JPH05194298A - Fluorine-containing alcohol - Google Patents

Abstract

PURPOSE:To provide a new compound having excellent softness, low-temperature characteristics, low refractive index, etc., and useful as a water and oil repellent, fluorine-containing acrylic rubber material, optical material, etc. CONSTITUTION:The compound of formula I (R is CF2CF2 or group of formula II; n is 2-7 when R is CF2CF2 and n is 1-7 when R is group of formula II), e.g. the compound of formula III. The compound of formula I can be produced by reacting a perfluoroalkyl iodide of formula IV with fuming sulfuric acid and hydrolyzing the obtained sulfuric acid ester.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel fluorine-containing alcohol, particularly as a raw material for (meth) acrylate used as a water and oil repellent and as an intermediate raw material for other fluorine-containing compounds. It relates to very useful compounds.

[0002]

Fluorine-containing alcohols are used as raw materials for fluorine-containing alkyl acrylates and methacrylates, and polymers obtained by polymerizing them alone or with alkyl acrylates, methacrylates and the like are used as water- and oil-repellent agents. The conventionally known fluorine-containing alcohol is a type having a linear perfluoroalkyl group as a fluorine-containing group, and is therefore rigid and crystalline. The polymer of acrylate or methacrylate derived from this fluorine-containing alcohol has a drawback that the texture of the fiber is impaired when it is used as a water and oil repellent.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a useful novel fluorine-containing alcohol represented by the general formula (I), which has been heretofore unknown and is described below. This fluorine-containing alcohol is useful for producing a fluorine-containing polymer in which the above-mentioned drawbacks of the conventional fluorine-containing alcohol are eliminated.

[0004]

That is, the present invention has the general formula
(I):

[Chemical 4] (In the formula, R is —CF ₂ CF ₂ — or

[Chemical 5] N is an integer of 2 to 7 when R is —CF ₂ CF ₂ —, and R is

[Chemical 6] Is an integer of 1 to 7).

The fluorine-containing alcohol represented by the general formula (I) of the present invention can be easily synthesized by a known method such as the method described in German Patent No. 1214660. That is, the following formula (II)

[Chemical 7] (Where m and R are as described above), a perfluoroalkyl iodide represented by the above general formula (I) is hydrolyzed by reacting it with a fuming sulfuric acid to convert it into a corresponding sulfuric ester. Can be obtained. In this case, with respect to 1 mol of perfluoroalkyl iodide,
1-5 mol of sulfuric acid anhydride in fuming sulfuric acid, especially 1.5-2.
It is preferable to use fuming sulfuric acid so as to be 5 mol. The reaction conditions are preferably adjusted as appropriate, but the reaction temperature is 0 to 100 ° C, particularly 15 to 50 ° C for 1 to 50 hours, especially 2 to 20 ° C.
It is preferable to react for a time. The amount of water used for the hydrolysis reaction is 2 to 50 times the volume of fuming sulfuric acid,
It is particularly preferable to use 5 to 20 times. The reaction conditions include a reaction temperature of 20 to 150 ° C., particularly 70 to 100 ° C. for 2 to 50 hours,
It is particularly preferable to react for 5 to 25 hours.

The perfluoroalkyl iodide represented by the above formula (II) can be synthesized by the following known method. Oligomerization

[Chemical 8] Iodination 1) Iodoetherification

[Chemical 9] 2) Halogen exchange / decarbonylation

[Chemical 10] Ethylene addition

[Chemical 11] (N is R is -CF ₂ CF ₂ - is a 2-7 integer if the, R is

[Chemical formula 12] In the case of, an integer of ~ 7)

The oligomerization here is carried out, for example, by adding hexafluoropropylene oxide (HFPO) of the formula (a) to a metal fluoride-aprotic solvent system such as cesium fluoride (CsF) and potassium fluoride (KF) at low temperature. By blowing under, the HFPO oligomeric acid fluoride of formula (b) can be obtained. There are two methods for the terminal iodination of (1), and the oligomeric acid fluoride of the formula (b) separated in the iodoetherification of 1) is treated with tetrafluoromethane in the presence of the same alkali metal fluoride as described above in an aprotic solvent. The terminal iodide of the formula (C) can be obtained by reacting ethylene and iodine. In 2) halogen exchange / decarbonylation reaction, the formula
The oligomeric acid fluoride of (b) is converted to the acid iodide of the formula (d) by a halogen exchange reaction in an alkali metal iodide such as LiI or MgI ₂ or an alkaline earth metal iodide-aprotic solvent, Next, the terminal iodide of the formula (e) can be obtained by decarbonylation by ultraviolet irradiation. In the ethylene addition reaction, the perfluoroalkyl iodide of the formula (II) can be obtained by blowing ethylene into the terminal iodide in the presence of an azo compound such as azobisisobutylnitrile or a peroxide radical addition catalyst.

[0008]

EXAMPLES Example-1 A 500 ml four-necked flask was charged with the following formula (IIa)

[Chemical 13] 200 g of perfluoroalkylethyl iodide
(0.33 mol) was charged and 211 g of 25% fuming sulfuric acid was added dropwise from the dropping funnel over 1 hour while controlling the temperature at 10 to 25 ° C. After completion of dropping, the mixture was stirred at room temperature for 3 hours. Then, 2 liters of water was charged into a 5 liter 4-necked flask, and then the above reaction mixture was added dropwise by a dropping funnel over 2 hours. After the dropping yield, the mixture was heated and stirred at 70 to 90 ° C for 5 hours. After cooling, the separated organic layer was washed with water three times,
Distillation under reduced pressure produces a distillate of boiling point 103 ℃ / 80mmHg 132
g (yield 81%) was obtained. Next, this compound was subjected to elemental analysis, IR spectrum and ¹ H-NMR, ¹⁹ F-
The results shown below were obtained when the NMR was measured. The structures of the compounds obtained from these results are

[Chemical 14] Was confirmed.

[0009] Elemental analysis C H O F Calcd * (%) 24.2 1.0 9.7 65.1 Found (%) 24.3 1.0 9.6 65.1 (* as _{C 10 H 5 O 3 F 17} ) IR spectrum (see Figure 1) characteristic absorption: 3,350 cm ^-1 (-OH) 1,100 to 1,340 cm ^-1 (C-F) ¹ H-NMR spectrum (solvent: CCl ₄ , internal standard: CH
Cl ₃ ) 2.3 to 2.9 (m, 2H, -C-CH ₂ -O) 2.8 (s, 1H, -C-OH) 3.8 to 4.1 (k, 2H, C-CH ₂ -C) ¹⁹ F-NMR spectrum (Internal standard: CF ₃ COOH)

[Chemical 15] (In the formula, a to f represent each fluorine atom) a: -3.05 ppm b: -4.64 ppm c: -6.96 ppm d: -50.12 ppm e: -52.25 ppm f: -67.03 ppm

Example-2 Instead of the perfluoroalkylethyl iodide represented by the formula (IIa) in Example-1, the following formula (IIb):

[Chemical 16] 255 g of perfluoroalkylethyl iodide
The procedure of Example 1 was repeated except that (0.33 mol) was used. As a result, 157 g of a fraction with a boiling point of 151 ° C / 100 mmHg (yield
72%) was obtained. Elemental analysis, IR of this compound
When the spectrum, ¹ H-NMR and ¹⁹ F-NMR were measured, the results shown below were obtained. The structures of the compounds obtained from these results are

[Chemical 17] Was confirmed.

[0011] Elemental analysis C H O F Calcd * (%) 23.5 0.8 9.7 66.0 Found (%) 23.7 0.7 9.9 65.7 (* as _{C 13 H 5 O 4 F 23} ) IR spectrum (see Figure 2) characteristic absorption: 3,350 cm ^-1 (-OH) 1,100 to 1,340 cm ^-1 (C-F) ¹ H-NMR spectrum (solvent: CCl ₄ , internal standard: CH
Cl ₃ ) 2.3 to 2.9 (m, 2H, -C-CH ₂ -O) 2.6 (s, 1H, -C-OH) 3.9 to 4.1 (t, 2H, C-CH ₂ -C) ¹⁹ F-NMR spectrum (Internal standard: CF ₃ COOH)

[Chemical 18] (In the formula, a to f represent each fluorine atom) a: -3.05 ppm b: -4.62 ppm c: -6.97 ppm d: -50.10 ppm e: -52.28 ppm f: -67.01 ppm

Example-3 In Example-1, instead of the perfluoroalkylethyl iodide represented by the formula (IIa), the following formula (IIc):

[Chemical 19] 200 g of perfluoroalkylethyl iodide
The procedure of Example 1 was repeated except that (0.33 mol) was used. As a result, 124 g of a fraction having a boiling point of 124 ° C / 98 mmHg (yield
76%) was obtained. Elemental analysis, IR of this compound
When the spectrum, ¹ H-NMR and ¹⁹ F-NMR were measured, the results shown below were obtained. The structures of the compounds obtained from these results are

[Chemical 20] Was confirmed.

[0013] Elemental analysis C H O F Calcd * (%) 24.2 1.0 9.7 65.1 Found (%) (as _{* C 10 H 5 O 3 F} 17) 24.5 1.1 9.5 64.9 IR spectrum (see FIG. 3) characteristic absorption: 3,350 cm ^-1 (-OH) 1,100 to 1,340 cm ^-1 (C-F) ¹ H-NMR spectrum (solvent: CCl ₄ , internal standard: CH
Cl ₃ ) 1.9 to 2.8 (m, 2H, -C-CH ₂ -O) 3.1 (s, 1H, -C-OH) 3.7 to 4.2 (t, 2H, C-CH ₂ -C) ¹⁹ F-NMR spectrum (Internal standard: CF ₃ COOH)

[Chemical 21] (In the formula, a to g represent each fluorine atom) a: -3.17 ppm b: -4.63 ppm c: -6.16 ppm d: -11.11 ppm e: -40.35 ppm f: -52.31 ppm g: -67.52 ppm

[0014]

The fluorinated alcohol of the present invention is a novel substance and is useful as a raw material for fluoroalkyl acrylate and fluoroalkyl methacrylate. Also, these alone or alkyl acrylate,
A polymer obtained by polymerizing with alkyl methacrylate or the like is useful as a water and oil repellent. In particular, since the fluorine-containing alcohol of the present invention has an ether bond in the perfluoro group, it has excellent flexibility, low temperature properties, low refractive index, etc. It is particularly useful as an intermediate raw material for a fluoroalkyl (meth) acrylate applied to a water-repellent, oil-repellent agent, a fluorine-containing acrylic rubber material having excellent low temperature properties, an optical material, and the like.

[Brief description of drawings]

FIG. 1 is a view showing an IR chart of a compound synthesized in Example 1.

FIG. 2 is a view showing an IR chart of a compound synthesized in Example 2.

FIG. 3 shows an IR chart of the compound synthesized in Example 3.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Koichi Yamaguchi Izumi Hitomi, Matsuida Town, Usui District, Gunma Prefecture 10 Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory

Claims (1)

[Claims] 1. General formula (I): (In the formula, R is —CF ₂ CF ₂ — or N is an integer of 2 to 7 when R is —CF ₂ CF ₂ —, and R is Is an integer of 1 to 7).