JPH01305045A - Method for producing fluorine-containing diol - Google Patents

Abstract

NEW MATERIAL:The fluorine-containing diol of formula I (Rf is 4-20C perfluoroalkyl; n is 1 or 2). USE:A resin modifier capable of improving the water- and oil-repellency, low refractive index, water-absorption and weather resistance and increasing the elasticity of resin. PREPARATION:The objective compound of formula I can be produced by reacting (A) an epoxy compound of formula III with (B) >=1mol-equivalent, preferably >=5mol-equivalent (based on the component A) or water in the presence or (C) 0.01-5wt.% (based on the compound of formula III) or a catalyst consisting of inorganic acid (e.g., concentrated sulfuric acid) or organic acid (e.g., p-toluenesulfonic acid) in a non-reactive organic solvent selected from ketones, ethers, sulfoxides and sulfones under heating and stirring at 30-100 deg.C. The starting epoxy compound of formula III can be easily produced by reacting a compound of formula II with epichlorohydrin in the presence of an alkali metal hydroxide.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a novel fluorine-containing diol useful as a resin modifier and a method for producing the same.

(Prior art and its problems) Known fluorine-containing diols are compounds represented by the general formula C (where Rf is a perfluoroalkyl group having 1 to 20 carbon atoms and X is a CHt, SOs, or SO group). It is used as a modifier to impart water and oil repellency, low refractive index, etc. to resins (Japanese Patent Publication No. 62-22982).

Special Publication No. Sho 62-22983 1% Kai Sho 53-8490
9, Japanese Patent Application Laid-Open No. 62-22735, German Patent No. 1568378).

In recent years, there has been a demand for improved water and oil repellency and low refractive index properties of resins, and when the above-mentioned known fluorine-containing diols are used as intermediates for such applications, water and oil repellency, Although an improvement in low refractive index can be seen, compounds in which X in formula (I) is an SOI or SO group have the drawbacks of high water absorption and poor weather resistance. Also, X in formula C1 is C
Although the above-mentioned drawbacks of the metal compound, which is HI, have been improved, the resin synthesized using it has the drawback of poor elasticity.

(Objective of the Invention) The present inventors have solved the above problems, and have improved water repellency, oil repellency, and low refractive index, as well as water absorption.

In order to provide a fluorine-containing diol that can improve weather resistance and increase elasticity, as a result of intensive research, it was discovered that a fluorine-containing diol having an ether bond in the molecule achieves the above objectives, and the present invention Reached.

(Structure of the Invention) That is, according to the present invention, Rf(CHI) n0cHt CHCH* Of(・
...' (1) A fluorine-containing diol is obtained, characterized in that R7 in the H C formula is represented by a perfluoroalkyl group having 4 to 20 carbon atoms, and n is an integer of 1 or 2.

The fluorine-containing diol of the present invention can act as a condensed monomer by the reaction of two hydroxyl groups present in the molecule, and the perfluoroalkyl group has properties such as water repellency, oil repellency, and low refractive index. It imparts properties unique to fluorine compounds, and since it does not contain SOI or So groups, it eliminates water absorption and improves weather resistance.Furthermore, the ether bond present in the molecule imparts flexibility to the molecule. This increases the elasticity of the resin.

The fluorine-containing diol of the present invention is thus a more useful compound as a resin modifier than conventional ones.

In the fluorine-containing diol represented by the general formula (1) of the present invention, Rf is a perfluoroalkyl group having a limited number of carbon atoms of 4 to 2G, and may be either a linear type or a branched type. Good too. Further, n is an integer of 1 or 2.

The present invention also provides an epoxy compound represented by the general formula (in the formula, Rf is a perfluoroalkyl group having 4 to 20 carbon atoms, n is an integer of 1 or 2) and water, using an inorganic or organic acid as a catalyst, to produce a ketone. ft.
The present invention provides a method for producing a fluorine-containing diol characterized by the above-mentioned general formula 2m. In the production method of the present invention, the epoxy compound represented by the general formula (1) is prepared by combining a compound represented by the general formula (% formula %] C (in which Rf and n are the same as the general formula fil) and shrimp chlorohydrin with an alkali metal compound. It can be easily obtained by reaction in the presence of hydroxide (U.S. Pat. No. 3,361,685, U.S. Pat. No. 3,417,03).
(See specification No. 5).

Further, the compound represented by the general formula a) is a common compound and can be easily obtained as a raw material for the fluorochemical industry. Specifically, it is as follows.

CsF+5CHtCHtOH, CtFtaCHtOHC
m Fty CHt CHz OH The water used is used in an amount of 1 mol or more, preferably 5 mol equivalent or more, based on the compound represented by the general formula fffl, and the amount of the acid catalyst used is usually 1 mol or more, preferably 5 mol equivalent or more, based on the compound represented by the general formula + ffl. The acid used may be mineral acids such as sulfuric acid, hydrochloric acid or nitric acid, or organic acids such as acetic acid or p-toluenesulfonate. The reaction is carried out at 30 to 100°C, preferably 60°C.
This is carried out by heating and stirring at a temperature range of 90°C to 90°C.

EXAMPLES Next, the present invention will be specifically explained with reference to Examples, but the following Examples do not limit the scope of the present invention.

Example 1 SOO with thermometer, stirrer, reflux condenser 102, 7 g (0-225 m-) y 5 ornl water, 1,4-dio** as solvent 7300 rrtl, f
1J sulfuric acid 065d was added, and the system was vigorously heated to 80° C. using an oil bath, and stirred for 12 hours. As a result of gas chromatography analysis, the disappearance of the epoxide and the presence of reaction products were confirmed.

After neutralizing the reaction mixture by adding Tic Ca (OH) t, the generated precipitate was filtered and distilled under reduced pressure to obtain 83,2I.
A product (jelly-like) was obtained. The yield at that time was 77.
9%. The boiling point of the product obtained is 106℃10, 1t
It was m Hi. IJ 3100~ by infrared spectroscopy
36003. 2900cm, 1260~-1
There was a heater at +1120.

The following 7 fragments were obtained by gas mass analysis.

(m/e, relative intensity, attribution) 474 (1,2%.

+ M), 457 (2,1% r M-OH), 443 (
15%, M-CH,OH), 413 (6,3s.

OH 61 (100%, CH(,'t(,0I()) Example 2 Into the apparatus used in Example 1, m-), 20 m of water, and 150 m/m of acetate as a solvent were added.
.

1 dIk of concentrated hydrochloric acid was added, and the inside of the system was heated to 60° C. using an oil bath, and stirred for 18 hours. As a result of gas chromatography analysis conducted under the same conditions as in Example 1, the disappearance of the epoxide and the presence of reaction products were confirmed. By vacuum distillation, 5
A product of 3.1.9 was obtained (yield 52 cm).

Example 3 1. Dimethyl sulfoxide (
The reaction was carried out under the same conditions as in Example 1, except that the reaction temperature was 90°C.

The same operation as in Example 1 was performed to obtain 67.4 fl of a product. The yield at that time was 611%.

Example 4 30042,0 equipped with thermometer, stirrer and reflux condenser
9 (o, 1 mcJ) *20 g of water, 1 g as solvent
．． Add 150 mj of 4-dioxa and 0.2 M of concentrated sulfuric acid 1
The system was heated to 80° C. using an oil bath and stirred for 20 hours. As a result of gas chromatography analysis, the disappearance of the epoxide and the presence of reaction products were confirmed.

After neutralizing the reaction mixture with Ca(OH)2,
The generated precipitate was filtered and distilled under reduced pressure to obtain a 37.2y product (jelly-like). The yield at that time was 85.0%.

The boiling point of the product obtained was 125°C 70, 2 mx [(
It was 9.

3100-3aoocrn by infrared spectroscopy.

A heater was present at 2900 crrL and 1260 to 1120 cIft.

Example 5 Tetrahydrofuran (3
001M) + p-) luenesulfonic acid (instead of concentrated sulfuric acid)
o, s, l, except that the reaction temperature was 70°C fIJ
The reaction was carried out under the same conditions as in Example 4, and a 26.9 p product was obtained by the same operation as in Example 4.

The yield at that time was 61.5%.

Patent applicant: Mitsubishi Metals Corporation

Claims (2)

[Claims] (1) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・(I) (In the formula, R_f is a perfluoroalkyl group having 4 to 20 carbon atoms, and n is an integer of 1 or 2) A fluorine-containing diol characterized by: (2) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・(I
I) (wherein R_f is a perfluoroalkyl group having 4 to 20 carbon atoms, n is an integer of 1 or 2) and water (using an inorganic or organic acid as a catalyst, ketones, ethers, A method for producing a fluorine-containing diol represented by the general formula (I), characterized by carrying out the reaction in a non-reactive organic solvent selected from the group consisting of sulfoxides and sulfones.