SU1761759A1 - Method of hexaarylhydroxycyclotriphosphazenes synthesis - Google Patents

Abstract

Usage: as modifying additives for synthetic and natural polymers, additives to lubricating oils. The essence of the invention: a product of hexaphenyloxycyclotriphosphazene M3R3 (OSEH5) b, BF SzbNzoMzOErz, yield 98-99%. Reagent 1: Systat b. Reagent 2: CeHsOH. Reagent 3: alkali. Reaction conditions: in a two-phase system, water is an aromatic hydrocarbon in the presence of a phase transfer catalyst — tetrabutylammonium bromide or iodide together with a linear or cyclic aliphatic polyester with a molar ratio of tetrabutylammonium bromide or tetrabutylammonium iodide, reagent 1 and reagent 2, equal to (1,2- 1.5): 1: (8-10), volume ratio of aqueous and organic phases, equal to (1.0-2.0): 1 concentration of reagent 1 0.15-0.3 mol / l, concentration of reagent 3 1 , 0-2.0 mol / l at 75-95 ° C for 9-12 hours. 1 tab.

Description

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WITH

The invention relates to the chemistry of elemental compounds, specifically to the synthesis of cyclic oligomeric phosphazenes, in which all halogen atoms are replaced by aryloxy groups used as modifying additives for synthetic and natural polymers, lubricant additives.

A known method for the preparation of hexaaryloxycyclotriphosphazenes by the reaction of hexa-chlorocyclotriphosphazene (HCP) with sodium phenol in tetrahydrofuran medium, however, this method is not very technological, since it involves the steps of drying and purification of solvents and phenols, as well as the preparation of phenols. In addition, it is highly explosive and flammable.

flammable solvents and metallic sodium.

The closest to the claimed method is the preparation of hexaphenoxycyclotriphosphine by the reaction at the phase separation between a solution of 0.05 mol of HCFC in 100 ml of chlorobenzene and a solution of 12 ml of water with 0.3 mol of phenol. 0.3 mol of potassium hydroxide and 0.018 mol of tetrabutyl phosphonium bromide for 3 hours at 25-30 ° C and 21 hours at 95 ° C. In this case, hexaphenoxycyclotriposphenate is obtained with a purity of 95.8% and a theoretical yield of 92.7%.

The disadvantage of this method should be considered a long process time and a rather significant loss of the product. In addition, it should be noted relatively

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low availability used in the prototype phase transfer catalyst.

The purpose of the invention is to reduce the duration of the process and increase the yield of the target products.

 The goal is achieved by the fact that these derivatives are obtained by reacting HCFC dissolved in an aromatic hydrocarbon with a solution of the corresponding phenol in an aqueous alkali solution, in the presence of a phase transfer catalyst for bromide or tetrabutylammonium iodide (KMP-1) together with a linear or cyclic aliphatic polyether —kylene glycols (alkylene-ethylene or propylene) with a molecular weight of 150-600, dicyclohexyl-18-crown-6, dibenzo-18-Krakn-6) (KMP-2) with a ratio of KMP-1 and KMP-2 ( in moles per mole alkylene oxide star na) 1: (3-5), molar ratio of KMP-1 and HCF 1.2-1.5: 1, volume ratio of aqueous and organic phases 1.0-2.0: 1, molar ratio of phenol and HCFC (8-10): 1, HCF concentration 0.15-0.3 mol / l, alkali concentration 1.0-2.0 mol / l, reaction temperature 75-95 ° C for 9-12 h.

The difference between the proposed method and the known one is that the phase transfer catalyst additionally contains a linear or cyclic aliphatic polyether and the process is carried out at a ratio of reagents indicated in the claims. As it turned out, their joint use enhances the activity of each of them, i.e. there is a synergistic effect (see examples 24 and 25).

In determining the variation intervals for these factors, we were guided by the following: the yield of pure hexaaryloxycyclotriphosphazenes should be 97% and there should be no loss of HCFC due to hydrolysis, i.e. The total yield of the crude mixture of aryloxycyclotriphosphazenes should be 100%.

Assuming the remaining conditions remain constant at a molar ratio of KMP-2 and KMP-1 3: 1, the loss of HCFC due to hydrolysis tends to increase, and with a further increase in the content of KMP-2 relative to KMP-1 5: 1, the results remain unchanged. A decrease in the molar ratio of KMP-1 and HCP of 1.2: 1 leads to a decrease in the yield of pure hexaaryloxycyclotri-phosphazenes, and an increase of 1.5 to an increase in the degree of hydrolysis of HCFC. Similar effects produce, respectively, a decrease in the concentration of HCFC in the organic phase of 0.15 mol / l and an increase of 0.3 mol / l; the increase in the volume ratio of the aqueous and organic phases is 2.0: 1 and its decrease is 1.0: 1; a decrease in the reaction temperature of 75 ° C and an increase of 95 ° C; a decrease in alkali concentration of 1.0 mol / l and an increase of 2.0 mol / l. When the reaction time decreases by 9 h and the molar ratio of phenol and HCFC 8: 1, the yield of pure hexaaryloxycyclotriphosphazenes decreases,

and an increase in the reaction time of 12 hours and a molar ratio of phenol and the results of the reaction do not change.

Thus, the inventive method allows to obtain

hexaaryloxycyclotriphosphazenes with a yield of 97% and without loss of HCFC on hydrolysis, using all the advantages of conducting the reaction at the phase separation, due to the detected synergistic effect of these phase transfer catalysts when used together.

Example 1. To a solution of 3.48 g (0.01 mol) of HCFC in 50 ml of nitrobenzene (HCFC concentration 0.2 mol / l), the solution is poured into

75 ml of water (volume ratio of aqueous and organic phases 1: 5: 1) 4.5 g of sodium hydroxide (alkali concentration 1.5 mol / l), 8.42 g of phenol (0.09 mole, molar ratio of phenol and HCP 9: 1), 4.5 g tetrabutylammonium bromide (molar ratio KMP-1 and HCF 1.4: 1) and 2.28 g polyethylene glycol mol.m. 150 (per propylene oxide unit 0.052 mol, molar ratio of KMP-2 and KMP-1 is 4: 1) and lead

the reaction with stirring 10 h at 85 ° C. Then, the organic layer was separated, the solvent was distilled off under vacuum, and 6.92 g (100% HCFC yield) of a mixture of 98% hexafenoxycyclotriposphosphazene and 2% pentaphenoxychloro-citlothosphazene were obtained. The composition of the mixture is determined from the total integrated intensity of the lines of the corresponding components in the NMR 31P spectrum and elemental analysis data.

Examples 2-25. Examples are similar to example 1 in the sequence of operations. The specific conditions for their performance are shown in the table.

Thus, the proposed method

allows to obtain hexaaryloxycyclotriphosphazenes with an increased rate with a yield of 97% without loss of hexachlorocyclotriphosphine due to hydrolysis.

Claims (1)

Invention Formula The method of producing hexaaryloxycyclotrophosphazenes of the general formulas Pz # (OAg) b, where Ar is unsubstituted or substituted phenyl, by reacting hexachlorocyclotriphosphazene with the corresponding phenol and alkali in a two-phase water-aromatic hydrocarbon system in the presence of a tetrabutylammonium halide catalyst and 75% -95 characterized in that, in order to reduce the duration of the process and increase the yield of target products, bromide or iodide tetrabutyl is used as a phase transfer catalyst moni together with liP r.  and e. TBAB, TBA, TEA6 — tetrabutylammonium bromide, iodide, and tetraethylammomy bromide, respectively, GOG ISO, & OG, 600 — poly (ethylene glycol) mol.i. 15C, and 600, respectively, PPG 200, 250 - polypropylene glycols and 200 m 250 m 250, respectively, DCH-18-k-b - dicyclohexylNo-mraum-b, 6-18-k-6 - dibenzo-18-craone-6 , example 2, form a mixture of tetraphenoxychloro - cyclotrifosphaeene and trioeioxythoichloocytes otridosoaena, in example 25 a mixture of hexahhporcinlotrifosfeeem and its mom- and diphenoxy-displaced derivatives is formed, and example 25 gives a molar ratio of KHfbZ and Diphenoxy-displaced derivatives, and in example 25, the molar ratio of KHfbZ is given and the diphenoxy-displaced derivatives, and the molar ratio of KHfbZ is given in Example 25 and the diphenoxyl displaceable derivatives; 0 linear or cyclic aliphatic polyether with a molar ratio of components 1: (3-5) and the process is carried out with a molar ratio of tetrabutylammonium bromide or iodide, hexachlorocyclo trifosfazene and phenol equal to 1.2-1.5: 1: 8- 10, the volume ratio of the aqueous and organic phases, equal to 1.0-2.0: 1, the concentration of hexachlorocyclotriphosphazene 0.15-0.3 mol / l, the concentration of alkali 1.0 to 2.0 mol / l for 9-12 h