4
976 Liu et al.
Macromolecules, Vol. 35, No. 13, 2002
presence of benzophenone. Dimethyl sulfoxide (DMSO) was
distilled prior to use.
Syn th esis. 9,9-Dihexylfluorene-2,7-bis(trimethylene bor-
2
7
onate) (1), 2,5-bis[3-(N,N-dimethylamino)-1-oxapropyl]-1,4-
dibromobenzene (2), 1,4-dibromo-2,5-dimethoxybenzene, and
1
,4-dibromohydroquinone were prepared according to the
1
1
procedures reported in the literature. A detailed synthesis
of P 1 and its quaternized salt P 3 was described in our previous
2
8
report.
,5-Bis[3-(N,N-d iet h yla m in o)-1-oxa p r op yl]-1,4-d ib r o-
2
1
1
m oben zen e, 3. A 500 mL round-bottom flask with magnetic
spin bar was charged with anhydrous potassium carbonate
(72.0 g, 521.0 mmol), 2-(diethylamino)ethyl chloride hydro-
chloride (22.6 g, 131.0 mmol), and 300 mL of acetone. The
stirred mixture was sparged with nitrogen for 15 min followed
by the addition of 2,5-dibromohydroquinone (15.0 g, 56.0
mmol). After 15 min of additional sparging, the reaction
mixture was brought to reflux for 3 days. Acetone was
removed, and the reaction mixture was diluted with 300 mL
of water, dissolving all salts. The product was extracted with
ether, and the combined organic layer was washed with 10%
NaOH(aq) (2 × 100 mL), water (2 × 100 mL), and brine (1 ×
1
4
00 mL). The solution was dried over MgSO , filtered, and
stripped of solvent by vacuum evaporation to yield crude oily
solids. The crude solid was recrystallized from MeOH/H O to
afford 3 (12.5 g, 48.4%) as white crystals. H NMR (300 MHz,
CDCl , ppm): δ 7.12 (s, 2H), 4.04-3.99 (t, 4H, J ) 6.03 Hz),
.92-2.88 (t, 4H, J ) 6.22 Hz), 2.68-2.61 (q, 8H, J ) 7.09
2
1
3
2
1
3
Hz), 1.10-1.05 (t, 12 H, J ) 7.21 Hz). C NMR (75 MHz,
CDCl , ppm): δ 150.25, 118.47, 110.92, 70.01, 51.55, 47.98,
2.10. Anal. Calcd for C18 Br : C, 46.37; H, 6.49; N,
3
1
6
H
30
N
2
O
2
2
.01; Br, 34.28. Found: C, 46.65; H, 5.99; N, 5.99; Br, 34.32.
P oly[{2,5-b is[3-(N,N-d iet h yla m in o)-1-oxa p r op yl]-1,4-
p h en yl}-co-a lt-2,7-(9,9-d ih exylflu or en e)], P 2. To the mix-
ture of 9,9-dihexylfluorene-2,7-bis(trimethylene boronate) (251
mg, 0.499 mmol), 2,5-bis[3-(N,N-diethylamino)-1-oxapropyl]-
1
,4-dibromobenzene (233 mg, 0.500 mmol), tetrabutylammo-
nium chloride (80 mg) and tetrakis(triphenylphosphine) pal-
ladium [Pd(PPh ] (10 mg) was added a degassed mixture of
mL of toluene ([monomer] ) 0.25 M) and 2 mL of 2 M
a
Reagents and conditions: (i) Br , CCl , RT; (ii) BBr ,
2
4
3
3
)
4
2 2 2 3
CH Cl , 0 °C to RT; (iii) K CO , 2-(dimethylamino)ethyl
3
2 3
chloride hydrochloride, acetone, reflux, 3 days; (iv) K CO ,
2-(diethylamino)ethyl chloride hydrochloride, acetone, reflux,
3 days.
potassium carbonate aqueous solution. The mixture was
vigorously stirred at 75 °C for 48 h. After the mixture was
cooled to room temperature, it was poured into 200 mL of
methanol and deionized water (10:1). A fibrous solid was
obtained by filtration. The solid was washed with methanol,
water and then methanol. After being washed for 24 h in a
Soxhlet apparatus with acetone to remove oligomers and the
P oly[{2,5-b is[3-(N,N,N-t r iet h yla m in o)-1-oxa p r op yl]-
1
,4-p h en yl}-co-a lt-2,7-(9,9-d ih exylflu or en e) d ibr om id e],
P 5 (60% Qu a ter n ized ). A 100 mL flask with a magnetic spin
bar was charged with the polymer P 2 (100 mg) dissolved in
catalyst residues, the resulting polymer P 2 was obtained (370
5
0 mL of THF. To this solution was added bromoethane (1.09
1
mg, 57.1%) as a white fibrous solid. H NMR (300 MHz, CDCl
3
,
g, 10.0 mmol) and 12 mL of DMSO. The solution was stirred
at room temperature for 2 days. THF and extra bromoethane
were evaporated. The polymer was precipitated by the addition
of about 100 mL of acetone to the flask, collected by centrifu-
gation, washed with chloroform, acetone, and dried overnight
ppm): δ 7.80-7.78 (br, 2H), 7.60 (br, 4H), 7.12 (s, 2H), 4.17
br, 4H, -OCH ), 2.92 (br, 4H, -CH N), 2.66 (br, 8H, -NCH
CH ), 2.05 (br, 4H), 1.12-0.78 (br, 34H). H NMR (75 MHz,
CDCl , ppm): δ 150.74, 150.49, 140.02, 137.07, 131.46, 128.31,
(
2
2
2
-
1
3
3
1
3
2
8
24.35, 119.40, 116.92, 68.65, 55.21, 52.08, 47.98, 40.81, 31.90,
in vacuo at 50 °C. The desired polymer P 5 (54 mg, 46.2%) was
0.23, 24.22, 22.91, 14.20, 12.13. FT-IR (KBr, cm-1): 2962,
927, 2856, 2810, 1509, 1461, 1381, 1203, 1132, 1052, 1035,
1
obtained as light pink color powders. H NMR (300 MHz, CD
3
-
OD, ppm): δ 7.80-7.78 (br, 2H), 7.60 (br, 4H), 7.12 (s, 2H),
.45 (br, 4H, -OCH ), 3.55 (br, 4H, -CH N), 3.20 (br, 10.4H,
NCH CH ), 2.05 (br, 4H), 1.12-0.78 (br, 37H). FT-IR (KBr,
cm ): 2925, 2855, 2629, 2475, 1622, 1511, 1462, 1393, 1202,
88, 870, 822, 753. Anal. Calcd for C43
H
62
O
2
N
2
2
‚H O: C, 80.82;
4
2
2
H, 9.84; N, 4.27. Found: C, 79.68; H, 9.79; N, 4.35.
-
2
3
P oly[{2,5-b is[3-(N,N,N-t r iet h yla m in o)-1-oxa p r op yl]-
-1
1
,4-p h en yl}-co-a lt-2,7-(9,9-d ih exylflu or en e) d ibr om id e],
1
030, 829, 754.
P 4 (30% Qu a ter n ized ). A 100 mL flask with a magnetic spin
bar was charged with the polymer P 2 (100 mg) dissolved in
P oly[{2,5-b is[3-(N,N,N-t r iet h yla m in o)-1-oxa p r op yl]-
,4-p h en yl}-co-a lt-2,7-(9,9-d ih exylflu or en e) d ibr om id e],
1
5
0 mL of THF. Bromoethane (1.09 g, 10.0 mmol) was added
P 6 (80% Qu a ter n ized ). According to the procedure for P 5,
after 100 mg of P 2 was treated with bromoethane in DMSO/
THF (1:4) at 50 °C for 5 days, the desired polymer P 6 (62 mg,
to this solution, and the mixture was stirred at room temper-
ature for 24 h. THF and extra bromoethane were evaporated.
The polymer was precipitated by the addition of about 100 mL
of acetone to the flask, collected by centrifugation, washed with
chloroform and acetone, and dried overnight in vacuo at 50
1
50.0%) was obtained as light pink color powders. H NMR (300
MHz, CD
(s, 2H), 4.45 (br, 4H, -OCH
11.2H, -NCH CH ), 2.05 (br, 4H), 1.12-0.78 (br, 39H).
NMR (50 MHz, CD OD, ppm): δ 153.66, 152.34, 142.57,
3
OD, ppm): δ 7.80-7.78 (br, 2H), 7.60 (br, 4H), 7.12
°
C. The desired polymer P 4 (72 mg, 66.2%) was obtained as
2
), 3.55 (br, 4H, -CH N), 3.20 (br,
2
1
13
off-white powders. H NMR (300 MHz, CDCl
3
, ppm): δ 7.80-
.78 (br, 2H), 7.60 (br, 4H), 7.12 (s, 2H), 4.17 (br, 4H, -OCH ),
.92 (br, 4H, -CH N), 2.66 (br, 9.2H, -NCH CH ), 2.05 (br,
H), 1.12-0.78 (br, 36H). FT-IR (KBr, cm ): 2966, 2927
2
3
C
7
2
4
2
3
2
2
-
3
139.42, 134.44, 131.29, 126.10, 121.62, 119.10, 66.87 (64.88
weak), 58.10 (weak), 57.78, 55.91, 53.61, 42.34, 33.93, 31.93,
1
-1
(weak), 2857 (weak), 1509, 1461, 1381, 1202, 1050, 887, 822,
26.44, 24.76, 15.50, 10.51, 9.03. FT-IR (KBr, cm ): 2927, 2855,
2622, 2472, 1622, 1511, 1462, 1394, 1202, 1039, 829, 771.
7
53.