RU1835405C - Oligomer stibazane as antipyrene for epoxy resin and a technique of production of oligomer stibazane - Google Patents

Abstract

Usage: the proposed compounds can be used in those fields of technology where materials with reduced flammability are required. SUBSTANCE: new chemical compounds are proposed - oligomeric stibazanes of the general formula. 1 R-Sb-Kill where R R1 p I / LR R, R, H, C1, C1, OH „O, 6-20. The proposed oligomeric stibazans are prepared by reacting antimony p-chloride with ammonium chloride at equimolar ratios in simi tetrachloroethane medium in the presence of a catalyst selected from the group consisting of zinc chloride, barium chloride, magnesium chloride at 110- for 25-50 hours. 2 tablets, che

Description

The invention relates to the chemistry of polymers and is a new class of hetero-chain high molecular weight compounds, namely oligomeric stibazanes of the formula

N - Sb-N-f

R jn

where R is H, C1,

R is C1, OH, O, n is 6-20.

This class of compounds is macromolecules having a fundamental difference in the composition of the structural unit from traditional hydrocarbons, as well as currently known inorganic polymer formations, “It allows one to clearly classify an oligomeric Compound having a macrochain with antimony-nitrogen bonds” Compounds of a new class may find application in industries requiring materials with reduced flammability.

Substances having similar bonds are represented by the following chemical formulas: Sb (NHCHj. CHg CH5) i (,), sb (NceHy) (ocg5) 5,

8b (OSGNu) ghSbNr. The way they are half

ate

4b. Oh Xia

For information on this, see Hass Dieter Cech Dieterc Versuche zur Darstellung stabiler Antimon (V) - Stick-Stoff-Verbindungen. ZpChem, 1970, 10, No. 2, (75-76), nems

They are not polymers, since they do not form macromolecules with a significant degree of polymerization, and nitrogen does not belong to bridging elements, therefore, the claimed oligomers and these compounds belong to different classes

The aim of the invention is the creation of oligomeric stibazanes of the formula

M

hN

-Sb- /

R RI C,

R i

N

AND

where R is H, C1,

R1 - GL, OH, O

tg 6-2025

as high molecular weight inorganic compounds of a new class,

This goal is achieved by the synthesis of chemical compounds of a new structure (3 °

1

where R R

C1, OH, O, p - 6-20,

and a method for their preparation, which consists in the fact that p-tetrachloride antimony is reacted with ammonium chloride in an equimolar ratio, in the medium of sim-tetrachloroethane in the presence of a catalyst salt of divalent metals or a mixture thereof, at a temperature of 110-1 5 ° C for 25 - 50 hours followed by isolation of the target product

The new product is a resinous substance. When applied to a solid surface, it forms a film that is stable in air. The resulting substance is not soluble in benzene, о-, xylene vapor, toluene, dioxane, hexane, concentrated hydrochloric acid, 2,5-vinylpyridine, , In water, methanol, ethanol, acetone, tetrahydrofuran, the product destruc

- g

k - Q

§

twenty

25

(3o

35

at

at

45

fifty

55

it forms a white powder. “In concentrated sulfuric acid, dimethyl sulfoxide, dimethylformamide, the product dissolves, and in the last two solvents the dissolution is accompanied by pink and yellow staining.,

A new class of compounds was studied and found to be useful as an antipyretic additive to epoxy.

Example r 1C Synthesis of oligost-basano

In the reaction flask, 29.9 g (0.1 mol) of antimony p-chloride and 5.35 g (0.1 mol) of 1 finely ground ammonium chloride in a solvent of 70 ml of symtetrachloroethane are reacted with stirring into the system 0.207 g (0.001 mol) of Bad catalyst was added. The reaction mixture was heated to, synthesis was carried out for 30 hours. The hydrogen chloride generated during the reaction was neutralized with a 0.1 N NaOH solution. Then the system is cooled to room temperature and filtered under vacuum. The solid and liquid phases are separated, from which the solvent is removed by vacuum. The resulting material is dried in vacuum at a temperature of 100-120 ° C. The melting point of the product is 210-230 ° C. Product yield: 10.11 g (, 83% K)

Product gross formula SbNiCl OH

Found,%: Sb 51.01, H 0, M, C1 29.93, N 11.810

Calculated: Sb 51.05, H 0.2; C1 29.95, N 11.81,

Mol.m. 700 (cryosconically in dimethyl sulfoxide). Identification of the oligomer was carried out according to elemental analysis, YK and NMR spectroscopy. In the IR spectra, characteristic absorption bands are observed: 270-280 (Sb-) f 320-330 (), in addition, the following frequencies are characteristic of the framing spectra : 307 336 cm (8b-C1), 25 (Sb-0), 1600-1610 (NH), 1 50 -80 cm Ch-C1).

NMR spectroscopy showed that when studying the resonance frequencies for KN and LiCl, the signal of the initial monomer — ammonium chloride and the oligomer obtained — does not coincide, indicating its different structure in comparison with the monomer and the position of nitrogen and chlorine in the product

The relative viscosity of the 1.0% solution in dimethylformamide is 1.1-1.15 o

The following examples are presented in table 1

Example 80 In a reaction flask, 29.9 g (0.1 mol) of antimony dichloride and 5.35 g (0.1 mol) of finely divided ammonium chloride in sim-tetrachloroethane medium were taken in the amount of 70 ml with stirring. 0.207 g (0.001 mol) of BaC14 was added to the mixture. The reaction mixture is heated to 135 ° C, synthesis is carried out for 50 hours. The hydrogen chloride generated during the reaction is neutralized with 0.1 N0 NaOH solution, then the system is cooled to room temperature and filtered under vacuum. 20- 25 ml of dimethylformamide and left for a while, then dimethylformamide and solvent were removed by vacuum. The resulting material was dried in vacuum at 1 ° C-170 ° C. The melting point of the product was 210-220 ° C. The product yield was 12.9 g (7,).

Gross formula SbNzCl3OH2.

Found,%: Sb No., No. N 10.29, C1 38.97, 0 5.8

Thus, from all the cases considered, the optimal yield of stibazane of the general structural formula is achieved at a maximum temperature of 145 ° C, using a mixture of catalysts in a molar ratio of BaC12, MgCla and ZnCl2 1: 3: 2, within 25 hours (see example 7) synthesis time up to 55 hours does not lead to an increase in product yield.

Useful properties have been identified in oligostibazan

The study of the ability to reduce the flammability of the composition based on epok1835 05

The odon resin, which was evaluated by the value of the oxygen index, showed that oligomeric stibazan has high antipyretic efficiency. With a mass ratio of oligostibazane and epoxy resin of 1:20, the oxygen index increases by more than 50%.

As a comparison, the effective composition was used: bis (allyloxymethyl) phosphinic acid, hexabromobenzene and copper acetate. The properties of the oligostibazane epoxy resin composition are presented in Table 2

Thus, the claimed oligomeric stebazanes can be used in industries

requiring the use of low flammability materials based on epoxy resin

Claims (1)

The claims 1 „Oligomeric stibazan of the general formula N- R Sb-n-f P where R is H, C1, R is C1, OH, O, n 6-20, as a flame retardant for epoxy pitches 2 о A method for producing oligomeric stibazan, in which p-antimony is reacted with ammonium chloride at an equimolar ratio in the medium of sim-tetrachloroethane in the presence of a catalyst selected from the group consisting of zinc chloride, barium chloride, magnesium chloride, at 1101 5 ° P for 25-50 hours Table 1 C1 C1 --NlW $ b-N-OH C1J TO Composition / ° (CHf CH-CIS-0-CH21RSON; Sc (cn3 (oo) 4; sevg6 12 33 37.5 36 fifty