JPH0655685B2 - Fluorine-containing divinyl ether and method for producing the same - Google Patents

Description

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

(Problems to be Solved by the Prior Art and Invention) Hydrocarbon-based resins having a crosslinked structure have been used in many fields because of their excellent properties. However, reports on highly fluorinated crosslinked polymers have not been reported. Not much. For example, Japanese Patent Application Laid-Open No. 62-59610 discloses a divinyl compound. A method for producing a fluorinated crosslinked polymer using is disclosed. However, when the double bond is not sufficiently utilized for crosslinking, a cyclized structure is partially formed, and when it is copolymerized with another fluorinated monomer. It is described that a crosslinked resin cannot be obtained with a high polymerization rate unless the divinyl compound is 50 mol% or more.
Also, regarding the polymerization of CF ₂ = CFCF = CF ₂ as another divinyl compound, Journal of Polymer Science B
Volume 6, pages 639-642 (1968),
This divinyl compound has poor polymerizability, and even if it is polymerized at 60 ° C. for 1 week, the polymerization rate is 15 to 18%.

Therefore, the object of the present invention is useful as a cross-linking agent of a fluorine-containing polymer having good polymerizability in view of the problems of conventionally known divinyl compounds, and also as a useful intermediate raw material such as a water repellent treatment agent and a coating agent. It is to provide a novel fluorine-containing divinyl compound.

(Means for Solving the Problems) The inventors of the present invention have conducted extensive studies on the relationship between the chemical structure of a fluorine-containing divinyl compound having good polymerizability and the polymerizability, and succeeded in synthesizing a novel divinyl compound, It was found that the compound is a compound that can achieve the above object.

That is, the present invention has the following general formula [I] Is a fluorine-containing divinyl ether represented by.

In the above general formula [I], k and m are each an integer of 0 or more, but in consideration of difficulty in obtaining raw materials, polymerizability of perfluorovinyl groups at both ends, and prevention of side reaction during polymerization. Then, it is preferably an integer of 0 to 2. In the general formula [I], l may be an integer of 2 or more, but is preferably an integer of 2 to 6 for the same reason as above.

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)
By measuring, it is possible to know the specific atomic group present in the compound represented by the above general formula [I] of the present invention. As a typical example of the compound represented by the general formula [I], the following formula The IR chart of the compound represented by is shown in FIG.

(B) Composition formula corresponding to each observed peak (generally, a value 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.

(C) ¹⁹ F- NMR spectrum (hereinafter abbreviated as ¹⁹ F-NMR.); By measuring the (trichlorofluoromethane reference representing the high magnetic field side is positive ppm), the general formula (I) It is possible to know the bonding mode of the fluorine atom present in the compound shown. Further, ¹ H-nuclear magnetic resonance spectrum (hereinafter, abbreviated as ¹ H-NMR) (tetramethylsilane standard; low magnetic field side is defined as positive and expressed in ppm)
The binding mode of hydrogen atoms existing in the compound can be known by measuring

As typical examples of the compound represented by the above general formula [I] of the present invention, the following formula The ¹⁹ F-NMR chart of the compound represented by
^{The 1} H-NMR chart is shown in FIG.

(C) Obtain each weight% of carbon, hydrogen, and fluorine by elemental analysis, and then add the weight% of each recognized element to 1
By subtracting from 00, the weight% of oxygen can be calculated, and therefore the composition formula of the compound can be determined.

The method for producing the compound of the present invention represented by the general formula [I] may be any method, but the method described below is preferable.

That is, the following formula [II] Is a method of reacting a fluorine-containing diol represented by with an alkali metal or an alkali metal hydride and then reacting with tetrafluoroethylene.

First, the fluorine-containing diol represented by the general formula [II] is reacted with an alkali metal or an alkali metal hydride (hereinafter, this reaction is referred to as an alcoholation reaction). Here, as the alkali metal, Li, Na, K or the like is used, and as the alkali metal hydride, LiH, NaH, KH or the like is used. The alkali metal or alkali metal hydride is generally used in an amount of 2 mol or more, preferably 2 to 4 mol, based on the fluorine-containing diol represented by the general formula [II].

A solvent is preferably used in the alcoholation reaction. Examples of suitable solvents are aprotic solvents such as diethyl ether, dibutyl ether, dioxane, monobram, diglyme and tetraglyme. The reaction temperature is not particularly limited, but is preferably selected from the range of -20 ° C to 50 ° C. The reaction time is generally selected from the range of several minutes to several hours.

Next, the product obtained in the above alcoholation reaction is reacted with tetrafluoroethylene (hereinafter, this reaction is referred to as a vinyl etherification reaction). The vinyl etherification reaction is carried out in the same reactor after the above alcoholation reaction. You can do it by introducing fluoroethylene,
It is also possible to use a reactor different from the alcoholation reaction, transfer the solution of the product obtained by the alcoholation reaction to the reactor, and then introduce tetrafluoroethylene.
Examples of the solvent used in the reaction include the solvent for the alcoholation reaction described above.
The pressure of tetrafluoroethylene introduced in the reaction is usually selected in the range of 3 to 50 kg / cm ² , preferably 5 to 30 kg / cm ² . The reaction temperature in the reaction is not particularly limited, but is preferably selected from the range of 0 ° C to 140 ° C. The reaction time varies depending on the type of raw material, but is usually selected from the range of 10 minutes to 7 days, preferably 3 hours to 4 days.

After completion of the reaction, excess tetrafluoroethylene may be released, and then heat treatment may be performed at 80 to 160 ° C. if necessary.

Thus, the fluorinated divinyl ether of the present invention can be produced.

(Effect) The fluorine-containing divinyl ether represented by the general formula [I] is
Perfluorodivinyl ether CF ₂ ＝ CFOR ′ _f OCF ＝ CF
₂ (R ' _f is a perfluoroalkylene group) and a perfluorodivinyl compound, for example, CF ₂ = CFCF = CF ₂ , shows very good polymerizability as compared with known compounds. Also especially other monomers such as perfluoromonovinyl ether CF
₂ = CFOR ″ _f (R ″ _f is a perfluoroalkyl group); perfluoroolefin, for example, CF ₂ ═CF ₂ , CF ₃ CF═C
F ₂ ; fluoroolefin, for example, ClCF = CF ₂ , CF ₂ = CH
Also in the copolymerization with F or the like, a fluorine-containing crosslinked polymer can be obtained by polymerizing at a high polymerization rate in a wide composition.

Therefore, the fluorinated divinyl ether of the present invention is useful as a cross-linking agent and also as a raw material for synthesizing a fluorinated compound such as a water repellent and a coating agent by utilizing a reactive double bond.

(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 300 m stainless autoclave was charged with 1.8 g NaH and 30 m pre-dried dioxane, A solution of 9.6 g predissolved in 20 m dioxane was added with stirring at 20 ° C over 10 minutes. After the addition is complete
After introducing tetrafluoroethylene to 20 kg / cm ^2, the pressure of tetrafluoroethylene was carried out for 40 hours at 30 ° C. while maintaining the 20 kg / cm ^2. After completion of the reaction, tetrafluoroethylene was released, the reaction product was poured into water, extracted with ether, and then the ether layer was washed with water. Next, this ether solution was dehydrated with Na ₂ SO ₄ and then distilled to obtain 7.6 g of a fraction having a boiling point of 80 to 82 ° C./20 mmHg. The structures of the compounds of the fraction are IR, MS, ¹⁹ F-NMR,
^{By 1} H-NMR and elemental analysis It was confirmed that

B) IR (chart is shown in FIG. ¹ ) 2975 cm ^-1 (-CH _2- ) 1835 cm ^-1 (-OCF = CF ₂ ) 1050 to 1400 cm ^-1 (-CF _2- ) 945 cm ^-1 (-OCH _2- ) b) MS M / e: 327 _{M / e: 111 (CH 2} OCF = CF 2) c) showed Chiyato ^{1 H-NMR, 19 F-} NMR ( in FIGS. 2 and 3). Example 2 The same operation as in Example 1 was carried out except that Na was used instead of NaH, and HOCH ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ OH was used.
From this, CF ₂ = CFOCH ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ OCF = CF ₂ was obtained.

The structure of the product is IR, MS, ¹⁹ F-NMR, ¹ H-N
Confirmed by MR and elemental analysis.

B) IR 2975cm^-1 (-CH₂-) 1845 cm^-1 (-OCF = CF₂) 1050-1400 cm^-1 (-CF₂-) 945 cm^-1 (-OCH₂-) B) MS M / e: 311 (CF₂= CFOCH₂CF₂CF₂CF₂CF₂
) M / e: 111 ( CH₂OCF = CF₂Example 3 By the same method as described in detail in Examples 1 and 2.
To synthesize the fluorine-containing divinyl ethers listed in Table 1.
did. Table 1 shows the synthesized fluorine-containing divinyl ether.
Characteristic absorption value and MS in the infrared absorption spectrum of tell
The results are also shown.

Was carried out copolymerization of Example 4 each fluorinated divinyl ethers obtained in Examples 1 to 3 and _{CF 2 = CFOCF 2 CF 2 CF} 3.

A mixture of the above-mentioned comonomer having a composition of 30, 50, 70 and 90 mole% of the fluorine-containing divinyl ether of the present invention was added to a glass ampoule, and (CF ₃ CF ₂ CO _{2 2} was used as a polymerization initiator). It was added so as to be 2 mole% with respect to the total amount of vinyl ether and comonomer.
Then immerse the ampoule in dry ice-methanol,
A vacuum pump filled nitrogen with atmospheric pressure. Ampoule at 20 ℃
It was immersed in the oil bath for 24 hours under shaking. Then, the temperature of the oil bath was raised to 100 ° C. and the polymerization was continued for 5 hours. All the contents of the ampoule became a translucent white solidified substance.
Each of the obtained polymers was taken out from the ampoule and immersed in trichlorotrifluoroethane under reflux for 5 hours to extract unpolymerized monomer and low polymer. Then, after drying under reduced pressure at 100 ° C., the weight of each polymer was measured, and the polymerization rate of each polymer was determined by the following formula from the weight when charged in an ampoule.

The obtained results are shown in the following table.

As a comparison, instead of the fluorine-containing divinyl ether of the present invention,
Polymerization was carried out in the same manner as above using CF ₂ = CFOCF ₂ CF ₂ OCF = CF ₂ , and the results are also shown in the table.

[Brief description of drawings]

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

Claims (1)

[Claims] (1) The following formula A fluorine-containing divinyl ether represented by. (2) The following formula The fluorine-containing diol represented by the formula (1) is reacted with an alkali metal or an alkali metal hydride and then with tetrafluoroethylene.
The method for producing a fluorinated divinyl ether according to the item (1).