A surfactant composition, its preparation and use

Abstract

The application provides a surfactant composition, a preparation method and application thereof, and belongs to the technical field of surfactants. The surfactant composition comprises an amphoteric ion surfactant and a non-ionic surfactant, and the mass ratio is 5-7:2-3. The structural formula of the amphoteric ion surfactant is as follows, and R is an alkyl chain with C12-16. The surfactant composition prepared by the application has the advantages of providing abundant foam and low irritation, high dirt removal capacity, good washing effect, simple preparation method, mild synthesis condition, high yield, and wide application prospect. The composition is particularly suitable for the field of commercial washing, and is used as a washing emulsifier, and is particularly suitable for commercial laundry, and covers various scenes such as in-store laundry service and factory textile washing.

Description

Technical Field

[0001] This invention relates to the field of surfactant technology, and more specifically to a surfactant composition, its preparation method, and its application. Background Technology

[0002] Betaine surfactants are a typical class of zwitterionic surfactants. Their molecular structure contains both cationic (quaternary ammonium) and anionic (carboxylic acid, sulfonic acid, etc.) groups. They exhibit good stability and compatibility under different pH conditions and are widely used in personal care, oilfield chemistry, industrial cleaning and other fields.

[0003] Currently, domestic research reports on betaine surfactants mainly focus on improving their foaming, thickening, and hard water resistance through modification of hydrophilic and hydrophobic groups in low- and medium-carbon chains. However, some problems remain in the synthesis of higher-carbon-chain betaine surfactants. For example, during the amidation reaction to synthesize the intermediate product palmitamidopropyl dimethyl tertiary amine, the acid value is difficult to reduce, and the product has a darker color. While the conversion rate of betaine using fatty acid methyl esters as raw materials is as high as 99.7%, the production cost using fatty acid methyl esters is high, making industrialization difficult. Summary of the Invention

[0004] The purpose of this invention is to provide a surfactant composition, its preparation method, and its applications. This composition provides abundant foam with low irritation, while exhibiting strong detergency and excellent washing effect. The preparation method is simple, the synthesis conditions are mild, and the yield is high, demonstrating broad application prospects. This composition is particularly suitable for the commercial laundry sector, serving as a detergent emulsifier, especially applicable to commercial laundries, covering various scenarios such as in-store laundry services and factory textile washing.

[0005] The technical solution of this invention is implemented as follows:

[0006] This invention provides a surfactant composition comprising an amphoteric surfactant and a nonionic surfactant in a mass ratio of 5-7:2-3;

[0007] The structural formula of the zwitterionic surfactant is shown in Formula I:

[0008]

[0009] Formula I;

[0010] R=C12-16 alkyl chain.

[0011] As a further improvement of the present invention, the nonionic surfactant is selected from at least one of C12-C14 secondary alcohol ethoxylates having 2 to 5 moles of ethoxylated secondary alcohol ethoxylates, C8-C16 secondary alcohol ethoxylates having 7 to 11 moles of ethoxylated secondary alcohol ethoxylates, and C10-C20 straight-chain alcohol ethoxylates having 6 to 10 moles of ethoxylated linear alcohol ethoxylates.

[0012] Preferably, the active ingredients are SECOL-30, Tergitol™ 15-S-3, Tergitol™ 15-S-5, Tergitol™ 15-S-7, Tergitol™ 15-S-9, Tergitol™ 15-S-12, Neodol™ 25-7, Neodol™ 25-9, and Alcohols C12–16.

[0013] As a further improvement of the present invention, the preparation method of the zwitterionic surfactant is as follows:

[0014] S1. Glycerol and thionyl chloride were mixed and reacted to prepare intermediate 1, with the following structure: ;

[0015] S2. N-methyl-1,3-propanediamine was reacted with an alkyl acyl chloride to prepare intermediate 2, with the following structure: ;

[0016] S3. Intermediate 1 and intermediate 2 are reacted to obtain intermediate 3, with the following structure: ;

[0017] S4. React intermediate 3 with sodium chloroacetate to obtain the product.

[0018] As a further improvement of the present invention, the molar ratio of glycerol and thionyl chloride in step S1 is 1:3-3.3.

[0019] As a further improvement of the present invention, the molar ratio of N-methyl-1,3-propanediamine and alkyl acyl chloride in step S2 is 1:0.9-1, and the alkyl acyl chloride is selected from at least one of dodecyl acyl chloride, tridecyl acyl chloride, tetradecyl acyl chloride, pentadecyl acyl chloride and hexadecyl acyl chloride.

[0020] As a further improvement of the present invention, the molar ratio of intermediate 1 and intermediate 2 in step S3 is 1:2.9-3.

[0021] As a further improvement of the present invention, the molar ratio of intermediate 3 and sodium chloroacetate in step S4 is 1:3-3.5.

[0022] The present invention further protects a method for preparing the above-mentioned surfactant composition, wherein an amphoteric surfactant and a nonionic surfactant are mixed uniformly to obtain a surfactant composition.

[0023] The present invention further protects the use of the above-mentioned surfactant composition in the preparation of detergents, laundry liquids, emulsifiers, stain removers, shampoos, and shower gels.

[0024] This invention further protects an amphoteric surfactant constituting the above-mentioned surfactant composition, the structural formula of which is shown in Formula I:

[0025]

[0026] Formula I;

[0027] R=C12-16 alkyl chain.

[0028] The present invention has the following beneficial effects:

[0029] This invention addresses the problem of incomplete amidation reactions by using the reaction of acyl chloride and amino groups, which improves the reactivity. It can be carried out rapidly at room temperature without the need for high temperature and high pressure, making it suitable for systems with high steric hindrance or long-chain fatty acid derivatives. It significantly reduces unreacted amine residues and eliminates the need for expensive chemical reagents. The resulting zwitterionic surfactant has a high yield and is easy to industrialize.

[0030] Compared with traditional amphoteric surfactants, the zwitterionic surfactant prepared by this invention has amide groups and longer carbon chains introduced into its molecules, thus exhibiting good foam stability, biodegradability, and low toxicity. Its compatibility is also greatly improved. At the same time, due to the introduction of multiple quaternary ammonium groups and carboxyl groups, its surface activity is greatly improved and its surface tension is reduced compared with traditional betaine surfactants, and it also has better foaming ability and detergency.

[0031] This invention utilizes amphoteric surfactants that exhibit cationic or anionic properties at different pH levels, demonstrating excellent interfacial activity. These surfactants can co-adsorb with nonionic surfactants at the oil / water interface, forming a denser adsorption layer, significantly reducing oil-water interfacial tension and enhancing detergency. The combination of amphoteric and nonionic surfactants forms mixed micelles, improving their structure and stability. The nonionic surfactant provides a larger hydrophobic region, while the amphoteric surfactant provides charge regulation and steric hindrance, synergistically enhancing the solubilization and emulsification capabilities for oil stains. Nonionic surfactants are insensitive to calcium and magnesium ions, while amphoteric surfactants possess excellent calcium soap dispersing power and electrolyte resistance. The combination maintains high washing performance in hard water, preventing precipitation and improving stability in practical applications. Amphoteric surfactants exhibit good wetting and dispersing properties on fabrics or hard surfaces, while nonionic surfactants excel at emulsifying greases. Their synergistic effect accelerates the detachment of dirt from the surface and ensures stable dispersion in the washing liquid, preventing redeposition.

[0032] The surfactant composition prepared by this invention provides abundant foam with low irritation, while exhibiting strong detergency and excellent washing effect. The preparation method is simple, the synthesis conditions are mild, the yield is high, and it has broad application prospects. Attached Figure Description

[0033] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0034] Figure 1 This is a synthetic route diagram for the zwitterionic surfactant of the present invention. Detailed Implementation

[0035] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0036] Example 1

[0037] like Figure 1 A method for synthesizing an amphoteric surfactant, comprising the following steps:

[0038] S1. 0.1 mol glycerol was added to 100 mL of dichloromethane, and 30 mL of a sulfoxide solution containing 0.3 mol sulfoxide was added dropwise. The mixture was stirred and reacted for 2 h. The solvent was removed under reduced pressure to obtain intermediate 1. ESI-MS calculated value: C3H6Cl3(M+H) + 148.43, measured value: 148.4, yield: 94%. NMR results: 1 H NMR (300MHz, CDCl3) δ4.25 (m, 2H), 3.65 (t, 4H).

[0039] S2. Under nitrogen protection, 0.1 mol N-methyl-1,3-propanediamine and 0.09 mol dodecyl chloride were added to 200 mL dichloromethane, followed by 0.5 mol triethylamine. The mixture was heated under reflux with stirring for 3 h. The reaction was then stopped, filtered, and the solvent and excess triethylamine were removed under reduced pressure. Ethanol was added for recrystallization, followed by filtration, washing, and drying to obtain intermediate 2. ESI-MS calculated value: C 17 H 37 N₂O(M+H) + 285.48, measured value: 285.5, yield: 90%. NMR results: 1 H NMR (300MHz, CDCl3) δ8.0 (br, 1H), 3.2 (m, 2H), 2.57 (m, 2H), 2.45 (s, 3H), 2. 19 (t, 2H), 2.0 (br, 1H), 1.57-1.62 (m, 4H), 1.29-1.33 (m, 18H), 0.91 (t, 3H).

[0040] S3. 0.1 mol of intermediate 1 and 0.29 mol of intermediate 2 were added to 200 mL of dichloromethane, followed by 2 mol of triethylamine. The mixture was heated to reflux and stirred for 4 h. The reaction was then stopped, filtered, and the solvent and excess triethylamine were removed under reduced pressure. Acetone was added for recrystallization, followed by filtration, washing, and drying to obtain intermediate 3. ESI-MS calculated value: C 54 H 111 N6O3(M+H) + 892.49, measured value: 892.5, yield: 87%. NMR results: 1 H NMR (300MHz, CDCl3) δ8.2 (br, 3H), 3.35 (m, 6H), 3.09 (m, 1H), 2.34-2.42 (m, 10H) , 2.27 (s, 9H), 2.19 (t, 6H), 1.57-1.62 (m, 12H), 1.27-1.33 (m, 54H), 0.96 (t, 9H).

[0041] S4. Add 0.3 mol sodium chloroacetate to a mixed solution of isopropanol and water (volume ratio 1:2), adjust the pH to 7.5, and after complete dissolution, add 0.1 mol intermediate 3, heat to 85℃, stir for 6 h, remove isopropanol and water by rotary evaporation, add excess isopropanol to dissolve the crude product, and filter to remove excess inorganic salts, obtaining a yellow liquid. Finally, repeatedly rotary evaporate the yellow liquid, repeating the operation 5 times to obtain the product. ESI-MS calculated value: C 40 H 117 N6O9(M+H) + 826.38, measured value: 826.4, yield: 90%. NMR results: 1 H NMR (300MHz, CDCl3) δ8 (br, 3H), 4.82 (m, 1H), 4.32 (s, 6H), 3.75-3.82 (m, 6H), 3.2-3.24 ( m, 10H), 3.30 (s, 9H), 2.96 (t, 6H), 1.89-1.92 (m, 12H), 1.28-1.38 (m, 54H), 0.99 (t, 9H).

[0042] Example 2

[0043] like Figure 1 A method for synthesizing an amphoteric surfactant, comprising the following steps:

[0044] S1. Add 0.1 mol of glycerol to 100 mL of dichloromethane, add 30 mL of a sulfoxide solution containing 0.33 mol of sulfoxide, stir and mix for 2 h, remove the solvent under reduced pressure to obtain intermediate 1;

[0045] S2. Under nitrogen protection, 0.1 mol N-methyl-1,3-propanediamine and 0.1 mol hexadecyl chloride were added to 200 mL of dichloromethane, followed by 0.5 mol triethylamine. The mixture was heated under reflux and stirred for 3 h. The reaction was stopped, filtered, and the solvent and excess triethylamine were removed under reduced pressure. Ethanol was added for recrystallization, followed by filtration, washing, and drying to obtain intermediate 2.

[0046] S3. Add 0.1 mol of intermediate 1 and 0.3 mol of intermediate 2 to 200 mL of dichloromethane, add 2 mol of triethylamine, heat under reflux and stir for 4 h, stop the reaction, filter, remove solvent and excess triethylamine under reduced pressure, add acetone to recrystallize, filter, wash, dry, and obtain intermediate 3.

[0047] S4. Add 0.35 mol sodium chloroacetate to a mixed solution of isopropanol and water (volume ratio 1:2), adjust the pH to 7.5, and after complete dissolution, add 0.1 mol intermediate 3, heat to 85℃, stir and react for 6 h, remove isopropanol and water by rotary evaporation, add excess isopropanol to dissolve the crude product, and filter to remove excess inorganic salts to obtain a yellow liquid. Finally, repeatedly rotary evaporate the yellow liquid, repeat the operation 5 times, and obtain the product.

[0048] Example 3

[0049] like Figure 1 A method for synthesizing an amphoteric surfactant, comprising the following steps:

[0050] S1. Add 0.1 mol of glycerol to 100 mL of dichloromethane, add 30 mL of a dichloromethane solution containing 0.315 mol of dichloromethane dropwise, stir and mix for 2 h, remove the solvent under reduced pressure to obtain intermediate 1;

[0051] S2. Under nitrogen protection, 0.1 mol N-methyl-1,3-propanediamine and 0.095 mol pentadecyl chloride were added to 200 mL of dichloromethane, followed by 0.5 mol triethylamine. The mixture was heated under reflux and stirred for 3 h. The reaction was stopped, filtered, and the solvent and excess triethylamine were removed under reduced pressure. Ethanol was added for recrystallization, followed by filtration, washing, and drying to obtain intermediate 2.

[0052] S3. Add 0.1 mol of intermediate 1 and 0.295 mol of intermediate 2 to 200 mL of dichloromethane, add 2 mol of triethylamine, heat under reflux and stir for 4 h, stop the reaction, filter, remove solvent and excess triethylamine under reduced pressure, add acetone to recrystallize, filter, wash, dry, and obtain intermediate 3.

[0053] S4. Add 0.32 mol sodium chloroacetate to a mixed solution of isopropanol and water (volume ratio 1:2), adjust the pH to 7.5, and after complete dissolution, add 0.1 mol intermediate 3, heat to 85℃, stir and react for 6 h, remove isopropanol and water by rotary evaporation, add excess isopropanol to dissolve the crude product, and filter to remove excess inorganic salts to obtain a yellow liquid. Finally, repeatedly rotary evaporate the yellow liquid, repeat the operation 5 times to obtain the product.

[0054] Example 4

[0055] This embodiment provides a surfactant composition comprising the zwitterionic surfactant prepared in Example 1 and Tergitol™ 15-S-5 in a mass ratio of 5:2.

[0056] Preparation method: Mix the zwitterionic surfactant and Tergitol™ 15-S-5 evenly to obtain a surfactant composition.

[0057] Example 5

[0058] This embodiment provides a surfactant composition comprising the zwitterionic surfactant prepared in Example 2 and Tergitol™ 15-S-3 in a mass ratio of 7:3.

[0059] Preparation method: Mix zwitterionic surfactant and Tergitol™ 15-S-3 evenly to obtain surfactant composition.

[0060] Example 6

[0061] This embodiment provides a surfactant composition comprising the zwitterionic surfactant prepared in Example 3 and SECOL-30 in a mass ratio of 6:2.5.

[0062] Preparation method: Mix the zwitterionic surfactant and SECOL-30 evenly to obtain a surfactant composition.

[0063] Comparative Example 1

[0064] The difference from Example 3 is that the mass ratio of the zwitterionic surfactant and SECOL-30 prepared in Example 3 is 20:1.

[0065] Comparative Example 2

[0066] The difference compared to Example 3 is that the mass ratio of the zwitterionic surfactant and SECOL-30 prepared in Example 3 is 1:20.

[0067] Test Example 1: Surface Tension Measurement

[0068] Solutions of various concentrations were prepared using the products obtained in Examples 1-6 and Comparative Examples 1-2. The surface tension of each solution was measured at (25±0.1)℃, and γ-lgc curves were plotted. The concentration corresponding to the inflection point on the curve is the critical micelle concentration (CMC). The results are shown in Table 1.

[0069] Table 1

[0070] As can be seen from the table above, the products obtained in Examples 1-6 of the present invention have low critical micelle concentration and surface tension.

[0071] Test Example 2: Emulsification Determination

[0072] The emulsification properties of the synthesized target products were determined by using liquid paraffin, tetrafluoroethylene, benzene, and turpentine as oil phases, respectively, with the products prepared in Examples 1-6 and Comparative Examples 1-2 as oil phases, and the water separation time method was used.

[0073] Prepare a 1 g / L aqueous solution of the product. Pour 40 mL of the aqueous solution into a 100 mL stoppered graduated cylinder, then add 40 mL of the oil phase. Shake vigorously up and down 50 times, then let stand. Record the time required for 10 mL of water to separate out; this value represents the relative emulsifying power of the product. Repeat the test 3 times and take the average value.

[0074] The results are shown in Table 2.

[0075] Table 2

[0076] As can be seen from the table above, the products obtained in Examples 1-6 of this invention have good emulsifying properties.

[0077] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A surfactant composition, characterized in that, It includes zwitterionic surfactants and nonionic surfactants in a mass ratio of 5-7:2-3; The structural formula of the zwitterionic surfactant is shown in Formula I: Formula I; R=C12-16 alkyl chain; The nonionic surfactant is selected from at least one of the following: C12-C14 secondary alcohol ethoxylates having 2 to 5 moles of ethoxylated secondary alcohol ethoxylates, C8-C16 secondary alcohol ethoxylates having 7 to 11 moles of ethoxylated secondary alcohol ethoxylates, and C10-C20 straight-chain alcohol ethoxylates having 6 to 10 moles of ethoxylated linear alcohol ethoxylates.

2. The surfactant composition according to claim 1, characterized in that, The preparation method of the zwitterionic surfactant is as follows: S1. Glycerol and thionyl chloride were mixed and reacted to prepare intermediate 1, with the following structure: ; S2. N-methyl-1,3-propanediamine was reacted with an alkyl acyl chloride to prepare intermediate 2, with the following structure: ; S3. Intermediate 1 and intermediate 2 are reacted to obtain intermediate 3, with the following structure: ; S4. React intermediate 3 with sodium chloroacetate to obtain the product.

3. The surfactant composition according to claim 2, characterized in that, The molar ratio of glycerol and thionyl chloride in step S1 is 1:3-3.

3.

4. The surfactant composition according to claim 2, characterized in that, In step S2, the molar ratio of N-methyl-1,3-propanediamine to alkyl acyl chloride is 1:0.9-1, and the alkyl acyl chloride is selected from at least one of dodecyl acyl chloride, tridecyl acyl chloride, tetradecyl acyl chloride, pentadecyl acyl chloride, and hexadecyl acyl chloride.

5. The surfactant composition according to claim 2, characterized in that, The molar ratio of intermediate 1 and intermediate 2 in step S3 is 1:2.9-3.

6. The surfactant composition according to claim 2, characterized in that, The molar ratio of intermediate 3 and sodium chloroacetate in step S4 is 1:3-3.

5.

7. A method for preparing a surfactant composition according to any one of claims 1-6, characterized in that, A surfactant composition is prepared by uniformly mixing amphoteric surfactants and nonionic surfactants.

8. The use of a surfactant composition as described in any one of claims 1-6 in the preparation of a detergent.

9. An amphoteric surfactant constituting the surfactant composition of claim 1, characterized in that, Its structural formula is shown in Formula I: Formula I; R=C12-16 alkyl chain.

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