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MHz, CDCl3): d (ppm) 143.82, 136.74, 132.64, 132.48,
124.56, 123.98, 67.32, 25.74, 25.68, 25.66.
under reduced pressure. The oily product was purified by
silica gel column chromatography (CH2Cl2:hexane 5 1:2 v/v)
to give 7 in 72% yield (1.82 g).
9,90-(5-(((Tert-butyldimethylsilyl)oxy)methyl)-1,3-
phenylene)bis(9H-carbazole) (5)
1H NMR (400 MHz, CDCl3): d (ppm) 8.19 (d, J 5 7.58 Hz, 4H)
7.77 (s, 1H), 7.74 (s, 2H), 7.58 (d, J 5 8.22 Hz, 4H), 7.47 (t,
4H), 7.41 (d, J 5 4.68 Hz, 4H), 7.34 (t, 4H), 6.74 (q, 1H), 5.80
(d, J 5 17.58 Hz, 1H), 5.29 (d, J 5 10.58 Hz, 1H), 4.78 (s, 2H),
4.72 (s, 2H); 13C NMR (100 MHz, CDCl3) : d (ppm) 142.43,
142.38, 139.75, 139.72, 139.68, 138.4, 136.44, 128.7, 126.59,
122.54, 122.46, 122.02, 121.58, 121.50, 109.48, 109.43,
109.39, 72.54.
Compound 4 (5 g, 13 mmol) and carbazole (4.83 g, 28
mmol) were dissolved in 30 mL toluene under argon.
Sodium tert-butoxide (NaOt-Bu; 6.32 g, 65 mmol) was
ꢀ
added to the mixture, which was then stirred at 60 C for 1
h.
Next,
tris(dibenzylidene
acetone)dipalladium(0)
(Pd2(dba)3; 0.60 g, 0.65 mmol) and tri-tert-butylphosphine
(P(t-Bu)3, 0.13 g, 0.65 mmol) were added into the mixture,
ꢀ
which was then heated to 110 C. After stirring for 8 h, the
General Procedure for Polymerization
Poly(9,90-(5-(((4-(7-(4-(((3-methyloxetan-3-
yl)methoxy)methyl)phenyl)octan-3-yl)benzyl)oxy)methyl)-
1,3-phenylene)bis(9H-carbazole)) (P(mCP-Ox))
reaction mixture was extracted with CH2Cl2 and washed
with water. The organic layer was then dried over Na2SO4
and concentrated under reduced pressure. The resulting
dark brown oil was purified by silica-gel column chroma-
tography (CH2Cl2: hexane 5 1:3 v/v) to give 5 in 70% yield
(5.08 g).
A solution of monomer 1 (7) and monomer 2 (9) (at a feed-
ing molar ratio of 7:9 5 m:n) in anhydrous toluene was
degassed under nitrogen for 30 min. AIBN (0.41 mg, 0.0025
mmol) was added to the mixture and heated to 80 ꢀC. The
reaction mixture was allowed to stir at 80 ꢀC for 48–60 h.
The resultant polymer was then precipitated in methanol.
The crude polymer was collected by filtration and then puri-
fied by Soxhlet extraction with acetone and chloroform, suc-
cessively. The final product was obtained by precipitation of
the chloroform solution into methanol. The pure copolymer
was dried under vacuum for 24 h.
1H NMR (300 MHz, CDCl3): d (ppm) 8.28 (d, J 5 7.68 Hz,
4H), 7.75 (s, 1H), 7.73 (s, 2H), 7.60 (d, J 5 8.22 Hz, 4H), 7.46
(t, 4H), 7.31(t, 4H), 5.02 (s, 2H), 0.90 (s, 9H), 0.13 (s, 6H);
13C NMR (100 MHz, CDCl3): d (ppm) 142.68, 142.43, 139.72,
139.68, 139.60, 126.65, 122.69, 121.33, 119.74, 110.67,
109.45, 30.59.
(3,5-Di(9H-carbazol-9-yl)phenyl) methanol (6)
Compound 5 (5.0 g, 9.04 mmol) was dissolved in THF under
argon. A 3-M solution of HCl (27 mL) was added dropwise
into the mixture. The reaction mixture was allowed to stir at
room temperature for 4 h. After reaction completion, the
mixture was extracted with CH2Cl2 and washed with water.
The organic layer was then dried over Na2SO4 and concen-
trated under reduced pressure. The product was obtained by
precipitation into hexane to provide 6 in 93% yield (3.68 g).
P(mCP-Ox)-I. Molar feeding ratio (m:n 5 1:1); yield: 47.62%;
1H NMR (400 MHz, CDCl3): d (ppm) 7.90 (br, 2H), 7.34 (br,
8H), 6.80 (br, 2H), 6.27 (br, 2H), 4.22 (br, 4H), 3.22 (br, 1H),
1.11 (br, 3H); anal. calcd.: C 83.9; H 6.85; N 3.48.
P(mCP-Ox)-II. Molar feeding ratio (m:n 5 1:2); yield: 61.97%;
1H NMR (400 MHz, CDCl3): d (ppm) 7.90 (br, 3H), 7.34 (br,
11H), 6.80 (br, 2H), 6.27 (br, 2H), 4.22 (br, 5H), 3.22 (br,
1H), 1.11 (br, 4H); anal. calcd.: C 83.66; H 6.39; N 3.57.
1H NMR (300 MHz, CDCl3) : d (ppm) 8.19 (d, J 5 6.00 Hz,
4H), 7.77 (s, 1H), 7.74 (s, 2H), 7.58 (d, J 5 6.00 Hz, 4H), 7.47
(t, 4H), 7.34 (t, 4H), 4.98 (d, J 5 6.00 Hz, 2H), 2.03 (t, 1H),
13C NMR (100 MHz, CDCl3): d (ppm) 145.01, 140.79, 139.75,
126.51, 126.47, 126.41, 126.40, 126.37, 126.32, 124.46,
124.31, 124.12, 123.97, 123.85, 120.75, 120.66, 120.60,
120.55, 120.54, 110.02, 109.95, 109.86, 104.99, 77.58, 77.26,
76.94, 64.87, 64.68, 64.49.
P(mCP-Ox)-III. Molar feeding ratio (m:n 5 1:4); yield:
46.30%; 1H NMR (400 MHz, CDCl3): d (ppm) 7.90 (br, 6H),
7.34 (br, 18H), 6.80 (br, 2H), 6.27 (br, 3H), 4.22 (br, 5H),
3.22 (br, 1H), 1.11 (br, 6H); anal. calcd.: C 82.80; H 6.08; N
4.24.
Poly(9,90-(5-(((4-(7-phenyloctan-3-yl)benzyl) oxy)methyl)-
1,3-phenylene)bis(9H-carbazole)) (P(mCP-Ph))
9,90-(5-(((4-Vinylbenzyl)oxy)methyl)-1,3-phenylene)bis(9H-
carbazole) (7)
Monomer 1 (0.7 g, 1.26 mmol) and styrene (0.01 g, 0.14
mol) were dissolved in anhydrous toluene and degassed
under nitrogen for 30 min. AIBN (0.41 mg, 0.0025 mmol)
was added to the mixture, which was then heated to 80 ꢀC
for 120 h under argon. The mixture was poured into metha-
nol to collect the precipitate. The crude polymer was col-
lected by filtration and then purified by Soxhlet extraction
with acetone and chloroform, successively. The final product
was obtained by precipitation of chloroform solution into
methanol. Then, the product was dried under vacuum for
24 h to obtain P(mCP-Ph) as a white solid in a yield of
60%.
NaH (0.12 g, 5.01 mmol) was suspended in 35-mL anhy-
ꢀ
drous DMF at 0 C. Compound 5 (2.0 g, 4.56 mmol) in DMF
was added dropwise into the mixture and the mixture was
allowed to stir for 1 h. Next, 1-(chloromethyl)-4-vinylben-
zeneꢀ(0.76 g, 5.01 mmol) in DMF was also added dropwise
at 0 C over a 15-min period; the reaction mixture was then
stirred at room temperature for 12 h. After the reaction was
completed, the reaction mixture was extracted with CH2Cl2
and washed with water; the mixture was extracted again
with diethyl ether and washed with water. The combined
organic layers were dried over Na2SO4 and concentrated
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JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY 2014, 52, 707–718
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