CN114601741A - Selenium sulfide shampoo composition - Google Patents

Selenium sulfide shampoo composition Download PDF

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CN114601741A
CN114601741A CN202210399632.4A CN202210399632A CN114601741A CN 114601741 A CN114601741 A CN 114601741A CN 202210399632 A CN202210399632 A CN 202210399632A CN 114601741 A CN114601741 A CN 114601741A
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selenium sulfide
shampoo composition
carbon spheres
porous micron
micron carbon
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CN114601741B (en
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梁小龙
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Zhejiang Lingkang Enterprise Management Co ltd
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/23Sulfur; Selenium; Tellurium; Compounds thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/006Antidandruff preparations
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/02Preparations for cleaning the hair
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B19/00Selenium; Tellurium; Compounds thereof
    • C01B19/04Binary compounds including binary selenium-tellurium compounds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41Particular ingredients further characterized by their size
    • A61K2800/412Microsized, i.e. having sizes between 0.1 and 100 microns
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41Particular ingredients further characterized by their size
    • A61K2800/413Nanosized, i.e. having sizes below 100 nm

Abstract

The invention provides a selenium sulfide shampoo composition, which is characterized in that the balance moving direction of electrolyte is reasonably controlled by adding a pH value and a complexing agent, nano selenium sulfide particles are uniformly deposited on the surface of a carbon microsphere intermittently contacted with a cathode, although the selenium sulfide has a nano size, the selenium sulfide is attached to the surface of the carbon microsphere in a micron range, so that the selenium sulfide cannot poison scalp due to over-small size, and the selenium sulfide shampoo composition is simple and easy to obtain in preparation process, synthesized in one step, and has the yield and efficiency far higher than those of similar products on the premise of maintaining high purity and high dandruff removal.

Description

Selenium sulfide shampoo composition
Technical Field
The invention belongs to the field of daily chemicals, relates to a preparation method of a shampoo composition, and particularly designs a selenium sulfide shampoo composition.
Background
The shampoo is prepared by compounding surfactant as main component, and has effects of cleaning scalp and hair and maintaining beauty
The product is a daily chemical product which is used by people in large quantity in daily life. The shampoo comprises the components of a cleanser, hair care ingredients, hair moistening grease, a conditioner, an anti-dandruff antipruritic agent, a preservative, a thickening agent, a chelating agent, a thickening agent, an ultraviolet absorbent, nutrient elements and the like, wherein the main effective substance of the shampoo is an anionic surfactant, and the proper surfactant can achieve the effects of rich foam, low irritation, high cleanliness and weak degreasing force.
Earlier people only used shampoo to clean hair, and along with the improvement of living standard, people began to require multiple functions, such as
Removing dandruff, softening hair, and preventing greasy feeling. The anti-dandruff shampoo is a product added with anti-dandruff components such as climbazole, piroctone olamine salt, zinc pyrithione and the like, and has a great proportion in the whole shampoo market because a great number of people have dandruff.
The dandruff is the scale of our scalp, and is scientifically called as "pityriasis capitis". The horny cells on the scalp under normal conditions gradually differentiate and grow from the bottom of the epidermis layer, then gradually move to the surface layer of the scalp, and finally slowly differentiate to form the horny layer on the scalp, and finally the horny layer falls off under the influence of related body metabolic enzymes to form a fine particle which cannot be seen by naked eyes. However, if there is an abnormal increase in the keratinocytes in our scalp area, there is an increase in dandruff, and as more stratum corneum cells are sloughed off and adhered together, they become visible as flaky scales on our naked eye.
There are generally three causes of abnormal proliferation of scalp keratinocytes:
first, if the scalp microbial balance is broken and a plurality of microorganisms exist in the scalp, wherein a fungus which takes sebum as food exists, namely malassezia, if the fungus is excessively proliferated, the cuticle of the user is excessively proliferated, and the cuticle forms flaky scales. This is also the reason why many shampoos containing antifungal drugs are available on the market, and are selected according to their own actual situation.
Secondly, excessive sebum secretion is also a large reason for abnormal proliferation of malassezia, but if the sebum secretion is too low, the scalp lacks protective components, the water locking function is insufficient, the scalp is easily dried and itchy, and scalp inflammation or scalp function barrier weakening can be caused seriously. Meanwhile, daily life work and rest, mental state and eating habits are clean and sanitary, and the sebum secretion condition of the scalp of people is also influenced.
Third, the barrier function of the stratum corneum of scalp, makes a important barrier for protecting scalp against the outside, and has the function of water locking, so as to prevent the scalp from drying and itching due to water loss, therefore, the function and integrity of the stratum corneum barrier are obvious, and the importance of protecting the health of scalp is obvious.
The therapeutic medicine for dandruff mainly comprises external keratolytic agents such as sulfur, salicylic acid and the like, and broad-spectrum antifungal medicines such as ketoconava, selenium disulfide, zinc rhodanate, and proxerone ethanolamine, wherein the clinical use effect of the antifungal medicines is better, and the antifungal medicines are often prepared into shampoo for convenient use. The curative effects of the above medicines are different, and here we mainly introduce selenium sulfide antifungal shampoo.
In the prior art, selenium sulfide is prepared by reacting selenious acid with hydrogen sulfide, hydrogen sulfide gas is introduced into selenious acid solution to generate selenium sulfide, and the product selenium sulfide is obtained after filtering, drying and crushing, wherein the method has low utilization rate of hydrogen sulfide, and hydrogen sulfide is easy to pollute the environment, such as a CN102060277A selenium sulfide production method, which comprises the following steps: according to the concentration of 100-200 g/L, preparing a selenium dioxide aqueous solution under a stirring state, filtering, preparing a filtered sodium sulfide aqueous solution according to the concentration of 150-350 g/L, simultaneously dropwise adding sodium sulfide glacial acetic acid into the stirred selenium dioxide aqueous solution, continuously stirring to promote reaction, putting the solution after the reaction into a centrifugal machine for centrifugal separation to obtain a selenium disulfide product, washing the product to be neutral, and drying to obtain the selenium disulfide product, wherein the yield and the purity obviously need to be improved.
For example, CN109650353A discloses a preparation method of high-purity selenium disulfide, which is characterized by comprising the following steps: A. dissolving raw material selenium in a nitric acid solution; B. crystallizing and separating out selenious acid after reaction in the solution; C. dissolving selenious acid crystals in water and filtering to prepare a saturated solution; D. stirring the saturated solution, and adding an ammonium sulfide solution and a glacial acetic acid solution into the saturated solution, or adding an ammonium hydrogen sulfide solution and a glacial acetic acid solution; E. adding absolute ethyl alcohol or absolute methyl alcohol into the mixed solution obtained in the step D, and then continuing stirring; stirring, standing and aging; F. filtering, and washing the filtrate with alcohol for several times; and drying after washing. The purity of the selenium disulfide finally prepared by the process is as high as 99.99 percent, which is enough to meet the high purity requirement. Although the purity is high, the obvious preparation process is extremely complex, and the purity is high, but the yield is insufficient.
In addition, regarding electrochemical synthesis of selenium sulfide, the prior art has been on the way, but a preparation method of electrochemically synthesizing a selenium simple substance is disclosed, for example, CN202110797078 discloses a selenium sulfide composite powder for hair washing, wherein the selenium sulfide is uniformly dispersed on the surface of a nano microsphere in a nano form, and can be directly mixed with a hair washing composition for use, sedimentation separation does not easily occur in the composition, and the mixing of the selenium sulfide and the hair washing solution is not required during use, so that the selenium sulfide composite powder is simple and convenient, carbon sphere particles can be used as an active carbon hair washing water additive, the generation of dandruff can be reduced, the secretion of grease can be reduced, and the selenium sulfide composite powder has an obvious inhibiting effect on malassezia, and the electrochemical deposition principle is 6H++SeO3 2-+4e-→3H2O + Se, then preparing selenium sulfide through vulcanization, and then removing excessive sulfur through sublimed sulfur to obtain high-purity selenium sulfide.
Disclosure of Invention
Based on the technical problems of complex preparation process, low purity and low yield of the selenium sulfide prepared in the prior art, the invention provides the selenium sulfide shampoo composition, wherein the selenium sulfide is prepared by an electrochemical method, the balance moving direction of electrolyte is reasonably controlled by adding a pH value and a complexing agent, nano selenium sulfide particles are uniformly deposited on the surfaces of carbon microspheres intermittently contacted with a cathode, although the selenium sulfide has a nano size, the selenium sulfide is attached to the surfaces of the carbon spheres in a micron range, so that the selenium sulfide cannot be too small in size to poison the scalp, and the preparation process is simple and easy to obtain, one-step synthesis is realized, and the yield and the efficiency are far higher than those of similar products on the premise of maintaining high purity and high dandruff removal.
Specifically, the method comprises the following steps: a selenium sulfide shampoo composition comprises nano selenium sulfide/porous micron carbon spheres, polyethylene glycol, glycerol, bentonite, hydroxypropyl trimethyl ammonium chloride, N-oleoyl-N-methyl taurate, essence and water, wherein the nano selenium sulfide/porous micron carbon spheres, the polyethylene glycol, the glycerol, the bentonite, the hydroxypropyl trimethyl ammonium chloride, the N-oleoyl-N-methyl taurate, the essence and the water are in a mass ratio of (2-2.5): (0.8-1.2): (1-1.5): (1.7-2.2): (0.3-0.5): (1.2-1.5): (0.1-0.2): (5-7);
the preparation process of the nano selenium sulfide/porous micron carbon spheres is as follows:
(1) pretreatment of porous micron carbon spheres: adding a proper amount of porous micron carbon spheres into a multi-mouth flask, then adding 200ml of 1-2M sodium hydroxide aqueous solution, heating to 97-100 ℃ under the condition of stirring, condensing and refluxing cooling water for 40-60min, naturally cooling, washing and filtering a large amount of deionized water until the pH value is 7.5 +/-0.3, and preparing into 10-12g/L hydroxylated porous micron carbon sphere suspension;
(2) the nano selenium sulfide/porous micron carbon spheres are synthesized through electrochemistry, and the preparation process is as follows:
(a) dissolving 30-40 mM sodium selenate decahydrate and 90-120 mM ammonium bisulfide in deionized water, adding 0.03-0.05g diethylenetriamine pentacarboxylate, and adjusting pH to 8-9 with hydrochloric acid.
(b) Inserting an inert anode and a cathode into the electrolyte, dividing the electrolyte into catholyte and anolyte by using an ion exchange membrane, introducing the hydroxylated porous micron carbon sphere suspension obtained in the step (1) into a cathode chamber, adjusting the pH of the catholyte to 7.5 +/-0.3, switching on a power supply under stirring adjustment, performing cathodic electrolysis reduction, wherein the electrolysis voltage is 3-5V, the time is 15-20min, the stirring speed is 300-500rpm, monitoring the pH concentration of the catholyte in real time during the electrolysis process, and adding sulfuric acid at a proper time to maintain the pH value to be constant to 7.5 +/-0.3;
(c) and stopping the power supply and leading out the catholyte.
(3) And filtering, washing and drying the catholyte to obtain the nano selenium sulfide/porous micron carbon spheres.
Furthermore, the purity of the nano selenium sulfide is more than 99.99%, and the particle size of the nano selenium sulfide is 20-200 nm.
Furthermore, the loading amount of the selenium sulfide in the nano selenium sulfide/porous micron carbon spheres is 4-6wt.
Further, the porous micro carbon spheres have a particle size distribution with D90 of 7-12 μm.
Further, the ion exchange membrane is an anion exchange membrane.
Further, the drying is vacuum freeze drying, wherein the freezing time is 12-16h, the temperature is less than-35 ℃, and the vacuum degree is 10-12 Pa.
Furthermore, the selenium sulfide shampoo composition is matched with shampoos or shampoos of other brands for use, and the mass percentage of selenium sulfide in the finally obtained shampoo composition is not more than 1.0%.
The principle of electrochemical preparation of nano selenium sulfide/porous micron carbon spheres is as follows:
firstly, regarding porous micron carbon sphere suspension, the porous micron carbon sphere is purchased from the market, the porous micron carbon sphere has the particle size distribution that D90 is 7-12 μ M, but the surface has a large amount of grease and amorphous carbon sheets or other impurities and is hydrophobic, so the surface pretreatment is necessary, the pretreatment mode is that a proper amount of porous micron carbon spheres are added into a multi-mouth flask, then 200ml of 1-2M sodium hydroxide aqueous solution is added, the mixture is heated to 97-100 ℃ under the stirring condition, cooling water is condensed and refluxed for 40-60min, the mixture is naturally cooled, a large amount of deionized water is washed and filtered until the pH value is 7.5 +/-0.3, and the hydroxylated porous micron carbon sphere suspension is prepared to be 10-12 g/L; the existence of the hydroxyl groups effectively improves the suspension effect of the carbon spheres in the subsequent catholyte, and avoids agglomeration and suspension on the surface of the catholyte, as shown in figure 1.
The main components of the electrolyte are sodium selenate decahydrate, ammonium bisulfide and diethylenetriamine pentacarboxylate, namely Na exists in water+、NH4+、SeO4 2-And HS-At this time, the wholeThe electrolyte is alkaline, and the pH value is adjusted to 8-9 by adding acid such as sulfuric acid and hydrochloric acid, so that the solution can be ionized and moved, and the reaction formula is shown as follows, SeO4 2- + 4HS- + 4H+ ⇌ SeS4 2- + 4H2O, the equilibrium of ionization occurring during the lowering of the pH value of the solution, is shifted to the right, and in addition, the complexing agent is diethylenetriamine pentacarboxylate to SeS4 2-The complexing ability of the complex is obviously larger than that of SeO4 2-Further increasing the balance to move to the right, forming more SeS4 2-
Then, when a voltage is applied to the electrolyte, the following reaction [ SeS ] occurs4]2- + 2e- + 2H2O → SeS2 +2HS- +2OH-I.e. SeS is formed on the surface of the cathode2Particles, SeS accompanying the occurrence of electrolysis2Particles forming a film covering the cathode surface, said SeS2The film has strong binding force on the surface of the cathode and cannot be effectively stripped, particularly for a porous inert titanium plate cathode, SeS deposited on the surface of the cathode2Difficult to recycle and may affect the conductivity of the cathode.
The hydroxylated porous micron carbon spheres are introduced into the cathode, the carbon spheres are conductive microspheres, the microspheres continuously impact the cathode under the condition of stirring speed of 300-500rpm, and electrolytic reduction [ SeS ] occurs in the process of contacting with the surface of the cathode4]2- + 2e- + 2H2O → SeS2 +2HS- +2OH-As mentioned above, a local alkaline environment is formed on the surface of the carbon spheres contacted with the cathode, so that the pH of the catholyte is reduced, and the selenium sulfide deposition on the cathode is facilitated, therefore, the pH concentration of the catholyte needs to be monitored in real time in the electrolytic process, and the pH value is maintained to be constant at 7.5 +/-0.3 by adding sulfuric acid at a proper time, and is consistent with the concentration of the hydroxylated porous micron carbon spheres, and the optimal microsphere deposition SeS is obtained in the pH concentration range2The range is the necessary condition, and the finally obtained anti-dandruff component on the surface of the nano selenium sulfide/porous micron carbon spheres is shown in the attached figure 2.
The beneficial technical effects are as follows:
(1) the selenium sulfide is prepared by an electrochemical method, the balance moving direction of electrolyte is reasonably controlled by adding a pH value and a diethylenetriamine pentacarboxylate complexing agent, nano selenium sulfide particles are uniformly deposited on the surface of the carbon microsphere intermittently contacted with a cathode, the preparation process is simple and easy to obtain, the selenium sulfide is synthesized by one step, and the yield and the efficiency are far higher than those of similar products.
(2) The relative sizes of the selenium sulfide and the carbon spheres are reasonably controlled, and the relative sizes of the selenium sulfide and the carbon spheres are cooperated with the nanometer active component and the micron macroscopic carrier, so that the unstable phenomena that the selenium sulfide lotion is easy to layer and the like due to overlarge particle size (such as larger than 50 mu m) of the selenium sulfide in the selenium sulfide lotion are effectively overcome, or the risk that the selenium sulfide lotion passes through a skin barrier probability and causes toxic and side effects on the skin due to overlarge particle size (such as smaller than 1 mu m) of the selenium sulfide is increased.
(3) Although the selenium sulfide has a nanometer size, the selenium sulfide is attached to the surface of a carbon sphere in a micrometer range, so that the selenium sulfide does not poison the scalp due to the fact that the selenium sulfide is too small in size, the preparation process is simple and easy to obtain on the premise of maintaining high purity and high dandruff removal, the yield and the efficiency are far higher than those of similar products due to one-step synthesis.
Drawings
FIG. 1 SEM image of hydroxylated porous carbon microspheres obtained by pretreatment according to the invention.
FIG. 2 is a TEM image of nano-selenium sulfide/porous micro-carbon spheres prepared in example 2 of the present invention.
Detailed Description
Example 1
A selenium sulfide shampoo composition comprises nano selenium sulfide/porous micron carbon spheres, polyethylene glycol, glycerol, bentonite, hydroxypropyl trimethyl ammonium chloride, N-oleoyl-N-methyl taurate, essence and water, wherein the nano selenium sulfide/porous micron carbon spheres, the polyethylene glycol, the glycerol, the bentonite, the hydroxypropyl trimethyl ammonium chloride, the N-oleoyl-N-methyl taurate, the essence and the water are in a mass ratio of (2): (0.8): (1): (1.7): (0.3): (1.2): (0.1): (5).
The preparation process of the nano selenium sulfide/porous micron carbon sphere deionized water comprises the following steps:
(1) pretreatment of porous micron carbon spheres: adding a proper amount of porous micron carbon spheres into a multi-mouth flask, then adding 200ml of 1M sodium hydroxide aqueous solution, heating to 97 ℃ under the condition of stirring, condensing and refluxing cooling water for 40min, naturally cooling, washing with a large amount of deionized water, filtering until the pH value is 7.5 +/-0.3, and preparing into a 10g/L hydroxylated porous micron carbon sphere suspension.
(2) The nano selenium sulfide/porous micron carbon spheres are synthesized through electrochemistry, and the preparation process is as follows:
(a) dissolving 30mM sodium selenate decahydrate and 90mM ammonium bisulfide in deionized water, adding 0.03g of diethylenetriamine pentacarboxylate, stirring uniformly, and adjusting the pH value to 8 by using hydrochloric acid to obtain the electrolyte.
(b) Inserting an inert anode and a cathode into the electrolyte, dividing the electrolyte into catholyte and anolyte by using an ion exchange membrane, introducing the hydroxylated porous micron carbon sphere suspension obtained in the step (1) into a cathode chamber, adjusting the pH of the catholyte to 7.5 +/-0.3, switching on a power supply under the condition of stirring, carrying out cathodic electrolysis reduction, wherein the electrolysis voltage is 3V, the time is 15min, the stirring speed is 300rpm, monitoring the pH concentration of the catholyte in real time during electrolysis, and adding sulfuric acid at a proper time to maintain the pH value to be 7.5 +/-0.3.
(c) And stopping the power supply and leading out the catholyte.
(3) And filtering, washing, air-cooling, freeze-drying and drying the catholyte, wherein the freezing time is 12 hours, the temperature is less than-35 ℃, and the vacuum degree is 10-12Pa, so that the nano selenium sulfide/porous micron carbon spheres are obtained.
Example 2
A selenium sulfide shampoo composition comprises nano selenium sulfide/porous micron carbon spheres, polyethylene glycol, glycerol, bentonite, hydroxypropyl trimethyl ammonium chloride, N-oleoyl-N-methyl taurate, essence and water, wherein the nano selenium sulfide/porous micron carbon spheres, the polyethylene glycol, the glycerol, the bentonite, the hydroxypropyl trimethyl ammonium chloride, the N-oleoyl-N-methyl taurate, the essence and the water are in a mass ratio of (2-2.5): (0.8-1.2): (1-1.5): (1.7-2.2): (0.3-0.5): (1.2-1.5): (0.1-0.2): (5-7).
The preparation process of the nano selenium sulfide/porous micron carbon sphere deionized water comprises the following steps:
(1) pretreatment of porous micron carbon spheres: adding a proper amount of porous micron carbon spheres into a multi-mouth flask, then adding 250ml of 1.5M sodium hydroxide aqueous solution, heating to 98.5 ℃ under the condition of stirring, condensing and refluxing cooling water for 50min, naturally cooling, washing and filtering by a large amount of deionized water until the pH value is 7.5 +/-0.3, and preparing into 11g/L hydroxylated porous micron carbon sphere suspension.
(2) The nano selenium sulfide/porous micron carbon spheres are synthesized through electrochemistry, and the preparation process is as follows:
(a) dissolving 35 mM sodium selenate decahydrate and 105 mM ammonium bisulfide in deionized water, adding 0.04g diethylenetriamine pentacarboxylate, stirring uniformly, and adjusting pH to 8.5 with hydrochloric acid to obtain electrolyte.
(b) Inserting an inert anode and a cathode into the electrolyte, dividing the electrolyte into catholyte and anolyte by using an ion exchange membrane, introducing the hydroxylated porous micron carbon sphere suspension obtained in the step (1) into a cathode chamber, adjusting the pH of the catholyte to 7.5 +/-0.3, switching on a power supply under stirring adjustment, carrying out cathodic electrolytic reduction, wherein the electrolytic voltage is 4V, the time is 17.5min, the stirring speed is 400rpm, monitoring the pH concentration of the catholyte in real time in the electrolytic process, and adding sulfuric acid at a proper time to maintain the pH value to be 7.5 +/-0.3.
(c) And stopping the power supply and leading out the catholyte.
(3) And filtering, washing, air-cooling, freeze-drying and drying the catholyte, wherein the freezing time is 14 hours, the temperature is less than-35 ℃, and the vacuum degree is 10-12Pa, so that the nano selenium sulfide/porous micron carbon spheres are obtained.
Example 3
The preparation process of the nano selenium sulfide/porous micron carbon sphere deionized water comprises the following steps:
(1) pretreatment of porous micron carbon spheres: adding a proper amount of porous micron carbon spheres into a multi-mouth flask, then adding 300ml of 2M sodium hydroxide aqueous solution, heating to 100 ℃ under the condition of stirring, condensing and refluxing cooling water for 60min, naturally cooling, washing with a large amount of deionized water, filtering until the pH value is 7.5 +/-0.3, and preparing into a 12g/L hydroxylated porous micron carbon sphere suspension.
(2) The nano selenium sulfide/porous micron carbon spheres are synthesized through electrochemistry, and the preparation process is as follows:
(a) dissolving 40 mM sodium selenate decahydrate and 120 mM ammonium bisulfide in deionized water, adding 0.05g of diethylenetriamine pentacarboxylate, stirring uniformly, and adjusting the pH value to 9 by using hydrochloric acid to obtain the electrolyte.
(b) Inserting an inert anode and a cathode into the electrolyte, dividing the electrolyte into catholyte and anolyte by using an ion exchange membrane, introducing the hydroxylated porous micron carbon sphere suspension obtained in the step (1) into a cathode chamber, adjusting the pH of the catholyte to 7.5 +/-0.3, switching on a power supply under the condition of stirring, carrying out cathodic electrolysis reduction, wherein the electrolysis voltage is 5V, the time is 20min, the stirring speed is 500rpm, monitoring the pH concentration of the catholyte in real time during electrolysis, and adding sulfuric acid at a proper time to maintain the pH value to be 7.5 +/-0.3.
(c) And stopping the power supply and leading out the catholyte.
(3) And filtering, washing, air-cooling, freeze-drying and drying the catholyte, wherein the freezing time is 16 hours, the temperature is less than-35 ℃, and the vacuum degree is 10-12Pa, so that the nano selenium sulfide/porous micron carbon spheres are obtained.
Comparative example 1
A selenium sulfide shampoo composition comprises nano selenium sulfide/porous micron carbon spheres, polyethylene glycol, glycerol, bentonite, hydroxypropyl trimethyl ammonium chloride, N-oleoyl-N-methyl taurate, essence and water, wherein the nano selenium sulfide/porous micron carbon spheres, the polyethylene glycol, the glycerol, the bentonite, the hydroxypropyl trimethyl ammonium chloride, the N-oleoyl-N-methyl taurate, the essence and the water are in a mass ratio of (2-2.5): (0.8-1.2): (1-1.5): (1.7-2.2): (0.3-0.5): (1.2-1.5): (0.1-0.2): (5-7).
The preparation process of the nano selenium sulfide/porous micron carbon sphere deionized water comprises the following steps:
(1) pretreatment of porous micron carbon spheres: adding a proper amount of porous micron carbon spheres into a multi-mouth flask, then adding 250ml of 1.5M sodium hydroxide aqueous solution, heating to 98.5 ℃ under the condition of stirring, condensing and refluxing cooling water for 50min, naturally cooling, washing and filtering by a large amount of deionized water until the pH value is 7.5 +/-0.3, and preparing into 11g/L hydroxylated porous micron carbon sphere suspension.
(2) The nano selenium sulfide/porous micron carbon spheres are synthesized through electrochemistry, and the preparation process comprises the following steps:
(a) dissolving 35 mM sodium selenate decahydrate and 105 mM ammonium bisulfide in deionized water, and uniformly stirring to obtain the electrolyte.
(b) Inserting an inert anode and a cathode into the electrolyte, dividing the electrolyte into catholyte and anolyte by using an ion exchange membrane, introducing the hydroxylated porous micron carbon sphere suspension obtained in the step (1) into a cathode chamber, adjusting the pH of the catholyte to 7.5 +/-0.3, switching on a power supply under the condition of stirring, carrying out cathodic electrolysis reduction, wherein the electrolysis voltage is 4V, the time is 17.5min, the stirring speed is 400rpm, monitoring the pH concentration of the catholyte in real time during electrolysis, and adding sulfuric acid at a proper time to maintain the pH value to be 7.5 +/-0.3.
(c) And stopping the power supply and leading out the catholyte.
(3) And filtering, washing, air-cooling, freeze-drying and drying the catholyte, wherein the freezing time is 14 hours, the temperature is less than-35 ℃, and the vacuum degree is 10-12Pa, so that the nano selenium sulfide/porous micron carbon spheres are obtained.
By examining the selenium sulfide content and size test in the micron of example 2 and comparative example 1, wherein the selenium sulfide loading in the nano selenium sulfide/porous micron carbon spheres in example 2 is 5.13 wt%, the nano size is intensively distributed around 120nm and the size is uniform, while the mixed solution is not added with diethylenetriamine pentacarboxylate and the pH adjustment is not carried out, the balance movement is hindered and the yield is low in the process of preparing the selenium sulfide by electrochemical reduction, the selenium sulfide loading in the nano selenium sulfide/porous micron carbon spheres is 0.782 wt%, the nano size is intensively distributed between 20 and 500nm, the particle size is large, the distribution is nonuniform, and the agglomeration phenomenon is obvious.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (7)

1. The selenium sulfide shampoo composition is characterized by comprising nano selenium sulfide/porous micron carbon spheres, polyethylene glycol, glycerol, bentonite, hydroxypropyl trimethyl ammonium chloride, N-oleoyl-N-methyl taurate, essence and water, wherein the nano selenium sulfide/porous micron carbon spheres, the polyethylene glycol, the glycerol, the bentonite, the hydroxypropyl trimethyl ammonium chloride, the N-oleoyl-N-methyl taurate, the essence and the water are mixed according to a mass ratio of (2-2.5): (0.8-1.2): (1-1.5): (1.7-2.2): (0.3-0.5): (1.2-1.5): (0.1-0.2): (5-7);
the preparation process of the nano selenium sulfide/porous micron carbon spheres is as follows:
(1) pretreatment of porous micron carbon spheres: adding a proper amount of porous micron carbon spheres into a multi-mouth flask, then adding 200ml of 1-2M sodium hydroxide aqueous solution, heating to 97-100 ℃ under the condition of stirring, condensing and refluxing cooling water for 40-60min, naturally cooling, washing and filtering a large amount of deionized water until the pH value is 7.5 +/-0.3, and preparing into 10-12g/L hydroxylated porous micron carbon sphere suspension;
(2) the nano selenium sulfide/porous micron carbon spheres are synthesized through electrochemistry, and the preparation process comprises the following steps:
(a) dissolving 30-40 mM sodium selenate decahydrate and 90-120 mM ammonium bisulfide in deionized water, adding 0.03-0.05g of diethylenetriamine pentacarboxylate, uniformly stirring, and adjusting the pH value to 8-9 by using hydrochloric acid to obtain electrolyte;
(b) inserting an inert anode and a cathode into the electrolyte, dividing the electrolyte into catholyte and anolyte by using an ion exchange membrane, introducing the hydroxylated porous micron carbon sphere suspension obtained in the step (1) into a cathode chamber, adjusting the pH of the catholyte to 7.5 +/-0.3, switching on a power supply under stirring adjustment, performing cathodic electrolysis reduction, wherein the electrolysis voltage is 3-5V, the time is 15-20min, the stirring speed is 300-500rpm, monitoring the pH concentration of the catholyte in real time during the electrolysis process, and adding sulfuric acid at a proper time to maintain the pH value to be constant to 7.5 +/-0.3;
(c) stopping the power supply, and leading out catholyte;
(3) and filtering, washing and drying the catholyte to obtain the nano selenium sulfide/porous micron carbon spheres.
2. The selenium sulfide shampoo composition according to claim 1, wherein the purity of the nano selenium sulfide is greater than 99.99%, and the particle size of the nano selenium sulfide is 20-200 nm.
3. The selenium sulfide shampoo composition according to claim 1, wherein the amount of selenium sulfide loaded in the nano selenium sulfide/porous micro carbon spheres is 4-6 wt.%.
4. The selenium sulfide shampoo composition of claim 1 wherein the porous micro carbon spheres have a particle size distribution with a D90 range of 7 to 12 μm.
5. The selenium sulfide shampoo composition of claim 1, wherein the cathode is a titanium electrode and the ion exchange membrane is an anion exchange membrane.
6. The selenium sulfide shampoo composition according to claim 1 wherein the drying in step (3) is vacuum freeze drying at a temperature of less than-35 ℃ for 12 to 16 hours and a vacuum of 10 to 12 Pa.
7. The selenium sulfide shampoo composition as claimed in claim 1, wherein the selenium sulfide shampoo composition is used in combination with shampoos or shampoos of other brands to obtain a final selenium sulfide shampoo composition having a mass percent of not more than 1.0%.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113620258A (en) * 2021-07-14 2021-11-09 郑小青 Selenium sulfide composite powder for hair washing
CN113633576A (en) * 2021-07-14 2021-11-12 郑小青 Dandruff-removing itching-relieving hair washing composition
CN113633559A (en) * 2021-07-14 2021-11-12 郑小青 Preparation method of dandruff-removing and itching-relieving shampoo
CN114010514A (en) * 2021-10-08 2022-02-08 大有药业扬州有限公司 Micronized selenium disulfide active antifungal lotion

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113620258A (en) * 2021-07-14 2021-11-09 郑小青 Selenium sulfide composite powder for hair washing
CN113633576A (en) * 2021-07-14 2021-11-12 郑小青 Dandruff-removing itching-relieving hair washing composition
CN113633559A (en) * 2021-07-14 2021-11-12 郑小青 Preparation method of dandruff-removing and itching-relieving shampoo
CN114010514A (en) * 2021-10-08 2022-02-08 大有药业扬州有限公司 Micronized selenium disulfide active antifungal lotion

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
罗雯等: "空心碳球负载二硫化硒复合材料作为锂离子电池正极材料", 物理化学学报, vol. 32, no. 8, pages 1999 - 2006 *

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