JP2955597B1 - Azeotropic compositions and azeotrope-like compositions containing hydrofluoroethers - Google Patents

Abstract

An object of the present invention is to provide a high performance alternative to CFC and HCFC that has minimal impact on the global environment. SOLUTION: CF ₃ CF ₂ CH ₂ OCHF ₂ (62 to 9)
9% by weight) and cyclopentane (38 to 1% by weight).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an azeotropic composition and an azeotropic composition.

[0002]

2. Description of the Related Art Conventionally, chlorofluorocarbons (CFCs), hydrofluorocarbons (CFCs), hydrophobes, solvents, detergents, heat transfer media, working fluids, reaction solvents, paint solvents, extractants, drainers, and desiccants have been used. Fluorocarbons (HCFCs) have been widely used. However, it has been pointed out that these CFCs and HCFCs destroy the stratospheric ozone layer and have serious adverse effects on ecosystems on the earth, including humans, and their production is currently banned or restricted. In order to cope with such a problem, there is a demand for alternative compounds to CFCs and HCFCs that do not destroy the ozone layer even when released into the atmosphere. Water-based, hydrocarbon-based (HC), and alternative compounds for applications such as refrigerants, foaming agents, solvents, cleaning agents, heat transfer media, working fluids, reaction solvents, paint solvents, extractants, drainers, and desiccants Hydrofluorocarbon (HFC), Hydrofluoroether (HFE)
And many others have been proposed. In the case of aqueous systems, many proposals have been made mainly for uses such as solvents and cleaning agents. Many of the water systems are nonflammable and have little effect on the environment, such as global warming and stratospheric ozone depletion, but their performance may not be sufficient, and equipment such as wastewater treatment is required. Is left. In the case of the HC system, it has been proposed for use in a wide range of fields such as refrigerants, foaming agents, solvents, cleaning agents, heat transfer media, working fluids, reaction solvents, paint solvents, extractants, drainers, and desiccants. . As an advantage of the HC system, there are few effects such as global warming and destruction of the ozone layer in the stratosphere. In the field of foaming agents, cyclopentane and the like have been proposed, but since the gas has a high thermal conductivity, when used as a foaming agent for insulating polyurethane foam such as refrigerators,
Insulation performance decreases. This leads to increased power consumption and indirectly affects global warming. HFC
In the case of a system, it is proposed for use in a wide range of fields such as a refrigerant, a foaming agent, a solvent, a cleaning agent, a heat transfer medium, a working fluid, a reaction solvent, a coating solvent, an extractant, a drainer, and a desiccant. Since the HFC system does not contain chlorine, iodine, bromine and other atoms that destroy ozone, the effect on the ozone layer is almost zero. However, many nonflammable HFCs have a long atmospheric life, and there is a concern that they will affect global warming. Also in the case of the HFE system, it has been proposed for use in a wide range of fields such as a refrigerant, a foaming agent, a solvent, a cleaning agent, a heat transfer medium, a working fluid, a reaction solvent, a coating solvent, an extractant, a drainer, and a drying agent. Since the HFE system does not include atoms that destroy ozone, such as chlorine, iodine, and bromine, the effect on the ozone layer is almost zero. According to the estimation, HFE having a plurality of hydrogens has relatively little reactivity with OH radicals in the atmosphere and a short life span in the atmosphere, and thus has little effect on global warming. However, when HFE is used alone, the required performance may not be sufficiently exhibited.
When a plurality of HFEs are mixed, compatibility with the polyol,
CF such as refrigerant characteristics, detergency, surface tension, and thermal conductivity of gas
In many cases, physical properties required as substitutes such as C and HCFC are improved. However, when mixed non-azeotropically, there are the following problems. For example, in the case of cleaning applications, when evaporation of the cleaning agent occurs during cleaning, the composition of the cleaning liquid changes,
Stable operation becomes difficult. Similarly, in the case of the refrigerant, the composition changes due to the leakage of the refrigerant, and the heat pump performance decreases. Further, in the case of foaming applications, uniform foaming becomes difficult due to the difference in boiling points. Particularly, in the production of a rigid polyurethane foam for heat insulation of an electric refrigerator or the like, the uniformity of foaming has a great influence on the heat insulation performance. Also,
Cyclopentane is desired to have a blowing agent having a high boiling point and a boiling point closer to room temperature.

[0003]

SUMMARY OF THE INVENTION The present invention provides a high performance CFC or HCF with minimal impact on the global environment.
The task is to provide an alternative to C.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, according to the present invention, the code of HFEs is HFE-347mcf: 3,3,3,2,2-pentafluoropropyldifluoromethyl ether (CF
₃ CF ₂ CH ₂ OCHF ₂ ) when defined as HFE-34
7mcf (62 to 99% by weight) and cyclopentane (3
Azeotrope or azeotrope-like composition consisting of HFE-347mcf (68 to 82% by weight) and cyclopentane (32 to 18% by weight). -Like composition, and HFE-347
An azeotropic or azeotrope-like composition consisting of mcf (61 to 87% by weight) and n-pentane (39 to 13% by weight), preferably HFE-347 mcf (52 to 66% by weight) and n-pentane (48 Or 34% by weight).

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the azeotropic composition and the azeotropic composition according to the present invention will be described in detail. Note that an azeotropic composition is a composition that has no difference between the composition of a liquid phase and a composition of a gaseous phase under a constant pressure and behaves as if it were a single substance.
It does not change the composition of the composition after repeated condensation. On the other hand, the azeotropic composition has a gas phase composition and a liquid phase composition similar to each other, and when applied to a foaming agent or the like, the composition can be regarded as practically the same.

A composition comprising 62 to 99% by weight of HFE-347mcf and 28 to 1% by weight of cyclopentane, preferably a composition comprising 68 to 82% by weight of HFE-347mcf and 32 to 18% by weight of cyclopentane The compositions of the liquid phase and the gas phase of these compositions are close to each other, and are azeotropic compositions that can be regarded as practically the same. More preferably, HFE-347mcf is 71.9 to 73.
98.1% by weight and 28.1 to 26.1% by weight cyclopentane, more preferably 72.70% HFE-347mcf.
Compositions with 89% by weight and 27.11% by weight cyclopentane are azeotropic compositions. This azeotropic composition has a minimum azeotropic point and an azeotropic temperature of 3 at atmospheric pressure (760 mmHg).
4.43 ° C. In addition, HFE-347mcf is 61
To 87% by weight and 39 to 13% by weight of n-pentane
A composition comprising, preferably HFE-347mcf, 5
In compositions comprising 2 to 66% by weight and 48 to 34% by weight of n-pentane, the compositions of the liquid phase and the gas phase of these compositions are close to each other, and are azeotrope-like compositions which can be regarded as practically the same. . More preferably, HFE-347mcf is 60.
0 to 62.0% by weight and n-pentane is 40.0 to 38.0% by weight, more preferably HFE-347mc
Compositions where f is 61.00% by weight and n-pentane is 39.00% by weight are azeotropic compositions. This azeotropic composition has a minimum azeotropic point and an azeotropic temperature at atmospheric pressure (760 mmH
g) is 28.65 ° C.

[0007] The HFE used in the present invention can be easily synthesized by a known method. Examples of the synthesis include the following methods. _{HFE-347mcf: C 2 F 5} CH 2 OH + KOH + CHClF 2 → C 2 F 5 C
H ₂ OCHF ₂

The composition according to the present invention may further contain various stabilizers when used under severe conditions. Specific examples of such a stabilizer include the following. 1,2-butylene oxide, styrene oxide, propylene oxide, 2,6-di-t-
Butyl-p-cresol, pt-butylphenol,
p-cresol, p-methoxyphenol, t-butylcatechol, isoeugenol, eugenol, thymol, butylhydroxyanisole, propargyl alcohol, α-methylstyrene, ethyl acrylate, methyl acrylate, allyl glycidyl ether, isoprene,
Glycidyl methacrylate, diethyl glycol monomethacrylate, vinyl toluene, methyl methacrylate,
1-nitropropane, 2-nitropropane, nitroethane, nitrobenzene, nitromethane, 2,5-di-t-
Amyl hydroquinone, 2,5-di-t-butyl hydroquinone and the like. In addition, homologues and derivatives of these compounds can also be expected to have an effect. These stabilizers may be used alone or in combination of two or more. The amount of the stabilizer used depends on the type of the stabilizer and the like.
It is about 5 to 10% by weight, and more preferably about 0.01 to 5% by weight.

When the present composition is used for a solvent, a detergent, a reaction solvent, a solvent for paints, an extractant, a drainer, a desiccant, etc., it is necessary to further improve the dissolving power, detergency, etc. Depending on the requirements, additives such as various organic solvents and surfactants can be added. As the organic solvent, known methanol, ethanol, 2-propanol, methylene chloride, 1,2-
Dichloroethylene and the like can be mentioned, and its addition amount is usually 1 to 20%, preferably 2 to 10%. Examples of the surfactant include sorbitan fatty acid esters such as sorbitan monooleate and sorbitan trioleate, polyoxyethylene sorbite fatty acid esters such as polyoxyethylene sorbite tetraoleate, and polyoxyethylene monolau. Polyethylene glycol such as a rate
Fatty acid esters, polyoxyethylene lauryl ester
Polyoxyethylene alkyl ethers such as ter, polyoxyethylene alkylphenyl ethers such as polyoxyethylene nonylphenyl ether, polyoxyethylene alkylamine fatty acid amides such as polyoxyethylene oleamide, etc. Nonionic surfactants may be used, and these may be used alone or in combination of two or more. For the purpose of synergistically improving the detergency and the interfacial action, a cationic surfactant or an anionic surfactant may be used in combination with these nonionic surfactants. The amount of the surfactant used depends on the type and the like, but is usually 0.1 to 20% by weight of the composition of the present invention.
And more preferably about 0.3 to 5% by weight. These compositions are particularly suitable as flux cleaners, cleaning solvents, degreasing cleaners, and desiccants, and are extremely useful as alternatives to conventional Freon 113 and 1,1,1-trichloroethane. Specific uses include removal agents for flux, grease, oil, wax, ink, etc., and electronic components (printed circuit boards, liquid crystal displays,
Magnetic recording parts, semiconductor materials, etc.), electric parts, precision machine parts, resin processed parts, optical lenses, cleaning agents for clothes and the like, and desiccants and the like. As the cleaning method, a conventionally used method such as immersion, spraying, boiling cleaning, ultrasonic cleaning, steam cleaning or a combination thereof can be adopted.

The composition of the present invention can also be used as a foaming agent for polyurethane foam or as a heat insulating gas. The compatibility between the foaming agent and the polyol is case-by-case depending on the type thereof, but generally, when HFE alone is used, the compatibility with the polyol is low. However, compatibility is often improved by mixing multiple HFEs. Since the composition obtained in the present invention contains a mixture of different types of HFE,
Compared to HFE alone, it has better compatibility with polyol, but as shown by the present inventors in a previous application, a fluorine-based surfactant is used to increase compatibility with polyol. It is also possible. When the use of a surfactant is not preferred, the composition can be mixed with a polyol immediately before foaming to produce a rigid urethane foam.

In the production of a rigid urethane foam using the composition of the present invention, the composition, a polyol, a polyisocyanate, a catalyst, water, a surfactant and a foam stabilizer are mixed and reacted. Polyisocyanates include aromatic, cycloaliphatic,
A chain aliphatic type is included, and a bifunctional type generally used conventionally is used. As such, for example, tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, tolidine diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, dicyclohexyl methane diisocyanate, etc. Is mentioned. These are used alone or in the form of a mixture.

The polyol includes a polyether-based polyol, a polyester-based polyol, a polyhydric alcohol, a hydroxyl group-containing diethylene-based polymer and the like, and the use of a polyether-based polyol is preferred. It is also possible to use a polyol containing a polyether-based polyol as a main component and other polyols such as a polyester-based polyol. Examples of the polyether polyol include, in addition to polypropylene glycol, polytetramethylene glycol and modified products thereof, sugars, polyhydric alcohols, compounds containing active hydrogen such as alkanolamines as initiators, and propylene oxide, ethylene oxide,
Those to which cyclic ethers such as epichlorohydrin and butylene oxide are added are preferably used. The polyester-based polyol includes a condensation-based polyester polyol, a lactone-based polyester polyol, a polycarbonate polyol, and the like. As a polyol, usually
Those having a hydroxyl value of 100 to 1,000 are used.

The catalyst includes an organometallic catalyst and an organic amine catalyst. As the organometallic catalyst, an organotin compound is preferably used, and examples thereof include stannasoctoate, stannaslaurate, dibutyltin dilaurate, dibutyltin dimaleate, dibutyltin diacetate, and dioctyltin diacetate. Examples of the organic amine catalyst include tertiary amines such as triethylenediamine,
N-ethylmorpholine, triethylamine, N, N,
N ′, N′-tetramethylhexamethylenediamine, bis (2-dimethylaminoethyl) ether, N, N ′,
N'-triethylethanolamine and the like.

In the present invention, as described above, a fluorine-containing surfactant having a perfluoroalkyl group is used as a surfactant in connection with the use of a fluorine-containing ether as a foaming agent. In the present invention, since the surface tension of the fluorinated ether compound in the composition used as the blowing agent is low, the compatibility of the blowing agent with the polyol can be controlled by using a fluorinated surfactant. The amount of the fluorinated surfactant is 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight, per 100 parts by weight of the foaming agent. Examples of the fluorinated surfactant include the following. _{(1) RfSO 2 NR- (C} 2 H 4 O) nH (2) RfSO 2 NR-CH 2 COOK (3) RfSO in ₃ M wherein formula, Rf represents a perfluoroalkyl group, R represents an alkyl group , M represents NH ₄ , K or Na, n
Indicates a number of 10 to 2.

The foaming agent of the present invention is used in an amount of 5 to 50 parts by weight, preferably 15 to 50 parts by weight, per 100 parts by weight of the polyol.
A 30 parts by weight, the use of such amount of blowing agent, 20 kg / m ³ or more, in particular, can be obtained a rigid polyurethane foam having a density of 30~80kg / m ^3. The reaction temperature of the raw material mixture is 15 to 90C, preferably 20 to 60C, more preferably 20 to 35C. The method for producing the rigid polyurethane foam includes various conventionally known methods, and the rigid polyurethane foam in the present invention can be produced by a one-shot method or a prepolymer method. Further, as a foaming method for obtaining the foam, various foaming methods such as in-situ foaming, slab foaming, injection foaming (filling method, molding method), laminate foaming, and spray foaming can be adopted.

The composition of the present invention may be used in addition to the above-mentioned foaming agent, as well as a refrigerant,
It can also be used as a heat transfer medium, working fluid, and the like.

[0017]

Next, the present invention will be described in more detail with reference to examples.

Example 1 A gas-liquid equilibrium composition and a boiling point were measured using a mixture of HFE-347mcf and cyclopentane as a sample with a circulation-type gas-liquid equilibrium measuring apparatus (capacity: 35 cc). HFE-34
A mixed sample having a constant composition of 7mcf and cyclopentane was placed in a sample container and heated. The heating was adjusted so that the dropping rate of the vapor-phase condensate became appropriate, and stable boiling was achieved.
Hold for more than 0 minutes. After confirming that the pressure and the boiling point were stable, the pressure and the boiling point were measured. The liquid phase and the gas phase condensate were sampled, and the composition of the sampled solution was analyzed by gas chromatography. Table 1 shows the results. From the above experimental results, HFE-347mcf was 7
2.89% by weight and 27.11% by weight of cyclopentane
Is an azeotropic composition having a boiling point of 34.43 ° C. at atmospheric pressure (760 mmHg). Where HF
Compositions of the present invention having E-347mcf in the range of 72-99% by weight and cyclopentane in the range of 28-1% by weight have a composition of gas phase and liquid phase within 10% and HFE-347.
mcf 68-82% by weight and cyclopentane 32
The composition of the present invention in the range of 1 to 18% by weight has a composition of the gas phase and the liquid phase of 5% or less, and is an azeotropic composition which can be regarded as the same composition in practical use.

Example 2 An experiment was conducted in the same manner as in Example 1 except that n-pentane was used instead of cyclopentane. Table 2 shows the results.

[0020]

[Table 1] HFE-347mcf vapor concentration _{(x 2): x 2 =} 100-x 1 (wt%) liquid phase concentration of cyclopentane _{(y 2): y 2 =} 100-y 1 (wt%)

[0021]

[Table 2] Gas phase concentration of HFE-347mcf (x ₂ ): x ₂ = 100−x ₁ (wt%) Liquid phase concentration of n-pentane (y ₂ ): y ₂ = 100−y ₁ (wt%)

[0022]

Industrial Applicability The composition of the present invention is advantageously used as a substitute for CFC and HCFC which has little effect on the global environment and has high performance.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor, Namon Takada 6th floor, Hongo Wakai Building, Hongo 2-40-17, Hongo, Bunkyo-ku, Tokyo Project for New Refrigerants, etc. (72) Hiroshi Yamamoto, Inventor 6-floor Hongo Wakai Building, Hongo 2-40-17, Bunkyo-ku, Tokyo New Research Project Room for New Refrigerants, etc. (72) Inventor Akira Sekiya 1-1-1, Higashi, Tsukuba, Ibaraki Pref. Toshiro Fujimori, Examiner in the Technical Research Institute (58) Field surveyed (Int. Cl. ⁶ , DB name) C07C 43/12 CA (STN) CAOLD (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. The hydrofluoroether code is HF
_{E-347mcf: CF 3 CF 2} CH 2 OCHF 2 and when defined, azeotropic compositions consisting HFE-347mcf and cyclopentane or azeotrope-like composition. 2. The hydrofluoroether code is HF
_{E-347mcf: CF 3 CF 2} CH 2 OCHF 2 and when defined, azeotropic compositions consisting HFE-347mcf and n- pentane or azeotrope-like composition.