A composite surfactant and its preparation method and application

Abstract

The application discloses a composite surfactant and a preparation method and application thereof, and the composite surfactant comprises a nonionic surfactant, a silicon-containing phosphate surfactant and deionized water; the silicon-containing phosphate surfactant has a structure shown in the following formula A, wherein n=10, 12, 14 or 16. The composite surfactant provided by the application has excellent surface activity, and has strong acid and alkali resistance and heat stability through the compounding between the silicon-containing phosphate surfactant and the nonionic surfactant, and can be widely applied to the fields of daily-use chemical industry, food, medicine, textile and oil exploitation.

Description

Technical Field

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

[0002] Surfactants are substances that significantly reduce the surface tension of a target solution. They possess fixed hydrophilic and lipophilic groups and can be oriented to fit together on the surface of the solution. Surfactants can be classified into ionic surfactants (including cationic and anionic surfactants), amphoteric surfactants, compound surfactants, and other surfactants.

[0003] Phosphate ester surfactants are an important class of anionic surfactants. Based on their source, phospholipids can be divided into two main categories: synthetic phospholipids and natural phospholipids. The main difference between them is that synthetic phospholipids can be molecularly designed according to actual needs, thus synthesizing target products with diverse properties and structures as required, while the structure of natural phospholipids is determined by nature.

[0004] Phosphate ester surfactants have many excellent properties and are widely used in various fields. Their excellent properties mainly include good solubility, emulsification, low critical micelle concentration, ability to reduce surface tension of solution, easy biodegradability, and low irritation. Moreover, their resistance to electrolytes, acids and alkalis, antistatic properties, and thermal stability are much better than those of general anionic surfactants.

[0005] To date, alkyl phosphates and polyether phosphates are the two most commonly used phosphate surfactants internationally. Polyether phosphates generally possess good water solubility, emulsifying properties, and detergency due to their hydrophilic molecular structure. Furthermore, both mono- and diester phosphates contain hydroxyl groups, thus exhibiting strong acidity. Direct use without neutralization can cause significant irritation. Therefore, before being added to daily chemical products, phosphate esters must be neutralized with an alkali to form salts.

[0006] However, the acid and alkali resistance and thermal stability of phosphate ester surfactants in existing technologies still need to be improved. Furthermore, with the continuous development and progress of science and materials, the surface activity of single phosphate ester surfactants is gradually failing to meet the needs of production and research.

[0007] Therefore, there is an urgent need for a composite surfactant containing phosphate esters that has excellent surface activity, strong acid and alkali resistance, and high thermal stability. Summary of the Invention

[0008] Purpose of the invention: In view of the deficiencies of the prior art, the purpose of this invention is to provide a composite surfactant containing phosphate ester with excellent surface activity, strong acid and alkali resistance and thermal stability, as well as its preparation method and application.

[0009] Technical solution:

[0010] In one aspect, this invention provides a composite surfactant comprising a nonionic surfactant, a silica-phosphate surfactant, and deionized water;

[0011] The silicon-containing phosphate surfactant has the structure shown in Formula A:

[0012]

[0013] Where n = 10, 12, 14, 16.

[0014] Furthermore, the nonionic surfactant is selected from one of fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, or polyoxyethylene alkylolamide.

[0015] Another aspect of the present invention provides a method for preparing any one of the above-mentioned composite surfactants, comprising the following steps:

[0016] (1) 4-(trimethylsilyl)phenol was esterified by phosphating agent and hydrolyzed to obtain a silicon phosphate surfactant;

[0017] (2) The composite surfactant is prepared by mixing a nonionic surfactant and a silica phosphate surfactant.

[0018] This invention produces a silicon-containing phosphate surfactant by esterification and hydrolysis of 4-(trimethylsilyl)phenol with a phosphating agent. Through its phosphate ester structure, it has good hydrophilicity and foaming ability, and thus has excellent emulsifying, dispersing and wetting properties. Its properties are close to those of natural phospholipids, and it has low irritation.

[0019] Furthermore, the specific method of step (1) is as follows:

[0020] S1. Add phosphorus oxychloride, pyridine, 4-(trimethylsilyl)phenol and tetrahydrofuran to a reactor in an ice-water bath, and stir the reaction for 4-6 hours;

[0021] S2. Add a mixed solution of alkyl alcohol and tetrahydrofuran dropwise to the reactor of step S1, heat to 30-40℃ and stir for 4-6 hours;

[0022] S3. Add deionized water to the reactor in step S2, heat to 50-60℃ and react for 2-4 hours, then add sodium ethoxide and stir until homogeneous. After cooling, filtering, washing and drying, the silicone phosphate surfactant is obtained.

[0023] This invention introduces a benzene ring structure and a methylsilicon structure into the phosphate ester structure. The excellent stability of the benzene ring structure and the methylsilicon structure can significantly improve its acid and alkali resistance and thermal stability. Furthermore, the methylsilicon structure can further reduce the surface tension of the liquid, thereby improving its surface activity.

[0024] Further, in step S1, the mass ratio of phosphorus oxychloride, pyridine, and 4-(trimethylsilyl)phenol is (1.5-1.8):(1-1.5):(1-1.2).

[0025] Furthermore, in step S2, the mass ratio of the alkyl alcohol to the 4-(trimethylsilyl)phenol in step S1 is 1-1.5:1.

[0026] Furthermore, in step S2, the alkyl alcohol is selected from one of n-decanol, n-dodecylol, n-tetradecylol, or n-hexadecylol.

[0027] Further, the specific method of step (2) is as follows: in the reactor, a nonionic surfactant, a silica phosphate surfactant and deionized water are added, mixed and the pH is adjusted to 8-10 to obtain the composite surfactant.

[0028] This invention combines a silica-containing phosphate surfactant with a nonionic surfactant, and through the synergistic effect of the anionic and nonionic surfactants of the two, the surface activity of the composite surfactant can be further improved.

[0029] Furthermore, the mass ratio of the nonionic surfactant, the silica-containing phosphate surfactant, and the deionized water is (3-5):(3-5):(90-100).

[0030] Finally, the present invention provides the application of any of the above-mentioned composite surfactants in the fields of daily chemical industry, food, medicine, textile and oil extraction.

[0031] Beneficial effects:

[0032] (1) The composite surfactant provided by the present invention has excellent surface activity ability through the combination of silica phosphate surfactant and nonionic surfactant, and has strong acid and alkali resistance and thermal stability. It can be widely used in daily chemical, food, medicine, textile and oil extraction fields.

[0033] (2) The composite surfactant provided by the present invention is a silicon phosphate surfactant prepared by esterification and hydrolysis of 4-(trimethylsilyl)phenol with a phosphating agent. Through the phosphate ester structure, it has good hydrophilicity and foaming ability, and thus has excellent emulsifying, dispersing and wetting properties. Its properties are close to those of natural phospholipids and it has low irritation.

[0034] (3) The silica phosphate surfactant in the composite surfactant provided by the present invention introduces benzene ring structure and methylsilicon structure into the phosphate ester structure. Through the excellent stability of benzene ring structure and methylsilicon structure, its acid and alkali resistance and thermal stability can be significantly improved. Furthermore, the methylsilicon structure can further reduce the surface tension of the liquid, thereby improving the surface activity.

[0035] (4) The composite surfactant provided by the present invention can further improve the surface activity of the composite surfactant by combining a silica phosphate surfactant with a nonionic surfactant and through the synergistic effect of the anionic and nonionic surfactants of the two. Detailed Implementation

[0036] The present invention will be described below with reference to specific implementation schemes. It should be noted that the following embodiments are examples of the present invention and are only used to illustrate the invention, not to limit it. Other combinations and various modifications within the scope of the present invention can be made without departing from the spirit or scope of the invention. The reagents and equipment are conventional reagents and equipment in this technical field. Preparation of Silicate Phosphate Surfactant-1

[0037] The silica-phosphate-containing surfactant-1 was prepared by the following steps:

[0038] S1. Add 5g of phosphorus oxychloride, 4g of pyridine, 3g of 4-(trimethylsilyl)phenol and 50mL of tetrahydrofuran to an ice-water bath reactor, and stir the reaction for 6 hours.

[0039] S2. Add 4g of n-decyl alcohol and 50mL of tetrahydrofuran solution dropwise to the reactor of step S1, heat to 35℃ and stir for 6 hours;

[0040] S3. Add deionized water to the reactor in step S2, heat to 60°C and react for 3 hours, then add 5g of sodium ethoxide, stir evenly, cool, filter, wash and dry to obtain the silicon phosphate surfactant-1.

[0041] Mass spectrometry data of silicic phosphate surfactant-1: The product was analyzed by LC-MS, and the m / z of the product was 404.17 (100.0%), 405.73 (58.6%), 406.74 (15.3%), and 407.86 (3.2%).

[0042] Preparation of silicone phosphate surfactant-2

[0043] The preparation method is basically the same as that of the silicone phosphate surfactant-1, except that n-decyl alcohol is replaced with an equal amount of n-hexadecyl alcohol.

[0044] Preparation of Silicate Phosphate Surfactant-3

[0045] The preparation method is basically the same as that of silicic acid ester surfactant-1, except that 4-(trimethylsilyl)phenol is replaced with an equal amount of p-methylphenol.

[0046] Preparation of Silicate Phosphate Surfactant-4

[0047] The preparation method is basically the same as that of silicic acid ester surfactant-1, except that 4-(trimethylsilyl)phenol is replaced with an equal amount of 1,2-epoxyoctane.

[0048] Example 1

[0049] The composite surfactant is prepared by the following steps:

[0050] In a reactor, 5 wt% of fatty alcohol polyoxyethylene ether AEO-9, 5 wt% of silica-containing phosphate surfactant-1 and 90 wt% of deionized water were added, mixed, and the pH was adjusted to 8 to obtain the composite surfactant.

[0051] Example 2

[0052] The process is basically the same as in Example 1, except that the silica-containing phosphate surfactant-1 is replaced with an equal amount of silica-containing phosphate surfactant-2.

[0053] Example 3

[0054] The basic formula is the same as in Example 1, except that fatty alcohol polyoxyethylene ether AEO-9 is replaced with an equal amount of dodecylphenol polyoxyethylene ether.

[0055] Comparative Example 1

[0056] The process is basically the same as in Example 1, except that the silica phosphate surfactant-1 is replaced with an equal amount of sodium dodecylbenzenesulfonate.

[0057] Comparative Example 2

[0058] The process is basically the same as in Example 1, except that fatty alcohol polyoxyethylene ether AEO-9 is replaced with an equal amount of silica-phosphate surfactant-1.

[0059] Comparative Example 3

[0060] The process is basically the same as in Example 1, except that the silica phosphate surfactant-1 is replaced with an equal amount of fatty alcohol polyoxyethylene ether AEO-9.

[0061] Comparative Example 4

[0062] The process is basically the same as in Example 1, except that the silica-containing phosphate surfactant-1 is replaced with silica-containing phosphate surfactant-3.

[0063] Comparative Example 5

[0064] The process is basically the same as in Example 1, except that the silica-containing phosphate surfactant-1 is replaced with silica-containing phosphate surfactant-4.

[0065] Performance testing

[0066] Surface tension testing: At room temperature (20°C), the products of Examples 1-3 and Comparative Examples 1-5 were diluted with water to a 0.1 wt% aqueous solution, and their surface tension was measured by the platinum plate method. The average value was taken after three repeated measurements to obtain the surface tension of each product.

[0067] Thermal stability test: The products of Examples 1-3 and Comparative Examples 1-5 were diluted with water to a 0.1 wt% aqueous solution and stored at 54°C for 14 days. The surface tension was measured by the platinum plate method. The average value was taken after three repeated measurements. The surface tension of each product was measured to be -2.

[0068] Acid resistance test: The products of Examples 1-3 and Comparative Examples 1-5 were diluted with water to a 0.1 wt% aqueous solution, the pH was adjusted to 3, and the products were stored at 54°C for 14 days. The surface tension was measured by the platinum plate method. The average value was taken after three repeated measurements. The surface tension of each product was measured to be -3.

[0069] Alkali resistance test: The products of Examples 1-3 and Comparative Examples 1-5 were diluted with water to a 0.1 wt% aqueous solution, the pH was adjusted to 12, and the products were stored at 54°C for 14 days. The surface tension was then measured by the platinum plate method. The average value was taken after three repeated measurements. The surface tension of each product was measured to be -4.

[0070]

[0071] According to the comparison of the test results of Examples 1-3 and Comparative Example 1, the composite surfactant provided by the present invention has better surface activity than the composite surfactants commonly used in the prior art, and has strong acid and alkali resistance and thermal stability.

[0072] According to the comparison of the test results of Examples 1-3 and Comparative Examples 2-3, the composite surfactant provided by the present invention can further improve surface activity and enhance acid and alkali resistance and thermal stability through the compounding of silica phosphate surfactant and nonionic surfactant.

[0073] According to the comparison of the test results of Examples 1-3 and Comparative Examples 4-5, the silica-containing phosphate surfactant in the composite surfactant provided by the present invention can effectively improve its surface activity, acid and alkali resistance and thermal stability through the benzene ring structure and methylsilicon structure in its structure.

[0074] The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the content of the present invention and implement it. They should not be used to limit the scope of protection of the present invention. All equivalent changes or modifications made in accordance with the spirit and essence of the present invention should be covered within the scope of protection of the present invention.

Claims

1. A composite surfactant, characterized in that, It contains nonionic surfactants, silica-phosphate surfactants, and deionized water; The silicon-containing phosphate surfactant has the structure shown in Formula A: ， Where n = 10, 12, 14, 16; The nonionic surfactant is selected from one of fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, or polyoxyethylene alkylolamide.

2. The method for preparing the composite surfactant according to claim 1, characterized in that, Includes the following steps: (1) 4-(trimethylsilyl)phenol was esterified with a phosphating agent and hydrolyzed to obtain a silicone phosphate surfactant; (2) The composite surfactant is prepared by mixing a nonionic surfactant and a silica phosphate surfactant.

3. The method for preparing the composite surfactant according to claim 2, characterized in that, The specific method for step (1) is as follows: S1. Add phosphorus oxychloride, pyridine, 4-(trimethylsilyl)phenol and tetrahydrofuran to a reactor in an ice-water bath, and stir the reaction for 4-6 hours; S2. Add a mixed solution of alkyl alcohol and tetrahydrofuran dropwise to the reactor of step S1, heat to 30-40℃ and stir for 4-6 hours; S3. Add deionized water to the reactor in step S2, heat to 50-60℃ and react for 2-4 hours, then add sodium ethoxide and stir until homogeneous. After cooling, filtering, washing and drying, the silicone phosphate surfactant is obtained.

4. The method for preparing the composite surfactant according to claim 3, characterized in that, In step S1, the mass ratio of phosphorus oxychloride, pyridine, and 4-(trimethylsilyl)phenol is (1.5-1.8):(1-1.5):(1-1.2).

5. The method for preparing the composite surfactant according to claim 3, characterized in that, In step S2, the mass ratio of alkyl alcohol to 4-(trimethylsilyl)phenol in step S1 is 1-1.5:

1.

6. The method for preparing the composite surfactant according to claim 3, characterized in that, In step S2, the alkyl alcohol is selected from one of n-decanol, n-dodecylol, n-tetradecylol, or n-hexadecylol.

7. The method for preparing the composite surfactant according to claim 2, characterized in that, The specific method of step (2) is as follows: In the reactor, add nonionic surfactant, silica phosphate surfactant and deionized water, mix and adjust pH to 8-10 to obtain the composite surfactant.

8. The method for preparing the composite surfactant according to claim 7, characterized in that, The mass ratio of the nonionic surfactant, the silica phosphate surfactant and the deionized water is (3-5):(3-5):(90-100).

9. The application of the composite surfactant according to claim 1 in the fields of daily chemical industry, food, medicine, textile or oil extraction.

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