JP2505519B2 - Fluorine-containing silyl compound and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel fluorine-containing silyl compound and a method for producing the same.

(Problems to be Solved by Prior Art and Invention) Conventionally, compounds having a perfluoroorganic group and a silyl group in the same molecule are raw materials of various useful materials that make the best use of the characteristics of the perfluoroorganic group and the silyl group. It is used as a compound. For example, a dehydration condensate of trifluoropropylmethyldihydrosilane is commercially available as a solvent-resistant and heat-resistant silicone oil. US patent
No. 3484470 has the following formula 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 used as a clad material for an optical fiber after being copolymerized with another silyl compound. Things have been proposed.

However, the known compounds as described above do not necessarily have strong adhesive strength when used as a surface treatment agent, and when polymerized, the mechanical strength of the polymer is not always sufficient. Had the drawbacks.

(Means for Solving the Problem) In view of the above points, the inventors of the present invention act as an effective cross-linking agent when copolymerized with other monomers, and when highly polymerized alone Gives a crosslinked polymer,
Furthermore, as a result of intensive research aimed at obtaining a fluorine-containing compound having strong adhesion to a substrate when used as a surface treatment agent, as a result, a novel compound having 2 to 4 silicon atoms in one molecule has been obtained. The present invention has been completed by successfully producing such a fluorinated silyl compound and finding that the compound achieves the above object.

That is, the present invention provides the following general formula [I] R _f O-R-SiR ₁ R ₂ R ₃ ) _n [I] Is a fluorinated silyl compound.

In the above general formula [I], R _f may be any group as long as it is a divalent to tetravalent perfluoro organic group. Particularly preferred groups in the present invention are groups represented by the following general formula.

Divalent _{groups: CF 2 X + 1, -CF} 2 CFYO (CF 2 CFYO) y (CF 2) X + 1 (OCFYCF 2) z OCFYCF 2 -, 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], an alkylene group is adopted as R without any limitation, but an alkylene group having 3 to 8 carbon atoms is generally preferable. For example, the general formula The alkylene 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 a carbon number in the range of 1 to 3 for reasons such as easy availability of raw materials and easy synthesis of the compound of the present invention. It is preferable.

Next, in the general formula [I], as the halogen atom represented by R ₁ , R ₂ and R ₃ , fluorine, chlorine, bromine and iodine are used. In the general formula [I], R ₁ , R ₂ and R ₃
The alkyl group and the alkoxy group represented by are not particularly limited, but preferably have a carbon number of 1 to 4 for reasons such as easy availability of raw materials and reactivity of the product. Further, the alkyl group and the alkoxy group represented by R ₁ , R ₂ and R ₃ may be partially fluorinated. Specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a trifluoropropyl group, a butyl group and a 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 [I], n can take the 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) 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 a typical example of the compound represented by the above general formula [I] of the present invention, the following formula The IR chart of the compound represented by is shown in FIG.

(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. Further, ¹ H- nuclear magnetic resonance spectrum (hereinafter abbreviated to ¹ H-NMR.); Hydrogen present in the compounds by measuring the (tetramethylsilane reference downfield positive, expressed in ppm) You can know the bonding mode of atoms.

As a typical example of the compound represented by the above general formula [I] of the present invention, the following formula The ¹⁹ F-NMR chart and the ¹ H-NMR chart of the compound represented by are shown in FIG. 2 and FIG. 3, respectively.

(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, silicon, 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 method for producing the compound represented by the above general formula [I] of the present invention is not particularly limited and may be any method, but for example, it can be suitably produced by the following method.

General formula [II] R _f OR ') _n [II] And a fluorine-containing alkenyl ether compound represented by the following formula [III] H-SiR ₁ R ₂ R ₃ [III] This is a method of reacting with a silane compound represented by and hydrolyzing as necessary.

The fluorine-containing alkenyl ether compound represented by the above formula [II] can be produced by the following method.

The following general formula [IV] _{(R 'f m COF) n} [IV] And an acid fluoride compound represented by the following general formula [V] R'-X [V] The fluorine-containing alkenyl ether compound represented by the above formula [II] can be produced by reacting with the alkenyl halide compound represented by the formula (1) in the presence of a fluorine ion. (However, the relationship between R _f in the above formula [II] and R ′ _f in the above formula [IV] is such that when n = 2, R _f = −CF ₂ −R ′ _f
-CF _2- , and when n = 3 And when n = 4 Is. ) The acid fluoride compound represented by the above general formula [IV] is
It can be manufactured by a known method. For example:

Among divalent acid fluoride compounds, those represented by FOC (CF ₂ ) _x-1 COF (where x is an integer of 1 or more) may be commercially available products, or methods such as electrolytic fluorination It may be manufactured in. The divalent acid fluoride compound represented by FOC (CF ₂ ) _x-1 COF is 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: ClF _{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 1 or more, and y is an integer of 0 or more. ] And an epoxy compound represented by the following formula [VI] [However, R ″ is an alkyl group.] As NaF, KF, CsF, RbF, A
In the presence of gF, N (CH ₃ ) ₄ F, etc., in glymes such as diglyme, triglyme, and tetraglyme, and aprotic polar solvents such as acetonitrile, sulfolane, dimethylformamide, etc., at a temperature of -20 to 80 ° C. By reacting for several hours to several days, the compound shown below is obtained.

In case of ClF _{2l + 1} COF Is obtained, and In Case of, Is obtained. These compounds are represented by the general formula as follows:

By reacting for several hours to several days at a temperature of the resulting compound further S _b F ₅ or the like Lewis acid catalyst at room temperature to 150 DEG ° C., it is possible to convert the -CF ₂ OR "groups -COF group This reaction is generally represented by the following reaction formula.

In this way, a divalent acid fluoride compound can be obtained.

There are many possible methods for producing the trivalent acid fluoride compound. For example, the epoxy compound represented by the general formula [VI] is added to one of the --COF groups of one of the divalent acid fluoride compounds (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 by the method and further by reacting with the above-mentioned Lewis acid such as S _b F ₅ .

 The reaction looks like this:

As another method, a dimer is prepared from an epoxy compound represented by the general formula [VI] 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 -CO groups of FOCR _f COF with the epoxy compound represented by the general formula [VI] and further reacting with the Lewis acid catalyst such as SbF ₅ mentioned above. be able to. The reaction is as follows.

The reaction of the thus obtained acid fluoride compound represented by the general formula [IV] and the alkenyl halide compound represented by the general formula [V] is carried out in the presence of a fluorine anion. 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 of the above-mentioned raw material acid fluoride compound and alkenyl halide compound is not particularly limited,
Usually, it is equivalent to 4 to the -COF group of the acid fluoride compound.
It is preferred to use the alkenyl halide compound in a range of double equivalents.

An aprotic polar solvent, for example, glymes such as diglyme, triglyme, tetraglyme, etc .; acetonitrile; seleforane; dimethylformamide, etc., at a temperature of 0 to 200 ° C. for several hours to several days. By reacting, the fluorinated alkenyl ether compound represented by the general formula [II] can be obtained.

Next, the fluorine-containing silyl compound of the present invention represented by the general formula [I] is obtained by hydrosilylating the fluorine-containing alkenyl ether compound represented by the general formula [II] and, if necessary, further substituted with a halogen atom substituted with silicon. Can be obtained by the hydrolysis reaction of.

The hydrosilylation method is not particularly limited, and a known method of 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, and specifically, organic compounds such as dibenzoyl peroxide, dibutyl peroxide, dicumyl peroxide, butyl perbenzoate, butyl peracetate, and azobisisobutyronitrile can be used. Peroxides; transition metal compounds such as chloroplatinic acid, iridium chloride, ruthenium chloride, platinum black; and bases such as tetramethylethylenediamine and tributylamine.
The amount of the catalyst used in the reaction is generally in the range of 10 ^{−8 to} 0.3 equivalent, preferably 10 ^{−6 to} 0.2 equivalent with respect to the double bond present in the compound represented by the general formula [II]. Chosen from. The compound represented by the general formula [III] is
It is preferably used in the range of 1 to 3 equivalents relative to the double bond in the compound represented by the general formula [II]. Also,
The reaction can be carried out in a solvent which is substantially inert to the compounds represented by the general formula [II] and the general formula [III] and the catalyst, or can be carried out without a solvent. Furthermore, the reaction temperature in the reaction is generally 50 to
It is selected from the range of 300 ° C, preferably 80 to 200 ° C. The reaction time is 1 minute to 2 days, preferably 5 minutes to 24 hours.

Among the fluorine-containing silyl compounds of the present invention, a compound in which at least one of the substituents on the silicon atom is a hydroxyl group is obtained by hydrolyzing a compound in which at least one of the substituents on the silicon atom is a halogen atom or an alkoxy group. Can be obtained by

Further, the fluorinated silyl compound of the present invention can also be obtained by converting the substituent of a silicon atom after being produced by the method described above. For the conversion of the substituent of the silicon atom, a known method can be adopted without any limitation. For example, a halogen atom bonded to a silicon atom becomes an alkoxy group by reaction with an alcohol,
A hydrogen atom can be substituted with a reducing agent such as lithium aluminum hydride. Further, the halogen atom bonded to the silicon atom can be substituted with an alkyl group by a reaction with a carbon nucleophile such as a Grignard reagent. Further, the hydrogen atom bonded to the silicon atom is replaced with the corresponding halogen atom by the reaction with halogen or hydrogen halide.

(Effects) Of the fluorine-containing silyl compounds of the present invention represented by the above general formula [I], a compound having a halogen atom, a hydroxyl group or an alkoxy group in a silicon atom can be converted into a high molecular weight compound by a known method. it can. 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

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 general formula [I], the reaction point is different from the usual fluorosilicone treating agent. Since it is often used, it is firmly attached to the base material, and since the fluorine-containing silyl compounds are highly crosslinked, 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 of the present invention represented by the above general formula [I] can be a raw material for synthesizing other useful compounds. For example, a fluorinated silyl compound having a hydrogen atom in a silicon atom can be used as a novel fudorosilylating 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) An autoclave of 100 ml was charged with 11.6 g of anhydrous KF, 60 ml of dried diglyme, 12.2 g of allyl bromide and 12.3 g of perfluoroglutaryl fluoride, and heated at 100 ° C. for 67 hours while stirring. After completion of the reaction, the reaction solution is filtered, and the filtrate is distilled to obtain 10.7 g of a fraction of 121 to 123 ° C / 10 mmHg.
Obtained. The structure of the compound of the fraction is IR, ¹⁹ F-NMR, ¹ H-NMR,
It was confirmed by MR and elemental analysis that CH ₂ = CHCH ₂ OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ OCH ₂ CH = CH ₂ .

(A) IR 1660cm ^-1 (-CH ₂ CH = CH ₂ ) 1050 to 1400cm ^-1 (-CF _2- ) (b) ¹⁹ F-NMR, ¹ H-NMR Chemical shift (e), (f) 89.6 ppm (f), (h) 123.8 ppm (g) 121.0 ppm (a), (l) 5.21 ppm (b), (m) 5.36 ppm (c), (k) 5.90ppm (d), (j) 4.46ppm (C) MS M / e 364M ⁺ (Molecular ion peak) M / e 323M ⁺ -(CH ₂ CH = CH ₂ ) M / e 41 ⁺ CH ₂ CH = CH ₂ (B) In a Pyrex tube having an inner diameter of 25 mm, CH ₂ = CHCH ₂ O (CF ₂ ) ₅ OCH ₂ CH = CH ₂ 12.8 g obtained in the above (a), methyldichlorosilane 8.2 g, and 0.1 M isopropyl chloroplatinic acid were added. 70 μl of alcohol solution was added. Seal it, put it in an oil bath, 10
Heated at 0 ° C. for 18 hours. After cooling, it was opened and the contents were distilled to find a fraction with a boiling point of 128-130 ° C / 0.25 mmHg of 17.
1 g was obtained. The structure of the compound of the fraction is IR, ¹⁹ F-NMR, ¹ H
-By NMR, MS and elemental analysis, It was confirmed that

(A) IR 2930,2990 cm ^-1 (-CH _2- ) 1100 to 1300 cm ^-1 (-CF _2- ) (b) ¹⁹ F-NMR, ¹ H-NMR Chemical shift (e), (i) 84.7 ppm (f), (h) 123.8 ppm (g) 121.2 ppm (a), (m) 0.77 ppm (b), (l) 0.9 to 1.4 ppm (c), ( k) 1.5 to 2.2 ppm (d), (j) 4.04 ppm (c) MS M / e 592M ⁺ (molecular ion peak) Example 2 (a) In a 100 ml flask equipped with a condenser, a dropping funnel and a stirrer, 11.5 g of anhydrous KF and 60 ml of dry tetraglyme were placed, and then the reactor was cooled to 0 ° C. 21.4 g was added dropwise. After completion of the dropping, the mixture was stirred at room temperature for 30 minutes, and then 20.5 g of allyl bromide was added dropwise. Next, the reactor was placed in an oil bath, the temperature was raised to 100 ° C., and the reaction was continued for 66 hours. After completion of the reaction, the reaction solution was poured into ice water, the lower layer was separated, washed with water, and dried with MgSO ₄ . Next, this organic layer was filtered, and the filtrate was distilled, with a boiling point of 86 ° C / 4 mmHg. 20.3g was obtained. The structure of the compound is IR, ¹⁹ F-NMR, ¹ H
-Confirmed by NMR, MS and elemental analysis.

(A) IR 1655cm ^-1 (-CH ₂ CH = CH ₂ ) 1050 to 1400cm ^-1 (-CF _2- ) (b) ¹⁹ F-NMR ¹ H-NMR Chemical shift (e), (l) 85.1 ppm (f), (j) 79.4 ppm (g), (k) 142.2 ppm (h), (i) 84.3 ppm (a), (o) 5.23 ppm (b) , (P) 5.38ppm (c), (n) 5.92ppm (d), (m) 4.47ppm (c) MS M / e 546 M ⁺ (molecular ion peak) M / e 41 −CH ₂ CH = CH ₂ (B) Obtained in (a) above in a Pyrex tube with an inner diameter of 25 mm 20.3 g, methyldichlorosilane 9.3 g and chloroplatinic acid 0.
100 μl of 1M isopropyl alcohol solution was added and sealed. After heating to 110 ° C for 6 hours in oil, open the bottle,
When the contents were distilled, 24.8 g of a fraction having a boiling point of 134 to 137 ° C / 0.2 mmHg was obtained. The structure of the compound of the fraction is IR, ¹⁹ F
-NMR, ¹ H-NMR, MS and elemental analysis It was confirmed that

(A) IR (chart is shown in Fig. ¹ ) 1920,1990cm ^-1 (-CH _2- ) 1100-1300cm ^-1 (-CF _2- ) (b) ¹⁹ F-NMR, ¹ H-NMR ( Charts are shown in Figs. 2 and 3.) Chemical shift (e) 85.1ppm (f) 142.4ppm (g) 79.6ppm (h) 84.3ppm (a) 0.76ppm (b) 0.9 to 1.3ppm (c) 1.6 to 2.2ppm (d) 4.03ppm (c) MS Example 3 In the same manner as in Example 2- (b) From 10.2g and 3.9g dimethylchlorosilane 8.4g was obtained. The structure of the compound is IR, ¹⁹ F-NMR, ¹ H-NMR, MS
And confirmed by elemental analysis.

(B) IR 2920, 3000 cm ^-1 (-CH _2- ) 1100 to 1300 cm ^-1 (-CF _2- ) (b) ¹⁹ F-NMR, ¹ H-NMR Chemical shift (f) 85.0 ppm (g) 142.3 ppm (h) 79.4 ppm (i) 84.3 ppm (a), (b) 0.40 ppm (c) 0.7 to 0.8 ppm (d) 1.6 to 2.0 ppm (e) 4.00 ppm (C) MS Example 4 Same as Example 2- (b) From 18.59g and 9.7g trichlorosilane 18.0g was obtained. The structure of the compound is IR, ¹⁹ F-NMR, ¹ H-NM.
Confirmed by R, MR, and elemental analysis.

(A) IR 2920,2990 cm ^-1 (C-H) 1100 to 1350 cm ^-1 (-CF ^2- ) (b) ¹⁹ F-NMR, ¹ H-NMR Chemical shift (d) 85.0 ppm (e) 142.2 ppm (f) 79.6 ppm (g) 84.6 ppm (a) 1.1 to 1.7 ppm (b) 1.7 to 2.3 ppm (c) 4.07 ppm Example 5 (a) 200 ml autoclave After adding 48.5 g of anhydrous CsF, 70 ml of dry tetraglyme and 32.9 g of allyl bromide, 11.0 g of oxalyl fluoride was introduced from a cylinder at 35 ° C, and stirring was continued at 50 ° C for 4 hours. After the reaction was completed, the filtrate was poured into ice water, the lower layer was separated, and then distilled to remove 73 ~
17.7 g of a fraction of 74 ° C./40 mmHg was obtained. The structure of the compound of the fraction was confirmed by IR, ¹⁹ F-NMR, ¹ H-NR, MS and elemental analysis to be CH ₂ = CHCH ₂ OCF ₂ CF ₂ OCH ₂ CH = CH ₂ .

(A) IR 1655cm ^-1 (-CH ₂ CH = CH ₂ ) 1080 to 1300cm ^-1 (-CF _2- ) (b) ¹⁹ F-NMR, ¹ H-NMR Chemical shift (e), (f) 89.3ppm (a), (i) 5.21ppm (b), (j) 5.35ppm (c), (h) 5.90ppm (d), (g) 4.43ppm (c) MS M / e 214 M ⁺ (Molecular ion peak) M / e 41 ⁺ CH ₂ CH = CH ₂ (b) Obtained in (a) above in a Pyrex tube with an inner diameter of 25 mm (CH ₂ = CHCH ₂ OCF _{2 2} 12.7 g , Methyldichlorosilane 14.32
g and 0.4 g of RuCl ₃ were added. After sealing this, 120 ° C for 2
After heating for 4 hours, opening the bag and distilling the contents,
19.9 g of a fraction having a boiling point of 124 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

(A) IR 2910,2990 cm ^-1 (-CH _2- ) 1100 to 1250 cm ^-1 (-CF _2- ) (b) ¹⁹ F-NMR, ¹ H-NMR Chemical shift (e) 89.7 ppm (a) 0.76 ppm (b) 0.9 to 1.4 ppm (c) 1.6 to 2.1 ppm (d) 3.92 ppm (c) MS M / e 407 M ⁺ (molecular ion peak) -Cl Example 6 (a) 200 ml of dried tetraglyme and 1.6 g of anhydrous KF were placed in a 500 ml three-necked flask equipped with a stirrer, a reflux condenser at a temperature of -20 ° 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.

(A) 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
After adding 70 ml (trade name: manufactured by Dyupon), 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.

(A) 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 M / e 241 (C) In a 200 ml autoclave, anhydrous KF3 2.0 g, dried diglyme 80 ml, allyl bromide 80.0 g 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-NM.
It was confirmed by R, MS and elemental analysis.

(A) IR 1660cm ^-1 (-CH ₂ CH = CH ₂ ) 1050 to 1400cm ^-1 (-CF _2- ) (b) ¹⁹ F-NMR, ¹ H-NMR Chemical shift (e) 88.5 ppm (f) 126.9 ppm (g) 78.8 ppm (h) 141.7 ppm (i) 88.6 ppm (a), (l) 5.35 ppm (b), (m) 5.21 ppm (c), ( k) 5.92 ppm (d), (j) 4.48 ppm (c) MS M / e 468 M ⁺ (molecular ion peak) M / e 41 ⁺ CH ₂ CH = CH ₂ (d) Example 1- (b), In the same manner as described in detail in 2- (b), CH ₂ = CHCH ₂ O (CF ₂ ) ₃ OCF (CF ₂ OCH ₂ CH = CH ₂ ) ₂ and HSi (C
H ₃ ) From Cl ₂ I got The structure of the compound was confirmed by IR, ¹⁹ R-NMR, ¹ H-NMR, MS and elemental analysis.

(A) IR 2920,2990 cm ^-1 (-CH _2- ) 1050 to 1400 cm ^-1 (-CF _2- ) (b) ¹⁹ F-NMR, ¹ H-NMR Chemical shift (e) 88.7 ppm (f) 126.9 ppm (g) 78.8 ppm (h) 141.6 ppm (i) 88.7 ppm (a), (m) 0.76 ppm (b), (l) 0.9 to 1.4 ppm (c) , (K) 1.5 to 2.2 ppm (d), (j) 4.00 ppm (c) MS Example 7 (a) 150 ml of dried tetraglyme and 12.0 g of anhydrous KF were placed in a 300 ml three-necked flask equipped with a stirrer, a reflux condenser at a temperature of -20 ° C and a dropping funnel. Cool the reactor to 0 ° C and perfluoroglutaryl fluoride 3
After 0.0 g was added dropwise over 10 minutes, 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. 2 after the dropping
After stirring for an hour, the temperature of the reactor was raised to room temperature and stirring was continued for another 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 M / e 81 ⁺ CF ₂ OCH ₃ (B) Using a method similar to that described in detail in Example 6- (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 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 Examples 1- (a), 2- (a) and 6- (c), From I got The structure of the compound was confirmed by IR, ¹⁹ F-NMR, ¹ H-NMR, MS and elemental analysis.

(A) IR 1660,990,915cm ^-1 (-CH ₂ CH = CH ₂ ) 1050 to 1400cm ^-1 (-CF _2- ) (b) MS M / e 511 ⁺ (CF ₂ ) ₅ OCF (CF ₂ OCH ₂ in _{CH = CH 2) 2 M /} e 245 + CF (CF 2 OCH 2 CH = CH 2) 2 (d) example 1- (b), similar to that described in detail in 2-(b) mETHOD (CH ₂ = CHCH ₂ OCF) ₂ CFO (CF ₂ ) ₅ OCF (CF ₂ OCH ₂ CH = CH)
_{From 2} and HSi (CH ₃ ) Cl ₂ I got The structure of the compound was confirmed by IR, ¹⁹ F-NMR, ¹ H-NMR, MS and elemental analysis.

(A) IR 2930,2990cm ^-1 (-CH _2- ) 1050 to 1400cm ^-1 (-CF _2- ) (b) MS Example 8 (a) In Example 1- (a), 12.5 g of methallyl chloride was used instead of allyl bromide, and anhydrous KF10.
Reaction was carried out in the same manner as in Example 1- (a) except that 0 g and 10.5 g of perfluoroglutaryl fluoride were used. I got The structure of the compound was confirmed by IR, ¹⁹ F-NMR, ¹ H-NMR, MS and elemental analysis.

(A) IR 1100 to 1400 cm ^-1 (-CF _2- ) (b) MS M / e 392 M ⁺ (Molecular ion peak) (B) By the same method as described in detail in Example 1- (b), 2- (b). From HSi (CH ₃ ) Cl ₂ I got The structure of the compound was confirmed by IR, ¹⁹ F-NMR, ¹ H-NMR, MS and elemental analysis.

(B) IR 2910,2990cm ^-1 (-CH _2- ) 1100 to 1350cm ^-1 (-CF _2- ) (b) MS M / e 620 M ⁺ (Molecular ion peak) Example 9 25 ml of hexane was added to a 100 ml flask containing a magnetic stir bar.
And cooled to 0 ° C. 2.6 g of methanol with stirring,
Obtained in Example 2 after adding 6.4 g of pyridine 15.0 g was gradually added dropwise. After stirring for 20 minutes, the pyridine hydrochloride was removed by filtration, and the solvent was evaporated under reduced pressure. When the residue was distilled, 10.3 g of a fraction of 143-144 ° C / 0.2 mmHg was obtained. The compound of the fraction is IR, ¹⁹ F-NMR, ¹
By H-NMR, MS and elemental analysis It was confirmed that

(A) IR 2850, 2950, 2990 cm ^-1 (-CH _2- ) 1150 to 1350 cm ^-1 (-CF _2- ) (b) ¹⁹ F-NMR, ¹ H-NMR Chemical shift (f) 84.1 ppm (g) 142.4 ppm (h) 79.5 ppm (i) 85.0 ppm (a) 0.05 ppm (b) 3.46 ppm (c) 0.3 to 0.8 ppm (d) 1.5 to 2.1 ppm (e) 4.00 ppm ^{(c) MS M / e 758 M -} ( molecular ion ^{peak) M / e 105 + Si (} OCH 3) 2 CH 3 example 10 water 35ml to 100ml flask with a bypass line containing the rotor, ether 15ml and NaHCO ₃ 4.0 g was added and obtained in Example 3 with vigorous stirring 7.4 g was added dropwise. After reacting for 6 hours, the organic layer was separated, washed with saturated brine, dried over CaSO ₂ , and the solvent was distilled off. After drying the residue at 90 ° C under reduced pressure, the IR was measured to be 3350.
Since the absorption derived from the SiOH group was observed near cm ^-1 , It turned out that it was converted to.

Example 11 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. Synthesized in a similar manner as described in detail in Examples 1-5 with vigorous stirring, A solution of 6.9 g of ether was added dropwise with gentle reflux of ether. After the addition was completed, the mixture was refluxed for 6 hours, and then inorganic salts were removed using a Soxhlet extractor. After distilling off the ether, fractional distillation Was obtained in an amount of 3.1 g. The structure of the compound is IR, ¹⁹ F-NMR, ¹ H-NMR.
And MS confirmed.

Example 12 20 ml ether in a 100 ml flask containing a rotor and was synthesized in a similar manner as described in detail in Examples 1-8. 6.2 g was added, and a CH ₃ MgBr ether solution prepared in advance was added thereto. After completion of the reaction, the mixture was poured into ice water to separate the organic layer, which was dried and the solvent was distilled off. ¹ H of this compound
There is a corresponding absorption in -SiCH ₃ to 0.02ppm was measured -NMR It was found that

Example 13 The fluorine-containing silyl compounds shown in Table 1 were synthesized by the same method as described in detail in Examples 1 to 11.
The results of MS of the synthesized fluorinated silyl compound are also summarized in Table 1.

Application Example Obtained in Example 9 Dissolve 5 parts by weight in 100 parts by weight of methanol, then add 0.1
A plate of diethylene glycol bisallyl abonate polymer which had been previously alkali-treated was immersed in a treatment solution containing 0.2 part by weight of N-hydrochloric acid, 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)
None of the 100 squares peeled off.

As a comparison, CF ₃ CH ₂ CH ₂ Si (OCH ₃ ) ₂ CH ₃ 10 parts by weight, 100 parts by weight of methanol and 0.2 parts by weight of 0.1N hydrochloric acid were used to prepare a treatment liquid, and diethylene glycol was preliminarily alkali-treated in the same manner as the application agent. When a plate of the bisallyl carbonate polymer was treated in the same manner as in the application example and a cross-cut tape test was conducted, 38 pieces were peeled off in 100 squares.

[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 2, respectively.

Claims (2)

(57) [Claims] 1. A general formula R _f O—R—SiR ₁ R ₂ R ₃ ) _n A fluorine-containing silyl compound represented by. 2. The general formula R _f OR ′) _n And a fluorine-containing alkenyl ether compound represented by the following formula H-SiR ₁ R ₂ R ₃ With a silane compound represented by the formula: R _f O—R—SiR ₁ R ₂ R ₃ ) _n A method for producing a fluorinated silyl compound represented by: