SU602513A1 - Method of preparing polyorganophosphasenes - Google Patents

Description

I

This invention relates to the field of the synthesis of heat-resistant carborane-containing polyphosphazenes, which can be used as coatings, bonding for layered and cast, scattering materials, adhesives.

A known method for producing polyorganophosphazene of the general formula-j TJ P lu, where T may be alkyl, aryl, fluoroalkyl and fluoroaryl, amino-alkoxy, aryloxy, fluoroalkoxy, and fluoroaryloxy groups .l

These polyorgan Ophosphazenes were synthesized by the interaction of polyorg (NOPhosphazenes and nucleophilic agent S) with an organic solvent, namely, by the reaction of nucleophilic substitution of chlorine atoms in polydichlorophosphazene by the interaction of the latter with either Grignardre or With Na-glypol xg1mi aliphatic patterns or aliphatic patterns. mixtures of benzene and tetrahydrofuran. These are solid or rubber-like substances, the chemical and thermal stability of which is determined by the nature of the groups framing the bases th polymer chain. From these points of view, the most interesting polyaryloxy and polyhaloaryloxyphosphazene oxazalis. However, according to the thermogravimetric analysis (TGA) data in air at 500-BOO C, the majority of the above polymers are almost completely decomposed. According to TGA data, the heating rate is 4.5 / min) the decrease in the weight of these polyorganophosphazenes in an inert erg-. de voshe than. on air. So, for a polymer of formula () 2l

the coke residue in air at 500,600 ° C is 55%, and in nitrogen at 390 C - 43%.

The aim of the invention is to increase the heat resistance of polyorganophosphazenes;

The goal is accomplished by using lithium carborane-containing phenol and alcohol as a nucleophilic agent. The process is carried out according to the following scheme: + iO-R-C - CH L I Jn where-Y-SNg ,. The reaction is carried out at room temperature, in a solution of tetrahydrofuran, at a molar ratio of initial reagents of 1; 2, respectively. According to the data of thermal-mechanical analysis (temperature rise rate of C / min, load of 100 g 04 mm) obtained by the proposed method of poly- (chloro-o-car Loranylbenzyloxy) phosphazene, it softens around. When heated, it melts when this polymer is heated (4 times min), decreases its weight, it is 25% at 620 ° C and practically remains at this level further heated to 900 ° C. A Yermogravimetric study of the ethere polymer in an atmosphere of gels showed that the polymer sample did not change in weight when heated to 900 ° G. The study of poly (chloro-o-carboranylbenzyloxy) phosphazene by the method of IR spectroscopy showed that all the main bands that characterize this class of compounds are present in its JK spectrum. The presence of carboranic groups in the polymer is indicated by the absorption band at 2600, which is identified as the stretching vibrations of the B – H bond of the carborane core. ° Thus, the carborane-containing, polychlorophosphazene. Based on this thermogravimetric analysis, it does not change in weight when heated in an inert atmosphere to 900 ° C; at n. Greet it in air for up to 2.5 hours, the coke residue is 75% of the initial weight of the polymer, which significantly exceeds the known polyaryloxyphosphate in this respect; The polymers obtained are dissolved in acetone, tetrahydrofuran, dioxane, ethyl alcohol. Example. To a solution of 0.29 g (0.0025 M) in 20 ml of tetrahydrofuran is added dropwise at room temperature, with stirring, a benzene solution of г g CH prepared from 1.25 g (0, OOЬO m) benzyl xyo-o-carboran and 0, 32 g (0.0050 m) butyl lithium. The reaction mixture is stirred at this temperature for 5 hours. The lithium chloride precipitate formed as a result of the reaction is filtered off, the solvents are evaporated in a vacuum pump of a water jet pump, and the solid; the residue after evaporation, purify two I Jn 0-RC-CH 0 / ratnim by transferring tetrahydrofuoane from a solution into water and then. From the solution in tetrahydrofuran to the ether. 0.49 g of a purely powdered substance is obtained with a melting point of 200-225 ° C. (in a capillary). Output about 60% of the calculated for the compound of the formula Tp / cg-j j LOS H / H C CH .oH, o Found,%: C 31.69; H 5.60; B 3i, 53; P 9.26; From 10.68. N 4.23; С Н Ю-РМОСЕ Calculated,%: С32,76; H 5.10; B 32.80; R 9.3,; N 4.24 jCE 10.74. .. 7 0.16 dl / g. (for 0.5% solution in ethanol). Example2. To a solution of 0.29 .g (0.0025 M) PMSEG N in 14 ml of tetrahydrofuran, p-drop under a stirring, at room temperature, a benzene solution of 1.66 g, (0.0065 m) of 1 lithium carborano-containing phenol prepared from , 65 g (0.0065 m) and 0.42 g (0.0065 m) butyl lithium. Further processing and isolation of the product is carried out as in Example 1. 0.32 g of a substance of 0.1 dl / g is obtained (for a 0.5% solution in this: 1 mole). Yield about 40% of that calculated for the compound of the formula. G / t i-Ptce) K-J.j, Found,% at 31.68. n, gv, „rkose Calculated,%: B32.80. Primerz, To a solution of 1.15 g (0.01 M) -pNCe2ln in 35 ml of tetrahydro Furan are added dropwise, (stirring, at room temperature, a benzene solution of 14 "OSdH4 CHgCg CH, prepared from 2.5 g {0.0 L M), jCg-CH and 0.64 g (O, O1K) butyl lithium. -After stirring the reaction mixture for 6 hours from a solution of vnapt by the synthesis of solvents 2.41 substances were obtained with 0.12 dl / g (for a 0.5% solution in ethanol) containing 13.59% boron. Example4. To a solution of o-caobonyl-L1-methylate prepared from 2 g (0.0155 M) of oximetx1-o-carboran and 0.75 g (0.0117 M) s. HUU was added dropwise 0.58 g (0.0050 MGSRMM. The further processing is carried out as in example I. The polymer yield 70% Ch1 1.7 dl / g.

Found %; In 46.64,

Calculated,%: B 45,98. The results of thermogravimetric analysis of carborane-containing phosphazones

and polyaryloxy- and -polyhaloarylg of Yuxiphosphazone -K1 PRa w (ascent rate of temperature 4,) are given in the table

Claims (1)

1. US patent 3169933, 260-2, 1965.