JP2009067687A - Method for producing fluorine-containing epoxy compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for production by which a fluorine-containing epoxy compound can be more efficiently prepared. <P>SOLUTION: The method for producing the fluorine-containing epoxy compound comprises a first reaction step of reacting a fluoroalkyl iodide represented by Rf<SP>1</SP>-I or I-Rf<SP>2</SP>-I [wherein, Rf<SP>1</SP>and Rf<SP>2</SP>are each a straight-chain or a branched polyfluorocarbon group having at least one fluorine group on a carbon atom adjacent to the iodine group (-I)] with an unsaturated alcohol represented by CR<SP>1</SP>R<SP>2</SP>=CR<SP>3</SP>-CR<SP>4</SP>R<SP>5</SP>(OH) [wherein, R<SP>1</SP>to R<SP>5</SP>are each independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or an aralkyl group] in the presence of a radical catalyst and affording an unsaturated alcohol-fluoroalkyl iodide adduct and a second reaction step of reacting the resultant adduct with a basic compound and providing the fluorine-containing epoxy compound. In the method for producing the fluorine-containing epoxy compound, the first reaction step is carried out in the presence of the fluorine-containing epoxy compound. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing a fluorine-containing epoxy compound, more specifically, a first product obtained by reacting a fluoroalkyl iodide with an unsaturated alcohol in the presence of a radical catalyst to obtain an unsaturated alcohol-fluoroalkyl iodide adduct. The present invention relates to a method for producing a fluorine-containing epoxy compound comprising a reaction step and a second reaction step in which the unsaturated alcohol-fluoroalkyl iodide adduct is reacted with a basic compound to obtain a fluorine-containing epoxy compound.

  The fluorine-containing epoxy compound becomes a polymerizable fluorine-containing monomer by reacting with itself or acrylic acid. It is known that a polymer obtained from such a monomer is useful for imparting water and oil repellency to paper products and fiber products.

  Conventionally, a fluorine-containing epoxy compound includes a first reaction stage for obtaining an unsaturated alcohol-fluoroalkyl iodide adduct in the presence of a radical catalyst in the presence of a fluoroalkyl iodide and an unsaturated alcohol, and the obtained adduct is a base. It is manufactured through a second reaction stage in which a fluorine-containing epoxy compound is obtained by reacting with a functional compound (usually in the form of an aqueous solution). A conventional method for producing a fluorine-containing epoxy compound is carried out by a batch (or batch) operation using a tank-type stirred reactor.

  On the other hand, Patent Document 1 proposes that the first reaction stage and the second reaction stage be performed in a single process as a method for producing a fluorine-containing epoxy compound in a simple and short process. Patent Document 1 discloses a method of obtaining a fluorine-containing epoxy compound by reacting a fluoroalkyl iodide and an unsaturated alcohol in the presence of a palladium catalyst and a base.

  Also, with respect to the first reaction stage, in order to improve the conversion rate of fluoroalkyl iodide, the first reaction stage is carried out in the presence of an additive, and as this additive, water, a basic compound (as it is or in the form of an aqueous solution) In Patent Document 2, it is proposed to use at least one selected from the group consisting of metal oxides, silver compounds and epoxy compounds.

JP-A 63-17858 Japanese Patent Publication No. 7-20899 Hideho Okamoto, “Applicability of microreactors to green processes”, Pharmacia, 2005, Japan Pharmaceutical Association, Vol. 41, No. 7, p664

  However, the method of Patent Document 1 has a problem that the reaction requires a long time (specifically, 6 to 18 hours) and the yield of the fluorine-containing epoxy compound is low (specifically, 23 to 79%). . In addition, there is a cost difficulty in that a palladium catalyst that is more expensive than a radical catalyst is used.

  Therefore, unlike the method of Patent Document 1, the first reaction stage and the second reaction stage are not carried out in a single process, and the fluoroalkyl iodide and the unsaturated alcohol are conventionally used in the presence of a radical catalyst. The first reaction stage for obtaining an unsaturated alcohol-fluoroalkyl iodide adduct and the second reaction stage for obtaining the fluorine-containing epoxy compound by reacting the obtained adduct with a basic compound (aqueous solution) are carried out. Therefore, it is more efficient and practical to produce a fluorine-containing epoxy compound.

  When producing a fluorine-containing epoxy compound by dividing into a first reaction stage and a second reaction stage as in the prior art, water, a basic compound is applied to the first reaction stage by applying the method of Patent Document 2 It is conceivable to carry out the first reaction stage (as is or in the form of an aqueous solution) in the presence of at least one additive selected from the group consisting of metal oxides, silver compounds and epoxy compounds. According to Patent Document 2, it is described that the conversion rate of fluoroalkyl iodide can be increased. Therefore, by applying the method of Patent Document 2 to the first reaction stage, iodination in the first reaction stage is performed. It is considered that the conversion rate of the fluoroalkyl can be increased, and consequently the yield of the fluorine-containing epoxy compound obtained in the second reaction stage can be increased.

  However, the method of Patent Document 2 is intended only for the reaction of obtaining an unsaturated alcohol-fluoroalkyl iodide adduct, and does not take into account obtaining a fluorine-containing epoxy compound as a target substance. In the method of Patent Document 2, when water or an aqueous solution is used as the additive, the reaction cannot be carried out in a phase-homogeneous system, and the loss is large if an additive other than water is used in a large amount, and an epoxy compound is used as the additive. For this, it is necessary to perform an operation for separating unnecessary additives.

  So far, the manufacturing method which can obtain a fluorine-containing epoxy compound more efficiently is not established.

  The present invention provides a first reaction stage in which an unsaturated alcohol-fluoroalkyl iodide adduct is obtained by reacting a fluoroalkyl iodide with an unsaturated alcohol in the presence of a radical catalyst, and the resulting adduct is reacted with a basic compound. It is an object of the present invention to provide a method for producing a fluorine-containing epoxy compound comprising a second reaction step for obtaining a fluorine-containing epoxy compound, and to provide a production method capable of obtaining the fluorine-containing epoxy compound more efficiently. Is.

［式中、Ｒｆ^１、Ｒｆ^２、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４およびＲ^５は上記と同じである］で表わされる含フッ素エポキシ化合物を得る第２反応段階を含んで成る、含フッ素エポキシ化合物の製造方法において、該第１反応段階を該含フッ素エポキシ化合物の存在下にて実施することを特徴とする製造方法が提供される。
尚、本明細書において、一般式（ａ^１）で表わされるヨウ化フルオロアルキルをモノヨウ化フルオロアルキルとも言い、一般式（ａ^２）で表わされるヨウ化フルオロアルキルをジヨウ化フルオロアルキルとも言うものとする。一般式（ａ^１）で表わされるモノヨウ化フルオロアルキルを用いる場合は、一般式（ｃ^１）で表わされる含フッ素エポキシ化合物が、一般式（ａ^２）で表わされるジヨウ化フルオロアルキルを用いる場合は、一般式（ｃ^２）で表わされる含フッ素エポキシ化合物が得られる。 According to one aspect of the present invention, the following general formula (a ¹ ) or (a ² )
Rf ¹ -I (a ¹ )
^{I-Rf 2 -I ··· (a} 2)
Wherein Rf ¹ and Rf ² are linear or branched polyfluorocarbon groups having at least one fluorine group at the carbon atom adjacent to the iodine group (—I), and ,
The following general formula (b)
CR ¹ R ² = CR ³ -CR ⁴ R ⁵ (OH) (b)
Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or an aralkyl group, Reacting in the presence of a radical catalyst to obtain an unsaturated alcohol-fluoroalkyl iodide adduct, and reacting the unsaturated alcohol-fluoroiodide adduct with a basic compound, General formula (c ¹ ) or (c ² )

[Wherein Rf ¹ , Rf ² , R ¹ , R ² , R ³ , R ⁴ and R ⁵ are the same as described above], which comprises a second reaction step to obtain a fluorine-containing epoxy compound represented by In the manufacturing method of a fluorine epoxy compound, the manufacturing method characterized by implementing this 1st reaction step in presence of this fluorine-containing epoxy compound is provided.
In this specification, the fluoroalkyl iodide represented by the general formula (a ¹ ) is also referred to as monofluoroiodide, and the fluoroalkyl iodide represented by the general formula (a ² ) is also referred to as diiodinated fluoroalkyl. To do. When the monoiodinated fluoroalkyl represented by the general formula (a ¹ ) is used, the fluorine-containing epoxy compound represented by the general formula (c ¹ ) uses the diiodinated fluoroalkyl represented by the general formula (a ² ). A fluorine-containing epoxy compound represented by the general formula (c ² ) is obtained.

  In the first reaction stage, a side reaction produces a bimolecular cyclized product and hydrogen iodide (HI) that have reacted with two unsaturated alcohol molecules. The presence of hydrogen iodide will inhibit the main reaction.

  On the other hand, according to the production method of the present invention, the first reaction step is carried out in the presence of the fluorine-containing epoxy compound, so that hydrogen iodide reacts with the fluorine-containing epoxy compound and unsaturated alcohol-fluoroiodide. Since an alkyl adduct is generated, hydrogen iodide that inhibits the main reaction can be quickly removed, and thus a high conversion of fluoroalkyl iodide can be obtained.

  Fluorine-containing epoxy compounds generally have a homogeneous phase together with reaction raw materials (fluoroalkyl iodide and unsaturated alcohol), catalyst (radical catalyst) and reaction product (unsaturated alcohol-fluoroalkyl iodide adduct). Thus, the first reaction stage can be carried out in a phase-homogeneous system, whereby the reaction raw material and the catalyst are in sufficient contact and a higher conversion of fluoroalkyl iodide can be obtained. However, it should be noted that the present invention is not limited to this, and a phase-homogeneous system may not be obtained depending on the reaction raw materials and reaction conditions used.

  Furthermore, even if a fluorine-containing epoxy compound is used to remove hydrogen iodide in the first reaction stage, the unsaturated alcohol-fluoroalkyl iodide adduct generated in this reaction is regenerated as a fluorine-containing epoxy compound in the second reaction stage. So there is no loss.

  In addition, since the fluorine-containing epoxy compound used in the first reaction stage is the target substance in the second reaction stage, additional separation operation can be performed even if it remains in the reaction mixture without reacting completely in the first reaction stage. There is no need to do it.

In the fluoroalkyl iodide, for example, Rf ¹ and Rf ^{2 in the} general formulas (a ¹ ) and (a ² ) may be a linear perfluorocarbon group. In this case, Rf ² has one iodine group at each end of the carbon chain.

  The first reaction step may be carried out in the absence of a solvent. As a result, the reaction raw material and the catalyst can be in direct direct contact with each other, and a higher conversion of fluoroalkyl iodide can be obtained.

  The first reaction stage and the second reaction stage are each preferably carried out under a pressure of 0.1 to 50 MPa. By applying a higher pressure, the reaction can be performed at a higher temperature while maintaining the reaction raw material in a liquid state, and the reaction efficiency (for example, the reaction rate) can be increased. The temperature and pressure conditions may be different or the same in the first reaction stage and the second reaction stage.

  In one embodiment of the present invention, at least a fluoroalkyl iodide, an unsaturated alcohol, a radical catalyst, and a fluorine-containing epoxy compound are supplied to the first microspace, and the first reaction stage is performed while circulating in the first microspace. Proceed to obtain an intermediate reaction mixture containing an unsaturated alcohol-fluoroalkyl iodide adduct, and then supply the intermediate reaction mixture and the basic compound solution to the second microspace to circulate in the second microspace. In the meantime, the second reaction stage proceeds to obtain the final reaction mixture containing the fluorine-containing epoxy compound as a fluorous phase.

  In the conventional method using a tank-type stirred reactor, since the addition reaction to the unsaturated alcohol is accompanied by a rapid exotherm, it is necessary to charge the radical catalyst in parts, and it takes a long time to complete the reaction. I don't get it. Even with the method of Patent Document 2, the same problem may occur when the scale is increased.

  On the other hand, according to the above aspect of the present invention, both the first reaction stage and the second reaction stage are allowed to proceed in a minute space, and the heat transfer area per unit volume of the reaction mixture is larger. Since stricter temperature control can be realized, it is not necessary to charge the radical catalyst in a divided manner, and the reaction can be completed in a very short time.

In the present invention, the “microspace” refers to the width of a flow path through which a fluid for reaction (in the present invention, a liquid material including a reaction raw material, a catalyst, a reaction product, etc .: hereinafter also referred to as a reaction mixture). Is a micro-order or milli-order (about 1 μm or more and 1 cm or less), specifically about 10 to 5000 μm space. For example, the cross-sectional area of the flow path is about 3.1 × 10 ^{−6 to} 7.9 × It may be a space that is 10 ⁻¹ cm ² . The channel width and the channel cross-sectional area may be different or the same between the first minute space and the second minute space.

  In the above aspect of the present invention, the supply to the first minute space is performed by dividing the supply into the first raw material containing at least fluoroalkyl iodide and the fluorine-containing epoxy compound and the second raw material containing at least an unsaturated alcohol and a radical catalyst. You may do it. Thereby, a reaction raw material etc. can be appropriately supplied to a 1st micro space from two supply ports. However, the present invention is not limited to this and may be supplied separately using a suitable solvent.

  In the above aspect of the present invention, the fluorine-containing epoxy compound contained in the final reaction mixture is supplied to the first microspace by returning a part of the final reaction mixture obtained from the second microspace to the first microspace. The supply to the first microspace and the second microspace may be continuously performed to continuously obtain the final reaction mixture containing the fluorine-containing epoxy compound. Thereby, this can be manufactured continuously, partially recycling the fluorine-containing epoxy compound.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method which can obtain a fluorine-containing epoxy compound more efficiently is provided.

  More specifically, in the production method of the present invention, hydrogen iodide that inhibits the main reaction can be quickly removed in the first reaction stage, and thus a high conversion of fluoroalkyl iodide can be obtained. In addition, although depending on the reaction raw material used, generally, the first reaction stage can be carried out in a phase-homogeneous system. A high conversion can be obtained. Furthermore, since the fluorine-containing epoxy compound used in the first reaction stage is regenerated in the second reaction stage, there is no loss. Further, since the fluorine-containing epoxy compound is a target substance, it is not necessary to perform an additional separation operation. Such a production method of the present invention is very efficient and industrially extremely advantageous.

  The manufacturing method of the fluorine-containing epoxy compound in one embodiment of this invention is demonstrated referring drawings.

  First, a mixture of a fluoroalkyl iodide and a corresponding fluorine-containing epoxy compound is prepared as the first raw material A1.

The fluoroalkyl iodide is represented by the following general formula (a ¹ ) or (a ² )
Rf ¹ -I (a ¹ )
^{I-Rf 2 -I ··· (a} 2)
It is represented by

In the above formula, Rf ¹ and Rf ² are linear or branched polyfluorocarbon groups having at least one fluorine group at the carbon atom adjacent to the iodine group (—I). The number of carbon atoms in Rf ¹ and Rf ² can be, for example, 1 to 23, preferably 2 to 12, but is not limited thereto.
In general, Rf ¹ and Rf ² are linear perfluorocarbon groups, Rf ¹ is represented by CF ₃ (CF ₂ ) _n-1- , and Rf ² is represented by-(CF ₂ ) _n-. (In these formulas, n is an integer of 1 or more, for example 1 to 23, preferably 2 to 12). In such a case, the fluoroalkyl iodide may be a telomer obtained, for example, by telomerization with tetrafluoroethylene.

As the fluoroalkyl iodide, at least one selected from the group consisting of those represented by the above general formula (a ¹ ) or (a ² ) may be used, and two or more may be used. For example, the monoiodinated fluoroalkyl represented by the above general formula (a ¹ ) and the diiodinated fluoroalkyl represented by the above general formula (a ² ) may be used together. Further, for example, two or more kinds of fluoroalkyl iodides having different numbers of n may be used regardless of whether they are monoiodinated fluoroalkyl or diiodinated fluoroalkyl. In this case, the number of n is relatively small. A fluoroalkyl iodide having a relatively large number of n can be dissolved in the fluoroalkyl iodide and used.

で表わされるものである。
ヨウ化フルオロアルキルが、上記の一般式（ａ^２）で表わされるジヨウ化フルオロアルキルである場合は、含フッ素エポキシ化合物は、以下の一般式（ｃ^２）

で表わされるものであり、更に、以下の一般式（ｃ^２’）

で表わされるものが混在していてもよい。 The fluorine-containing epoxy compound corresponds to the fluoroalkyl iodide used. When the fluoroalkyl iodide is a monoiodinated fluoroalkyl represented by the above general formula (a ¹ ), the fluorine-containing epoxy compound has the following general formula (c ¹ )

It is represented by
When the fluoroalkyl iodide is a diiodinated fluoroalkyl represented by the above general formula (a ² ), the fluorine-containing epoxy compound has the following general formula (c ² )

In addition, the following general formula (c ^{2 ′} )

What is represented by may be mixed.

In the above formula, Rf ¹ and Rf ² are the same as those described above for the fluoroalkyl iodide, and R ¹ , R ² , R ³ , R ⁴ and R ⁵ are the same as those described below for the unsaturated alcohol. It is. When two or more kinds of fluoroalkyl iodides are used, a fluorine-containing epoxy compound corresponding to at least one of them may be used. Two or more kinds of fluorine-containing epoxy compounds respectively corresponding to two or more kinds of fluoroalkyl iodides may be used. May be used.

  The amount of the fluorine-containing epoxy compound may be about 0.01 to 0.3 molar equivalent relative to 1 molar equivalent of fluoroalkyl iodide (based on iodine group, the same shall apply hereinafter). If the fluorine-containing epoxy compound is 0.01 mole equivalent or more, hydrogen iodide produced by the side reaction can be sufficiently removed, and if it is 0.3 mole equivalent or less, as will be described later, it is acceptable for recycling. It is.

  On the other hand, a mixture of unsaturated alcohol and radical catalyst is prepared as the second raw material A2.

The unsaturated alcohol has the following general formula (b)
CR ¹ R ² = CR ³ -CR ⁴ R ⁵ (OH) (b)
It is represented by

In the above formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or an aralkyl group.

  The amount of unsaturated alcohol is preferably about 1.2 to 4 molar equivalents relative to 1 molar equivalent of fluoroalkyl iodide. If the unsaturated alcohol is about 1.2 molar equivalents or more, a preferred conversion or selectivity is obtained, and if it is 4 molar equivalents or less, the loss is acceptable.

  The radical catalyst may be any radical generation source, but is preferably one that decomposes at the reaction temperature to generate radicals. Specifically, azo compounds such as azobisisobutyronitrile (AIBN), azobisdimethyl barrel nitrile, azobiscyclohexanecarbonitrile, or benzoyl peroxide, lauroyl peroxide, tertiary butyl hydroperoxide, ditertiary butyl A peroxide such as a peroxide may be mentioned. The radical catalyst can be dissolved in an unsaturated alcohol.

  The amount of the radical catalyst is preferably 1/10000 to 1/5 times the molar equivalent with respect to the fluoroalkyl iodide. If the radical catalyst is 1/5 times the molar equivalent or more, the heat generation becomes intense, and all the catalyst is not consumed and the loss increases. If the radical catalyst is 1 / 10,000 times molar equivalent or less, the reaction rate is slow.

  Next, referring to FIG. 1, a first raw material A1 which is a liquid mixture of a fluoroalkyl iodide and a fluorine-containing epoxy compound and a second raw material A2 which is a liquid mixture of an unsaturated alcohol and a radical catalyst are respectively prepared. 1 is supplied to the minute space 1 and circulates in the interior.

The first reaction stage proceeds while flowing through the first microspace 1, and a main reaction occurs in which an unsaturated alcohol-fluoroalkyl iodide adduct is produced from the fluoroalkyl iodide and the unsaturated alcohol in the presence of a radical catalyst. In addition, in addition to this, a side reaction may occur in which the unsaturated alcohol is further consumed to generate a bimolecular cyclized product and hydrogen iodide (HI). When hydrogen iodide is present, the main reaction is inhibited. In the present embodiment, the generated hydrogen iodide is rapidly reacted with a fluorine-containing epoxy compound to produce an unsaturated alcohol which is a reaction product of the main reaction. -A fluoroalkyl iodide adduct can be obtained.
As an example, in the first reaction stage, a case in which a fluoroalkyl monoiodide represented by the general formula (a ¹ ) and an allyl alcohol that is an unsaturated alcohol are reacted in the presence of a radical catalyst (Cat ·). As shown in FIG.

  Although hydrogen iodide can inhibit the main reaction, in this embodiment, since it reacts with the fluorine-containing epoxy compound, a high conversion of fluoroalkyl iodide can be obtained.

  In the present embodiment, the first reaction stage generally proceeds in a phase-homogeneous system and does not use a solvent, so that the reaction raw material and the catalyst are in sufficient contact, resulting in a higher conversion of the fluoroalkyl iodide. Rate can be obtained.

  In addition, since the heat transfer area per unit volume of the reaction mixture is larger in the first minute space, it is easy to remove heat, so the radical catalyst can be charged at a time and the reaction can be completed in a very short time. It is. According to the present embodiment, it is not necessary to divide and charge the radical catalyst in the first reaction stage, and there is no need to open or close the reactor for this purpose, and there is an advantage that operational safety is improved.

  The first reaction stage can be carried out, for example, at a temperature of about 50-200 ° C., preferably about 60-120 ° C. and a pressure of about 0.1-50 MPa, preferably 0.2-5 MPa. In the first reaction stage, the temperature is controlled by, for example, the temperature of a thermostatic bath (not shown in FIG. 1), and the pressure is, for example, a back pressure valve (not shown in FIG. 1) behind the first minute space. ) Can be appropriately adjusted. By setting the reaction pressure to a pressure higher than atmospheric pressure, the reaction can be performed at a higher temperature while maintaining the reaction raw material in a liquid state, and the reaction efficiency (for example, reaction rate) can be increased. In addition to allowing the reaction to proceed with a smaller amount of radical catalyst, the effect of reducing impurities can be obtained.

The first microspace has a channel width of, for example, about 10 to 5000 μm, preferably about 100 to 2000 μm, and for example, about 3.1 × 10 ^{−6 to} 7.9 × 10 ⁻¹ cm ² , preferably It may have a channel cross-sectional area of about 3.1 × 10 ^{−4 to} 0.13 cm ² . The flow path length of the minute space can be appropriately set so as to obtain a predetermined residence time (or reaction time) according to the flow rate. Such a “microspace” may be a suitably dimensioned tubular reactor flow path. Further, it may be each flow path (or channel) of a reactor or a mixer known as “microreactor” or “micromixer” in fields such as pharmaceutical and synthetic chemistry (for example, Non-Patent Document 1). See

  Thereafter, referring to FIG. 1, an intermediate reaction mixture (including an unsaturated alcohol-fluoroalkyl iodide adduct) obtained through the first reaction stage in the first microspace 1 and a basic compound solution A3 are obtained. It supplies to the 2nd minute space 2, and distribute | circulates the inside.

  As the basic compound, for example, an alkali metal hydride, hydroxide, carbonate, hydrogen carbonate, amine such as triethylamine, N, N-dimethylaniline, pyridine, preferably sodium hydroxide or potassium hydroxide is used. be able to. The amount of the basic compound is appropriately selected within the range of 1 to 5 molar equivalents relative to the fluoroalkyl iodide. As the solvent, water, a hydrocarbon solvent, an alcohol solvent, an ether solvent, a halogen solvent, acetonitrile, dimethylformamide, dimethyl sulfoxide, or the like can be used alone or in an appropriate mixture. In particular, when the basic compound is sodium hydroxide or potassium hydroxide, the solvent is preferably water.

上記の式中、Ｒｆ^１、Ｒｆ^２、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４およびＲ^５は上述の通りである。 The second reaction stage proceeds while flowing through the second microspace 2, and the unsaturated alcohol-fluoroalkyl iodide adduct reacts with the basic compound to produce the following general formula (c ¹ ) or (c ² ): And a fluorine-containing epoxy compound corresponding to the fluoroalkyl iodide used as a reaction raw material.

In the above formula, Rf ¹ , Rf ² , R ¹ , R ² , R ³ , R ⁴ and R ⁵ are as described above.

  The second reaction stage can be carried out, for example, at a temperature of about 50-200 ° C., preferably about 60-120 ° C. and a pressure of about 0.1-50 MPa, preferably 0.2-5 MPa. Also in the second reaction stage, the temperature is controlled, for example, by controlling the temperature of a thermostatic bath (not shown in FIG. 1), and the pressure is, for example, a back pressure valve (not shown in FIG. 1) behind the second minute space. Can be adjusted as appropriate. By setting the reaction pressure to a pressure higher than atmospheric pressure, the reaction can be performed at a higher temperature while maintaining the reaction raw material in a liquid state, and the reaction efficiency (for example, reaction rate) can be increased. The effect that impurities are reduced is obtained. The first reaction stage and the second reaction stage may be the same or different in temperature and pressure.

The second minute space also has a channel width of, for example, about 10 to 5000 μm, preferably about 100 to 2000 μm, and for example, about 3.1 × 10 ^{−6 to} 7.9 × 10 ⁻¹ cm ² , preferably It may have a channel cross-sectional area of about 3.1 × 10 ^{−4 to} 0.13 cm ² and the same description as described above for the first microspace may apply. However, the first microspace and the second microspace may have the same or different channel width, channel cross-sectional area, channel length, and the like.

  Thereafter, referring to FIG. 1, the reaction mixture obtained through the second reaction stage in the second minute space 2 is extracted into the container 3, and the fluorous phase is recovered as the final reaction mixture. The obtained final reaction mixture contains a fluorine-containing epoxy compound as a target substance.

  Since the fluorine-containing epoxy compound used for the first raw material A1 becomes an unsaturated alcohol-fluoroalkyl iodide adduct in the first reaction stage, and is regenerated as a fluorine-containing epoxy compound in the second reaction stage, the loss is reduced. Absent.

  Further, since the fluorine-containing epoxy compound used in the first raw material A1 is a target substance in the second reaction stage, even if it remains in the intermediate reaction mixture without reacting completely in the first reaction stage, It is not necessary to carry out an additional separation operation after the end of the reaction phase.

  In addition, when 2 or more types of fluoroalkyl iodides are used for the reaction raw material, the fluorine-containing epoxy compound corresponding to each may exist in the final reaction mixture. Although not essential to the present invention, after obtaining the final reaction mixture, these fluorine-containing epoxy compounds may be appropriately separated as desired.

  A part of the obtained final reaction mixture (fluorus phase) may be recycled to be used as a fluorine-containing epoxy compound for the first raw material A1, and returned to the first minute space. In this way, while supplying a part of the fluorine-containing epoxy compound contained in the final reaction mixture to the first minute space, the supply to the first minute space and the second minute space is continuously performed, and the fluorine-containing epoxy compound is continuously supplied. The final reaction mixture containing the epoxy compound can be obtained continuously. In this embodiment, since supply, distribution (reaction) and recovery are continuously performed, there is an advantage that it is suitable for mass production and the quality of the obtained fluorine-containing epoxy compound is stable. However, the present invention is not limited to this, and the present invention can also be implemented in a batch manner.

Example 1
First, an apparatus as shown in FIG. 3 was prepared.
A stainless steel tube having an inner diameter of 1.0 mm and a total length of 1.5 m is used as a reaction tube (microtube) that defines the first minute space (first reaction channel) 1, and the second minute space (second reaction channel). ) A stainless steel tube having an inner diameter of 1.0 mm and a total length of 6.0 m was used as a reaction tube (microtube) defining 2. The cross section of these tubes was circular, and the cross sectional area of the flow path was 7.85 × 10 ⁻³ cm ² . Although two thermostats C1 and C2 are shown in FIG. 3, in reality, a common thermostat is used, and a portion of the stainless tube forming the first microspace 2 and the second microspace 2 is 100. It was kept in a thermostat maintained at ° C. FIG. 3 shows a back pressure valve and a check valve between the stainless steel tube forming the first micro space 1 and the stainless steel tube forming the second micro space 2. Is omitted, and the pressure is set to about 1.0 MPa only for the back pressure valve downstream of the second minute space. Thereby, the temperature of the first microspace and the second microspace is about 100 ° C., and the pressure is about 1.0 MPa (the pressure loss can be ignored). Syringe pumps were used as the pumps P1 to P3. Moreover, in order to ensure sufficient mixing of the intermediate reaction mixture and the basic compound solution, a static mixer M was used.

Next, the first raw material A1, the second raw material A2, and the basic compound solution A3 were prepared.
As the first raw material A1, CF ₃ (CF ₂ ) ₃ I is used as the fluoroalkyl iodide, and 3-perfluorobutyl-1,2-epoxypropane is used as the corresponding fluorine-containing epoxy compound. Mixed at a molar ratio of 1.
In the second raw material A2, azobisisobutyronitrile (AIBN) is used as the radical catalyst, allyl alcohol is used as the unsaturated alcohol, and AIBN is converted into allyl alcohol so that the molar ratio thereof is 0.005: 1. Dissolved.
As the basic compound solution A3, an 18.2 wt% aqueous potassium hydroxide solution was used.

A first raw material A1 (CF ₃ (CF ₂ ) ₃ I and 3-perfluorobutyl-1,2-epoxypropane) was charged into a syringe pump P1, and then a stainless tube at a supply rate of 0.091 ml / min. It supplied continuously to the 1st minute space 1 (reaction channel) of the inside. In addition, the first raw material A2 (AIBN and allyl alcohol) is charged into the syringe pump P2 and continuously from there to the first micro space 1 (reaction channel) in the stainless tube at a supply rate of 0.045 ml / min. Supplied.

  Then, the basic compound solution (potassium hydroxide aqueous solution) A3 is charged into the syringe pump P3, and at a supply rate of 0.144 ml / min, together with the intermediate reaction mixture coming out of the first microspace 1 Then, it was continuously supplied to the second minute space 2 (reaction channel) in the stainless steel tube through the static mixer M.

  The reaction mixture that emerged from the second microspace 2 was withdrawn into the container 3, and the fluorous phase was recovered as the final reaction mixture.

  The first reaction stage proceeds while flowing through the first minute space 1, and the second reaction stage proceeds while flowing through the second minute space 2. Each reaction step is completed in each minute space (in the stainless steel tube), and the residence time in the stainless steel tube can be regarded as the reaction time. The residence time in the stainless steel tube is shown in Table 1 as the reaction time.

The recovered final reaction mixture (fluorus phase) was analyzed by gas chromatography, conversion of CF ₃ (CF ₂ ) ₃ I, selectivity to 3-perfluorobutyl-1,2-epoxypropane as the target substance And the yield was calculated. The results are shown in Table 1.

(Example 2)
The same operation as in Example 1 was performed except that the temperature in the thermostatic bath was 110 ° C.
The recovered final reaction mixture (fluorus phase) was analyzed by gas chromatography, conversion of CF ₃ (CF ₂ ) ₃ I, selectivity to 3-perfluorobutyl-1,2-epoxypropane as the target substance And the yield was calculated. The results are shown in Table 1.

(Example 3)
The temperature in the thermostat is set to 110 ° C., and for the first raw material A1, CF ₃ (CF ₂ ) ₅ I is used as the fluoroalkyl iodide, and 3-perfluorohexyl-1, as the corresponding fluorine-containing epoxy compound, Using 2-epoxypropane, the feed rate of the first raw material A1 (CF ₃ (CF ₂ ) ₅ I and 3-perfluorohexyl-1,2-epoxypropane) was set to 0.049 ml / mi, and the second raw material A2 ( The same operation as in Example 1 was performed except that the supply rate of AIBN and allyl alcohol was 0.019 ml / min and the supply rate of the basic compound solution (aqueous potassium hydroxide solution) was 0.061 ml / min. It was.
The collected reaction mixture was subjected to gas chromatography, and the conversion rate of CF ₃ (CF ₂ ) ₅ I, the conversion rate to the target substance 3-perfluorohexyl-1,2-epoxypropane, and the yield were calculated. The results are shown in Table 1.

Example 4
The temperature in the thermostatic chamber was set to 110 ° C., and for the first raw material A1, I (CF ₂ ) ₄ I was used as the fluoroalkyl iodide, and 1,4-bis (2 ′, 3′-epoxypropyl) -perfluoro-n-butane and the first raw material A1 (I (CF ₂ ) ₄ I and 1,4-bis (2 ′, 3′-epoxypropyl) -perfluoro-n- Butane) was supplied at 0.071 ml / min, the second raw material A2 (AIBN and allyl alcohol) was supplied at 0.065 ml / min, and the basic compound solution (potassium hydroxide aqueous solution) was supplied at a rate of 0.8. The same operation as in Example 1 was performed except that the flow rate was 208 ml / min.
The recovered reaction mixture was subjected to gas chromatography to convert I (CF ₂ ) ₄ I to 1,4-bis (2 ′, 3′-epoxypropyl) -perfluoro-n-butane as the target substance. Conversion and yield were calculated. The results are shown in Table 1.

(Example 5)
The total length of the stainless steel tube, which is a reaction tube (microtube) that defines the first minute space (first reaction channel), is 4.0 m, the temperature in the thermostatic chamber is 110 ° C., and for the first raw material A1, I (CF ₂ ) ₆ I is used as the fluoroalkyl iodide, and 1,6-bis (2 ′, 3′-epoxypropyl) -perfluoro-n-hexane is used as the fluorine-containing epoxy compound corresponding thereto. The feed rate of the raw material A1 (I (CF ₂ ) ₆ I and 1,6-bis (2 ′, 3′-epoxypropyl) -perfluoro-n-hexane) was set to 0.054 ml / min, and the second raw material A2 ( Except that the supply rate of AIBN and allyl alcohol) was 0.051 ml / min, and the supply rate of the basic compound solution (potassium hydroxide aqueous solution) was 0.123 ml / min.施例 was subjected to the same procedure as 1.
The collected reaction mixture was subjected to gas chromatography to convert I (CF ₂ ) ₆ I to 1,6-bis (2 ′, 3′-epoxypropyl) -perfluoro-n-hexane, which is the target substance. Conversion and yield were calculated. The results are shown in Table 1.

In one Embodiment of this invention, it is a schematic schematic diagram of the apparatus used in enforcing the manufacturing method of a fluorine-containing epoxy compound. It is a figure explaining the main reaction and side reaction in the 1st reaction stage of the manufacturing method of a fluorine-containing epoxy compound. It is a schematic diagram of the apparatus used in the Example of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 1st micro space 2 2nd micro space 3 Container A1 1st raw material (fluoroalkyl iodide and fluorine-containing epoxy compound)
A2 Second raw material (unsaturated alcohol and radical catalyst)
A3 Basic compound solution P1, P2, P3 Pump C1, C2 Thermostatic bath M Static mixer

Claims (9)

The following general formula (a ¹ ) or (a ² )
Rf ¹ -I (a ¹ )
^{I-Rf 2 -I ··· (a} 2)
[Wherein Rf ¹ and Rf ² are linear or branched polyfluorocarbon groups having at least one fluorine group at the carbon atom adjacent to the iodine group (—I)]. When,
The following general formula (b)
CR ¹ R ² = CR ³ -CR ⁴ R ⁵ (OH) (b)
Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or an aralkyl group, Reacting in the presence of a radical catalyst to obtain an unsaturated alcohol-fluoroalkyl iodide adduct, and reacting the unsaturated alcohol-fluoroiodide adduct with a basic compound, General formula (c ¹ ) or (c ² )

[Wherein Rf ¹ , Rf ² , R ¹ , R ² , R ³ , R ⁴ and R ⁵ are the same as described above], which comprises a second reaction step to obtain a fluorine-containing epoxy compound represented by In the method for producing a fluorine epoxy compound, the first reaction step is carried out in the presence of the fluorine-containing epoxy compound. The production method according to claim 1, wherein Rf ¹ and Rf ² are linear perfluorocarbon groups.   The process according to claim 1 or 2, wherein the first reaction step is carried out in the absence of a solvent.   The manufacturing method in any one of Claims 1-3 which implements a 1st reaction stage and a 2nd reaction stage under the pressure of 0.1-50 Mpa, respectively. At least a fluoroalkyl iodide, an unsaturated alcohol, a radical catalyst, and a fluorine-containing epoxy compound are supplied to the first microspace, and the first reaction stage is allowed to proceed while flowing through the first microspace. An intermediate reaction mixture comprising a fluoroalkyl adduct is obtained, and then
The intermediate reaction mixture and the basic compound solution are supplied to the second microspace, and the second reaction stage is allowed to proceed while flowing through the second microspace, so that the final reaction mixture containing the fluorine-containing epoxy compound is converted into a fluorous phase. The manufacturing method in any one of Claims 1-4 obtained.   The supply to the first minute space is performed by dividing into a first raw material containing at least a fluoroalkyl iodide and a fluorine-containing epoxy compound and a second raw material containing at least an unsaturated alcohol and a radical catalyst. Production method.   By returning a part of the final reaction mixture obtained from the second microspace to the first microspace, the fluorine-containing epoxy compound contained in the final reaction mixture is supplied to the first microspace, while the first microspace and the first microspace are supplied. The production method according to claim 5 or 6, wherein the final reaction mixture containing the fluorine-containing epoxy compound is continuously obtained by continuously supplying the two minute spaces.   The manufacturing method according to claim 5, wherein each of the first minute space and the second minute space has a flow path width of 10 to 5000 μm. The manufacturing method according to claim 5, wherein each of the first minute space and the second minute space has a flow path cross-sectional area of 3.1 × 10 ^{−6 to} 7.9 × 10 ⁻¹ cm ² .

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