JPH01211593A - Production of fluorine-containing silyl compound and production thereof - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (Rf is 2-4 valent perfluoro organic group; R is alkylene; R1-R3 are H, halogen, OH, alkyl or alkoxy; n is 2-4). EXAMPLE:A compound expressed by formula II. USE:A crosslinking agent, surfactant, hydrosilylating agent or synthetic compound for other compound having high fluorine content and good heat resistance, low-temperature characteristic, mechanical characteristic and electrical characteristic. PREPARATION:A fluorine-containing alkenyl ether compound expressed by formula III (R' is alkenyl) is reacted with a silane compound expressed by the formula H-SiR1R2R3 and as necessary the resultant compound is hydrolyzed.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a novel fluorine-containing silyl compound and a method for producing the same.

(Prior art and problems to be solved by the invention) Conventionally, compounds having a perfluoro organic group and a silyl group in the same molecule have been used as raw materials for various useful materials that take advantage of the characteristics of the perfluoro organic group and the silyl group. It is used as a chemical compound.

For example, a dehydrated condensate of trifluoropropylmethyldihydrosilane is commercially available as a silicone oil that has solvent resistance and heat resistance. Also, U.S. Patent No. 348447
The specification of No. 0 proposes the use of a compound represented by the following formula as a raw material for a water-repellent and oil-repellent treatment agent for woven fabrics.

Furthermore, Japanese Patent Application Laid-Open No. 62-47605 proposes that a compound represented by the following formula (%) be copolymerized with other silyl compounds and then used as a cladding material for optical fibers.

However, when the known compounds mentioned above are used as surface treatment agents, their adhesive strength is not necessarily strong, and when they are polymerized, the mechanical strength of the polymer is not necessarily sufficient. It had such drawbacks.

c) In view of the above points, the present inventors have found that when copolymerized with other monomers, it acts as an effective crosslinking agent, and when polymerized alone, it acts as a highly effective crosslinking agent. As a result of intensive research aimed at obtaining a crosslinked polymer and also a fluorine-containing compound that has strong adhesion to a substrate when used as a surface treatment agent, it was found that - The present inventors succeeded in creating a new fluorine-containing silyl compound having four silicon atoms, and also discovered that this compound achieves the above object, leading to the completion of the present invention.

R, the present invention relates to the following general formula [13 %formula%[ This is a fluorine-containing silyl compound represented by

In the above general formula [11], Rf may be any divalent to tetravalent perfluoroorganic group. Particularly suitable groups in the present invention are groups represented by the following general formula.

Divalent group: +CF2, 1 -CF2CF'fO(ff2c?FYo)y(CF2
),, (CCF'1CF2 v "σ2-.

CF2 CF2 Trivalent group: F2- F2- Tetravalent group: CF2- Among the di- to tetravalent perfluoro organic groups shown in the above general formula, the perfluoroalkyl group represented by Y is the one that is available from the raw materials. For ease of use, it is preferable that the carbon number is 1 to 4. Also, X may be an integer of 1 or more, but it is preferably in the range of 1 to 7, and y and 2 are good if they are integers of 0 or more, but generally they are in the range of 0 to 3. It is preferable that there be.

Next, in the above general formula [I], R can be an alkylene group without any restriction, but generally has a carbon number! An alkylene group having 1 to 8 atoms is preferable, and an alkylene group represented by the general formula % is preferably employed in the present invention.

The number of carbon atoms in the alkyl group in the above formula is not particularly limited, but the number of carbon atoms is generally in the range of 1 to 3 for reasons such as ease of obtaining raw materials and ease of synthesizing the compound of the present invention. It is preferable.

Next, the halogen atoms represented by + R1, R2, and R3 in the general formula CI) are fluorine.

Chlorine, bromine and iodine are used. In addition, in the general formula CI), an alkyl group represented by R, R2 and R5,
The alkoxy group is not particularly limited, but for reasons such as ease of obtaining raw materials and reactivity of the product,
It is preferable that it is in the range of ~4. Further, the alkyl group and alkoxy group represented by R, R2 and R5 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. Further, 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.

Further, in the general formula CII, n can be an integer of 2 to 4.

The compound represented by the general formula CI) of the present invention is a new compound, and its structure can be confirmed by the following means.

(a) Infrared absorption spectrum C is hereinafter abbreviated as IR. )
By measuring , it is possible to know the specific atomic group present in the compound represented by the general formula CII of the present invention.

FIG. 1 shows an IR chart of a compound represented by the following formula as a representative example of the compound represented by the general formula CII of the present invention.

1 mouth) 19F-nuclear magnetic resonance spectrum (hereinafter referred to as 19y-
It is abbreviated as NMR. ) (trichlorofluoromethane standard: positive on the high magnetic field side and expressed in ppm), it is possible to know the bonding mode of the fluorine atoms present in the compound represented by the general formula C1). Also, 1H-
By measuring nuclear magnetic resonance spectra (hereinafter abbreviated as IH-NMR) (tetramethylsilane standard; positive on the low magnetic field side, expressed in ppm), the bonding mode of hydrogen atoms present in the compound can be determined. You can know.

A 19F-NMR chart of a compound represented by the following formula as a representative example of the compound represented by the general formula CII of the present invention is shown in FIG. 2, and an IH-=NMR chart is shown in FIG.

C/S) Mass spectrum (hereinafter abbreviated as MS) is measured, and the composition corresponding to each observed peak (generally expressed as M / e, which is the ion mass M divided by the ion charge number e). By calculating the formula, it is possible to know the molecular weight of the compound subjected to measurement and the bonding mode of each atomic group within the molecule.

(d) By elemental analysis, the weight percent of each of carbon, hydrogen, and halogen can be determined, and the weight percent of oxygen can be calculated by subtracting the sum of the weight percent of each recognized element from 100. Therefore, The compositional formula of the compound can be determined.

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

This is a method in which a fluorine-containing alkenyl ether compound represented by the general formula [■] Rf+OR')n [■] is reacted with a silane compound represented by the following formula [III] H-8iR1R2R3cm, and hydrolyzed if necessary.

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

The following general formula CIVI (R'fga1cOF). The acid fluoride compound represented by [IV) and the following general formula % formula % [However, 1J R/ is an alkenyl group, and X is a halogen atom. The fluorine-containing alkenyl ether compound represented by the above formula [■] can be produced by reacting the alkenyl halide compound represented by j in the presence of fluorine ions. (However, Rf in the above formula [■] and R′f in the above formula [■],
The relationship is Rf--CF2-R' when n=2
f-CF2-, and when n=3, Rf-CF2-R'
F2- F2- with f-CF2-. ) The acid fluoride compound represented by the above general formula CIV) is
It can be manufactured by a known method. For example:

Among the divalent acid fluoride compounds, those represented by FOC (CF2) You may do so. F.O.
The divalent acid fluoride compound represented by C' (CF2) C'F2)
In the case of 2COF, you can get the following books.

[However, y and 2 are integers of 0 or more.] The divalent acid fluoride compound can also be produced by the following method. Monovalent carboxylic acid fluoride compound C2F2t+10OF represented by the following formula [t is an integer of 1 or more] is a fluorine atom or a fluoroalkyl group, X is an integer of 1 or more, and y & an integer of 10 or more be. ] An epoxy compound represented by the following formula CVI'3 [However, R
'' is an alkyl group.] is a fluorine ion-generating compound, and NaF +KF
, C5P7, RbF, AgF, N(C
Hs) Glyme such as diglyme, triglyme, tetraglyme, and acetonide IJ in the presence of 4F etc.
Le.

By reacting in an aprotic polar solvent such as sulfolane or dimethylformamide at a temperature of -20 to 80°C for several hours to several days, the following compound can be obtained.

can be obtained and can be obtained. These compounds are represented by the following general formula.

R#fCFCOF CF20R# By further reacting the obtained compound with a Lewis acid catalyst such as 8bF5 at a temperature of room temperature to 150°C for several hours to several days, the -CF20R" group can be converted to a -COF group. This reaction is generally expressed by the following reaction formula.

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

Many methods are possible for producing trivalent acid fluoride compounds. For example, one -〇〇F group of a divalent acid fluoride compound (generally expressed as FOCRfCOF, where Rf is a perfluoro organic group) has the general formula [■]
React the epoxy compound shown by the method described above,
Furthermore, a hexavalent acid fluoride compound can be obtained in the same manner as in reaction formula (1) by reacting with a Lewis acid such as SbF5 described above.

The reaction looks like this:

Another method is to create a dimer by catalyzing a fluorine anion from an epoxy compound represented by the general formula [■],
Furthermore, a trivalent acid fluoride compound can be obtained using a Lewis acid catalyst such as 8bF5 according to the dimer reaction formula CII. The reaction is as follows.

SbF5 1--→FOCCF2CF20C'FC"OFFOF Furthermore, the tetravalent acid fluoride compound is FO('RfCOF's both 100F groups and the general formula C■
) can be produced by reacting an epoxy compound represented by the following formula, and further reacting with a Lewis acid catalyst such as SbF5 described above. The reaction is as follows.

The reaction between the acid fluoride compound represented by the general formula [fV] thus obtained and the alkenyl halide compound represented by the general formula [■] is carried out in the presence of a fluorine anion.

Fluoride ions are obtained by fluoride ion generating compounds. As the fluorine ion generating compound, a compound represented by the following formula is preferably used. The amount of fluorine ions present is not particularly limited and can be adopted from a wide range.
In general, a range of equivalent to 4 times equivalent to 100F' groups of the acid fluoride compound is suitable.

The reaction ratio of the acid fluoride compound and the alkenyl halide compound, which are the raw materials described above, is not particularly limited, but is usually equivalent to 4 to 100 F groups of the acid fluoride compound.
It is preferred to use alkenyl halide compounds in the double equivalent force range.

The above-mentioned raw materials are heated at a temperature of about 0°C to 200°C for several hours using an aprotic polar solvent such as glymes such as diglyme, triglyme, and tetraglyme, acetonitrile, sulfolane, and dimethylformamide. By reacting for several days, the fluorine-containing alkenyl ether compound represented by the general formula [■] can be obtained.

Next, the fluorine-containing silyl compound of the present invention represented by the general formula [I] can be obtained by hydrosilylating the fluorine-containing alkenyl ether compound represented by the general formula [11], and optionally further substituting silicon. ...Can be obtained by hydrolysis reaction of rogene atoms.

The method of hydrosilylation is not particularly limited, and generally known methods for hydrosilylating compounds having double bonds are employed. It is preferable to use a catalyst in the hydrosilylation reaction. As a catalyst, known books can be used without any restrictions, and specifically, dibenzoyl peroxide,
Dibutyl peroxide, dicumyl peroxide.

Organic peroxides such as butyl perbenzoate, butyl peracetate, azobisin butyronitrile; 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 determined by the general formula Cl
) for the double bond present in the compound represented by 10
-6 to 0.3 equivalents, preferably 10-6 to 0.2 equivalents. The compound represented by the general formula [III] is preferably used in an amount of 1 to 3 times the equivalent of the double bond in the compound represented by the general formula CIII. In addition, the reaction is carried out by the general formula [■] and the general formula [■].
The reaction can be carried out in a solvent that is substantially inert to the compound and catalyst represented by (2), or it can be carried out without a solvent. Furthermore, the reaction temperature in this reaction is generally selected from the range of 50 to 500°C, preferably 80 to 200°C. Further, 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, compounds in which one or more substituents on a silicon atom are a hydroxyl group include compounds in which one or more substituents on a silicon atom are a rogen atom or an alkoxy group. can be obtained by hydrolyzing.

Moreover, the fluorine-containing silyl compound of the present invention can also be obtained by converting the substituent of the silicon atom after producing it by the method described above. For conversion of substituents on silicon atoms, known methods can be employed without any restrictions. For example, a rogen atom bonded to a silicon atom can be replaced by an alkoxy group by reaction with an alcohol, or by a hydrogen atom by a reducing agent such as lithium aluminum hydride. A halogen atom bonded to a large silicon atom can be substituted with an alkyl group by reaction with a carbon nucleophile such as a Grignard reagent. Furthermore, the hydrogen atom bonded to the silicon atom is replaced by the corresponding halogen atom by reaction with... halogen or hydrogen atom.

(Effect) Among the fluorine-containing silyl compounds of the present invention represented by the general formula [I], compounds having a nitrogen atom, a hydroxyl group, or an alkoxy group in a silicon atom can be induced into a high molecular weight compound by a known method. I can do things. Unlike ordinary silicon-based polymers, this high-molecular-weight compound has a high fluorine content (and is highly cross-linked), so it has good heat resistance, low-temperature properties, and mechanical properties, as well as good electrical properties. It has many characteristics such as good quality.

When the surface of fibers, resins, glass, etc. is treated by a known method using the fluorine-containing silyl compound of the present invention represented by the general formula III), unlike ordinary fluorosilicone treatment agents, it does not react. Because of the large number of dots, it adheres strongly to the base material, and because the fluorine-containing silyl compounds are highly crosslinked, the properties such as water and oil repellency and low refractive index derived from fluorine atoms are maintained for a long time. It has the following characteristics.

Furthermore, the fluorine-containing silyl compound of the present invention represented by the general formula [■] can serve as a raw material for the synthesis of other useful compounds. For example, a fluorine-containing silyl compound having a hydrogen atom in its silicon atom can be used as a new hydrosilylating agent.

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

Example 1 (a) Anhydrous KF11.61 in a 100-
1. Dried diglyme 60-, allyl bromide 12.2
g and perfluoroglutaryl fluoride 12.3.
After adding 9, the mixture was heated at 100°C for 67 hours while stirring. After the reaction is completed, the reaction solution is filtered, the filtrate is distilled, and the structure of the compound in the fraction 121-b is -IR, 19F-NMR.

CH2-CHC by jH-NMR, MS and elemental analysis
H20CF2CF2CF2CF2CF20C'H2C'
It was confirmed that it was H-C'H2.

(a) IR 1660cm-' (-CH2CH-CH
2) 1050-1400α (-CF2-) (b) 19F-NMR, 1) (-NMR<e), (i)
89.6 ppm (f), (h)
125.8 ppm (, g) 121
．． 0 ppm (ω, (1) 5.21 ppm (b), (c) 5.36 ppm (c),
(5.90 ppm(d), (j
) 4.46 ppm MS M/e 564 M” (molecular ion peak) M
/e 325 M”-(CH2CH-CH2)M/
e 41 "CH2CH-CH2 (b) Into a Pyrex tube with an inner diameter of 25 cm, add the CH2 obtained in (a) above.
-CHCH20(CF2),,0CH2CH-CH
212,8y, 8.2g of methyldichlorosilane and 70βt of 0.1M isopropyl alcohol solution of chloroplatinic acid
I put it in. This was sealed, placed in an oil bath, and heated at 100° C. for 18 hours. After cooling, the container was opened and the contents were distilled to obtain a fraction with a boiling point of 128-130°C, 10.25% H, and 17.1F. The structure of the compound in this fraction is I
R.

It was confirmed to be ct ct by 19F-NMR, IH=NMR, MS, and elemental analysis.

(a) lR 2930, 2990 tan-' (-CH2-) 1100
~1300α-' (-CF2-) (b) 19
F-NMR, 'H-NMR (e), (i) 84.7
ppm (f), (h) 123.8 ppm (g)
12 j, 2 T) E) m(a), (b)
0.77 ppm(b), <1) 0.9~
1.4 ppm (C), Saka) 1.5-2.2 ppm (d), (j) 4.04 ppm (c) MS M/e 592 M” (molecular ion peak) 113 5i-CH5t Example 2 (a) After putting 11.5 g of anhydrous KF and 60-g of dry tetraglyme into a 100-ml flask equipped with a condenser, dropping funnel, and stirrer, the reactor was cooled to 0°C, and CF'30F .

Ta. After the dropwise addition was completed, the mixture was stirred at room temperature for 30 minutes, and then allyl bromide 20.5II 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 the reaction was completed, the reaction solution was poured into ice water, and the lower layer was separated, washed with water, and dried with MgSO4. Next, this organic layer was filtered and the filtrate was distilled to give CH2-C'HC'H20C'F2CF'OC'F2C with a boiling point of 86"C/4 miHg.
F'20CF'C'F'20C'H2C)J-CI(2
20.3Ii of c'Flsc'F'3 was obtained. The structure of the compound is IR,1
Confirmed by 9F-NMR, IH-NMR, MS, and elemental analysis.

(a) IR 1655cyy+-' (-CH2CH-C
H2) 1050~1400cm-'(-('F2
) 19F-NMR IH-NMR (f) (j) (e), (485,1 ppm (f), (j) 79°4 ppm (g
), (k) 142.2 ppm (h),
(i) 84.3 ppm(a), (
o) 5.2'5ppm (b),
(p) 5.38 ppm (c),
(ω 5.92 ppm (dJ, h)
4.47 ppm (c) MS M/e 546 M” (molecular ion peak) M/
e 41 -CH2CH-CH2(b) Inner diameter 2
9.3I of F3 methyldichlorosilane obtained in (a) above and chloroplatinic acid + 7') in 5 types of Pyrex tubes.
100 μt of 0.1M isopropyl alcohol solution I was added and sealed. 6 hours in an oil bath.

After heating to 110°C, the container was opened and the contents were distilled to obtain 24.8.9 fractions with a boiling point of 134-137°C and 10.2°Cm Hi. The structure of the compound in this fraction is IR
, 19F-NMR, IH-NMR, MS, and elemental analysis.

(B) IR (Chart shown in Figure 1) 1920
, 1990c1n-' (-CH2-) 1100~
1500cm-' (-CF2-) (b) 19F-N
MR, jH-NMR (Charts are shown in Figures 2 and 3.) (e) 85.1 ppm (f)
142.4 ppm (g) 79.6
ppm (h) 84.31 ppm (a) 0.76 ppm (b) 0-9~1.3 ppm (c)
1, 6-2.2 ppm (d) 4.03 ppm (c) MS M/. 661 M+ (molecular ion peak) t Example 3 8.4 I of CF5 dimethylchlorosilane was obtained from 3.91 in the same manner as in Example 2-(b). The structure of the compound is IR,19F-NM
Confirmed by R, IH-NMR, MS and elemental analysis.

(a) lR 2920,3000cIn (CH2)1100~1
300crn-' (CF2-) (b) 19
F-NMR, 1H-NMR (f) 85・Oppm (ω 142・3ppm can) 79・4ppm (i) 84.3 ppm (a), (b) 0-40 ppm (
c) 0.7-0.8 ppm (d) 1.6-2.0 ppm (e)4.
00 pl)m (c)MS C,1M/e
135 ”CH2CH2CH25iCH5CH
3 Example 4 In the same manner as in Example 2-(b), 1 was obtained from trichlorosilane 9.7II. The structure of the compound is IR, 19F-NMR.

Confirmed by IH-NMR, MS, and elemental analysis.

(a) lR 2920, 2990 wound-' (C-H) 11 DO~
1350crP1-' (CF2) (b)
j? F-NMR, IH-NMR (td)
85.0 ppm(e) 142-2
7) pm(f) 79.6 ppm(g
) 84.6 ppm (a) 1, 1-1.7 ppm (b)
1.7-2. ．． 3 ppm (c) 4.07 p
pm Example 5 (a) 20 g of anhydrous CsF in an autoclave 48.
After adding 5 g of dry tetraglyme, 7 Q m of dry tetraglyme, and 52.9 lI of allyl bromide, 11.01-35°C of oxalyl fluoride was introduced from a cylinder, and stirring was continued at 50°C for 4 hours. After the reaction is complete, pour the filtrate into ice water,
After separating the lower layer, 17.71 fractions of fraction 75-b were obtained by distillation. The structure of the compound in this fraction is +
CH2-C'HCH20CF2CF20CH2CH-C by I R, 19F-NMR, IH-NMR, MS and elemental analysis
It was confirmed that it was H2.

(a) lR 1655 picture-' (-CH2CH-CH2)
1080~1600α-1 (-C!F2-) (b)
19F'-NMR, IH-NMR (e), (f)
89.5 ppm(a), (i)5.2
1 ppm (b), Cj) 5.35 ppm (c)
, (h) 5.90 ppm (d) ,
(g) 4-43 r3pm (c) MS M/e 214 M” (molecular ion peak) M/e
41 +CH2CH-C'H2 (b) (CH2
-CHCH20CF2+12.71-Methyldichlorosilane 14.32.9 and 0.4I of RuCl3 were charged. After sealing this and heating it at 120℃ for 24 hours, it was opened and the contents were distilled, and the boiling point was 124-127.
C. 10.3 dens H, 9 fractions were obtained at 19.5) JF.

The structure of the compound in this fraction is IR, 19F-NMR, IH
-NMR.

By MS and elemental analysis It was confirmed that.

(A) XR 2910, 29901″″1 (~CH2-)110
0~1250cn-' (-CF2-) (low
19F-NMR, IH-NMR (e)
89.7 ppm(a) 0.76 p
pm(b) 0-9~1.4 ppm(c')
1.6-2.1 ppm(d)
3.92 ppm (c) MS M/e 407 M" (molecular ion peel) -C
Lt M/e 113" 8i-CH5 Station Example 6 (a) Dry tetraglyme 200- and anhydrous KF 1.61 in a 500-three flask equipped with a stirrer, a reflux condenser at a temperature of -20°C and a dropping funnel. The reactor was cooled to 5°C, and the
After dropping CH390.0J over 30 minutes, stirring was continued for 16 hours.

The condenser of the reactor was removed, a distillation device was attached, and a fraction with a boiling point of 79° C./26 m Hll was obtained by distillation. The structure of this fraction is IR.

By 19F-NMR, jH-NMR, MS, and elemental analysis.

CHsOC'F2CF'2C'F20CFCFCF20
It was confirmed that it was CH3.

(B) lR 2900, 3000, 3030α (-CH3) 189
0α-'(-COF') Naka) MS M/e 181 CJOCF2CF2CF2"M
/e 81 CF20CH5 (b) SbF55. After adding Oy and Krytx AZ (trade name: DuPont) for 70 minutes, the reactor was cooled to 0°C and C'H30C"F2C
'F2C'F20C'FC'F 76.0.9■ CF20("H.

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 CHsF. After continuing stirring at 100° C. for 4 hours, FCCF2C'F20 C was obtained by direct distillation from the reactor. The structure of the compound is IR, 19F-NMR.

Confirmed by MS and elemental analysis.

(a) IR 18850(-C'OF) (b) "F -NMR CF(e) ω -23,7ppm (b) 118.9 ppm(c)
82.9 oorn(rl) 11
7.4 ppm(e), (f') -21
,3ppm(c) MS M/e 241 M/e 147 FCCF2CF2”(C)2
00- autoclave, anhydrous KF32.0 #,
Dry diglyme 8o- and allylbu 39.61/ were added and reacted at 120"C for 24 hours to obtain CF20CH2CH-CH2 33.2#. The structure of this compound is IR.

Confirmed by 19F-NMR, IH-NMR, MS, and elemental analysis.

(a) IR 1660crn-' (-CH20H-CH
2) 1 oso ~ 1400 (Ml-' (CF2-
) (b) +9F-NMR, 1H-NMR (c) (k)
(mJ chemical shift (e) 88.5 ppm (f)
126.9 ppm (g) 78.8
pan (h) 141.7 ppm (i) 88.6 ppm (a), (1) 5.55 pan (b
), (c) 5.21 pT).

(c) , (k) 5.92 pDm (d) (,j) 4.48 ppme
MS M/e 46B M” (molecular ion peak) M/e
41 "CH2CH=CH2(a) CH2-CH=H20(CF2), 0CF(CF20
CIhCH-CH2) 2 and H8i (CHs)C1
2 to ct C
I got 1. The structure of the compound is rR,"F-NMR.

Confirmed by IH-NMR, MS and elemental analysis.

(A) IR 2920, 2990cm (-CH2-) 1050
~14001M (-CF2-) (B) 19F-
NMR, IH-NMR(e) 88-7p
pm (f) 126-9 pDm (g) 78.8 ppm (Company) 1 41.6 ppm (i)
88.7 ppm(a),
0.76 ppm(b), (1) 0.9-1.4
ppm (c), (k) 1.5-2.2 ppm
m(d), <j) 4.00 ppm (c) MS t t Example 7 Copy) Attach a stirrer, a reflux condenser at a temperature of -20°C, and a dropping funnel. I added Grime 150wJ and anhydrous Kp12.0&. Cool the reactor to 0 °C and add perfluorogluta 11
After dropping 30.0 g of fluoride over 10 minutes,
Stir for another 1 hour to fully generate alkoxide.44.
2.9 was gradually added dropwise over 60 minutes. After finishing dropping, 2
After stirring for an hour, the reactor temperature was raised to room temperature and stirred for an additional 6 hours.

Remove the reactor condenser and install the distillation device 1
By M distillation, 3B, 6& was obtained. The structure of the compound is IR.

Confirmed by 19F-NMR, IH-NMR, MS, and elemental analysis.

(a) lR 3030,3000j2900α (-CH,)188
1) cIn-' (-COF) (0) MS
.

M/e 225” CF20CFCFCF
'2CcHS M/e 81 +CF20CH.

+11 M/e 47 CF(b) was obtained using a method similar to that detailed in Example 6-(b). The structure of the compound is IR, 19F-NMR.

Confirmed by MS9 elemental analysis.

(a) IR 1890LM-' (-COF) 1 unit)
'9F-NMR (a), (b), (j), (k) -21
,5ppm(c),(i) 117.0
ppm(d), (ω 80.2 ppm
(e), (g) 123.0 ppm(f)
121.1 ppm (c) MS M/e 391'(?F (c) Examples 1-(a), 2-(a) and 6-(
Using a method similar to that detailed in c),
From this, we obtained . The structure of the compound is IR, 19F-NMR, I
E(- Confirmed by NMR, MS and elemental analysis.

(a) lR 1660,990,915 tan-'(-CH2C'H
-C'H2)1050~1400cIn-' (C
F2- ) (B) MS M/e 511” (CF2) 50CF (CF3C
O(zcHG(2)2M/e 245 ”CF
(CF20CH2CH=CH2)2(a Example 1-(
b), 2-(b) in the same way as explained in detail in h
G Tsukuda)2 and H8i (CH,)C12. The structure of the compound is IR, 19F-NMR.

Confirmed by +H-NMR, MS and elemental analysis.

(B) lR 2950,2990crn-' (CH2-)105
0~1400c! n-" (CF2-) (b) MS t I t M/e 113 " 5iCH5t Example 8 (a') In Example 1-(a), using methallyl chloride 12.511 instead of allyl bromide +
4, anhydrous KF10.0.9, barfluoroglutaryl fluoride 10.5. Example 1-(
The reaction was carried out in the same manner as for ω. The structure of the compound is IR, 19F-NMR.

Confirmed by +H-NMR, MS and elemental analysis.

1100-1400cIn-'(-CF'2-)(
b) MS M/6 392 M” (molecular ion beak) M/e
55 +C'H2C=CH20H.

(b) CH2-C-CH20(CF2)50CH2-C-CH in a manner similar to that detailed in Examples 1-(bl), 2-(b+)
Obtain ct CH, CH5ct from 2 and AHS=H3 H8i CCH,)CF2. The structure of the compound is IR,"F-NMR.

Confirmed by IH-NMR, MS and elemental analysis.

(a) lR 2910, 2990ctn-' (CH2) 11 o
o~1350crn-' (-CF2-) (+7)
MS M/e 620 M" (molecular ion beak)
- and cooled to 0°C. methanol while stirring 2.
61/, t obtained in Example 2 after addition of 6.41 pyridine 15.0. P was gradually added dropwise. After stirring for 20 minutes, pyridine hydrochloride was removed by filtration, and the solvent was distilled off under reduced pressure. When the residue was distilled, 10.3 g of fraction 143-b was obtained. IR of the compound in the fraction, 1
It was confirmed to be CF3 by 9F-NMR, iH-NMR, MS, and elemental analysis.

(a) lR 2B50.2950.2990ctpt-' (-C
H2-) 1150-1550cy-' (-C
F2-1 (b) 19F-NMR, 18-NMR
(f) 84.1 ppm (g) 142.4 ppm (h) 79.5゜pm (i) 85.0.

Gloss 0.05 pDm (b) 3.46 ppm (cl O, 3-0.8 ppm (d)
15-2.1 ppm (e) 4.00 pl) m (c) MS M/e 758 M” (molecular ion beak) M/e
105 ”5l (OCHs>2CHs Example 1
0 With a side tube containing a rotor 10 [water in a 1 mg flask 35-
．． Ether 15- and NaE (Cox 4.09) were added, and 7641 in Example 3 was added dropwise with vigorous stirring. After reacting for 6 hours, the organic layer was separated, washed with saturated brine, and dried with CaSO2. The solvent was distilled off.
After drying under reduced pressure at 0°C, the IR was measured to be 53507?
? The observation of absorption originating from the 8i0H group near +1'' revealed that it had been converted to cH5CIF'3.

Example 11 Ether 2 Q wj , LLAtH40,3 in a 100-flask equipped with a stirrer and a reflux condenser
I put 5 and 9. While vigorously stirring, the combined H3 monotyl solution was added dropwise in a manner similar to that described in detail in Examples 1 to 5, such that the ether was gently refluxed. After the dropwise addition was completed, the solution was refluxed for 6 hours, and then the inorganic salts were removed using a Soxhlet extractor. After distilling off the ether, fractional distillate 3.1.9 was obtained. The structure of the compound is IR
.

Confirmed by 19F-NMR, IH-NMR and MS.

Example 12 A 100-ml flask containing a rotor was charged with 6.2 g of ether 20- and t synthesized in a manner similar to that described in detail in Examples 1 to 8, and the previously prepared CH3My
An ethereal solution of Br was added. After the reaction was completed, the organic layer was separated by pouring into ice water, dried, and the solvent was distilled off. When IH-NMR of this compound was measured, it was 0.02 p
It was found that there was an absorption corresponding to pm kC-8iC'H5 and that H3 was obtained.

Example 13 The fluorine-containing silyl compounds shown in Table 1 were synthesized using the same method as described in detail in Examples 1 to 11. Note that Table 1 also abbreviates the MS results of the synthesized fluorine-containing silyl compounds.

Application Example Dissolve 5 ff parts of CF obtained in Example 9 in 100 parts by weight of methanol, and further add 0.
．． The diethylene glycol bisallyl carbonate-hf coalescence, which had been previously treated with alkali, was completely immersed in a treatment solution containing 0.2 parts by weight of 1N hydrochloric acid, and then cured by heating at 100° C. for 2 hours. The obtained sample was immersed in boiling water for 1 hour and then dried. On the surface of this sample, cross-cut 100 squares by inserting 11 parallel lines vertically and horizontally at 1-inch intervals with a knife, then apply cellophane tape on top of the cross-cuts, and then peel off the tape (cross-cut tape Test) As a result, out of 100 squares, no squares were peeled off.

As a comparison, CF3CH2CH25i(OCHs)2
CH310 parts by weight, methanol 100 parts by weight and 0.1
A treatment solution was prepared from 0.2 parts by weight of N-hydrochloric acid.

A plate of diethylene glycol bisallyl carbonate*-) polymer that had been previously treated with alkali in the same manner as in the application example was treated in the same manner as in the application example, and when a cross-cut tape test was performed, the sample peeled off in 100 squares. is 68
There were pieces.

[Brief explanation of the drawing]

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

Claims (2)

[Claims] (1) General formula R_f■O-R-SiR_1R_2R_3)_n [However, R_f is a divalent to tetravalent perfluoro organic group, R is an alkylene group, and R_1, R_2, and R_3 are the same or different hydrogen atoms, respectively. an atom, a halogen atom, a hydroxyl group, an alkyl group, or an alkoxy group, and n is an integer of 2 to 4. ] A fluorine-containing silyl compound represented by (2) General formula Rf■OR')_n [However, R_f is a divalent to tetravalent perfluoro organic group, R' is an alkenyl group, and n is an integer of 2 to 4. ] A fluorine-containing alkenyl ether compound represented by the following formula H-SiR_1R_2R_3 [However, R_1, R_2 and R_3 are the same or different hydrogen atoms, halogen atoms, alkyl groups or alkoxy groups, respectively. ] The following formula Rf■O-R-SiR is characterized by reacting with a silane compound represented by and hydrolyzing if necessary.
_1R_2R_3)_n [However, R_f is a di- to tetravalent perfluoro organic group, R is an alkylene group, and R
_1, R_2, and R_3 are the same or different hydrogen atoms, halogen atoms, hydroxyl groups, alkyl groups, or alkoxy groups, respectively, and n is an integer of 2 to 4. ] A method for producing a fluorine-containing silyl compound.