JPH0684316B2 - Method for stabilizing perfluoro compound - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for stabilizing a perfluoro compound for obtaining a perfluoro organic compound that generates little hydrogen fluoride even when heated. For more details,
The present invention relates to a method for stabilizing a substantially perfluorinated hydrocarbon compound or amino compound.

[Problems to be Solved by Prior Art and Invention]

Perfluoroorganic compounds are chemically stable, have high thermal conductivity, are nonflammable, and are nontoxic, so they are the media for electronic component reliability testing, media for direct cooling of electronic components, and vapor phase solder. It is used as a heat medium for attachment.
However, when a perfluoroorganic compound is used as a heating medium or the like, there is a problem that hydrogen fluoride is generated when heated at a high temperature, especially to its boiling point. Since hydrogen fluoride is highly corrosive, it causes corrosion of the material of the apparatus and damage to electronic parts even if it is generated in a very small amount. Therefore, a perfluoro organic compound that does not generate hydrogen fluoride has been desired.

Therefore, the perfluorinated organic compound obtained by fluorination has been purified in order to increase its purity and make it more stable. For example, an alkaline amine treatment in which a perfluoroorganic compound is refluxed for a long time in a mixture of a high-concentration aqueous sodium hydroxide solution and diisobutylamine,
Alcolate-amine treatment of refluxing a perfluoroorganic compound for a long time in a mixture of sodium methoxide or sodium ethoxide and diisobutylamine, distillation, purification by gas chromatography and the like have been carried out. However, it is difficult to obtain a perfluoro organic compound that hardly generates hydrogen fluoride even by the above-mentioned purification method, and an efficient method for treating the perfluoro organic compound has been desired.

[Means for Solving the Problems]

Therefore, the present inventors have continued earnest research for the purpose of obtaining a perfluoroorganic compound which does not generate hydrogen fluoride even when heated and can be suitably used as a heat medium and the like. As a result, they have found that the above object can be achieved by irradiating a fluorinated product containing a perfluoroorganic compound obtained by fluorinating an organic compound with ultraviolet rays, and completed the present invention.

That is, the present invention, obtained by fluorination of a hydrocarbon compound or an amino compound, to the reaction product consisting essentially of a perfluoro compound, without adding a fluorinating agent,
It is a method for stabilizing a perfluoro compound, which comprises irradiating with ultraviolet rays.

The perfluoroorganic compound that can be used in the present invention can be adopted without any limitation as long as it does not have a bond that is cleaved by ultraviolet irradiation. Here, examples of the bond that is cleaved by irradiation with ultraviolet rays include an ether bond, a thioketel bond, a bond between a halogen other than fluorine and carbon, and a bond forming a carbonyl group and a —SO ₂ F group. Perfluoro organic compound having these bonds, because it is partially decomposed by ultraviolet irradiation described later,
Not preferred in the present invention.

The perfluoro organic compound in the present invention is obtained by fluorinating an organic compound having a carbon-hydrogen bond, especially a hydrocarbon compound or an amino compound. As the organic compound, a compound that does not have a bond that is cleaved by irradiation with ultraviolet rays is generally adopted as in the above-mentioned perfluoro organic compound. However, even if the organic compound has a bond that is cleaved by UV irradiation, the bond is cleaved by fluorination, and the resulting perfluoroorganic compound does not have the bond as a result. In some cases, for the purpose of producing such a perfluoro organic compound, the organic compound as a raw material thereof may have a bond that is cleaved by ultraviolet irradiation.

Examples of the organic compound used as a raw material for fluorination to obtain the perfluoroorganic compound in the present invention include:
For example, aliphatic or aromatic hydrocarbons; aliphatic or aromatic primary amines, secondary amines, tertiary amines, and other amines. Among these, particularly preferable are liquid organic compounds having 4 to 60 carbon atoms, and further 5 to 30 carbon atoms. Specific examples of these organic compounds are pentane, hexane, heptane, octane, cyclohexane,
Aliphatic hydrocarbons such as methylcyclohexane, dimethylcyclohexane, decalin and methyldecalin; benzene, toluene, xylene, naphthalene, anthracene,
Aromatic hydrocarbons such as phenanthrene; amines such as tripropylamine, tributylamine, tripentylamine, trihexylamine, butyldipentylamine and dibutylpropylamine.

As a method for producing a perfluoro organic compound, a known fluorination method using the above organic compound as a raw material can be adopted without any limitation. For example, a direct fluorination method using a fluorine gas, an electrolytic fluorination method, a fluorination method using a high-valent metal fluoride, or a fluorination method in which these are appropriately combined is suitably adopted. Thus, a fluorinated product containing a perfluoro organic compound corresponding to the raw material organic compound is obtained.

In the present invention, the perfluorinated organic compound thus obtained, preferably a fluorinated product containing a perfluoroorganic compound further purified by neutralization, distillation or a known method, is the object of ultraviolet irradiation treatment. Irradiation with ultraviolet rays is performed without adding a fluorinating agent such as fluorine gas or hydrogen fluoride. Especially done in. When fluorine gas is present, it is not possible to obtain a perfluoroorganic compound in which generation of hydrogen fluoride during heating is suppressed. The atmosphere at the time of UV irradiation is N ₂ if fluorine gas is substantially present.
It may be an inert atmosphere using gas or Ar gas, or an oxidizing atmosphere using air or the like.

The method of ultraviolet irradiation is not particularly limited. In general, a mercury lamp or other known ultraviolet ray source that emits ultraviolet rays having a wavelength of 190 nm to 400 nm or light containing the same can be used. The light source may be placed in the treatment liquid, or may be irradiated from the outside through a material through which ultraviolet rays pass well. Materials that allow ultraviolet rays to pass satisfactorily include glass; single crystal sapphire; vinylidene fluoride polymer, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-ethylene copolymer, tetraflutroethylene-perme Examples thereof include fluorocarbon resins such as fluoroalkyl vinyl ether copolymers and chlorotrifluoroethylene polymers. Since a slight amount of hydrogen fluoride may be generated during irradiation of ultraviolet rays, it is preferable to protect the surface of glass such as quartz glass used as an ultraviolet ray transmitting material with a hydrofluoric acid resistant resin. Since the time of UV irradiation varies depending on the target perfluoroorganic compound, it is desirable to determine it by conducting an experiment in advance. Generally, 5 minutes to 200 hours and about 1 hour to 50 hours are suitable. Either a flow system or a batch system can be adopted as the reaction mode.

The temperature in ultraviolet irradiation suppresses the decomposition of the perfluoroorganic compound, and in order to sufficiently exert the effects of the present invention,
It is preferably selected from 10 to 200 ° C, more preferably 50 to 150 ° C.

After the ultraviolet ray treatment, hydrogen fluoride liberated by the ultraviolet ray treatment may be removed by a method such as neutralization or adsorption, if necessary.

〔effect〕

When a fluorinated product containing a perfluoroorganic compound obtained by fluorinating an organic compound such as a hydrocarbon compound or an amino compound is heated as it is to the boiling point or a high temperature above the boiling point, hydrogen fluoride is generated and the heating is performed for a long time. Even if it continues, a small amount of hydrogen fluoride continues to be generated. However, the fluorinated product that has been subjected to the ultraviolet irradiation treatment by the method of the present invention does not substantially generate hydrogen fluoride even when heated.

Since the fluorinated product treated by the method of the present invention hardly generates hydrogen fluoride, it can be preferably used as a heat medium for vapor phase soldering, a test medium for electronic components, artificial blood, etc. .

〔Example〕

The following examples are provided to describe the present invention more specifically, but the present invention is not limited to these examples.

Example 1 Anhydrous hydrofluoric acid and three kinds of trialkylamines shown in Table 1 were used as raw materials, and the concentration of the latter was set to 10% by weight, and electrolysis was performed using a nickel electrolytic cell (electrode area 10 dm ² , current 20 A capacity 3.5 l). Fluorination was started.While continuously supplying anhydrous hydrofluoric acid and trialkylamine, the resulting fluorinated product was intermittently withdrawn from the lower portion of the electrolytic cell with 40% by weight aqueous sodium hydroxide solution. Refluxing in an equal volume mixture of diisobutylamine for 120 hours gave a fluorinated product based on perfluorolollyalkylamine.

150 g of the obtained fluorinated product was provided with a reflux condenser, an exterior temperature controller, a stirrer, and a window in which 40 mmφ disc-shaped quartz glass and tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer were superposed. It was placed in a 150 ml stainless steel container, and irradiated with ultraviolet rays from a distance of 1 cm while stirring with an ultra-high pressure mercury lamp (USH-250D, 250W manufactured by Ushio Inc.) under the conditions shown in Table 1. In both cases, the recovery rate after UV irradiation is almost 100% based on that before irradiation.
Therefore, almost no change in composition was observed.

100 g of the fluorinated product which had been subjected to ultraviolet irradiation was placed in a 200 ml eggplant-shaped flask having a reflux condenser in the upper part, heated, and boiled under atmospheric pressure for 5 hours. During this period, nitrogen gas at a flow rate of 80 ml / min was blown into the liquid to generate 50% hydrogen fluoride.
It was absorbed in ml of 0.01 N potassium hydroxide aqueous solution. Ion chromatographic analyzer (Yokogawa Kitatsuden, model IC
100) to determine the amount of hydrogen fluoride generated,
Amount of hydrogen fluoride generated per unit weight of fluorinated product [mg
-(HF) / kg- (fluorinated product)] was calculated. This value will be called the amount of hydrogen fluoride generated during boiling.

For comparison, Table 1 also shows the amount of hydrogen fluoride generated during boiling when ultraviolet irradiation was not performed.

Example 2 Two organic compounds shown in Table 2 were fluorinated with cobalt trifluoride. Nickel reactor with a stirrer filled with 1.8 kg of cobalt trifluoride powder (length 50 cm,
(Inner diameter 9 cm) was heated to 270 ° C., an organic compound was vaporized from one end of the reactor and supplied together with nitrogen gas. The fluorinated product flowing out from the reactor was condensed with a cooling trap to separate nitrogen gas and the like. After the reaction, most of the hydrogen fluoride contained in the fluorinated product was removed by bubbling with nitrogen gas, and the remaining hydrogen fluoride was neutralized with a 30% aqueous potassium hydroxide solution, washed with water, and washed with calcium chloride. After drying and distillation, a fluorinated product containing a perfluoroorganic compound shown in Table 2 as a main component was obtained.

The obtained fluorinated product was irradiated with ultraviolet rays in the same manner as in Example 1 under the conditions shown in Table 2, and then the amount of hydrogen fluoride generated during boiling was measured. The results are shown in Table 2. In each case, the recovery rate after irradiation with ultraviolet rays was almost 100% based on that before irradiation, and almost no change in composition was observed.

For comparison, Table 2 also shows the amount of hydrogen fluoride generated at the time of boiling when ultraviolet irradiation was not performed.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical indication C07C 209/90 9280-4H 211/15 9280-4H // A61K 9/107 K 7329-4C

Claims (1)

[Claims] 1. A perfluoro compound, which is obtained by fluorinating a hydrocarbon compound or an amino compound, and which is irradiated with ultraviolet rays without adding a fluorinating agent to a reaction product consisting essentially of the perfluoro compound. Method of stabilizing compounds