JP2563960B2 - Fluorine-containing ether compound and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel fluorine-containing ether compound, a fluorine-containing silyl compound, and a method for producing them.

(Problems to be Solved by Prior Art and Invention) Conventionally, a fluorine-containing compound composed of a fluorine-containing alkyl 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. Also, as a raw material for the synthesis of an epoxy compound having a fluorine-containing alkyl group by introducing an epoxy group into an alkenyl group by oxidation with peracid, further silylation of the alkenyl group to synthesize a silane compound having a fluorine-containing alkyl group. Widely used as a raw material.

Examples of the fluorine-containing compound having such a fluorine-containing alkyl group and an alkenyl group include, for example, U.S. Pat.
The following formula in the specification No. 222 In the compound is shown, also, U.S. Patent 4,029,867 Pat equation _{CF 3 - (CF 2) a} OCH 2 = CH = CH 2 (a is an integer between 2 to 13) Further, the compound represented by the following formula, in the British Patent 1,153,187 Compounds represented by are described. These known compounds are fluorine-containing compounds having a simple structure having a relatively small number of carbon atoms and a fluorine-containing organic group and one alkenyl group in the molecule.

On the other hand, a silyl compound having a fluorine-containing organic group in the molecule is used as a raw material compound for various useful materials that make use of the characteristics of the fluorine-containing organic group and the silyl group. For example, a dehydration condensate of trifluoropropylmethyldihydroxysilane is commercially available as a solvent-resistant and heat-resistant silicone oil. In addition, U.S. Pat. It has been proposed to use the compound represented by as a raw material for a water-repellent and oil-repellent treatment agent for woven fabric. In addition, JP-A-62-4760
No. 5 discloses that a compound represented by the following formula CF ₃ OCF (CF ₃ ) CH ₂ O (CH ₂ ) ₃ Si (CH ₃ ) Cl ₂ is copolymerized with other silyl compounds and then used as a cladding material for optical fibers. Proposed to be used.

However, known compounds having an alkenyl group or a silyl group together with the above-mentioned fluorine-containing organic group, the adhesive strength is not necessarily strong when used as a surface-treating agent, and when polymerized, The polymer has a drawback that the mechanical strength is not always sufficient.

(Means for Solving Problems) In view of the above points, the inventors of the present invention act as an effective cross-linking agent when copolymerized with another monomer, and when the monomer is polymerized alone, it is highly advanced. When a cross-linked polymer was given to the above, and when used as a surface treatment agent, further intensive studies were conducted for the purpose of obtaining a fluorine-containing compound having strong adhesion to a substrate. As a result, 2-4 in one molecule
The present inventors succeeded in producing a novel fluorine-containing ether compound having alkenyl groups and found that the compound achieves the above object. Further, from the above-mentioned fluorine-containing ether compound, a novel fluorine-containing silyl compound having 2 to 4 silicon atoms in one molecule has been successfully produced, and the compound is also a compound which achieves the above object. I found things and came to complete the present invention.

That is, the present invention provides the following general formula [I] RfOCFHCF ₂ OR) _n [I] The following general formula [II] RfOCFHCF ₂ OR'SiR ₁ R ₂ R ₃ ) _n [II] produced from the fluorine-containing ether compound represented by the formula and the compound of the above general formula [I] Is a fluorinated silyl compound.

First, the fluorine-containing ether compound represented by the above general formula [I] will be described.

In the above general formula [I], Rf may be any group as long as it is a divalent to tetravalent fluorine-containing organic group, but a preferable group is a group represented by the following general formula. Is.

Divalent group: CF ₂ CFYO) _y (CF ₂ ) _{x + 1} (OCFYCF _{2 z} , CH ₂ ) _{y + 1} (CF ₂ ) _x (CH _{2 z + 1} , Trivalent group: Tetravalent group: In the present invention, in at least one divalent to tetravalent perfluoroorganic group represented by the above general formula, the perfluoroalkyl group represented by Y is a C1-4 perfluoroalkyl group, x Is an integer in the range of 1 to 7, and y and z are integers in the range of 0 to 3.

Next, in the general formula [I], the alkenyl group represented by R is not particularly limited, but in the present invention, it is an alkenyl group having 2 to 18 carbon atoms. For example,
General formula (A) Alternatively, the general formula (B) The alkenyl group represented by is preferably used in the present invention. The alkyl group represented by A ¹ , A ² , A ³ , A ⁴ and A ⁵ in the above formula has a carbon number in the range of 1 to 3 for reasons such as ease of synthesis of the compound of the present invention. That is, when all of A ¹ , A ² and A ^{3 in the} general formula (B) are hydrogen atoms, the alkenyl group can have 2 carbon atoms. In addition, all of A ¹ , A ² , A ³ , A ⁴ and A ^{5 in the} general formula (A) have 3 carbon atoms.
When it is an alkyl group of, the carbon number of the alkenyl group is
Can take 18.

In the general formula [I], the alkyl group represented by R is not particularly limited, but in the present invention, it has 1 carbon atom.
~ 6 alkyl groups are used. Further, the alkyl group may have a fluorine atom, a chlorine atom, a bromine atom and an iodine atom in the group, and it does not matter at all. In the general formula [I],
Examples of the alkyl group suitably represented by R are methyl group, ethyl group, 2-bromoethyl group, 2
-Chloroethyl group, n-propyl group, isopropyl group, 3-
Trifluoro-n-propyl group, 2-chloro-n-propyl group, 2-bromo-n-propyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group and n-hexyl group Etc.

Further, in the general formula [I], the aryl group represented by R is not particularly limited, but an aryl group having a carbon number of 6 to 12 is generally preferable because of easy availability of raw materials and the like. In addition, R is a phenyl group or a naphthyl group.

In the general formula [I], n can be an integer of 2-4.

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) Infrared absorption spectrum (hereinafter abbreviated as IR)
It is possible to know the specific atomic group present in the compound represented by the general formula [I] of the present invention by measuring.

As a representative example of the compound represented by the above general formula [I] of the present invention, IR chart of the compound represented by the following formula CH ₂ = CHCH ₂ OCF ₂ CFHOCF ₂ CF ₂ OCFHCF ₂ OCF ₂ CH = CH ₂ is shown in FIG. It was shown to.

(B) ¹⁹ F-nuclear magnetic resonance spectrum (hereinafter, ¹⁹ F-NMR
Is abbreviated. ) (Trichlorofluoromethane standard; expressed in ppm with the high magnetic field side being positive), the binding mode of the fluorine atom present in the compound represented by the general formula [I] 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.

Typical examples of the general formula (I) compounds represented by the present invention, the ¹⁹ F-NMR Chiyato of the compound represented by the following formula _{CH 2 = CHCH 2 OCF 2 CFHOCF} 2 CF 2 OCFHCF 2 OCH 2 CH = CH 2 In Figure 2, ¹ H-
The NMR chart is shown in FIG.

(C) Composition formula corresponding to each observed peak (generally represented by M / e obtained by dividing ion mass M by the charge number e of ions) 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, the weight% of carbon, hydrogen, and halogen can be obtained, and the weight% of oxygen can be calculated by subtracting the sum of the weight% of each recognized element from 100. The composition formula of the compound can be determined.

The present invention also provides a method for producing the novel compound represented by the general formula [I]. Hereinafter, the production method will be described, but the novel compound represented by the above general formula [I] of the present invention may be synthesized by another method without depending on the production of the present invention.

The method for producing the compound represented by the above general formula [I] of the present invention includes the following general formula [III] RfOCF = CF ₂ ) _n [III] And a fluorine-containing vinyl ether compound represented by the following general formula [IV] R-OM [IV] Is a method of reacting the alkoxide compound represented by and contacting the obtained reaction product with alcohol or water.

In the above general formula [III], a fluorine-containing organic group having a valence of 2 to 4 is adopted as Rf without any limitation. In the method for producing the novel compound represented by the general formula [I] of the present invention, Rf is represented by the general formula of the present invention because of the ease of synthesizing the fluorine-containing vinyl ether compound represented by the general formula [III]. It is the same as Rf in the novel compound represented by the formula [I]. The fluorine-containing vinyl ether compound represented by the general formula [III] may be synthesized by any method. Hereinafter, a synthesis example of the fluorine-containing vinyl ether compound represented by the general formula [III] will be described.

Among the divalent fluorine-containing vinyl _{ether, CF 2 = CFO (CF 2} CFYO) y (CF 2) x + 1 (OCFYCF 2) z OCF = CF
₂ (provided that Y is F or a perfluoroalkyl group having 1 to 4 carbon atoms, x is an integer of 1 to 7, and y and z are 0
Is an integer of ˜3. ) Is (However, x is an integer of 1 to 7.) Tetrafluoroethylene oxide (hereinafter, abbreviated as TFEO) is reacted with a divalent acid fluoride compound and then hexafluoropropylene oxide (hereinafter, referred to as TFEO). , HFPO). It can be obtained by directly reacting HFPO with a divalent acid fluoride compound represented by and then thermally decomposing it. For example, In the case of, the following is obtained.

[However, Y is F or a perfluoroalkyl group having 1 to 4 carbon atoms, and y and z are integers of 0 to 3. 〕Also,
Of the fluorine-containing vinyl ether compound represented by the general formula [III], CF ₂ = CFO (CH ₂ ) _{y + 1} (CF ₂ ) _x (CH ₂ ) _{z + 1} OCF = CF ₂ (where x is 1 to 7 is an integer of 7, and y and z are integers of 0 to _3. ) is represented by HO (CH ₂ ) _{y + 1} (CF ₂ ) _x (CH ₂ ) _{z + 1} OH 2 It can be obtained by converting a hydric alcohol into an alkoxide with an alkali metal or an alkali metal hydride and then reacting it with tetrafluoroethylene.

Further, the divalent fluorine-containing vinyl ether compound can also be produced by the following method. That is, a monovalent carboxylic acid fluoride compound ZClF ₂ lCOF represented by the following formula [Z is a halogen atom or a hydrogen atom, and l is an integer of 1 or more. ] Or [Y is a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, Z is a halogen atom or a hydrogen atom,
x is an integer of 1 to 7 and y is an integer of 0 to 3. ] And an epoxy compound represented by the following formula [V] [However, R ″ is an alkyl group.] As NaF, KF, CsF, RbF, A
Climes such as diglyme, triglyme, and tetraglyme in the presence of gF, N (CH ₃ ) ₄ F, etc .; acetonitrile;
Sulfolane; by reacting in an aprotic polar solvent such as dimethylformamide at a temperature of −20 to 80 ° C. for several hours to several days, the compound shown below is obtained.

In the case of ZClF ₂ COF 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 a temperature of room temperature to 150 ° C. for several hours to several days, the —CF ₂ OR ″ group can be converted to a —COF group. The reaction is generally represented by the following reaction formula (I).

Thus obtained divalent acid fluoride compound
By reacting with HFPO and then thermally decomposing, a divalent fluorine-containing vinyl ether compound can be obtained.

Next, many methods are conceivable for producing a trivalent compound in the fluorine-containing vinyl ether compound represented by the general formula [III]. For example, one of the divalent acid fluoride compounds (generally represented by FOCR ″ fCOF, where Rf ″ is a fluorine-containing organic group) is the epoxy compound represented by the general formula [V] as described above. The trivalent acid fluoride compound can be obtained in the same manner as in the reaction formula (I) by reacting with the above method and further reacting with the above-mentioned Lewis acid such as SbF ₅ .

 The reaction is as follows.

Further, a dimer is prepared from an epoxy compound represented by the general formula [V] by using a fluorine anion as a catalyst, and the dimer is converted to a trivalent acid by a Lewis acid catalyst such as SbF ₅ according to the reaction formula (I). A fluoride compound can be obtained. The reaction is as follows.

The trivalent acid fluoride compound thus obtained is reacted with HFPO and then thermally decomposed to obtain a trivalent fluorine-containing vinyl ether compound.

Further, in the fluorine-containing vinyl ether compound represented by the above general formula [III], the tetravalent compound is FOCR ″ fCOF
A tetravalent acid fluoride compound can be obtained by reacting a COF group with an epoxy compound represented by the general formula [V] and further reacting with the Lewis acid catalyst such as SbF ₅ mentioned above. It can be obtained by reacting an acid fluoride compound with HFPO and then thermally decomposing it. 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 alkoxide compound represented by the general formula [IV]. In the above general formula [IV], R represents an alkenyl group having 2 to 18 carbon atoms, an alkyl group having 1 to 6 carbon atoms, a phenyl group or a naphthyl group. In addition, the general formula [I
V], as the alkali metal represented by M, lithium, sodium, potassium, rubidium and cesium are used without any limitation.

The alkoxide compound represented by the general formula [IV] is
A commercially available product can be used as it is. Further, when the alkoxide compound is synthesized, the reaction mixture obtained in the synthetic reaction can be used as it is.

The reaction between the fluorine-containing vinyl ether compound represented by the general formula [III] and the alkoxide compound represented by the general formula [IV] is carried out in the presence or absence of a solvent. When using a solvent, an aprotic solvent can be used without any limitation. For example, ether, tetrahydrofuran, diglyme, tetraglyme, acetonitrile, dimethylformamide, benzene, toluene,
Xylene etc. can be used conveniently.

In the reaction for producing the compound represented by the general formula [I], the alkoxide compound represented by the general formula [IV] is used in an amount of -OCF = CF of the fluorine-containing vinyl ether compound represented by the general formula [III]. _For 1 equivalent of ₂ units, 0.
A range of 05 to 4 equivalents, preferably 0.1 to 2 equivalents is suitable. However, when the alkoxide compound represented by the general formula [IV] is used in an amount of 1 equivalent or less relative to 1 equivalent of —OCF═CF ₂ group, the alcohol corresponding to the alkoxide compound described below is added to the above alkoxide compound in a sum. -OCF = CF ₂
It is preferable to add it to the reaction system in an amount of 1 equivalent or more relative to the group.

The reaction temperature can be selected from a wide range, and preferably-
It can be selected from the range of 20 ° C to 150 ° C. The reaction time is selected from the range of several minutes to several days, preferably 10 minutes to 5 days, though it depends on the amount ratio of the raw material compounds.

By contacting the reaction product obtained by the above reaction with alcohol or water, the fluorine-containing ether compound represented by the above general formula [I] of the present invention can be obtained.
The method of contacting with alcohol or water is not particularly limited and any method can be adopted. For example, a method of introducing the reaction mixture obtained by the above reaction into alcohol or water, a method of introducing alcohol or water into the reaction mixture obtained by the above reaction, and the like can be mentioned. In addition, the above general formula [II
The reaction product obtained by the reaction and the alcohol can also be contacted by reacting the compound represented by I] with the compound represented by the general formula [IV] in a solvent containing alcohol.

The alcohol used here preferably corresponds to the alkoxide compound represented by the general formula [IV]. The amount of alcohol or water used is usually selected from the range of 1 equivalent to an excess amount with respect to 1 equivalent of —OCF═CF ₂ group of the fluorine-containing vinyl ether compound represented by the general formula [III].

By such a reaction, the fluorine-containing ether compound represented by the above general formula [I] of the present invention can be obtained.

In the above general formula [I], when R is an alkyl group having a halogen, it is reacted with a base such as an ammonium compound or a metal hydroxide so that R is an alkenyl group. ] It can also be converted into the compound shown by.

The present invention also provides the fluorine-containing silyl compound represented by the general formula [II] and a method for producing the same.

In the general formula [II], Rf may be any group as long as it is a divalent to tetravalent fluorine-containing organic group. In the present invention, in the general formula [I] of the present invention, It is the same as Rf in the novel compound shown. In the general formula [II], R'may be an alkylene group without any limitation, but in the present invention, it is an alkylene group having 2 to 18 carbon atoms. For example,
General formula (C) Alternatively, the general formula (D) The alkylene group represented by is preferably used in the present invention. The alkyl group represented by A ¹ , A ² , A ³ , A ⁴ and A ⁵ in the above formula is not particularly limited in carbon number, but in the present invention, the compound of the present invention can be synthesized. The carbon number is in the range of 1 to 3 for reasons such as easiness. That is, when A ¹ , A ² and A ³ in the above formula (D) are all hydrogen atoms, the alkylene group may have 2 carbon atoms. When all of A ¹ , A ² , A ³ , A ⁴ and A ⁵ in the above formula (C) are alkyl groups having 3 carbon atoms, the alkylene group can have 18 carbon atoms.

Next, in the general formula [II], as the halogen atom represented by R ₁ , R ₂ and R ₃ , fluorine, chlorine, bromine and iodine are used. Further, in the general formula [II], R ₁ , R ₂ and R ₃
The alkyl group and the alkoxy group represented by are not particularly limited, but in the present invention, an alkyl group having 1 to 4 carbon atoms, for the reason of reactivity of the product,
It is an alkoxy group. The alkyl group and alkoxy group represented by R ₁ , R ₂ and R ₃ may be partially fluorinated. Specifically, as the alkyl group, a methyl group,
Examples thereof include ethyl group, propyl group, trifluoropropyl group, butyl group and trifluorobutyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a trifluoropropoxy group, a butoxy group and a trifluorobutoxy group.

Moreover, in the said general formula [II], n can take the integer of 2-4.

The fluorine-containing silyl compound represented by the general formula [II] of the present invention is a novel compound, and its structure is IR, ¹⁹ F-NMR,
^It can be confirmed by ¹ H-NMR, MS and elemental analysis.

As a typical example of the fluorine-containing silyl compound represented by the above general formula [II] of the present invention, the following formula In the compound represented by, in Figure 4 the IR Chiyato, ¹⁹
The F-NMR chart is shown in FIG. 5, and the ¹ H-NMR chart is shown in FIG.

The method for producing the compound represented by the general formula [II] of the present invention is not particularly limited and may be any method, for example, represented by the general formula [I] of the present invention. It can be easily derived from a compound in which R is an alkenyl group in the fluorine-containing ether compound. That is, the following general formula [VI] RfOCFHCF ₂ OR) _n [VI] The fluorine-containing ether compound represented by the following general formula [VI
I) HSiR ₁ R ₂ R ₃ (VII) The fluorinated silyl compound represented by the above general formula [II] of the present invention is reacted with a silane compound represented by the formula (hereinafter, this reaction is referred to as a hydrosilation reaction) and, if necessary, further hydrolyzed. The compound can be obtained.

The reaction and the starting compound in the production of the fluorine-containing silyl compound represented by the above general formula [II] of the present invention will be described in detail below.

The fluorinated alkenyl ether compound represented by the general formula [VI] is a compound of the novel compound represented by the general formula [I] of the present invention in which R is an alkenyl group having 2 to 18 carbon atoms. As explained.
Further, the silane compound represented by the general formula [VII],
Any compound having at least one hydrogen atom may be used, and commercially available products and compounds synthesized by known methods can be used without any limitation.

The method for the hydrosilylation reaction of the compound represented by the general formula [VI] of the present invention is not particularly limited, and a known method for hydrosilylating a compound having a double bond is generally used. A catalyst is preferably used for the hydrosilylation reaction. Any known catalyst can be used without any limitation. Specifically, organic peroxides such as dibenzoyl peroxide, dibutyl peroxide, dicumyl peroxide, butyl perbenzoate, butyl peracetate, and azoibisisobutyronitrile; chloroplatinic acid, iridium chloride, ruthenium chloride,
Examples include transition metal compounds such as platinum black; bases such as tetramethylethylenediamine and tributylamine. The amount of catalyst used in the reaction is generally the above general formula [V
^10-8 for the double bond present in the compound represented by [I]
To 0.3 equivalent, preferably 10 ^{−6 to} 0.2 equivalent. The compound represented by the general formula [VII] is preferably used in the range of 1.0 to 4.0 equivalents with respect to the double bond present in the compound represented by the general formula [VI]. The reaction can be carried out with a catalyst which is substantially inactive to the compounds represented by the general formula [VI] and the general formula [VII] and the catalyst, or without a solvent. Furthermore, the reaction temperature in the reaction is generally 50 to 300 ° C,
It is preferably selected from the range of 80 to 200 ° C. The reaction time is 1 minute to 2 days, preferably 5 minutes to 24 hours.

The fluorine-containing silyl compound of the present invention can be produced by the method described above and then converting the substituent of the silicon atom. For the conversion of the substituent of the silicon atom, a known method can be adopted without any limitation.
For example, a halogen atom and an alkoxy group bonded to a silicon atom can be converted into a hydroxyl group by hydrolysis. Further, the halogen atom bonded to the silicon atom is converted into an alkoxy group by a reaction with an alcohol, an alkyl group by a reaction with a carbon nucleophile such as a Grignard reagent, and a hydrogen atom by a reducing agent such as lithium aluminum hydride. It can be converted into an atom. Further, the hydrogen atom bonded to the silicon atom can be converted into a halogen atom by a reaction with halogen or hydrogen halide.

(Effect) The fluorinated ether compound represented by the above general formula [I] of the present invention is a compound useful as a raw material for producing various fluorinated compounds. In the fluorine-containing silyl compound represented by the general formula [II], which is easily obtained from the fluorine-containing ether compound represented by the general formula [I] of the present invention, a halogen atom, a hydroxyl group or an alkoxy group is added to a silicon atom. The compound having a bond can be derived into a high molecular weight compound by a known method. 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 properties, mechanical properties, and electrical properties. It has many features such as certain features.

Further, when the surface of the fiber, resin, glass or the like is treated by the known method using the fluorine-containing silyl compound of the present invention represented by the above general formula [II], the reaction point is different from the usual fluorosilicone treating agent. Since it is often present, it firmly adheres to the base material, and since the fluorine-containing silyl compounds are highly cross-linked, the properties such as water and oil repellency derived from the fluorine atom or low refractive index can be maintained for a long time. It has features.

Further, the fluorine-containing silyl compound represented by the above general formula [II] of the present invention can be a raw material for synthesizing other useful compounds. For example, a fluorine-containing silyl compound having a hydrogen atom bonded to a silicon atom can be used as a novel hydrosilylation reaction agent.

(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 (a) To a 500 ml three-necked flask equipped with a stirrer and a dropping funnel, 17.5 g of NaH and 150 ml of dried tetraglyme were placed. The flask was placed in an ice bath and 100 g of allyl alcohol was added dropwise over 90 minutes while stirring. After completion of dropping, the mixture was slowly added dropwise _{CF 2 = CFOCF 2 CF 2 OCF} = CF 2 92.1g After stirring at 20 minutes ice cooling. After completion of dropping, the mixture was stirred for 1 hour, poured into ice water, and the organic layer was separated. The organic layer was dried over MgSO ₄ , filtered, and then distilled to obtain 88.1 g of a fraction of 113 to 116 ° C./15 mmHg. The structure of the compound of the fraction was confirmed by IR, ¹⁹ F-NMR, ¹ H-NMR, MS and elemental analysis to be (CH ₂ = CHCH ₂ OCF ₂ CFHOCF _{2 2} ).

B) IR (Chart is shown in Fig. ¹ ) 1655cm ^-1 (-CH ₂ CH = CH ₂ ) 1050 to 1300cm ^-1 (-CF _2- ) b) ¹⁹ F-NMR, ¹ H-NMR ( The chart is shown in FIGS. 2 and 3.) Chemical shift (e) 88.0,90.0ppm (f) 142.2ppm (h) 88.7ppm (a) 5.21ppm (b) 5.36ppm (c) 5.84ppm (d) 4.41ppm (g) 5.75ppm c) MS M / e 410 M ⁺ (Molecular ion peak) M / e 41 ⁺ CH ₂ CH = CH ₂ (b) In a Pyrex tube with an inner diameter of 25 mm (CH ₂ ＝ CHCH ₂ OCF ₂ CFHOCF _{2 2} 12.7 g, methyldichlorosilane 14.3 g and platinum chloride) 120 μ of 0.1 M isopropyl alcohol solution of acid was put and sealed, and then in an oil bath for 7.5 hours, 1
After heating at 00 ° C and opening, and distilling the contents,
As a result, 17.3 g of a fraction having a boiling point of 125 to 127 ° C / 0.3 mmHg was obtained. The structure of the compound of the fraction was determined by IR, ¹⁹ F-NMR, ¹ H-NMR, MS and elemental analysis. It was confirmed that

B) IR (chart is shown in Fig. 4) 2940,3000 cm ^-1 (-CH _2- ) 1050 to 1300 cm ^-1 (-CF _2- ) b) ¹⁹ F-NMR, ¹ H-NMR (fifth Charts are shown in Figures and 6.) Chemical shift (e) 88.2,89.8ppm (f) 142.2ppm (h) 88.7ppm (a) 0.76ppm (b) 1.0 to 1.3ppm (c) 1.7 to 2.2ppm (d) 3.96ppm (g) 5.74ppm c) MS Example 2 (a) 0.2 g NaH and 50 ml dry ether in a 300 ml flask equipped with a stirrer, reflux condenser and dropping funnel.
I put it in. The flask was placed in an ice bath, and 62.5 g of 2-bromoethanol was gradually added dropwise while stirring. After the dropping is completed,
Under ice cooling, CF ₂ = CFOCF ₂ CF ₂ OCF = CF ₂ 44.1 g was gradually added dropwise, the temperature was raised, and the mixture was refluxed for 48 hours. After completion of the reaction, the mixture was poured into ice water, the organic layer was separated, dried over MgSO ₄ , and purified by distillation. The structure of the compound is IR, ¹⁹ F-NMR, ¹ H-NMR, MS.
And elemental analysis confirmed that it was (BrCH ₂ CH ₂ OCF ₂ CFHOCF _{2 2} .

A) IR 3000cm ^-1 (-CH _2- ) 1050 to 1350cm ^-1 (-CF _2- ) b) ¹⁹ F-NMR, ¹ H-NMR Chemical shift (c) 88.2,89.8ppm (d) 142.3ppm (f) 88.7ppm (a) 3.39ppm (b) 4.20ppm (e) 5.77ppm c) MS M / e 107 ⁺ CH ₂ CH ₂ Br M / e 463 M ⁺ −Br (b) 200m equipped with stirrer and reflux condenser
10.3 g of KOH, 50 ml of methanol and (BrCH ₂ CH ₂ OCF ₂ CFHOCF _{2 2} 35.0 g) obtained in the above (a) were placed in a flask and refluxed for 8 hours. After completion of the reaction, the reaction mixture was poured into ice water, by distillation after separating the organic layer _{(CH 2 = CHOCF 2 CFHOCF 2} 2 13.2
g got. The structure of the compound was confirmed by IR, ¹⁹ F-NMR, ¹ H-NMR, MS and elemental analysis.

A) IR 1655cm ^-1 (-CH = CH ₂ ) 1050 to 1350cm ^-1 (-CF _2- ) b) ¹⁹ F-NMR, ¹ H-NMR Chemical shift (d) 88.0,90.0ppm (e) 142.2ppm (g) 88.7ppm (a) 4.61ppm (b) 4.90ppm (c) 6.56ppm (f) 5.81ppm c) MS M / e 93 ⁺ CF ₂ OCH = CH ₂ M / e 241 CH ₂ = CHOCF ₂ CFHOCF ₂ CF ₂ ⁺ (c) In the same manner as described in detail in Example 1- (b). I got The structure of the compound was confirmed by IR, ¹⁹ F-NMR, ¹ H-NMR, MS and elemental analysis.

A) IR 2950,2990 cm ^-1 (-CH _2- ) 1050 to 1350 cm ^-1 (-CF _2- ) b) ¹⁹ F-NMR, ¹ H-NMR Chemical shift (d) 88.1,89.8ppm (e) 142.2ppm (g) 88.7ppm (a) 0.79ppm (b) 1.59ppm (c) 4.21ppm (f) 5.76ppm Example 3 (a) Stirrer, -20 200 ml of dried 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 ° C and a dropping funnel. 5 reactors
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.

B) IR 2900,3000,3030cm ^-1 (-CH ₃ ) 1890cm ^-1 (-COF) b) MS M / e 181 CH ₃ OCF ₂ CF ₂ CF ₂ ⁺ M / e 81 ⁺ CF ₂ OCH ₃ (B) In a 200 ml three-necked flask equipped with a condenser, dropping funnel and stirrer, 5.0 g of SbF ₅ and Krytox AZ
(Product name: made by DuPont) After adding 70 ml, 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 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. Continue stirring at 100 ° C for 4 hours, then by direct distillation from the reactor. I got The structure of the compound was confirmed by IR, ¹⁹ F-NMR, MS and elemental analysis.

B) IR 1885cm ^-1 (-COF) b) ¹⁹ F-NMR Chemical shift (a) -23.7ppm (b) 118.9ppm (c) 82.9ppm (d) 117.4ppm (e), (f) -21.3ppm c) MS (C) 10 ml of dried tetraglyme, 1.0 g of anhydrous KF and 200 ml of glass autoclave Added 65.2g. After cooling to −78 ° C. and degassing the inside of the autoclave, the temperature was raised to −10 ° C., and 150 g of HFPO was introduced over 5 hours while stirring at −10 ° C. When the stirring was stopped, it was divided into two layers. Take out the lower layer and distill it 96g was obtained. The structure of the compound was confirmed by IR, ¹⁹ F-NMR, MS and elemental analysis.

B) IR 1890cm ^-1 (-COF) 1050 to 1400cm ^-1 (-CF _2- ) b) MS (D) 90 g of Huomblin YR (trade name: manufactured by Asahi Glass Co., Ltd.) as a diluent in a 100 ml three-necked flask equipped with a stirrer and a distillation device 76.3g was put. The pressure in the reactor was reduced to 3 mmHg, and the mixture was stirred at 200 ° C. for 1 hour to obtain 42.1 g of distillate. Purification by distillation to give 29.6g of _{CF 2 = CFOCF 2 CF 2 CF} 2 OCF (CF 2 OCF = CF 2) 2. The structure of the compound was confirmed by IR, ¹⁹ F-NMR, MS and elemental analysis.

B) IR 1845cm ^-1 (-OCF = CF ₂ ) 1050 to 1400cm ^-1 (-CF _2- ) b) MS M / e 341 ⁺ CF (CF ₂ OCF = CF ₂ ) ₂ M / e 247 CF ₂ = CFOCF ₂ CF ₂ CF ₂ ⁺ (e) 4.3 g of NaH and 50 ml of dry diglyme were placed in a 200 ml three-necked flask equipped with a stirrer and a dropping funnel. The flask was placed in an ice bath, and 35.0 g of allyl alcohol was gradually added dropwise. After completion of the dropwise _{addition, CF 2 = CFOCF 2 CF 2} CF 2 OCF After stirring 30 minutes under ice-cooling (CF ₂ OCF = CF ₂₎ was gradually added dropwise ₂ 32.3 g. After the dropping, the temperature is raised to 1 at room temperature.
After stirring for a period of time, pour into ice water and separate the organic layer.
Dried with SO ₄ . Then, 27.3 g of CH ₂ = CHCH ₂ OCF ₂ CFHOCF ₂ CF ₂ CF ₂ OCF (CF ₂ OCFHCF ₂ OCH ₂ CH = CH ₂ ) ₂ was obtained by distillation. The structure of the compound is IR, ¹⁹ F-NMR, ¹ H-NMR, M
Confirmed by S and elemental analysis.

B) IR 1655cm ^-1 (-CH ₂ CH = CH ₂ ) 1050 to 1400cm ^-1 (-CF _2- ) b) MS M / e 441 ⁺ CF (CF ₂ OCFHCF ₂ OCH ₂ CH = CH ₂ ) ₂ M / e 41 ⁺ CH ₂ CH = CH ₂ (f) By the same method as described in detail in Example 1- (b), CH ₂ = CHCH ₂ OCF ₂ CFHOCF ₂ CF ₂ CF ₂ OCF (CF ₂ OCFHCF ₂ OCH ₂ CH = CH _{2) 2} and Cl ₃ Si (CH ₂ from _{HSiCl 3) 3 OCF 2 CFHOCF 2} CF 2 CF 2 OCF _{[CF 2 OCFHCF 2 O (CH 2} ) 3 SiCl 3 ] to give _2. The structure of the compound was confirmed by IR, ¹⁹ F-NMR, ¹ H-NMR, MS and elemental analysis.

B) IR 2940,2990cm ^-1 (-CH _2- ) 1050 to 1400cm ^-1 (-CF _2- ) b) MS M / e 709 ⁺ CF (CF ₂ OCFHCF ₂ O (CH ₂ ) ₃ SiCl ₃ ) ₂ M / e 133 ⁺ SiCl ₃ Example 4 (a) 150 ml of dried tetragram and anhydrous KF12.0 were put into a 300 ml three-necked flask equipped with a stirrer, a reflux condenser at a temperature of -20 ° C and a dropping funnel. 0 reactor
Cool to ℃, perfluoroglutaryl fluoride 30.0
After g was added dropwise over 10 minutes, the mixture was 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 further stirred for 6 hours.

Remove the condenser of the reactor, attach the distillation device, and steam 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.

B) IR 3030,3000,2900cm ^-1 (-CH ₃ ) 1880cm ^-1 (-COF) b) MS M / e 81 ⁺ CF ₂ OCH ₃ (B) Using a method similar to that described in detail in Example 3- (b), I got The structure of the compound was confirmed by IR, ¹⁹ F-NMR, MS and elemental analysis.

B) IR 1890cm ^-1 (-COF) b) ¹⁹ F-NMR Chemical shift (a), (b), (j), (k) -21.5ppm (c), (i) 117.0ppm (d), (h) 80.2ppm (e), (g) 123.0ppm (f) 121.1ppm c) MS (C) Using a method similar to that described in detail in Example 3- (c) and (d). (CF ₂ = CFOCF ₂ ) ₂ CFO (CF ₂ ) ₅ OCF (CF ₂ OCF = CF ₂ ) ₂ was obtained. The structure of the compound was confirmed by IR, ¹⁹ F-NMR, ¹ H-NMR, MS and elemental analysis.

(D) Using the same method as described in detail in Example 1- (a), (CF ₂ = CFOCF ₂ ) ₂ CFO (CF ₂ ) ₅ OCF (CF ₂ OCF = CF ₂ ) ₂ to (CH _{2 = CHCH 2 OCF 2 CFHOCF 2} ) 2 CFO (CF 2) 5 OCF (CF 2 OCFHCF 2 OCH 2 CH = CH 2) 2 was synthesized. The structure of the compound is IR, ¹⁹ F-NMR, ¹ H-NMR, MS
And confirmed by elemental analysis.

B) IR 1655cm ^-1 (-CH ₂ CH = CH ₂ ) 1050 to 1400cm ^-1 (-CF _2- ) b) MS M / e 441 ⁺ CF (CF ₂ OCFHCF ₂ OCH ₂ CH = CH ₂ ) ₂ M / e 41 ⁺ CH ₂ CH = CH ₂ (e) By the same method as described in detail in Example 1- (b), (CH ₂ = CHCH ₂ OCF ₂ CFHOCF ₂ ) ₂ CFO (CF ₂ ) ₅ OCF (CF ₂ OCFHCF ₂ OCH ₂ CH = CH ₂ ) ₂ I got The structure of the compound was confirmed by IR, ¹⁹ F-NMR, ¹ H-NMR, MS and elemental analysis.

B) IR 2945, 2990cm ^-1 (-CH _2- ) 1050 to 1400cm ^-1 (-CF _2- ) b) MS Example 5 (a) After putting 2.9 g of NaH and 50 ml of dioxane into a 200 ml flask equipped with a stirrer and a dropping funnel, under ice cooling.
12.6 g of HOCH ₂ (CF ₂ ) ₃ CH ₂ OH was gradually added dropwise. After completion of the dropping, the reaction solution was transferred to a 200 ml stainless steel autoclave, the autoclave was heated to 30 ° C., and pressurized with tetrafluoroethylene to 20 kg / cm ² . When stirring was continued for 5 hours, the absorption of tetrafluoroethylene stopped. After releasing unreacted tetrafluoroethylene, CF ₂ = CFOCH ₂ (CF ₂ ) ₃ CH ₂ OCF = CF ₂ was directly distilled from the autoclave. The structure of the compound was confirmed by IR, ¹⁹ F-NMR, ¹ H-NMR, MS and elemental analysis.

B) IR 2980cm ^-1 (-CH _2- ) 1835cm ^-1 (-CF = CF ₂ ) 1050 to 1400cm ^-1 (-CF _2- ) b) MS M / e 372 M ⁺ (Molecular ion peak) (b) In a 100 ml flask equipped with a stirrer and a dropping funnel, 1.9 g of NaH and 30 ml of ether were placed. The flask was immersed in ice water, and 13.6 g of allyl alcohol was gradually added dropwise with stirring. After stirring for 30 minutes under ice-cooling, 13.2 g of CF ₂ = CFOCH ₂ (CF ₂ ) ₃ CH ₂ OCF = CF ₂ obtained in (a) above was added, and then stirred at room temperature for 1 hour, and then placed in an ice bath. It was poured, the organic layer was separated, dried, and then distilled to obtain 12.1 g of CH ₂ = CHCH ₂ OCF ₂ CFHOCH ₂ (CF ₂ ) ₃ CH ₂ OCFHCF ₂ OCH ₂ CH = CH ₂ . The structure of the compound is IR, ¹⁹ F-NMR, ¹ H-NM.
Confirmed by R, MS and elemental analysis.

A) IR 2930, 2980cm ^-1 (-CH _2- ) 1655cm ^-1 (-CH ₂ CH = CH ₂ ) 1050 to 1400cm ^-1 (-CF _2- ) b) ¹⁹ F-NMR, ¹ H-NMR Chemical shift (e) 88.0ppm (f) 143.8ppm (i) 122.8ppm (j) 126.9ppm (a) 5.19ppm (b) 5.33ppm (c) 5.88ppm (d) 4.38ppm (g) 5.20ppm (h) 4.15ppm c) MS M / e 488 M ⁺ (Molecular ion peak) M / e 41 ⁺ CH ₂ CH = CH ₂ (c) In a Pyrex tube with an inner diameter of 20 mm, CH ₂ = CHCH ₂ obtained in (b) above OCF ₂ CFHOCH ₂ (CF ₂ ) ₃ CH ₂ OCFHCF ₂ OCH ₂ CH = CH ₂ 9.5 g, methyldichlorosilane 5.6 g and chloroplatinic acid 0.1
After adding 100 μ of M isopropyl alcohol solution, this was sealed. After heating in an oil bath at 90 ° C for 16 hours, the bag is opened, the contents are distilled, 10.2 g was obtained. The structure of the compound is IR, ¹⁹ F-NMR, ¹ H-NM.
Confirmed by R, MS and elemental analysis.

B) IR 2940,2990 cm ^-1 (-CH _2- ) 1050 to 1400 cm ^-1 (-CF _2- ) b) ¹⁹ F-NMR, ¹ H-NMR Chemical shift (e) 88.1ppm (f) 143.7ppm (i) 122.7ppm (j) 126.9ppm (a) 0.75ppm (b) 0.9 to 1.3ppm (c) 1.6 to 2.2ppm (d) 3.93ppm (g) 5.20 ppm (h) 4.13ppm c) MS Example 6 In a 100 ml flask containing a magnetic stirring bar, 25 m of hexane was added.
1 was charged and cooled to 0 ° C. 2.6 g of methanol with stirring,
Obtained in Example 1 after adding 6.4 g of pyridine 12.2 g was added dropwise. After stirring for 30 minutes, the precipitate was removed by filtration, and the solvent was evaporated under reduced pressure. When the residue was distilled off Was obtained 10.1 g. The structure of the compound is IR, ¹⁹ F-NMR, ¹ H
-Confirmed by NMR, MS and elemental analysis.

Example 7 35 ml of water, 15 ml of ether and 4.0 g of NaHCO ₃ were placed in a 100 ml flask with a side tube containing a rotor and obtained in Example 1 with vigorous stirring. 7.0 was added dropwise. After reacting for 6 hours, the organic layer was separated, washed with saturated brine, dried over CaSO ₄ , and the solvent was distilled off. After drying the residue at 90 ° C under reduced pressure, the IR was measured to be 3350.
Absorption derived from SiOH group was observed near cm ^-1. It was found that

Example 8 20 ml of ether and 0.35 g of LiAlH ₄ were placed in a 100 ml flask equipped with a stirrer and a reflux condenser. Synthesis was carried out in the same manner as described in detail in Example 1 with vigorous stirring. Was added dropwise to a solution of 10.0 g of ether so that the ether was gently refluxed. After the dropping was completed, the reaction was continued for 6 hours, and then inorganic salts were removed using a Soxhlet extractor. After distilling off the ether, fractional distillation 4.5g was obtained. The structure of the compound was confirmed by IR, ¹⁹ F-NMR, ¹ H-NMR and MS.

Example 9 20 ml of ether in a 100 ml flask with a side tube containing a rotor
And was synthesized in the same manner as described in detail in Example 1. Was added to this, and a previously adjusted ether solution of CH ₃ MgBr was added thereto. After the reaction was completed, the reaction mixture was poured into ice water to separate the organic layer, and then the solvent was distilled off. When ¹ H-NMR of this compound was measured, absorption of three hydrogen atoms was observed near 0.02 ppm. It was found that

Example 10 By a method similar to that described in detail in Examples 1 to 5,
The fluorine-containing ether compounds shown in Table 1 were synthesized. In addition, in Table 1, the characteristic absorption in the infrared absorption spectrum of the synthesized fluorine-containing ether compound and the results of MS are also summarized.

Example 11 The fluorine-containing silyl compounds shown in Table 2 were synthesized by the same method as described in detail in Examples 1-9.
Table 2 shows the MS of the synthesized fluorine-containing silyl compound.
The results are also summarized.

Application Example Obtained in Example 6 Dissolved in 100 parts by weight of methanol, 0.1N-hydrochloric acid
CR-3, which was prepared by adding 0.2 parts by weight of alkali to the alkaline solution.
A plate of 9 (polymer of diethylene glycol bisallyl carbonate) was dipped and then heat-cured at 100 ° C. for 2 hours. The obtained sample was immersed in boiling water for 1 hour and then dried. 11 parallel lines were put on the surface of this sample with a knife at 1 mm intervals vertically and horizontally, and 100 squares were cross-cut. After the cellophane tape was attached to the square, the tape was peeled off (cross-cut tape (Test) However, there was no peeled square in 100 squares.

Comparative application example A treatment solution was prepared from 10 parts by weight of CF ₃ CH ₂ CH ₂ Si (OCH ₃ ) ₂ CH ₃ , 100 parts by weight of methanol and 0.2 parts by weight of 0.1N hydrochloric acid.
A CR-39 plate that had been alkali-treated in advance was treated in the same manner as in the application example, and then a cross-cut tape test was conducted. 38 out of 100 squares were peeled off.

[Brief description of drawings]

FIG. 1, FIG. 2 and FIG. 3 show Example 1-
Infrared absorption spectrum of the compound obtained in (a), ¹⁹ F-
FIG. 4 is a nuclear magnetic resonance spectrum and a ¹ H-nuclear magnetic resonance spectrum, and FIGS. 4, 5 and 6 show Example 1-
Infrared absorption spectrum of the compound obtained in (b), ¹⁹ F-
It is a nuclear magnetic resonance spectrum and a ¹ H-nuclear magnetic resonance spectrum.

Claims (4)

(57) [Claims] 1. The following formula RfOCFHCF ₂ OR) _n A fluorine-containing ether compound represented by. 2. The following formula RfOCF = CF ₂ ) _n And a fluorine-containing vinyl ether compound represented by the following formula R-OM The method for producing a fluorine-containing ether compound according to claim (1), wherein the reaction product obtained is reacted with an alcohol or water. 3. The following formula RfOCFHCF ₂ OR′SiR ₁ R ₂ R ₃ ) _n A fluorine-containing silyl compound represented by. 4. The following formula RfOCFHCF ₂ OR) _n And a fluorine-containing ether compound represented by the following formula H-SiR ₁ R ₂ R ₃ The method for producing a fluorine-containing silyl compound according to claim (3), characterized in that the silane compound represented by the formula (3) is reacted and further hydrolyzed if necessary.