JP7132485B2 - Method for producing 1,1,1,3,3,3-hexafluoroisopropyl methyl ether, solid-liquid heterogeneous composition and 1,1,1,3,3,3-hexafluoroisopropyl methyl ether product - Google Patents

Description

The present invention relates to a method for producing 1,1,1,3,3,3-hexafluoroisopropylmethyl ether (hereinafter also referred to as HFE-356mmz).

HFE-356mmz is known as a useful compound that can be used as a heat transfer medium, foaming agent, cleaning agent, and the like.

HFE-356mmz is generally produced by using 1,1,1,3,3,3-hexafluoro-2-propanol (hereinafter also referred to as HFIP), a methylating agent and an alkaline compound ( For example, Patent Documents 1 and 2).

In the general production method of HFE-356mmz as described above, HFE-356mmz may be obtained as a mixture with raw materials such as HFIP and a methylating agent, and by-products. HFE-356mmz needs to be purified because high purity is required depending on its use.

As an example of this purification method, in Patent Document 3, an azeotropic composition of HFE-356mmz and HFIP is mixed with water, an alkaline carbonate aqueous solution or an acid having a pH of 5 to 9, and separated into two layers. A method for purifying HFE-356mmz by the iterative steps of is disclosed.

In addition, distillation is generally considered as an industrially convenient purification method, but as disclosed in Patent Document 4, HFE-356mmz and HFIP can form an azeotrope-like composition. Are known.

U.S. Pat. No. 3,346,448 U.S. Patent Application Publication No. 2010/0312019 Chinese Patent Application Publication No. 105566074 JP 2015-143359 A

According to the above-mentioned HFE-356mmz purification method, although impurities such as raw materials and by-products contained in HFE-356mmz can be reduced to a certain extent, HFE-356mmz dissolves in the water layer, increasing the amount of loss. Therefore, it cannot be said that it is necessarily a suitable purification method.

The present invention has been made against such a background, and an object of the present invention is to provide an efficient method for producing high-purity HFE-356mmz, including a purification step of HFE-356mmz.

The present inventors have made intensive studies to solve the above problems. As a result, it was found that by contacting a composition containing HFE-356mmz and predetermined impurities with a predetermined adsorbent, the content of impurities can be reduced and high-purity HFE-356mmz can be obtained. I completed the present invention.

That is, the present invention includes the following inventions.
[Invention 1]
(A) 1,1,1,3,3,3-hexafluoroisopropyl methyl ether;
(B) 1,1,1,3,3,3-hexafluoro-2-propanol;
(C) at least one compound selected from the group consisting of dimethyl ether, halomethane, and methyl p-toluenesulfonate is brought into contact with an adsorbent to obtain 1,1,1,3,3,3-hexafluoro purifying the isopropyl methyl ether;
The adsorbent is a silica-alumina solid adsorbent,
A method for producing 1,1,1,3,3,3-hexafluoroisopropyl methyl ether.
[Invention 2]
the composition comprising:
(D) further adding at least one compound selected from the group consisting of p-toluenesulfonic acid, p-toluenesulfonate, a compound represented by C ₄ H ₃ F ₅ O, and 2,2,2-trifluoroethyl methyl ether; The method of invention 1, comprising:
[Invention 3]
Invention 1 or wherein the adsorbent is at least one selected from the group consisting of X-type zeolite, ZSM-5-type zeolite, allophane, L-type zeolite, beta-type zeolite, mordenite-type zeolite, Y-type zeolite and A-type zeolite 2. The method described in 2.
[Invention 4]
The method according to any one of Inventions 1 to 3, wherein the adsorbent is at least one selected from the group consisting of X-type zeolite, ZSM-5-type zeolite, allophane, L-type zeolite, beta-type zeolite and mordenite-type zeolite. .
[Invention 5]
The method according to any one of inventions 1 to 4, wherein the adsorbent contains protons, alkali metal ions or alkaline earth metal ions as cations.
[Invention 6]
The adsorbent includes X-type zeolite containing protons, Na ions, K ions or Ca ions, ZSM-5 type zeolite containing protons, Na ions, K ions or Ca ions, protons, Na ions, K ions or Ca ions. The method according to invention 1 or 2, which is L-type zeolite or allophane.
[Invention 7]
(A) 1,1,1,3,3,3-hexafluoroisopropyl methyl ether;
(B) 1,1,1,3,3,3-hexafluoro-2-propanol;
(C) A solid-liquid heterogeneous composition comprising a composition containing at least one compound selected from the group consisting of dimethyl ether, halomethane and methyl p-toluenesulfonate, and a silica-alumina solid adsorbent.
[Invention 8]
the composition comprising:
(D) further adding at least one compound selected from the group consisting of p-toluenesulfonic acid, p-toluenesulfonate, a compound represented by C ₄ H ₃ F ₅ O, and 2,2,2-trifluoroethyl methyl ether; The composition according to invention 7, comprising:
[Invention 9]
The silica-alumina solid adsorbent is at least one selected from the group consisting of X-type zeolite, ZSM-5-type zeolite, allophane, L-type zeolite, beta-type zeolite, mordenite-type zeolite, Y-type zeolite and A-type zeolite. The composition according to Invention 7 or 8, which is
[Invention 10]
Inventions 7 to 9, wherein the silica-alumina solid adsorbent is at least one selected from the group consisting of X-type zeolite, ZSM-5-type zeolite, allophane, L-type zeolite, beta-type zeolite and mordenite-type zeolite. A composition according to any of the preceding claims.
[Invention 11]
The composition according to any one of Inventions 7 to 10, wherein the silica-alumina solid adsorbent contains protons, alkali metal ions or alkaline earth metal ions as cations.
[Invention 12]
The silica-alumina solid adsorbent is X-type zeolite containing protons, Na ions, K ions or Ca ions, ZSM-5 type zeolite containing protons, Na ions, K ions or Ca ions, protons, Na ions, The composition according to invention 7 or 8, which is an L-type zeolite containing K ions or Ca ions, or allophane.
[Invention 13]
a solid-liquid heterogeneous composition according to Inventions 7 to 12;
1,1,1,3,3,3-hexafluoroisopropyl, which is in direct contact with the solid-liquid heterogeneous composition and at least the contact portion is made of stainless steel, glass, or fluororesin. methyl ether product.

According to the present invention, it is possible to reduce the content of impurities from a composition containing HFE-356mmz and predetermined impurities, thereby providing an efficient method for producing high-purity HFE-356mmz.

Although the present invention will be described in detail below, the present invention should not be construed as being limited to the description of the embodiments and examples below.

The method for producing HFE-356mmz of the present invention (hereinafter sometimes referred to as the method of the present invention) includes a predetermined purification step of HFE-356mmz.

(Purification process of HFE-356mmz)
In the purification step of HFE-356mmz, HFE-356mmz is purified from a given composition. This composition (hereinafter also referred to as crude HFE-356mmz) contains at least the following components (A), (B) and (C):
(A) HFE-356mmz;
(B) HFIP;
(C) at least one compound selected from the group consisting of dimethyl ether, halomethane and methyl p-toluenesulfonate;

Crude HFE-356mmz may be a composition obtained by any process, and is generally obtained by reaction of HFIP and a methylating agent, but is not limited to this. Examples of the methylating agent include, but are not limited to, dimethyl sulfate, halomethane, methyl p-toluenesulfonate (hereinafter also referred to as PTSM), and the like. Here, halomethane specifically means fluoromethane, chloromethane, bromomethane and iodomethane, more specifically chloromethane and iodomethane.

In this specification, the (B) component and the (C) component contained in the crude HFE-356mmz are sometimes collectively referred to as impurities.

In a general method for producing HFE-356mmz, in addition to the above components (A), (B), and (C), (D) p-toluenesulfonic acid, p-toluenesulfonate, composition formula C ₄ H A compound represented by ₃ F ₅ O, 2,2,2-trifluoroethyl methyl ether (CF ₃ CH ₂ OCH ₃ ) and the like may be contained in the reaction product. In the present invention, crude HFE-356mmz may contain other components such as component (D).

The crude HFE-356mmz may contain water as another component. In some embodiments, it is preferred that the crude HFE-356mmz contain a low amount of water, for example, the amount of water in the crude HFE-356mmz is preferably 5% by weight or less, 3% by weight or less, or 1% by weight or less.

The contents of HFE-356mmz and impurities in the crude HFE-356mmz are not particularly limited. Usually, HFE-356mmz is 80% by mass or more and 99.9999% by mass or less, and the total of impurities and other components is 0.0001% by mass or more and 20% by mass or less. The smaller the total amount of impurities and other components, the better.

In the purification process of HFE-356mmz, a silica-alumina solid adsorbent is used as the adsorbent. Silica-alumina solid adsorbents include zeolites and clays (eg, allophane), which may be used in combination.

The shape of the adsorbent to be used is not particularly limited, and for example, it may be in any shape such as powder, granules, granules, etc., and those skilled in the art will appropriately determine the shape depending on the mode of contact with crude HFE-356mmz. It is selectable.

The silica/alumina (SiO ₂ /Al ₂ O ₃ ) ratio of the adsorbent used is not particularly limited. For example, 1 to 3000 is preferable, and 1.5 to 2000 is more preferable.
Normally, the type of adsorbent determines the value of the silica/alumina ratio, but if desired by those skilled in the art, the pore distribution, silica/alumina ratio, and other metal content can be changed by changing the formulation. is also possible, and such adsorbents may be used. Such formulations are known.

Usable zeolites include known natural zeolites, synthetic zeolites, and artificial zeolites. Specific examples include, but are not limited to:
A types such as 3A, 4A, 5A; ferrierite; MCM-22; ZSM-5; ZSM-11; SAPO-11; Clinoptilolite (clinoptilolite); mordenite (mordenite); chabazite; natrolite; gonnarudite; Cyte; erionite; faujasite; mutinaite; chernihiite;

Zeolites that can be used preferably contain protons, alkali metal ions or alkaline earth metal ions as cations, and particularly preferably zeolites containing protons, Na ions, K ions or Ca ions.

In one aspect of the present invention, the adsorbent used in the purification step of HFE-356mmz includes X-type zeolite, ZSM-5-type zeolite, allophane (Secado), L-type zeolite, beta-type zeolite, mordenite-type zeolite, and Y-type zeolite. Examples include zeolite and A-type zeolite, and these may be combined. Among them, X-type zeolite, ZSM-5-type zeolite, allophane (Secado), L-type zeolite, beta-type zeolite, and mordenite-type zeolite are preferable because they can significantly reduce both the (B) component and the (C) component. X-type zeolite containing protons, Na ions, K ions or Ca ions, ZSM-5 type zeolite containing protons, Na ions, K ions or Ca ions, L-type zeolite containing protons, Na ions, K ions or Ca ions, Allophane (Secado) is particularly preferred.

Various adsorbents are commercially available, for example, the HSZ series manufactured by Tosoh Corporation, the Zeorum (registered trademark) series manufactured by the same company, the MS series manufactured by Wako Pure Chemical Industries, Ltd., and the Secard series manufactured by Shinagawa Kasei Co., Ltd. include, but are not limited to.

The adsorbent to be used may contain water, but it is preferably less. In some embodiments, sorbents are used that have had their moisture content reduced by methods such as drying.
The method of contacting the crude HFE-356mmz with the adsorbent is not particularly limited as long as the HFE-356mmz is purified. For example, a batch method in which crude HFE-356mmz and an adsorbent are put into a container and contacted for a certain period of time to adsorb impurities in the crude HFE-356mmz to the adsorbent, and crude HFE-356mmz is placed in a packed tower filled with adsorbent. Examples include a distribution method and the like, but are not limited to these.

The crude HFE-356mmz provided can be a liquid or a gas upon contact with the adsorbent.

Other adsorbents may also be used along with the adsorbent in contact with the adsorbent. Such other adsorbents include zeolites other than the aforementioned zeolites, clay, alumina, silica, silica-alumina, activated carbon, composites and mixtures thereof, and the like.

Here, an example of the contact operation between the crude HFE-356mmz and the adsorbent is shown, but not limited to this. The temperature and pressure are not particularly limited, but the crude HFE-356mmz is usually contacted in a liquid state or a gaseous state. The pressure can be easily operated near normal pressure, but may be under reduced pressure or increased pressure.

The method of the present invention may include other steps in addition to the step of purifying HFE-356mmz. For example, if desired, before, after, or both of the purification steps of HFE-356mmz, a washing operation, a distillation operation, or an operation of contacting with other adsorbents described above may be performed.

When the adsorbent is fresh before use, both the amount that can be adsorbed and the adsorption rate are large, but after adsorbing a large amount of impurities, they decrease. In this case, the adsorbent can be regenerated by a technique called desorption operation. Specifically, the adsorbent can be regenerated by decompressing the adsorbent. At this time, the adsorbent may be heated after the pressure is reduced. The temperature for heating is not particularly limited, but is preferably 30° C. or higher and 300° C. or lower. Also, by cooling and collecting the gas generated during the desorption operation, it is possible to obtain a concentrate of the impurities adsorbed by the adsorbent.

[Solid-liquid heterogeneous composition]
At the request of a person skilled in the art, crude HFE-356mmz and an adsorbent are introduced into a container, and stored and stored as a solid-liquid heterogeneous composition of crude HFE-356mmz and adsorbent (hereinafter also referred to as a solid-liquid heterogeneous composition). It can also be transported. This makes it possible to provide HFE-356mmz products with reduced impurities contained in crude HFE-356mmz.

Such a container is not particularly limited as long as it is suitable for storing and transporting the heterogeneous solid-liquid composition. For example, the material of the contact portion with the solid-liquid heterogeneous composition includes stainless steel, glass, fluororesin, etc., but is not limited to these.

The amount of the solid-liquid heterogeneous composition introduced into the container is not particularly limited. Although it depends on the bulk specific gravity of the adsorbent, the mass ratio of crude HFE-356mmz/adsorbent is usually 0.1 or more and 200 or less, preferably 1 or more and 100 or less.

A low-temperature environment is desirable when storing and transporting a solid-liquid heterogeneous composition in a container. Specifically, it is -30°C or higher and 50°C or lower, preferably -20°C or higher and 30°C or lower. In addition, if the storage and transportation environment of the solid-liquid heterogeneous composition is high humidity, there is a concern that if the container is made of metal, it will corrode due to humidity, or moisture will enter the container when opening and closing the container. Therefore, low humidity is preferred.

EXAMPLES The method of the present invention will be described in detail below with reference to Examples, but the method of the present invention is not limited thereto.

The composition ratio of HFE-356mmz and impurities was measured by gas chromatography using an FID detector.

[Examples 1 to 10]
The adsorbent (5 g) shown in Table 2 was added to crude HFE-356mmz (50 g) before contact treatment shown in Table 2, and the mixture was stirred at room temperature (23° C.) and atmospheric pressure for 6 hours. After stirring, the mixture was filtered to obtain HFE-356mmz.

HFE-356mmz treated as described above was analyzed by gas chromatography to reveal dimethyl ether (Me ₂ O), HFIP, 2,2,2-trifluoroethyl methyl ether (CF ₃ CH ₂ OCH ₃ ) and HFE-356mmz. Table 2 summarizes how the GC area % of the film changed before and after the treatment. The Me ₂ O removal rate, HFIP removal rate, CF ₃ CH ₂ OCH ₃ removal rate, and HFE-356mmz retention rate in Table 2 were obtained by the following equations.
Me ₂ O removal rate = 100 x [1 - (GC % of Me 2 O after treatment/GC % of Me ₂ O before treatment)]
HFIP removal rate = 100 x [1-(GC% of HFIP after treatment/GC% of HFIP before treatment]
CF ₃ CH ₂ OCH ₃ removal rate = 100 x [1 - (GC% of CF ₃ CH ₂ OCH ₃ after treatment/GC% of CF ₃ CH ₂ OCH ₃ before treatment]
HFE-356mmz retention rate = 100 × (GC% of HFE-356mmz after treatment / GC% of HFE-356mmz before treatment)

[Examples 11 to 13]
The same treatment as in Examples 1 to 10 was performed except that the adsorbent (5 g) shown in Table 3 was added to the crude HFE-356mmz (50 g) before contact treatment shown in Table 3. The results are summarized in Table 3.

[Examples 14 to 26]
The adsorbent (5 g) shown in Table 4 was added to crude HFE-356mmz (50 g) before contact treatment shown in Table 4, and the mixture was stirred at room temperature (23° C.) under atmospheric pressure for 6 hours. After stirring, the mixture was filtered to obtain HFE-356mmz.

HFE-356mmz treated as described above was analyzed by gas chromatography to reveal chloromethane (CH ₃ Cl), HFIP, 2,2,2-trifluoroethyl methyl ether (CF ₃ CH ₂ OCH ₃ ) and HFE- Table 4 summarizes how the 356 mmz GC area % changed before and after the treatment. The CH ₃ Cl removal rate, HFIP removal rate, and HFE-356mmz retention rate in Table 4 were obtained by the following equations.
CH ₃ Cl removal rate=100×[1−(GC % of CH ₃ Cl after treatment/GC % of CH ₃ Cl before treatment)]
(However, if the CH ₃ Cl removal rate is a negative value, the CH ₃ Cl removal rate shall be 0.0%.)
HFIP removal rate = 100 x [1-(GC% of HFIP after treatment/GC% of HFIP before treatment]
HFE-356mmz retention rate = 100 × (GC% of HFE-356mmz after treatment / GC% of HFE-356mmz before treatment)

Claims (12)

(A) 1,1,1,3,3,3-hexafluoroisopropyl methyl ether;
(B) 1,1,1,3,3,3-hexafluoro-2-propanol;
(C) dimethyl ether ;
(D) at least one compound selected from the group consisting of p-toluenesulfonic acid, p-toluenesulfonate, a compound represented by C ₄ H ₃ F ₅ O, and 2,2,2-trifluoroethyl methyl ether; contacting a composition comprising with an adsorbent to purify 1,1,1,3,3,3-hexafluoroisopropyl methyl ether;
The adsorbent includes X-type zeolite containing protons, Na ions, K ions or Ca ions, ZSM-5 type zeolite containing protons, Na ions, K ions or Ca ions, protons, Na ions, K ions or Ca ions. L-type zeolite comprising, or allophane ,
A method for producing 1,1,1,3,3,3-hexafluoroisopropyl methyl ether. The adsorbent is X-type zeolite containing protons, Na ions, K ions or Ca ions, ZSM-5 type zeolite containing protons, Na ions, K ions or Ca ions, or allophane.
The method of claim 1. (A) 1,1,1,3,3,3-hexafluoroisopropyl methyl ether;
(B) 1,1,1,3,3,3-hexafluoro-2-propanol;
(C) a halomethane;
contacting a composition comprising with an adsorbent to purify 1,1,1,3,3,3-hexafluoroisopropyl methyl ether;
The adsorbent is ZSM-5 type zeolite containing protons, Na ions, K ions or Ca ions,
A method for producing 1,1,1,3,3,3-hexafluoroisopropyl methyl ether. the composition comprising:
(D) p-toluenesulfonic acid, p-toluenesulfonate, C ₄ H. ₃ F. ₅ 4. The method according to claim 3, further comprising at least one compound selected from the group consisting of a compound represented by O and 2,2,2-trifluoroethylmethyl ether. (A) 1,1,1,3,3,3-hexafluoroisopropyl methyl ether;
(B) 1,1,1,3,3,3-hexafluoro-2-propanol;
(C) at least one compound selected from the group consisting of dimethyl ether, halomethane and methyl p-toluenesulfonate;
contacting a composition comprising with an adsorbent to purify 1,1,1,3,3,3-hexafluoroisopropyl methyl ether;
The adsorbent is ZSM-5 type zeolite containing protons, Na ions, K ions or Ca ions,
A method for producing 1,1,1,3,3,3-hexafluoroisopropyl methyl ether. the composition comprising:
(D) p-toluenesulfonic acid, p-toluenesulfonate, C ₄ H. ₃ F. ₅ 6. The method according to claim 5, further comprising at least one compound selected from the group consisting of a compound represented by O and 2,2,2-trifluoroethylmethyl ether. (A) 1,1,1,3,3,3-hexafluoroisopropyl methyl ether;
(B) 1,1,1,3,3,3-hexafluoro-2-propanol ;
(C) dimethyl ether;
(D) at least one compound selected from the group consisting of p-toluenesulfonic acid, p-toluenesulfonate, a compound represented by C ₄ H ₃ F ₅ O, and 2,2,2-trifluoroethyl methyl ether; a composition comprising
X-type zeolite containing protons, Na ions, K ions or Ca ions, ZSM-5 type zeolite containing protons, Na ions, K ions or Ca ions, L-type zeolite containing protons, Na ions, K ions or Ca ions, Alternatively, a solid-liquid heterogeneous composition containing allophane . (A) 1,1,1,3,3,3-hexafluoroisopropyl methyl ether;
(B) 1,1,1,3,3,3-hexafluoro-2-propanol;
(C) a halomethane; and
ZSM-5 type zeolite containing protons, Na ions, K ions or Ca ions, and a solid-liquid heterogeneous composition. the composition comprising:
(D) p-toluenesulfonic acid, p-toluenesulfonate, C ₄ H. ₃ F. ₅ 9. The solid-liquid heterogeneous composition according to claim 8, further comprising at least one compound selected from the group consisting of a compound represented by O and 2,2,2-trifluoroethylmethyl ether. (A) 1,1,1,3,3,3-hexafluoroisopropyl methyl ether;
(B) 1,1,1,3,3,3-hexafluoro-2-propanol;
(C) at least one compound selected from the group consisting of dimethyl ether, halomethane and methyl p-toluenesulfonate;
ZSM-5 type zeolite containing protons, Na ions, K ions or Ca ions, and a solid-liquid heterogeneous composition. the composition comprising:
(D) p-toluenesulfonic acid, p-toluenesulfonate, C ₄ H. ₃ F. ₅ 11. The solid-liquid heterogeneous composition according to claim 10, further comprising at least one compound selected from the group consisting of a compound represented by O and 2,2,2-trifluoroethylmethyl ether. A solid-liquid heterogeneous composition according to any one of claims 7 to 11 ,
1,1,1,3,3,3-hexafluoroisopropyl, which is in direct contact with the solid-liquid heterogeneous composition and at least the contact portion is made of stainless steel, glass, or fluororesin. methyl ether product.