JPH0451560B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a novel fluoroalkoxy cyclic phosphonitrilate, and more specifically, a fluoroalkoxy cyclic phosphonitrilate having a 1,1,3-trihydroperfluorobutyloxy group. , its manufacturing method and uses. Applications of the substance according to the present invention (hereinafter referred to as "the compound") include nonflammable lubricating oils and hydraulic oils based on the basic skeleton, its constituent elements, and physical properties. [Prior Art] and [Problems to be Solved by the Invention] Generally, in the production of alkoxyphosphonitrilates, hydrogen halide scavengers such as tertiary amines such as pyridine and alkali metal salts such as potassium carbonate are used. Propoxyphosphonitrile, a useful flame retardant for rayon, is produced industrially by this method. However, in this method, fluoroalcohols do not react, and it is particularly difficult to produce fully substituted fluoroalkoxyphosphonitrites without residual chlorine or rearrangement. As a result of a detailed study of the physical properties of various fluoroalkoxy cyclic phosphonitrilates, the present inventors found that fluoroalkoxy cyclic phosphonitrilates with a molecular weight of 1,500 to 2,500 and having a fluoroalkoxy group having 3 to 7 carbon atoms exhibit physical properties as hydraulic fluids. have, especially
Those with a molecular weight of about 1,500 to 2,000 and having a fluoroalkoxy group with a carbon number of 4 to 6 are made of low-temperature flow, viscous,
I thought that it might have an appropriate value for vapor pressure, etc. Currently, fluoroalcohols that can be produced industrially include H(CF ₂ CF ₂ ) _X CH ₂ OH (mixture of X=1 to 7), CF ₃ CF ₂ (CF ₂ CF ₂ ), which is made from tetrafluoroethylene. _y CH ₂ OH (mixture of y = 1 to 7)
In addition to (CF ₃ ) ₂ CHOH, CF ₃ CFHCF ₂ CH ₂ OH, which uses hexafluoropropylene as raw material, CF ₃
There are CH ₂ OH, CF ₃ CF ₂ CH ₂ OH, etc. Alcohol made from tetrafluoroethylene is a mixture of telomers and requires fractional distillation for its purpose and use.
Additionally, there are problems in the handling of tetrafluoroethylene itself, making it impossible to transport, and there are safety issues during production. On the other hand, since hexafluoropropylene is easy to handle and does not undergo telomerization, it is essentially economical in terms of selectivity and yield for obtaining the desired product. Especially 1,
Since 1,3-trihydroperfluorobutanol can be obtained in a one-step reaction, it appears to be a suitable fluoroalcohol for the above applications. However, 1,1,3-trihydroperfluorobutanol undergoes dehydrofluorination under alkaline conditions, producing by-products as shown in the formula below and consuming the deoxidizing agent. It is thought that the cyclic phosphonitrilate was not obtained. Incompletely substituted products have poor heat resistance due to the remaining active halogen,
In addition, it has major drawbacks for this purpose, such as being hydrolyzed by moisture and causing metal corrosion. Incidentally, the results of a preliminary test conducted by the present inventor to determine the degree of elimination of hydrogen fluoride in the presence of equimolar amounts of various bases of 1,1,3-trihydroperfluorobutanol are shown in the table below.

[Means for solving problems]

In view of the above points, as a result of detailed reaction research, the present inventor has dehydrofluorinated 1,1,3-trihydroperfluorobutanol by carrying out the reaction while gradually adding sodium hydride. The present invention has been completed by developing a method for easily producing the compound in high yield without any problems. That is, the present invention has the following formula: [(CF ₃ CFHCF ₂ CH ₂ O) _n (HCF ₂ CF ₂ CF ₂ CF ₂
CH ₂ O) _2o-n (PN) _o ] ...() (In the formula, n3 or 4, m means an integer of 1≦m≦2n-1.) Fluoroalkoxy cyclic phosphonitrilate, 1 , 1,3-trihydroperfluorobutanol, 1,1,5-trihydroperfluoropentanol, and phosphonitrile chloride trimer or/and phosphonitrile chloride tetramer in a solvent while gradually adding sodium hydride. The present invention provides a method for producing the present compound represented by the above formula (), which is characterized by causing the compound to react, and a rotary pump oil containing the present compound represented by the above formula () as a main component. Phosphonitrile ring (PN) of compound of formula () _o
(CF ₃ CFHCF ₂ CH ₂ O) and (HCF ₂ CF ₂ CF ₂
CF ₂ CH ₂ O) and 1,1,3-trifluoroperfluorobutanol, which are raw material compounds, and 1,1,5-
Since it corresponds to the molar ratio of the charged molar ratio with trihydroperfluoropentanol, it is easy to set the value of m of the present compound and obtain the desired product as set. On the other hand, the value of n in the phosphonitrile ring can be determined to either 3 or 4 depending on whether a phosphonitrile chloride trimer or a phosphonitrile chloride tetramer is used as the raw material cyclic phosphonitrile chloride. can. In this way, the Compound can be obtained as a single compound with uniform n and m values by selecting the raw materials in advance and setting their blending ratio, but the Compound can be obtained as a mixture of various Compounds. Therefore, it is also possible to use a mixture of two types of cyclic phosphonitrile chloride as raw materials. Although the reaction mechanism of the present invention described above has not been fully elucidated, since it is a solid-liquid heterogeneous reaction between sodium hydride and the reaction liquid, the reaction on the sodium hydride surface is rate-limiting, and the dehydrofluorination reaction is It seems to be suppressed. The method of the present invention is considered to be very effective not only for the production of the subject compound, but also for the esterification reaction of acid chlorides, etc. using 1,1,3-trihydroperfluorobutanol and 2-hydroperfluoroisopropanol. It will be done. [Examples, etc.] Example 1 45.5 g (0.25 mol) of 1,1,3-trihydroperfluorobutanol and Charge 58 g (0.25 mol) of 1,1,5-trihydroperfluoropentanol, 23 g (0.2 unit mol) of phosphonitrile chloride tetramer, and 300 ml of ethyl ether, and add 10 g (0.48 mol) of sodium hydride powder to a powder injector. ) and install it. While stirring, sodium hydrogen powder was gradually added from a powder injector, and the reaction was carried out at 36°C for 4 hours. After the reaction, add cold water to the system to dissolve the formed salt, then add 100 ml of ether, separate and wash with water 4 times, dehydrate with magnesium sulfate, and distill off the solvent and excess fluoroalcohol. 84 g (92%) of pale yellow crude product was obtained. The residual active chlorine concentration of this product was 0.002%, indicating almost complete replacement, and there was no concern about stability against heat and moisture. However, the number of theoretical plates is 50
Rectification is performed using a stage precision fractionator. Boiling point 199~
The main fraction was collected at 200°C/0.1mmHg. The specific gravity of this liquid is 1.78 (at 20°C), the viscosity is 160 centistokes (at 40°C), and the refractive index is 1.3559 (at 20°C)
It was hot. Gas chromatography using silicon OV-17 revealed that this compound is a single component, as shown in the infrared absorption spectrum (Figure 1) at 1350 cm ^-1.
The presence of a tetrameric P=N ring skeleton was confirmed from the absorption of Confirm that the ratio is 1:1, and add tetrakis(1,1,3-trihydroperfluorobutyloxy)tetrakis(1,
It was confirmed that the product was 1,5-trihydroperfluoropentyloxy)cyclotetraphosphonitrilate (hereinafter referred to as compound A). Example 2 68.3 g (0.375 mol) of 1,1,3-trihydroperfluorobutanol and 29 g (0.125 mol) of 1,1,5-trihydroperfluoropentanol
Using the same equipment as in Example 1, the reaction was carried out in the same manner and the treatment was carried out in the same manner to obtain 78 g (90.3 g) of pale yellow liquid.
%) was obtained. The residual active chlorine concentration of this product is
0.003%, and 190 to 191 by rectification as in the previous example.
The main fraction at °C/0.2 mmHg was collected. The physical properties of this liquid are specific gravity 1.77 (20℃), viscosity 150 centistokes (40℃), refractive index 1.3571 (20℃), gas chromatography, infrared absorption spectrum (3
Figure), proton nuclear magnetic resonance spectrum (Figure 4)
The product was confirmed to be hexakis(1,1,3-trihydroperfluorobutyloxy)bis(1,1,5-trihydroperfluoropentyloxy)cyclotetraphosphonitrilate (hereinafter referred to as compound B). Example 3 22.8 g (0.125 mol) of 1,1,3-trihydroperfluorobutanol and 87 g (0.375 mol) of 1,1,5-trihydroperfluoropentanol
Perform the reaction, treatment, etc. in the same manner as in the previous example using
A main fraction of 210-211°C/0.1 mmHg was obtained. Analysis similar to the previous example revealed that this compound was bis(1,1,3-
It was confirmed that it was trihydroperfluorobutyloxy)hexakis(1,1,5-trihydroperfluoropentyloxy)cyclolattephosphonitrilate. The residual active chlorine concentration of this compound is 0.001%, the physical properties are specific gravity 1.78 (20℃), viscosity 177 centistokes (40℃), and refractive index 1.3547.
(20℃). Reference Example Using 91 g (0.5 mol) of 1,1,3-trihydroperfluorobutanol, the reaction was carried out in the same manner as in the previous example.
After treatment, 73 g (89.7%) of a pale yellow liquid with an active chlorine concentration of 0.0002% was obtained. Obtained by distillation. boiling point
The main fraction at 175-177°C/0.04mmHg was a slightly yellow liquid that crystallized by standing overnight. As a result of analysis, this compound was found to be octakis (1,1,3
-trihydroperfluorobutyloxy) cyclolatetephosphonitrilate. Comparative Example 1 Using 91 g (0.5 mol) of 1,1,3-trihydroperfluorobutanol, 23 g (0.2 unit mol) of phosphonitrile chloride trimer, and 61 g (0.6 mol) of triethylamine, a reaction was carried out at 78°C for 6 hours in an acetonitrile solvent. , the same process as in the previous example was carried out, and 8 g of yellow viscous liquid and raw alcohol were added.
73g was recovered. Analysis of this yellow viscous liquid in the same manner as in the previous example revealed that it was a mixture of unknown structure. Comparative Example 2 9.6 g of sodium pieces shredded into approximately 1 mm squares (0.42
The reaction and treatment were carried out in the same manner as in Reference Example, and after distillation, 31.5 g (38.7%) of the main fraction with a boiling point of 150-200°C/0.1 mmHg was obtained. The active chlorine concentration of this product was 3.0%. Example 4 45.5 g (0.25 mol) of 1,1,3-trihydroperfluorobutanol, 58 g (0.25 mol) of 1,1,5-trihydroperfluoropentanol, and 23 g (0.2 unit mol) of phosphonitrile chloride trimer were mixed with ethyl The same reaction was carried out at 36°C for 7 hours using the apparatus of Example 1 using 10 g (0.42 mol) of sodium hydride dissolved in 300 ml of ether, and 82 g of yellow viscous liquid was obtained by carrying out the same treatment.
(90%). The residual active chlorine concentration was 0.005%. Rectification was carried out in the same manner as in Example 1, and the boiling point was 169.
The main fraction at ~170°C/0.3mmHg was collected. This compound was analyzed in the same manner as in Example 1, and gas chromatography showed that it was a single component, and from the absorption at 1250 cm ^-1 in the infrared absorption spectrum (Figure 5), it was found that the trimeric P=N ring skeleton was present. The presence of 5 to 6 ppm in the proton nuclear magnetic resonance spectrum (Figure 6)
From the ratio of the peak integral value between 1,5
-trihydroperfluoropentyloxy) cyclotetriphosphonitrilate (hereinafter referred to as compound C). The measured physical property values are
Specific gravity 1.78 (20℃), viscosity 90 centistokes (40
℃), and the refractive index was 1.3526 (at 20℃). Example 5 30.3 g (0.167 mol) of 1,1,3-trihydroperfluorobutanol and 77.3 g (0.333 mol) of 1,1,5-trihydroperfluoropentanol
The reaction, treatment, and rectification were carried out in the same manner as in Example 4, and the main fraction with a boiling point of 180 to 181°C/0.3 mmHg was collected. Analyzes were conducted in the same manner as in the previous example, and the results of gas chromatography, infrared absorption spectrum (Figure 7), and proton nuclear magnetic resonance spectrum (Figure 8) revealed that this compound was bis(1,1,3-trihydroperfluorinated). butyloxy)tetrakis(1,1,5-trihydroperfluoropentyloxy)cyclotriphosphonitrilate (hereinafter referred to as Compound D)
It was confirmed that Example 6 75.8 g (0.417 mol) of 1,1,3-trihydroperfluorobutanol and 19.3 g (0.083 mol) of 1,1,5-trihydroperfluoropentanol
The reaction, treatment, rectification, and analysis were carried out in the same manner as in the previous column. -trihydroperfluoropentyloxycyclotriphosphonitrilate. Physical property measurement value is specific gravity 1.78
(20°C), viscosity 83 centistokes (40°C), and refractive index 1.3549 (20°C). Examples 7 to 10 Compounds A, B, C, and D were individually used in a 7-day continuous operation test using a rotary vane type two-stage vacuum pump, and the results are shown in the following table. Regardless of which oil was used, a steady state was reached within 1 to 2 hours after the start of operation, and after that, no changes other than fluctuations due to external temperature were observed and the results were good. After the test, the oil showed only slight turbidity due to the sliding material, but there was no change in the pump body or physical properties such as viscosity, and it was found that compounds A, B, C, and D
was confirmed to be suitable as rotary pump oil.

〔Effect of the invention〕

The present invention uses 1, 1, 3, which are likely to cause dehydrofluorination.
- Even trihydroperfluorobutanol can be reacted with cyclic phosphonitrile chloride without dehydrofluorination, and fully substituted fluoroalkoxy cyclic phosphonitrile can be obtained in high yield. We have discovered a manufacturing method, which has made it possible to provide a new fluoroalkoxy cyclic phosphonitrilate suitable as a rotary pump oil, which has high industrial applicability.

[Brief explanation of drawings]

FIG. 1 shows an infrared absorption spectrum of the compound obtained in Example 1, and FIG. 2 shows a proton nuclear magnetic resonance spectrum of the same compound. FIG. 3 shows an infrared absorption spectrum of the compound obtained in Example 2, and FIG. 4 shows a proton nuclear magnetic resonance spectrum of the same compound. FIG. 5 shows an infrared absorption spectrum of the compound obtained in Example 4, and FIG. 6 shows a proton nuclear magnetic resonance spectrum of the same compound. FIG. 7 shows an infrared absorption spectrum of the compound obtained in Example 5, and FIG. 8 shows a proton nuclear magnetic resonance spectrum of the same compound.

Claims (1)

[Claims] 1 Formula [(CF ₃ CFHCF ₂ CH ₂ O) _n (HCF ₂ CF ₂ CF ₂ CF ₂
CH ₂ O) _2o-n (PN) _o ] (wherein n means 3 or 4, m means an integer of 1≦m≦2n-1). Reacting 1,1,3-trihydroperfluorobutanol, 1,1,5-trihydroperfluoropentanol, and phosphonitrile chloride trimer or/and phosphonitrile chloride tetramer while gradually adding sodium hydride. The formula [(CF ₃ CFHCF ₂ CH ₂ O) _n (HCF ₂ CF ₂ CF ₂ CF ₂
A method for producing a fluoroalkoxy cyclic phosphonitrite represented by CH ₂ O) _2o-n (PN) _o ] (in the formula, n is 3 or 4, and m is an integer of 1≦m≦2n-1). Formula [(CF ₃ CFHCF ₂ CH ₂ O) _n (HCF ₂ CF ₂ CF ₂ CF ₂
CH ₂ O) _2o-n (PN) _o ] (where n is 3 or 4, m is an integer of 1≦m≦2n-1) as the main component. rotary pump oil.