JP2006342087A - Nonionic fluorine-containing surfactant and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a functionalized and highly functional nonionic fluorine-containing surfactant useful as an antistatic agent, a leveling agent, a dispersing agent, an emulsifying agent, a defoaming agent or the like; and to provide a method for producing the surfactant. <P>SOLUTION: The nonionic fluorine-containing surfactant is represented by general formula (1) (wherein, R is a 1-6C alkyl group; and n is a number of 3-50). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a nonionic fluorine-containing surfactant useful as an antistatic agent, a leveling agent, a dispersant, an emulsifier, an antifoaming agent, and the like, and a method for producing the same.

  In general, a fluorocarbon chain is introduced into the molecule of a compound as a useful method for imparting properties such as water / oil repellency, anti-adhesion properties, chemical resistance, flame retardancy, and insulation properties to the compound to be modified. This method is widely used in fields such as surfactants, electrical and electronic parts, paints, surface treatment agents, and multifunctional synthetic resins.

  As the fluorocarbon-introducing agent, perfluorocarbon, especially branched perfluorocarbon, is particularly effective because it provides a high reforming effect. In this case, the hexafluoropropene trimer which is not only relatively inexpensive as a fluorine-containing compound but also has a high degree of branching is a kind of fluorocarbon chain introducing agent or a preparation raw material thereof that is extremely useful in practice.

  In this field, particularly in the field of surfactants, in order to enable the wider use of such perfluoropropene trimers, a plurality of functional groups are introduced into the fluorocarbon chain of the trimer to increase the functionality. There is a demand for technology for developing functional surfactants.

As a prior art document related to such a request, Patent Document 1 is known. Patent Document 1 discloses a fluorine-containing surfactant obtained by directly reacting a perfluoropropene trimer with a polyvalent hydroxy compound having a polyethylene glycol chain and a polypropylene glycol chain as essential components. However, only one of a plurality of reaction points of the trimer is used, and the fluorine-containing surfactant does not meet the above requirement.
JP 59-52520 A

  An object of the present invention is to provide a multifunctional nonionic fluorine-containing surfactant having a multifunctional group in order to meet the above-described demand.

（式中、Ｒは、炭素原子数が１〜６のアルキル基を示し、ｎは３〜５０の数を示す。） That is, the present invention relates to a nonionic fluorine-containing surfactant represented by the following general formula (1):

(In the formula, R represents an alkyl group having 1 to 6 carbon atoms, and n represents a number of 3 to 50.)

  In said general formula (1), R shows a C1-C6, Preferably 1-2 alkyl group, n shows the number of 3-50, Preferably 8-22.

  A preferred method for producing the nonionic fluorine-containing surfactant is a method according to the present invention described below.

（式中、Ｒは、炭素原子数が１〜６、好ましくは１〜２のアルキル基を示す。）

（式中、ｎは、１〜５０、好ましくは８〜２２の数を示す。） That is, the present invention provides a fluorine-containing ether compound represented by the following general formula (2) and an alcohol represented by the following general formula (3) in an aprotic polar solvent in the presence of an alkali metal alkoxide catalyst. The present invention also relates to a method for producing a nonionic fluorine-containing surfactant represented by the general formula (1), characterized in that:

(In the formula, R represents an alkyl group having 1 to 6, preferably 1 to 2 carbon atoms.)

(In the formula, n represents a number of 1 to 50, preferably 8 to 22.)

The fluorine-containing ether compound represented by the general formula (2) includes, for example, a compound represented by the following formula (4) (a compound corresponding to a main trimer of hexafluoropropene) and an excessive amount of alcohol. ROH (wherein R is as defined above) in an aprotic polar solvent (for example, tetrahydrofuran or the like) or an alkali metal alkoxide catalyst (for example, potassium t-butoxide or the like) or an alkali carbonate catalyst (for example) For example, it can be obtained by reacting in the presence of potassium carbonate or the like. This reaction is usually performed at −20 ° C. to + 80 ° C. for 1 to 24 hours.

  Examples of the aprotic polar solvent used in the reaction of the fluorine-containing ether compound (2) and the alcohol (3) include tetrahydrofuran, diethyl ether, dimethoxyethane, N, N-dimethylformamide, N, N-dimethylacetamide, Examples are solvents selected from the group consisting of N-methylpyrrolidone, dimethyl sulfoxide and any mixtures thereof, with tetrahydrofuran being particularly preferred.

  Examples of the alkali metal alkoxide catalyst include sodium t-butoxide, potassium t-butoxide and the like, and potassium t-butoxide is particularly preferable.

  The amount of the alkali metal alkoxide catalyst used is usually 1.0 to 3.0 mol, preferably 1.1 to 1.3 mol, relative to 1 mol of the fluorinated ether compound represented by the general formula (2). If the amount is less than 1.0 mol, the reaction does not proceed sufficiently. Moreover, when it exceeds 3.0 mol, a reaction system will become complicated and a yield will fall.

  The amount of the alcohol represented by the general formula (3) is usually 0.8 to 2.0 mol, preferably 1., based on 1 mol of the fluorinated ether compound represented by the general formula (2). When the amount is from 0 to 1.3 mol, and less than 0.8 mol, the fluorine-containing ether represented by the general formula (2) becomes excessive, which is not practical. Moreover, when it exceeds 2.0 mol, removal of alcohol will become difficult.

  The temperature of the above reaction is usually −20 ° C. to + 80 ° C., preferably 0 ° C. to 30 ° C. If it is lower than −20 ° C., a sufficient reaction rate cannot be obtained, and if it is higher than + 80 ° C. , The reaction system becomes complicated and the yield decreases.

The reaction time depends on the above-mentioned reaction components, the type of catalyst, the reaction temperature, and the like, but is 1 to 24 hours, preferably 2 to 6 hours.

Hereinafter, the present invention will be described by way of examples.
Example 1
In a three-necked flask (50 ml) equipped with a dropping funnel, 6.02 g (12 mmol) of a fluorine-containing ether compound represented by the following formula (5), 4.00 g of polyethylene glycol monomethyl ether (average molecular weight: 400) (10 mmol) and 10 g of tetrahydrofuran were added. On the other hand, a solution prepared by dissolving 1.34 g (12 mmol) of potassium t-butoxide in 10 g of tetrahydrofuran was put into a dropping funnel, and the solution was gradually added dropwise to the above flask contents with stirring over about 30 minutes. . After completion of the dropping, stirring was further continued for 3 hours at room temperature (20 to 25 ° C.).
The reaction mixture was then transferred to a 100 ml round bottom flask, the solvent was evaporated using a rotary evaporator, and then subjected to an extraction treatment using 30 ml of ethyl acetate and 30 ml of water once. Subsequently, the organic layer was treated with 30 ml of saturated brine, and the extract was subjected to solvent evaporation using a rotary evaporator to obtain a crude product. The crude product was subjected to column chromatography purification using 50 g of alumina to obtain 6.28 g of a compound represented by the following formula (4) (yield: 73%).

The physical properties of the compound (6) are shown in Table 1 below.

Example 2
In a three-necked flask (50 ml) equipped with a dropping funnel, 6.02 g (12 mmol) of the fluorine-containing compound represented by the above formula (5), 10.00 g of polyethylene glycol monomethyl ether (average molecular weight: 1000) ( 10 mmol) and 10 g of tetrahydrofuran were added. On the other hand, a solution prepared by dissolving 1.34 g (12 mmol) of potassium t-butoxide in 10 g of tetrahydrofuran was put into a dropping funnel, and the solution was gradually added dropwise to the above flask contents with stirring over about 30 minutes. . After completion of the dropping, stirring was further continued for 3 hours at room temperature (20 to 25 ° C.).
The reaction mixture was then transferred into a 100 ml round bottom flask and the solvent was evaporated using a rotary evaporator. After adding 10 g of acetonitrile and allowing to stand for 1 day, a precipitate was collected by filtration and the solvent was evaporated twice to obtain a crude product. By treating the crude product with an ion exchange resin, 2.76 g of a compound represented by the following formula (7) was obtained (yield: 37%).

The physical properties of the compound (7) are shown in Table 2 below.

Nonionic fluorine-containing surfactants according to the present invention include, for example, antistatic agents for plastic surfaces, leveling agents for photoresists, dispersants for polytetrafluoroethylene, additives for mold release agents, emulsifiers and antifoaming agents, etc. As particularly useful.

Claims (7)

Nonionic fluorine-containing surfactant represented by the following general formula (1):

(In the formula, R represents an alkyl group having 1 to 6 carbon atoms, and n represents a number of 3 to 50.) Reacting a fluorine-containing ether compound represented by the following general formula (2) and an alcohol represented by the following general formula (3) in an aprotic polar solvent in the presence of an alkali metal alkoxide catalyst. The method for producing a nonionic fluorine-containing surfactant according to claim 1, characterized in that:

(In the formula, R represents an alkyl group having 1 to 6 carbon atoms.)

(In formula, n shows the number of 3-50.)   A solvent in which the aprotic polar solvent is selected from the group consisting of tetrahydrofuran, diethyl ether, dimethoxyethane, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide and any mixtures thereof The method according to claim 2.   The process according to claim 2 or 3, wherein the alkali metal alkoxide catalyst is sodium t-butoxide or potassium t-butoxide.   The alcohol represented by the general formula (3) is used in an amount of 0.8 to 2.0 mol with respect to 1 mol of the fluorinated ether compound represented by the general formula (2). the method of.   The method according to any one of claims 2 to 5, wherein the alkali metal alkoxide catalyst is used in an amount of 1.0 to 3.0 mol with respect to 1 mol of the fluorine-containing ether compound represented by the general formula (2). The process according to any one of claims 2 to 6, wherein the reaction is carried out at a temperature of -20 to 80 ° C.