JP2955598B1 - Azeotropic composition and azeotrope-like composition containing 2,2,1,1-tetrafluoroethyl 2 ', 2', 2'-trifluoroethyl ether - 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: CHF ₂ CF ₂ OCH ₂ CF ₃ (49 to 7)
Azeotropic or azeotrope-like composition consisting of 3% by weight) and cyclopentane (51 to 27% 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. According to the present invention, that is, when the code of the HFEs is defined as HFE-347pc-f: CHF ₂ CF ₂ OCH ₂ CF ₃ , HFE-347pc-f (49 to 7)
Azeotropic or azeotrope-like composition consisting of cyclopentane (51 to 27% by weight), preferably HF
An azeotropic or azeotrope-like composition consisting of E-347pc-f (55 to 68% by weight) and cyclopentane (45 to 32% by weight), and HFE-347pc-f (38
Azeotropic or azeotrope-like composition consisting of n-pentane (62 to 36% by weight) and n-pentane (62 to 36% by weight), preferably HFE-347pc-f (45 to 58% by weight) and n
An azeotropic or azeotrope-like composition comprising pentane (55 to 42% by weight) is provided.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The azeotropic and azeotropic composition-like compositions according to the present invention will be described in detail below. 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 49 to 73% by weight of HFE-347pc-f and 51 to 27% by weight of cyclopentane, preferably 55 to 68% by weight of HFE-347pc-f and 45 to 32% by weight of cyclopentane. Are azeotropic compositions in which the compositions of the liquid phase and the gas phase of these compositions are similar and can be regarded as practically the same. More preferably, HFE-347pc-f is 63.1.
To 65.1% by weight and cyclopentane from 36.9 to 34.9% by weight, more preferably HFE-347pc
-F 64.07% by weight and cyclopentane 35.9
Compositions that are 3% by weight are azeotropic compositions. This azeotropic composition has the lowest azeotropic point and the azeotropic temperature is atmospheric pressure (760 m
38.12 ° C. in mHg).

A composition comprising 38 to 64% by weight of HFE-347pc-f and 62 to 36% by weight of n-pentane, preferably 45 to 58% by weight of HFE-347pc-f and 55 to 55% by weight of n-pentane. The compositions composed of 42% by weight are compositions in which the compositions of the liquid phase and the gas phase of these compositions are close to each other, and are azeotropic compositions which can be regarded as practically the same. More preferably, HFE-347pc-f is 49.5.
To 51.5% by weight and n-pentane is 50.5 to 4
8.5% by weight, more preferably HFE-347pc-
Compositions where f is 50.47% by weight and n-pentane is 49.53% by weight are azeotropic compositions. This azeotropic composition has a minimum azeotropic point and an azeotropic temperature at atmospheric pressure (760 mmH
g) is 30.87 ° C.

[0008] The HFE used in the present invention can be easily synthesized by a known method. Examples of the synthesis include the following methods. _{HFE-347pc-f: CF 2} = CF 2 + CF 3 CH2OH + KOH →
CHF ₂ CF ₂ OCH ₂ CF ₃

The composition according to the present invention may further contain various stabilizers when used under severe conditions. Specific examples of such a stabilizer are illustrated below. 1,2-butylene oxide, styrene oxide, propylene oxide, 2,6-di-t-butyl-p-cresol, p
-T-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-amylhydroquinone, 2,
5-di-t-butylhydroquinone 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 varies depending on the type of the stabilizer and the like, but the amount used is usually about 0.005 to 10% by weight based on the composition of the present invention.
More preferably, it is about 0.01 to 5% by weight.

[0010] The composition of the present invention comprises a solvent, a detergent, a reaction solvent,
When used for applications such as paint solvents, extractants, drainers, and desiccants, various organic solvents and additives such as surfactants are added as necessary to further improve the dissolving power and detergency. be able to. Known organic solvents include 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%. Surfactants include sorbitan monooleate,
Sorbitan fatty acid esters such as sorbitan trioleate and sorbitan tetraoleate of polyoxyethylene
Polyoxyethylene sorbite fatty acid esters such as polyoxyethylene monolaurate, polyethylene glycol fatty acid esters such as polyoxyethylene monolaurate, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene Nonionic surfactants such as polyoxyethylene alkylphenyl ethers such as nonylphenyl ether, and polyoxyethylene alkylamine fatty acid amides such as polyoxyethylene oleic acid amide, and the like. Or a 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 varies depending on the type and the like, but is usually 0.1 to 10% of the composition of the present invention.
It is about 20% by weight, and more preferably about 0.3 to 5% by weight.

These compositions are, in particular, flux detergents,
It is suitable as a cleaning solvent, a degreasing cleaning agent, and a desiccant drying agent, and is extremely useful as a substitute for conventional Freon 113 and 1,1,1-trichloroethane. Specific applications include flux, grease, oil, wax, and ink removers, electronic components (printed circuit boards, liquid crystal displays, magnetic recording components, semiconductor materials, etc.), electrical components, precision machinery components, Examples include detergents for resin-processed parts, optical lenses, clothing, and the like, and drainers and desiccants. 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 obtained in the present invention can also be used as a foaming agent for polyurethane foam or a heat insulating gas. The compatibility between the foaming agent and the polyol is case-by-case depending on their type, but generally, in the case of HFE alone,
Poor compatibility with polyol. However, compatibility is often improved by mixing multiple HFEs. Since the composition obtained in the present invention is a mixture of different types of HFE, it has better compatibility with the polyol than HFE alone, but as the present inventors have already shown in previous applications. It is also possible to use a fluorine-based surfactant to increase the compatibility with the polyol. If the use of a surfactant is not preferred, the composition may 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 proportion of the foaming agent of the present invention is 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 present composition 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.

[0019]

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-347pc-f and cyclopentane as a sample with a circulation-type gas-liquid equilibrium measuring apparatus (capacity: 35 cc). HFE-3
A mixed sample having a constant composition of 47 pc-f 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 maintained for 40 minutes or more. 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-347pc-f
Is 64.07% by weight and 35.93% by weight of cyclopentane is an azeotropic composition having a boiling point of 38.12 ° C. at atmospheric pressure (760 mmHg). Here, the composition of the present invention having HFE-347pc-f in the range of 49 to 72% by weight and cyclopentane in the range of 51 to 27% by weight has a composition of the gas phase and the liquid phase within 10%, and the HFE
The composition of the present invention having -347 pc-f in the range of 55 to 68% by weight and cyclopentane in the range of 45 to 32% by weight has a composition of the gaseous phase and the liquid phase of 5% or less. It is a boiling-like composition.

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.

[0022]

[Table 1]

[0023]

[Table 2]

[0024]

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-347pc-f: An azeotropic composition or an azeotrope-like composition composed of HFE-347pc-f and cyclopentane when defined as CHF ₂ CF ₂ OCH ₂ CF ₃ . 2. The hydrofluoroether code is HF
E-347pc-f: An azeotropic composition or an azeotropic composition composed of HFE-347pc-f and n-pentane when defined as CHF ₂ CF ₂ OCH ₂ CF ₃ .