JPH05213855A - Compounds bearing fluoroalkylsulfonate group and production thereof - Google Patents

Abstract

PURPOSE:To provide a novel compound whose polymer is useful as an acid catalyst of excellent catalyst activity with no swelling properties. CONSTITUTION:A compound of formula I [Q is (CXY)n-CFH, (CXY)n-1-CZ=CF, (X, Y, Z are H, F; n is 0, 1; but is not 0, when (CXY)n-1-CZ=CF); M is H, base], for example, sodium 4-(4-vinylphenyl)-1,1,2-trifluorobutanesulfonate. The compound of formula I is obtained by sulfonating a compound of formula II with a sulfonating agent such as hydrogen sulfite salt in the presence of a phase-transfer catalyst such as tetrabutylammonium chloride and a radical inhibitor such as t-butylcatechol. The polymer of the compound of formula I is strongly acidic and can be used as an acid catalyst in alkylation reaction, isomerization reaction between xylene and toluene, aromatic nitration and Friedel-Crafts reaction.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel compound having a fluoroalkylsulfonic acid group and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, a polymer having a structure represented by the following general formula (A) is generally known.

[0003]

[Chemical 5]

[In the formula, p is 1 or 2, and m is an integer of 2 or more.] Such a polymer may be used alone as a resin or may be supported on a carrier and used as an acid catalyst. Known (for example, Japanese Examined Patent Publication No. 41-7949)
Publication, Japanese Examined Patent Publication No. 43-21408, Takaomi Satokawa, “Functional Fluorine-Containing Resin,” Nikkan Kogyo Shimbun, 1982,
See page 108 etc.).

This polymer requires Friedel-Crafts type reaction such as acylation reaction, Fries rearrangement reaction, and alkylation reaction, in which a conventional acid catalyst requires an equal amount or more for the reaction and it is difficult to recover the catalyst after the reaction. In the above, the catalyst has excellent catalytic properties such that the reaction is achieved with a small amount used and the recovery and regeneration are easy.

[0006]

However, such a polymer has a low functional group density of the strong acid group as an active ingredient, that is, a low content rate of the structure represented by the general formula (A), depending on its production method. Alternatively, there is a problem that the swelling property is high and the mechanical strength as a catalyst cannot be maintained.

[0007]

The present invention provides -CF = CF.
The monomer having _two sulfonated, by polymerizing them, it is an object to efficiently produce a polymer and a polymer having a high fluoroalkyl sulfonic acid functionalized group density. Further, the present invention provides a precursor of a strong acidic polymer having a large ion exchange capacity and a small swelling property, and a strong acidic polymer. That is, the present invention relates to a compound having a fluoroalkylsulfonic acid represented by the general formulas (I) and (II) or a salt thereof in claims 1, 2 and 4 above.

The present invention will be described in detail below. The compound having a fluoroalkylsulfonic acid group of the present invention can be produced by sulfonation of the monomer represented by the general formula (III) in the above-mentioned claim 3.

The monomer of the general formula (III) can be obtained from p-chlorostyrene as a raw material by the following synthetic route. That is, a Grignard reagent is synthesized from p-chlorostyrene and reacted with a compound represented by A- (CXY) _n —CF═CF ₂ to obtain a monomer (III).

[0010]

[Chemical 6]

As used herein, A- (CXY) _n -CF = C
In F ₂ , A represents Cl, Br, I, and X and Y are H or F. N is an integer of 0 or more, preferably 10 or less. Specifically, ClCF = CF
₂ , BrCF = CF ₂ , ICF = CF ₂ , ClCH ₂ C
F = CF ₂ , BrCH ₂ CF = CF ₂ , ICH ₂ CF =
_{CF 2, ClCF 2 CF = CF} 2, BrCF 2 CF = C
F ₂ , ICF ₂ CF = CF ₂ , ClCH ₂ CH ₂ CF =
CF ₂ , BrCH ₂ CH ₂ CF = CF ₂ , ICH ₂ CH
₂ CF = CF _{2 and the} like.

Next, the monomer (III) can be sulfonated as described below to obtain the monomer (I ') or (I ").

[0013]

[Chemical 7]

The sulfonation method includes the monomer (III)
In a reaction medium consisting of an organic solvent and water, using a phase transfer catalyst selected from a quaternary ammonium salt and a quaternary phosphonium salt, and a sulfonating agent in the presence of a radical inhibitor. In the present invention, when the ammonium salt is used as the phase transfer catalyst, only the compound represented by the general formula (I ′) is produced, and when the phosphonium salt is used, mainly the compound represented by the general formula (I ″) is used. Generate,
A small amount of the compound (I ') is also produced. The quaternary ammonium salt used as a phase transfer catalyst, for example, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide,
Tetrabutylammonium sulfate, trioctylammonium chloride, tetrabutylammonium bromide,
Tetrapropylammonium bromide, tetraphenylammonium chloride, tetraphenylammonium bromide, tetraphenylammonium iodide and the like can be mentioned.

Examples of the quaternary phosphonium salt include tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium iodide, tetraphenylphosphonium bromide, tetraphenylphosphonium chloride and tetraphenylphosphonium iodide. .. The sulfonating agent used in the present invention includes bisulfite and sulfite,
Examples thereof include sodium hydrogen sulfite, potassium hydrogen sulfite, cesium hydrogen sulfite, sodium sulfite, potassium sulfite, and cesium sulfite. As the organic solvent, general organic solvents can be applied. For example, benzene,
Toluene, xylene, chlorobenzene, nitrobenzene, chloroform, tetrahydrofuran, methanol,
Examples thereof include ethanol, isopropanol, ethyl acetate, acetic acid, acetone and the like, and preferable examples include hydrophobic organic solvents such as toluene, xylene, chlorobenzene and chloroform.

The radical inhibitors used in the present invention include t-butylcatechol, p-methoxyphenol,
Examples thereof include hydroquinone, benzoquinone, and pyrogallol. To carry out the present invention, a required amount of a sulfonating agent, a phase transfer catalyst, a radical inhibitor, an organic solvent and water are added to the monomer represented by the general formula (III), and the mixture is reacted at a predetermined temperature to carry out the sulfonation. To do.

The sulfonation reaction seems to have higher reactivity as the temperature rises, but in consideration of the polymerization of the monomers used, it is generally preferable to carry out at the reflux temperature of the solvent used, for example, When benzene is used as the solvent, the temperature is preferably 80 ° C, and when chloroform is used as the solvent, the temperature is preferably around 70 ° C. The reaction time varies depending on the type of the phase transfer catalyst, but is generally preferably 5 to 70 hours.

The base represented by M is determined by the type of sulfonating agent used. Therefore, as an example of M, sodium, potassium,
Examples include cesium. Further, when M is hydrogen, it becomes a very strong acid, which is very unstable and easily polymerizes, so that isolation is difficult. Further, the polymer (II) of the present invention can be obtained by polymerizing a compound having a fluoroalkylsulfonic acid group represented by the general formula (I). Specifically, in addition to the homopolymer of the monomer (I ′), the homopolymer of the monomer (I ″), the copolymer of the monomers (I ′) and (I ″), the monomer (I ′) ) And / or (I ″) and other polymerizable monomers.

Specifically, as described above, in the monomer (I) of the present invention, a compound in which M is a hydrogen atom is very likely to be polymerized, and is polymerized immediately when the sulfonate is converted to a free form. Therefore, it is easy to obtain homopolymers and copolymers of the following monomers (I ′) and (I ″).

[0020]

[Chemical 8]

(Wherein x is an integer of 2 or more and y is an integer of 1 or more) and the like, and the molecular weight of these polymers is about 1,000 to 1,000,000. Also,
Since the polymer of the present invention is produced by polymerizing a monomer having a fluoroalkylsulfonic acid group, it is 2.6 meg / g.
It has the above high functional group density.

Although the polymer of the present invention is novel, the method used for specifying the structure of a general linear copolymer cannot be applied to the specification of the structure in many cases. This is because the polymer of the present invention is often insoluble in a solvent for the measurement necessary for the structure identification, so that the structure identification measuring method using various spectra cannot always be used. Therefore, in the present invention, the method used for structure identification is to determine the composition ratio by elemental analysis of the obtained polymer and to identify the atomic groups present in the polymer by infrared absorption spectrum (IR). It is a method of identifying by.

In short, the polymer of the present invention can be measured for its various basic physical properties and chemical compositions, but it is impossible to specify the sequence of repeating units, the three-dimensional structure, etc. In such a case, the identification is carried out in the same manner as the three-dimensional crosslinked polymer as described in the following publications. (Yamabe and Senoo, "Ion Exchange Resin Membrane" (Gihodo 1964)
Year) p. 17-21 or Kakihana and Mori, "Introduction to Ion Exchange" (Hirokawa Shoten 1969) p. 19-20).

[0024]

EXAMPLES The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Reference Example P- (3,4,4-trifluoro-3-butenyl) styi
Len synthesis 0.53g magnesium in a 50ml 4-neck flask
(22 mmol) and dry tetrahydrofuran (TH
F) 20 ml was put and p-chlorostyrene was added dropwise under an argon atmosphere to prepare a Grignard reagent. 200
In a 4-ml flask with 4-ml, 4-bromo-1,1,2-trifluoro-1-butene (CF ₂ = CFCH ₂ CH ₂ B
r) 3.78 g (20 mmol), tetrahydrofuran 20 ml, and cuprous bromide 60 mg (0.42 mmol) were placed in a 200 ml flask, and the prepared p-chlorostyrene Grignard reagent was added dropwise under an argon atmosphere. After stirring for 1 hour, 50 mg of t-butylcatechol
Was added and hydrolyzed with 15 ml of water. After extraction with 15 ml of ethyl ether and drying over magnesium sulfate, the ethyl ether was distilled off and the residue was distilled under reduced pressure. As a result, P- (3,4,4-trifluoro-3-butenyl)
1.25 g of styrene were obtained. The yield of this product is 2
It was 9.5% and the boiling point was 64-68 ° C / 2 mmHg.

(1) Elemental analysis value Actual measurement value C (%) 68.19, H (%) 5.14, F
(%) 26.22 Calculated value C (%) 67.92, H (%) 5.22, F
(%) 26.86

[0027]

[Chemical 9]

[0028]

[Chemical 10]

[0029]

[Chemical 11]

Example 1 17.7 g (83.4 mmo) of P- (3,4,4-trifluoro-3-butenyl) styrene obtained in the above reference example
l), 25.0 g of NaHSO ₃ (240.0 mmo
l), solvent (H ₂ O 50 ml, chloroform 50 m
l), t-butylcatechol 0.3 g (2 mol% / P
-(3,4,4-trifluoro-3-butenyl) styrene), tetrabutylammonium bromide 2.9 g (1
0 mol% / P- (3,4,4-trifluoro-3-butenyl) styrene) was placed in the flask and reacted at 70 ° C. for 15 hours.

Gas chromatography (SE-30 1
When the organic layer of the reaction solution was analyzed by a 5% 2 m column), the conversion rate of P- (3,4,4-trifluoro-3-butenyl) styrene as a raw material was 62.5%. After the reaction, post-treatment was performed by the following method. The post-treatment temperature was 20 ° C. or lower in order to suppress the polymerization of the product.

First, H ₂ O in the aqueous layer was evaporated under reduced pressure and the obtained solid was extracted with isopropanol. After extraction,
The insoluble solid was filtered off, isopropanol was evaporated from the filtrate under reduced pressure, the remaining white solid 1 was dissolved in H ₂ O, and an acid type ion exchange resin (Diaion SAIB-Na type, trade name) was passed through. It was The H ₂ O of the aqueous solution after passing was evaporated under reduced pressure, the resulting white solid 2 was extracted with isopropanol, the insoluble solid was filtered off, and the isopropanol was evaporated under reduced pressure to give the product 4- (4- Vinylphenyl)-
2.8 g of sodium 1,1,2-trifluorobutanesulfonate (yield 10.6%; used P- (3,4,4
-Trifluoro-3-butenyl) styrene standard) was obtained.

Its structure is elemental analysis, ¹ H-NMR, ¹³ C
-NMR, ¹⁹ F-NMR and IR suggested that it was sodium 4- (4-vinylphenyl) -1,1,2-trifluorobutanesulfonate. The analysis results are shown below. An IR chart is shown in FIG.

(1) Elemental analysis result Measured value C (%) 45.90, H (%) 3.56, S
(%) 9.75, F (%) 17.52 Calculated value C (%) 45.57, H (%) 3.82, S
(%) 10.14, F (%) 18.02

[0035]

[Chemical 12]

Δ (ppm) a 2.80 (d 2.0H J (C H ₂ -C F H) =
20.9 Hz) b 3.45 (t 1.9H) c 5.21 (d 1.1H J (Hc-He) = 1
0.8 Hz) d 5.68 (d 1.0H J (Hd-He) = 1
7.9 Hz) e 6.62 (dd 1.0H) f 5.70 (m 0.7H, J (HF) = 48.6
Hz) g 7.24 h 7.26

[0037]

[Chemical 13]

Δ (ppm) A 26.5 B 29.5 C 114.5 D 127.4 E 128.7 F 135.7

[0039]

[Chemical 14]

Δ (ppm) a 113.6, 118.8 (AB type) J (AB) = 262.0 Hz b 203.3 (m) (5) IR (kBr, cm ^-1 ) 1620 (- _{CH = CH 2) 1200-1300 (C} -F, s = 0 asym) 1060 (s = 0 sym)

Example 2 1.77 g (8.3 mmol) of P- (3,4,4-trifluoro-3-butenyl) styrene, NaHSO ₃ 2.
5 g (24.0 mmol), solvent (H ₂ O 5.0 m
1, benzene 5.0 ml), t-butylcatechol 0.03 g (2 mol% / P- (3,4,4-trifluoro-3-butenyl) styrene), tetrabutylphosphonium bromide 0.28 g (10 mol% / P). -(3
4,4-trifluoro-3-butenyl) styrene) was put in the flask and reacted at 80 ° C. for 15 hours.

By ¹⁹ F-NMR of the reaction solution, 4- (4-
It was revealed that sodium vinylphenyl) -1,2,2-trifluoro-2-butenesulfonate was produced. In addition, 4- (4-vinylphenyl) -1,
A very small amount of sodium 2,2-trifluorobutanesulfonate was obtained. Gas chromatography (SE-30
When the organic layer of the reaction solution was analyzed by a 15% 2 m column), the conversion rate of P- (3,4,4-trifluoro-3-butenyl) styrene was 48.2%.

[0043]

[Chemical 15]

Chemical shift value (ppm) a 108.0 ppm b 172.8 ppm

Example 3 (Production of Polymer) 4- (4-vinylphenyl) -1,1, obtained in Example 1,
Sodium 2-trifluorobutanesulfonate 0.20
g was dissolved in about 10 ml of H ₂ O and passed through a strongly acidic ion exchange resin (Diaion SKIB-H type, trade name) column (inner diameter 1.2 cm, height 15 cm). By evaporating the solvent from the solution after passing, 0.19 g of a brown polymer insoluble in the organic solvent was obtained. The analysis was performed by elemental analysis and IR. The results are shown below. An IR chart is shown in FIG.

[0046]

[Table 1]

[0047] (2) IR (kBr, cm -1) 1040cm -1 (s = 0) 1100~1250cm -1 (C-F, s = 0)

(3) Ion exchange capacity 2.9 meq /
g The functional group density calculated from the elemental analysis value of S was 2.7 m.
eq / g, which was in good agreement.

Application example Evaluation reaction (1-Koch reaction of 1-hexene) 70 ml, Hastelloy C
Into the micro-autoclave, the acid catalyst obtained in Example 3 above, 20 mmol of 1-hexane, and 200 of methanol were added.
mmol was added, and carbon monoxide was injected under pressure (about 100 k.
g / cm ² ). Temperature 150 ℃, Pressure 150kg / cm ²
Then, it was reacted for 3 hours. The case where the polymer of the present invention is used and the case where a commercially available perfluorosulfonic acid resin (manufactured by DuPont, trade name Nafion NR50) are used are compared and summarized in Table 1. As a result, the polymer of the present invention (Example 3) produced less hydrate than the commercially available resin when compared with the same acid amount, and showed good results.

[0050]

[Table 2]

[0051]

INDUSTRIAL APPLICABILITY The polymer having a fluoroalkylsulfonic acid group of the present invention is strongly acidic and can be used as an excellent acid catalyst. This catalyst can be used, for example, in an alkylation reaction, an isomerization reaction of toluene and xylene, an aromatic nitration reaction or a Friedel-Crafts reaction, an olefin carbonylation reaction (Koch reaction), and the like. Compared with the obtained fluorinated polymer catalyst, it has no swelling property and is excellent in catalytic activity.

The fluoroalkylsulfonic acid group-containing monomer of the present invention is useful as a precursor of a fluoroalkylsulfonic acid group-containing polymer, and can be used as an acid catalyst or a raw material for an ion exchanger. .. Furthermore, according to the method of the present invention, such a compound having a useful fluoroalkylsulfonic acid group can be industrially advantageously produced.

[Brief description of drawings]

FIG. 1 is an IR chart of the compound of the present invention produced in Example 1. The vertical axis represents absorbance and the horizontal axis represents wavelength (nm).

FIG. 2 is an IR chart of the compound of the present invention (polymer) produced in Example 3. The vertical axis represents absorbance and the horizontal axis represents wavelength (n
m).

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location C08F 12/20 MJY 7211-4J 12/30 MJY 7211-4J // C07B 61/00 300

Claims (4)

[Claims] 1. A compound having a fluoroalkyl sulfonic acid group, which is represented by the following general formula (I). [Chemical 1] {In the formula, Q is-(CXY) _n -CFH- or-(CX
Y) _n-1 -CZ = CF- (X, Y and Z each represent a hydrogen atom or a fluorine atom, n represents 0 or an integer of 1 or more,-(CXY) _n-1 -CZ = CF In the case of −, n is not 0.) and M represents a hydrogen atom or a base. } 2. A polymer having a structural unit represented by the following general formula (II), obtained by polymerizing a polymerizable compound containing at least the compound of general formula (I) according to claim 1. [Chemical 2] {In the formula, P represents an integer of 1 or more, and Q represents-(CXY)
_{n -} CFH- or-(CXY) _n-1 -CZ = CF- (wherein X, Y and Z each independently represent a hydrogen atom or a fluorine atom, n represents 0 or an integer of 1 or more,-
In the case of (CXY) _n-1 -CZ = CF-, n is not 0. }, M represents a hydrogen atom or a base. } 3. A compound represented by the following general formula (III) is used in a reaction medium consisting of an organic solvent and water, a quaternary ammonium salt or a quaternary phosphonium salt as a phase transfer catalyst in the presence of a radical inhibitor. The method for producing a compound according to claim 1, wherein the compound is sulfonated with a sulfonating agent. [Chemical 3] {In the formula, X and Y each represent a hydrogen atom or a fluorine atom, and n represents 0 or an integer of 1 or more. } 4. A polymer having a structural unit containing a fluoroalkylsulfonic acid group represented by the following general formula (II). [Chemical 4] {In the formula, p represents an integer of 1 or more, and Q is-(CXY)
_{n -} CFH- or-(CXY) _n-1 -CZ = CF- (wherein X, Y and Z each independently represent a hydrogen atom or a fluorine atom, n represents 0 or an integer of 1 or more,-
In the case of (CXY) _n-1 -CZ = CF-, n is not 0. ) And M represent a hydrogen atom or a base. }