JP2002060387A - Fluorine-containing oxirane compound and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photocurable or thermocurable fluorine-containing oxirane compound easy to regulate the fluorine content thereof, good in compatibility with other polar monomers or polar polymers, having low refractive index, and giving high mechanical strength and transparency when cured, and to provide a method for producing the above oxirane compound. SOLUTION: This fluorine-containing oxirane compound is represented by formula (1) or (2) (wherein, A is a 3-30C univalent organic group having at least one oxirane ring; and substituents R1, R2 and R3 are each F or a 1-10C perfluoroalkyl). The method for producing the above oxirane compounds is also provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a fluorine-containing oxirane compound and a method for producing the same. More specifically,
The present invention relates to a fluorine-containing oxirane compound which can be suitably used as a fluorine-containing monomer material, a low-refractive-index resin composition material, a monomer component of a photocurable or thermosetting composition, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, a material having a low refractive index has been utilized to provide a cladding material for an optical transmission fiber, a material for an antireflection film such as an optical lens, a film, and a glass for a CRT, or an optical fiber or an optical lens. Fluorine-based compounds are suitably used as optical adhesives. Further, since the fluorine-based compound has water repellency and oil repellency, it is also used as an antifouling coating material. As one of such fluorine compounds, a monofunctional fluorine-containing oxirane compound is known, and more specifically, 2,2,3,3,4,4,
4-heptafluorobutyloxirane (Cas # 176
5-92-0) or ((16, 16, 17, 1
7,18,18,18-heptafluorooctadecyl)
Oxy) methyl) oxirane (Cas # 123490-
99-3) and the like are known. However, these monofunctional fluorine-containing oxirane compounds have a structure in which the fluorine-containing structure is limited to a linear perfluoroalkyl group or the like, and the selection range of the fluorine-containing structure is narrow, or the synthesis method is complicated. There was a problem. Further, there was also a problem that these monofunctional fluorine-containing oxirane compounds had insufficient compatibility with other polar monomers and polar polymers.

Further, as a fluorine compound, a polyfunctional fluorine-containing oxirane compound is also known, and for example, the following general formula (1) disclosed in Japanese Patent Application Laid-Open No. 6-174956.
A dioxirane compound represented by the formula (9);
No. 702 discloses a dioxirane compound represented by the following general formula (21).

[0004]

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(In the formula, the symbol M is a substituent represented by the following formula (20), and the number of repetitions n is an arbitrary integer.)

[0006]

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(In the formula, the symbol Z represents a hydrogen atom (H) or a fluoroalkyl group having 1 to 13 carbon atoms.)

[0008]

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(In the formula, the number of repetitions m represents an arbitrary integer.)

However, these polyfunctional fluorine-containing oxirane compounds have a molecular structure in which an oxirane ring is bonded by a fluorine-containing organic group. Therefore, when the fluorine content is changed, the distance between cross-linking points changes accordingly. There was a problem. Therefore, when the fluorine content was increased, adverse effects such as deterioration of the mechanical properties of the cured product obtained from the polyfunctional fluorine-containing oxirane compound were observed. In addition, since these polyfunctional fluorine-containing oxirane compounds do not have a reactive double bond in the molecule, they have poor radical reactivity, and further undergo structural transformation using these as raw materials while leaving the oxirane ring. It was difficult to do. Further, there has been a problem that the above-mentioned compound which is not contained in the reactive double bond molecule has poor compatibility with other polar monomers and polar polymers.

[0011]

Therefore, the present inventors have introduced a fluorinated structure containing a reactive double bond and an oxirane ring (epoxy group) into a specific site of a fluorine-based compound, thereby obtaining the following: It has been found that a fluorinated oxirane compound capable of exhibiting the following characteristics can be obtained. Adjustment of the fluorine content is easy. Good compatibility with other polar monomers and polar polymers. Since the fluorine content can be relatively increased, the refractive index can be reduced. It has nucleophilic reactivity, electrophilic reactivity, and radical reactivity. When cured, excellent mechanical strength and transparency can be exhibited. That is, the object of the present invention is to take advantage of such properties, for example, a fluorinated oxirane compound suitable as one of the cladding constituent materials of optical transmission fibers and such a fluorinated oxirane compound can be efficiently obtained. It is to provide a manufacturing method.

[0012]

The present invention provides a mixture of compounds represented by the following general formulas (1) and (2):
Alternatively, it is a fluorine-containing oxirane compound containing any one compound.

[0013]

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[0014]

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[In the general formulas (1) and (2), the symbol A
Has at least one oxirane ring and has 3 to 3 carbon atoms.
30 represents a monovalent organic group, and the substituents R ¹ , R ² , and R ³ represent a fluorine atom or a perfluoroalkyl group having 1 to 10 carbon atoms. ]

With such a fluorine-containing oxirane compound, a fluorine-containing structure having a reactive double bond and an oxirane ring as a reactive functional group are contained at predetermined positions, respectively, and excellent reactivity is obtained. In addition, when cured, excellent mechanical strength and transparency can be exhibited. Further, such a fluorine-containing oxirane compound can be easily produced by reacting a hydroxyoxirane compound with a perfluoroolefin compound. Therefore, even in the case of polyfunctionality, the fluorine content can be easily changed by, for example, changing the type of perfluoroolefin compound. And even when changing the fluorine content, the skeleton itself containing the oxirane ring structure derived from the hydroxyoxirane compound is not changed even after the reaction with the perfluoroolefin, so the curing behavior as the fluorinated oxirane compound and the obtained cured product It has less influence on the mechanical properties of the device.

In constituting the present invention, the fluorinated oxirane compound represented by the general formula (1) or (2) is represented by the following general formulas (3), (4) and (5). ) Or a fluorine-containing oxirane compound represented by the general formula (6).

[0018]

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[0019]

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[0020]

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[0021]

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[Substituents R ¹ in the general formulas (3) to (6),
R ² and R ³ are the same as those in the general formula (1). ]

Another embodiment of the present invention provides a compound represented by the following general formula (1):
A method for producing a fluorinated oxirane compound represented by the formula: wherein a hydroxyoxirane compound represented by the following general formula (7) and a perfluoroolefin compound represented by the following general formula (8) are used as a phase transfer catalyst A process for producing a fluorinated oxirane compound, characterized in that the reaction is carried out in the presence.

A-OH (7) [The symbol A in the general formula (7) is the same as that in the general formula (1). ] C _m F _2m (8) [repeating number m in the general formula (8) is an integer from 2 to 12. ]

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION [First Embodiment] A first embodiment is a mixture of compounds represented by the general formulas (1) and (2), or a fluorine-containing compound containing any one of the compounds. It is an oxirane compound.

(1) Oxirane Structure (A) As the oxirane ring structure contained in A in the general formulas (1) and (2), at least one oxirane ring (sometimes referred to as epoxy or ethylene oxide). It is not particularly limited as long as it is a monovalent organic group having 3 to 30 carbon atoms. For example, a glycidylmethyl group, a glycidylethyl group, a glycidylpropyl group,
Examples include an epoxycyclohexylmethyl group, an epoxycyclohexylethyl group, and an epoxycyclohexylpropyl group. However, a glycidylmethyl group is preferable because the fluorine content is adjusted to a suitable amount and particularly excellent reactivity is obtained. The number of oxirane rings is not particularly limited, but is preferably 1 to 6. The reason for this is that if the number of oxirane rings exceeds 6, the fluorine content in the fluorinated oxirane compound may decrease. Therefore, it is more preferable that the number of oxirane rings is 1 to 2.

[0027] (2) a fluorine-containing structure substituents ^{R 1,} R 2, ^{R 3} substituents ^R 1 contained in the fluorine-containing ^structure, R 2, ^{R 3} are each independently a fluorine atom or having 1 to 10 carbon atoms A perfluoroalkyl group, more preferably a compound of the formula C _n F
_2n-1, a fluorinated monovalent radical (n in each formula is an integer from 2 to 12.) Formula C _n F _2n H or the formula C _n F _{2n + 1} is represented by. However, a fluorine-containing group represented by the formula C _n F _2n-1 is more preferable because it can be easily introduced into a molecule.

Fluorine content The fluorine content in the fluorine-containing oxirane compound is preferably adjusted to 20% by weight or more, more preferably 30% by weight or more, by changing the fluorine-containing structure and the like. . The reason for this is that if the fluorine content is less than 20% by weight, the refractive index increases, and when used as a cladding material or an antireflection film, it may not be possible to exhibit predetermined optical characteristics. The fluorine content in the fluorinated oxirane compound can be measured by using the alizarin complexone method. The same applies to the determination of the fluorine content.

(3) Specific Examples Specific examples of the fluorinated oxirane compound represented by the general formula (1) include 2- [1-pentafluoroethyl-2,
2-bis (trifluoromethyl) ethenyloxymethyl] oxirane, 2- [1,2,2-tris (trifluoromethyl) ethenyloxymethyl] oxirane, 2-
[1-Pentafluoroethyl-2,2-bis (trifluoromethyl) ethenyloxyethyl] oxirane, 2-
[1,2,2-tris (trifluoromethyl) ethenyloxyethyl] oxirane, 2- [1,2-bis (trifluoromethyl) -2-pentafluoroethylethenyloxymethyl] oxirane, 2- [1 , 2,2-Tris (pentafluoroethyl) ethenyloxymethyl] oxirane, 2- [1,2-bis (trifluoromethyl)-
2-pentafluoroethylethenyloxyethyl] oxirane, 2- [1,2,2-tris (pentafluoroethyl) ethenyloxyethyl] oxirane, 1,3-bis (glycidyloxy) -2- [1-pentane Fluoroethyl-2,2-bis (trifluoromethyl) ethenyloxy] propane, 1,3-bis (glycidyloxy)-
2- [1,2,2-tris (trifluoromethyl) ethenyloxy] propane and the like. Specific examples of the fluorine-containing oxirane compound represented by the general formula (2) include 2- [1-fluoro-1-pentafluoroethyl-2,2-bis (trifluoromethyl) ethoxymethyl] oxirane, -[1-Fluoro-1,2,2-tris (trifluoromethyl) ethoxymethyl] oxirane, 2- [1-fluoro-1-pentafluoroethyl-
2,2-bis (trifluoromethyl) ethoxyethyl]
Oxirane, 2- [1-fluoro-1,2,2-tris (trifluoromethyl) ethoxyethyl] oxirane,
2- [1-fluoro-1,2-bis (trifluoromethyl) -2-pentafluoroethylethoxymethyl] oxirane, 2- [1-fluoro-1,2,2-tris (pentafluoroethyl) ethoxymethyl] Oxirane, 2
-[1-Fluoro-1,2-bis (trifluoromethyl) -2-pentafluoroethylethoxyethyl] oxirane, 2- [1-fluoro-1,2,2-tris (pentafluoroethyl) ethoxyethyl] oxirane ,
1,3-bis (glycidyloxy) -2- [1-fluoro-1-pentafluoroethyl-2,2-bis (trifluoromethyl) ethoxy] propane, 1,3-bis (glycidyloxy) -2- [ 1-fluoro-1,2,2-
Tris (trifluoromethyl) ethoxy] propane and the like. Among these specific examples, 2- [1-pentafluoroethyl-2,2-bis (trifluoromethyl)
[Ethenyloxymethyl] oxirane is more preferable because it is relatively inexpensive and the cured product has excellent transparency. Also, 1,3-bis (glycidyloxy)-
2- [1-Pentafluoroethyl-2,2-bis (trifluoromethyl) ethenyloxy] propane is also preferable because of its high reactivity and excellent mechanical strength of the cured product.

[Second Embodiment] A second embodiment is a method for producing a fluorine-containing oxirane compound represented by the general formula (1). That is, the method for producing the fluorine-containing oxirane compound represented by the general formula (1) is not particularly limited. For example, a hydroxyoxirane compound represented by the general formula (7) and a hydroxyoxirane compound represented by the general formula (8) It is preferable to react the represented perfluoroolefin compound in the presence of a phase transfer catalyst. The reason is that the fluorine-containing oxirane compound represented by the general formula (1) can be obtained very efficiently, for example, in a yield of 80% or more.
Hereinafter, raw materials and reaction conditions for carrying out the second embodiment will be described.

(1) Hydroxyoxirane Compound The hydroxyoxirane compound represented by the general formula (7) may be any compound as long as it has an oxirane ring and a hydroxyl group. For example, glycidol, 2-methylglycidol, -Ethylglycidol, 2-propylglycidol, 2-fluoroglycidol, 2,2
-Difluoroglycidol, 2,3-difluoroglycidol, 2,3,3-trifluoroglycidol, 3-
Glycidol derivatives such as phenylglycidol and 2-methyl-3-phenylglycidol; 2-hydroxymethylcyclohexene oxide, 3-hydroxymethylcyclohexene oxide, 3,4-epoxytricyclo (5,2,1,0,2,6) Hydroxy compounds having an alicyclic epoxy group such as decanol; glycidyl ether derivatives of polycyclic compounds such as beta estradiol-3-glycidyl ether; glycerin-1,3-diglycidyl ether, glycerin-1,2-diglycidyl ether Glycidyl ether derivatives of polyols such as, 3- (bis (glycidyloxymethyl) methoxy) -1,2-propanediol, pentaerythritol triglycidyl ether; and the like, alone or in combination of two or more. . Of these, glycidol has the lowest molecular weight among the glycidol derivatives, so that the fluorine content of the obtained fluorine-containing oxirane compound can be maximized.
3-Diglycidyl ether is a more preferable compound because it is easily available and can introduce a plurality of epoxy groups without reducing the fluorine content.

(2) Perfluoroolefin compound As the perfluoroolefin compound represented by the general formula (8), hexafluoropropene, hexafluoropropene dimer (dimer), hexafluoropropene trimer (trimer), Hexafluoropropene tetramer, hexafluoropropene pentamer, hexafluoropropene hexamer, tetrafluoroethylene, tetrafluoroethylene dimer, tetrafluoroethylene trimer, tetrafluoroethylene tetramer, tetrafluoroethylene pentamer Mers,
One kind of tetrafluoroethylene hexamer, octafluoroisobutene and the like may be used alone or in combination of two or more kinds.

Among these perfluoroolefin compounds, they are liquid at ordinary temperature, have excellent reaction operability, and have good reactivity, and are composed of isomers represented by the following formulas (9) and (10). Hexafluoropropene dimer and hexafluoropropene trimer comprising isomers represented by the following formulas (11) and (12) are more preferably used. The hexafluoropropene dimer and hexafluoropropene trimer used here are represented by the following formulas (9), (10), (11),
It may contain not only the compound represented by (12) but also a mixture of these compounds.

[0034]

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[0035]

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[0036]

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[0037]

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(3) Type of phase transfer catalyst The type of phase transfer catalyst is not particularly limited.
For example, ammonium salts such as tetra-n-butylammonium bromide, tetra-n-butylammonium chloride, tetramethylammonium bromide, tetramethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium chloride, triphenylmethylphosphonium bromide, Phosphonium salts such as phenylmethylphosphonium chloride and the like may be used alone or in combination of two or more. In particular, tetra-n-butylammonium bromide and tetra-n-methylammonium bromide are preferably used from the viewpoint of suppressing side reactions and the ease of purification operation. Addition amount The addition amount of the phase transfer catalyst to be used is not particularly limited, either. For example, it is preferable to set the value within the range of 0.00001 to 1 mol based on 1 mol of the hydroxyoxirane compound. . The reason for this is that when the amount of the phase transfer catalyst is less than 0.00001 mol, the effect as a catalyst is poor and the reaction addition rate may decrease,
On the other hand, if the amount of the phase transfer catalyst exceeds 1 mol, the purification operation after the reaction may be difficult.
Therefore, the addition amount of the phase transfer catalyst is more preferably set to a value within the range of 0.0001 to 0.5 mol per 1 mol of the hydroxyoxirane compound.
More preferably, the value is in the range of 0.1 mol.

(4) Reaction conditions Reaction molar ratio The reaction molar ratio of the hydroxyoxirane compound represented by the general formula (7) to the perfluoroolefin compound represented by the general formula (8) is 1:10 to 10: It is preferable that the value be in the range of 1. The reason for this is that if the reaction molar ratio is outside these ranges, a large amount of unreacted components may remain, or the reactivity and heat resistance of the obtained fluorinated oxirane compound may be reduced. Therefore, the reaction molar ratio between the hydroxyoxirane compound represented by the general formula (7) and the perfluoroolefin compound represented by the general formula (8) is set to a value within the range of 2: 8 to 8: 2. Is more preferable, and the value is more preferably in the range of 3: 7 to 7: 3.

Reaction Temperature The reaction temperature is not particularly limited, either. For example, the reaction temperature is preferably in the range of -20 to 100 ° C. The reason for this is that when the reaction temperature is lower than −20 ° C., the reactivity between the hydroxyoxirane compound and the perfluoroolefin compound may be remarkably reduced. This is because it may be difficult to control the reaction. Therefore, the reaction temperature is more preferably set to a value in the range of -10 to 70C, and further preferably to a value in the range of -5 to 50C.

Reaction Time The reaction time between the hydroxyoxirane compound and the perfluoroolefin compound is not particularly limited, but is preferably, for example, a value within the range of 1 to 100 hours. The reason for this is that if the reaction time is less than 1 hour, unreacted components may be significantly increased, while if the reaction time exceeds 100 hours,
This is because side reactions may occur or economic disadvantages may occur. Therefore, the reaction time between the hydroxyoxirane compound and the perfluoroolefin compound is 3 hours.
More preferably, the value is within a range of 72 hours.
More preferably, the value is within a range of 48 hours.

Basic Substance The type of basic substance used when reacting the perfluoroolefin compound with the hydroxyoxirane compound is not particularly limited, but inorganic compounds exhibiting weak basicity may be used. preferable. Specific examples include potassium carbonate and sodium carbonate.

Solvent When reacting the hydroxyoxirane compound with the perfluoroolefin compound, it is preferable to use a solvent. By using the solvent in this manner, the concentration of the reactive species can be adjusted, side reactions can be suppressed, and the reaction temperature can be easily controlled. In addition, the type of the solvent used is not particularly limited as long as it is other than an acidic substance that reacts with an oxirane group or a compound having an active hydroxyl group that reacts with a perfluoroolefin, for example, methylene chloride, a chlorofluorocarbon-based solvent, Hexane, cyclohexane, dimethylformamide, dimethyl sulfoxide, sulfolane hexamethylphosphoramide, acetonitrile, acetone, diphenyl ether,
Diglyme, etc., alone or in combination of two or more. Note that a particularly preferred solvent is methylene chloride. Furthermore, regarding the amount of solvent used,
The sum of the hydroxyoxirane compound and the perfluoroolefin compound in the solution is 10 to 90 in the reaction product.
It is preferable to add so as to have a value within the range of% by weight. The reason for this is that when the concentration is outside these ranges, the reaction rate may be significantly reduced or a side reaction may proceed.

[0044]

Hereinafter, embodiments of the present invention will be described in detail.
The scope of the present invention is not limited to the description of these examples. In the examples, the amounts of the respective components mean parts by weight unless otherwise specified.

Example 1 (Preparation of Fluorine-Containing Oxirane Compound) 400 g of hexafluoropropene dimer was placed in a 0.5-liter separable flask equipped with a stirrer, a cooler and a dropping funnel.
(1.33 mol, manufactured by Nippon Mektron Co., Ltd., CHEMI
NOX HFP-D) and 4.0 g of potassium carbonate (0.0
3 moles) and 40 g of methylene chloride were stirred uniformly, and then 0.8 g (0.002 moles, manufactured by Wako Pure Chemical Industries, Ltd.) of tetra-n-butylammonium bromide was used as a phase transfer catalyst. Was added. Next, a mixed solution of 51 g of glycidol represented by the formula (13) (0.69 mol, manufactured by Daicel Chemical Industries, Ltd.) and 40 g of methylene chloride was prepared in advance, and the mixed solution was cooled to room temperature (25 ° C.). ) Under conditions, it was dropped into the separable flask. After dropping,
The temperature in the separable flask was set to 35 using an oil bath.
Heating was continued for 24 hours while maintaining the temperature at ° C to obtain a reaction solution of hexafluoropropene dimer and glycidol. After the obtained reaction solution was air-cooled, potassium carbonate was separated by filtration, 200 g of water was further added, and the mixture was vigorously shaken to separate an aqueous layer and an organic layer. After that, collect only the organic layer,
Water was dried using 5 g of magnesium sulfate, then methylene chloride was distilled off under reduced pressure, and further vacuum distillation was performed at 45 ° C. and 0.7 mmHg to obtain 207 g of a colorless and transparent liquid purified product. .

[0046]

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(Evaluation of Fluorine-Containing Oxirane Compound) The obtained purified product was subjected to ¹ H-NMR measurement, ¹⁹ F-NMR measurement and infrared absorption spectrum measurement as described below, and was represented by the formula (14). 2- [1-pentafluoroethyl-2,2-bis (trifluoromethyl) ethenyloxymethyl] oxirane and 2- [1-pentafluoroethyl-2,2-bis (trifluoromethyl) ethenyloxymethyl] oxirane represented by the formula (15):
[1-Fluoro-1-pentafluoroethyl-2,2-
Bis (trifluoromethyl) ethoxymethyl] oxirane was identified as a mixture.

[0048]

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[0049]

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(1) NMR Measurement An NMR measurement device (MSL400, manufactured by BRUKER) was used.
Using the solvent CDCl ₃It measured on condition of. Including obtained
Of fluorine oxirane compounds¹FIG. 1 shows the H-NMR chart.
To¹⁹The F-NMR chart is shown in FIG.
As can be seen from FIG.¹On H-NMR chart
In addition, the following peaks were observed. δ = 2.64 (1H, m, oxirane ring), δ = 2.85 (1H, m, oxirane ring), δ = 2.90 (1H, m, oxirane ring), δ = 3.19 (1H, m, OCH) Δ = 3.29 (1H, m, OCH) Δ = 3.7-4.4 (3H, m, CH₂C, CH (CF
₃)₂)

As understood from FIG. 2, ¹⁹ F
-The following peaks were observed on the NMR chart. δ = −114.57 (2F, q, J = 18.9 Hz, C
F ₂ ) δ = −81.70 (3F, s, CF ₂ CF ₃ ) δ = −80.02 (3F, s, CF ₂ CF ₃ ) δ = −62.36 (3F, q, J = 8. 6Hz, CCF
₃ ) δ = −62.10 (3F, s, CCF ₃ ) δ = −60.18 (3F, q, J = 8.6 Hz, CCF
₃ ) δ = −57.28 (3F, s, CCF ₃ )

(2) Infrared absorption spectrum measurement Fourier transform infrared spectrometer (manufactured by JASCO Corporation,
Using JIR-5500), the infrared absorption spectrum of the obtained fluorine-containing oxirane compound was measured under the conditions of room temperature (25 ° C.), resolution of 4 cm ⁻¹ , gain of 1, scanning 10 times, and scanning speed TGS. . FIG. 3 shows the obtained infrared absorption spectrum chart. As can be understood from FIG. 3, the following characteristic peaks were observed on the infrared absorption spectrum chart, while it was confirmed that the observed hydroxyl group peaks disappeared in the starting hydroxyoxirane compound. Was. CH assignment 3070 cm ⁻¹ , 3012 cm ⁻¹ , 2
966cm ^-1 C = O attribution 1785 cm ^-1 C = C attributable 1639 cm ^-1 C-F attributable 1300～1100Cm ^-1

For reference, ¹ H-N of glycidol represented by the above formula (13) used as a raw material was used.
FIG. 4 shows an MR chart, and FIG. 5 shows an infrared absorption spectrum chart. FIG. 6 shows a ¹⁹ F-NMR chart of the hexafluoropropene dimer, and FIG. 7 shows an infrared absorption spectrum chart thereof.

(3) Measurement of Refractive Index When the refractive index of the obtained fluorine-containing oxirane compound was measured using an Abbe refractometer, _d n ²⁵ = 1.34.
Met.

Example 2 (Preparation of fluorinated oxirane compound) Instead of glycidol in Example 1, 90 g of glycerin-1,3-diglycidyl ether represented by the formula (16) (0.45 g) was used.
Mole, manufactured by Kyoeisha Chemical Co., Ltd., trade name Epolite 80M
Except for using F), the reaction was carried out in the same manner as in Example 1 to prepare a fluorine-containing oxirane compound. That is, after the obtained reaction solution was air-cooled, potassium carbonate was separated by filtration, 200 g of water was further added, and the mixture was shaken vigorously to separate into an aqueous layer and an organic layer. After that, collect only the organic layer,
The water was dried using 5 g of magnesium sulfate. Then
The methylene chloride was distilled off under reduced pressure to obtain 197 g of a pale yellow transparent liquid product.

[0056]

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(Evaluation of Fluorine-Containing Oxirane Compound) The obtained purified product was subjected to ¹ H-NMR measurement, ¹⁹ F-NMR measurement, infrared absorption spectrum measurement, and refractive index measurement in the same manner as in Example 1. ¹ about the obtained purified product
FIG. 8 shows an H-NMR chart, FIG. 9 shows a ¹⁹ F-NMR chart, and FIG. 10 shows an infrared absorption spectrum chart. From these charts, the purified product obtained is
1,3-bis (glycidyloxy) -2- [1-pentafluoroethyl-2,2-bis (trifluoromethyl) ethenyloxy] propane represented by the formula (17):
It is a mixture with 1,3-bis (glycidyloxy) -2- [1-fluoro-1-pentafluoroethyl-2,2-bis (trifluoromethyl) ethoxy] propane represented by the formula (18). Identified.

[0058]

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[0059]

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As understood from FIG. 8, ¹ H-
The following peaks were observed on the NMR chart. δ = 2.61 (2H, br, oxirane ring) δ = 2.79 (2H, m, oxirane ring) δ = 3.15 (2H, br, oxirane ring) δ = 3.4 to 4.0 (10H) _{, m, C H 2 OCH 2} , C
_{H 2 C H CH 2, C} H (CF 3) 2)

As understood from FIG. 9, ¹⁹ F
-The following peaks were observed on the NMR chart. δ = -117.28 (2F, m, CF 2) δ = -87.11 (3F, s, CF 2 C F 3) δ = -84.62 (3F, m, CF 2 C F 3) δ = _{-84.05 (3F, m, CF 2} C F 3) δ = -65.34 (3F, s, CCF 3) δ = -64.91 (3F, s, CCF 3) δ = -63.48 ( 3F, s, CCF ₃ ) δ = −62.77 (3F, s, CCF ₃ ) δ = −60.15 (3F, s, CCF ₃ )

As can be understood from FIG.
The following peaks were observed on the chart. CH attribution 3058 cm ⁻¹ , 3002 cm ⁻¹ , 2
917 cm ^-1 , 2877 cm ^-1 C = O assignment 1785 cm ^-1 C = C assignment 1635 cm ^-1 CF assignment 1300 to 1100 cm ^-1

For reference, FIG. 11 shows a ¹ H-NMR chart and FIG. 12 shows an infrared absorption spectrum chart of glycerin diglycidyl ether represented by the formula (16) used as a raw material.

[0064] Also, in the same manner as in Example 1, where the refractive index of the obtained fluorine-containing oxirane compound was measured, _d n
²⁵ = 1.45.

[0065]

According to the fluorine-containing oxirane compound of the present invention, the fluorine content can be easily adjusted, the compatibility with other polar monomers and polar polymers is good, and the fluorine content can be relatively controlled. As a result, it has a low refractive index, is capable of anionic curing and cationic curing, and when cured further, can exhibit excellent mechanical strength and transparency. Further, according to the method for producing a fluorinated oxirane compound of the present invention, a fluorinated oxirane compound having a low refractive index and good compatibility with other polar monomers and polar polymers can be produced in a high yield. It became so.

[Brief description of the drawings]

FIG. 1 is a diagram showing a ¹ H-NMR spectrum of a fluorine-containing oxirane compound obtained in Example 1.

FIG. 2 is a diagram showing a ¹⁹ F-NMR spectrum of the fluorine-containing oxirane compound obtained in Example 1.

FIG. 3 is a view showing an infrared absorption spectrum of the fluorinated oxirane compound obtained in Example 1.

FIG. 4 is a chart showing a ¹ H-NMR spectrum of a hydroxyoxirane compound used in Example 1.

FIG. 5 is a view showing an infrared absorption spectrum of a hydroxyoxirane compound used in Example 1.

FIG. 6 is a diagram showing a ¹⁹ F-NMR spectrum of hexafluoropropene dimer used in Examples 1 and 2.

FIG. 7 is a view showing an infrared absorption spectrum of hexafluoropropene dimer used in Examples 1 and 2.

FIG. 8 is a chart showing ¹ H-NMR spectrum of a fluorine-containing oxirane compound obtained in Example 2.

9 shows a ¹⁹ F-NMR spectrum of the fluorinated oxirane compound obtained in Example 2. FIG.

FIG. 10 is a graph showing an infrared absorption spectrum of the fluorinated oxirane compound obtained in Example 2.

FIG. 11 is a chart showing ¹ H-NMR spectrum of a hydroxyoxirane compound used in Example 2.

FIG. 12 is a view showing an infrared absorption spectrum of a hydroxyoxirane compound used in Example 2.

Claims (3)

[Claims] 1. A fluorine-containing oxirane compound comprising a mixture of compounds represented by the following general formulas (1) and (2), or one of the compounds. Embedded image Embedded image [In the general formulas (1) and (2), the symbol A represents a monovalent organic group having 3 to 30 carbon atoms having at least one oxirane ring, and the substituents R ¹ , R ² , and R ³ are each a fluorine atom. Alternatively, it represents a perfluoroalkyl group having 1 to 10 carbon atoms. ] 2. The compounds represented by the general formulas (1) and (2) are represented by the following general formulas (3), (4),
The fluorine-containing oxirane compound according to claim 1, which is a compound represented by the general formula (5) or (6). Embedded image Embedded image Embedded image Embedded image [The substituents R ¹ , R ² and R ³ in the general formulas (3) to (6) are the same as those in the general formula (1). ] 3. A method for producing a fluorine-containing oxirane compound represented by the general formula (1) according to claim 1, wherein the hydroxyoxirane compound is represented by the following general formula (7):
A method for producing a fluorinated oxirane compound, which comprises reacting a perfluoroolefin compound represented by the following general formula (8). A-OH (7) [The symbol A in the general formula (7) is the same as the content of the general formula (1). ] C _m F _2m (8) [repeating number m in the general formula (8) is an integer from 2 to 12. ]