J.Y. Jang, J.Y. Do / Reactive & Functional Polymers 91-92 (2015) 28–34
29
M-III (70% isolated yield): 1H NMR (300 MHz, CDCl3)
d
Table 1
The refractive indices of several sulfur, sulfoxide and sulfone molecules from
prediction and literature data.
a
(ppm) = 1.80 (s, 3H), 1.98 (s, 3H), 3.32–3.39 (m, 4H), 4.26 (s, 2H),
5.61 (s, 1H), 6.16 (s, 1H); 13C NMR (75.4 MHz, CDCl3)
d
Calculatedb
a
Molecule
Mw (g/mol)
nD
(ppm) = 18.3, 27.60, 39.6, 64.1, 71.8, 126.0, 136.0, 166.9. LC-MS,
m/z: 219.05 [M + 1].
nD
Molar
Molar
volume
(cm3)
MO2-III (96% isolated yield): 1H NMR (300 MHz, CDCl3) d
(ppm) = 1.68 (s, 3H), 1.89 (s, 3H), 4.02–4.15 (m, 4H), 4.57 (s, 2H),
refractivity
(cm3)
5.78 (s, 1H), 6.07 (s, 1H); 13C NMR (75.4 MHz, CDCl3)
d
Me2S
62.1
78.1
94.1
90.2
88.2
104.2
120.2
1.435
1.479
1.423
1.442
1.503
1.520
1.482
1.425
1.480
1.402
1.440
1.515
1.549
1.486
19.3
20.2
20.1
28.6
26.6
27.4
27.3
75.5
71.1
82.6
108.5
88.2
86.2
95.3
Me2SO
Me2SO2
Et2S
(ppm) = 14.5, 18.2, 49.3, 62.6, 71.9, 127.7, 135.436, 165.9. IR (KBr,
cmꢀ1): mmax 3383 (OH), 1326 (SO2), 1126 (SO2), 1073. LC-MS,
m/z: 283.02 [M + 1].
THTc
THT-oxided
Sulfolane
2.3. Polymer synthesis: a general procedure
a
b
c
Literature data from the Merk index.
Industry standard physchem prediction models provided by ACD/Labs.
Tetrahydrothiophene (THT).
A flask was charged with a mixture of M-III (0.60 g), methyl
methacrylate (MMA) (1.40 g), and a catalytic amount of AIBN
(3.0 mol%), and the mixture was dissolved in tetrahydrofuran
(THF) (9.0 mL) (20 wt.%). The reaction mixture was deoxygenated
by N2 flow for 10 min and then heated at 70 °C for 12 h under N2
conditions. The resulting mixture was poured into methanol
(40 mL) to precipitate a polymer product. The resulting solid was
filtered, dissolved in THF (9 mL), and poured into methanol
(40 mL). After standing overnight, the polymer was collected by fil-
tration and dried in a vacuum oven (50 °C) to give an acrylate
copolymer, PM-III (1.78 g, 89%).
d
Tetrahydrothiophene 1-oxide (THT-oxide).
2. Experimental
2.1. Materials and characterization
All reagents were purchased from Sigma–Aldrich Chemical Co.
(Yongin, Korea) and the reagent-grade solvents were dried when
necessary and purified by vacuum distillation. 1H NMR and 13C
NMR spectroscopy experiments (Bruker AM-300 spectrometer)
were used to characterize the molecular structures of the interme-
diate compounds and functional methacrylate monomers. The
mass spectra were recorded on an Agilent 1200LC/1100 MSD SL
2.4. Oxidation of a polymer: a general procedure
(i) O3-oxidation: polymer PM-III (0.50 g) was dissolved in
CHCl3 (20 mL) and kept at ꢀ78 °C. The solution was treated
with excess bubbling O3 for 2 h and then with N2 flow at
room temperature to remove the dissolved O3. The resulting
mixture was concentrated to a volume of ca. 5 mL under
reduced pressure and poured into methanol to precipitate
a polymer. The polymer was collected by filtration and dried
in a vacuum oven (50 °C) to give an oxidized polymer, PM-
III(O) (0.49 g, 98%).
(ii) m-CPBA-oxidation: polymer PM-III (0.50 g) was dissolved in
THF (20 mL), and m-CPBA (m-chloroperoxybenzoic acid,
78%) (0.91 g) was added at room temperature. The reaction
mixture was heated at 70 °C for 9 h. The resulting mixture
was poured into methanol to precipitate a polymer. The
polymer was collected by filtration and dried in a vacuum
oven (50 °C) to give an oxidized copolymer, PM-III(O2)
(0.48 g, 96%).
mass spectrometer.
A MAGNA-IR 750 spectrometer (Nicolet
Instrument Co., USA) recorded the FTIR spectra. The refractive
indices of the polymer films were measured by an Abbe
Refractometer (DR-M4). TGA analysis was performed on a TAG/
SDTA 851e. The molecular weights of the polymers were deter-
mined by an Agilent PL-20 instrument using a polystyrene stan-
dard. Ozone was generated using a model PC57-10 laboratory
ozonizer.
2.2. Synthesis of monomer methacrylates: M-IV (a general procedure)
To a stirred solution of intermediate alcohol, Me (1.50 g,
10 mmol) in dichloromethane (MC) (30 mL), methacrylic anhy-
dride (94%, 1.66 mL, 10.5 mmol), triethylamine (1.53 mL,
11.0 mmol), and 4-dimethylaminopyridine (30 mg) were added
in order. The mixture was stirred at room temperature for 12 h.
The resulting mixture was diluted with MC, washed with water,
and dried over anhydrous MgSO4. The solvent was removed by
evaporation under reduced pressure. The residue was subjected
to column chromatography on silica gel to give an acrylate mono-
mer, M-IV (1.94 g, 89%). 1H NMR (300 MHz, CDCl3) d (ppm) = 1.92
(s, 3H), 2.82 (s, 4H), 2.98–3.08 (m, 1H), 3.15–3.25 (m, 2H), 4.32–
4.42 (m, 2H), 5.58 (s, 1H), 6.14 (s, 1H); 13C NMR (300 MHz,
CDCl3) d (ppm) = 27.5, 28.9, 31.1, 42.2, 64.1. LC-MS, m/z: 219.05
[M + 1].
PM-I: 1H NMR (300 MHz, CDCl3) d (ppm) = 0.82 (br), 0.91 (t),
1.00 (br), 1.21 (br), 1.35–1.52 (m), 1.53–1.64 (m), 1.77–1.99 (m),
2.59 (m), 2.75 (m), 3.58 (s), 4.20 (br). IR (KBr, cmꢀ1): mmax 1730
(C@O), 1270, 1240, 1192, 1149 (CAO), 1063. GPC (THF, polystyrene
standard): Mn = 18.2 kDa, Mw = 40.4 kDa.
PM-I(O): 1H NMR (300 MHz, CDCl3) d (ppm) = 0.75 (br), 0.95
(br), 1.47 (br), 1.60–2.05 (m), 2.65–3.05 (m), 3.54 (s), 4.24 (br). IR
(KBr, cmꢀ1): mmax 1727 (C@O), 1438, 1391, 1270, 1233, 1186,
1149 (CAO), 1035 (SO). GPC (THF, polystyrene standard):
Mn = 20.1 kDa, Mw = 38.2 kDa.
M-I (89% isolated yield): 1H NMR (300 MHz, CDCl3)
d
PM-I(O2): 1H NMR (300 MHz, DMSO-d6) d (ppm) = 0.75 (br),
0.95 (br), 1.39–1.60 (br), 1.61–2.05 (m), 3.17 (br), 3.33 (br), 3.55
(s), 4.26 (br). IR (KBr, cmꢀ1): mmax 1730 (C@O), 1323 (SO2), 1270,
1240, 1192, 1149 (CAO), 1130 (SO2), 1063. GPC (THF, polystyrene
standard): Mn = 21.3 kDa, Mw = 41.5 kDa.
(ppm) = 0.92 (t, 3H), 1.38–1.48 (m, 2H), 1.51–1.60 (m, 2H), 1.95
(s, 3H), 2.58 (t, 2H), 2.79 (t, 2H), 4.30 (t, 2H), 5.59 (s, 1H), 6.13 (s,
1H); 13C NMR (75.4 MHz, CDCl3) d (ppm) = 13.7, 18.4, 22.0, 30.3,
31.7, 32.1, 64.0, 125.9, 136.1, 167.2. LC-MS, m/z: 203.11 [M + 1].
M-II (90% isolated yield): 1H NMR (300 MHz, CDCl3)
d
PM-II: 1H NMR (300 MHz, CDCl3) d (ppm) = 0.83 (br), 1.00 (br),
1.20 (br), 1.42 (br), 1.75–2.05 (m), 2.68–2.83 (m), 3.58 (s), 4.10 (br).
IR (KBr, cmꢀ1): mmax 1729 (C@O), 1270, 1241, 1190, 1146 (CAO),
1063. GPC (THF, polystyrene standard): Mn = 16.5 kDa,
Mw = 33.8 kDa.
(ppm) = 1.84 (s, 3H), 2.03 (s, 3H), 2.58–2.82 (m, 6H), 4.19 (t, 2H),
5.49 (s, 1H), 6.01 (s, 1H); 13C NMR (75.4 MHz, CDCl3)
d
(ppm) = 15.4, 18.3, 30.3, 31.7, 34.0, 63.8, 125.9, 135.9, 167.0. LC-
MS, m/z: 221.07 [M + 1].