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(m, 40H, protons of aromatic ring); 29Si NMR (ppm, CDCl3):
232.72, 277.73, 279.02, 279.21, and 279.42. MALDI-TOF-
mass (product 1 Na1): 1176.1 Da.
1,4-Dipropargyloxybutane: 4.12 (d, 4H, ACHBCCH2OA), 3.53
(m, 4H, AOCH2CH2CH2CH2OA), 2.41 (t, 2H, ACHBCCH2OA),
1.67 (m, 4H, AOCH2CH2CH2CH2OA);
Synthesis of 3,13-Dibrompropyloctaphenyl DDSQ
1,6-Dipropargyloxyhexane: 4.12 (d, 4H, ACHBCCH2OA), 3.50
(t, 4H, AOCH2CH2CH2CH2CH2CH2OA), 2.41 (t, 2H, ACHB
CCH2OA), 1.60 (m, 4H, AOCH2CH2CH2CH2CH2CH2OA), 1.38
(m, 4H, AOCH2CH2CH2CH2CH2CH2OA);
To a flask equipped with a magnetic stirrer, 1,13-dihydro
DDSQ (5.44 g, 4.71 mmol), anhydrous toluene (50 mL) and
allyl bromide (2.28 g, 18.84 mmol) were charged. The flask
was connected to a Schlenk line to degas by a repeated
exhausting–refilling process with highly pure nitrogen and
the Karstedt catalyst was added with vigorous stirring. The
hydrosilylation was performed at 95 ꢀC for 36 h. The sol-
vents were removed via rotary evaporation and a viscous liq-
uid was afforded. The solids were washed with 100 mL of
methanol twice. After dried in vacuo at 40 ꢀC for 24 h, the
product (5.73 g) was obtained with the yield of 87%.
1,8-Dipropargyloxyoctane, 4.12 (d, 4H, ACHBCCH2OA), 3.50
[t, 4H, AOCH2CH2(CH2CH2)2CH2CH2OA], 2.41 (t, 2H, ACHB
CCH2OA), 1.58 [m, 4H, AOCH2CH2(CH2CH2)2CH2CH2OA],
1.32 [m, 8H, AOCH2CH2(CH2CH2)2CH2CH2OA];
1,10-Dipropargyloxydecane (dissolved in DMSO-d6): 4.30 (t, 2H,
ACHBCCH2OA), 3.35 (q, 4H, ACHBCCH2OA), 1.38 [m, 4H,
AOCH2(CH2CH2)4CH2OA], 1.22 [m, 12H, AOCH2(CH2CH2)4
CH2OA].
FTIR (cm21, KBr windows):1131 (ms, SiAOASi), 571 (ms,
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CABr). H NMR (ppm, CDCl3): 7.14–7.50 (m, 40H, protons of
Synthesis of Organic–Inorganic Copolymers via Click
Polymerization
aromatic ring), 0.32 [s, 3H, AOSiCH3CH2CH2CH2Br], 0.85 [m,
2H, AOSiCH3CH2CH2CH2Br], 1.94 [m, 2H, AOSiCH3CH2CH2
CH2Br], and 3.27 [m, 2H, AOSiCH3CH2CH2CH2Br]. 29Si NMR
(ppm, CDCl3): 218.5, 278.3, and 279.5 ppm.
To a flask equipped with a magnetic stirrer, one a,x-dia-
lkynyl-terminated oligoethylene (1.0 mmol), 3,13-diazidopro-
pyloctaphenyl DDSQ (1.32 g, 1.00 mmol), PMDETA (0.21 ml,
0.10 mmol), and 1,4-dioxane (10 mL) were charged. The sys-
tem was purged with argon for 30 min and then CuBr
(0.14g, 1.00 mmol) was added. Then, the system was purged
with argon for additional 5 min. The polymerization was
performed at 50 ꢀC for at least 24 h. After cooled to room
temperature, 20 mL of THF was added to the reacted mix-
ture and the solution was passed through a basic alumina
column to remove the catalyst and the solution was concen-
trated via rotary evaporation and dropped into 200 mL of n-
hexane to afford the precipitates. The resulting product was
Synthesis of 3,13-Diazidopropyloctaphenyl DDSQ
To a flask equipped with a magnetic stirrer, 3,13-dibro-
mopropyloctaphenyl DDSQ (5.0 g, 3.58 mmol), sodium
azide (1.40 g, 21.48 mmol), and anhydrous THF (100
mL) were charged and 100 mL of anhydrous DMF was
added at room temperature with vigorous stirring. The
reaction was performed at room temperature for 24 h.
The resultant mixture was dropped in 50 mL of the mix-
tures of methanol with water (volume, 50/50) to afford
the precipitates. This procedure was repeated thrice to
purify the product. After dried in a vacuum oven at 40
ꢀC for 24 h, the product (3.93 g) was obtained with the
yield of 83%.
ꢀ
obtained after dried in vacuo at 30 C for 24 h. The polymers
were subjected to gel permeation chromatography (GPC) to
measure the molecular weights and molecular weight distri-
bution and the results of the polymerizations are summar-
ized in Table 1.
FTIR (cm21, KBr windows): 2098 (ms, AN3), 1131 (ms,
SiAOASi). 1H NMR (ppm, CDCl3): 7.14–7.50 (m, 40H, pro-
tons of aromatic ring), 0.32 (s, 3.1H, AOSiCH3CH2CH2CH2N3),
0.77 [m, 2.0H, AOSiCH3CH2CH2CH2N3, 1.68 [m, 2.2H, AOSi
CH3CH2CH2CH2N3], 3.13 [t, 2.0H, OSiCH3CH2CH2CH2N3].
Measurement and Techniques
Nuclear Magnetic Resonance Spectroscopy
The 1H NMR measurements were carried out on a Varian
Mercury Plus 400 MHz NMR spectrometer at 25 ꢀC. The
samples were dissolved with deuterated chloroform (CD3Cl)
or dimethylsulfone (DMSO-d6) and the solutions were meas-
ured with tetramethylsilane as an internal reference.
Synthesis of a,x-Dialkynyl-terminated Oligoethylenes
To a 250-mL flask equipped with a magnetic stirrer, sodium
hydride (2.03 g, 50.75 mmol) and anhydrous THF (100 mL)
were changed and then one diol (12.69 mmol) dissolved in 50
mL of anhydrous THF was added to the flask. At room temper-
ature, the mixture was stirred for 3 h and then 4.53 g (38.06
mmol) propargyl bromide dissolved in 30 mL of anhydrous
THF was added dropwise within 30 min. After the reaction
was performed at room temperature for 24 h, the salts (NaBr
and excess NaH) were removed via filtration and the solution
was concentrated with rotary evaporation. After the top oil
layer was isolated and eliminated, the liquid product was
Matrix-Assisted Ultraviolet Laser Desorption/Ionization
Time-of-Flight Mass Spectroscopy
Gentisic acid (2,5-dihydroxybenzoic acid) was used as the
matrix with dichloromethane as the solvent. The matrix-
assisted ultraviolet laser desorption/ionization time-of-flight
mass spectroscopy (MALDI-TOF-MS) experiment was carried
out on an IonSpec HiResMALDI mass spectrometer equipped
with a pulsed nitrogen laser (k 5 337 nm; pulse with 5 3
ns). This instrument was operated at an accelerating poten-
tial of 20 kV in reflector mode. Sodium is used as the catio-
nizing agent and all the data shown are for positive ions.
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obtained. The product was subjected to H NMR spectroscopy:
1,2-Dipropargyloxyethane: 4.20 (t, 4H, CHBCCH2OA), 3.71
(d, 4H, AOCH2CH2OA), 2.43 (t, 2H, ACHBCCH2OA);
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JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY 2013, 00, 000–000
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