JPH0822828B2 - Fluorine-containing alkenyl ether compound - Google Patents

Description

TECHNICAL FIELD The present invention relates to a polyvalent fluorine-containing alkenyl ether compound which is novel and useful as a raw material for synthesizing various fluorine-containing compounds.

(Problems to be Solved by Prior Art and Invention) Conventionally, a fluorine-containing compound comprising a perfluoroalkyl group and an alkenyl group has been used as a raw material for many useful compounds by utilizing a reactive alkenyl group. . For example, it is used for synthesizing a fiber treating agent by copolymerizing with another monomer. In addition, it is oxidized with peracid to introduce an epoxy group into an alkenyl group, and as a raw material for synthesizing an epoxy compound having a perfluoroalkyl group, further silylation of the alkenyl group is performed to synthesize a silane compound having a perfluoroalkyl group. Widely used as a raw material.

Examples of such a fluorine-containing compound having a perfluoroalkyl group and an alkenyl group include, for example, US Pat.
No. 382,222 In the specification of US Pat. No. 4,029,867, a compound represented by the following formula CF _3- (CF ₂ ) _a OCH ₂ CH = CH ₂ (a is an integer between _{2 and} 13) In addition, the compound represented by the following formula in U.S. Pat. Compounds represented by are described. These known compounds are fluorine-containing compounds having a simple perfluoroalkyl group having a relatively small number of carbon atoms and one alkyl group in the molecule. These compounds as they are, or after epoxidation and silylation, are treated with fiber treatment agents, water and oil repellents,
It is only used as a coating agent.

In view of these points, the present invention acts as an effective cross-linking agent after epoxidation or silylation or when it is copolymerized with another monomer as it is, and is highly cross-linked when it is simply polymerized. The purpose is to obtain a fluorine-containing compound that gives a polymer.

Then, as a result of repeated studies for achieving the above object, the present inventors have succeeded in producing a novel fluorine-containing alkenyl ether compound having 2 to 4 alkenyl groups in one molecule through an ether bond. They have succeeded, and have found that the compound is a compound that achieves the above object, and completed the present invention.

That is, the present invention provides the following general formula [I] Rf- (CF ₂ OR) _n [I] Is a fluorinated alkenyl ether compound represented by.

In the general formula [I], Rf may be any group as long as it is a divalent to tetravalent perfluoro organic group. However, -CFYO which Rf is described later _{(CF 2 CFYO) y (CF} 2) x (OCFYCF 2) z OCFY- (Y is a fluorine atom or a perfluoroalkyl group, x is an integer of 1 or more, y and z is an integer greater than or equal to 0.), except when y + z = 0, 1 or 2. Particularly preferred groups in the present invention are groups represented by the following general formula.

Among the divalent to tetravalent perfluoroorganic groups represented by the above general formula, the perfluoroalkyl group represented by Y preferably has 1 to 4 carbon atoms from the viewpoint of easy availability of raw materials. Further, x may be an integer of 1 or more, but is preferably in the range of 1 to 7, and y and z may be an integer of 0 or more, but is generally in the range of 0 to 3. preferable.

Next, in the general formula [I], R is an alkenyl group without any limitation. Generally, an alkenyl group having 3 to 8 carbon atoms is preferable. For example, the following general formula The alkenyl group represented by is preferably used in the present invention. The alkyl group in the above formula is not particularly limited in carbon number, but generally has 1 to 3 carbon atoms for reasons such as easy availability of raw materials and easy synthesis of the compound of the present invention.
It is preferably in the range of.

The compound represented by the above general formula [I] of the present invention is a novel compound, and its structure can be confirmed by the following means.

(A) By measuring an infrared absorption spectrum (hereinafter abbreviated as IR), it is possible to know the specific atomic group existing in the compound represented by the above general formula [I] of the present invention.

As typical examples of the compound represented by the above general formula [I] of the present invention, 1,5-bis (2-propenoxy) -1,1,2,2,3,
An IR chart of 3,4,4,5,5-decafluoropentane is shown in FIG.

(B) ¹⁹ F-the magnetic resonance spectrum (hereinafter abbreviated as ¹⁹ F-NMR) (trichlorofluoromethane standard; high magnetic field side is defined as positive and expressed in ppm) to obtain the above general formula [I] The binding mode of the fluorine atom present in the compound represented by can be known. In addition, ¹ H-nuclear magnetic resonance spectrum (hereinafter, abbreviated as ¹ H-NMR) (tetramethylsilane standard; low magnetic field side is positive and expressed in ppm) to measure hydrogen atoms present in the compound. You can know the binding mode of.

As typical examples of the compound represented by the above general formula [I] of the present invention, 1,5-bis (2-propenoxy) -1,1,2,2,3,
The ¹⁹ F-NMR chart for 3,4,4,5,5-decafluoropentane is shown in FIG. 2, and the ¹ H-NMR chart is shown in FIG.

(C) A composition formula corresponding to each observed peak (generally, a value represented by M / e obtained by dividing the ion mass M by the charge number e of the ion) by measuring a mass spectrum (hereinafter abbreviated as MS) By calculating, it is possible to know the molecular weight of the compound used for the measurement and the binding mode of each atomic group in the molecule.

(D) By elemental analysis, each weight% of carbon, hydrogen, and halogen is obtained, and the weight% of oxygen can be calculated by subtracting the sum of the weight% of each recognized element from 100. Therefore, the composition formula of the compound can be determined.

The present invention also provides a new method for producing a novel compound represented by the general formula [I]. The aforementioned U.S. Patent 3,382,222
Fluorine-containing compounds having a perfluoroalkyl group and an alkenyl group described in the specification and British Patent 1,153,187 are fluoroketones and alkenyl halides,
Alternatively, there is no report that it was synthesized by a reaction of an alkali metal salt of a perfluoro tertiary alcohol with an alkenyl halide, or a reaction of a perfluorocarboxylic acid fluoride with an alkenyl halide. As a result of studying the reaction between an acid fluoride compound and an alkenyl halide compound, the present inventors have found that a fluorinated alkenyl ether compound is surprisingly easily and efficiently produced, and completed the production method of the present invention.

Hereinafter, the production method will be described, but the novel compound represented by the general formula [I] of the present invention may be synthesized by other methods without depending on the production method of the present invention.

The production method of the present invention has the following general formula [II] Rf- (COF) _n [II]. And an acid fluoride compound represented by the following general formula [III] RX [III] Is a method of reacting with an alkenyl halide compound represented by

In the above general formula [II], as Rf, a divalent to tetravalent perfluoro organic group is adopted without any limitation. Generally, from the viewpoint of easiness of synthesis of the acid fluoride compound represented by the above general formula [II], various divalent to tetravalent perfluoro organic groups described in the explanation of the general formula [I] are preferable. The above general formula [II]
The acid fluoride compound represented by can be synthesized by a known method. The specific method is as follows, for example.

Of the divalent acid fluoride compounds, those represented by FOC (CF ₂ ) _{x + 1} COF may be commercially available products, or may be produced by a method such as electrolytic fluorination.
The divalent acid fluoride compound represented by (CF ₂ ) _{x + 1} COF is
further Other divalent acid fluoride compounds can be obtained by reacting with other perfluoroalkylene oxides. For example, in the case of FOC (CF ₂ ) ₂ COF, the following is obtained.

[However, y and z are integers of 0 or more] The divalent acid fluoride compound can also be produced by the following method. Monovalent carboxylic acid fluoride compound represented by the following formula: C ₁ F _{2l + 1} COF [l is an integer of 1 or more. ] Or [Y is a fluorine atom or a perfluoroalkyl group,
x is an integer of 0 or more, and y is an integer of 0 or more. ] And an epoxy compound represented by the following formula [IV] [However, R'is an alkyl group. ] And as a fluorine ion-generating compound, NaF, KF, CsF, Rb
In the presence of F, AgF, N (CH ₃ ) ₄ F, etc., in the presence of diglyme, triglyme, tetraglyme and other glymes, and acetonitrile, sulfolane, dimethylformamide and other non-ptronic polar solvents at a temperature of -20 to 80 ° C. The compound shown below is obtained by reacting under several hours to several days.

Is obtained, and In Case of, Is obtained. These compounds are represented by the general formula as follows:

By further reacting the obtained compound with a Lewis acid catalyst such as SbF ₅ at room temperature to 150 ° C. for several hours to several days, the —CF ₂ OR ′ group can be converted to a —COF group. This reaction is generally represented by the following reaction formula.

A divalent acid fluoride compound can be obtained by the above reaction.

There are many possible methods for producing the trivalent acid fluoride compound. For example, an epoxy compound represented by the general formula [IV] is added to one -COF group of a divalent acid fluoride compound (generally represented by FOCR ″ _f COF, where R ″ _f is a perfluoro organic group). A trivalent acid fluoride compound can be obtained in the same manner as in the reaction formula [I] by reacting with the above-mentioned method and further reacting with the above-mentioned Lewis acid such as SbF ₅ .

 The reaction is as follows.

As another method, a dimer is prepared from an epoxy compound represented by the general formula [IV] by using a fluorine anion as a catalyst, and the dimer is further reacted with a Lewis acid catalyst such as SbF ₅ according to the reaction formula [I]. A trivalent acid fluoride compound can be obtained. The reaction is as follows.

Further, a tetravalent acid fluoride compound is produced by reacting both -SOF groups of FOCR ″ _f COF with an epoxy compound represented by the general formula [IV], and further reacting with a Lewis acid catalyst such as CbF ₅ mentioned above. The reaction is as follows.

Next, the other raw material of the compound represented by the general formula [I] of the present invention is an alkenyl halide compound represented by the general formula [III]. In the general formula [III], R
As the alkenyl group represented by, a hydrocarbon group having a double bond is employed without any limitation, but from the viewpoint of reactivity with the acid fluoride compound represented by the general formula [II], it has 3 to 8 carbon atoms. Alkenyl groups are preferred. Among them, the alkenyl group specifically described for the general formula [I] is particularly preferable. Further, in the above general formula [III], each atom of fluorine, chlorine, bromine, or iodine can be used as X without any limitation.

Specific examples of the alkenyl halide compound preferably used in the present invention are as follows. Examples include allyl chloride, allyl bromide, allyl iodide, crotyl chloride, crotyl bromide, crotyl iodide, prenyl chloride, prenyl bromide, prenyl iodide, methallyl chloride, methallyl bromide, and methallyl iodide. it can.

The above-described acid fluoride compound and alkenyl halide compound are reacted in the presence of fluorine ions. Fluoride ions are obtained by a fluoride ion generating compound.

As the fluorine ion-generating compound, the following formula The compound represented by is preferably used. The amount of fluorine ions present is not particularly limited and is adopted from a wide range,
Generally, the equivalent to the -COF group of the acid fluoride compound
A range of 4 equivalents is preferred.

The reaction ratio between the acid fluoride compound and the alkenyl halide compound in the above-mentioned raw materials is not particularly limited, but usually, the alkenyl halide compound is used in the range of equivalent to 4 times equivalent to the -COF group of the acid fluoride compound. preferable.

The above raw materials are reacted with an aprotic polar solvent, for example, glymes such as diglyme, triglyme, tetraglyme; acetonitrile; sulfolane; dimethylformamide, etc., at room temperature to about 200 ° C. for several hours to several days. By doing so, the fluorinated alkenyl ether compound of the present invention can be obtained.

(Effect) The fluorine-containing alkenyl ether compound of the present invention is a compound useful as a raw material for producing various fluorine-containing compounds. For example, by generally epoxidizing an alkenyl group with peracid, etc. [Rf and n are the same as those in the above general formula [I]. ] The polyvalent epoxy compound shown by these can be obtained. Also, if epoxidation is partially performed [However, p + q = n, and Rf and n are the same as those in the above general formula [I]. ] The compound can also be obtained. Any of these compounds can be a raw material for synthesizing a new epoxy resin. Further, the compound having 1 to 4 silyl groups can be derived by performing hydrosilation on the alkenyl group using chloroplatinic acid or the like as a catalyst. Further, from this compound, a high molecular weight compound can be derived by hydrolysis similarly to the usual organohalogenosilane. Unlike ordinary silicone polymers, this high molecular weight compound has a high fluorine content and is highly crosslinked, so it has good heat resistance, low temperature characteristics and mechanical characteristics, as well as good electrical characteristics. It has various characteristics such as

(Examples) In order to more specifically describe the present invention, examples will be described below, but the present invention is not limited to these examples.

Example 1 11.6 g of anhydrous KF, 60 ml of dry diglyme, 12.2 g of allyl bromide and 12.3 g of perfluoroglutaryl fluoride were placed in a 100 ml autoclave and then heated at 100 ° C. for 67 hours while stirring. After completion of the reaction, the reaction solution was filtered and the filtrate was distilled to obtain 10.7 g of a fraction at 121 to 123 ° C / 10 mmHg.
The structures of the compounds of the fraction ^{is, IR, 19 -NMR, 1 H} -NMR, it is _{CH 2 = CHCH 2 OCF 2 CF} 2 CF 2 CF 2 CF 2 OCH 2 CH = CH 2 is the MS and elemental analysis confirmed.

(A) IR (Chart is shown in Fig. ¹ ) 1660,980,915Cm ^-1 (-CH ₂ CH = CH ₂ ) 1050 to 1400cm ^-1 (-CF _2- ) (b) ¹⁹ F-NMR, ¹ 1 H-NMR (Charts are shown in FIGS. 2 and 3) (C) MS M / e 364 M ⁺ (Molecular ion peak) M / e 323 M ⁺ -(CH ₂ CH = CH ₂ M / e 41 ₊ CH ₂ CH = CH ₂ Example 2 (a) Stirrer, -20 200 ml of dry tetraglyme and 1.6 g of anhydrous KF were placed in a 500 ml three-necked flask equipped with a reflux condenser having a temperature of ℃ and a dropping funnel.
Cooled to After 90.0 g was added dropwise over 30 minutes, stirring was continued for 16 hours.

The condenser of the reactor was removed, a distillation apparatus was attached, and a fraction having a boiling point of 79 ° C / 26 mmHg was obtained by distillation. The structure of the fraction was determined by IR, ₁₉ F-NMR, ¹ H-NMR, MS, and elemental analysis. Was confirmed.

(A) IR 2900,3000,3030cm ^-1 (-CH ₃ ) 1890cm ^-1 (-COF) (b) MS (B) A condenser, a dropping funnel, and a stirrer were attached.
Crytox AZ with 5.0 g SbF _{5 in a} 200 ml three-necked flask
After adding 70 ml of (brand name ... made by DuPont), cool the reactor to 0 ° C, 76.0 g was added dropwise over 20 minutes. After the dropping was completed, the temperature was gradually raised and the temperature was elevated to 80 ° C. Gas started to be generated from the reaction solution at 60 ° C. As a result of analysis, this gas was CH ₃ F. After continuing stirring at 100 ° C for 4 hours, distill directly from the reactor. I got The structure of the compound was confirmed by IR, ¹⁹ F-NMR, MS and elemental analysis.

(A) IR 1885 cm ^-1 (-COF) (b) ¹⁹ F-NMR (C) MS (C) In a 200 ml autoclave, 32.0 g of anhydrous KF, 80 ml of dry diglyme, 80.0 g of allyl bromide and Put 39.6g, react at 120 ℃ for 24 hours, 33.2g was obtained. The structure of the compound is IR, ¹⁹ F-NMR, ¹ H-NMR, M
S, confirmed by elemental analysis.

(A) IR 1660,995,910 cm ^-1 (-CH ₂ CH = CH ₂ ) 1050 to 1400 cm ^-1 (-CF _2- ) (b) ¹⁹ F-NMR, ¹ H-NMR (C) MS M / e 468 M ⁺ (molecular ion peak) M / e 41 ⁺ CH ₂ CH = CH ₂ Example 3 (a) 300 ml equipped with a stirrer, a reflux condenser at a temperature of -20 ° C, and a dropping funnel. 150 ml of dried tetraglyme and 12.0 g of anhydrous KF were placed in the three-necked flask. 0 reactor
Cooled to ℃, perfluoroglutaryl fluoride 30.g
Was added dropwise over 10 minutes, and the mixture was further stirred for 1 hour to sufficiently generate alkoxide.

While keeping the reactor at 0 ° C 44,2 g was gradually added dropwise over 30 minutes. After completion of dropping, the mixture was stirred for 2 hours, the temperature of the reactor was raised to room temperature, and the mixture was further stirred for 6 hours.

Remove the condenser of the reactor, attach the distillation device, and 38.6 g was obtained. The structure of the compound is IR, ¹⁹ F-NMR, ¹ H-NM.
It was confirmed by R, MS and elemental analysis.

(A) IR 3030,3000,2900cm ^-1 (-CH ₃ ) 1880cm ^-1 (-COF) (b) MS (B) Using a method similar to that described in detail in Example 2- (b), From I got The structure of the compound was confirmed by IR, ¹⁹ F-NMR, MS and elemental analysis.

(A) IR 1890cm ^-1 (-COF) (b) ¹⁹ F-NMR (C) MS (C) Using a method similar to that described in detail in Examples 1 and 2- (c), From I got The structure of the compound was confirmed by IR, ¹⁹ F-NMR, ¹ H-NMR, MS and elemental analysis.

(B) IR 1660,990,915cm ^-1 (-CH ₂ CH = CH ₂ ) 1050 to 1400c ^-1 (-CF _2- ) (b) MS M / e 511 ⁺ (CF ₂ ) ₅ OCF (CF ₂ OCH ₂ CH = CH ₂ ) ₂ M / e 245 ⁺ CF (CF ₂ OCH ₂ CH = CH ₂ ) ₂ Example 4 In Example 1, 12.5 g of methallyl chloride was used instead of allyl bromide, and anhydrous KF10.0 g, per Reaction was performed in the same manner as in Example 1 except that 10.5 g of fluoroglutaryl fluoride was used. I got The structure of the compound was confirmed by IR, ¹⁹ F-NMR, ¹ H-NMR, MS and elemental analysis.

(A) IR (B) MS Example 5 In the same manner as in Example 1, the results of the reaction of perfluoroglutaryl fluoride and allyl bromide with various fluorides are shown in Table 1.

Example 6 In the same manner as in Example 1, the reaction of perfluoroglutaryl fluoride with various alkenyl halides in the presence of KF is shown in Table 2.

Example 7 The fluorine-containing alkenyl ether compounds shown in Table 3 were synthesized by the same method as described in detail in Examples 1 to 4. Table 3 also shows the results of characteristic absorption and MS in the infrared absorption spectrum of the synthesized fluorine-containing alkenyl ether compound.

[Brief description of drawings]

1, 2 and 3 are the infrared absorption spectrum, ¹⁹ F-nuclear magnetic resonance spectrum and ¹ H-nuclear magnetic resonance spectrum of the compound obtained in Example 1, respectively, and FIG. FIG. 5 shows the infrared absorption spectrum and ¹⁹ F-nuclear magnetic resonance spectrum of the compound obtained in Example 2, respectively.

Claims (1)

[Claims] (1) General formula Rf- (CF ₂ OR) _n A fluorine-containing altinyl ether compound represented by: