CN109721723B

CN109721723B - Surfactant, method for producing the same, and solution containing the same

Info

Publication number: CN109721723B
Application number: CN201711463691.9A
Authority: CN
Inventors: 邱锡海; 庄忠哲; 林雅慧
Original assignee: Sino Japan Chemical Co ltd
Current assignee: Sino Japan Chemical Co ltd
Priority date: 2017-10-31
Filing date: 2017-12-28
Publication date: 2021-07-06
Anticipated expiration: 2037-12-28
Also published as: TW201918276A; CN109721723A; TWI648096B

Abstract

The invention relates to a surfactant, a preparation method thereof and a solution containing the surfactant. The surfactant of the present invention has a structure represented by the following formula (I):

in the formula (I), R₁Represents an alkyl group having 8 to 30 carbon atoms, an alkylphenyl group or a structure represented by the following formula (II); r₂Represents a C2-4 alkoxy group, wherein R₂Alkyl of (2) with R₁An O-bond; r₃Represents an alkyl group having 3 to 18 carbon atoms, an alkoxy group having 3 to 18 carbon atoms, a phenol group or an o-cresol group; n represents a number in the range of 0 to 100; and m represents a number in the range of 0.1 to 10;

in the formula (II), R₄Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; z represents an integer of 1 to 3, and "" represents a bond. The surfactant of the invention has good defoaming property and wetting permeability.

Description

Surfactant, method for producing the same, and solution containing the same

Technical Field

The invention relates to a surfactant, in particular to a surfactant with good defoaming property, wetting permeability and small gelling concentration difference and application thereof.

Background

The general surfactant has a structure with Lipophilic groups and hydrophilic groups, and the HLB (Hydrophile lipophile Balance) value of the surfactant can be adjusted by different Lipophilic groups and hydrophilic groups, so that the surfactant can have different emulsifying abilities and interface properties (such as defoaming property, wetting permeability, dilutability, gelling concentration and the like), and further meet different application requirements.

Because the molecular chain end of the common surfactant is active alkyl, when the surfactants are applied, foams formed by solution oscillation are not easy to eliminate, and the applicability of the surfactants is reduced. Therefore, in order to effectively improve the defoaming property of the surfactant, an alkyl reagent (e.g., aryl alkyl halide or dialkyl sulfate) is generally used to perform a capping reaction on the terminal active hydrocarbon group of the surfactant to replace the terminal active hydrocarbon group and further improve the defoaming property.

However, the alkyl reagents used in the capping reaction are toxic materials, and the waste materials formed by the reaction are environmentally friendly. In addition, after the above reaction is completed, the formed product must be further purified by washing with water by adding a large amount of water, and unreacted reactants are removed by phase separation. Accordingly, the reaction process is complicated, and a large amount of raw material cost and energy cost are consumed.

In view of the above, it is desirable to provide a surfactant having good defoaming property and wetting permeability, a method for preparing the same, and a solution containing the same, so as to improve the drawbacks of the conventional surfactant, the method for preparing the same, and the solution containing the same.

Disclosure of Invention

Therefore, one aspect of the present invention is to provide a surfactant having a specific structure and having good defoaming property and wetting permeability by a capping group.

Another aspect of the present invention is to provide a method for preparing a surfactant, which can prepare the surfactant by a single-step reaction.

It is a further aspect of the present invention to provide a solution comprising the aforementioned surfactant.

According to one aspect of the present invention, a surfactant is provided. The surfactant has a structure shown in the following formula (I):

in the formula (I), R₁Represents an alkyl group having 8 to 30 carbon atoms, an alkylphenyl group or a structure represented by the following formula (II); r₂Represents a C2-4 alkoxy (alkoxy) group, wherein R is₂Alkyl of (2) with R₁An O-bond; r₃Represents an alkyl group having 3 to 18 carbon atoms, an alkoxy group having 3 to 18 carbon atoms, a phenol group or an o-cresol group; n represents a number in the range of 0 to 100; and m represents a number in the range of 0.1 to 10;

in the formula (II), R₄Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; z represents an integer of 1 to 3, and "" represents a bond.

According to an embodiment of the present invention, the aforementioned R₁Represents an alkyl phenyl group or a structure shown as a formula (II).

According to another embodiment of the present invention, the aforementioned R₂Represents a C2-3 alkoxy group.

According to another embodiment of the present invention, the difference of the gelling concentration of the surfactant at 4 ℃ is less than 20 weight percent.

According to another aspect of the present invention, a method for producing a surfactant is provided. The preparation method is to provide a mixture and carry out a single-step reaction on the mixture to obtain the surfactant.

Wherein the mixture comprises a compound (A) represented by the following formula (III-1) and a compound (B) represented by the following formula (III-2):

in the formula (III-1), R₁Represents an alkyl group having 8 to 30 carbon atoms, an alkylphenyl group or a styrenated phenyl group; r₂Represents a C2-4 alkoxy group, wherein R₂The terminal oxygen atom of (a) is bonded to a hydrogen atom; and n represents a number in the range of 0 to 100; in the formula (III-2), R₃Represents an alkyl group having 3 to 18 carbon atoms, an alkoxy group having 3 to 18 carbon atoms, a phenol group or an o-cresol group.

According to an embodiment of the present invention, the mixture comprises a catalyst (C).

According to another embodiment of the present invention, the catalyst (C) is used in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the total amount of the compound (A) represented by the aforementioned formula (III-1).

According to another embodiment of the present invention, the reaction temperature of the aforementioned single-step reaction is 50 ℃ to 120 ℃.

According to yet another aspect of the invention, a solution is provided. This solution contains the aforementioned surfactant.

The surfactant has a specific structure, and has good defoaming property and wetting permeability. Secondly, the method for producing the surfactant of the present invention does not require a large amount of organic solvent or water, thereby reducing the burden on the environment and eliminating the cost required for purification. In addition, the preparation method can prepare the surfactant by only one step reaction, thereby reducing complicated experimental procedures and reducing energy cost.

Detailed Description

The making and using of embodiments of the present invention are discussed in detail below. It should be appreciated, however, that the embodiments provide many applicable inventive concepts that can be embodied in a wide variety of specific contexts. The specific embodiments discussed are merely illustrative and do not limit the scope of the invention.

The term "single step reaction" as used herein means that the mixture is subjected to only one step reaction to obtain the surfactant of the present invention. It should be noted that the single-step reaction referred to herein may comprise multiple reaction mechanisms rather than a single reaction mechanism. These reaction mechanisms may include a mechanism of reducing the activation energy of the reaction by the catalyst material, a ring-opening mechanism of the epoxide, and a chain polymerization bonding mechanism. Depending on the composition of the mixture, the aforementioned reaction mechanisms may or may not occur simultaneously, or in a different order than that described.

The surfactant of the present invention is prepared by providing a mixture comprising a compound (A) represented by the following formula (III-1) and a compound (B) represented by the following formula (III-2):

in the formula (III-1), R₁Represents an alkyl group having 8 to 30 carbon atoms, an alkylphenyl group or a styrenated benzeneA group; r₂Represents a C2-4 alkoxy (alkoxy) group, wherein R is₂The terminal oxygen atom of (a) is bonded to a hydrogen atom; and n represents a number in the range of 0 to 100; in the formula (III-2), R₃Represents an alkyl group having 3 to 18 carbon atoms, an alkoxy group having 3 to 18 carbon atoms, a phenol group or an o-cresol group.

The aforementioned alkyl group having a carbon number of 8 to 30 may be a straight chain alkyl group or a branched chain alkyl group. In some embodiments, an alkyl group having a carbon number of 8 to 30 may include, but is not limited to, n-octyl, isooctyl, 2-ethylhexane, n-nonyl, isononyl, 2-methyloctyl, 3-methyloctyl, 4-methyloctyl, 5-methyloctyl, 6-methyloctyl, 2-ethylheptyl, 3-ethylheptyl, 4-ethylheptyl, 5-ethylheptyl, 2-propylhexane, 3-propylhexane, n-decyl, isodecyl, 2-methylnonyl, 3-methylnonyl, 4-methylnonyl, 5-methylnonyl, 6-methylnonyl, 7-methylnonyl, 2-ethyloctyl, 3-ethyloctyl, 4-ethyloctyl, 5-ethyloctyl, 6-ethyloctyl, 2-propylheptyl, 4-ethylheptyl, 5-ethyloctyl, 6-ethyloctyl, 2-ethylheptyl, and C-ethylheptyl groups, 3-propylheptyl, 4-propylheptyl, 2-butylhexyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, 2-pentylnonyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, n-heneicosyl, n-docosyl, n-tricosyl, n-tetracosyl, or n-pentacosyl, other suitable alkyl segments, or any combination thereof.

When R is₁When the alkyl represents an alkyl group having a carbon number of less than 8, an excessively short alkyl chain segment has a defect of poor wetting and permeability; when R is₁When the alkyl group having more than 30 carbon atoms is represented, the excessively long alkyl chain segment has a defect that the difference between the solubility and the gel concentration is large. Preferably, when R is₁When representing an alkyl group, the carbon number of the alkyl group may be 8 to 25, and more preferably 8 to 18.

When R is₁When represents an alkylphenyl group, the carbon number of the alkyl substituent may be 8 to 18, and the alkyl substituent may be a straight-chain alkyl group or a branched-chain alkyl group. In some embodiments, when R₁When an alkylphenyl group is represented, the bonding position of the alkyl substituent on the phenyl group is not particularly limited.

In some embodiments, the number of alkyl substituents on the aforementioned alkylphenyl groups may be more than one. In other words, the phenyl group may have at least one alkyl substituent. In such embodiments, when the number of alkyl substituents is greater than 1, such alkyl substituents may be the same or different.

When R is₁When represents a styrenated phenyl group, R₁May have a structure represented by the following formula (II):

When R is₁May have a structure represented by the formula (II), z may preferably be 2. When z is 3, the prepared surfactant has better defoaming property and wetting permeability.

In some embodiments, R₁Preferably, it may represent an alkylphenyl group or a styrenated phenyl group. When R is₁When the surfactant is alkyl phenyl or styrenated phenyl, the prepared surfactant has better defoaming property and wetting permeability.

In some embodiments, when R₁Represents alkyl phenyl or styrenated phenyl, and when the prepared surfactant is applied to paint, the benzene ring group of the surfactant can be used as a wetting, penetrating and dispersing aid, so that the intersolubility of the surfactant is effectively improved.

In the formula (III-1), R₂The C2-4 alkoxy group may be an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group or an isobutoxy group. In some embodiments, R₂Preferably represents a C2-3 alkoxy group. For example, R₂May be a hypoethoxy, hypopropoxy or hypoisopropoxy group. When R is₂When the carbon number is a C2-3 alkoxy group, the prepared surfactant has better defoaming property and wetting permeability.

In some embodiments, n may preferably be 1 to 50, and more preferably may be 5 to 30.

In the formula (III-2), R₃The alkyl group having a carbon number of 3 to 18 represented may be a straight chain alkyl group or a branched chain alkyl group. In some embodiments, an alkyl group having a carbon number of 3 to 18 may include, but is not limited to, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, 2-ethylhexane, n-nonyl, isononyl, 2-methyloctyl, 3-methyloctyl, 4-methyloctyl, 5-methyloctyl, 6-methyloctyl, 2-ethylheptyl, 3-ethylheptyl, 4-ethylheptyl, 5-ethylheptyl, 2-propylhexane, 3-propylhexyl, n-decyl, isodecyl, 2-methylnonyl, 3-methylnonyl, 4-methylnonyl, 5-methylnonyl, 6-methylnonyl, 7-methylnonyl, 2-ethyloctyl, 2-propylhexyl, n-decyl, isodecyl, 2-methylnonyl, 3-methylnonyl, 4-methylnonyl, 5-methyl, 3-ethyloctyl, 4-ethyloctyl, 5-ethyloctyl, 6-ethyloctyl, 2-propylheptyl, 3-propylheptyl, 4-propylheptyl, 2-butylhexyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, 2-pentylnonyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, other suitable alkyl segments, or any combination of the foregoing. If R is₃Represents an alkyl group, and when the number of carbon atoms is less than 3, R is₃The groups are too small, so that the prepared surfactant has poor defoaming property and wetting permeability. If R is₃When the number of carbon atoms of the alkyl group is more than 18, R is a number of carbon atoms₃The groups are oily, so that the mutual solubility of the subsequently prepared surfactant and water is poor, and the applicability of the surfactant is reduced. In some embodiments, R₃The carbon number of the alkyl group represented may be preferably 4 to 12.

In the formula (III-2), R₃The alkoxy group having 3 to 18 carbon atoms may be a linear alkoxy group or a branched alkoxy group. In some embodiments, R₃The alkoxy group having a carbon number of 3 to 18 may include, but is not limited to, n-propoxy, isopropoxy, n-butoxy, isobutoxy, n-pentoxy, isopentoxy, n-hexoxy, isohexoxy, n-heptoxy, isoheptoxy, n-octoxy, isooctoxy, 2-ethylhexoxane, n-nonoxy, isononoxy, 2-methylhexoxy, n-nonoxy, isononoxy, and C3 to C18Octyloxy group, 3-methyloctyloxy group, 4-methyloctyloxy group, 5-methyloctyloxy group, 6-methyloctyloxy group, 2-ethylheptyloxy group, 3-ethylheptyloxy group, 4-ethylheptyloxy group, 5-ethylheptyloxy group, 2-propylhexone, 3-propylhexyloxy group, n-decyloxy group, isodecyloxy group, 2-methylnonyloxy group, 3-methylnonyloxy group, 4-methylnonyloxy group, 5-methylnonyloxy group, 6-methylnonyloxy group, 7-methylnonyloxy group, 2-ethyloctyloxy group, 3-ethyloctyloxy group, 4-ethyloctyloxy group, 5-ethyloctyloxy group, 6-ethyloctyloxy group, 2-propylheptyloxy group, 3-propylheptyloxy group, 4-propylheptyloxy group, 2-butylhexyloxy group, N-undecyloxy, n-dodecyloxy, n-tridecyloxy, n-tetradecyloxy, 2-pentylnonyloxy, n-pentadecyloxy, n-hexadecyloxy, n-heptadecyloxy, n-octadecyloxy, other suitable oxyalkyl segments, or any combination of the foregoing. Similarly, if R₃When the carbon number is outside the above range, the resulting surfactant has poor defoaming property and wetting permeability. In some embodiments, R₃The number of carbons of the oxyalkyl group represented may be preferably 4 to 12.

In some embodiments, R is as described above₁When it is an alkyl group having 8 to 30 carbon atoms, R₃Preferably a lipophilic group (e.g., phenol group or o-cresol group) to balance the hydrophilic-lipophilic balance of the resulting surfactant, thereby adjusting the defoaming property and wetting permeability of the resulting surfactant.

In some embodiments, the compound (B) represented by the formula (III-2) may be used in an amount of 5 to 50 parts by weight, preferably 10 to 40 parts by weight, and more preferably 15 to 35 parts by weight, based on 100 parts by weight of the total amount of the compound (A) represented by the formula (III-1).

After the mixture is uniformly mixed, the mixture is subjected to a single-step reaction to prepare the surfactant. When the single-step reaction is carried out, the compound (A) represented by the aforementioned formula (III-1) may be reacted with the compound (B) represented by the formula (III-2), wherein the epoxy group bond in the formula (III-2) may be broken and bonded to form a surfactant. In some embodiments, the reaction temperature of the single-step reaction may be 60 ℃ to 140 ℃, preferably 70 ℃ to 130 ℃, and more preferably 90 ℃ to 110 ℃.

In some embodiments, the aforementioned mixture may optionally comprise a catalyst (C), wherein catalyst (C) may comprise an acid catalyst or a base catalyst. In some embodiments, catalyst (C) may include, but is not limited to, triphenylphosphine, triethylamine, sodium hydroxide, potassium hydroxide, aluminum chloride, boron trifluoride, tetraalkylammonium salts, tetraisopropoxytin, zinc perchlorate, other suitable catalyst materials, and any combination thereof.

When the mixture contains the catalyst (C), the activation energy of the individual reaction mechanisms and the activation energy of the overall reaction mechanism of the aforementioned single-step reaction can be reduced, thereby making the single-step reaction easier to proceed and enhancing the reaction performance of the single-step reaction.

In some embodiments, the catalyst (C) may be used in an amount of 0.1 to 5 parts by weight, and preferably 0.5 to 3 parts by weight, based on 100 parts by weight of the total amount of the compound (A) represented by the formula (III-1). When the amount of the catalyst (C) is less than 0.1 part by weight, too small a catalyst content cannot effectively reduce the reaction activation energy of the single-step reaction without having the effect of improving the reaction efficiency. When the catalyst (C) is used in an amount of more than 5 parts by weight, an excessive catalyst content does not further enhance the reaction performance in addition to increasing the raw material cost.

After the single-step reaction, the prepared surfactant has the structure shown in the following formula (I):

in formula (I), m represents a number in the range of 0.1 to 10, and R₁、R₂、R₃The definitions of n and n are as described above, and are not described herein.

In some embodiments, m may preferably be a number in the range of 0.5 to 3. When m is less than 0.1, the prepared surfactant has poor defoaming property and wetting permeability; when m is greater than 10, the prepared surfactant has poor wetting permeability.

In some embodiments, the surfactants prepared by the present invention have better dilutability and low temperature fluidity. In general, unmodified surfactants generally have a greater range of gel regions. In a general method for evaluating the range of the gelling region of the surfactant, the gelling concentration of the surfactant-containing aqueous solution is 10 weight percent as the lowest concentration, 100 weight percent as the highest concentration, and the surfactant is prepared into 10 sample aqueous solutions by a method of increasing the concentration difference by 10 weight percent for evaluation. The term "gelling" as used herein refers to a phenomenon in which an aqueous solution containing a surfactant gels and the fluidity is reduced or even does not have fluidity.

In other words, the wider the concentration range of the aqueous solution that gels, the more likely the aqueous solution prepared by the surfactant will gel and not flow at a specific temperature. Generally, as the operation temperature is decreased, the gelling concentration range of the surfactant is wider, and the surfactant is more easily gelled and solidified in a low temperature environment and is not easily diluted, thereby limiting the applicability.

In some embodiments, after the single-step reaction, the reaction product (i.e., the surfactant) may be further purified to remove catalyst (C) and/or residual reactants. However, this purification operation does not require a large amount of water for the phase separation purification, and thus no waste liquid is produced. In some embodiments, the product obtained from the single-step reaction can be further heated to a temperature above 100 ℃ to remove the catalyst (C) from the reaction product. Wherein, after the catalyst (C) is removed by heating, the obtained product can be further filtered to improve the purity of the prepared surfactant.

The method for preparing the surfactant does not need to add extra solvent, so that the surfactant prepared by refining and purifying a large amount of water is not needed after the single-step reaction is carried out, and the energy cost and the raw material cost can be greatly reduced. Next, in the single-step reaction of the present invention, it is not necessary to add an alkyl reagent (e.g., an aryl alkyl halide or a dialkyl sulfate) to carry out the capping reaction, it is not necessary to wash out unreacted reactants with water, and it is not necessary to generate a waste liquid, and therefore, it is not necessary to purify the obtained product (i.e., the surfactant) by a purification step such as phase separation. Accordingly, the present invention can more simply and efficiently produce the surfactant by the single-step reaction.

In some embodiments, the resulting surfactants have good defoaming and wetting permeability properties, and small differences in gel concentration. In such embodiments, the surfactants of the invention have a difference in gel concentration at low temperatures (e.g., 4 ℃) of less than 20 weight percent.

In one application, the invention also discloses a solution containing the surfactant. The surfactant of the present invention has good defoaming property and wetting permeability, so that the solution containing the surfactant can be used for inhibiting the defoaming property of the process, improving the dispersion of the composition of the solution, and/or improving the emulsifying capacity of the solution. In addition, the surfactant has smaller gelling concentration difference, so that the solution containing the surfactant has wider application temperature range and better low-temperature freeze-thaw stability, and further has better dilutability and low-temperature freezing resistance.

For example, the solution comprising the surfactant of the present invention may include, but is not limited to, detergents, pigment dispersants, textile scouring agents, other suitable solutions comprising surfactants, or any combination of the foregoing solutions.

In addition, because the surfactant has good defoaming property, wetting permeability, emulsifying capacity, surface tension property and small difference of gelling concentration, the surfactant can be used in other suitable application fields and environmental temperatures based on application requirements.

Secondly, in order to improve the applicability of the surfactant, the surfactant prepared by the invention is preferably clear liquid, and has good dispersibility in the solution containing the surfactant.

The following examples are provided to illustrate the present invention, but not to limit the invention, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention.

Preparation of the surfactant

The following are surfactants of examples 1 to 6 prepared according to table 1.

Example 1

First, 100 parts by weight of polyoxyethylene octyl phenyl ether, and 2.6 parts by weight of potassium hydroxide were added to the reaction tank. Then, 29 parts by weight of butyl glycidyl ether was slowly dropped into the reaction vessel. After the mixture is uniformly mixed, the temperature of the reaction tank is set to 100 to 110 ℃ to perform a single-step reaction on the mixture. After the reaction is completed, adding adsorbent and water, and heating the reaction tank to over 100 deg.C for refining. After potassium hydroxide was removed, the resultant product was filtered to obtain the surfactant of example 1 shown by the following formula (IV-1). The obtained surfactants were evaluated in the following evaluation manners of defoaming property, surface tension, wetting permeability and gelation evaluation, wherein the evaluation items of defoaming property, surface tension and wetting permeability gave the results shown in Table 2-1 and the evaluation items of gelation evaluation gave the results shown in Table 2-2.

In the formula (IV-1), R₁₁Represents octyl benzene; n is₁Represents 12; and m is₁Represents 1.0.

Examples 2 to 6

The surfactants of examples 2 to 6 were prepared by the same synthesis method as that of example 1, except that the types and amounts of the reactants were changed in examples 2 to 6, and the formulations and reaction conditions thereof were as shown in table 1. Wherein, the surfactants prepared in examples 2 to 6 have the structures shown in the following formulas (IV-2) to (IV-6), respectively. The obtained surfactants were evaluated in the following manners of defoaming property, surface tension and wetting permeability, and the results are shown in table 2-1. In addition, the surfactant obtained in example 2 was further evaluated in the evaluation manner of gel evaluation, and the results thereof are shown in table 2-2.

In the formula (IV-2), R₁₂Represents an alkyl group having 9 to 11 carbon atoms; n is₂Represents 10; and m is₂Represents 0.5.

In the formula (IV-3), R₁₃Represents

R₄₃Represents a hydrogen atom; z is a radical of₃Represents 2; n is₃Represents 13; and m is₃Represents 1.0.

In the formula (IV-4), R₁₄Represents dodecyl; n is₄Represents 12.0; and m is₄Represents 1.0.

In the formula (IV-5), R₁₅Represents an alkyl group having 12 to 14 carbon atoms; n is₅Represents 12.0; and m is₅Represents 1.0.

In the formula (IV-6), R₁₆Represents an alkyl group having 9 to 11 carbon atoms; n is₆₁Represents 8.0; n is₆₂Represents 2.0; and m is₆Represents 1.0.

Comparative examples 1 to 4

Comparative examples 1 to 4 use a general commercially available surfactant, and the manufacturers and models thereof are listed below, respectively. The surfactants of comparative examples 1 to 4 were evaluated in the following manners of evaluating defoaming property, surface tension and wetting permeability, respectively, and the results thereof are shown in table 2-1. In addition, the surfactants of comparative examples 1 and 2 were further evaluated in the evaluation manner of gel evaluation, and the results obtained are shown in table 2-2.

Comparative example 1: a polyoxyethylene alkylphenyl ether of SINOPOL 866, available from Mitsui synthetic chemical Co., Ltd.

Comparative example 2: a polyoxyethylene alkyl ether manufactured by midday synthetic chemical corporation and having a model number of SINOPOL D1910.

Comparative example 3: polyoxyethylene styrene aryl ether manufactured by midday synthetic chemical corporation and having a model number of SINOPOL 613.

Comparative example 4: a polyoxyethylene polyoxypropylene alkyl ether of type SINOPOL 1907HB, manufactured by Zhongri synthetic chemical Co., Ltd.

Comparative example 5

First, 100 parts by weight of polyoxyethylene octyl phenyl ether and 4.0 parts by weight of sodium hydroxide were added to a reaction tank. Then, 12.4 parts by weight of chlorotoluene (Benzyl Chloride) was slowly dropped into the reaction vessel. After the mixture is uniformly mixed, the temperature of the reaction tank is heated to 100 ℃ to 110 ℃ to carry out end-capping reaction. After the reaction is finished, adding pure water into the reaction tank, and uniformly stirring. Then, the temperature was raised to 90 ℃ and left to stand. After the solution in the reaction tank was separated into layers, the aqueous layer was removed.

Glauber salt (Glauber salt) and pure water were added to the reaction tank and stirred uniformly. Then, the temperature was raised to 90 ℃ and left to stand. After the solution was separated, the aqueous layer was removed. Then, pure water was added to the reaction tank and heated to 100 ℃ or higher under negative pressure to remove chlorotoluene, and the surfactant of comparative example 5 shown by the following formula (IV-7) was obtained. The obtained surfactant was evaluated in the following manners of defoaming property, surface tension and wetting permeability, and the results are shown in table 2-1.

In the formula (IV-7), R' represents octylbenzene; and n' represents 14.

Evaluation item

1. Defoaming property

The defoaming property was evaluated by the Ross method (Ross-Mile test; ISO-696-1975). In brief, the surfactants of the foregoing examples 1 to 6 and comparative examples 1 to 5 were prepared into aqueous solutions to be tested with concentrations of 0.1 weight percent and 1.0 weight percent, respectively, and 1000mL of the aqueous solution to be tested was placed in a thermostatic bath at 25 ℃. After 30 minutes, 200mL of the thermostatically treated aqueous solution to be tested were rinsed and wetted onto the Ross-Mile column. After washing and wetting, the aqueous solution to be tested is drained, and 50mL of the aqueous solution to be tested is added into a Ross-Mile column without foam. Then, 200mL of the thermostated aqueous solution to be assayed was injected from the upper end of the Ross-Mile column and injected into the column over a period of 20 to 25 seconds. Next, the foam height (i.e., bubble height) of the solution after injection into the Ross-mill column was recorded and the time was started, and after 5 minutes, the foam height (i.e., bubble height) was observed and recorded.

Then, the foregoing steps were repeated at least three times, and the foaming height and defoaming height after each solution injection were recorded and the average height thereof was calculated.

2. Surface tension

The surfactants of the foregoing examples 1 to 6 and comparative examples 1 to 5 were prepared into aqueous solutions to be tested with concentrations of 0.1 weight percent and 1.0 weight percent, respectively, and the aqueous solutions to be tested were placed in an environment at 25 ℃. After at least 120 minutes, the surface tension of the aqueous solution to be measured is measured using a surface tension machine well known in the art.

3. Permeability to wetting

The surfactants of the foregoing examples 1 to 6 and comparative examples 1 to 5 were prepared into aqueous solutions to be measured with concentrations of 0.1 weight percent and 1.0 weight percent, respectively, and the aqueous solutions to be measured were placed in an environment at 25 ℃ for 30 minutes, and then a piece of circular flannelette (2.5 cm in diameter and 0.3 cm in thickness) was nipped with tweezers and gently placed on the surface of the solution to be measured, and the time required for falling from the liquid surface to the cup bottom was recorded, and the above steps were repeated at least three times, and the average value thereof was calculated.

4. Assessment of gelation

The surfactants of example 1, example 2, comparative example 1 and comparative example 2 were respectively configured as sample aqueous solutions, wherein the concentration distribution of the sample aqueous solutions was between 10 weight percent and 100 weight percent, and the incremental concentration differences were all 10 weight percent. Accordingly, the surfactant of each of the examples and comparative examples can be prepared into 10 sample aqueous solutions with different concentrations.

Then, these sample aqueous solutions were placed in an environment of 4 ℃ and after 1 day, 5 days, 10 days, and 30 days, whether the sample aqueous solutions had a gelling phenomenon was visually observed and evaluated on the following criteria:

very good: the sample aqueous solution was a liquid solution having good fluidity.

□: the aqueous sample solution was a highly viscous liquid solution with poor fluidity.

And (delta): the aqueous sample solution had gelled somewhat and appeared cloudy (hazy).

Gamma rays: the aqueous sample solution had gelled completely to a solid state.

As can be seen from the evaluation results in Table 2-1, the surfactant of the present invention has good defoaming property, wetting permeability and surface tension property. Accordingly, the surfactant of the present invention can be suitably used as a composition of a solution such as a detergent, a dispersant or a scouring agent, and can improve defoaming property, cleaning property, dispersibility and the like required for the above solutions.

Next, as can be seen from the evaluation results of the "gelation evaluation" carried in table 2-2, the surfactant of the present invention has a small difference (less than 20 wt%) in gelation concentration under a low temperature environment (e.g., 4 ℃). Therefore, the surfactant has better dilutability and good fluidity at low temperature, and can be suitable for a wider application temperature range, thereby improving the application convenience.

In addition, the method for preparing the surfactant can prepare the surfactant by a single-step reaction, and the single-step reaction does not need to add a solvent into a reaction tank additionally. After the reaction is finished, the invention does not need to use a large amount of water to clean and purify the prepared surfactant. Therefore, the method for manufacturing the surfactant can greatly reduce the raw material cost of the surfactant and can reduce the material and energy consumed by the back-end purification step.

Although the present invention has been described with reference to the above embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention.

TABLE 1

A-1 polyoxyethylene octyl phenyl ether

A-2 polyoxyethylene alkyl ether (alkyl having 9 to 11 carbon atoms)

A-3 polyoxyethylene styrene aryl ether

A-4 polyoxyethylene dodecyl ether

A-5 polyoxyethylene alkyl ether (alkyl having 12 to 14 carbon atoms)

A-6 Polyoxyethylene polyoxypropylene alkyl ether of the national synthetic chemical Co., Ltd, and its type 1907HFB

(where the EO/PO ratio is 8.0/2.0)

B-1 butyl glycidyl ether (butyl glycidyl ether)

B-2 o-cresol glycidyl ether (o-cresol glycidyl ether)

B-3 phenyl glycidyl ether (phenyl glycidyl ether)

C-1 Potassium hydroxide

C-2 sodium hydroxide

C-3 Triphenylphosphine

Claims

1. A surfactant, characterized in that the surfactant has a structure represented by the following formula (I):

in the formula (I), R₁Represents an alkyl group having 8 to 30 carbon atoms, an alkylphenyl group or a structure represented by the following formula (II); r₂Represents a C2-4 alkoxy group, wherein R₂Alkyl of (2) with R₁An O-bond; r₃Represents an alkoxy group having a carbon number of 3 to 18, a phenol group or an o-cresol group; n represents a number in the range of 5 to 100; and m represents a number in the range of 0.1 to 10;

2. The surfactant of claim 1, wherein R is₁Represents an alkyl phenyl group or a structure shown as a formula (II).

3. The surfactant of claim 1, wherein R is₂Represents a C2-3 alkoxy group.

4. The surfactant of claim 1 having a difference in gelling concentration at 4 ℃ of less than 20 weight percent.

5. A method for producing a surfactant, comprising:

providing a mixture, wherein the mixture comprises a compound (A) represented by the following formula (III-1) and a compound (B) represented by the following formula (III-2):

in the formula (III-1), R₁Represents an alkyl group having 8 to 30 carbon atoms, an alkylphenyl group or a structure represented by the following formula (II); r₂Represents a C2-4 alkoxy group, wherein R₂The terminal oxygen atom of (a) is bonded to a hydrogen atom; and n represents a number in the range of 0 to 100;

in the formula (II), R₄Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; z represents an integer of 1 to 3, and "") represents a bond;

in the formula (III-2), R₃Represents an alkoxy group having a carbon number of 3 to 18, a phenol group or an o-cresol group; and

subjecting the mixture to a single step reaction to obtain the surfactant of any one of claims 1 to 4.

6. The method for producing a surfactant according to claim 5, wherein the mixture contains a catalyst (C).

7. The method for producing a surfactant according to claim 6, wherein the catalyst (C) is used in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the total amount of the compound (A) represented by the formula (III-1).

8. The method for producing a surfactant according to claim 5, wherein the reaction temperature of the single-step reaction is 60 ℃ to 140 ℃.

9. A solution comprising the surfactant of any one of claims 1 to 4.