JP4346992B2 - Glycerin ether derivative, nonionic surfactant and method for producing the glycerin ether derivative - Google Patents

Description

  The present invention relates to a glycerin ether derivative, a nonionic surfactant, and a method for producing the glycerin ether derivative. More specifically, the present invention relates to a novel glycerin ether derivative obtained by reacting a glycerin with an acrylate ester, and a high performance comprising the same. The present invention relates to a method for efficiently producing a non-ionic surfactant and a glycerin ether derivative under mild conditions and without generation of by-products.

  A surfactant is a substance that adsorbs or arranges at a gas-liquid, liquid-liquid, or liquid-solid interface and significantly changes the properties of the surface or interface in a small amount. It is said that the property of adsorbing surfactants is attributed to the structural specificity of surfactants. Generally, the dilute solution changes the interfacial energy, and the aqueous solution reduces surface tension. Widely used in various fields. Specifically, it is used in various fields such as cleaning, cosmetics, deinking agents, pharmaceuticals, agricultural chemicals, fibers, plastics, paper, and energy.

This surfactant has polarity and is soluble in water, hydrophilic groups that have affinity for water and non-polar organic solvents, or both lipophilic groups and hydrophobic groups that have affinity Can be roughly classified into anionic surfactants, cationic surfactants, amphoteric surfactants and nonionic surfactants.
Among the surfactants, nonionic surfactants are surfactants that do not have a group capable of dissociating into ions, and include ether type, ether ester type, ester type, and nitrogen-containing type.
A polyethylene glycol fatty acid ester is known as the ester type. This polyethylene glycol fatty acid ester has a monoester type in which one end of polyethylene glycol is esterified and a diester type in which both ends are esterified, both of which have low toxicity, low skin irritation, etc. and excellent biodegradability. ing. As a method for producing this nonionic surfactant, for example, a method in which ethylene oxide is reacted with a higher fatty acid such as oleic acid at a high temperature and a high pressure of 130 ° C. or higher is disclosed (for example, see Patent Document 1). However, in such a production method, since the reaction conditions are severe and the molecular weight of the polymer portion composed of repeating units of ethylene oxide is distributed, there is a disadvantage that the performance cannot be sufficiently exhibited (for example, Non-patent document 1).

Further, it is disclosed that a condensate of polyethylene glycol and linolenic acid produced in advance can be used as a stable emulsifier (for example, see Patent Document 2). However, Patent Document 2 also describes that a high temperature of 140 to 150 ° C. is necessary for the reaction between polyethylene glycol and linolenic acid.
Thus, in the conventional technique for producing polyethylene glycol fatty acid esters, the method of addition polymerization of ethylene oxide to higher fatty acids requires high temperature and high pressure, and the product sufficiently functions as a surfactant. In addition, the method of condensing a higher fatty acid and polyethylene glycol requires a high temperature and also has a problem that by-products may be generated and purification may be required.
German Patent 694178 US Pat. No. 2,473,798 "Functional surfactant" supervised by Mitsuo Tsunoda, published by CMC

  The present invention has been made under the circumstances as described above, a novel glycerin ether derivative that can be produced by a simple process under mild conditions and without generation of by-products, and a high-performance nonionic property comprising the same. The object is to provide a surfactant.

  As a result of intensive studies to achieve the above object, the present inventor has an excellent function as a nonionic surfactant by adding glycerin to an alkyl acrylate in the presence of a basic compound. It has been found that a glycerin ether derivative exhibiting the above can be efficiently obtained by a simple process under mild conditions, without generation of by-products. The present invention has been completed based on such findings.

That is, the present invention
(1) General formula (I)

(In the formula, (A) is a residue obtained by removing all hydroxyl groups from glycerin, diglycerin or triglycerin, x is an integer of 0 to 4, n is an integer of 1 to 3, where x + n is an integer of 3 to 5. Yes, Q is the general formula (a)

A group represented by, R represents straight-chain having a carbon number of 4 to 18, branched or cyclic alkyl or alkenyl group having a carbon number of 4 to 18, y is an integer of 1 to 3, p is an integer of 0 In the case where there are a plurality of Qs, the plurality of Qs may be the same as or different from each other. )
A glycerol ether derivative represented by:
(2) The glycerin ether derivative according to (1), wherein (A) is a residue obtained by removing all hydroxyl groups from glycerin or diglycerin, and x is an integer of 0 to 3 in general formula (I).
(3) In the general formula (a), R is one group selected from the group consisting of n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, 2-ethylhexyl group and lauryl group (1 ) Or glycerin ether derivative according to (2),
(4) A nonionic surfactant comprising the glycerol ether derivative according to any one of (1) to (3) above,
(5) General formula (II) in the presence of a basic compound
_{CH 2 = CH-COOR ··· (} II)
(Wherein, R is a straight, branched or cyclic alkyl or alkenyl group having 4 to 18 carbon atoms in the carbon number 4 to 18.)
An alkyl acrylate represented by the general formula (III)

(In the formula, m represents an integer of 1 to 3.)
The method for producing a glycerin ether derivative according to any one of (1) to (3) above, wherein ( 6 ) the basic compound is sodium t-butoxide, potassium a method for producing a glycerin ether derivative according to the above (5), which is at least one compound selected from t-butoxide, sodium methoxide, sodium hydroxide, and potassium hydroxide;
Is to provide.

According to the present invention, a glycerin ether derivative useful as a high-performance nonionic surfactant can be produced by a simple process under mild conditions, and a nonionic interface comprising the glycerin ether derivative. An active agent can be provided.
In addition, the method for producing a glycerin ether derivative of the present invention has characteristics such as no generation of by-products and no adverse effects on the environment.

The glycerin ether derivative of the present invention has the general formula (I)

It has the structure represented by these.
In the said general formula (I), (A) is the residue remove | excluding the hydroxyl group from glycerol, diglycerol, or triglycerol, x is an integer of 0-4, n is an integer of 1-3, Q is general formula (a).

R is an alkyl group having 4 to 18 carbon atoms, y is an integer of 0 to 3, p is an integer of 0 to 10, and when there are a plurality of Q, the plurality of Q are the same or different from each other Also good.
When the number of carbon atoms of the alkyl group represented by R is less than 4, the performance as a surfactant is inferior. When p exceeds 10, the performance as a surfactant is poor.
The alkyl group having 4 to 18 carbon atoms of R may have an unsaturated bond in the molecule, and may be linear, branched or cyclic. Examples of such alkyl groups include various butyl groups, pentyl groups, hexyl groups, n-octyl groups, 2-ethylhexyl groups, n- or isodecyl groups, lauryl groups, isododecyl groups, myristyl groups, isotetradecyl groups. Group, palmityl group, isohexadecyl group, stearyl group, isooctadecyl group, oleyl group, cyclohexyl group, isoboranyryl group and the like.

The present invention also provides the nonionic surfactant of the present invention comprising the glycerol ether derivative represented by the general formula (I).
The non-ionic surfactant of the present invention has high performance, and the surface tension (24 ° C.) of the 1 mass% aqueous solution is usually about 28 to 40 mN / m, and the critical micelle concentration (cmc). Is usually about 0.1 to 3 mmol / liter.

The glycerin ether derivative represented by the general formula (I) can be produced very efficiently by a simple process and mild reaction conditions according to the method of the present invention shown below.
That is, the glycerin ether derivative is represented by the general formula (II) in the presence of a basic compound.
CH ₂ = CH-COOR (II)
(Wherein, R is as defined above), an alkyl acrylate ester represented by:
General formula (III)

It is manufactured by making the glycerol represented by these react.
In the formula, m represents an integer of 1 to 3, glycerin when m is 1, diglycerin when m is 2, and triglycerin when m is 3.
In the production method of the present invention, the number of Q in the general formula (I) is determined mainly by the molar ratio of the raw material alkyl acrylate / glycerin used.
For example, when glycerin is used as the glycerin, when the molar ratio of alkyl acrylate ester / glycerin is about 1, a compound in which the number of Q is 1 and the number of OH is mainly formed, and the molar ratio is about In 2, the compound in which the number of Q is 2 and the number of OH is 1 is mainly produced.
As a solvent for producing the glycerin ether derivative, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone are preferably used.

  In this method, basic compounds used as a catalyst include sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, alkali metal alkoxides such as sodium t-butoxide, potassium t-butoxide; sodium hydroxide, Alkali metal hydroxides such as potassium hydroxide; Alkali metal carbonates such as sodium carbonate and potassium carbonate; Na or K-substituted ion exchange resins (one-exchange resins having hydroxyl groups substituted with Na or K) and the like It is done. These may be used alone or in combination of two or more, among which sodium t-butoxide, potassium t-butoxide, sodium hydroxide and potassium hydroxide are preferred.

The basic compound is generally used in a proportion of 0.1 to 10 mol%, preferably 0.5 to 3 mol%, based on the glycerol used. In addition, since this basic compound is not normally melt | dissolving during reaction, it is important to perform reaction under effective stirring.
Examples of the acrylic acid alkyl ester represented by the general formula (II) include butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, myristyl acrylate, palmityl acrylate, stearyl acrylate, and oleyl acrylate.
Examples of the glycerols represented by the general formula (III) include glycerol, diglycerol and triglycerol.
The proportions of these acrylic acid alkyl esters and glycerols are appropriately selected according to the type of glycerol ether derivative desired.

The reaction temperature is usually selected in the range of 30 to 60 ° C. The reaction time depends on the reaction temperature, the type and amount of the basic compound, and cannot be generally defined, but is usually about 1 to 10 hours, preferably 3 to 5 hours.
The reaction-terminated liquid is usually neutralized with phosphoric acid or the like, filtered, and then the solvent is distilled off to obtain a dendritic product, which can be used as a nonionic surfactant.
Thus, according to the method of the present invention, a desired glycerin ether derivative can be efficiently obtained under mild conditions, without generation of by-products, and with simple post-treatment.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these Examples.
In addition, the physical property of the product obtained in each Example was measured in accordance with the following method.
(1) Surface tension The surface tension of a 1% by mass aqueous solution was measured by a drop volume method at a temperature of 24 ° C. in accordance with JIS 3362-1990.
(2) Critical micelle concentration (cmc)
The surface tension was measured by changing the solution concentration, and the critical micelle concentration (cmc) was determined from the inflection point.

In a 300 mL separable flask equipped with a nitrogen inlet tube, a thermocouple, and a stirring device, 9.21 g of glycerin, 18.43 g of 2-ethylhexyl acrylate and N. 30 mL of N-dimethylformamide was charged and stirred while introducing nitrogen. While stirring, 0.19 g of sodium-t-butoxide was added and heated in an oil bath at 35 ° C. for 4 hours. After adding 70 mg of phosphoric acid and stirring for 5 minutes, filtration was performed and the solvent was distilled off to obtain a product. The yield was 25.15 g (91% yield).
The surface tension and critical micelle concentration (cmc) of a 1% by mass aqueous solution of this product were measured. The results are shown in Table 1.
Gel permeation chromatography (GPC) of this product was measured, each fraction of GPC was fractionated, and the structure was analyzed by ¹ H-NMR analysis. FIG. 1 and FIG. 2 show ¹ H-NMR charts. ^{From 1} H-NMR, it was found that the product had the following structures (IV) and (V).

  In a 300 mL separable flask equipped with a nitrogen introduction tube, a thermocouple, and a stirrer, 9.21 g of glycerin, 12.82 g of butyl acrylate and N. 30 mL of N-dimethylformamide was charged and stirred while introducing nitrogen. While stirring, 0.19 g of sodium t-butoxide was added and heated in an oil bath at 35 ° C. for 4 hours. After adding 70 mg of phosphoric acid and stirring for 5 minutes, filtration was performed and the solvent was distilled off to obtain a product. The yield was 18.5 g (84% yield). The surface tension and critical micelle concentration (cmc) of a 1% by mass aqueous solution of this product were measured. The results are shown in Table 1.

  In a 300 mL separable flask equipped with a nitrogen introduction tube, a thermocouple, and a stirrer, 9.21 g of glycerin, 24.04 g of lauryl acrylate and N. as a solvent were added. 30 mL of N-dimethylformamide was charged and stirred while introducing nitrogen. While stirring, 0.19 g of sodium t-butoxide was added and heated in an oil bath at 35 ° C. for 4 hours. After adding 70 mg of phosphoric acid and stirring for 5 minutes, filtration was performed and the solvent was distilled off to obtain a product. The yield was 31.92 g (94% yield). The surface tension and critical micelle concentration (cmc) of a 1% by mass aqueous solution of this product were measured. The results are shown in Table 1.

In a 300 mL separable flask equipped with a nitrogen inlet tube, a thermocouple, and a stirrer, 9.21 g of glycerin, 36.86 g of 2-ethylhexyl acrylate, and N. as a solvent were added. 50 mL of N-dimethylformamide was charged and stirred while introducing nitrogen. While stirring, 0.38 g of sodium t-butoxide was added and heated in an oil bath at 35 ° C. for 4 hours. After adding 150 mg of phosphoric acid and stirring for 5 minutes, the precipitated white solid was filtered and the solvent was distilled off to obtain the product. The yield was 39.16 g (yield 85%). The surface tension and critical micelle concentration (cmc) of a 1% by mass aqueous solution of this product were measured. The results are shown in Table 1. As a result of ¹ H-NMR measurement of the product, it was found that the product had the following structures (VI) and (VII).

  In a 300 mL separable flask equipped with a nitrogen introduction tube, a thermocouple, and a stirrer, 9.21 g of glycerin, 25.64 g of butyl acrylate and N. as a solvent were added. 50 mL of N-dimethylformamide was charged and stirred while introducing nitrogen. While stirring, 0.38 g of sodium t-butoxide was added and heated in an oil bath at 35 ° C. for 4 hours. After completion of the reaction, 150 mg of phosphoric acid was added and stirred for 5 minutes, and then the precipitated white solid was filtered and the solvent was distilled off to obtain the product. The yield was 33.8 g (87% yield). The surface tension and critical micelle concentration (cmc) of a 1% by mass aqueous solution of this product were measured. The results are shown in Table 1.

  In a 300 mL separable flask equipped with a nitrogen inlet tube, a thermocouple, and a stirrer, 16.6 g of diglycerin, 18.43 g of 2-ethylhexyl acrylate and N. as a solvent were added. 30 ml of N-dimethylformamide was charged and stirred while introducing nitrogen. While stirring, 0.19 g of sodium t-butoxide was added and heated in an oil bath at 35 ° C. for 4 hours. After adding 70 mg of phosphoric acid and stirring for 5 minutes, the precipitated white solid was filtered and the solvent was distilled off to obtain the product. The yield was 28.31 g (81% yield). The surface tension and critical micelle concentration (cmc) of a 1% by mass aqueous solution of this product were measured. The results are shown in Table 1.

  According to the present invention, it is possible to provide a novel glycerin ether derivative that can be produced by a simple process under mild conditions and without generation of by-products. It can be used in various fields such as cleaning, cosmetics, pharmaceutical / agrochemical formulations, printing, paint, paper / pulp, plastic, compatibilization and the like.

2 is a ¹ H-NMR chart of a product of formula (IV) obtained in Example 1. FIG. 2 is a ¹ H-NMR chart of a product of formula (V) obtained in Example 1. FIG.

Claims (6)

Formula (I)

(In the formula, (A) is a residue obtained by removing all hydroxyl groups from glycerin, diglycerin or triglycerin, x is an integer of 0 to 4, n is an integer of 1 to 3, where x + n is an integer of 3 to 5. Yes, Q is the general formula (a)

A group represented by, R represents straight-chain having a carbon number of 4 to 18, branched or cyclic alkyl or alkenyl group having a carbon number of 4 to 18, y is an integer of 1 to 3, p is an integer of 0 In the case where there are a plurality of Qs, the plurality of Qs may be the same as or different from each other. )
The glycerol ether derivative represented by these.   The glycerin ether derivative according to claim 1, wherein in general formula (I), (A) is a residue obtained by removing all hydroxyl groups from glycerin or diglycerin, and x is an integer of 0 to 3.   In the general formula (a), R is one group selected from n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, 2-ethylhexyl group and lauryl group. The glycerol ether derivative as described.   A nonionic surfactant comprising the glycerin ether derivative according to any one of claims 1 to 3. In the presence of a basic compound, the general formula (II)
_{CH 2 = CH-COOR ··· (} II)
(Wherein, R is a straight, branched or cyclic alkyl or alkenyl group having 4 to 18 carbon atoms in the carbon number 4 to 18.)
An alkyl acrylate represented by the general formula (III)

(In the formula, m represents an integer of 1 to 3.)
The manufacturing method of the glycerol ether derivative in any one of Claims 1-3 characterized by reacting glycerol represented by these.   The method for producing a glycerin ether derivative according to claim 5, wherein the basic compound is at least one compound selected from sodium t-butoxide, potassium t-butoxide, sodium methoxide, sodium hydroxide, and potassium hydroxide. .

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