A method for producing functional surfactant

Abstract

The invention relates to the technical field of surfactants, and discloses a method for producing a functional surfactant. The surfactant is prepared by using polytetrahydrofuran sulfonic acid derivatives and 2-chloro-N,N,N-trimethylethylammonium chloride as raw materials through a substitution reaction, wherein the polytetrahydrofuran sulfonic acid derivative is prepared by using polytetrahydrofuran diol as a starting raw material, firstly end-capping the polytetrahydrofuran diol by using epichlorohydrin, and then using a phase transfer catalyst to make the polytetrahydrofuran diol and N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid undergo continuous and uninterrupted ring-opening polymerization, thereby forming a polytetrahydrofuran derivative having a large amount of sulfonic acid anions in the structure and having a block structure, namely, the polytetrahydrofuran sulfonic acid derivative. The surfactant prepared by the method has strong emulsification ability, good stability and good use value.

Description

Technical Field

[0001] The invention relates to the technical field of surfactants, and in particular to a method for producing a functional surfactant. Background Art

[0002] Surfactant is a substance with a special molecular structure, which contains both hydrophilic and hydrophobic groups in its molecular structure, so that it can significantly reduce the surface tension or interfacial tension on the liquid surface or the interface between two phases. At present, surfactants mainly include cationic surfactants, anionic surfactants, amphoteric surfactants and nonionic surfactants. Relatively speaking, nonionic surfactants have better solubility in water and organic solvents, and have good compatibility with other types of surfactants, but the comprehensive performance of nonionic surfactants is not good enough and the emulsification ability is poor. Amphoteric surfactants, with their unique molecular structure, can show the characteristics of both anionic surfactants and cationic surfactants in solution. This special molecular structure makes the biggest feature of amphoteric surfactants is that they can both give and accept protons, so they can form a double electric layer structure in the solution, thus having better stability and emulsification and dispersibility. In addition, amphoteric surfactants also have good softness and smoothness, antistatic properties, bactericidal and antifungal properties, etc. These characteristics make it have broad application prospects in many fields. However, amphoteric surfactants are pH-sensitive. Near the isoelectric point, the solubility will decrease, which in turn affects its application effect under different pH environments.

[0003] In order to make up for the defects of various surfactants, surfactants with special structures can be prepared. For example, the invention patent with application number CN202010610482.8 discloses a surfactant, a method for synthesizing a surfactant and an application thereof, and a surfactant containing both quaternary ammonium salt and polyethylene glycol fragments in the structure is prepared, which can take advantage of each other and produce complementary advantages. Therefore, by designing the molecular structure, a surfactant containing both block structures in the structure can be prepared to improve the defects in the prior art. Summary of the invention

[0004] In order to solve the problems mentioned in the background technology, the object of the present invention is to provide a method for producing a functional surfactant.

[0005] The purpose of the present invention can be achieved through the following technical solutions:

[0006] A method for producing a functional surfactant, wherein the surfactant is prepared from the following raw materials:

[0007] Polytetrahydrofuransulfonic acid derivatives;

[0008] 2-Chloro-N,N,N-trimethylethylammonium chloride;

[0009] The production method is as follows:

[0010] Add polytetrahydrofuran sulfonic acid derivative and 1,4-dioxane into a bottle filled with nitrogen, shake well, then add the catalyst into the bottle, then turn on the heating, when the temperature is maintained at 50-60°C, keep it for 1-2 hours, then add 2-chloro-N,N,N-trimethylethylammonium chloride, after the addition, raise the temperature to 65-70°C, keep it warm for 6-8 hours under stirring, cool it down and discharge it, and the surfactant can be obtained.

[0011] Specifically, the structure of the polytetrahydrofuran sulfonic acid derivative contains an active hydroxyl substituent produced by a ring-opening reaction, which can undergo nucleophilic substitution with the halogen substituent in the structure of 2-chloro-N,N,N-trimethylethylammonium chloride under the action of a catalyst, thereby producing a polytetrahydrofuran derivative containing both a sulfonic acid anion and a quaternary ammonium cation in the structure, i.e., a functional surfactant.

[0012] As a further embodiment of the present invention, the polytetrahydrofuran sulfonic acid derivative is prepared by the following method:

[0013] The epoxy-terminated polytetrahydrofuran diol and toluene are stirred and mixed evenly, and then N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid and a phase transfer catalyst are added to the formed mixed solution. After the addition, the temperature is controlled at 70-80 ° C, and stirred for 9-12 hours under nitrogen protection, and then the solvent is evaporated to remove, and the polytetrahydrofuran sulfonic acid derivative can be obtained.

[0014] Specifically, under the action of a phase transfer catalyst, the epoxy substituent at the end of the epoxy-terminated polytetrahydrofuran diol structure can undergo uninterrupted ring-opening addition with the active hydroxyl group in the N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid structure to form a polytetrahydrofuran derivative having a block structure and containing a large amount of sulfonic acid anions, namely, a polytetrahydrofuran sulfonic acid derivative.

[0015] As a further embodiment of the present invention, the epoxy-terminated polytetrahydrofuran diol is prepared by the following method:

[0016] Mix polytetrahydrofuran diol and toluene, shake well, add excess epichlorohydrin, and add phase transfer catalyst at the same time. After the addition, stir at 80-90°C for 1-3h, then reduce the temperature to 65-75°C, slowly add sodium hydroxide aqueous solution, stir for 2-4h, evaporate the solvent, cool and discharge the material to obtain epoxy-terminated polytetrahydrofuran diol.

[0017] Specifically, under the action of a phase transfer catalyst, the substituted hydroxyl group in the structure of polytetrahydrofuran diol first undergoes a ring-opening addition reaction with the epoxy group in the structure of epichlorohydrin to form an intermediate product, and then under the action of sodium hydroxide, the hydroxyl group produced by the ring-opening reaction reacts with halogen chlorine to form a closed ring, thereby achieving epoxy end-capping of the polytetrahydrofuran diol to obtain epoxy-end-capped polytetrahydrofuran diol.

[0018] As a further embodiment of the present invention, the molar ratio of the epoxy-terminated polytetrahydrofuran diol to N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid is 1:1-1.2.

[0019] As a further embodiment of the present invention, it is characterized in that the phase transfer catalyst is at least one of tetrabutylammonium bromide, tetramethylammonium bromide, tetrabutylammonium chloride or triethylamine.

[0020] As a further embodiment of the present invention, the number average molecular weight of the polytetrahydrofuran diol is 2000.

[0021] As a further embodiment of the present invention, the mass fraction of the sodium hydroxide aqueous solution is 40-50%.

[0022] As a further embodiment of the present invention, the catalyst is at least one of sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate.

[0023] As a further embodiment of the present invention, the mass ratio of the polytetrahydrofuran sulfonic acid derivative to 2-chloro-N,N,N-trimethylethylammonium chloride is 1:0.1-0.25.

[0024] Beneficial effects of the present invention:

[0025] The present invention prepares a surfactant having a large amount of sulfonic acid anions, quaternary ammonium cations and fatty alcohol ether structures in its structure, which not only has good solubility but also can show excellent stability and emulsification ability. According to tests, the surfactant prepared by the present invention has an active emulsification force of up to 1220 / s, a foaming height of 28 mL, and an initial surface tension of 23.18 mN / m, showing excellent comprehensive performance.

[0026] Of course, any product implementing the present invention does not necessarily need to achieve all of the advantages described above at the same time. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings required for describing the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other accompanying drawings can be obtained based on these accompanying drawings without paying creative work.

[0028] Figure 1 This is the infrared analysis test chart of epoxy-terminated polytetrahydrofuran diol, polytetrahydrofuran sulfonic acid derivatives and surfactants. DETAILED DESCRIPTION

[0029] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0030] Example 1

[0031] Preparation of epoxy-terminated polytetrahydrofuran diol:

[0032] 1.5 g of polytetrahydrofuran diol with a number average molecular weight of 2000 and toluene were mixed, and after shaking, 1.2 g of epichlorohydrin and 0.1 g of tetrabutylammonium bromide were added. After the addition was completed, the mixture was stirred at 85° C. for 2 h, and then the temperature was lowered to 70° C., and 1 mL of a 48% sodium hydroxide aqueous solution was slowly added dropwise. After stirring for 3 h, the solvent was evaporated, and the temperature was lowered to obtain epoxy-terminated polytetrahydrofuran diol.

[0033] The infrared test image of the epoxy-terminated polytetrahydrofuran diol is as follows Figure 1 As shown in the figure, the analysis shows that there is no characteristic absorption peak related to hydroxyl in the infrared spectrum, and the peak at 938cm -1 A characteristic absorption peak related to the epoxy group appeared at .

[0034] Example 2

[0035] Preparation of polytetrahydrofuran sulfonic acid derivatives:

[0036] 1.2 g of the epoxy-terminated polytetrahydrofuran diol prepared in Example 1 of the present invention and toluene were stirred and mixed uniformly, and then 0.14 g of N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid and 0.05 g of tetrabutylammonium bromide were added to the resulting mixed solution. After the addition, the temperature was controlled at 75 ° C. and stirred for 12 hours under nitrogen protection. Then, the solvent was evaporated to obtain a polytetrahydrofuran sulfonic acid derivative.

[0037] The infrared spectrum of the polytetrahydrofuran sulfonic acid derivative is as follows: Figure 1 As shown, compared with epoxy-terminated polytetrahydrofuran diol, its -1 The characteristic absorption peak of OH for hydroxyl group appeared at 1368cm -1 and 1158cm -1 A new characteristic absorption peak of sulfonic acid S=O appeared at .

[0038] Example 3

[0039] Preparation of functional surfactants:

[0040] Add 1 g of the polytetrahydrofuran sulfonic acid derivative prepared in Example 2 of the present invention and 1,4-dioxane to a bottle filled with nitrogen, shake well, then add 0.5 g of sodium hydroxide to the bottle, then turn on the heating, when the temperature is maintained at 55°C, keep it for 1 hour, then add 0.2 g of 2-chloro-N,N,N-trimethylethylammonium chloride, after the addition, raise the temperature to 70°C, keep it warm for 6 hours under stirring, cool it down and discharge it, and the surfactant can be obtained.

[0041] The infrared test image of this surfactant is shown in Figure 1 , rubber and polytetrahydrofuran sulfonic acid derivatives, which are at 1431cm -1 1472cm -1 A new CN characteristic absorption peak of quaternary ammonium salt appeared.

[0042] Test Case

[0043] a. The surfactant in Example 3 was diluted 200 times with purified water, and the surface tension of the surfactant at room temperature was tested using a fully automatic surface tension meter using a platinum sheet method. After leaving it for 1 month, the surface tension test was performed again to evaluate the stability of the surfactant;

[0044] b. The surfactant of Example 3 was prepared into an aqueous solution with a concentration of 1 g / L, 20 mL was measured, mixed with No. 5 white oil, poured into a container with a scale, homogenized at a speed of 500 r / min for 1 min, then allowed to stand, and the time consumed to separate 5 mL of aqueous phase was recorded. Generally speaking, the longer the consumption time, the better the emulsification ability of the surfactant;

[0045] c. Prepare a surfactant aqueous solution with a concentration of 1 g / L, transfer 20 mL into a container with a scale, shake for 30 seconds, let it stand, and record the bubble height;

[0046] The results are shown in Table 1:

[0047]

[0048] The test results show that the surfactant prepared by the present invention has good emulsifying ability, strong stability and excellent comprehensive performance.

[0049] Specific examples are used herein to illustrate the principles and implementation methods of the present invention. The description of the above embodiments is only used to help understand the method of the present invention and its core ideas, including the best mode, and also enable any technician in the field to practice the present invention, including making and using any device or system, and implementing any combined method. It should be pointed out that for ordinary technicians in this technical field, without departing from the principle of the present invention, the present invention can also be improved and modified, and these improvements and modifications also fall within the scope of protection of the claims of the present invention. The scope of patent protection of the present invention is defined by the claims and may include other embodiments that can be thought of by those skilled in the art. If these other embodiments have structural elements similar to the literal expression of the claims, or if they include equivalent structural elements that are not substantially different from the literal expression of the claims, then these other embodiments should also be included in the scope of the claims.

[0050] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that the technical solutions described in the aforementioned embodiments may still be modified, or some of the technical features may be replaced by equivalents. Such modifications or replacements will not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for producing a functional surfactant, characterized in that: The surfactant is made from the following raw materials: Polytetrahydrofuransulfonic acid derivatives; 2-Chloro-N,N,N-trimethylethylammonium chloride; The production method is as follows: Add polytetrahydrofuran sulfonic acid derivative and 1,4-dioxane to a bottle filled with nitrogen, shake well, then add the catalyst to the bottle, then turn on the heating, when the temperature is maintained at 50-60°C, keep it for 1-2 hours, then add 2-chloro-N,N,N-trimethylethylammonium chloride, after the addition, raise the temperature to 65-70°C, keep it warm for 6-8 hours under stirring, cool it down and discharge it, so as to obtain a surfactant; The polytetrahydrofuran sulfonic acid derivative is prepared by the following method: The epoxy-terminated polytetrahydrofuran diol and toluene are stirred and mixed uniformly, and then N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid and a phase transfer catalyst are added to the resulting mixed solution. After the addition is complete, the temperature is controlled at 70-80 ° C, and stirred for 9-12 hours under nitrogen protection, and then the solvent is evaporated to remove, so as to obtain a polytetrahydrofuran sulfonic acid derivative; Described epoxy-terminated polytetrahydrofuran diol is prepared by the following method: Mix polytetrahydrofuran diol and toluene, shake well, add excess epichlorohydrin, and add phase transfer catalyst at the same time. After the addition, stir at 80-90°C for 1-3h, then reduce the temperature to 65-75°C, slowly add sodium hydroxide aqueous solution, stir for 2-4h, evaporate the solvent, cool and discharge the material to obtain epoxy-terminated polytetrahydrofuran diol.

2. The method for producing a functional surfactant according to claim 1, characterized in that: The molar ratio of the epoxy-terminated polytetrahydrofuran diol to N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid is 1:1-1.

2.

3. The method for producing a functional surfactant according to claim 1, characterized in that: The phase transfer catalyst is at least one of tetrabutylammonium bromide, tetramethylammonium bromide, tetrabutylammonium chloride or triethylamine.

4. The method for producing a functional surfactant according to claim 1, characterized in that: The number average molecular weight of the polytetrahydrofuran diol is 2000.

5. The method for producing a functional surfactant according to claim 1, characterized in that: The mass fraction of the sodium hydroxide aqueous solution is 40-50%.

6. The method for producing a functional surfactant according to claim 1, characterized in that: The catalyst is at least one of sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate.

7. The method for producing a functional surfactant according to claim 1, characterized in that: The mass ratio of the polytetrahydrofuran sulfonic acid derivative to 2-chloro-N,N,N-trimethylethylammonium chloride is 1:0.1-0.25.

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