PREPARATION AND PROPERTIES OF CO-OLIGOMERS
475
products were thermally stable up to 310°C, and
revealed electric conductivity of 10–14 S/cm and para-
magnetic properties, making them promising materials
for development of conductive materials.
664, 704, 763, 881, 918, 1003, 1074, 1140, 1276,
1306, 1434, 1467, 1503, 1543, 1602, 3112. Н NMR
1
spectrum (DMSO-d6), δ, ppm: 0.7–2.4 (СН2), 2.9–4.6
(СН), 7.5–8.7 (Н3, Н5), 6.4–7.4 (Ph, Н5'), 5.8–6.5 (Н3',
Н4'). Found, %: С 67.00; Н 5.71; N 27.29. С20 Н21N7.
Other copolymers (IIIa, IIIb, IIId, and IIIe) were
prepared similarly.
EXPERIMENTAL
1-Vinyl-1,2,4-triazole I was prepared and purified
as described elsewhere [30]; bp 43°С (3 mmHg), nD20
1.5100. N-Vinyl-2-phenylpyrrole II was prepared from
acetophenone and acetylene via the Trofomov reaction
in KОН–DMSO medium [18, 31]: bp 94°С (1 mmHg).
The solvents (benzene and diethyl ether) were distilled
before use [32]. Azobisisobutyronitrile AIBN was
twice re-crystallized from ethanol.
ACKNOWLEDGMENTS
This work was performed using the facilities of
Baikal Analytical Center for Collective Usage, Siberian
Branch, Russian Academy of Sciences.
REFERENCES
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Elemental analysis was performed using a Thermo
Finnigan Flash EA 1112 analyzer. IR spectra (KBr
pellet or thin film) were recorded using a Bruker
Vertex 70 spectrometer at 400–4000 cm–1. 1Н
(400.13 MHz) and 13С (100.61 MHz) NMR spectra
(solution in DMSO-d6) were recorded using a Bruker
DPX-400 instrument at room temperature, relative to
TMS. Intrinsic viscosity was measured using an
Ubbelohde viscometer at 20°С (DMF). Copoly-
merization rate constants were calculated using the
Kelen–Tudos method [29]. Turbidimetry titration was
performed at 20°C registering the absorbance with a
KFK-2 photometer (λ 670 nm; 0.1 wt % solution in
dioxane; water as precipitating agent). ESR spectra
were recorded using an ELEXSYS E-580 Bruker
impulse radio spectrometer at room temperature.
Thermal analysis was run using a MOM Q-1500
Paulik–Paulik–Erdey (Hungary) during heating at
10 deg/min up to 700°C at DTA sensitivity of 1/10.
Electric conductivity was determined using an E6-13A
standard teraohmmeter (the specimens were pelletized
at 700 kg/cm2). Doping with iodine was performed via
gas diffusion during 24 h.
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Copolymerization affording product IIIc. A
mixture of 0.54 g (5.7 mmol) of monomer I, 0.96 g
(5.7 mmol) of monomer II, 0.03 g (0.18 mmol, 2 wt %)
of AIBN, and benzene (0.75 g) was put in an ampoule
and bubbled with argon; the ampoule was sealed. The
reaction was run at 70°C during 48 h. The product was
isolated via precipitation in a 3 : 1 diethyl ether –
petroleum ether mixture, washed with diethyl ether,
and dried in vacuum (1 mmHg ) at room temperature
to constant mass. Yield 0.23 g (15%); light-yellow
powder, soluble in ethanol, acetone, acetonitrile,
DMSO, DMF, and 1,4-dioxane. IR spectrum, ν, cm–1:
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Korzhova, S.A., Ermakova, T.G., and Trofimov B.A.,
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 2 2015