CN107235880B - One kind cationic surfactant containing selenium and its application - Google Patents

Abstract

The invention discloses a cationic surfactant containing selenium. The structural formula of the surfactant is as shown in the general formula (1), wherein, R ₁ is benzyl, phenyl, phenethyl, phenbutyl or C ₃ ~ C ₁₈ straight chain or branched chain alkyl; R ₂ is C ₂ ~C ₁₈ straight chain or branched chain alkyl; M is a substituted amine or nitrogen-containing heterocycle, and M adopts general formula (2), general formula ( 3) or represented by general formula (4), wherein, R ₃ is an anion with a negative charge. The surfactant of the present invention can be used in the formula design and production of daily detergents and cosmetics, while providing the relevant basic properties of the surfactant, it has the functions of sterilization, anti-dandruff and anti-itching, anti-scalp seborrheic dermatitis and anti-aging skin function.

Description

A kind of selenium-containing cationic surfactant and application thereof

technical field

The invention relates to the technical field of fine chemicals, in particular to a novel cationic surfactant containing trace element selenium in a hydrophobic tail chain and its application.

Background technique

Selenium (Se), one of the essential trace mineral nutrients for the human body, plays an important role in many key metabolic processes in the human body. It has been regarded as an important food source antioxidant, not only as a selenium enzyme or as The active ingredient of protein, scavenging free radicals, protecting cell membranes from oxidation, enhancing the body's immunity, and antagonizing the toxicity of mercury, arsenic, cadmium, and thallium, and having insulin-mimetic effects such as lowering blood sugar and regulating insulin-mediated metabolic processes . Therefore, how to use the nutrition of selenium to improve the quality of life of human beings has always been the goal pursued by people.

In the formula of traditional daily chemical care products, selenium disulfide has been used as an important component of anti-dandruff, anti-itch, anti-fungal, and anti-scalp seborrheic dermatitis. However, selenium disulfide powder cannot be dissolved in water or In oil, the cleaning and care products containing selenium disulfide often show multi-phase instability, and even need to be used as a suspending agent alone. This greatly reduces the contact area of selenium disulfide with the skin, reducing its efficacy. Secondly, this poor dispersion can easily lead to local high-concentration enrichment of selenium disulfide, which is not easy to clean, and may even bring some side effects (such as hair damage).

Surfactants are an indispensable fine chemical product in daily care products, and different types of surfactants often have different functional applications. In daily care products, the current surfactants can only perform a specific function, resulting in the need to add a variety of different surfactants to meet different needs in a formula. If two or more of these functions can be integrated into the same surfactant molecular structure, it is expected to greatly reduce the complexity of the formulation.

Contents of the invention

Aiming at the above-mentioned problems in the prior art, the applicant of the present invention provides a cationic surfactant containing selenium and its application. The surfactant of the present invention can be used in the formula design and production of daily detergents and cosmetics, while providing the relevant basic properties of the surfactant, it has the functions of sterilization, dandruff and itching, anti-scalp seborrheic dermatitis and anti-aging skin function.

Technical scheme of the present invention is as follows:

A selenium-containing cationic surfactant is characterized in that said surfactant structural formula is as shown in general formula (1):

R ₁ -Se-R ₂ -M

Formula (1)

Wherein, R ₁ is benzyl, phenyl, phenethyl, phenbutyl or C ₃ ~ C ₁₈ linear or branched alkyl;

R ₂ is a C ₂ -C ₁₈ linear or branched alkyl group;

M is a substituted amine or a nitrogen-containing heterocycle, and M is represented by general formula (2), general formula (3) or general formula (4):

Wherein, R ₃ is an anion with a negative charge.

The _R3 is chloride ion, bromide ion, iodide ion, sulfate ion, phenylsulfonate ion, p-toluenesulfonate ion, phosphate ion, alkylsulfonate ion, alkylphosphate ion, acetate ion, One of the citrate ions.

An application of the selenium-containing cationic surfactant, the selenium-containing cationic surfactant can be used in shampoos, shower gels, skin care lotions, scented soaps, bactericidal disinfectants, and anti-inflammatory creams.

A shampoo containing the cationic surfactant containing selenium, which contains 0.001-25 parts by weight of the cationic surfactant containing selenium in every 100 parts by weight of the shampoo.

A shower gel containing the cationic surfactant containing selenium, which contains 0.001-25 parts by weight of the cationic surfactant containing selenium in every 100 parts by weight of the shower gel.

The skin care emulsion containing the selenium-containing cationic surfactant contains 0.001-25 parts by weight of the selenium-containing cationic surfactant per 100 parts by weight of the skin care emulsion.

The beneficial technical effects of the present invention are:

The selenium-containing cationic surfactant of the present invention not only has basic physical and chemical properties such as sterilization and antistatic properties of general cationic surfactants, but also has anti-oxidation and free radical scavenging properties that general surfactants do not have, and has the effect of treating skin inflammation, and has Excellent formula compounding and synergistic performance.

When the surfactant of the present invention is used in shampoo, it can not only eliminate static electricity, enhance the softness of hair, but also can partially replace selenium disulfide, and exert the effects of removing dandruff, relieving itching, antifungal and anti-scalp seborrheic dermatitis .

The selenium-containing shampoo, selenium-containing shower gel, and selenium-containing skin care lotion composed of surfactants of the present invention all have good skin antioxidant properties and free radical scavenging capabilities, exhibit good anti-aging functions, and can effectively promote inflammation. The repair of inflammatory skin, eliminate the discomfort of inflammatory skin.

Compared with inorganic selenium disulfide particles, the surfactant of the present invention has better dispersibility in the system, can be completely dissolved in other components of the formula, and can better play anti-dandruff, anti-pruritic, anti-fungal and anti-inflammatory properties. Efficacy in seborrheic dermatitis of the scalp.

Detailed ways

Below in conjunction with embodiment, the present invention is described in detail.

Example 1

Preparation of benzylselenidedecyltrimethylammonium bromide cationic surfactant:

Under the protection of nitrogen, take 1.0mmol benzylselenide undecyl bromide, dissolve it in 10mL tetrahydrofuran, add 1.0mL 33% trimethylamine ethanol solution to the system dropwise, and stir the mixture at 50°C for 24h; after the reaction, The solvent was spin-dried, and the crude product was recrystallized with methanol and petroleum ether to obtain a white solid, which was dried in vacuo. The yield of benzylselenidedecyltrimethylammonium bromide was 93.9%, and the active substance content was 99.0% after analysis ~99.6% range.

Example 2

Preparation of PhenylSelenium Undecylpyridinium Chloride Cationic Surfactant

Add 10mmol phenylselenium undecyl chloride, 10mmol pyridine and 20mL ethanol successively to the reaction flask, heat and stir under reflux for 5h; spin the solvent to dryness, and recrystallize the crude product 3 times with acetone/ethanol mixed solvent to obtain benzene The yield of selenideundecylpyridinium chloride is 88%, and the content of the active substance is in the range of 98.7% to 99.5% after analysis.

Example 3

Preparation of PhenylSelenium Tridecylpyrrolidinium Iodide Cationic Surfactant

Add 5mmol of phenylethylselenidetridecyl iodide, 50mmol of 1-methyltetrahydropyrrole and 20mL of ethanol in sequence in the reaction flask, heat and stir under reflux for 8h; spin the solvent to dryness, and recrystallize the crude product with acetone/ethanol mixed solvent Three times, phenethylselenium tridecylpyrrolidinium iodide can be obtained, the yield is 93%, and the active substance content is in the range of 98.7% to 99.5% through analysis.

Example 4

Preparation of Cationic Surfactant Phenylbutyl Selenium Nonyltrimethylammonium Bromide

Under the protection of nitrogen, take 1.0mmol of phenylbutylselenide nonyl bromide in 10mL of ethanol, add dropwise 1.0mL of 33% trimethylamine ethanol solution to the system, and stir the mixture under reflux at 70°C for 6h; The solvent was spin-dried, and the crude product was recrystallized with acetone and petroleum ether to obtain a white solid, which was dried in vacuo. The yield of phenbutylselenonyltrimethylammonium bromide was 95.9%, and the content of the active substance was 99.1% to 99.7% after analysis. %scope.

Example 5

Preparation of Decylselenopropylpyridinium Iodide Cationic Surfactant

Add 10mmol decylselenopropyl iodide, 10mmol pyridine and 20mL acetonitrile in turn to the reaction flask, heat and stir under reflux for 10h, spin the solvent to dryness, and recrystallize the crude product 3 times with ethyl acetate/ethanol mixed solvent to obtain decane The yield of phenylselenopropylpyridinium iodide is 84%, and the content of the active substance is in the range of 98.4% to 99.2% after analysis.

Test case:

1. Biochemical properties of selenium-containing cationic surfactants

Get respectively the selenium-containing cationic surfactant that embodiment 1～5 makes: benzylselenium undecyltrimethylammonium bromide, phenylselenium undecylpyridinium chloride, phenylethylselenium decathoxylate In vitro 1,1- Diphenyl-2-picrylhydrazine (DPPH, CAS No. 1898-66-4) free radical scavenging experiment, using the same concentration of vitamin C solution as in vitro 1,1-diphenyl-2-picrylhydrazine (DPPH, CAS No. 1898-66-4) Comparative example of free radical scavenging experiments. The test results are shown in Table 1.

Get respectively the selenium-containing cationic surfactant that embodiment 1～5 makes and be mixed with the aqueous solution of 100mg/mL, and respectively act on the experimental bacterium suspension of escherichia coli, Staphylococcus aureus and Candida albicans, observe the present invention The bactericidal effect of the embodiment surfactant solution adopts the same concentration of dodecyltrimethylammonium chloride as the comparative example of the bactericidal experiment. The bactericidal effect data are shown in Table 1 below.

Table 1

As can be seen from the test data in Table 1, the DPPH free radical scavenging rate of 5 kinds of selenium-containing cationic surfactants exemplified by the examples of the present invention were all higher than 90% when the concentration was 50 μg/mL, while the vitamin C of the comparative example was at a concentration of 50 μg/mL. The DPPH free radical scavenging rate was only 75% when it was 50 μg/mL.

The embodiment of the present invention surfactant solution all can show stronger bactericidal effect in 5min, and bactericidal logarithm value all reaches more than 1 (the bigger bactericidal logarithm value, the stronger bactericidal ability), and comparative example dodecyl trimethyl Ammonium chloride is 1.46, 0.85 and 0.26 successively to the bactericidal logarithms of three kinds of bacteria, showing that the surfactant of the present invention has better bactericidal effect.

2. Preparation of selenium-containing skin care emulsion

Take 25g of commercially available skin care emulsion, add 0.1% to 2.5% by mass fraction of the selenium-containing cationic surfactant obtained in Example 1 of the present invention, stir and mix evenly, and obtain the selenium-containing skin care emulsion.

Accelerated tests at 45° C. and -4° C. of the obtained selenium-containing skin care emulsion prove that the formula stability of the selenium-containing skin care emulsion is good.

Take the selenium-containing skin care emulsion added with 1.5% of the selenium-containing cationic surfactant obtained in Example 1 of the present invention, and prepare a 1% aqueous solution to carry out in vitro DPPH free radical scavenging test, and the scavenging rate is as high as 97%.

Local inflammation of the skin can be treated by conditioning the skin in a conventional manner with the selenium-containing skin care lotion of the present invention. It is sufficient to apply an effective amount of a selenium-containing skin care lotion to the preferably moistened body part. The effective amount generally ranges typically from 1 g to about 50 g, preferably from 1 g to 20 g. The results of volunteer experiments show that all selenium-containing skin care lotions have a significant effect on eliminating local inflammation of the skin. Compared with the effect of applying selenium-free skin care lotion, the skin after applying selenium-containing skin care lotion is more supple and elastic, and the skin Aging is visibly slowed down.

3. Preparation of selenium-containing shower gel

Take 50 g of commercially available shower gel, add 0.2% to 2.5% by mass fraction of the selenium-containing cationic surfactant obtained in Example 3 of the present invention, stir and mix evenly, and obtain the selenium-containing shower gel.

Gained selenium-containing shower gel proves that the formula stability of selenium-containing shower gel is compared with commercially available shower gel through 45 ℃ and -4 ℃ accelerated tests and has no significant difference, illustrates that the prepared selenium-containing cationic surfactant in the embodiment has good Formulation compatibility.

Take the selenium-containing shower gel added with 2.5% of the selenium-containing cationic surfactant obtained in Example 3 of the present invention, and make a 1% aqueous solution to carry out in vitro DPPH free radical scavenging test, and the scavenging rate is as high as 97.8%.

The improved Ross-Miles method was used to measure the foam performance of the obtained selenium-containing shower gel, and its foamability and foam stability were improved by more than 50% compared with the commercially available shower gel, and the foam was more delicate and smooth.

Use the selenium-containing body wash of the present invention in a conventional manner to cleanse and condition the skin, especially to treat local inflammations of the skin, apply an effective amount of the selenium-containing body wash to preferably moistened body parts, and leave it for 1-5 minutes , wash off the selenium-containing shower gel with clear water, and the effective amount ranges from about typically 1 g to about 50 g, preferably from 1 g to 15 g. According to volunteer experiments, compared with the raw material shower gel, the skin after washing with selenium-containing shower gel appears smoother, more hydrated, and more elastic, and has a significant inhibitory and improvement effect on skin itching symptoms and local inflammation.

4. Preparation of selenium-containing shampoo

Take 50 g of commercially available shampoo, add 0.5% to 2.5% of the selenium-containing cationic surfactant obtained in Example 4 of the present invention, stir and mix evenly, and then obtain the selenium-containing shampoo.

Gained selenium-containing shampoo proves that the formula stability of selenium-containing shampoo is compared with commercially available shampoo through 45 ℃ and -4 ℃ accelerated test, shows that the prepared selenium-containing cationic surface activity in the embodiment The agent has good formulation compatibility.

Take the selenium-containing shampoo added with 0.5% of the selenium-containing cationic surfactant obtained in Example 4 of the present invention, and prepare a 1% aqueous solution for in vitro DPPH free radical scavenging experiment, and the scavenging rate is as high as 95.8%.

The improved Ross-Miles method was used to measure the foam performance of the obtained selenium-containing shampoo, and its foaming and foam stabilizing properties were both improved by more than 40% compared with the commercially available raw material shampoo, and the foam was more delicate and smooth.

Using the selenium-containing shampoo of the present invention in a conventional manner to cleanse and condition the hair and skin, especially to treat dandruff, itching and local inflammation of the skin, an effective amount of the selenium-containing shampoo is applied to the preferably moistened hair. On the hair or other parts of the body, after leaving it for 1-5 minutes, the shampoo containing selenium is washed off with water, and the effective amount ranges from about typically 1 g to about 25 g, preferably 2 g to 10 g. Experiments by volunteers show that compared with raw shampoos, shampoos containing selenium have better hair combability and stronger luster, and have obvious effects on seborrheic dermatitis and itching symptoms of the scalp after being used for a period of time. Inhibiting effect, dandruff is visibly reduced.

Claims (6)

1. a selenium-containing cationic surfactant is characterized in that said surfactant structural formula is as shown in general formula (1): R ₁ -Se-R ₂ -M Formula (1) Wherein, R ₁ is benzyl, phenyl, phenethyl, phenbutyl or C ₃ ~ C ₁₈ linear or branched alkyl; R ₂ is a C ₂ -C ₁₈ linear or branched alkyl group; M is a nitrogen-containing heterocycle, and M is represented by general formula (3) or general formula (4): Wherein, R ₃ is an anion with a negative charge. 2. cationic surfactant according to claim 1, is characterized in that described R ₃ is chloride ion, bromide ion, iodide ion, sulfate ion, phenylsulfonate ion, p-toluenesulfonate ion, phosphate ion , an alkylsulfonate ion, an alkylphosphate ion, an acetate ion, or a citrate ion. 3. the application of the described selenium-containing cationic surfactant of claim 1, is characterized in that described selenium-containing cationic surfactant can be used for shampoo, shower gel, skin care lotion, perfumed soap, bactericidal disinfectant, anti-inflammatory cream middle. 4. A hair shampoo containing the selenium-containing cationic surfactant according to claim 1, characterized in that 0.001 to 25 parts by weight of the selenium-containing cationic surfactant is contained in every 100 parts by weight of the hair shampoo. 5. A shower gel containing the selenium-containing cationic surfactant according to claim 1, characterized in that 0.001 to 25 parts by weight of the selenium-containing cationic surfactant is contained in every 100 parts by weight of the shower gel. 6. A skin care lotion containing the selenium-containing cationic surfactant according to claim 1, characterized in that 0.001 to 25 parts by weight of the selenium-containing cationic surfactant is contained in every 100 parts by weight of the skin care lotion.