JPH01172353A - Fluorine-containing alkenyl ether compound and production thereof - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I (Rf is bifunctional - tetrafunctional organic group; R is alkenyl; m is 0 or 1; n is 2-4). USE:A synthetic raw material for various fluorine-containing compounds. PREPARATION:A compound shown by formula II is reacted with a compound shown by formula III (X is halogen) in the presence of fluorine ion in an aprotic polar solvent (e.g. diglyme or DMF) at room temperature - 200 deg.C for several hours - several days to give a compound shown by formula I. The fluorine ion is obtained from a compound shown by the formula MF [M is Na, K, Cs, Ag, Rb or N(CH3)4] and the amount of the fluorine ion used is preferably in the ratio of equivalent - 4 times as much as equivalent based on -COF group shown by formula II.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a polyvalent fluorine-containing alkenyl ether compound that is novel and useful as a raw material for the synthesis of various fluorine-containing compounds, and a method for producing the same.

(Prior art and problems to be solved by the invention) Conventionally, fluorine-containing compounds consisting of a perfluoroalkyl group and an alkenyl group have been used as raw materials for many useful compounds by utilizing the reactive alkenyl group. There is. For example, it is used in the synthesis of fiber treatment agents by copolymerizing with other monomers. Further, K is a silane compound having a perfluoroalkyl group by silylating the alkenyl group, which is used as a raw material for synthesizing an epoxy compound having a perfluoroalkyl group by introducing an epoxy group into an alkenyl group by oxidation with a peracid. It is widely used as a synthetic raw material.

Examples of such fluorine-containing compounds having a perfluoroalkyl group and an alkenyl group include U.S. Pat.
382,222, the compound represented by the following formula is also disclosed in U.S. Patent No. 4,029,86.
In the specification of No. 7, a compound represented by the following formula % is further described in British Patent No. 1.153.1.
No. 87 Meiji describes a compound represented by the following formula. These known compounds are fluorine-containing compounds having a simple structure with a relatively small number of carbon atoms and a perfluoroalkyl group and one alkyl group in the molecule. These compounds can be used as they are or after epoxidation or silylation to be used as fiber treatment agents, water and oil repellents,
It is only used as a coating agent.

In view of these points, the present invention has been developed to act as an effective crosslinking agent when copolymerized with other monomers after epoxidation or silylation, or to be highly crosslinking when polymerized alone. The purpose of the present invention is to obtain a fluorine-containing compound that gives a polymer with the following properties.

As a result of repeated research to achieve the above object, the present inventors have discovered - a novel fluorine-containing alkenyl ether compound having 2 to 4 VC alkenyl groups in the molecule via an ether bond; The present invention was completed by successfully producing the compound and by discovering that the compound achieves the above object.

That is, the present invention provides the following general formula [11 %formula%) This is a fluorine-containing alkenyl ether compound represented by

In the above general formula [I], Rf can be any divalent to tetravalent non(-fluoro organic group). Particularly suitable groups in the present invention include the following general groups. It is a group as shown in the formula.

Divalent group: 4-CF2+ to 10 FYO(CF2CFYO)y (CF2)x(
OCFYCF2 )zOCFY -0FO(CF2CF
YO) y (CF2)
The perfluoroalkyl group represented by Y preferably has 1 to 4 carbon atoms from the viewpoint of easy availability of raw materials. Also, X
may be an integer of 1 or more, but is preferably in the range of 1 to 7, and y and 2 may be integers of 0 or more, but generally preferably in the range of 0 to 3.

Next, in general formula #1, R may be an alkenyl group and may be employed without restriction, but an alkenyl group having 5 to 8 carbon atoms is generally preferred. For example, alkenyl groups represented by the following general formula are preferably employed in the present invention. The alkyl group in the above formula is not particularly limited in number of carbon atoms, but generally has 1 to 3 carbon atoms for reasons such as ease of obtaining raw materials and ease of synthesizing the compound of the present invention.
It is preferable that it is in the range of .

In the above general formula CI), m is O or 1, but when m is 0, n is 2, and when m is 1, -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 (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.

As a representative example of the compound represented by the general formula CII of the present invention, 1,5-bis(2-propenoxy 1-1.1.2
．． 2.5.3.4.4.5°5-Decafluoropentane The IR chart is shown in Figure 1.

(b) 19F-nuclear a gas resonance spectrum (hereinafter referred to as 1?p-
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 CI). 1H-Nuclear Magnetic Resonance Svector C is hereinafter abbreviated as 1H-NMR.

) (tetramethylsilane standard; low magnetic field side is positive, pp
The bonding mode of the hydrogen atoms present in the compound can be determined by measuring the amount (represented by m).

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

(c) Measure the mass spectrum (hereinafter abbreviated as MS) and find the composition formula corresponding to the observed traversal peak (generally expressed as M/e, which is the ion mass M divided by the ion charge number e). By calculating, 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.

(iv) By elemental analysis, the weight percent of each of carbon, hydrogen, and...logene is 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 present invention also provides a new method for producing the novel compound represented by general formula [1]. The aforementioned U.S. Pat. No. 3,382.
The fluorine-containing compounds having a perfluoroalkyl group and an alkenyl group described in No. 222 and British Patent No. 1,153.187 are fluorine-containing compounds containing a fluoroketone and an alkenyl halide, or a perfluoro 85th alcohol. It is synthesized by a reaction between an alkali metal salt and an alkenyl halide, and there is no report on its synthesis by a reaction between a perfluorocarboxylic acid fubide and an alkenyl halide. The present inventors investigated the reaction between acid fluoride compounds and alkenyl halide compounds, and found that fluorine-containing alkenyl ether compounds were produced surprisingly easily and efficiently.
The manufacturing method of the present invention has been completed.

The production method will be explained below, but the general formula [I
The novel compound represented by ] may be synthesized not only by the production method of the present invention but also by other methods.

The packaging method of the present invention is to combine an acid fluoride compound represented by the following general formula [1 [] 18 formula% and an alkenyl...ride compound represented by the following general formula (1 [[] This method involves reacting in the presence of ions.

In the above general formula Cn], Rf is a divalent to tetravalent perfluoroorganic group without any restriction.

Generally, from the viewpoint of ease of synthesis of the acid fluoride compound represented by the general formula CIII, the various divalent to tetravalent perfluoro organic groups already mentioned in the explanation of the general formula [■] are suitable. The acid fluoride compound represented by the above general formula [0] can be synthesized by a known method. The specific method is as follows, for example.

Of the divalent acid fluoride compounds, those indicated by FOC(CF2)x+ and COF may be commercially available, or may be obtained by a method such as electrolytic fluorination. A divalent acid fluoride compound represented by Foe(C"F2)a or COF can be converted into another divalent acid fluoride compound by reacting with a fluoroalkylene oxide. For example, FOC
In the case of '(CF2)2COF, the following is obtained.

[However, y and 2 are integers of 0 or more.] Furthermore, the divalent acid fluoride compound can also be prepared by the following method. A monovalent carboxylic acid fluoride compound represented by the following formula CIF2t+1COF [t is an integer of 1 or more. ] Or, a nitrogen atom or a perfluoroalkyl group, &su, X is 1
y is an integer greater than or equal to 0, and y is an integer greater than or equal to 0. ] and an epoxy compound represented by the following formula [fV] (where R'
is an alkyl group. ] and NaF as the fluorine ion generating compound.

K F = Cs F , Rb F −kl F , N
Glymes such as diglyme, triglyme, tetraglyme, and acetonitrile in the presence of (CH3) 4F and the like.

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.

In the case of 011122m+1COF, C'trlF2m
+1 ("F20C"FC'OFC?2OR') is obtained, and these compounds are represented by the following general formula.

R'fCFCOF CF20R' The obtained compound is further reacted with a Lewis acid catalyst such as K5t)F5 at a temperature of room temperature to 150°C for several hours to several days, thereby converting -CF20R' group into -C'OF group. can be converted. This reaction is generally expressed by the following reaction formula.

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

Many methods are possible for producing hexavalent acid fluoride compounds. For example, one 100F group of a divalent acid fluoride compound (expressed as FOCp and fCOF for boat fishing, where R″f is a perfluoroorganic group) has the general formula [IV
A trivalent acid fluoride compound can be obtained in the same manner as in reaction formula (1) by reacting the epoxy compound shown by the above method and further reacting with the above Lewis acid such as SbF5.

The reaction is as follows.

SbF5 FOCRfCF20CFCOF COF Another method is to create a 2t body from an epoxy compound represented by the general formula [■] using a fluorine anion as a catalyst.
Furthermore, a trivalent acid fluoride compound can be obtained from the 2t form of K using a Lewis acid catalyst such as SbF5 according to reaction formula CI). The reaction is as follows.

” Emua 2゜200F. . 2 Zan○F Furthermore, the tetravalent acid fluoride compound is obtained by reacting both -COF groups of FOCR5COF with an epoxy compound represented by the general formula [■], and further by reacting the above-mentioned S
It can be produced by reacting with a Lewis acid catalyst such as bF5. The reaction is as follows.

Next, the other raw material for the compound represented by the general formula C1) of the present invention is an alkenyl halide compound represented by the general formula CI[I).

In the above general formula Cu1l), the alkenyl group represented by R may be a hydrocarbon group having a double bond without any restriction, but from the viewpoint of reactivity with the acid fluoride compound shown in the above general formula Cl). , an alkenyl group having 3 to B carbon atoms is preferred.

Among these, the alkenyl groups specifically described in the above general formula [1] are particularly preferred. Furthermore, the general formula CII[)
In the middle, X is fluorine, chlorine, and bromine.

Alternatively, each atom of iodine may be used without any restriction.

Specific examples of alkenyl-ride compounds preferably used in the present invention are as follows. Allyl chloride, allyl bromide, allyl iodide, crotyl chloride, lytyl bromide, crotyl iodide, prenyl chloride, prenyl bromide, prenyl iodide, methallyl chloride, methallyl bromide, methallyl iodide, etc. can be mentioned.

The acid fluoride compound and alkenyl halide compound described above react in the presence of fluorine ions. 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 ion present is not particularly limited and can be adopted from a wide range, but generally it is preferably in the range of equivalent to 4 times equivalent to the -C''OF group of the acid fluoride compound.

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 the alkenyl halide compound in a double equivalent range.

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

(Effects) The fluorine-containing alkenyl ether compound of the present invention is a compound useful as a raw material for producing various fluorine-containing compounds.

For example, by epoxidizing the realkenyl group with a peracid or the like, n is the same as in the general formula El). ] A polyvalent epoxy compound can be obtained. or,
When epoxidation is partially carried out, o+q-n, and Rf and n are the same as in the above general formula [1]. ] can also be obtained. All of these compounds can be used as raw materials for the synthesis of new epoxy resins.

Furthermore, alkenyl groups can be hydrosilylated using chloroplatinic acid or the like as a catalyst to derive a compound having 1 to 4 silyl groups. From this compound,
Similar to ordinary organologenosilane, high molecular weight compounds can be derived by hydrolysis.

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, mechanical properties, and good electrical properties. It has many characteristics such as:

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

Example 1 11.6 g of anhydrous KF, 60 g of dry diglyme, and 12.2 g of allyl bromide in a 100-g autoclave! After adding q and perfluoroglutaryl fluoride 12.5.9, the mixture was heated at 100°C for 67 hours with stirring.

After the reaction is completed, the reaction solution is filtered and the filtrate is distilled to give 121
~b The structure of the compound in this fraction is IR, 19F-NMR.

CH2-CHC by +H-NMR, MS and elemental analysis
H20CF2CF2CF2CF2CF2()CH2CH
-CH2 was confirmed.

(B) IR (The chart is shown in Figure 1.) 1 (5
60,980,915bi-1(-C'H2C)(-CH
2) 1050~1400cy-' (CF2
) (b) 19F-NMR, 'H-NMR (Chart shown in Figure 2. Figure 6.) (d) (e) (f') (g) (h) (i) Cj
) (e), (i) 89-6 ppm (f'1. (hJ 123.8 ppm (g)
121. Oppm (a), (4) 5.21 ppm (b), (c) 5.36 ppm (c), (m
5.90 rrpm(d), (j) 4
．． 46 ppm (c) MS M/e 364 M+ (molecular ion peak) M/e
323 M”-(CH2CH-CH2)M/e
41 ”CH2CH-CH2 Example 2 100 equipped with condenser, m lower funnel, and stirrer
- After putting 11.5 g of anhydrous KF and 6 o- of dry tetraglyme into a flask, the reactor was cooled to O''CJ/cCJ/c. After stirring at room temperature for 60 minutes, allyl bromide 20.5II was added dropwise. did.

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, one reaction solution was poured into ice water.
After separating the lower layer, it was washed with water and dried with M, @804. Next, this organic layer was filtered and the filtrate was distilled.
A boiling point of 86"C/4 m Hg was obtained at 20.3.9. The structure of the compound is:

Confirmed by IR, 19F-NMR, 'H-NMR, MS, and elemental analysis.

(b) IR (Chart shown in Figure 4) 1655.
990.905■-1(-CHCH-C'H2)105
(If-1400cm (-CF2-)C port)
19F'-NMR (chart shown in Figure 5).

H-NMR chemical shift co), (1) 85.1 ppm rf), (i) 79-4 ppm (g)
, (k) 142.2 ppm (hl, (i) 84.3 ppm (a)
, (o) 5.23 ppm (b) , (p) 5.38 ppm (
c) e (n)5.92 r)om(d)+(m
) 4.4 7 Dpm(c)
MS M/e 546 M+ (molecular ion peak) M/
e 41 CH2CH-CH2 Example 6 (a) Dry Tetraglyme 200- and 1.6 g of anhydrous KF were placed in a 50-32 flask equipped with a stirrer, a reflux condenser at a temperature of -20°C, and a dropping funnel. . Cool the reactor to 5°C, C7,'>cFcF,o
After dropping CH,90,011 over 50 minutes,
Stirring was continued for 6 hours.

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

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

CH30C'F2CF'2C'F20CF'C'F'C
It was confirmed that it was F20CHs.

(a) lR 2900, 3000, 3030m-'(-C'H5
) 1890 cm-1 (-COF 1 〇 mouth) MS M/e 181 CH30CF2CF2CF2”
M/e 81 +CF20CH.

M/e 47 ÷ 9 F (b) 5 bFs in a 200-three flask equipped with a condenser, dropping funnel, and stirrer 5. After adding Oy and Krytx AZ (trade name: DuPont) for 70 minutes, the reactor was cooled to 0°C and CH30CF2CF
'2C'F20C'FCF 76.0.9CH20C
H5 was added dropwise over 20 minutes. After the dropwise addition 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 the analysis,
This gas was CH3F'. After continuing stirring at 100° C. for 4 hours, FCC'72CF20CF F was obtained by direct distillation from the reactor. The structure of the compound is IR, 19F-NMRI
Confirmed by MS and elemental analysis.

(a) IR 1885cm-' (-COF) (1:I) 19F-NMR (a) -23.7ppm (b) 1 18.9 ppm (c)
82.9 ppm (d) 1 1 7.4 ppm (e) −(
f) 21.3 ppmf MS M/e 241 M/e 147 FCCF2CF2””CF (c) Add anhydrous KF32 to the 2oogIi autoclave.
．． 011. Dry diglyme 80-, allilub 39.61
and reacted at 120°C for 24 hours.

CF20CH2CH-CH2 CH2-CHCH20CF2CF2CF20CF Hibiki CF200H2CH-CH2 33-2. I got P. The structure of this compound is rR.

Confirmed by 19F-NMR, +H-IJMR, MS, and elemental analysis.

(a) lR 1660,995,910 equipment (-CH2CH-CH2
)1050~1400m-'(-CF2-)(b)
19F-NMR, IH-NMR ((・l
(k) (+n) Chemical shift (e) 8 B, 5 pan (f) 126.9 ppm (g) 78.8 ppm (h) 141
．． 7 ppm (i) 88.6 ppm (a), (45,350pm (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 CH2CH=CH2 Example 4 (a) Dry tetraglyme 150- and anhydrous KF12. OII
I put it in. The reactor was cooled to 0°C, and 30.0 # of perfluoroglutaryl fluoride was added dropwise over 10 minutes, followed by further stirring for 1 hour to fully generate alkoxide.
．． 2N was gradually added dropwise over 60 minutes. After finishing dropping,
Stir for 2 hours, raise the reactor temperature to room temperature, and continue stirring for 6 hours.
Stir for 5 hours.

Remove the reactor condenser, install the distillation device,
Distillation gave 38.6.9. The structure of the compound is IR.

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

(a) lR 3050-! 1000.29001-' (-CH3)
1880rm-' (-COF) (b) MS + M/θ 225 CF20CF ("F view C5'2cc'H3 + M/e 81 CF20CH5(b)
C'F2CX''H5C'F12n using a method similar to that detailed in Example 3-(b).

from I got it. The structure of this compound is IR, F-NMR.

Confirmed by MS and elemental analysis (7).

(a) IR 1890m-” (-COF) (b) F-NMR (a), (b), (j), (k) -21
,5now(c),(i)117-ODpllll
(d), (h) 80.2 ppm (
e), (Tenku 123.Oppm(f)1 2
1-1 ppm e MS M/e 391 +1 (c) Using a method similar to that detailed in Examples 1, 2 and 5-(c), was obtained. The structure of the compound is IH, 19F-NMR, I
Confirmed by H-NMR, MS and elemental analysis.

(a) IR 1660,990,915L-rn-1(-CH2CH
-CH2) 1050-1400tM-1 (CF2)
(b) MS M/e 511” (CF2) 50CF (CF20
C) T2C) I42) 2M/e 245 +C
F (CF 20 CH2CH-CH212 Example 5 In Example 1, methallyl chloride 12.5.9 was used instead of allyl bromide b, anhydrous KF 10.0
1/, perfluoroglutaryl fluoride 10.5
．． The reaction was carried out in the same manner as in Example 1, except that 9 was used. The structure of the compound is IR, 19F-NMR.

Confirmed by jH-NMR, MS and elemental analysis.

(a) IR CF5 1660-915.890d (-C;CH2)11
00~1400α (-CF2-) (b)
MS M/e 392 M” (molecular ion beak) M
/ e 55 "CH2C=CH2CF5 Example 6 In the same manner as in Example 1, the reaction of no-fluoroglutaryl fluoride, allyl bromide, and various fluorides is shown in Table 1.

Table 2 shows the results of the reaction of perfluoroglutaryl fluoride and various alkenylno-lides in the presence of KF in the same manner as in Example 1.

Margin Example 8 Below, by the same method as explained in detail in Examples 1 to 5,
Fluorine-containing alkenyl ether compounds shown in Table 3 were synthesized. Table 3 also abbreviates the characteristic absorption in the infrared absorption spectrum and the MS results of the synthesized fluorine-containing alkenyl ether compounds.

Below margin

[Brief explanation of the drawing]

Figures 1, 2 and 3 are the infrared absorption spectrum, 1F-nuclear magnetic resonance spectrum and 1H-nuclear magnetic resonance spectrum of the compound obtained in Example 1, respectively;
The figure and FIG. 5 are an infrared absorption spectrum and a 19F-nuclear magnetic resonance spectrum of the compound obtained in Example 2, respectively.

Claims (2)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ However, R_f is a divalent to tetravalent perfluoro organic group,
R is an alkenyl group, m is 0 or 1, and n is 2
It is an integer of ~4. A fluorine-containing alkenyl ether compound represented by (2) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ However, R_f is a divalent to tetravalent perfluoro organic group,
m is 0 or 1, and n is an integer of 2 to 4. An acid fluoride compound represented by the general formula R-X [However, R is an alkenyl group and X is a halogen atom. ] A general formula characterized by reacting an alkenyl halide compound represented by the following in the presence of fluorine ions ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [However, R_f is a divalent to tetravalent perfluoro organic group. , R is an alkenyl group, m is 0 or 1, and n is an integer of 2 to 4. ] A method for producing a fluorine-containing alkenyl ether compound.