WO2015170637A1

WO2015170637A1 - Non-ionic surfactant and non-ionic surfactant production method

Info

Publication number: WO2015170637A1
Application number: PCT/JP2015/062775
Authority: WO
Inventors: 将基森田; 紗菜伊藤
Original assignee: 株式会社ニイタカ
Priority date: 2014-05-08
Filing date: 2015-04-28
Publication date: 2015-11-12
Also published as: JPWO2015170637A1; JP5857167B1

Abstract

This non-ionic surfactant is characterized by having a structure represented by general formula (1) and by having an acetal structure formed by a reaction between an alcohol and a hydrophilic vinyl ether. (In general formula (1), R¹ is a residue derived from an alcohol, (AO)n are oxyalkylene groups derived from hydrophilic vinyl ethers and are the same or different, n represents the average number of moles of oxyalkylene groups added and is a number 1-400. X is a hydrogen atom or a hydrocarbon group optionally having a substituent.)

Description

Nonionic surfactant and method for producing nonionic surfactant

The present invention relates to a nonionic surfactant and a method for producing a nonionic surfactant.

Nonionic surfactants are widely used as materials blended in cleaning compositions for kitchens, bathrooms, kitchens and the like.

Patent Document 1 discloses an ether-terminated poly (oxyalkylated) alcohol as a nonionic surfactant.

Patent Document 1 describes a method of forming an ether-terminated poly (oxyalkylated) alcohol by reacting an alkoxylated alcohol obtained by adding an oxyalkylene group to an alcohol and an α-olefin.

JP 2007-16031 A

In the method of forming an ether-terminated poly (oxyalkylated) alcohol described in Patent Document 1, when an α-olefin having an ether group is used, an oxygen atom derived from a hydroxyl group at the terminal of the alkoxylated alcohol and α- A compound having an acetal structure containing an oxygen atom derived from an ether group of an olefin is obtained.

When a compound having such an acetal structure is used as a nonionic surfactant, the hydrophilic group portion becomes an oxyalkylene group portion derived from an alkoxylated alcohol, particularly an oxyethylene group portion. On the other hand, the hydrophobic group portion becomes a carbon chain portion derived from an alkoxylated alcohol and a carbon chain portion derived from an α-olefin.

Here, the alkoxylated alcohol is produced by adding an oxyalkylene group to the hydroxyl group of the alcohol, and the carbon chain portion of the alcohol becomes a carbon chain portion contained in the alkoxylated alcohol, so that the compound having an acetal structure It can become a hydrophobic group part of a nonionic surfactant consisting of
Here, there are several commercially available alkoxylated alcohols, but there are not many types of alcohols used as starting materials for alkoxylated alcohols that are easily available. Therefore, the partial structure of the carbon chain contained in the alkoxylated alcohol that can be selected as the hydrophobic group portion of the nonionic surfactant made of a compound having an acetal structure is limited.

For this reason, there is a problem that the choice of the structure of the nonionic surfactant made of a compound having an acetal structure is insufficient, and a method for producing a nonionic surfactant with many choices of structure has been desired. In addition, nonionic surfactants having various structures obtained by such a production method have been desired.

The present invention has been made to solve the above-described problems, and provides nonionic surfactants having various structures, and production of nonionic surfactants having many structural options. It aims to provide a method.

In general, there are many substances that are readily available as alcohols. Therefore, when alcohol can be used as the starting material for the acetal reaction, various types of carbon chains can be introduced into the compound having an acetal structure as compared with the case where an alkoxylated alcohol is used as the starting material. As a result, various structures can be selected as the hydrophobic group portion of the nonionic surfactant made of a compound having an acetal structure.
In addition, it is advantageous in terms of cost if an alcohol which is less expensive than the alkoxylated alcohol can be used as a starting material.

In the method described in Patent Document 1, the hydrophilic group portion is an oxyalkylene group portion contained in the alkoxylated alcohol.
Here, the present inventors examined using alcohol as it is for acetalization reaction, without adding an oxyalkylene group to alcohol and using it for acetalization reaction.
In the process, it was considered to supply the hydrophilic group portion from the α-olefin side, not from the alcohol side. Then, a hydrophilic vinyl ether in which a hydrophilic group such as an oxyalkylene group is added to the end of a vinyl compound having a hydroxyl group at the end to form a structure that becomes a hydrophilic group portion is prepared, and the hydrophilic vinyl ether and an arbitrary alcohol are prepared. It was conceived that the acetal structure was formed by reacting.
The acetal structure obtained by this reaction is an acetal structure containing an oxygen atom derived from a hydroxyl group of alcohol and an oxygen atom derived from hydrophilic vinyl ether. And when using the compound which has this acetal structure as a nonionic surfactant, a hydrophilic group part turns into an oxyalkylene group part derived from hydrophilic vinyl ether, especially an oxyethylene group part.

Since the carbon chain derived from alcohol is introduced as it is into the nonionic surfactant thus obtained, a number of selectable alcohol structures can be introduced, and various non-ionic surfactants having desired characteristics can be introduced. An ionic surfactant is provided.

That is, the nonionic surfactant of the present invention has a structure represented by the following general formula (1),
It has an acetal structure formed by reaction of alcohol and hydrophilic vinyl ether.

(In General Formula (1), R ¹ is a residue derived from alcohol, (AO) n is an oxyalkylene group which may be the same or different, derived from a hydrophilic vinyl ether, and n is an oxyalkylene. Represents the average number of moles of the group added, and is a number from 1 to 400. X is a hydrocarbon group which may have a substituent or a hydrogen atom)

The nonionic surfactant of the present invention has an acetal structure formed by a reaction between an alcohol and a hydrophilic vinyl ether, and has a residue R ¹ derived from the alcohol. Since there are many types of alcohols available and many structures can be selected as R ¹ , it can be a nonionic surfactant having various structures.

In the nonionic surfactant of the present invention, R ¹ in the general formula (1) is preferably a hydrocarbon group having 8 to 20 carbon atoms.
When R ¹ is a hydrocarbon group having 8 to 20 carbon atoms, a structure suitable as a hydrophobic group portion is obtained. Alcohols having a hydrocarbon group having 8 to 20 carbon atoms are preferred because they are particularly easily available and can be easily produced at low cost.

In the nonionic surfactant of the present invention, the oxyalkylene group in the general formula (1) is an oxyethylene group, an oxypropylene group or an oxybutylene group, respectively, and the ratio of the oxyethylene group contained in the oxyalkylene group Is desirably 50 mol% or more.
When the ratio of the oxyethylene group contained in the oxyalkylene group is 50 mol% or more, the hydrophilicity of the oxyalkylene group portion is increased, and a structure suitable as the structure of the hydrophilic group portion is obtained.

In the nonionic surfactant of the present invention, X in the general formula (1) is a hydrocarbon group which may have a substituent, and desirably has a structure represented by the following general formula (2). .

(In general formula (2), R ² is a hydrocarbon group which may have a substituent)

That X in the general formula (1) is a hydrocarbon group means that the terminal of the nonionic surfactant is not a hydroxyl group.
When the terminal of the nonionic surfactant is a hydroxyl group, when a composition in which the nonionic surfactant coexists with the chlorine agent is prepared, the hydroxyl group of the nonionic surfactant terminal and the chlorine agent In some cases, chlorine reacts to deactivate both the nonionic surfactant and the chlorine agent.
By making the end of the nonionic surfactant a hydrocarbon group, the hydroxyl group at the end of the nonionic surfactant and the chlorine of the chlorinating agent are prevented from reacting with each other. It can be an ionic surfactant.
In addition, if the terminal end of the nonionic surfactant is a hydroxyl group, the terminal hydroxyl group is oxidized and anionized in an alkaline environment, resulting in a structure similar to that of the anionic surfactant. It may increase.
By making the terminal of the nonionic surfactant a hydrocarbon group, the terminal structure of the nonionic surfactant is prevented from being anionized, and the nonionic surfactant becomes a low-foaming nonionic surfactant.
The low-foaming nonionic surfactant is suitable for use in washing with an automatic washing machine.

The method for producing the nonionic surfactant of the present invention comprises:
A vinyl group of a hydrophilic vinyl ether having a structure represented by the following general formula (3);
An acetalization step of forming an acetal bond by reacting a hydroxyl group of an alcohol having a structure represented by the following general formula (4) to produce a nonionic surfactant having a structure represented by the following general formula (1) It is characterized by doing.

(In the general formula (3), (AO) p is an oxyalkylene group which may be the same or different, p represents the average number of added moles of the oxyalkylene group, and is a number from 1 to 400. X is A hydrocarbon group which may have a substituent or a hydrogen atom)

(In general formula (4), R ¹ is a residue of alcohol)

In the method for producing a nonionic surfactant of the present invention, unlike the conventional method for forming an acetal structure, a hydrophilic group portion is supplied from a hydrophilic vinyl ether, and a carbon chain derived from alcohol is introduced as it is.
Since there are many kinds of available alcohols and many structures can be selected as R ¹ , non-ionic surfactants having various structures can be produced according to the production method of the present invention. A variety of nonionic surfactants can be provided.

In the method for producing a nonionic surfactant of the present invention, X in the nonionic surfactant having the structure represented by the general formula (1) obtained by the acetalization step is a hydrogen atom, The nonionic surfactant having the structure represented by the formula (1) has a hydroxyl group at its end,
It is desirable to produce a nonionic surfactant having a structure represented by the following general formula (2) by modifying the hydrogen atom of the hydroxyl group into a hydrocarbon group which may have a substituent.

By modifying the hydrogen atom of the hydroxyl group located at the terminal of the nonionic surfactant to a hydrocarbon group, a nonionic surfactant having high chlorine stability and low foaming property can be produced.

In the method for producing a nonionic surfactant of the present invention, the reaction for modifying the hydrogen atom of the hydroxyl group to a hydrocarbon group which may have a substituent is performed by dialkyl sulfate, dialkyl carbonate, alkyl halide, trialkyloxo. A reaction in which the hydrogen atom is substituted with a hydrocarbon group by the action of a nium salt, an alkyl ester of alkane sulfonic acid, or an alkyl ester of arene sulfonic acid is desirable.
When these alkylating agents are used, the hydrogen atom of the hydroxyl group located at the end of the nonionic surfactant can be replaced with a hydrocarbon group.

In the method for producing a nonionic surfactant of the present invention, the reaction for modifying the hydrogen atom of the hydroxyl group to a hydrocarbon group which may have a substituent is carried out by the following general formula (5). A nonionic surfactant having a structure represented by the following general formula (6) is obtained by reacting with a (poly) oxyalkylene alkyl ether having the structure shown to increase the number of oxyalkylene groups added. It is desirable to manufacture.

(In general formula (5), q represents the average number of moles added of the oxyalkylene group and is a number from 1 to 399.)

(In general formula (6), p + q represents the average number of moles of oxyalkylene group added and is a number from 1 to 400.)

According to the above reaction, in addition to the reaction of modifying the hydrogen atom of the hydroxyl group to an optionally substituted hydrocarbon group, the hydrophilicity of the nonionic surfactant is increased by increasing the number of oxyalkylene groups added. The reaction to be adjusted can be carried out simultaneously in one stage.

In the method for producing a nonionic surfactant of the present invention, the hydrophilic vinyl ether having the structure represented by the general formula (3) is:
X is a hydrophilic vinyl ether having a structure represented by the following general formula (7), which is a hydrocarbon group which may have a substituent,
Performing an acetalization step of reacting the vinyl group of the hydrophilic vinyl ether having the structure represented by the general formula (7) with the hydroxyl group of the alcohol having the structure represented by the general formula (4) to form an acetal bond; It is desirable to produce a nonionic surfactant having a structure represented by the following general formula (2).

(In General Formula (7), R ² is a hydrocarbon group which may have a substituent)

In the above step, the acetalization step is performed using a hydrophilic vinyl ether in which a hydrogen atom of a hydroxyl group located at a terminal is previously modified to a hydrocarbon group.
Even by such a process, it is possible to obtain a nonionic surfactant in which a hydrocarbon group is modified from the hydroxyl group hydrogen atom located at the end of the nonionic surfactant. The agent has high chlorine stability and becomes a low foaming surfactant.

In the method for producing a nonionic surfactant of the present invention, dialkyl sulfate, dialkyl carbonate, alkyl halide, trialkyl are bonded to the hydroxyl group hydrogen atom located at the terminal of the hydrophilic vinyl ether having the structure represented by the following general formula (8). A structure represented by the above general formula (7) is obtained by reacting an oxonium salt, an alkyl ester of alkane sulfonic acid, or an alkyl ester of arene sulfonic acid to replace the hydrogen atom with a hydrocarbon group. Performing a step of obtaining a hydrophilic vinyl ether having
It is desirable to use for the acetalization step.

When these alkylating agents are used, the hydroxyl group hydrogen atom located at the end of the hydrophilic vinyl ether is substituted with a hydrocarbon group, and the hydroxyl atom located at the end is hydrophilically modified to a hydrocarbon group in advance. Vinyl ether can be obtained and used in the acetalization step.

In the method for producing a nonionic surfactant of the present invention, a polyoxy having a structure represented by the following general formula (5) is attached to a hydroxyl group located at the end of a hydrophilic vinyl ether having a structure represented by the following general formula (9). By reacting an alkylene alkyl ether,
A step of obtaining a hydrophilic vinyl ether having a structure represented by the general formula (7) by modifying the hydrogen atom of the hydroxyl group to a hydrocarbon group which may have a substituent and increasing the number of oxyalkylene groups added And
It is desirable to use for the acetalization step.

(In general formula (9), pq represents the average number of moles added of the oxyalkylene group, and is a number from 0 to 399.)

According to the above reaction, in addition to the reaction of modifying the hydrogen atom of the hydroxyl group located at the end of the hydrophilic vinyl ether to a hydrocarbon group which may have a substituent, hydrophilicity is increased by increasing the number of oxyalkylene groups added. The reaction for adjusting the hydrophilicity of vinyl ether can be carried out simultaneously in one step. And such hydrophilic vinyl ether can be obtained and used for an acetalization process.

In the method for producing a nonionic surfactant of the present invention, the alcohol having the structure represented by the general formula (4) preferably has 8 to 20 carbon atoms.
When the alcohol has 8 to 20 carbon atoms, it is suitable as the alcohol to be used because it has a structure suitable as a hydrophobic group moiety.

Another embodiment of the nonionic surfactant of the present invention has a structure represented by the following general formula (19),
It has an acetal structure formed by the reaction of polyhydric alcohol and hydrophilic vinyl ether.

(In general formula (19), u is an integer of 2 or more, Z is a residue derived from a u-valent polyhydric alcohol, and (AO) n is the same or different derived from a hydrophilic vinyl ether. An oxyalkylene group which may be substituted, n represents the average number of moles added of the oxyalkylene group and is a number from 1 to 400. X is a hydrocarbon group or a hydrogen atom which may have a substituent.

The nonionic surfactant has an acetal structure formed by reacting a polyhydric alcohol with a polyhydric alcohol and a hydrophilic vinyl ether, and the acetal structure exists as much as the valence of the polyhydric alcohol. . When the compound having an acetal structure is used as a nonionic surfactant, the hydrophilic group portion becomes an oxyalkylene group portion derived from a hydrophilic vinyl ether, particularly an oxyethylene group portion.
Since the carbon chain derived from the polyhydric alcohol is introduced as it is into the nonionic surfactant thus obtained, a large number of selectable alcohol structures can be introduced, and various properties having desired characteristics can be introduced. Nonionic surfactants are provided.

The nonionic surfactant of the present invention can be a nonionic surfactant having various structures.
Moreover, according to the method for producing a nonionic surfactant of the present invention, nonionic surfactants having various structures can be produced, and various nonionic surfactants having desired characteristics are provided. Can do.

FIG. 1 is an NMR spectrum of the nonionic surfactant synthesized in Production Example 1. FIG. 2 is an NMR spectrum of the nonionic surfactant synthesized in Production Example 2. FIG. 3 is an NMR spectrum of the nonionic surfactant synthesized in Production Example 3.

Hereinafter, the nonionic surfactant of this invention and the manufacturing method of the nonionic surfactant of this invention are demonstrated.
The nonionic surfactant of the present invention has a structure represented by the following general formula (1),
It has an acetal structure formed by reaction of alcohol and hydrophilic vinyl ether.

The structure represented by the general formula (1) has an acetal structure (—O—CH (CH ₃ ) —O—) formed by the reaction of alcohol and hydrophilic vinyl ether. It has a residue R ¹ derived from an alcohol represented by

(In general formula (4), R ¹ is a residue of alcohol)

In the present specification, “alcohol” includes a compound having a phenolic hydroxyl group.
R ¹ is not particularly limited as long as it is a residue derived from an alcohol, but examples thereof include the following structures in which an OH group is removed from an alcohol.

Examples of the alcohol include linear or branched aliphatic alcohols, which may or may not have an unsaturated bond. Desirable examples of the aliphatic alcohol include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexyl alcohol, nonyl alcohol, decyl alcohol, isodecyl alcohol, undecyl alcohol, lauryl alcohol, Dodecyl alcohol, tridecyl alcohol, myristyl alcohol, tetradecyl alcohol, pentadecyl alcohol, cetyl alcohol, hexadecyl alcohol, isohexadecyl alcohol, heptadecyl alcohol, stearyl alcohol, octadecyl alcohol, isostearyl alcohol, elaidyl alcohol, oleyl alcohol , Linoleyl alcohol, elide linoleyl alcohol, linolenyl alcohol , Elide linoleyl alcohol, ricinoleyl alcohol, nonadecyl alcohol, arachidyl alcohol (eicosanol), 2-octyldodecan-1-ol, heneicosanol, behenyl alcohol (1-docosanol), erucyl alcohol, Tricosanol, lignoceryl alcohol (1-tetracosanol), pentacosanol, seryl alcohol, 1-heptacosanol, montanyl alcohol (1-octacosanol), 1-nonacosanol, myricyl alcohol (1-triacontanol), 1- Hentriacontanol, 1-dotriacontanol, gedyl alcohol (1-tetratriacontanol) and the like can be mentioned.

Examples of the alcohol include alkylphenols, and alkylphenols having a linear or branched alkyl chain. Desirable examples of the alkylphenol include 4-tert-butylphenol, 4-octylphenol, nonylphenol, dodecylphenol, octylcresol and the like.

R ¹ is preferably a residue derived from an alcohol having 8 to 20 carbon atoms, and more preferable examples of the alcohol having 8 to 20 carbon atoms include octanol, 2-ethylhexyl alcohol, decyl alcohol, Decyl alcohol, lauryl alcohol, dodecyl alcohol, myristyl alcohol, tetradecyl alcohol, cetyl alcohol, hexadecyl alcohol, isohexadecyl alcohol, stearyl alcohol, octadecyl alcohol, isostearyl alcohol, oleyl alcohol, arachidyl alcohol (eicosanol), and 2-octyldodecan-1-ol and the like.
R ¹ may have a substituent, and the substituent is preferably halogen (F—, Cl—, Br— or I—). R ¹ may contain an ether bond.

Examples of the hydrophilic vinyl ether include hydrophilic vinyl ethers having a structure represented by the general formula (3).

In each chemical formula in this specification, the average addition mole number of the oxyalkylene group is, as a rule, the average addition mole number of the oxyalkylene group in the produced nonionic surfactant is n, and the oxyalkylene group in the hydrophilic vinyl ether. The average number of moles added is represented by p.
For example, the average addition mole number of the oxyalkylene group in the nonionic surfactant represented by the general formula (1) is n, and the average addition mole number of the oxyalkylene group in the hydrophilic vinyl ether represented by the general formula (3) is p. ing.
Here, p does not necessarily indicate a number different from n, and p in the hydrophilic vinyl ether may be the same as the average added mole number n of the nonionic surfactant to be produced.
When a nonionic surfactant having an acetal structure is produced without further increasing the oxyalkylene group with respect to the hydrophilic vinyl ether represented by the general formula (3), p and n are the same number.

Examples of AO (oxyalkylene group) include oxyethylene group (EO), oxypropylene group (PO), and oxybutylene group (BO). The hydrophilic vinyl ether may contain only one kind of oxyethylene group, oxypropylene group, or oxybutylene group, or may contain plural kinds of these. The unit of the repeating structure of the oxyethylene group, oxypropylene group, or oxybutylene group is not particularly limited.

Further, the ratio of the oxyethylene group contained in the oxyalkylene group is preferably 50 mol% or more, and more preferably 60 mol% or more.
When the ratio of the oxyethylene group contained in the oxyalkylene group is 50 mol% or more, the hydrophilicity of the oxyalkylene group portion is increased, and a structure suitable as the structure of the hydrophilic group portion is obtained.

The average added mole number p of AO in the hydrophilic vinyl ether is 1 to 400, and a preferable range of p is 3 to 100, and a more preferable range is 5 to 50.
When the hydrophilic vinyl ether is a mixture of a plurality of compounds having different numbers of added moles of AO p, the number of moles of AO contained in each of the hydrophilic vinyl ether molecules is an integer value. Since the measured value when measured is measured as an average value of the added mole number of AO contained in each molecule of the hydrophilic vinyl ether, this is used as the average added mole number.
The hydrophilic vinyl ether may be a mixture of a plurality of compounds having different types of AO. The addition format of AO may be block addition or random addition, and the addition format is not particularly limited.

Examples of the hydrophilic vinyl ether contained in the general formula (3) include a structure in which X is a hydrogen atom in the general formula (3), that is, a (poly) oxyalkylene monovinyl ether having a structure represented by the general formula (8).

Non-ion having an acetal structure when an alcohol having a structure represented by the general formula (4) is selected as the alcohol and a (poly) oxyalkylene monovinyl ether having a structure represented by the general formula (8) is selected as the hydrophilic vinyl ether The structure of the surfactant is a structure represented by the following general formula (10).

Specific examples of (poly) oxyalkylene monovinyl ether include (poly) oxyethylene monovinyl ether, (poly) oxypropylene monovinyl ether, (poly) oxybutylene monovinyl ether, (poly) oxyethylene (poly) oxypropylene monovinyl ether, (Poly) oxyethylene (poly) oxybutylene monovinyl ether, (poly) oxypropylene (poly) oxybutylene monovinyl ether, and the like.

As the (poly) oxyalkylene monovinyl ether, commercially available (poly) oxyethylene monovinyl ether, such as ethylene glycol monovinyl ether, diethylene glycol monovinyl ether, triethylene glycol monovinyl ether, and the like can be used.
Moreover, an oxyethylene group or an oxypropylene group may be further added to these commercially available products to produce a polyoxyalkylene monovinyl ether, which may be used for the production of a nonionic surfactant.
In the present specification, (poly) of (poly) oxyalkylene monovinyl ether includes both an oxyalkylene chain having one oxyalkylene group addition and a polyoxyalkylene chain having a plurality of additions. Meaning.

The hydrophilic vinyl ether contained in the general formula (3) has a structure in which X is a hydrocarbon group which may have a substituent in the general formula (3), that is, the hydrophilicity of the structure represented by the general formula (7). Vinyl ether is mentioned.

Nonionic surfactant having an acetal structure when an alcohol having a structure represented by the general formula (4) is selected as the alcohol and a hydrophilic vinyl ether having a structure represented by the general formula (7) is selected as the hydrophilic vinyl ether Is a structure represented by the following general formula (2).

The hydrocarbon group R ² which may have a substituent is an aliphatic alkyl group (methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group). Group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group and the like.
When the terminal structure of the hydrophilic vinyl ether is a hydrocarbon group which may have a substituent, X becomes a hydrocarbon group R ² which may have a substituent by reacting the alcohol with the hydrophilic vinyl ether.
Further, as the substituent of the hydrocarbon group, halogen (F—, Cl—, Br— or I—) is desirable. Further, the hydrocarbon group may contain an ether bond.

When X is a hydrocarbon group R ² which may have a substituent, the hydroxyl group at the end of the nonionic surfactant is prevented from reacting with chlorine of the chlorinating agent, so that chlorine stability is improved. It can be a high nonionic surfactant.
Further, when X is a hydrocarbon group R ² which may have a substituent, the terminal structure of the nonionic surfactant is prevented from being anionized, and the low-foaming nonionic surfactant is prevented. It becomes.
The low-foaming nonionic surfactant is suitable for use in washing with an automatic washing machine.

The method for producing a nonionic surfactant of the present invention includes a vinyl group of a hydrophilic vinyl ether having a structure represented by the following general formula (3) and a hydroxyl group of an alcohol having a structure represented by the following general formula (4). It is characterized in that a nonionic surfactant having a structure represented by the following general formula (1) is produced by carrying out an acetalization step of forming an acetal bond by reacting with the above.

(In the general formula (4), ^{R 1} is a residue of an alcohol)

Examples of the hydrophilic vinyl ether having the structure represented by the general formula (3) and the alcohol having the structure represented by the general formula (4) include those already described.

The reaction of the vinyl group of the hydrophilic vinyl ether and the hydroxyl group of the alcohol can be carried out by mixing the hydrophilic vinyl ether and the alcohol, and further adding an acid catalyst for reaction. This reaction may be performed in a solvent such as an organic solvent as necessary.

For example, when a hydrophilic vinyl ether having a p-mol oxyethylene group added thereto as a hydrophilic vinyl ether is reacted with an alcohol represented by the general formula (4), the reaction is represented by the reaction represented by the following reaction formula (11). The nonionic surfactant of the invention is produced.

Examples of the acid catalyst include p-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, pyridinium p-toluenesulfonate, trifluoromethanesulfonic acid, sulfuric acid, hydrochloric acid, and an acidic ion exchange resin. Of these, p-toluenesulfonic acid or methanesulfonic acid is desirable because it is easy to handle and inexpensive.

As the organic solvent used in the above reaction, a general organic solvent can be used, and methylene chloride, chloroform, acetonitrile, tetrahydrofuran (THF), toluene, chlorobenzene, methyl tert-butyl ether and the like can be used.

The reaction is completed by neutralization of the acid catalyst. Although it does not specifically limit as a base used for neutralization, Powder, such as sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, or those solutions etc. can be used.

The reaction conditions can be appropriately determined depending on the type and amount of the starting material. For example, 10 mol of hydrophilic vinyl ether and 11 mol of alcohol are mixed, and 1 to 10 mol% of p-toluenesulfonic acid is added as an acid catalyst. Examples include a method of stirring for 1 hour to overnight (10 hours) at room temperature, adding sodium bicarbonate to terminate the reaction, filtering, and then distilling off the solvent and unreacted hydrophilic vinyl ether or alcohol.

The method for producing a nonionic surfactant of the present invention includes a vinyl group of a hydrophilic vinyl ether having a structure represented by the general formula (3) and a hydroxyl group of an alcohol having a structure represented by the general formula (4). The acetalization step of forming an acetal bond by reacting is required as an essential step, and before and after this step, at least one step selected from the group consisting of the following (a), (b) and (c) is performed Thus, a nonionic surfactant whose terminal structure is a hydrocarbon group may be obtained, and the number of oxyalkylene groups added to the nonionic surfactant may be adjusted.
(A) A step of modifying a hydrogen atom of a hydroxyl group located at a hydrophilic vinyl ether end or a nonionic surfactant end obtained by an acetalization step into a hydrocarbon group which may have a substituent.
(B) A step of increasing the number of oxyalkylene groups added by adding alkylene oxide to a hydroxyl group located at a hydrophilic vinyl ether end or a nonionic surfactant end obtained by an acetalization step.
(C) By reacting (poly) oxyalkylene alkyl ether having a structure represented by the following general formula (5) with a hydrophilic vinyl ether terminal or a nonionic surfactant terminal obtained by an acetalization step, A step of simultaneously performing the step (a) and the step (b) in one step.

As step (a),
Step (a1): a step of substituting the hydrogen atom of the hydroxyl group located at the end of the hydrophilic vinyl ether with a hydrocarbon group that may have a substituent, and
Step (a2): A step of substituting the hydrogen atom of the hydroxyl group located at the terminal of the nonionic surfactant obtained by the acetalization step with a hydrocarbon group which may have a substituent.
In any of the steps (a1) and (a2), the substitution reaction with a hydrocarbon group is a dialkyl sulfate, a dialkyl carbonate, an alkyl halide, a trialkyloxonium salt, an alkyl ester of an alkanesulfonic acid, or an arenesulfonic acid. The reaction is preferably a reaction in which the hydrogen atom is substituted with a hydrocarbon group by the action of an alkyl ester.
The hydrocarbon group to be substituted with these alkylating agents is preferably a methyl group, a butyl group or a benzyl group from the viewpoint of easy availability of the alkylating agent.
Examples of specific alkylating agents include dimethyl sulfate, dibutyl sulfate, dimethyl carbonate, methyl halide (methyl chloride, methyl bromide, methyl iodide), butyl halide (butyl chloride, butyl bromide, butyl iodide), Benzyl halide (benzyl chloride, benzyl bromide, benzyl iodide), trialkyloxonium salt and triethyloxonium salt (trimethyloxonium tetrafluoroborate, triethyloxonium tetrafluoroborate, etc.) as trialkyloxonium salt, alkanesulfone Examples include triflate (methyl triflate, butyl triflate, benzyl triflate) and mesylate as acid alkyl ester, tosylate as alkyl ester of arenesulfonic acid, and the like.
When these alkylating agents are used, the hydrogen atom of the hydroxyl group located at the end of the nonionic surfactant can be replaced with a hydrocarbon group.
The conditions for causing these alkylating agents to act may be known alkylation (ether synthesis) conditions, but it is desirable to carry out the reaction under basic conditions to which sodium hydroxide or sodium hydride is added.

For example, the reaction for substituting the hydrogen atom of the hydroxyl group located at the end of the nonionic surfactant obtained in the acetalization step is represented by the following reaction formula (12).

(In the reaction formula (12), R ² -Y is an alkylating agent, and Y is a residue obtained by removing an alkyl group from the alkylating agent.)

As step (b),
Step (b1): increasing the number of oxyalkylene groups added to the hydrophilic vinyl ether by adding alkylene oxide to the hydroxyl group located at the end of the hydrophilic vinyl ether; and
Step (b2): A step of increasing the number of oxyalkylene groups added to the nonionic surfactant by adding alkylene oxide to the hydroxyl group located at the terminal of the nonionic surfactant obtained by the acetalization step. ,

As a specific example of the step (b1), for example, (poly) oxyethylene monovinyl ether in which p mol of an oxyethylene group is added as shown in the following reaction formula (13) is prepared, and q mol of ethylene oxide is further added, A step of producing polyoxyethylene monovinyl ether having an average addition mole number of oxyethylene groups of p + q moles may be mentioned.

(In Reaction Formula (13), p + q is the average number of moles of oxyethylene group added, and is a number from 1 to 400)

In addition, as shown in the following reaction formula (14), (poly) oxyethylene monovinyl ether in which p mol of oxyethylene group is added is prepared, and r mol of propylene oxide and / or butylene oxide is further added to obtain an average of oxyethylene groups A polyoxyethylene polyoxyalkylene monovinyl ether having an addition mole number of p mole and an average addition mole number of oxypropylene group and oxybutylene group of r mole can be produced.

(In the reaction formula (14), p is the average number of moles of oxyethylene groups added, r is the sum of the average number of moles of oxypropylene groups and oxybutylene groups, and p + r is a number from 1 to 400. (Reaction Formula (14) shows propylene oxide as a representative of propylene oxide and / or butylene oxide.)

In addition, when two or more kinds of ethylene oxide, propylene oxide, and butylene oxide are simultaneously reacted with (poly) oxyethylene monovinyl ether, polyoxyalkylene monovinyl ether to which alkylene oxide is randomly added can be obtained.

As a specific example of the step (b2), for example, after producing a nonionic surfactant having an acetal structure in which p mol of an oxyethylene group is added as shown in the following reaction formula (15), q mol of ethylene oxide is further added. A step of producing a nonionic surfactant having an average addition mole number of oxyethylene groups of p + q mole by addition is exemplified.

(In Reaction Formula (15), p + q is the average number of moles of oxyethylene group added, and is a number from 1 to 400)
In the above reaction formula (15), other alkylene oxides such as propylene oxide and butylene oxide may be used instead of ethylene oxide.

As step (c),
Step (c1): Hydrocarbon group which may increase the number of added oxyalkylene groups by reacting (poly) oxyalkylene alkyl ether at the end of hydrophilic vinyl ether and may have a hydrogen atom of hydroxyl group as a substituent Step to denature.
Step (c2): The nonionic surfactant terminal obtained by the acetalization step is reacted with (poly) oxyalkylene alkyl ether to increase the number of oxyalkylene groups added and to replace the hydroxyl group hydrogen atom. A step of modifying to a hydrocarbon group which may have a group.

As a specific example of the step (c1), for example, (poly) oxyethylene monovinyl ether in which p mol of oxyethylene group is added as shown in the following reaction formula (16) is prepared, and q mol of oxyethylene group is added (poly ) A step of reacting oxyethylene alkyl ether to produce a hydrophilic vinyl ether having an average addition mole number of oxyethylene groups of p + q mol and a terminal being a hydrocarbon group is mentioned.

(In Reaction Formula (16), p + q is the average number of moles of oxyethylene group added, and is a number from 1 to 400)

In step (c1), a hydroxyl group at the terminal of (poly) oxyethylene alkyl ether to which q mole of oxyethylene group has been added is modified to easily remove a tosyl group, mesyl group, trifuryl group, etc. Then, the reaction may be carried out as shown in the following reaction formula (17) to produce a hydrophilic vinyl ether having an average addition mole number of oxyethylene groups of p + q mole and a terminal being a hydrocarbon group. In this way, the step of reacting after modifying the hydroxyl group at the terminal of (poly) oxyethylene alkyl ether also reacts with (poly) oxyalkylene alkyl ether having the structure represented by formula (5) in step (c). Included in the process.

(In reaction formula (17), p + q is the average number of moles of oxyethylene group added and is a number from 1 to 400. W is a substituent that can be easily removed.)

As a specific example of the step (c2), for example, after producing a nonionic surfactant having an acetal structure in which p mol of an oxyethylene group is added as shown in the following reaction formula (18), q mol of the oxyethylene group is Examples include a step of reacting the added polyoxyethylene alkyl ether to produce a nonionic surfactant having an average addition mole number of oxyethylene groups of p + q mol and a terminal being a hydrocarbon group.

(In the reaction formula (18), p + q is the average number of moles of oxyethylene group added and is a number from 1 to 400)
Also in the step (c2), as shown in the reaction formula (17), the hydroxyl group at the terminal of the (poly) oxyethylene alkyl ether to which q mole of oxyethylene group is added may be reacted.
The oxyethylene group in the reaction formulas (16) to (18) may be another oxyalkylene group such as an oxypropylene group or an oxybutylene group.

An example of a desirable form of the method for producing a nonionic surfactant of the present invention is that X in the nonionic surfactant having the structure represented by the general formula (1) obtained by the acetalization step is a hydrogen atom. The nonionic surfactant having the structure represented by the general formula (1) has a hydroxyl group at its terminal, and the hydrocarbon group which may have a substituent on the hydrogen atom of the hydroxyl group In this mode, a nonionic surfactant having a structure represented by the following general formula (2) is produced.

This form is a form in which the hydrogen atom at the terminal of the nonionic surfactant obtained by the acetalization step is modified with a hydrocarbon group, and the step (a2) is carried out after the acetalization step, the step after the acetalization step ( The form in which the step (a2) is performed after performing the b2), the form in which the step (c2) is performed after the acetalization process, and the form in which the process (c2) is performed after performing the step (b2) after the acetalization process are applicable. .

An example of a desirable form of the method for producing the nonionic surfactant of the present invention is that the hydrophilic vinyl ether having the structure represented by the general formula (3) is a hydrocarbon group in which X may have a substituent. A hydrophilic vinyl ether having a structure represented by the following general formula (7), a vinyl group of the hydrophilic vinyl ether having a structure represented by the general formula (7) and a structure represented by the general formula (4). In this embodiment, a nonionic surfactant having a structure represented by the following general formula (2) is produced by carrying out an acetalization step in which an acetal bond is formed by reacting a hydroxyl group of an alcohol having the same.

This form is a form in which the hydrogen atom at the end of the hydrophilic vinyl ether is modified with a hydrocarbon group before the acetalization process and used in the acetalization process. The form in which the step (a1) is performed before the acetalization process, the acetalization process A mode in which the step (a1) is performed after the step (b1) is performed before, a mode in which the step (c1) is performed before the acetalization step, and a step (c1) after the step (b1) is performed before the acetalization step. This corresponds to the form of performing.

Moreover, the nonionic surfactant of the present invention has a structure represented by the following general formula (19),
It may be a nonionic surfactant characterized by having an acetal structure formed by the reaction of a polyhydric alcohol and a hydrophilic vinyl ether.

The nonionic surfactant is the same as the nonionic surfactant described above except that the polyhydric alcohol is used as the alcohol and the molar ratio of the hydrophilic vinyl ether is changed according to the valence of the alcohol. It can be manufactured by the same method.
Examples of the polyhydric alcohol include ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol and the like.

The nonionic surfactant of this invention is suitable as a material mix | blended in a cleaning composition.
Hereinafter, an example of the cleaning composition using the nonionic surfactant of the present invention will be described.
In the cleaning composition, for example, (B) a chlorine agent can be blended in addition to (A) the nonionic surfactant of the present invention. When it is set as an alkaline cleaning composition, (C) an alkali agent can be contained.

The concentration of the nonionic surfactant (A) of the present invention in the cleaning composition is not particularly limited, but is desirably 0.1 to 30% by weight, preferably 0.5 to 25% by weight. % Is more desirable, and 0.5 to 20% by weight is even more desirable.

As the chlorinating agent (B), for example, chlorinated isocyanurate (sodium chlorinated isocyanurate, potassium chlorinated isocyanurate, etc.), trichloroisocyanuric acid, hypochlorite (sodium hypochlorite, Potassium hypochlorite, calcium hypochlorite, etc.).
Moreover, 1 type in these chlorine agents may be used, and 2 or more types may be used together.
When the nonionic surfactant (A) of the present invention contained in the cleaning composition does not have a hydroxyl group at the molecular end, the acetal structure does not react with the chlorinating agent (B), so in the cleaning composition Inactivation of the chlorine agent (B) is prevented.
The concentration of the chlorine agent (B) in the cleaning composition is not particularly limited, but it is desirable that it be blended so that the effective chlorine concentration is 0 to 45% by weight. The concentration of the chlorine agent is preferably 0 to 50% by weight, and more preferably 2 to 50% by weight.
When a plurality of types of chlorinating agents are used, the concentration of the chlorinating agent is determined as a total value of the concentration of each chlorinating agent.
Moreover, it is desirable that the content of the chlorinating agent (B) with respect to the content of the nonionic surfactant (A) of the present invention is the same or greater, and the content of the chlorinating agent with respect to the content of the nonionic surfactant The ratio of chlorinating agent / nonionic surfactant is preferably 1 to 100, more preferably 1 to 20, and further preferably 1 to 6.
A detergent composition containing a relatively large amount of chlorine agent can exhibit high bleaching and bactericidal properties.

As the alkali agent (C), an alkali metal or alkaline earth metal salt can be used, and the kind thereof is not particularly limited, but sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, hydrogen carbonate. Sodium, potassium hydrogen carbonate, sodium metasilicate, sodium sesquisilicate, sodium orthosilicate, potassium metasilicate, potassium sesquisilicate, potassium orthosilicate and the like are desirable.
These alkaline agents may be hydrated.
Among these, at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium orthosilicate, potassium orthosilicate, sodium metasilicate, potassium metasilicate, and hydrates thereof is desirable. When these alkali agents are used, an alkali cleaner having a high detergency can be obtained.
Moreover, 1 type in these alkaline agents may be used and 2 or more types may be used together.
The concentration of the alkaline agent (C) is not particularly limited, but is preferably 2 to 90% by weight, more preferably 5 to 80% by weight, and 12 to 80% by weight. More desirable.
When a plurality of types of alkali agents are used, the concentration of the alkali agent is determined as a total value of the concentrations of the respective alkali agents.

The pH of the detergent composition is not particularly limited, but from the viewpoint of the stability of the terminal acetal structure of the nonionic surfactant (A) of the present invention, it should be in a neutral to alkaline range. Is desirable.
In the case of a neutral detergent composition, the pH is desirably 6 or more and less than 9, and in the case of a weakly alkaline detergent composition, the pH is desirably 9 or more and less than 12, and is strongly alkaline. When it is set as a cleaning composition, it is desirable that pH is 12 or more.
The pH may be measured using a commercially available pH meter or the like. For example, the pH can be measured using a model D-21 manufactured by Horiba, Ltd.

When a chlorinating agent is blended in the cleaning composition, both the cleaning effect by the nonionic surfactant, the bleaching by the chlorinating agent, and the bactericidal effect can be exhibited. In addition, a cleaning composition that is made alkaline by adding an alkali agent can further exert a cleaning effect on oil stains and the like due to the alkali agent.

The above-mentioned detergent composition is blended with a detergent composition such as a polymer dispersant (D), a chelating agent (E), a solvent / process agent (F), a solubilizer (G), etc., as necessary. Other components may be contained. Moreover, you may contain surfactant other than the nonionic surfactant (A) of this invention.
Examples of the polymer dispersant (D) include polyacrylic acid, polyaconitic acid, polyitaconic acid, polycitraconic acid, polyfumaric acid, polymaleic acid, polymethaconic acid, poly-α-hydroxyacrylic acid, polyvinylphosphonic acid, and sulfonated polymaleic acid. Olefin-maleic acid copolymer, maleic anhydride diisobutylene copolymer, maleic anhydride styrene copolymer, maleic anhydride methyl vinyl ether copolymer, maleic anhydride ethylene copolymer, maleic anhydride ethylene crosslink copolymer Polymer, maleic anhydride vinyl acetate copolymer, maleic anhydride acrylonitrile copolymer, maleic anhydride acrylic ester copolymer, maleic anhydride butadiene copolymer, maleic anhydride isoprene copolymer, maleic anhydride and Derived from carbon monoxide Poly-β-ketocarboxylic acid, itaconic acid, ethylene copolymer, itaconic acid aconitic acid copolymer, itaconic acid maleic acid copolymer, itaconic acid acrylic acid copolymer, malonic acid methylene copolymer, itaconic acid fumaric acid Examples thereof include copolymers, ethylene glycol ethylene terephthalate copolymers, vinyl pyrrolidone vinyl acetate copolymers, and metal salts thereof. Of these, sodium polyacrylate (average molecular weight Mw = 3,000 to 30,000), polymaleic acid-sodium acrylate, olefin-sodium maleate copolymer, etc. are preferably used from the viewpoint of cost and economy. It is done.
Examples of the chelating agent (E) include ethylenediaminetetraacetic acid (EDTA), hydroxyethylethylenediaminetriacetic acid (HEDTA), nitrilotriacetic acid (NTA), diethylenetriaminepentaacetic acid (DTPA), 2-phosphonobutane-1,2,4-tricarboxylic acid, Ethylenediaminesuccinic acid (EDDS), hydroxyethyliminodiacetic acid (HIDA), glutamic acid diacetic acid (GLDA), methylglycine diacetic acid (MGDA), aspartic acid diacetic acid (ASDA), tripolyphosphoric acid, polyacrylic acid and their salts ( Sodium salts, potassium salts, etc.), polyaspartic acid compounds represented by the following formula (20), iminodisuccinic acid compounds represented by the following formula (21), and iminodiacetic acid represented by the following formula (22) System compounds.

Wherein (20), M is the same or different and -H, -Na, -K or -NH _4. s and t are integers]

[In formula (21), M is the same or different and is —H, —Na, —K or —NH ₄ . ]

[In Formula (22), M is the same or different and is —H, —Na, —K or —NH ₄ . ]

The concentration of the chelating agent in the cleaning composition is not particularly limited, but is preferably 0 to 80% by weight, more preferably 0 to 70% by weight, and 15 to 50% by weight. It is further desirable that
Examples of the solvent (F) include water and commonly used organic solvents. The process agent (F) is an extender in the case where the dosage form is solid, and preferably has a neutral pH, and examples thereof include sodium sulfate and powdered silica.
Examples of the solubilizer (G) include xylene sulfonic acid, cumene sulfonic acid, caprylic acid, octylic acid and salts thereof, alkyl diphenyl ether disulfonate, and the like.

Examples for more specifically explaining the present invention are shown below, but the present invention is not limited to these examples.

(Production Example 1)
To a methylene chloride solution (10 ml) of 5.6 g of dodecyl alcohol, 1 mol% of methanesulfonic acid was mixed as a catalyst, 3.6 g of diethylene glycol monovinyl ether was added, and the mixture was stirred overnight (10 hours) at room temperature. Sodium bicarbonate was added to terminate the reaction, and after filtration, the solvent was distilled off to obtain a nonionic surfactant (A-1).

(Production Example 2)
To a methylene chloride solution (10 ml) of 2-ethylhexanol (10 ml), 1 mol% of methanesulfonic acid was mixed as a catalyst, 3.6 g of diethylene glycol monovinyl ether was added, and the mixture was stirred overnight (10 hours) at room temperature. Sodium bicarbonate was added to terminate the reaction, and after filtration, the solvent was distilled off to obtain a nonionic surfactant (A-2).

(Production Example 3)
To a THF solution (50 mL) of diethylene glycol monomethyl ether (4.8 g), 4.5 g of potassium t-butoxy was added and cooled to 0 ° C. Then, 7.6 g of p-toluenesulfonyl chloride was added and stirred at 0 ° C. for 30 minutes. This solution was added to a THF solution (25 mL) of 5.5 g of diethylene glycol monovinyl ether and 5.2 g of t-butoxypotassium, and stirred at 30 ° C. overnight (10 hours). Filtration was performed to distill off volatile substances. To 4.0 g of the obtained product, 2.4 g of 2-ethylhexyl alcohol was mixed, 1 mol% of methanesulfonic acid was added as a catalyst, and the mixture was stirred overnight (10 hours) at room temperature. Sodium hydrogen carbonate was added to terminate the reaction, and after filtration, a nonionic surfactant (A-3) was obtained.
The obtained nonionic surfactant comprises a vinyl group of hydrophilic vinyl ether in which the average addition mole number p of oxyethylene group is 4 in the general formula (3) and X is a methyl group, and 2-ethylhexyl alcohol. It is a nonionic surfactant having an acetal structure obtained by reacting with a hydroxyl group of

(Production Example 4)
To a methylene chloride solution (10 ml) of tetradecyl alcohol 4.3 g, 1 mol% of methanesulfonic acid was mixed as a catalyst, 2.6 g of diethylene glycol monovinyl ether was added, and the mixture was stirred overnight (10 hours) at room temperature. Sodium bicarbonate was added to terminate the reaction, filtration was performed, and the solvent was distilled off. To a THF solution (10 ml) of 3.5 g of the obtained product, 2.7 g of triethylene glycol 2-bromoethyl methyl ether and 1.2 g of potassium t-butoxy were added and refluxed at 70 ° C. overnight (10 hours). Stir. Sulfuric acid was added to terminate the reaction, filtration was performed, and the solvent was distilled off to obtain a nonionic surfactant (A-4).
The obtained nonionic surfactant has an average addition mole number p of oxyethylene group of 6 in the above general formula (3), X is a methyl group, a vinyl group of hydrophilic vinyl ether, and tetradecyl alcohol. It is a nonionic surfactant having an acetal structure obtained by reacting with a hydroxyl group.

(Production Example 5)
To 6.6 g of diethylene glycol monovinyl ether, 29 g of propylene oxide and 10 mol% of t-butoxypotassium as a catalyst were added and stirred at room temperature for 5 days. Sulfuric acid was added to terminate the reaction, filtration was performed, and excess propylene oxide was distilled off. From the weight difference between the added propylene oxide and the distilled propylene oxide, it was confirmed that the average added mole number of oxypropylene groups in the oxypropylene group adduct was 3. To the obtained product (6.1 g) in methylene chloride solution (10 ml), 1 mol% of methanesulfonic acid was mixed as a catalyst, decyl alcohol (3.2 g) was added, and the mixture was stirred overnight (10 hours) at room temperature. Sodium bicarbonate was added to terminate the reaction, and after filtration, the solvent was distilled off to obtain a nonionic surfactant (A-5).
The obtained nonionic surfactant has an average addition mole number p of oxyalkylene group of 5 in the above general formula (3) (average addition mole number of oxyethylene group is 2, average addition mole number of oxypropylene group is 3) A nonionic surfactant having an acetal structure obtained by reacting a vinyl group of a hydrophilic vinyl ether in which X is a hydrogen atom with a hydroxyl group of decyl alcohol.

(Production Example 6)
To a THF solution (10 ml) of 2.6 g of diethylene glycol monovinyl ether were added 3.9 g of 1-bromooctane and 2.3 g of potassium t-butoxy, and the mixture was refluxed and stirred overnight (10 hours) at 70 ° C. Sulfuric acid was added to terminate the reaction, filtration was performed, and the solvent was distilled off. 1 mol% of methanesulfonic acid as a catalyst was mixed with 2.4 g of the obtained product in methylene chloride solution (10 ml), 0.5 g of ethanol was added, and the mixture was stirred overnight (10 hours) at room temperature. Sodium bicarbonate was added to terminate the reaction, filtration was performed, and the solvent was distilled off to obtain a nonionic surfactant (A-6).
The obtained nonionic surfactant has an average addition mole number p of oxyalkylene group of 2 in the above general formula (3), X is an octyl group, vinyl group of hydrophilic vinyl ether, and ethanol hydroxyl group. Is a nonionic surfactant having an acetal structure obtained by reacting

(Production Example 7)
3 mol% of methanesulfonic acid as a catalyst was mixed with 9.2 g of glycerol in methylene chloride (10 ml), 40 g of diethylene glycol monovinyl ether was added, and the mixture was stirred overnight (10 hours) at room temperature. Sodium bicarbonate was added to terminate the reaction, and after filtration, the solvent was distilled off to obtain a nonionic surfactant (A-7).
The obtained nonionic surfactant has an average addition mole number p of oxyalkylene group of 2 in the above general formula (3), and a vinyl group of hydrophilic vinyl ether in which X is a hydrogen atom, and a hydroxyl group of glycerin. Is a nonionic surfactant having an acetal structure obtained by reacting
This residue in the formula (19) Z is derived from glycerin, u = 3, the (AO) n is _(EO) 2, X corresponds to the non-ionic surfactant of structure a hydrogen atom.

(Production Example 8)
To a THF solution (10 ml) of 1.3 g of the nonionic surfactant (A-2) produced in Production Example 2, 0.7 g of 1-bromobutane and 0.6 g of potassium t-butoxy were added overnight (10 hours). The mixture was refluxed and stirred at 70 ° C. Sulfuric acid was added to terminate the reaction, filtration was performed, and the solvent was distilled off to obtain a nonionic surfactant (A-8).
The obtained nonionic surfactant comprises a vinyl group of hydrophilic vinyl ether in which the average addition mole number p of the oxyalkylene group in the above general formula (3) is 2, and 2-ethylhexyl alcohol. It is a nonionic surfactant having an acetal structure obtained by reacting with a hydroxyl group of

(Production Example 9)
A chloroform solution (25 mL) of 7.5 g of polyethylene glycol monomethyl ether having an average addition mole number of oxyethylene groups of 17 was cooled to 0 ° C., and then 1.5 equivalents of pyridine and 2 equivalents of p-toluenesulfonyl chloride were added. In addition, the mixture was stirred at 0 ° C. for 30 minutes. This solution was added to a chloroform solution (25 mL) of 1.3 g of diethylene glycol monovinyl ether and 1.2 g of potassium t-butoxy and stirred at 30 ° C. overnight (10 hours). Filtration was performed to distill off volatile substances. To a 4.4 g methylene chloride solution (10 ml) of the obtained product, 1.4 g of octadecyl alcohol was mixed, 1 mol% of methanesulfonic acid was added as a catalyst, and the mixture was stirred overnight (10 hours) at room temperature. Sodium bicarbonate was added to terminate the reaction, and after filtration, the solvent was distilled off to obtain a nonionic surfactant (A-9).
The obtained nonionic surfactant has an average addition mole number p of oxyethylene group of 19 in the above general formula (3), and a vinyl group of hydrophilic vinyl ether in which X is a methyl group, and a hydroxyl group of octadecyl alcohol. It is a nonionic surfactant having an acetal structure obtained by reacting with a group.

1 to 3 are NMR spectra of the nonionic surfactants synthesized in Production Examples 1 to 3, respectively. In any case, a peak derived from an acetal structure was confirmed in the vicinity of 4.6 to 4.8 (ppm).

(Measurement of surface tension)
A mixed solution was prepared by mixing 0.1 part by weight of the nonionic surfactant (A-3) and 99.9 parts by weight of water, and the surface tension of this mixed solution was measured using an automatic surface tension meter K100 manufactured by KRUSS. As a result, it was 28 mN / m at 25 ° C.

Claims

It has a structure represented by the following general formula (1),
A nonionic surfactant characterized by having an acetal structure formed by reaction of alcohol and hydrophilic vinyl ether.

(In General Formula (1), R 1 is a residue derived from alcohol, (AO) n is an oxyalkylene group which may be the same or different, derived from a hydrophilic vinyl ether, and n is an oxyalkylene. Represents the average number of moles of the group added, and is a number from 1 to 400. X is a hydrocarbon group which may have a substituent or a hydrogen atom)
The nonionic surfactant according to claim 1, wherein R 1 in the general formula (1) is a hydrocarbon group having 8 to 20 carbon atoms.
The oxyalkylene group in the general formula (1) is an oxyethylene group, an oxypropylene group or an oxybutylene group, respectively, and the proportion of the oxyethylene group contained in the oxyalkylene group is 50 mol% or more. 2. A nonionic surfactant according to 2.
The nonionic group according to any one of claims 1 to 3, wherein X in the general formula (1) is a hydrocarbon group which may have a substituent, and has a structure represented by the following general formula (2). Surfactant.

(In general formula (2), R 2 is a hydrocarbon group which may have a substituent)
A vinyl group of a hydrophilic vinyl ether having a structure represented by the following general formula (3);
An acetalization step of forming an acetal bond by reacting a hydroxyl group of an alcohol having a structure represented by the following general formula (4) to produce a nonionic surfactant having a structure represented by the following general formula (1) A method for producing a nonionic surfactant, comprising:

(In the general formula (3), (AO) p is an oxyalkylene group which may be the same or different, p represents the average number of added moles of the oxyalkylene group, and is a number from 1 to 400. X is A hydrocarbon group which may have a substituent or a hydrogen atom)

(In general formula (4), R 1 is a residue of alcohol)

(In General Formula (1), R 1 is a residue derived from alcohol, (AO) n is an oxyalkylene group which may be the same or different, derived from a hydrophilic vinyl ether, and n is an oxyalkylene. Represents the average number of moles of the group added, and is a number from 1 to 400. X is a hydrocarbon group which may have a substituent or a hydrogen atom)
X in the nonionic surfactant having the structure represented by the general formula (1) obtained by the acetalization step is a hydrogen atom, and the nonionic surfactant having the structure represented by the general formula (1) The agent has a hydroxyl group at its end,
The nonionic surfactant having a structure represented by the following general formula (2) is produced by modifying a hydrogen atom of the hydroxyl group into a hydrocarbon group which may have a substituent. A method for producing a nonionic surfactant.

(In general formula (2), R 2 is a hydrocarbon group which may have a substituent)
The reaction for modifying the hydrogen atom of the hydroxyl group to a hydrocarbon group which may have a substituent is a dialkyl sulfate, a dialkyl carbonate, an alkyl halide, a trialkyloxonium salt, an alkyl ester of alkane sulfonic acid, or an arene sulfone. The method for producing a nonionic surfactant according to claim 6, wherein the reaction is to replace the hydrogen atom with a hydrocarbon group by acting an alkyl ester of an acid.
In the reaction of modifying the hydrogen atom of the hydroxyl group to an optionally substituted hydrocarbon group, the hydroxyl group is reacted with a (poly) oxyalkylene alkyl ether having a structure represented by the following general formula (5). The nonionic surfactant according to claim 6, wherein the nonionic surfactant having a structure represented by the following general formula (6) is produced in combination with a reaction for increasing the number of oxyalkylene groups added. Manufacturing method.

(In general formula (5), q represents the average number of moles added of the oxyalkylene group and is a number from 1 to 399.)

(In general formula (6), p + q represents the average number of moles of oxyalkylene group added and is a number from 1 to 400.)
The hydrophilic vinyl ether having the structure represented by the general formula (3) is:
X is a hydrophilic vinyl ether having a structure represented by the following general formula (7), which is a hydrocarbon group which may have a substituent,
Performing an acetalization step of reacting the vinyl group of the hydrophilic vinyl ether having the structure represented by the general formula (7) with the hydroxyl group of the alcohol having the structure represented by the general formula (4) to form an acetal bond; The method for producing a nonionic surfactant according to claim 5, wherein a nonionic surfactant having a structure represented by the following general formula (2) is produced.

(In General Formula (7), R 2 is a hydrocarbon group which may have a substituent)

(In general formula (2), R 2 is a hydrocarbon group which may have a substituent)
Dialkyl sulfate, dialkyl carbonate, alkyl halide, trialkyloxonium salt, alkyl ester of alkanesulfonic acid, or arene at the hydrogen atom of the hydroxyl group located at the end of the hydrophilic vinyl ether having the structure represented by the following general formula (8) By reacting the hydrogen atom with a hydrocarbon group by acting an alkyl ester of sulfonic acid, and performing a step of obtaining a hydrophilic vinyl ether having a structure represented by the general formula (7);
The manufacturing method of the nonionic surfactant of Claim 9 used for the said acetalization process.
By reacting a hydroxyl group located at the end of a hydrophilic vinyl ether having a structure represented by the following general formula (9) with a polyoxyalkylene alkyl ether having a structure represented by the following general formula (5),
A step of obtaining a hydrophilic vinyl ether having a structure represented by the general formula (7) by modifying the hydrogen atom of the hydroxyl group into a hydrocarbon group which may have a substituent and increasing the number of oxyalkylene groups added. And
The manufacturing method of the nonionic surfactant of Claim 9 used for the said acetalization process.

(In general formula (9), pq represents the average number of moles added of the oxyalkylene group, and is a number from 0 to 399.)

(In general formula (5), q represents the average number of moles added of the oxyalkylene group and is a number from 1 to 399.)
The method for producing a nonionic surfactant according to any one of claims 5 to 11, wherein the alcohol having the structure represented by the general formula (4) has 8 to 20 carbon atoms.
It has a structure represented by the following general formula (19),
A nonionic surfactant characterized by having an acetal structure formed by the reaction of a polyhydric alcohol and a hydrophilic vinyl ether.

(In general formula (19), u is an integer of 2 or more, Z is a residue derived from a u-valent polyhydric alcohol, and (AO) n is the same or different derived from a hydrophilic vinyl ether. An oxyalkylene group which may be substituted, n represents the average number of moles added of the oxyalkylene group and is a number from 1 to 400. X is a hydrocarbon group or a hydrogen atom which may have a substituent.