X. Zhu, B. Zhu, T. Han et al.
Synthesis of 1,3,5-tris(bromomethyl)benzene (3): The chemical com-
in chloroform and filtered. The filtrate was concentrated under reduced
pressure and added slowly to methanol at room temperature to form a
precipitate. Reprecipitation was performed three times and a bright-
yellow polymer was obtained after drying under vacuum at 408C. Yield:
pound was synthesized according to a modification of a previously re-
[
12a]
ported method.
bromosuccinimide (19.49 g, 109.5 mmol), and benzoyl peroxide (0.1986 g,
.82 mmol) in benzene (150 mL) was heated to initiate the reaction at a
A mixture containing mesitylene (5 mL, 36 mmol), N-
1
0
71%. H NMR (400 MHz, CDCl , 208C): d=0.42–0.98 (br, CH ), 0.98–
3
3
reflux temperature of 95Æ18C. Although the reaction was strongly exo-
thermic to ensure the solution boils, the self-reflux time of this system
was kept for only 0.5 h. To ensure the bromination reaction went to com-
pletion, the solution was reheated at reflux for several hours. After filter-
ing, the filtrate was washed with water and dried with anhydrous magne-
sium sulfate. The needle crystals were achieved as the solution was con-
2 3 2 2 2
1.45 (br, CH CH ), 1.45–2.45 (br, NCH CH ), 3.60–4.65 (br, NCH ), 5.78–
8.85 (m, Ar-H), 9.62–10.28 ppm (br, CHO); C NMR (400 MHz, CDCl3,
1
3
208C): d=14.25 (CH ), 22.75 (CH CH ), 27.10 (CH CH ), 29.12
3
3
2
2
2
(CH CH ), 29.96 (CH CH ), 31.71 (NCH CH ), 43.42 (NCH ), 109.19
2
2
2
2
2
2
2
(Ar-C), 118.96–131.13 (Ar-C), 134.60 (Ar-C), 138.27–140.62 (Ar-C),
144.38 (Ar-C), 191.86 ppm (CHO); IR (KBr): n˜ =3011, 2949, 2923, 2851,
centrated, with further recrystallization in a mixture of ethanol and
2719, 1684, 1623, 1587, 1485, 1382, 1346, 1238, 1190, 1153, 1129, 955, 879,
1
À1
hexane (1:1). Yield: 88%. H NMR (400 MHz, CDCl
3
, 208C): d=4.455
798 cm
.
1
3
(
s, 6H; CH
2
Br), 7.353 ppm (s, 3H; Ar-H); C NMR (400 MHz, CDCl
3
,
Synthesis of a star copolymer with a hyperbranched conjugated polymer
core and many linear PEG arms (HCP-star-PEG): A solution containing
the hyperbranched conjugated polymer and a certain amount of PEG-
2
08C): d=32.61 (CH
2
Br), 129.87 (Ar-C), 139.28 ppm (Ar-C); IR (KBr):
n˜ =3026, 2971, 2921, 2850, 1803, 1713, 1611, 1458, 1439, 1217, 1170, 1123,
À1
9
86, 900, 861, 705, 591, 560 cm
.
2 2
CH CONHNH (6) in anhydrous THF was allowed to react under nitro-
Synthesis of 1,3,5-bis[(triphenylphosphonio)methyl]benzene tribromide
4): A solution of 1,3,5-tris(bromomethyl)benzene (1.45 g, 4.07 mmol),
triphenylphosphine (3.59 g, 13.67 mmol), and ethanol (60 mL) was heated
at reflux for 24 h under nitrogen. The solution was poured into THF
gen at 608C for 24 h. After cooling to room temperature, the solution
was concentrated and precipitated three times with anhydrous methanol.
The precipitate was dissolved in chloroform and washed with deionized
water several times and dried with anhydrous magnesium sulfate. The
product was obtained by removing the solvent under reduced pressure
(
(
2
200 mL) after being cooled to room temperature and concentrated to
0 mL. The white precipitate was filtered and thoroughly dried under
1
and drying in a vacuum at room temperature. Yield: 62%. H NMR
1
vacuum. Yield: 81%. H NMR (400 MHz, [D
J=7.825 Hz, 6H; CH Br), 6.68 (s, 3H; Ar-H), 7.44–7.49 (m, 18H; Ar-H),
.61–7.66 (m, 18H; Ar-H), 7.85 ppm (t, J=7.043 Hz, 9H; Ar-H);
6
]DMSO, 208C): d=4.88 (d,
(400 MHz, CDCl3, 208C): d=0.45–0.98 (br, CH ), 0.98–1.45 (br,
3
2
CH CH ), 1.45–2.50 (br, NCH CH ), 3.37 (br, OCH ), 3.38–4.98 (m,
2
3
2
2
3
7
2 2 2
CH CH O), 4.05–4.42 (br, NCH ), 6.25–8.85 (m, Ar-H), 9.40 (br, ArCH=
1
3
13
C NMR (400 MHz, [D
6
]DMSO, 208C) d=117.94 (CH
2
Br), 118.79 (Ar-
N), 10.1 (br, CHO), 10.2 ppm (br, NHCO); C NMR (400 MHz, CDCl3,
C), 130.83 (Ar-C), 130.95 (Ar-C), 134.31 (Ar-C), 134.40 (Ar-C),
208C): d=14.21 (CH ), 22.66 (CH CH ), 27.03 (CH CH ), 29.11
3
3
2
2
2
1
1
35.77 ppm (Ar-C); IR (KBr): n˜ =3054, 3007, 2858, 2784, 1592, 1486,
2 2 2 2 2 2 2
(CH CH ), 29.85 (CH CH ), 31.67 (NCH CH ), 43.50 (NCH ), 59.22,
61.81 (OCH ), 69.51–72.81 (OCH CH ), 109.43 (Ar-C), 123.12 (Ar-C),
3 2 2
À1
439, 1408, 1322, 1119, 1002, 974, 751, 724, 697, 517 cm
.
Synthesis of poly(ethylene glycol) monomethyl ether with ethyl acetate
terminals (PEG-CH COOC , 5): PEG monomethyl ether (M =2000,
0.40 g, 5.2 mmol) was fully dissolved in toluene (100 mL) and potassium
tert-butoxide (2.05 g, 18 mmol) dissolved in tert-butyl alcohol (30 mL)
was added. Then ethyl bromoacetate (3.2 mL, 28 mmol) was added
slowly over a period of 30 min. The solution was stirred at room tempera-
ture for 24 h, filtered, concentrated with dichloromethane, and precipitat-
ed in diethyl ether three times to obtain a white solid product. The pre-
128.77 (Ar-C), 132.23–134.27 (Ar-C), 138.29–140.74 (Ar-C), 144.27 (Ar-
C), 171.86 (Ar-CH=N), 191.86 ppm (CHO); IR (KBr): n˜ =3433, 2881,
2
2
H
5
n
1
1684, 1624, 1594, 1485, 1467, 1386, 1355, 1343, 1280, 1241, 1111, 964,
À1
843 cm
.
Self-assembly of the star copolymer HCP-star-PEG in mixed solvents:
HCP-star-PEG (20 mg) dissolved in chloroform (4 mL) was stirred uni-
formly before use. Under gentle stirring, different amounts of acetonitrile
were added dropwise to the chloroform solution to give certain content
in solution. The final concentration of HCP-star-PEG in the resultant so-
cipitate was dried under a vacuum at room temperature. Yield: 92%.
1
H NMR (400 MHz, [D
), 3.22 (s, 3H; OCH
OCH CH OCO), 4.70 ppm (s, 2H; OCOOCH
]DMSO, 208C): d=14.62 (CH ), 61.29 (OCH
OCH CH ), 170.52 ppm (C=O); IR (KBr): n˜ =2286, 1756, 1471, 1365,
346, 1283, 1240, 1115, 962, 841 cm
6
]DMSO, 208C): d=1.18 (t, J=7.043 Hz, 3H;
), 3.31–3.66 (m, 180H; OCH CH ), 4.22 (m, 2H;
); C NMR (400 MHz,
), 68.06–71.95
À1
À5
lution was set to 1 mgml (3.8ꢁ10 m). All procedures were performed
CH
3
3
2
3
2
at room temperature.
1
2
2
2
NMR spectroscopy: NMR spectra were recorded on a Varian Mercury
Plus 400 MHz spectrometer with deuteriated dimethyl sulfoxide
[
(
1
D
6
3
3
2
2
(
[D
thane (CD
08C. Tetramethylsilane (TMS) was used as the internal reference.
6
]DMSO), deuteriated chloroform (CDCl
3
), deuteriated dichlorome-
À1
.
2
Cl ) and deuteriated acetonitrile (CD
2
3
CN) as solvents at
Synthesis of poly(ethylene glycol) monomethyl ether with acylhydrazine
terminals (PEG-CH CONHNH 6): PEG-CH COOC (5; 10.00 g,
.8 mmol) was dissolved in methanol (100 mL) and a mixture of hydra-
2
2
2
,
2
2 5
H
FTIR spectroscopy: FTIR spectra were recorded on a Paragon 1000 in-
strument by using the KBr sample holder method.
4
zine hydrate (30 mL) and methanol (40 mL) was added to the solution
dropwise. After reaction for 24 h at room temperature, the solution was
filtered. Then most of the methanol solvent was removed under reduced
pressure. The concentrated solution was extracted with dichloromethane,
dried with anhydrous magnesium sulfate and precipitated with anhydrous
Gel permeation chromatography (GPC): The number-average molecular
weights (M ) and the polydispersity (M /M ) indices were determined by
n w n
gel permeation chromatography/multi-angle laser light-scattering (GPC-
MALLS). The gel permeation chromatography system consisted of a
Waters degasser, a Waters 515 HPLC pump, a 717 automatic sample in-
jector, a Wyatt Optilab DSP differential refractometer detector, and a
Wyatt miniDAWN multi-angle laser light-scattering detector. Three chro-
matographic columns (styragel HR3, HR4, and HR5) were used in series.
diethyl ether. The white precipitate was dried under a vacuum at room
1
temperature. Yield: 90%. H NMR (400 MHz, [D
6
]DMSO, 208C): d=
CH ), 3.87 (s, 2H;
); C NMR (400 MHz,
), 70.27–73.00 (OCH CH ),
3
.22 (s, 3H; OCH
OCH CH OCO), 8.87 ppm (s, 1H; CONHNH
]DMSO, 208C): d=60.89 (OCH
3
), 3.30–3.68 (m, 180H; OCH
2
1
2
3
2
2
2
À1
THF was used as the mobile phase at a flow rate of 1 mLmin at 308C.
[
D
6
3
2
2
The refractive index increment dn/dc was determined with a Wyatt Opti-
1
1
68.77 ppm (C=O); IR (KBr): n˜ =3425, 3323, 2889, 1676, 1471, 1365,
À1
lab DSP differential refractometer at 690 nm. Data analysis was per-
346, 1279, 1240, 1111, 959, 841 cm
.
[
19]
formed with Astra software (Wyatt Technology).
Synthesis of the hyperbranched conjugated polymer (HCP, 7): A solution
of sodium (0.083 g, 3.6 mmol) in anhydrous ethanol (5 mL) was added
dropwise at ambient temperature under nitrogen to a mixture of N-(n-
hexyl)-3,6-diformylcarbazole (2; 0.491 g, 1.6 mmol) and the phosphonium
salt 4 (0.915 g, 0.8 mmol) in anhydrous ethanol and dry chloroform (1:2,
Thermal gravimetric analysis (TGA): TGA measurements were per-
formed on a Perkin–Elmer TGA-7 thermogravimetric analyzer to investi-
gate the thermal stability of all samples in a nitrogen atmosphere from
À1
ambient temperature to 8008C at 208Cmin
.
3
0 mL). The mixture was stirred at room temperature overnight. The
Transmission electron microscopy (TEM): TEM studies were performed
with a JEOL JEM-100CX-II instrument at a voltage of 200 kV. Samples
were prepared by drop-casting micelle solutions onto carbon-coated
polymerization was quenched by adding dilute hydrochloric acid (2% in
water, 5 mL) and stirred for a few minutes. The resultant was dissolved
12716
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2010, 16, 12710 – 12717