JPS5849376A - Fluorine-containing ketal and acetal and preparation and use thereof - Google Patents

Abstract

NEW MATERIAL:A fluorine-containing ketal and acetal of formulaI[Rf is fluorine-containing aliphatic group; R1 and R2 are H, aliphatic group and aromatic group; R1 and R2 together may form a ring when they are aliphatic group; X and Y are H or 1-3C alkyl; (n) is an integer 0-6]. EXAMPLE:The compound of formula II. USE:Useful as a surface tension reducing agent for organic solvent coating materials or leveling agents of waxes, and capable of improving the wetting property for the untreated surface by reducing the surface tension of the organic solvent and imparting improved effects to various organic solvent treating agents, etc. PROCESS:A fluorine-containing epoxide of formula III is reacted with a carbonyl group-containing compound of formula IV in the presence of a catalyst at about 20-150 deg.C to afford the compound of formulaI. The raw material compound of formula IV is preferably used in a small excess.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to fluorine-containing ketals and acetals, their production methods, and their use as so-called surface tension reducing agents in organic solvent-based paints, wax leveling agents, and the like.

Generally known fluorine-based surfactants are effective in lowering the surface tension of water, but they are not sufficient surface tension lowering agents for organic solvents, and until now they have been excellent surface tension lowering agents for organic solvents. is not known.

In view of these circumstances, the present inventor conducted extensive research and discovered that certain new fluorine-containing ketals and acetals have an excellent ability to lower the surface tension of organic solvents, and have developed the present invention. completed.

That is, one gist of the present invention is the formula: [wherein, Rf is a fluorine-containing aliphatic group; When they are groups, they may be combined to form a ring. X and Y are hydrogen or have 1 to 3 carbon atoms
an alkyl group; n represents an integer of 0 to 6; ] Exists in fluorine-containing ketals and acetals shown in the following.

In the above formula CI'), the fluorine-containing aliphatic group represented by Rf refers to a fluorine-containing saturated or unsaturated, linear or branched, substituted or unsubstituted aliphatic group,
It also includes those in which an oxygen atom is interposed between carbon-carbon bonds. Preferred fluorine-containing aliphatic groups have 3 to 21 carbon atoms.
and/or a group having at least as many fluorine atoms as carbon atoms in the group.

When R1 and R2 are aliphatic groups, the aliphatic group is a saturated or unsaturated, substituted or unsubstituted group having 1 to 100 carbon atoms.
includes groups. When it is an aromatic group, it includes those with nuclear substitution or non-substitution.

Specific examples of the novel compound (1') of the present invention are as shown below. - ShinB bog Another gist of the present invention resides in a method for producing compound [11], which method comprises the following formula: [wherein Rf, X, Y and n have the same meanings as above. ] A fluorine-containing epoxide represented by the formula: % formula % [wherein R1 and R2 have the same meanings as above. ] It consists of reacting a carbonyl group-containing compound represented by:

Regarding the proportion of the two used, it is preferable to use the carbonyl group-containing compound in slight excess, except in the case of ketones used as a reaction medium as described later.

The reaction is generally carried out in the presence of a catalyst at a temperature in the range of about 20-150°C, optionally in a solvent. Examples of the catalyst include various complex compounds of boron trifluoride, sulfuric acid, sodium hydrogen sulfate, zinc chloride, aluminum chloride, and iron trichloride, among which various complex compounds of boron trifluoride are preferred. As a solvent, an excess of ketones as a reaction component may be used as a reaction medium, but when other solvents are used, compounds having no hydroxyl group or carbonyl group are preferred.

Examples of such solvents include ethers (eg, diethyl ether), benzenes (eg, 1'benzene, toluene), halogenated hydrocarbons (eg, evatrichlortrifluoroethane, methylene chloride), and the like.

Yet another aspect of the present invention resides in an organic solvent surface tension reducing agent which is an active ingredient in compound (-1')'.

The compound of the present invention [11 is a leveling and penetrating agent for various organic solvent (including emulsion-based) treatment agents such as paints, waxes, and magnetic powder compositions, and organic solvent-based water and oil repellent for resins and fibers. , sitting surface, treated surface modifier such as anti-stick agent, organic solvent f=71J
It can be particularly preferably used as a peelability improver, a powder processing agent such as a digestive agent for organic solvents, and the like. Lemo is also used for various purposes as a general surfactant. In such a case, the compound [1] of the present invention may be added in an amount of 0.001 to 10% by weight, preferably 0.01 to 5% by weight, based on the stock solution or raw material to be added.

The compound of the present invention lowers the surface tension of the organic solvent, thereby improving its dripping properties onto untreated surfaces, thereby imparting excellent effects to various organic solvent-based processing agents.

Next, Examples and Comparative Examples will be shown to specifically explain the present invention.

Example 1 In a 100-4 Tulo flask equipped with a thermometer, condenser and stirrer, 210 g of Cg Flg CH2-C gub H was added.
(0,019 mol), acetone 30g (0,52 mol)
and boron trifluoride ether, complex compounds o and ig were charged, and reacted for 5 hours with stirring on a hot water bath under refluxing acetone. Gas chromatography analysis confirmed that the epoxide compound Kanakura was consumed.

All excess acetone was distilled off from the reaction mixture, the residue was washed with acetonitrile, and then dissolved in tricofretrifluoroethane and filtered. Trichlorotrifluoroethane was distilled off from the p liquid to obtain 8.5 g (yield 76%) of the title compound in the form of a viscous liquid. Boiling point over 200°C.

The product compound was identified by hydrogen and fluorine NMR analysis. The results are shown in Tables 1 and 2 Table 1 Hydrogen NMR Analysis Table 2 Fluorine NMR Analysis From the results in Table 2, the presence of a perfluoroalkyl group having 19 fluorine atoms was confirmed.

Example 2 ゛g (0.81 mol) and a boron trifluoride ether complex compound were charged and reacted in a hot water bath at -160°C for 5 hours with stirring. Gas chromatography analysis confirmed that the entire amount of epoxide compound was consumed.

A7tonitrile was added to the reaction mixture, and the product was completely precipitated and separated, and then dissolved in trichlorotrifluoroethane. The solution was filtered, and trichlorIJ fluoroethane was distilled off from the p solution to obtain 8.1 g (yield: 68%) of the title compound as a colorless solid. Melting point: 41-42°C The product compound was identified by hydrogen and fluorine NMR analysis. The results are shown in Table 3. NM of Nafu1 Fluorine
The results of R analysis were almost the same as in Example 1.

Examples 3 to 6 and Comparative Examples 1 to 3 A 0.5% dimethylformamide or methyl ethyl ketone solution of the fluorine-containing compound shown in Table 4 (Comparative Example 1
does not contain fluorine-containing compounds. ) was prepared, and the surface tension of the organic solvent solution (also d organic solvent) was measured. Measurements were performed at 25°C using the Wilhelmy method. The results are shown in Table 4.

Note that Comparative Example 2 is an example of a fluorine-containing compound that is a cationic surfactant, and Comparative Example 3 is an example of a fluorine-containing compound that is an anionic surfactant.

Table 4 Example 7 0.1% of the compound obtained in Example 1 was added to a commercially available epoxy emulsion paint, and the mixture was stirred and adjusted.

Several drops of the obtained composition were dropped onto a glass plate using a dropper and allowed to air dry at room temperature. For comparison, the above epoxy paint was applied dropwise in the same manner and allowed to dry.

After drying, the results of comparative observation of the paint surface are shown in the attached reference photo.

The coating example on the left side of the photograph shows the case where the compound of the present invention was added, and the coating example on the right side of the photo shows the case without the addition. In the case of no additives, the relatively light-colored areas are areas where the surface is uneven and has four parts. As described above, when the compound of the present invention is added, the surface smoothness is significantly improved.

Patent applicant: Daikin Industries, Ltd.

Claims (1)

[Claims] [In the formula, Rf is a fluorine-containing aliphatic group; R1 and R2
1d are the same or different and represent hydrogen, an aliphatic group, or an aromatic group, and when R1 and R2 are aliphatic groups, they may be combined to form a ring 6) X and Y are hydrogen or have 1 to 1 carbon atoms; 3 alkyl group; n represents an integer of 0 to 6-. ] Fluorine-containing ketals and acetals. [In the formula, Rf represents a fluorine-containing aliphatic group; X and Y represent hydrogen or an alkyl group having 1 to 3 carbon atoms; li represents an integer of 0 to 6. ) and a fluorine-containing epoxide represented by the formula: R1-C-R2 1 [wherein R1 and R2 are the same or different and represent hydrogen, an aliphatic group, or an aromatic group, and R1 and an aliphatic group are [In the formula, RflRl, R2, X, Y and n have the same meanings as nil]. 3. A method for producing a fluorine-containing ketal and acetal, which is characterized by obtaining a compound containing a fluorine-containing ketal and an acetal. When R1 and R2 are aliphatic groups, they may be combined to form a ring. X and Y are hydrogen or an alkyl group having 1 to 3 carbon atoms; n is an integer of 0 to 6. ] A surface tension lowering agent for organic solvents containing a fluorine-containing ketal and acetal as active ingredients.