JPS6183280A - Fluorochlorohydrocarbon composition - Google Patents

Abstract

PURPOSE:To provide a fluorochlorohydrocarbon compsn. consisting of fluorochlorohydrocarbon, a boron compd. and a phosphite, which has excellent high temp. stability, decomposition controlling property and corrosion resistance and is useful as heat medium and foaming agent. CONSTITUTION:The compsn. is prepared by blending (A) 1-6C fluorochlorohydrocarbon (e.g. trichlorofluoromethane), (B) boron compd. selected from among (meta)boric acid (or alkali metal salt thereof), phenyl or alkyl ester of boric acid, phenylboronic acid (or phenyl or alkyl ester thereof), etc. and (C) phosphite selected from among 2-30C dialkyl phosphite, diphenyl phosphite and 7-45C dialkylpentaerythritol diphosphite in such blend ratios that (b)/(c) may be 5-95/95-5 by weight and (C+B) may be in 0.01-wt% of (A).

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a fluorochlorohydrocarbon composition, and more particularly to a composition comprising a fluorochlorohydrocarbon, a boron compound, and a phosphite ester. The composition of the present invention is useful as a heat transfer medium, a blowing agent in the production of plastic foam, and the like.

Prior art and its problems) ll+sai0ri00 hydrocarbon (hereinafter referred to as Oshi) is
Widely used as a refrigerant in refrigerators. In the refrigeration cycle of a refrigerator, the refrigerant reaches a high temperature in the compressor. Freon is a stable compound, so it does not decompose under normal refrigeration cycle conditions, but when the condensation temperature is high or the evaporation temperature is low, the temperature rise in the compressor is large.
May decompose.

Recently 0. ．． Power generation using a 7+ cycle using I has also been put into practical use, but in the above-mentioned refrigerators, 7 cycles, and 7 cycles, fluorocarbons, lubricating oil, and metals come into contact. In addition, heat transfer is also carried out by filling a tube with Furonia and using its sensible heat, and its evaporation and condensation processes. 7 and the metal come into contact. Furthermore, polyurethane, polystyrene,
When fluorocarbons are used as a blowing agent in the production of plastic foams such as polyethylene, polyethylene, polyvinyl chloride, and vinyl acetate copolymer, metals may also coexist. In such cases, fluorocarbons are easily decomposed due to the action of metals, and the degree of decomposition of fluorocarbons when they come in contact with lubricants and metals is greater than that when only fluorocarbons and lubricants come into contact. , it becomes a big thing.

In the usage of the fluorocarbon O'J as described above, the fluorocarbon is
．． 7. As the decomposition of lubricating oil progresses, the thermodynamic properties of the former deteriorate and the lubricating performance of the latter decreases.
Refrigerators and Rashi+Cycycles reduce their capacity. In addition, when F0:,I decomposes, bald gas is generated and corrodes the metal.Hydrogen is generated along with this metal corrosion, which also reduces the heat exchange characteristics of heat engines such as refrigerators. let

This also applies to the heat transfer equipment described above.

In order to cope with the rise in temperature at which fluorocarbons are used due to the recent improvement in the performance of equipment and equipment that use fluorocarbons, various methods for preventing decomposition of fluorocarbons and methods for removing decomposition products have been proposed. ing. For example, in order to prevent the decomposition of fluorocarbons, there is a method of adding furan to fluorocarbons (Japanese Patent Publication No. 40-22374), a method of adding nitrous oxide (Japanese Patent Application Laid-Open No. 48-49).
685), the method of adding phosphite (Japanese Patent Application Laid-Open No. 55-48277), the method of adding sial + rubesillierythritol diphosphite (Japanese Patent Application Laid-open No. 55-48277),
6-70082) have been proposed, and a method of adsorbing and removing decomposition products with an adsorbent is also known. However, none of these methods can be said to be sufficiently effective and have not yet been able to satisfy the advanced functionality currently required. That is, these additives are -1 cannot be prevented to a satisfactory degree from decomposition, or cannot be used in heat transfer equipment (such as heat pipes), foaming agents for plastics, etc.

Means for Solving the Problems In view of the above-mentioned problems of conventional Fu0.7 compositions, the present inventor conducted various experiments in order to obtain a Fu0shi composition with better stability and various performances. As a result of stacking the helmets, it was discovered that when a specific boron compound and phosphite ester are used together, the decomposition of fluorocarbons is extremely well suppressed, and the present invention has been completed. That is, the present invention provides fluorocarbons [1
The present invention provides a fluorinated COO hydrocarbon composition characterized by comprising a fluorine-free hydrocarbon, a boron compound, and a phosphite ester.

In the present invention, a fluorochlorohydrocarbon is a saturated aliphatic hydrocarbon in which at least one hydrogen is fluorine,
It also refers to a compound in which at least one hydrogen is replaced with chlorine, and has 1 to 6 carbon atoms, more preferably 1 or 2 carbon atoms. Preferred specific examples of fluorochlorohydrocarbons include ri00 difluoro methane, zig00 difluoro methane, tric DO fluoro methane y1 ri00 pentafluoro ethyl, dichloro 0 tetrafluor 0 ethyl, tritri 00
Examples include trifluoroethylene, but the fluorochlorohydrohydride used in the present invention is not limited to these.

In the present invention, boron compounds include boron oxide, boric acid, alkali metal salts of boric acid, metaboric acid, alkali metal salts of metaboric acid, phenyl esters and alkyl esters of boric acid, phenyl fg O-/ acid, phenylboronic acid. At least one member selected from the group consisting of phenyl esters and alkyl esters of , diphenylborinic acid, and phenyl esters and alkyl esters of diphenylborinic acid is used. When used in the form of an aryl ester, an alkyl group having 1 to 5 carbon atoms is preferred. In the case of sialkyl esters and trialkyl esters, the alkyl groups may be the same or different from each other. Preferred specific examples of boron compounds are as follows.

Boric acid type: boron oxide, boric acid, borax, potassium tetraborate, sodium metaborate, tnofenium
Zborate, diphenylborate, triphenylborate; methyl, ethyl, n-duropyl,
Mono-alkylborate, sial + ruborate, triall-alborate, etc. having a group such as isozypyl.

Phenyl type 0 cylic acid----Phenylboronic acid, tnophenyltnophenylbonate, diphenyltnophenylbonate; Al+R group and L2 are methyl, ethyl, n
Monoal + ruphenyl poronate, sial + ruphenyl poronate, etc. having groups such as 10 hir, isodzu D hir, etc.

Diphenylborinic acid type...Diphenylborinic acid,
tnophenyldiphenylpolinate; 'P I+, +
monoal+diphenylpolinates having a group such as methyl, ethyl, n-d-pyl, isod-d-pyl, etc. as a base group;

In the present invention, as the phosphite ester, at least one selected from the group consisting of alkyl esters, aryl esters, and lupesitaerythritol phosphites of phosphorous acid is used. Among these, preferred are sialyl phosphite having 2 to 30 carbon atoms, diphenyl phosphite, and ral+rubecitaerythritol diphosphite having 7 to 45 carbon atoms. In the case of realkyl esters, the alkyl groups may be the same or different. Preferred specific examples of phosphite esters are shown below.

Alkyl esters: dimethyl phosphite, diethyl phosphite, di-normal pylphosphite, diiso-pylphosphite, dibutyl phosphite, dilauryl phosphite, etc.

Aryl ester: diphenyl phosphite, etc.

Al + rubesitaerythritol phosphite...
- Diethyl becitaerythritol diphosphite, didecyl pentaerythritol diphosphite, didecyl pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, etc.

In the present invention, the blending ratio of the boron compound and the phosphite ester is 5 to 9 parts by weight in a total of 100 parts by weight of both.
5 parts by weight, the latter is 95 to 5 parts by weight. If the amount of the boron compound is less than 5 parts by weight or more than 95 parts by weight, the desired effect will not be fully achieved.

In the composition of the present invention, the total amount of the boron compound and phosphite ester used is not particularly limited, but is approximately 0.0% based on the weight of the powder. It is preferable to set it in the range of 1 to 100 yen. If the amount is less than about 0.011 Hill, the desired effect will not be fully achieved, whereas if it is more than about 5% by weight, no significant improvement in the effect will be observed.

The boron compound and phosphite ester may be added to the fushi as they are, or may be added after being dissolved in an appropriate solvent. Such a solvent can dissolve boron compounds and phosphite esters, and is itself free of fumes.
Suitable materials are those that dissolve in 7 without reacting with it and are stable against heat, such as methyl acrylate and tertiary tanol.

Effect of the invention According to the present invention, the following effects are achieved.

11 More stable at high temperatures than fushi compositions containing known stabilizers. For example, when using Triku00F11O0Metashi()0C11) as a working fluid, its service limit temperature can be raised by approximately 40°C by adding a boron compound and a phosphite ester. .

(2) Compared to known adhesive compositions, it does not decompose under conditions of contact with lubricating oil and/or metals.

(3) Corrosion to metal parts of devices and equipment is also lower than that of known adhesive compositions.

(4) It also exhibits excellent performance as a blowing agent for the production of plastic foams such as polyurethane, polystyrene, polystyrene, polyvinyl chloride, and ethylacetate copolymer.

EXAMPLES The features of the present invention will be further clarified by the following Examples and Comparative Examples.

Examples 1 to 8 and Comparative Example 1-7 A composition consisting of Triku00 Fluo0 Methane 2f and the additives shown in Table 1 was placed in a heat-resistant glass tube (inner diameter 6I11, outer diameter 1
OIIJ1 length 250W), and then add lubricating oil (J
IS Targoshi Oil No. 1) 0.02f and steel billet (JIS
5S4I, 2mm x 5m x 50m) and sealed.
After heating at 130° C. for a predetermined period of time, the appearance of the composition was observed, and the chlorine compounds present in the composition and the chlorine compounds adhering to the steel pieces were measured using an Iosic 0 Madograph. The results are shown in Table 1.

The appearance of the composition was evaluated based on the following criteria.

A: No change B: Colored yellow C: Colored brown 1st Table 1 (continued) As is clear from the results shown in Table 1, %'h'b ``When using xz boron compound and phosphite ester together,
The effect of suppressing the decomposition of chlorofluorocarbons is greater than when using known stabilizers.

Example 9 and Comparative Examples 8 to 1O A heating test was conducted in the same manner as in Comparative Examples 1 and 2.6 and Example 1, except that the amounts of Triku00 Fluo0 Metashi and lubricating oil were respectively set to IF. The results after heating for 480 hours are shown in Table 2.

Table 2 Example 10 and Comparative Examples 11 to 13 The amounts of Triku00 fluoromethane and lubricating oil were each 1 V, and three types of metal pieces (steel pieces similar to Examples 1 to 5,
2ga x 5mm x 50u Cu piece and 2 IIJK
A heating test was conducted in the same manner as Comparative Example 1.2.6 and Example 1, except that 5 pieces x 50 u pieces A, , e were used. Table 3 shows the results after heating for a predetermined period of time.

Table 3

Claims (3)

[Claims] (1) A fluorochlorohydrocarbon composition comprising a fluorochlorohydrocarbon, a boron compound, and a phosphite. (2) The weight ratio of boron compound and phosphite ester is 5
:95 to 95:5, and the total amount of both compounds is about 0.01 to about 5% by weight of the fluorochlorohydrocarbon according to claim 1. Composition. (3) The boron compound is boron oxide, boric acid, alkali metal salts of boric acid, metaboric acid, alkali metal salts of metaboric acid, phenyl esters and alkyl esters of boric acid, phenylboronic acid, phenyl esters and alkyl esters of phenylboronic acid. , diphenylborinic acid, phenyl esters and alkyl esters of diphenylborinic acid, and the phosphite is dialkyl phosphite having 2 to 30 carbon atoms, diphenyl phosphite and 7 to 7 carbon atoms. The fluorochlorohydrocarbon composition according to claim 1 or 2, characterized in that it is at least one selected from the group consisting of 45 dialkyl pentaerythritol diphosphites.