Deemed 4,6-desulfurisation acid as a monomer to obtain a heat-resistant polymers

 

(57) Abstract:

Usage: as a monomer to obtain a heat-resistant polymers. The inventive product - deemed 4,6-desulfurisation acid f-crystals I. BF C8H4O4N2S4exit 96,25% so pl. 218 22°C. Reagent 1: deemed 4,6-desulfosarcina acid. Reagent 2: P2S5. Reaction conditions: reagent ratio 1 (1 2) in the environment of pyridine at boiling point. The structure of f-crystals I:

The invention relates to the production of heterocyclic compounds containing two cyclic selftimer grouping in a single aromatic nucleus such as diimide 4,6-Desulfovibrio acid (dithio-m-bisharin), formulas

HNNH,

which can be used as a monomer for the synthesis of new geterotsiklicheskikh heat-resistant polymers, new polymers with a system of conjugate relations, as well as new reactive oligomers.

Known deemed 4,6-disulfonate - left acids HNNH on the basis of which to obtain polymers with-SO2- and-CO - groups in imenom cycle [E. P. Melnikov, A. B. Tagiev. Synthesis of polyimides with-SO2- and-CO-groups in imenom cycle. Azerb.chem.W. 1974, No. 2, S. 65]

You know Paul who / Europe. chem. W. 1976, No. 4, S. 46]

However, this monomer has limited solubility in common organic solvents and low reactivity in reactions of polycondensation. The polymers obtained based on it, are low molecular weight and mostly insoluble products.

The purpose of the invention, a new monomer having high reactivity and improved solubility.

This goal is achieved diimide 4,6-desulfurisation acid as a monomer to obtain a heat-resistant polymer, which is obtained by processing diimide 4,6-desulfosarcina acid pentasulfide phosphorus, taken in a molar ratio of 1:(1-2) in the environment heteroaromatic tertiary amine at the boiling temperature of the reaction mass within 1-3 hours

The reaction is carried out by addition with stirring of the dry powder pentasulfide phosphorus to a thin suspension of diimide 4,6-desulfosarcina acid in pyridine at 75-80aboutWith gradual increase of temperature up to 110-115aboutWith continued heating at this temperature for 1-3 h, then cooled the reaction mass to room temperature 15-20aboutAnd allocation of target prodnum way in contrast to the known analogue of the two carbonyl (C=0) group is replaced by a thiocarbonyl (C=S) group, it allows you to increase the reactivity and to improve the solubility of the target product.

The interaction of diimide 4,6-desulfurisation acid with 4,4"-diaminodiphenyl in the environment of the polar aprotic solvent at a temperature of 60-65aboutWith synthesized polymer with high molecular weight (logand 0.46 DL/g). It is well soluble in polar aprotic solvents and has a heat resistance up to 350aboutC.

P R I m e R 1. In a round-bottom three-neck flask with a capacity of 250 ml, equipped with a mechanical stirrer (through the gate), thermometer and reflux condenser, download a thin slurry 5,76 g (0.02 mol) of m-bisharin in 150 ml dry pyridine and the flask placed in an oil bath, the temperature was then raised to 75-80aboutC. With constant stirring to a thin suspension in one step add 9.80 g (0,042 mol) of pentasulfide phosphorus (in the form of finely pulverized dry powder) and continue heating. When 90-95aboutWith the reaction mixture dissolves and turns a dark orange homogeneous solution. Next, the temperature was raised to 110-115aboutWith and with stirring, boil for another 2 hours After cooling to room temperature the reaction mass becomes those who in the song data of the upper layer is separated from the dark brown of the lower layer. From light brown filtrate the solvent is distilled off under reduced pressure (3-4 mm RT.CT.) dry, and dark yellow solid residue is recrystallized from dry ethanol. Fallen light orange crystals are collected, filtered and dried in vacuum at 60-70aboutC to constant weight. The selected substance is a light orange powder product. Output 6,16 g (96,25% of theoretical), so pl. 218-220aboutC.

Found, 30,38; N 1,40; N Of 8.47, S 39,55.

WITH8H4ABOUT4N2S4.

Calculated With 30,02; N 1,26; 8,75 N; S 40,04.

In the infrared spectrum has absorption bands at 2980-2840 cm-1(NH), 1480-1440 and 1420 cm-1(C=S), 1390-1360 and 1180-1140 cm-1(SO2-), 1320-1280 cm-1(C-N), which correspond lit. data.

P R I m m e R 2. The conditions of the reaction and selection of the target product similar to example 1, but at 110-115aboutWith the stirring is continued for 3 hours Output dithio-m-bisharin is 96% of theoretical so pl. 218-220aboutC.

In the infrared spectrum has absorption bands at 2980-2840 cm-1(NH), 1480-1440 and 1420 cm-1(C=S), 1390-1360 and 1180-1140 cm-1(SO2-) 1320-1280 cm-1(C-N).

P R I m e R 3. Unlike the 16-219aboutC.

In the infrared spectrum has absorption bands at 2980-2840 cm-1(NH), 1480-1440 and 1420 cm-1(C=S), 1320-1280 cm-1(C-N), 1390-1360 and 1180-1140 cm-1(SO2-).

P R I m e R 4. Acquisition and allocation of dithio-m-bisharin carried out under conditions analogous to example 1, with the only difference that the pyridine take in 200 ml. Exit 94% of theoretical, so pl. 218-220aboutC. the infrared spectrum has absorption bands at 2980-2840 cm1(NH), 1480-1440 and 1420 cm-1(C=S), 1390-1360 and 1180-1140 cm-1(-SO2-) 1320-1280 cm-1(WITH-N).

P R I m e R 5. Conditions of the acquisition and allocation analogously to example 1, the only difference is that the pyridine take in the amount of 100 ml. Output 90% so pl. 218 to 221aboutC.

In the infrared spectrum has absorption bands at 2980-2840 cm-1(NH), 1480-1440 and 1420 cm-1(C=S), 1390-1360 and 1180-1140 cm-1(SO2-), 1320-1280 cm-1(C-N).

P R I m e R 6. Unlike example 1, pentasulfide phosphorus charge in the amount of 4.90 g (0,021 mol). The yield is 85% of theoretical so pl. 216-218aboutC.

In the infrared spectrum has absorption bands at 2980-2840 cm-1(NH), 1480-1440 and 1420 cm-1(C=S), 1390-1360 and 1180-1140 cm-1(SO2-), 1320-1280 cm-1(C-N).

P R I m e R 7. the ndimethylacetamide (DMAA) with vigorous stirring once added 1.20 g of (3.75 mmole) dithio-m-bisharin (tankomaster powder). Get a homogeneous solution was yellowish-orange color, which persists for 20 min stirring at 18-20aboutC. Then the reaction mass is painted in a light brown color. Next, the temperature of the reaction mass was raised to 60-65aboutWith and continue stirring for 2 hours By the end of the experience obtained viscous solution turns brown, it is cooled to 18-20aboutC and poured into 400 ml of water. The reaction product precipitated as a dark yellow powder, which is collected, filtered, washed with water and dried in vacuum at 60-70aboutC to constant weight. The resulting substance is a yellowish brown solid product. Output -1,15 g (96% of theoretical).logand 0.46 DL/g (0.5 g of polymer in 100 ml of DMAA in the 30aboutC). According to TGA, thermal degradation of the polymer in air begins at 350aboutC.

Found, With 54,48; N. Of 2.54; N, 14.24 From; S 15,18.

[ C20H12O4N4S2n< / BR>
Calculated With 55,04; N 2,77; N 14,66; S 14,60.

In the infrared spectrum has absorption bands at 1645-1625 cm-1(C=N), 3000-2800 cm-1(NH), 1340-1300 and 1180-1150 cm-1(SO2-) that correspond lit.data.

The monomer (dithio-m-bisharin) obtained above OPI high reactivity, due to the substitution of two carbonyl (C=O) groups on more mobile thiocarbonyl (C=S) group;

improved solubility, due to the disappearance of hydrogen bonds, as in contrast to the carbonyl (C=O) groups, thiocarbonyl (C=S) group does not form hydrogen bonds with the NH-group;

low melting point (so pl. 218-220aboutFor dithio-m-bisharin, and for Matricaria so pl. 410aboutC) due to the disappearance of hydrogen bonds;

the polymer obtained on its basis is a high molecular weight (logand 0.46 DL/g), has a high solubility in polar aprotic solvents and heat resistance up to 350aboutCompared to the low molecular weight (logof 0.2 DL/g) and insoluble polymers derived from m-bisharin.

< / BR>
as the monomer for heat-resistant polymers.

 

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