CN1121406C - Synthesis process of aryloxy cyclotrinitrile phosphide - Google Patents

Abstract

The present invention discloses a synthesizing method of an aryloxy trichloro phosphonitrile compound. Hexachloro phosphonitrile, trichloro phosphonitrile and substituted phenol are used, and the compound of the present invention is prepared through reflux of 1 to 15 hours in the presence of solid alkali in reaction media. The method has the advantages of simple operation, reduced energy consumption and shortened reaction period.

Description

Synthetic method of aryloxy cyclotriphosphazene compound

The invention describes a synthesis method of an aryloxy cyclotriphosphazene compound.

Most countries in the world have formulated their own aviation development plans. In particular, the United States has successively formulated advanced tactical combat development plans and comprehensive high-performance turbine engine technology plans, which put forward higher requirements for the performance of aero engines. High-load, high-performance aircraft will inevitably cause the lubricating oil system to withstand extremely high operating temperatures when flying at high speeds. It is estimated that when the Mach number is 2.5, the temperature of the main lubricating oil is about 204°C; when the Mach number is 3, the temperature of the main lubricating oil is about 260°C. When current liquid lubricants work at these temperatures, their oxidation stability, thermal stability, and evaporation are difficult to meet the requirements. Therefore, developed countries have begun to develop non-ester lubricating oils, such as fluoroether triazines, perfluoropolyethers, perfluoroalkyl ethers, and polyphenylene ethers (5P4E). Due to the high price of fluoroether triazine, it is still in the early stage of development; perfluoropolyether and perfluoroalkyl ether are easy to corrode ferrous alloys at high temperatures, and have poor solubility and sensitivity to additives; although polyphenylene ether It has good high temperature stability and high auto-ignition temperature, but the pour point as high as 4°C greatly limits its use. Therefore, some researchers have turned their focus to cyclic phosphazenes in recent years.

Aryloxy, especially fluorinated aryloxyphosphazene and fluorinated alkoxyphosphazene derivatives have the advantages of high autoignition point, high thermal stability, high chemical stability and extremely low vapor pressure. The low-temperature fluidity and oxidation stability of phosphazene compounds that have been screened abroad such as bis(4-fluorophenoxy)-tetrakis-(3-trifluoromethylphenoxy)cyclotriphosphazene (X-1P) , self-ignition point, lubricity, and vapor pressure at moderate temperatures are better than 5P4E (US 5015405). At the same time, the phosphazene compound is a kind of good magnetic recording medium lubricant, which can reduce the static friction between the magnetic head/disk interface when added to the perfluoropolyether.

The traditional synthesis method of phosphazene compound is to complete the reaction at high temperature (110-160°C) and long time (16-48 hours).

The object of the present invention is to provide a kind of synthetic method of aryloxy cyclotriphosphazene compound.

The present invention is realized through the following measures:

式(I)中X为4-F，3-F，4-NO₂，4-Ph，4-CHO，4-CH₂OH，4-H，4-CH₃，4-OCH₃，4-F-3-CF₃，4-COOR，2-COOR，(R＝C1～C8烷基)，m＝0～6.式(I)化合物的合成方法包括：A)  使用原料为式(II)的六氯三聚磷腈和式(III)的取代酚。

B)  在反应介质中，在有固体碱存在下回流反应1～15小时。The aryloxy cyclotriphosphazene compound of general formula (I):

In formula (I), X is 4-F, 3-F, 4-NO ₂ , 4-Ph, 4-CHO, 4-CH ₂ OH, 4-H, 4-CH ₃ , 4-OCH ₃ , 4- F-3-CF ₃ , 4-COOR, 2-COOR, (R=C1～C8 alkyl), m=0～6. The synthesis method of the compound of formula (I) includes: A) The raw material used is formula (II) The hexachlorotripolyphosphazene and the substituted phenol of formula (III).

B) In the reaction medium, reflux for 1 to 15 hours in the presence of a solid base.

In the method for preparing formula (I), the reaction medium is acetonitrile and acetone.

In the method for preparing formula (I), the solid base is anhydrous potassium phosphate or anhydrous potassium carbonate.

In the method for preparing formula (I), the feeding ratio of substituted phenol and solid base relative to hexachlorotrimeric phosphazene is slightly excessive than the stoichiometric ratio, and the excess is 0.5% to 10% (mol).

The synthesis of the aryloxy ring triphosphazene compound involved in the present invention can be represented by the following chemical equation:

The invention has simple operation, can reduce energy consumption and shorten the reaction cycle.

The phosphazene compound of the formula (I) of the present invention can be used alone as a high-temperature lubricant and a computer hard disk surface lubricant, or as an additive to other high-temperature lubricants and hard disk surface lubricants.

In order to understand the present invention better, illustrate by embodiment:

Example 1: Synthesis of 2,2,4,4,6,6-bis(4-fluorophenoxy)-tetrakis(3-trifluoromethylphenoxy)-cyclotriphosphazene (X-1P)

Put 4.0g hexachlorotripolyphosphazene, 2.7g p-fluorophenol, 5.9mL m-trifluoromethylphenol, 16.0g anhydrous potassium phosphate, 250mL acetonitrile in a 500mL flask, stir vigorously, reflux for 8 hours, cool and filter , distill off the solvent acetonitrile, dissolve the residue in 100mL ethyl acetate, wash three times with 10% NaOH solution, dry over anhydrous Na ₂ SO ₄ , filter, distill off the ethyl acetate to obtain oily liquid products: 2, 2, 4, 4 , 6,6-bis(4-fluorophenoxy)-tetrakis(3-trifluoromethylphenoxy)-cyclotriphosphazene. The thermal decomposition temperature (TGA, N ₂ , heating rate 15°C/min) is 470°C. Example 2: Synthesis of 2,2,4,4,6,6-six (4-fluorophenoxy)-cyclotriphosphazene

4.0g hexachlorotripolyphosphazene, 8.1g p-fluorophenol, 10g anhydrous potassium carbonate, 180mL acetone, put in a 500mL flask, stir vigorously, after 7 hours of reflux reaction, cool, filter, distill off the solvent acetonitrile, and dissolve the residue in In 100 mL of ethyl acetate, washed three times with 10% NaOH solution, dried over anhydrous Na ₂ SO ₄ , filtered, and evaporated to remove ethyl acetate to obtain colorless crystals. The melting point is 126-127°C. The thermal decomposition temperature (TGA, N ₂ , heating rate 15°C/min) is 436°C.

Example 3:

Synthesis of 2,2,4,4,6,6-bis(3-trifluoromethylphenoxy)-tetrakis(butoxycarbonylphenoxy)-cyclotriphosphazene

Put 4.0g hexachlorotripolyphosphazene, 2.8g butyl p-hydroxybenzoate, 3.0mL m-trifluoromethylphenol, 30g anhydrous potassium phosphate, 250mL acetonitrile in a 500mL flask, stir vigorously, reflux for 12 hours, then cool , filtered, distilled off the solvent acetonitrile, the residue was dissolved in 100mL ethyl acetate, washed three times with 10% NaOH solution, dried over anhydrous Na ₂ SO ₄ , filtered, distilled off the ethyl acetate to obtain an oily liquid product. The thermal decomposition temperature (TGA, N ₂ , heating rate 15°C/min) is 380°C. Product evaluation:

The tribological properties were evaluated on an Optimol SRV friction and wear testing machine. Take X-1P as an example:

Experimental conditions: amplitude 1mm, frequency 25Hz, friction pairs are steel/steel and steel/aluminum. The steel ball is GCr15 with a diameter of 10mm, and the aluminum disc is AA2024 aluminum alloy. The results are listed in Table 1 (steel/aluminum, test time 30 minutes) and Table 2 (steel/steel, test time 90 minutes).

Table 1X-1P Friction and wear properties under steel/aluminum friction pair

Load/N Aluminum disc wear volume/mm ³ ×10 ³ friction coefficient

20 2.2 0.158

40 3.4 0.132

50 4.9 0.126

Table 2X-1P Friction and wear properties under steel/steel friction pair

Load/N Steel disc wear volume/mm ³ ×10 ³ friction coefficient

100 0.05 0.095

200 0.10 0.091

300 0.95 0.089

Claims (3)

1. the synthetic method of the aryloxy ring triphosphazene compound of general formula (I), In formula (I), X is 4-F, 3-F, 4-NO ₂ , 4-Ph, 4-CHO, 4-CH ₂ OH, 4-H, 4-CH ₃ , 4-OCH ₃ , 4- F-3-CF ₃ , 4-COOR or 2-COOR, R=C1~C8 alkyl, m=0~6, characterized in that the synthesis method comprises: Use raw material to be the hexachlorotripolyphosphazene of formula (II) and the substituted phenol of formula (III);

In the reaction medium, under the presence of anhydrous potassium phosphate or anhydrous potassium carbonate, the reaction is refluxed for 1-15 hours. 2. synthetic method as claimed in claim 1 is characterized in that reaction medium is acetonitrile, acetone. 3. The synthetic method as claimed in claim 1, the feeding ratio of substituted phenol and solid base with respect to hexachlorotrimeric phosphazene is slightly excessive than the stoichiometric ratio, excessive 0.5%～10% (mol).