EFFECT OF GLYCOLURIL AND ITS DERIVATIVES
133
The melting points were determined with Boetius
measurement uncertainty ±0.1°) and MP50 Melting
Table 1. Physico-mechanical parameters of TG rubbers for
external cover layers
(
Point System devices.
Parameter
Prescribed for TG grade
rubbers
The reaction progress and product purity were moni-
tored by thin-layer chromatography on standard Silufol
UV-254 plates. The chromatograms were visualized
with iodine vapor or UV lamp.
Nominal tensile strength, MPa
≥14.7
≥350
≤200
55–70
Relative elongation at break, %
2
,4,6,8-Tetraazabicyclo[3.3.0]octane-3,7-dione
glycoluril) (1). To 60 g (1.0 mol) of urea and 60 g of
water, 5.4 mL (0.1 mol) of concentrated sulfuric acid
d = 1.840) and 58 g of a 40% aqueous glyoxal solu-
Abrasion loss, mm3
(
Shore hardness A, units
(
tion (0.4 mol) were added with stirring. The mixture was
heated to boil and boiled for 20 min. The reaction mix-
ture was cooled to room temperature, and the precipitate
was filtered off, washed with 60 mL of water, and dried.
White crystalline powder was obtained. Yield of 1
Phosphorylated derivatives of tetra-N-methylol-
glycoluril (5) and (6). To 2.62 g (0.01 mol) of 2 and
1
.58 g (0.02 mol) of pyridine in benzene, 2.89 g (0.02
mol) of dimethyl phosphorochloridate was added at
°С. The mixture was heated at 60–70°С for 24 h. The
0
–
1
4
3
8.4 g (85%), mp 360°С. IR spectrum (KBr), ν, cm :
209 (NH), 1675 (C=O). H NMR spectrum (400 MHz,
reaction progress was constantly monitored by TLC.
1
The precipitate was filtered off and washed with ace-
DMSO), δ, ppm: 5.20 s (2H, CH), 7.13 s (4H, NH).
,4,6,8-Tetramethylol-2,4,6,8-tetraazabicyc-
lo[3.3.0]octane-3,7-dione (2). A suspension of 28.4 g
0.2 mol) of glycoluril 1 and 80 g of 40% formaldehyde
1
tone. Yield of 5, 6 2.0 g (50.25%). H NMR spectrum
2
(
400 MHz, DMSO), δ, ppm: 3.16 s [12H, 2P(OCH ) ],
3 2
4
5
2
.34 s [4H, 2CH P(O)], 4.52–4.62 m (4H, 2CH –OH),
2
2
(
.64 s (2H, CHCH), 3.21 s [6H, 2P(O)OCH ], 2.51–
3
solution was alkalized with a 20% NaOH solution to
рН 9–10, after which the mixture was stirred at 50°С
for 2 h. 70% of water was distilled off, and tetra-N-hy-
droxymethylglycoluril was separated and washed with
acetone. Yield of 2 26.2 g (50%), mp 136.5°С. IR spec-
3
1
.53 m [8H, 2P(CH ) ]. In the P NMR spectrum, there
2
2
are two signals at 1.0 [(CH ) P(O)OCH ] and 4.0 ppm
2
2
3
[
CH P(O)(OCH ) ]. However, we failed to separate
2 3 2
these products because of their affinity for the solvents.
The formulation for a polymeric compound of de-
creased combustibility is sought for empirically for each
specific article, and the suitability of one or another fire-
proofing agent as fire retardant can be judged only from
the experimental data.
–
1
trum (KBr), ν, cm : 1718.31 (С=О), 3337.39 (ОН).
1
H NMR spectrum (400 MHz, DMSO), δ, ppm: 5.47 s
(
2H, CH), 4.62–4.79 m (8H, CH2).
,6-Di(chloromethyl)-4,8-dihydroxy-2,4,6,8-
tetraazabicyclo[3.3.0]octane-3,7-dione (3). To 2.0 g
0.0076 mol) of 2 in acetonitrile, 8.4 g (0.0608 mol)
2
To bring the developed formulations into industrial
practice, it is necessary that the rubber obtained should
fully meet all the requirements, exhibit improved physi-
co-mechanical properties, and be sufficiently cheap in
production. Therefore, it is necessary to consider all the
regulations concerning difficultly combustible TG rub-
ber for mines (Tables 1 and 2). TG belts are intended
for underground operation at ore-mining enterprises and
coal mines with dist and gas hazard at ambient air tem-
perature of –25 to +60°С and humidity of up to 98%.
(
of phosphorus trichloride was added at 0–10°С. After
that, the mixture was stirred at 70–80°С for 24 h, and
the precipitate was filtered off and washed with aceto-
1
nitrile. Yield of 3 1.89 g (60.96%), mp 180°С. H NMR
spectrum (400 MHz, DMSO), δ, ppm: 5.48 s (2H, CH),
7
.12–7.23 m (4H, CH Cl), 4.65–4.76 m (4H, CH OH).
2 2
2
,6-Di(bromomethyl)-4,8-dihydroxy-2,4,6,8-
tetraazabicyclo[3.3.0]octane-3,7-dione (4). To 3.5 g
0.013 mol) of 2 in toluene, 18.08 g (0.06 mol) of phos-
(
phorus tribromide was added. The mixture was heated
at 60–90°С for 24 h. The resulting precipitate was fil-
tered off and washed with diethyl ether. Yield of 4 3.5 g
The rubber stocks under consideration included the
following components: rubbers, zinc white, P-324 car-
bon black, sulfur, sulfenamide Ts, magnesium oxide,
zinc stearate, Naftam, Diafen, and nitrosodiphenyl-
amine. The rubber stocks were prepared on rollers and
vulcanized in a press.
1
(62.5%), mp 160°С. H NMR spectrum (400 MHz,
DMSO), δ, ppm: 5.46 s (2H, CH), 7.14–7.21 m (4H,
CH Br), 4.67–4.73 m (4H, CH OH).
2
2
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 89 No. 1 2016