JPH10175950A - Production of functional group-containing and fluorine-containing peroxide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject compound by reacting a functional group- containing and fluorine-containing compound with a peroxide in a polyfluoro compound solvent having slight possibility of disruption of the ozonosphere. SOLUTION: A compound of formula I (Z<1> is a functional group substitutable with an ion exchange group; Rf<1> is a polyfluoroalkylene; X is a halogen) or a compound of formula II (Z<2> and Z<3> are each a functional group substitutable with an ion exchange group; Rf<2> and Rf<3> are each a polyfluoroalkylene) such as 1,1-dichloro-2,2,3,3,3-pentafluoropropene is reacted with hydrogen peroxide of a peroxide in a solvent such as a polyfluoroalkane to give a compound of formula III (Z<4> and Ff<4> are each Z<1> , Rf<1> , etc.; Z<5> and Rf<5> are each Z<1> , Rf<1> , etc.). The compound of formula III is not only useful as a radical polymerization initiator but also is capable of introducing a perfluoro substituent group containing an ion exchange group to an aromatic compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a functional group-containing fluorinated peroxide having a functional group convertible into an ion exchange group.

[0002]

2. Description of the Related Art Conventionally, 1,1,2-trichloro-1,2,2-trifluoroethane (hereinafter abbreviated as R113) has been used for producing difluoroalkanoyl peroxide. Its use is not preferred from the viewpoint of global environmental protection, since there is a concern that the layer will be destroyed.

[0003]

SUMMARY OF THE INVENTION The present invention relates to a functional group-containing fluorinated peroxide having a functional group which can be converted to an ion exchange group in a fluorinated solvent having no or little possibility of destroying the ozone layer. It provides a manufacturing method.

[0004]

According to the present invention, there is provided a fluorine-containing compound having a functional group represented by the following formula (4) or (5): hydrogenated fluorinated alkanes, perfluoroalkanes, perfluoroalkylamines, perfluoroethers. Boiling point selected from alcohols and perfluorocycloalkanes 20 to 35
A process for producing a functional group-containing fluorine-containing peroxide represented by Chemical Formula 6, characterized by reacting with a peroxide in a polyfluoro compound solvent at 0 ° C.

[0005]

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In the chemical formula 4, Z ¹ is a functional group which can be converted into an ion exchange group, Rf ¹ is a polyfluoroalkylene group which may have an ether bond, and X is a halogen atom. )

[0007]

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In the chemical formula (5), Z ² and Z ³ are the same or different, the functional groups which can be converted into ion-exchange groups, Rf ² and Rf ³ are the same or different, and polyfluoro which may have an ether bond. It is an alkylene group.

[0009]

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In the chemical formula 6, Z ⁴ -Rf ⁴ -is Z ¹ -Rf ¹
—, Z ² —Rf ² — or Z ³ —Rf ³ —, and Z ⁵
-Rf ⁵ -is Z ¹ -Rf ^1- , Z ² -Rf ² -or Z
³ -Rf ³ - it is.

In the above chemical formulas (4) to (6), -Z ¹ to -Z ⁵ are the same or different functional groups which can be converted into ion-exchange groups, and include -SO ₂ F, -CO ₂ R (R: alkyl group), −
C≡N or the like is preferable.

In the above formulas (4) to (6), -Rf ¹ -to -Rf
^5- is preferably the same or different and selected from

[0013]

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In the present invention, the reaction solvent has a boiling point of from 20 to 35 selected from hydrogen-containing fluorinated alkanes, perfluoroalkanes, perfluoroalkylamines, perfluoroethers and perfluorocycloalkanes.
It is a polyfluoro compound at 0 ° C. The boiling point of the polyfluoro compound is selected from the viewpoint of handleability, and the preferred boiling point of the polyfluoro compound is 40 to 300 ° C. These polyfluoro compounds can be used alone or as a mixture of two or more.

The hydrogen-containing fluorinated alkanes include 1,1
1-dichloro-2,2,3,3,3-pentafluoropropane, 1,3-dichloro-1,1,2,2,3-pentafluoropropane, 1,1-dichloro-1-fluoroethane, 2H , 3H-perfluoropentane, 1H-perfluorohexane, 1H, 4H-perfluorobutane, 1H-perfluorooctane, 1H-perfluorodecane, 1H, 1H, 1H, 2H, 2H-perfluorohexane, 1H, 1H , 1H, 2H, 2H-perfluorooctane, 1H, 1H, 1H, 2H, 2H-perfluorodecane, 3H, 4H-perfluoro-2-methylpentane, 2H, 3H-perfluoro-2-methylpentane, etc. Hydrogen-containing fluorinated alkanes having 2 to 10 carbon atoms are exemplified.

The perfluoroalkanes include perfluorohexane, perfluorooctane, perfluorodecane, perfluorododecane, perfluoro-2,7
6 to 6 carbon atoms such as dimethyloctane, hexafluoropropene dimer and hexafluoropropene trimer
12 perfluoroalkanes.

The perfluoroalkylamines include:
And perfluoroalkylamines such as perfluorotributylamine and perfluorotripropylamine.

The perfluoroethers include perfluorocyclic ethers such as perfluoro (2-butyltetrahydrofuran) and perfluorochain ethers such as perfluoropolyether.

As perfluorocycloalkanes,
Perfluorodecalin, perfluorocyclohexane,
Perfluoro (1,2-dimethylcyclohexane), perfluoro (1,3-dimethylcyclohexane), perfluoro (1,3,5-trimethylcyclohexane),
And perfluorocycloalkanes such as perfluoro (dimethylcyclobutane).

The amount of the above-mentioned reaction solvent is preferably adjusted so that the concentration of the compound of formula 6 to be formed is 1 to 50% by weight. If the concentration is too high, the yield and thermal stability of the compound of formula 6 will decrease, and if the concentration is too low, the volumetric efficiency of the reaction will be poor, which is industrially undesirable.

In the present invention, hydrogen peroxide, potassium peroxide, sodium peroxide, barium peroxide and the like are preferable as the peroxide to be reacted with the compound of formula 4 or 5. When using hydrogen peroxide, it is preferable to use it alone, and when using another peroxide, it can be used alone or as a mixture of two or more.

When using hydrogen peroxide, it is preferable to use a cocatalyst. As the cocatalyst, sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate and the like are preferable. These cocatalysts can be used alone or as a mixture of two or more.

When the reaction of the compound of the formula (4) with the peroxide is carried out, when the hydrogen peroxide is used as the peroxide, the compound of the formula (4): hydrogen peroxide: cocatalyst = 1: 1
It is preferably in the range of 0.3 to 20: 0.3 to 10, and particularly preferably in the range of 1: 0.5 to 10: 0.5 to 7.

When a peroxide other than hydrogen peroxide is used, the charged molar ratio is as follows: compound of formula 4: peroxide = 1:
It is preferably in the range of 0.3 to 20, especially 1: 0.
It is preferred to be in the range of 5 to 15.

If the molar ratio of the peroxide and the cocatalyst is too high, the yield of the compound of formula 6 is reduced, and if the molar ratio of the peroxide and the cocatalyst is too low, The reaction requires a long time and the yield of the product is undesirably reduced.

Further, the peroxide and the cocatalyst are preferably dissolved in water and used as an aqueous solution. In this case, the concentration of the peroxide or the cocatalyst in the aqueous solution is preferably 1 to 60% by weight, and particularly preferably 5 to 60% by weight. It is preferably in the range of ３０30% by weight. If the concentration is too high, the yield of the product will be reduced, and if it is too low, the reaction efficiency will be significantly reduced, which is not industrially preferable.

The amount charged when reacting the compound of formula (5) with a peroxide is half that of the compound of formula (4).

[0028] The reaction temperature is preferably in the range of -30 to + 50 ° C. If the reaction temperature is too low, a long time is required for the reaction. If the reaction temperature is too high, the reaction pressure is undesirably increased and the decomposition rate of the generated compound of formula (6) is undesirably increased.
The reaction time is preferably industrially 0.1 to 10 hours.

The compound of the formula (6) obtained by the present invention is useful not only as a radical polymerization initiator, but also as a perfluoro-substituted compound having an ion-exchange group or a substituent convertible to an ion-exchange group in an aromatic compound. Groups can be introduced. Such reactions are described, for example, in the Journal of Flu
orine Chemistry, Vol. 49, pp1-20, (1990) and Journal
of Fluorine Chemistry, Vol. 61, pp 253-272, (1993).

[0030]

EXAMPLE In a four-necked flask equipped with a stirrer, a thermometer and a dropping funnel, 3.30 g of 85% potassium hydroxide was placed.
(0.05 mol) and 28 g of water were added and dissolved. Then, under stirring, 1,3-dichloro-1,1,2,2,3-
After adding 122 g of pentafluoropropane (R225cb), the mixture was cooled to about 0 ° C., and 5.8% of 30% by weight aqueous hydrogen peroxide was added.
g (0.05 mol) was added.

Next, FSO ₂ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) C
OF 20.5 g (0.04 mol) and R225cb20.
A mixed solution with 5 g (0.04 mol) was added dropwise at 0 to 5 ° C over 20 minutes. After continuously stirring for 45 minutes,
The aqueous and organic phases were separated. The yield of the organic phase was 158 g. As a result of analyzing the organic phase by the iodometry method,
The yield was 68%.

In the measurement of ¹⁹ F-NMR (90 MHz, CFCl ₃ standard, addition of CDCl ₃ ), -CF in the starting material was
^{* A} peak based on (CF ₃ ) COF was observed at 132 ppm, but shifted to 141 ppm when left overnight at room temperature. This is due to the formation of the compound of Chemical Formula 9, which is a dimer of the radical of Chemical Formula 8.

[0033]

Embedded image FSO ₂ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ )

[0034]

Embedded image FSO ₂ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) -CF (CF ₃ ) OCF
₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₂ F

[0035]

By using the reaction solvent of the present invention, the desired compound of formula 6 can be obtained in high yield. The compound of formula 6 is not only useful as a radical polymerization initiator, but also can introduce a perfluoro substituent having an ion exchange group or a substituent convertible into an ion exchange group into an aromatic compound.

Claims (3)

[Claims] 1. The method of claim 1, wherein the functional group-containing fluorine-containing compound represented by the formula (1) or (2) is selected from hydrogen-containing fluorinated alkanes, perfluoroalkanes, perfluoroalkylamines, perfluoroethers and perfluorocycloalkanes. A method for producing a functional group-containing fluorine-containing peroxide represented by Chemical Formula 3, characterized by reacting with a peroxide in a selected polyfluoro compound solvent having a boiling point of 20 to 350 ° C. Embedded image (In the chemical formula ¹ , Z ¹ is a functional group which can be converted to an ion exchange group;
f ¹ is a polyfluoroalkylene group which may have an ether bond, and X is a halogen atom. ) (In the chemical formula ² , Z ² and Z ³ are the same or different, a functional group convertible to an ion exchange group, Rf ² and Rf ³ are the same or different, and a polyfluoroalkylene group which may have an ether bond. The formula is as follows. (Wherein, Z ⁴ -Rf ⁴ -is Z ¹ -Rf ^1- , Z ² -R
f ² - or Z ³ -Rf ³ - a and, Z ⁵ -Rf ⁵ - is ^{Z 1 -Rf 1 -, Z 2} -Rf 2 - or Z ³ -Rf ³ -
It is. ) Wherein ^{-Z 1, -Z 2, -Z 3} , -Z 4 and -
Z ⁵ is -SO ₂ F, -CO ₂ R: method according to claim 1 which is (R group) or -C≡N. 3. The method of claim 1, wherein the hydrogen-containing fluorinated alkane is 1,1-dichloro-2,2,3,3,3-pentafluoropropane and / or 1,3-dichloro-1,1,2,2,3-.
3. The process according to claim 1, which is pentafluoropropane.