COMPOSITION COMPRISING MONOCHLOROTRIFLUOROPROPENE AND STABILIZER, AND ITS APPLICATIONS

Abstract

To provide a composition which is excellent in solubility of various organic substances, presents no adverse effects on the global environment and is excellent in stability. A composition comprising a monochlorotrifluoropropene and at least one stabilizer selected from the group consisting of a carboxylic acid, a carboxylic acid salt and a carboxylic acid ion, characterized in that the content of the stabilizer to the total content of the monochlorotrifluoropropene and the stabilizer is from 0.1 to 500 mass ppm.

Claims

1. A composition comprising a monochlorotrifluoropropene and a stabilizer composed of at least one type selected from the group consisting of a carboxylic acid, a carboxylic acid salt and a carboxylic acid ion, characterized in that the content of the stabilizer is from 0.1 to 500 mass ppm to the total content of the monochlorotrifluoropropene and the stabilizer.

2. The composition according to claim 1, wherein the monochlorotrifluoropropene is 1-chloro-2,3,3-trifluoropropene.

3. The composition according to claim 1, wherein the monochlorotrifluoropropene is 1-chloro-3,3,3-trifluoropropene.

4. The composition according to claim 1, wherein the carboxylic acid is acetic acid, formic acid or fluoroacetic acid.

5. The composition according to claim 1, wherein the carboxylic acid salt is a salt formed from the carboxylic acid and a sodium salt, potassium salt, calcium salt, amine salt or quaternary ammonium ion.

6. The composition according to claim 1, wherein the total content of the monochlorotrifluoropropene and the stabilizer in the entire amount of the composition is at least 80 mass %.

7. A cleaning agent comprising the composition as defined in claim 1.

8. A cleaning method comprising bringing the composition as defined in claim 1 into contact with the surface of an article to remove a stain attached to the surface of the article.

9. The cleaning method according to claim 8, wherein the material of the surface of the article is composed of at least one type selected from the group consisting of a fiber, a metal, a resin, a rubber, glass and a ceramic.

10. The cleaning method according to claim 8, wherein the stain is composed of at least one type selected from the group consisting of carbon, oil and dust.

11. A composition for forming a coating film comprising a non-volatile organic compound and the composition as defined in claim 1.

12. A method for forming a coating film, comprising applying the composition for forming a coating film as defined in claim 11 to the surface of a substrate, and then evaporating off the monochlorotrifluoropropene to form a coating film containing the non-volatile organic compound.

13. An aerosol composition comprising the composition as defined in claim 1.

14. A heat transfer medium for a heat cycle system comprising the composition as defined in claim 1.

15. A heat cycle system using the heat transfer medium as defined in claim 14.

Description

EXAMPLES

[0141] In the following, the present invention will be described in detail with reference to Examples. However, the present invention is not limited to these Examples. Ex. 2 to 5, 8 to 11, 14 to 17, 20 to 23, 26 to 29, 32 to 34, 37 to 39, 42 to 44, 47 to 49, 52 to 54 and 57 to 59 are Examples of the composition of the present invention; and Ex. 1, 6, 7, 12, 13, 18, 19, 24, 25, 30, 31, 35, 36, 40, 41, 45, 46, 50, 51, 55, 56 and 60 are Comparative Examples.

[0142] The monochlorotrifluoropropene, carboxylic acids, carboxylic acid salts and carboxylic acid ions used in the preparation of the compositions are as shown below.

Production Example: Production of 244ca

[0143] To a 2-liter four-necked flask equipped with a stirrer, a gymrothe, a cooler and a glass distillation column (5 measured stages) filled with raschig rings, 1204 g (9.12 mol) of 2,2,3,3-tetrafluoropropanol (TFPO) and 12 g (0.17 mol) of N,N-dimethylformamide (DMF) were added. 1078 g (9.12 mol) of thionyl chloride was added dropwise, followed by stirring at room temperature for 12 hours. The reactor was heated to 100° C., and reaction distillation was carried out using a reflux timer with a reflux time/distillation time ratio of 5/1. The distilled 244ca was neutralized with a 20 mass % potassium hydroxide aqueous solution. The recovered 244ca (purity: 100 mass %) was 979 g (6.50 mol).

Production Example: Production of 1233yd

[0144] A plug-in tube (material: SUS316, inner diameter: 3 mm) was introduced into the center of a vertical fixed-bed reactor (material: SUS316, inner diameter: 22.6 mm×height: 200 mm), and a K-type thermocouple was inserted into it to measure the internal temperature. At the center of the reactor, alumina (N612N, manufactured by JGC Catalysts and Chemicals Ltd.) was filled, and this portion was used as a catalyst layer. The catalyst layer was heated to 300° C. by an electric furnace while supplying nitrogen gas at 300 mL/min and dried. Then, trifluoromethane (R-23) was supplied at 300 mL/min to activate the catalyst for about 10 hours until the composition of the outlet gas stabilized. A feedstock preheating mixing line having a gas feed line and feedstock supply line connected and heated to 70° C., was connected to the top of the reactor.

[0145] Nitrogen was supplied to the feedstock preheating mixing line through the gas feed line with the gas flow rate adjusted by using a mass flow controller. As the raw material, 3510 g of 244ca, was supplied into the feedstock preheating mixing line heated to 70° C. through the feedstock feed line with the linear velocity adjusted to 2 cm/sec by using a plunger pump, and the product was continuously taken out from the bottom of the reactor. The product taken out from the bottom of the reactor will be hereafter referred to as exit gas. While maintaining the reaction temperature at 375° C., the reaction was conducted continuously for 100 hours. The recovered exit gas was purified to yield 1010 g of 1233yd(Z) with 100 mass % purity and 147 g of 1233yd(E) with 100 mass % purity.

Preparation of 1233yd

[0146] 1233yd used in Examples was prepared by mixing so that the mass ratio of 1233yd(Z) to 1233yd(E) (1233yd(Z)/1233yd(E)) became 100/0, 95/5, or 90/10, and 2,6-di-t-butyl-p-cresol was added so as to be 10 mass ppm.

Preparation of Compositions

[0147] Compositions of Ex. 1 to 30 were prepared by mixing 1233yd and the ingredients shown in Table 1 in the mass ratios shown in Table 1. To prepare the compositions, the carboxylic acids used were formic acid (manufactured by FUJIFILM Wako Pure Chemical Corporation), acetic acid (manufactured by FUJIFILM Wako Pure Chemical Corporation), difluoroacetic acid (manufactured by FUJIFILM Wako Pure Chemical Corporation), and trifluoroacetic acid (manufactured by FUJIFILM Wako Pure Chemical Corporation).

[0148] Cleanability/Stability Test

[0149] SPCC specimens (25 mm×30 mm×2 mm thick) dipped in and coated with a 10-fold dilution of cutting oil Yushiroken FGS795 (manufactured by Yushiro Chemical Industry Co., Ltd.) and dried overnight in a dryer at 40° C., were used as test specimens.

Test Example 1

[0150] The compositions of Ex. 1 to 30 were prepared 150 ml each, and the compositions were placed each in a 300 ml two-necked flask and heat-refluxed at 40° C. for 72 hours in a heat-refluxing apparatus with a Liebig cooling tube attached to the top of the flask with the above test specimen coexisting in the liquid phase. 72 hours later, the test specimen was taken out, and the following evaluation was conducted. The compositions of Ex. 1 to 30 were evaluated by gas chromatography (GC7890, manufactured by Agilent) for the purity of monochlorotrifluoropropene by area %. 100 g was taken from each composition after testing and contacted with the same mass of ion-exchanged water, and the aqueous layer was collected after separation of the two layers. The collected water layer was measured by ion chromatography (HPIC INTEGRATION system, manufactured by Thermo Scientific, column for anion analysis: Dionex lonPac AS12A) to determine the chlorine ion concentration. Further, SPCC specimens were visually evaluated for changes in appearance before and after the test using the following standards. The results are shown in Table 1. [0151] ⊚: No change. [0152] ◯: Luster disappeared, but no practical problem. [0153] x: Corrosion is present.

[0154] Here, the “content of carboxylic acid to the total amount of 1233yd and carboxylic acid” in Tables 1, 2 and 3 discussed below, corresponds to the “content of the total of carboxylic acid, carboxylic acid salts and carboxylic acid ions to the content of the total of monochlorotrifluoropropene, carboxylic acid, carboxylic acid salts and carboxylic acid ions”.

TABLE-US-00001 TABLE 1 Carboxylic acid Content of carboxylic acid to the total 1233yd isomer amount of 1233yd Chlorine ratio 1233yd and purity ions Appearance 1233ydZ 1233ydE carboxylic acid [area [mass of test Ex. [mass %] [mass %] [mass %] %] ppm] specimen 1 100 0 Formic acid 0 99.5 0.2 ◯ 2 100 0 Formic acid 0.0001 >99.9 <0.2 ⊚ 3 100 0 Formic acid 0.001 >99.9 <0.2 ⊚ 4 100 0 Formic acid 0.01 >99.9 <0.2 ⊚ 5 100 0 Formic acid 0.05 >99.9 <0.2 ⊚ 6 100 0 Formic acid 0.5 >99.9 <0.2 X 7 95 5 Formic acid 0 99.5 0.2 ◯ 8 95 5 Formic acid 0.0001 99.5 <0.2 ⊚ 9 95 5 Formic acid 0.001 >99.9 <0.2 ⊚ 10 95 5 Formic acid 0.01 >99.9 <0.2 ⊚ 11 95 5 Formic acid 0.05 >99.9 <0.2 ⊚ 12 95 5 Formic acid 0.5 >99.9 <0.2 X 13 90 10 Formic acid 0 99.5 0.2 ◯ 14 90 10 Formic acid 0.0001 >99.9 <0.2 ⊚ 15 90 10 Formic acid 0.001 >99.9 <0.2 ⊚ 16 90 10 Formic acid 0.01 >99.9 <0.2 ⊚ 17 90 10 Formic acid 0.05 >99.9 <0.2 ⊚ 18 90 10 Formic acid 0.5 99.5 <0.2 X 19 100 0 Acetic acid 0 99.5 0.2 ◯ 20 100 0 Acetic acid 0.0001 >99.9 <0.2 ⊚ 21 100 0 Acetic acid 0.001 >99.9 <0.2 ⊚ 22 100 0 Acetic acid 0.01 >99.9 <0.2 ⊚ 23 100 0 Acetic acid 0.05 >99.9 <0.2 ⊚ 24 100 0 Acetic acid 0.5 >99.9 <0.2 X 25 100 0 Difluoro- 0 99.5 0.2 ◯ acetic acid 26 100 0 Difluoro- 0.0001 >99.9 <0.2 ⊚ acetic acid 27 100 0 Difluoro- 0.001 >99.9 <0.2 ⊚ acetic acid 28 100 0 Difluoro- 0.01 >99.9 <0.2 ⊚ acetic acid 29 100 0 Difluoro- 0.05 >99.9 <0.2 ◯ acetic acid 30 100 0 Difluoro- 0.5 >99.9 <0.2 X acetic acid

[0155] As can be seen from Table 1, the compositions of Ex. 2 to 5, 8 to 11, 14 to 17, 20 to 23 and 26 to 29 all have excellent monochlorotrifluoropropene stability, can remove cutting fluid from the specimens, and can also prevent corrosion of the specimens.

[0156] For the compositions of Ex. 2, 20 and 26, the compositions were further mixed with trans-1,2-dichloroethylene as the organic compound (A). Specifically, the mixture was made so that the mass ratio expressed as monochlorotrifluoropropene/trans-1,2-dichloroethylene was 80/20.

[0157] Also with respect to compositions in Ex. containing this organic compound (A) all had excellent monochlorotrifluoropropene stability and were able to remove cutting fluid from the specimens and further prevent corrosion of the specimens.

Test Example 2

[0158] Monochlorotrifluoropropene was changed to 1233zd(Z) (1233Z, manufactured by Central Glass Co., Ltd.), and compositions of Ex. 31 to 45 were prepared, and the same tests and evaluations as in Test Example 1 were conducted. The results are shown in Table 2.

TABLE-US-00002 TABLE 2 Carboxylic acid Content of carboxylic acid to the total amount Chlorine Appear- of 1233zdZ and 1233zdZ ions ance Trifluoro- carboxylic acid purity [mass of test Ex propene [mass %] [area %] ppm] specimen 31 1233zdZ Formic acid 0 99.5 1.3 ◯ 32 1233zdZ Formic acid 0.0001 >99.9 1.1 ⊚ 33 1233zdZ Formic acid 0.001 >99.9 <1.0 ⊚ 34 1233zdZ Formic acid 0.01 >99.9 <1.0 ⊚ 35 1233zdZ Formic acid 0.5 >99.9 <1.0 X 36 1233zdZ Acetic acid 0 99.5 1.3 ◯ 37 1233zdZ Acetic acid 0.0001 >99.9 1.1 ⊚ 38 1233zdZ Acetic acid 0.001 >99.9 <1.0 ⊚ 39 1233zdZ Acetic acid 0.01 >99.9 <1.0 ⊚ 40 1233zdZ Acetic acid 0.5 >99.9 <1.0 X 41 1233zdZ Trifluoroacetic 0 99.5 1.3 ◯ acid 42 1233zdZ Trifluoroacetic 0.0001 >99.9 1.1 ⊚ acid 43 1233zdZ Trifluoroacetic 0.001 >99.9 <1.0 ⊚ acid 44 1233zdZ Trifluoroacetic 0.01 >99.9 <1.0 ◯ acid 45 1233zdZ Trifluoroacetic 0.5 >99.9 <1.0 X acid

Production Example: Production of 1233zd(E)

[0159] Into a Hastelloy autoclave with an internal volume of 10 L equipped with a stirrer, zirconium chloride (77.8 g) and dichlorofluoromethane (3620 g) were charged, and while keeping the internal temperature to be at most 0° C., vinylidene fluoride (686 g) was introduced, followed by stirring for 2 hours. Then, while keeping the internal temperature to be at most 0° C., dichlorofluoromethane (3622 g) and vinylidene fluoride (2240 g) were introduced, followed by stirring for 2 hours. After the reaction was completed, the internal temperature of the autoclave was brought back to room temperature, the valve at the outlet of the liquid phase was opened, the content was taken out and filtered through a membrane filter (made of PTFE, pore diameter: 0.5 μm) to obtain the reaction product crude liquid (8580 g). The reaction product crude liquid was analyzed by using gas chromatography, whereby the content of 3,3-dichloro-1,1,1-trifluoropropane (243fa) was 57.4%. The reaction product crude liquid (6680 g) was distilled and purified to obtain 243fa (515 g) with 99.2% purity.

[0160] Into a Hastelloy autoclave with an internal volume of 2 L equipped with a stirrer, 243fa (515 g) and tetrabutylammonium chloride (5.13 g) were charged, and the autoclave was heated to 40° C. The reaction temperature was maintained at 40° C., a 20% sodium hydroxide aqueous solution (925 g) was added dropwise over 30 minutes, and stirring was continued for 3 hours, whereupon the organic layer (373 g) was recovered. After washing the recovered organic layer with water, it was analyzed by using gas chromatography, whereby the content of 1233zd(E) was 93.0% and the content of 1233zd(Z) was 5.23%. The organic layer (373 g) was distilled and purified to obtain 1233zd(E) (203 g) with 100% purity.

Test Example 3

[0161] The compositions in Ex. 46 to 60 were prepared by changing to 1233zd(E) (produced in the above Production Example) which was synthesized in the required amount by repeating the method in the Production Example, and were each sealed in a sealed PTFE test container in an environment of 40° C. and allowed to stand for 72 hours, whereupon the evaluation was conducted in the same manner as in Test Example 1. The results are shown in Table 3.

TABLE-US-00003 TABLE 3 Carboxylic acid Content of carboxylic acid to the total amount Chlorine Appear- Tri- of 1233zdE 1233zdE ions ance fluoro- and carboxylic purity [mass of test Ex. propene acid [mass %] [area %] ppm] specimen 46 1233zdE Formic acid 0 99.5 0.2 ◯ 47 1233zdE Formic acid 0.0001 >99.9 <0.2 ⊚ 48 1233zdE Formic acid 0.001 >99.9 <0.2 ⊚ 49 1233zdE Formic acid 0.005 >99.9 <0.2 ⊚ 50 1233zdE Formic acid 0.5 >99.9 <0.2 X 51 1233zdE Acetic acid 0 99.5 0.2 ◯ 52 1233zdE Acetic acid 0.0001 >99.9 <0.2 ⊚ 53 1233zdE Acetic acid 0.001 >99.9 <0.2 ⊚ 54 1233zdE Acetic acid 0.005 >99.9 <0.2 ⊚ 55 1233zdE Acetic acid 0.5 >99.9 <0.2 X 56 1233zdE Trifluoroacetic 0 99.5 0.2 ◯ acid 57 1233zdE Trifluoroacetic 0.0001 >99.9 <0.2 ⊚ acid 58 1233zdE Trifluoroacetic 0.001 >99.9 <0.2 ⊚ acid 59 1233zdE Trifluoroacetic 0.005 >99.9 <0.2 ◯ acid 60 1233zdE Trifluoroacetic 0.5 >99.9 <0.2 X acid

INDUSTRIAL APPLICABILITY

[0162] The composition of the present invention is a stable composition which is excellent in solubility of various organic substances, does not adversely affect the global environment and is stabilized and does not decompose. This composition is useful for a wide range of industrial applications, such as cleaning and coating applications, and can be used on articles made of various materials, such as metals, without adverse effects.