8 8 3
H F O
ꢀ
H, 1.90; F, 30.33.
condenser. The mixture was heated to 60 C with stirring, and this
PA-AE OH 2. Yield: 93.4%. M
cm ): 3460 (-OH), 1120e1300 (CeF). H NMR (500 MHz, DMSO,
n
¼ 10225; M
w
/M
n
¼ 1.92. IR (KBr,
temperature was maintained for 6 h. During this time, sodium
hydroxide (0.80 g, 0.02 mol) was added every half hour. The excess
of epoxy chloropropane was distilled off under reduced pressure.
The reaction mixture was cooled to room temperature and then
dissolved in benzene (40 mL). The resulting sodium chloride was
removed by filtration with a glass filter, then benzene was distilled.
The obtained copolymer was washed with methanol and dried at
room temperature under vacuum.
ꢁ
1
1
Table 1
Characterization of the fluorinated aromatic-aliphatic copolyethers.
b
Copolymer
12F-diol in
feed (mol%)
Yield
(%)
12F-diol
conversion
M
n
w n
M /M
a
(mol%)
Yield: 91.7%. M
n
¼ 10961; M
w
/M
n
¼ 1.86. IR (KBr, cmꢁ1):
PA-AE Me 1
PA-AE Me 2
PA-AE Me 3
PA-AE Me 4
PA-AE OH 1
PA-AE OH 2
PA-AE OH 3
PA-AE OH 4
PA-AE EP 1
PA-AE EP 2
PA-AE EP 3
PA-AE EP 4
0
25
50
75
0
25
50
75
0
95.3
92.6
95.1
93.6
90.2
93.4
94.1
91.4
91.7
94.3
92.5
90.4
e
10,733
10,625
11,636
11,257
10,736
10,225
11,261
11,602
10,961
11,726
12,989
11,829
1.46
2.03
1.96
1.78
2.05
1.92
1.85
1.73
1.86
2.33
2.38
1.58
93.1
94.2
94.1
e
1
1
3
120e1300 (CeF), 929.3 ( ). H NMR (500 MHz, CDCl , TMS):
d
(ppm) 7.49 (2H, d, 10 Hz), 7.33 (1H, s), 7.29 (1H, s), 7.19 (1H, s), 6.88
(
2H, d, 10 Hz), 4.27 (1H, d, 10 Hz), 4.03 (1H, s), 3.41 (1H, s), 2.92 (1H,
13
91.9
93.7
92.4
e
s), 2.76 (1H, s). C NMR (125 MHz, CDCl
3
, TMS): d (ppm) 158.4,
1
53.8, 150.1, 145.7, 143.7, 142.7, 141.9, 140.7, 139.9, 136.1, 135.5, 133.0,
19
130.5, 128.9, 118.8, 117.2, 115.6, 114.6, 101.8, 68.8, 50.1, 44.7. F NMR
(
470 MHz, CDCl
Anal. Calcd for C27
58.54; H, 2.21; F, 39.31.
3
, CFCl
3
):
d
(ppm) ꢁ138.2 (4F, m), ꢁ153.4 (4F, m).
25
50
75
93.6
94.3
91.6
H
12
F
8
O
4
: C, 58.70; H, 2.17, F, 27.54. Found: C,
a
FA-APE EP 2. Yield: 94.3%. M
cm ): 1120e1300 (CeF), 929.8 ( ). H NMR (500 MHz, CDCl
¼ 11726; M
/M
¼ 2.33. IR (KBr,
Molar ratio of [12F-diol]/[Me-HQ þ 12F-diol].
n
w
n
b
ꢁ1
1
Number average molecular weight determined by GPC.
3
,