CN113749984A

CN113749984A - Preparation method of shampoo composition

Info

Publication number: CN113749984A
Application number: CN202111178044.XA
Authority: CN
Inventors: 邱志新
Original assignee: Individual
Current assignee: Dai Yun
Priority date: 2021-10-09
Filing date: 2021-10-09
Publication date: 2021-12-07
Anticipated expiration: 2041-10-09
Also published as: CN113749984B

Abstract

The invention provides a preparation method of a shampoo composition, which is characterized in that a shampoo with high foamability, stability, proper viscosity and small irritation to scalp is obtained by using a compounded anionic surfactant, a cationic surfactant, an amphoteric surfactant and a nonionic surfactant, chloropyridine is oxidized by oxygen diffusion catalysis, the conversion rate of chloropyridine oxide is improved, the process is extremely short in time consumption, the production efficiency is remarkably improved on the premise of maintaining higher conversion rate and selectivity, and the purity and the conversion rate of a product are further improved when a shampoo anti-dandruff antipruritic ZPT is prepared, wherein the heavy metal content of the ZPT is less than 3.5 ppm.

Description

Preparation method of shampoo composition

Technical Field

The invention belongs to a preparation method of a shampoo composition, and particularly relates to a preparation method of a shampoo anti-dandruff antipruritic, wherein the anti-dandruff antipruritic is high-purity zinc pyrithione and is used for inhibiting and killing lipid fungi on scalp, and especially used for preparing shampoo or hair rinse additives.

Background

The skin of the head of a normal person has some fungal communities, wherein malassezia is a unicellular saccharomycete called pityrosporum orbicularis, which is widely present on the skin of the person, and the malassezia may cause skin inflammations such as seborrheic dermatitis, folliculitis, tinea versicolor and the like. At least seven different malassezia species, namely malassezia globosa, malassezia axacuminata and malassezia restricta are reported to be found in human sebum, six of the seven malassezia species are lipid-philic bacteria, wherein the malassezia globosa and the malassezia restricta are considered as the most likely pathogenic bacteria for dandruff, the malassezia globosa needs to take fatty acid from sebum as nutrition, and the hair contains a large number of hair follicles, so that a large amount of sebum is secreted, and a sufficient nutrition source is provided for the propagation of the malassezia globosa. Based on the above, in designing a shampoo with an anti-dandruff effect, inhibiting malassezia is a relatively effective method in terms of dandruff-forming three-factor sebum, malassezia and individual susceptibility, and anti-dandruff agents for inhibiting malassezia are added to shampoo, and common anti-dandruff agents include Zinc Pyrithione (ZPT), climbazole and Octopirox.

The invention only considers that zinc pyrithione, ZPT for short, is a high-efficiency anti-dandruff agent produced by Aoqi company in America, is applied to anti-dandruff products from 1967, the ZPT is supplied in the form of 48% water dispersion pulp and has broad-spectrum inhibition effect on gram-negative bacteria and gram-positive bacteria, the sterilization mechanism of the ZPT is that the ZPT serving as an ionophore penetrates through a cell membrane to bring protons into the cell, and then the ZPT leaves the cell by combining potassium ions, so that the shuttle and the shuttle are carried out to destroy the ion balance on two sides of the cell membrane, so that nutrient components can not be conveyed into the cell membrane to cause cell death,

with the development of science and technology, the improvement of living standard of people, the pyrithione salt series antibacterial agent becomes a recognized anti-dandruff antipruritic agent by the application effect of high efficiency, safety and broad spectrum, the pyrithione zinc is in the daily chemical industry by the high efficiency and safety sterilization effect of pyrithione zinc, the anti-dandruff antipruritic agent can inhibit the keratinization speed of cells, prevent the generation of dandruff, has low irritation to scalp, has an insoluble water system, is dispersed in shampoo by ultrafine particles of the pyrithione zinc in the shampoo, the pyrithione zinc fine particles are adsorbed on the surface of scalp during the shampoo, can inhibit bacteria for a long time, prevent the generation of dandruff, can dissolve the generated dandruff into invisible fine particles, can inhibit the growth of gram-positive bacteria, gram-negative bacteria and mould fungi after the shampoo containing pyrithione zinc products is used for a long time, not only can well remove dandruff, but also can delay aging, delay the generation of white hair and alopecia, can be mixed with most shampoo components.

The method for preparing zinc pyrithione is simple, and mainly comprises the steps of synthesizing zinc pyrithione through oxidation, sulfhydrylation and complexation, for example, CN201710769145, chongqing zhongpo scientific and technological limited company discloses a method for producing small-particle-size zinc pyrithione, which comprises the following steps: (1) oxidation reaction, (2) sulfhydrylation reaction, (3) sulfur removal, (4) salt forming reaction, and in the first step, the oxidation reaction: adding 2-chloropyridine, a catalyst and deionized water into a reaction bottle, heating to 60 ℃, slowly dropwise adding hydrogen peroxide (30 wt%), keeping the temperature at 70 ℃ for 3-5h after dropwise adding, and finishing the reaction when the 2-chloropyridine is less than 1 g. Cooling to 40 ℃, performing suction filtration, recovering the catalyst, dropwise adding liquid caustic soda into the filtrate to adjust the pH value to 5-6, adding 3.5g of activated carbon for decolorization, and performing suction filtration to obtain a first reaction solution; secondly, sulfhydrylation reaction: weighing 42 wt% of sodium hydrosulfide solution and 15 wt% of sodium hydroxide solution, adding the sodium hydrosulfide solution and the sodium hydroxide solution into a reaction bottle, stirring, heating to 60 ℃, dropwise adding the first reaction solution, keeping the temperature at 70 ℃ for 2-3 h after dropwise adding, and finishing the reaction when the qualitative content of the 2-chloropyridine nitrogen oxide is less than 2%. Cooling to 40 ℃ to obtain a second reaction solution; step three, removing sulfur: adding hydrochloric acid (31 wt%) into the second reaction solution, adjusting the pH value to 6-7, adding 8g of activated carbon for decolorization, and performing suction filtration to obtain an SPT solution; step four, salt forming reaction: and (2) introducing the SPT solution into a normally running supergravity bed at a mass flow of 1kg/min and the zinc salt solution at a mass flow of 0.994kg/min, collecting a salt-forming product from the lower part to a reaction kettle, preserving the temperature for 1h at 85-90 ℃, and then performing suction filtration, washing and drying to obtain the zinc pyrithione sulfate with the particle size of less than 2 microns.

CN201610266948 Binhiming hong fine chemical Co., Ltd for the production of uniform platelet zinc pyrithione, which comprises the steps of: the first step is as follows: and (3) oxidation reaction: adding 2-chloropyridine, a catalyst and deionized water into a reaction kettle, heating to 50-60 ℃, stirring for 1-2.5 h, slowly dropwise adding hydrogen peroxide, heating to 60-80 ℃, preserving heat for 3-5h, and then dropwise adding sodium hydroxide to adjust the pH value to 6-8 to generate a 2-chloro-N-oxypyridine solution; the second step is that: sulfhydrylation reaction: dropwise adding a sodium hydrosulfide solution and a sodium hydroxide solution into a reaction kettle of the 2-chloro-N-oxopyridine solution in the first step to adjust the pH value to 8-10, and stirring for 1-3 h at the temperature of 70-90 ℃ to generate a 2-mercapto-N-oxopyridine solution; the third step: acid stripping reaction: adding hydrochloric acid into the reaction kettle of the 2-mercapto-N-oxopyridine solution in the second step, and adjusting the pH value to 2-4; the fourth step: salt forming reaction: adding sodium hydroxide solution into the solution obtained in the third step to adjust the pH value to 8-10, and then carrying out suction filtration; the fifth step: and (3) complexing reaction: and (3) adding a ZnSO4 solution into the reaction kettle of the 2-mercapto-N-oxypyridine sodium salt obtained in the fourth step, reacting at the temperature of 70-90 ℃, preserving heat for 1-2h, and then performing suction filtration, washing and drying to obtain the platelet zinc pyrithione.

It can be clearly seen that the oxidation of 2-chloropyridine, which is the basic step in the preparation of ZPT, is usually carried out for 3-5h, and that pyridine oxidation is difficult as known to those skilled in the art, and pyridine chloride is more difficult to oxidize, so that the conversion of chloropyridine into 2-chloro-N-oxopyridine is relatively low, e.g. the catalytic synthesis of 2-chloropyridine-N-oxide by using Cuo's supported phosphotungstic acid in experiments using impregnation method to prepare SiO₂Supported phosphotungstic acid catalyst with 2-chloropyridine as catalystRaw materials, H₂O₂The method synthesizes 2-chloropyridine-N-oxide as an oxidant, discusses the influence of phosphotungstic acid load capacity, catalyst dosage, reactant proportion, reaction temperature, reaction time and the like on oxidation reaction, and has the optimal process conditions that the load capacity of phosphotungstic acid is 30 percent, the catalyst dosage is 3.3 percent, and N (2-chloropyridine): n (H)₂O₂) =1:6.0, reaction temperature 80^oC; the reaction time is 30h, the yield is up to 89.8%, and it can be clearly seen that the oxidation of 2-chloropyridine by using the traditional catalyst is long in oxidation time, extremely low in oxidation efficiency and needs to be improved.

Disclosure of Invention

Based on the technical problems, the shampoo with high foamability, stability, proper viscosity and small irritation to scalp is obtained by using the anionic surfactant, the cationic surfactant, the amphoteric surfactant and the nonionic surfactant which are compounded, in addition, the chloropyridine is catalyzed and oxidized by diffusing oxygen, the conversion rate of the chloropyridine oxide is improved, the process is extremely short in time consumption, the production efficiency is obviously improved on the premise of maintaining higher conversion rate and selectivity, and further, the purity and the conversion rate of the product are further improved when the ZPT (shampoo antidandruff antipruritic agent) is prepared, wherein the heavy metal content of the ZPT is less than 3.5 ppm.

The preparation method of the shampoo composition is characterized by comprising the following steps:

(A) dispersing ammonium lauryl sulfate, ammonium laureth sulfate, cocamidopropyl hydroxysultaine, C8-C14 alkyl polyglycoside with carbon chain number and ethylene glycol monostearate in deionized water according to the mass ratio, heating and stirring uniformly, and keeping the constant temperature at 70-75 ℃.

(B) Dissolving polyquaternium-10 and polydimethylsiloxane into deionized water according to the mass ratio, adding the solution into the solution obtained in the step (A), uniformly stirring, and cooling and keeping the temperature at 50-55 ℃;

(C) dissolving zinc pyrithione, kasong, essence and amino acid in deionized water according to the mass ratio, adding the solution into the solution obtained in the step (B), uniformly stirring, and cooling and keeping the temperature at 35-40 ℃;

(D) at the step (C)Adding sodium chloride into the obtained solution to adjust viscosity, adding citric acid to adjust pH to 6-7, adding deionized water to balance, and cooling to 25^oC, stirring for 30-40min,

the preparation method of the zinc pyrithione comprises the following steps:

(1) preparing 2-chloro-N-oxypyridine by electrocatalytic oxidation;

(2) sodium sulfydryl of 2-chloro-N-oxypyridine;

(3) complexing and synthesizing zinc pyrithione.

Further, the shampoo composition comprises the following components: 5-7wt.% of ammonium lauryl sulfate, 13-16wt.% of ammonium laureth sulfate, 5-6wt.% of cocamidopropyl hydroxysultaine, 1-1.5wt.% of alkylpolyglycoside having a carbon chain number of C8-C14, 100.75-1.5 wt.% of polyquaternium, 0.4-0.5 wt.% of polydimethylsiloxane, 2-4 wt.% of zinc pyrithione, 1-1.2wt.% of ethylene glycol monostearate, 0.05-0.1 wt.% of carson, 0.4-0.6 wt.% of sodium chloride, 1-1.5wt.% of amino acid; proper amount of citric acid and 1-1.2wt.% of essence.

Further, the electrocatalytic oxidation preparation of the 2-chloro-N-oxypyridine comprises the following steps:

(a) arranging an electrolytic cell: the electrolytic cell is divided into an anode chamber and a cathode chamber by using a cation exchange membrane, an anode is arranged in the anode chamber, and the anode is Ti/(Ru-Ir) O_xThe anode is provided with a gas diffusion electrode in the cathode chamber, the gas diffusion electrode comprises a gas diffusion layer, a metal mesh layer and a catalyst layer, and the active component of the catalyst layer is Co-Ru;

(b) introducing a mixed solution of sodium sulfate and sulfuric acid into the anode chamber to serve as an anolyte, wherein the use amount of the sodium sulfate is 5-7wt.%, the pH value is 2-3, introducing a sodium hydroxide aqueous solution of 2-chloropyridine into the cathode chamber to serve as a catholyte, the concentration of the 2-chloropyridine is 5-15wt.%, the pH value is 8-9, one side of the cathode chamber is provided with an oxygen chamber, and gas in the oxygen chamber and the catholyte in the cathode chamber are separated by a gas diffusion electrode;

(c) and (3) switching on a power supply, introducing gas into the gas chamber, introducing anolyte and a cathode into the anode chamber and the cathode chamber, and performing electrolytic oxidation on the 2-chloropyridine to obtain the 2-chloro-N-oxopyridine.

Further, the preparation method of the gas diffusion electrode comprises the following steps:

(1) preparing a diffusion layer: uniformly mixing ammonium bicarbonate, 25-30wt.% of PTFE emulsion and glycerol aqueous solution to obtain suspension, then mixing the suspension on pretreated carbon nano tube powder to obtain paste, rolling and molding, then heating at the temperature of 240 ℃ and 250 ℃ in a muffle furnace at the speed of 1 ℃/min, keeping the temperature for 30-40min, and naturally cooling to obtain a diffusion layer with the thickness of 250-: (60-70): (50-60), wherein the using amount of the glycerol aqueous solution is 1.5-2ml, and the volume ratio of the glycerol to the water is 1.5-2: 1;

(2) pretreating the metal mesh layer: cleaning the foamed nickel by using 0.02-0.05M hydrochloric acid, acetone and deionized water in sequence, and then carrying out vacuum drying at the temperature of 100-;

(3) preparing a catalyst layer: dissolving cobalt chloride and dodecacarbonyl triruthenium into a glycerol aqueous solution, adding 25-30wt.% of PTFE emulsion, uniformly mixing to obtain a suspension, mixing the suspension on the pretreated carbon nanotube powder to obtain a paste, rolling and molding, keeping the temperature at 210 ℃ at 1 ℃/min in a muffle furnace for 60-70min, and naturally cooling to obtain a catalyst layer with the thickness of 250-: (0.5-0.75);

(4) pressing: and stacking the diffusion layer, the metal mesh layer and the catalyst layer in sequence, and pressing by adopting pressure of 10-11Mpa and maintaining the pressure for 15-20s to obtain the gas diffusion electrode.

Further, the step (2) comprises the sodium sulfydryl salt of 2-chloro-N-oxypyridine: preparing a mixed solution of a sodium hydrosulfide solution and a sodium hydroxide solution with the pH =8.5-9.5, wherein the molar ratio of the sodium hydrosulfide to the sodium hydroxide is 1 (0.85-1), dropwise adding the oxidized 2-chloropyridine catholyte prepared in the step (1) into the mixed solution, reacting at the temperature of 50-60 ℃ for 1-2h, naturally cooling, adjusting the pH to 2-3 by using hydrochloric acid, reacting at normal temperature and pressure for 0.5-1h, adding the sodium hydroxide to adjust the pH =9-10, and reacting at normal temperature and pressure for 0.5-1h to obtain the pyrithione sodium salt solution.

Further, the step (3) is to complex and synthesize zinc pyrithione: adjusting pH of pyrithione sodium salt solution to 8-8.5, adding appropriate amount of ethanol, and adding water to obtain solution at 60-65%^oAdding ZnSO4 solution at 70-90 deg.C, reacting, maintaining for 1-1.5h, filtering, washing with hot water, 110-120-^oAnd C, drying for 1-1.5h, and crushing to obtain zinc pyrithione, wherein the molar ratio of the zinc sulfate to the sodium pyrithione is 1: 1.5-2.

Further, the purity of zinc pyrithione prepared by electrocatalysis is 97.5-99.3%, and zinc pyrithione with purity more than 99% is selected, wherein the heavy metal impurities are less than 3.5 ppm.

Further, the oxidation of the 2-chloropyridine results in a conversion of 2-chloro-N-oxopyridine of greater than or equal to 98 wt.%.

Further, the amino acid is selected from one or more of glycine, glutamic acid and lysine.

Further, the viscosity of the shampoo is 2500-.

The shampoo disclosed by the invention consists of an anionic surfactant, an amphoteric surfactant, a nonionic surfactant, a cationic surfactant, silicone oil and grease, an anti-dandruff antipruritic agent, a pearl agent, a nourishing agent, an antiseptic, a thickening agent, a pH regulator, essence and deionized water.

The anionic surfactant used in the shampoo comprises AB two types of ammonium lauryl sulfate and ammonium laureth sulfate which are matched to ensure that the shampoo has better foaming and cleaning performances, wherein the ammonium lauryl sulfate is an anionic surfactant with a carbon chain of 12, can form large flash bubbles, has high foaming speed but poor foam durability, and plays roles in generating foam and emulsifying in a shampoo system; the ammonium laureth sulfate belongs to alkyl ether sulfate, in order to connect alcohol ether group on the alkyl, improve the hydrophilicity, the better the hydrophilicity, the faster the foaming, the more stable the foam formed, through compounding two anionic surfactants show more excellent bubble nature and stability than single anionic surfactant.

The amphoteric surfactant is cocoamidopropyl hydroxysulfobetaine, has an anionic hydrophilic group and a cationic hydrophilic group on the structure, the hydrophilic group is positively charged in a strong acid system to present the characteristics of the cationic surfactant, the hydrophilic group is negatively charged in a strong alkali system to present the characteristics of the anionic surfactant, neutrality can be simultaneously presented in a neutral system, and the amphoteric surfactant is an auxiliary surfactant in shampoo and mainly plays roles in stabilizing and thickening, can obviously reduce the using amount of the anionic surfactant, reduces the irritation and toxicity of the shampoo, and thus maintains high foamability and stability.

The nonionic surfactant is C8-C14 alkyl polyglycoside, the alkyl polyglycoside is a green environment-friendly surfactant, is derived from plants and is easy to degrade, particularly the alkyl carbon chain with the carbon chain number of C8-C14 has the advantages of being mild, strong in emulsifying capacity and rich in foam, can improve the skin feeling of a product after use by being compounded with a common anionic surfactant, can greatly reduce irritation, and has the effects of stabilizing foam, thickening and the like.

Cationic surfactant: the technical personnel in the field all guide, the shampoo in the market at present mainly takes anionic surfactant as the main component, cationic surfactant is only used in the shampoo directly, the anionic surfactant and the cationic surfactant are mainly used in the shampoo to react, so that a water-insoluble substance is formed, but generally, the hair surface of people is negatively charged, and the positive charge of the cationic surfactant is combined with the negative charge of the hair, so that a lubricating film is formed on the hair surface, a lubricating effect is achieved, and the rough feeling of the hair is reduced. Therefore, on the premise of not forming insoluble substances, part of cationic surfactant can be properly added for forming a smooth and bright film on the hair surface and improving the glossiness of the hair, and in order to prevent direct reaction between anions and cations, the dosage, the molecular weight and the substitution degree of the cationic surfactant need to be clearly limited, the cationic surfactant used in the invention is polyquaternium-10, and the viscosity is JR-400 of 130 ten thousand cPs.

Silicone oil grease: the cationic surfactant can be preferentially adsorbed to the hair surface, and the silicone oil can be attached to polyquaternium-10 to increase the deposition on the hair during the hair washing process, so that a hydrophobic protective film is formed on the hair surface, and the hair is back to be smooth and bright and is easy to comb.

Removing dandruff and relieving itching: the zinc pyrithione and ZPT have obvious anti-dandruff effect, but the requirements are strict when in use: (1) the formula can not contain strong oxidant and strong reducing agent, (2) the water can not contain metal ions such as iron ions and copper ions, (3) the system can not use chelating agent such as EDTA and the like; (4) the purity of the shampoo is ensured, and particularly, the shampoo contains a large amount of toxic metal impurities, and the problems can cause that zinc pyrithione substances are converted into substances without sterilization effect or the shampoo can not reach the market use standard.

Pearling agent and essence: improve the appearance, obtain the shiny pearl effect, the essence is to produce the pleasant taste.

Nourishing agent: the amino acid and the amino acid are similar to proteins of hair, have good affinity, and can effectively permeate into the hair to repair the damaged hair.

Preservative: the kasong can prevent bacteria or mould from breeding, particularly, the shampoo contains the main components of a surfactant and grease which are easy to breed and cause the reduction of the quality guarantee period, and the kasong is a common preservative.

Thickening agent: the most used thickener in shampoo is sodium chloride, anionic surfactant and auxiliary surfactant in the system can form micelle when in high concentration, because counter ions are adsorbed on polar groups of the surfactant to reduce repulsive force between polar groups with same charges, the surfactant can be further promoted to form micelle, the critical micelle concentration is reduced, so that micelle is formed, the viscosity of the system is improved, the sodium chloride is the most direct and effective method for improving the viscosity of the shampoo, the viscosity of the system is improved along with the addition amount of the sodium chloride in a certain addition range, but when the addition amount of the sodium chloride exceeds a certain amount, the formation of the system micelle is damaged, so that the system viscosity is collapsed, the sodium chloride is required to be added into the shampoo as the thickener, and the addition amount is 0.4-0.6 wt.%.

pH regulator: citric acid is adjusted to pH =6-7, and under the appropriate pH condition, the surfactant can play the most role, and the invention is 6-7, and the acid is neutral and is suitable for the weak acidity of hair and scalp.

For removing dandruff and relieving itching: zinc pyrithione is described in detail below:

firstly, preparing oxidized 2-chloropyridine by electrocatalytic oxidation, wherein the electrocatalytic principle may be as follows: under alkaline conditions, by passing oxygen to the diffusion layer side of the cathode compartment gas diffusion electrode, said oxygen passing through the gas diffusion electrode, with H obtained by cathodic electrolysis⁺Hydrogen peroxide is formed by reacting 2 electrons to obtain active hydrogen peroxide with the specific equation of O₂+2H⁺+2e^-→H₂O₂The nitrogen atom in the dichloropyridine molecule contains a pair of lone pair electrons, so that the electronegativity of the nitrogen atom in the dichloropyridine is larger, the dichloropyridine has strong electron-withdrawing property, the oxygen element is transferred to the nitrogen element after the hydrogen peroxide is contacted, namely the strong oxidizing property of the hydrogen peroxide molecule transfers the oxygen element to 2-chloropyridine to obtain oxidized 2-chloropyridine, and in addition, the invention does not exclude O₂+H⁺2e^-→HO₂The chloropyridine is directly oxidized, and the process is more direct and is matched with the high conversion efficiency of the invention.

Based on the above possible procedures, the present invention should provide a reliable high performance cathode gas diffusion electrode.

In the prior art, the input of the oxygen source mainly comprises two kinds, one kind is that dissolved oxygen is used as the oxygen source, in a simple way, oxygen is directly introduced into the cathode chamber, and because the solubility of the oxygen is small and the specific surface area of a common cathode is also particularly low, the reaction sites of the cathode are small, so that the double effects of small solubility and few active sites are finally known, and the yield of the active oxide product is low and the current effect is lower. The second method takes diffused oxygen as an oxygen source, namely, by introducing oxygen-containing gas into the gas chamber, the gas reaches the catalyst layer through the diffusion layer and reacts with the electrolyte in gaps of the catalyst layer, so that the contact area and reaction sites of the reaction are greatly increased. The gas diffusion electrode contains a large amount of gaps, so that reaction gas can be easily transferred to the catalytic layer, and meanwhile, a large amount of electrolyte is arranged on the catalytic layer, and the reaction can be rapidly carried out. Compared with the common electrode, the electrode preparation process is more conventional, the traditional diffusion layer, the metal mesh layer and the active layer are prepared, then the gas diffusion electrode is obtained by pressing, the specific surface area of the diffusion layer is improved by a pore-forming agent, the selective catalytic performance of the active layer is improved by the selection of a catalyst, and the active component adopted by the invention is Co-Ru.

In addition, the catholyte of the present invention is alkaline, and the hydrogen peroxide is HO under alkaline conditions₂ ^-In ionic form, due to HO₂ ^-Ions and cathodes are negatively charged and repel each other, thus hindering HO₂ ^-The ions are in contact with the cathode to accept electrons from the cathode for reduction, thereby enabling HO₂ ^-The ions are accumulated and then the catalytic process is accelerated by the oxidation effect of the chloropyridine.

Advantageous technical effects

1. According to the invention, 2-chloropyridine is catalytically oxidized by the cathode, the obtained 2-chloro-N-oxypyridine has high conversion rate, the redundant 2-chloropyridine is not required to be separated by distillation, and the preparation process is simple and feasible.

2. The time for catalytically oxidizing the 2-chloropyridine by the cathode is extremely short, so that high oxidation conversion rate can be realized within half an hour, and the efficiency is high.

3. Through setting up high active gas diffusion electrode, gas diffusion electrode can show the utilization ratio and the current efficiency that improve oxygen, and then improves oxidation efficiency.

4. The ZPT prepared by the invention has high purity, the heavy metal impurity content is lower than 3.5ppm, the yield is high, the ZPT can be directly used as an additive of shampoo, the curative effect for treating dandruff is quick, and the cure rate is high.

5. The shampoo prepared by the invention has the advantages of large foamability, fine foam, strong stability, low irritation, good dandruff-removing and itching-relieving effects, high corrosion resistance, long shelf life, and good luster, smoothness and fullness of hair after use;

drawings

FIG. 1 is a graph showing the bubble characteristics of example 2 of the present invention, comparative example 1 and comparative example 2.

FIG. 2 is a diagram showing a bubble test object in example 2, comparative example 1 and comparative example 2 of the present invention.

FIG. 3 is a graph showing stability test curves of example 2 of the present invention, comparative example 1 and comparative example 2.

FIG. 4 is a graph showing the anti-dandruff and anti-itching effects of the shampoo of example 2 of the present invention.

FIG. 5 is a graph showing the effect of removing dandruff and relieving itching of comparative example 3 of the present invention.

Detailed Description

The steps for making the ZPT used in examples 1-3 of the present invention are completely the same, all as follows:

(1) preparing oxidized 2-chloropyridine by electrocatalytic oxidation;

(a) arranging an electrolytic cell: the electrolytic cell is divided into an anode chamber and a cathode chamber by using a cation exchange membrane, wherein the anode is arranged in the anode chamber, the anode is a Ti/(Ru-Ir) Ox anode, the cathode chamber is provided with a gas diffusion electrode, and the gas diffusion electrode comprises a gas diffusion layer, a metal mesh layer and a catalyst layer, and the active component of the catalyst layer is Co-Ru.

(b) Introducing a mixed solution of sodium sulfate and sulfuric acid into the anode chamber as an anolyte, wherein the use amount of the sodium sulfate is 6wt.%, the pH value is 2.5, introducing a sodium hydroxide aqueous solution of 2-chloropyridine into the cathode chamber as a catholyte, the concentration of the 2-chloropyridine is 10wt.%, the pH value is 8.5, one side of the cathode chamber is provided with an oxygen chamber, and the gas in the oxygen chamber and the catholyte in the cathode chamber are separated by a gas diffusion electrode.

(c) Switching on power supply, introducing gas into the gas chamber, introducing anolyte and catholyte into the anode chamber and the cathode chamberCarrying out an electrolytic oxidation of 2-chloropyridine to obtain 2-chloro-N-oxopyridine, the gas in the gas chamber being 55vol.% O₂/N₂Mixed gas, parameters of the electrolytic oxidation: electrode current density 23mA/cm²Electrolysis time 20min, temperature 42.5^oC。

(2) Sodium sulfhydrylation of oxidized 2-chloropyridine: sodium sulfydryl in the step (2): preparing a mixed solution of a sodium hydrosulfide solution and a sodium hydroxide solution with the pH =9, wherein the molar ratio of the sodium hydrosulfide to the sodium hydroxide is 1:0.9, dropwise adding the oxidized 2-chloropyridine catholyte prepared in the step (1) into the mixed solution, carrying out heat preservation reaction at 55 ℃ for 1.5h, naturally cooling, adjusting the pH to 2.5 by using hydrochloric acid, carrying out reaction at normal temperature and pressure for 0.75h, adding the sodium hydroxide to adjust the pH =9.5, and carrying out reaction at normal temperature and pressure for 0.75h to obtain a pyrithione sodium salt solution.

(3) Complexing and synthesizing zinc pyrithione: adjusting pH of pyrithione sodium salt solution to 8.25, adding appropriate amount of ethanol, and adjusting pH to 62.5^oAdding ZnSO4 solution under C, reacting at 80 deg.C, maintaining the temperature for 1.25h, filtering, washing with hot water, 115^oAnd C, drying for 1.25h, and crushing to obtain zinc pyrithione, wherein the molar ratio of the zinc sulfate to the sodium pyrithione is 1: 1.75.

The preparation method of the gas diffusion electrode comprises the following steps:

(1) preparing a diffusion layer: uniformly mixing ammonium bicarbonate, 27.5wt.% of PTFE emulsion and glycerol aqueous solution to obtain suspension, then mixing the suspension on pretreated carbon nano tube powder to obtain paste, rolling and molding, then heating at 245 ℃ at 1 ℃/min in a muffle furnace, keeping the temperature for 35min, and naturally cooling to obtain a 275-micron diffusion layer, wherein the mass ratio of ammonium nitrate to PTFE emulsion to carbon nano tube powder is (15): (65): (55) the using amount of the glycerol aqueous solution is 1.75ml, and the volume ratio of the glycerol to the water is 1.75: 1.

(2) Pretreating the metal mesh layer: and (3) washing the foamed nickel by using 0.035M hydrochloric acid, acetone and deionized water in sequence, and then carrying out vacuum drying for 5.5h at 105 ℃ to obtain the metal mesh layer.

(3) Preparing a catalyst layer: dissolving cobalt chloride and triruthenium dodecacarbonyl in a glycerol aqueous solution, adding 25-30wt.% of PTFE emulsion, uniformly mixing to obtain a suspension, mixing the suspension on pretreated carbon nanotube powder to obtain a paste, rolling and molding, heating at 205 ℃ at 1 ℃/min in a muffle furnace, keeping the temperature for 65min, and naturally cooling to obtain a 275 mu m catalyst layer, wherein the volume ratio of glycerol to water in the glycerol aqueous solution is 1.75:1, and the molar ratio of cobalt to ruthenium is 2: (0.6) and the Co-Ru loading was 7 wt.%.

(4) Pressing: and stacking the diffusion layer, the metal mesh layer and the catalyst layer in sequence, and pressing by adopting pressure of 10-11Mpa and pressure maintaining for 18s to obtain the gas diffusion electrode.

And (3) analyzing the purity of the ZPT product, selecting the product with the purity of 99 percent, and testing heavy metals of the product with the time consumption of about 270 min:

wherein the iron is 0.3573ppm, the lead is 0.6827 ppm, the chromium is 0.9132 ppm, the copper is 0.4251 ppm and the nickel is 0.7843.5 ppm.

In the preparation and use process of the shampoo, the strong complexation of heavy metals enables excessive heavy metals to be easily generated in products, particularly in the process of preparing 2-chloro-N-oxypyridine by oxidizing 2-chloropyridine, a high-concentration heavy metal catalyst is required in the traditional hydrogen peroxide preparation process, the catalyst can obviously remain in the oxydol, and further a large amount of heavy metals are remained in the 2-chloro-N-oxypyridine, in contrast, the active components of the catalyst exist in a cathode after coating and roasting, the binding force is strong, and the active components cannot be oxidized, so that an electrolyte cannot be introduced, namely, the precious metals in the 2-chloro-N-oxypyridine are extremely small, and finally, the content of harmful precious metals in the ZPT is lower than 3.5 ppm. Preparing the obtained ZPT to obtain shampoo.

Example 1

A preparation method of a shampoo composition comprises the following steps:

(A) dispersing 5wt.% of ammonium lauryl sulfate, 13wt.% of ammonium laureth sulfate, 5wt.% of cocamidopropyl hydroxysultaine, 1wt.% of C8-C14 alkyl polyglycoside and 1wt.% of ethylene glycol monostearate in deionized water according to the mass ratio, heating and stirring uniformly, and keeping the constant temperature at 70 ℃.

(B) Dissolving 0.75 wt.% of polyquaternium-10 and 0.4wt.% of polydimethylsiloxane into deionized water according to the mass ratio, adding the deionized water into the solution obtained in the step (A), uniformly stirring, and cooling and keeping the temperature at 50 ℃.

(C) Dissolving 2wt.% of zinc pyrithione, 0.05 wt.% of kasong, 1wt.% of essence and 1wt.% of amino acid in deionized water according to the mass ratio, adding the solution into the solution obtained in the step (B), uniformly stirring, cooling, and keeping the temperature at 35 ℃.

(D) Adding a proper amount of sodium chloride into the solution obtained in the step (C) to adjust the viscosity to about 3000cP, adding citric acid to adjust the pH to 6, adding the rest of deionized water, and cooling to 25 DEG^oAnd C, stirring for 30 min.

Example 2

A preparation method of a shampoo composition comprises the following steps:

(A) dispersing 6wt.% of ammonium lauryl sulfate, 14.5wt.% of ammonium laureth sulfate, 5.5wt.% of cocamidopropyl hydroxysultaine, 1.25wt.% of C8-C14 alkyl polyglycoside and 1.1wt.% of ethylene glycol monostearate in deionized water according to the mass ratio, heating and stirring uniformly, and keeping the constant temperature of 72.5 ℃.

(B) Dissolving 1.1wt.% of polyquaternium-10 and 0.45 wt.% of polydimethylsiloxane into deionized water according to the mass ratio, adding the deionized water into the solution obtained in the step (A), uniformly stirring, and cooling and keeping the temperature at 52.5 ℃.

(C) Dissolving 3wt.% of zinc pyrithione, 0.075wt.% of kasong, 1.1wt.% of essence and 1.25wt.% of amino acid in deionized water according to the mass ratio, adding the solution into the solution obtained in the step (B), uniformly stirring, cooling and keeping the temperature at 37.5 ℃.

(D) Adding a proper amount of sodium chloride into the solution obtained in the step (C) to adjust the viscosity to about 3000cP, adding citric acid to adjust the pH to 6.5, and cooling to 25 ℃ with the balance being deionized water^oAnd C, stirring for 35 min.

Example 3

A preparation method of a shampoo composition comprises the following steps:

(A) dispersing 7wt.% of ammonium lauryl sulfate, 16wt.% of ammonium laureth sulfate, 6wt.% of cocamidopropyl hydroxysultaine, 1.5wt.% of C8-C14 alkyl polyglycoside and 1.2wt.% of ethylene glycol monostearate in deionized water according to the mass ratio, heating and stirring uniformly, and keeping the constant temperature at 75 ℃.

(B) Dissolving 1.5wt.% of polyquaternium-10 and 0.5wt.% of polydimethylsiloxane into deionized water according to the mass ratio, adding the deionized water into the solution obtained in the step (A), uniformly stirring, and cooling and keeping the temperature at 50-55 ℃.

(C) Dissolving 4wt.% of zinc pyrithione, 0.1 wt.% of kasong, 1.2wt.% of essence and 1.5wt.% of amino acid in deionized water according to the mass ratio, adding the mixture into the solution obtained in the step (B), uniformly stirring, cooling, and keeping the temperature at 35-40 ℃.

(D) Adding a proper amount of sodium chloride into the solution obtained in the step (C) to adjust the viscosity to about 3000cP, adding citric acid to adjust the pH to 6.8, and cooling to 25 ℃ with the balance being deionized water^oAnd C, stirring for 40 min.

Comparative example 1

A preparation method of a shampoo composition comprises the following steps:

(A) dispersing 20.5wt.% of ammonium lauryl sulfate, 5.5wt.% of cocamidopropyl hydroxysulfobetaine, 1.25wt.% of C8-C14 alkyl polyglycoside and 1.1wt.% of ethylene glycol monostearate in deionized water according to the mass ratio, heating and stirring uniformly, and keeping the constant temperature at 72.5 ℃.

Comparative example 2

A preparation method of a shampoo composition comprises the following steps:

(B) Dissolving 0.45 wt.% of polydimethylsiloxane into deionized water according to the mass ratio, adding the solution into the solution obtained in the step (A), uniformly stirring, cooling, and keeping the temperature at 52.5 ℃.

Wherein comparative example 1 does not contain ammonium laureth sulfate, and comparative example 2 does not contain polyquaternium-10.

Foaming and stability testing:

25ml of the shampoo prepared in example 2 and comparative examples 1-2, using 25ml of deionized water, was placed in a graduated cylinder and stirred at high speed for 1min to determine the foam volume V1 using the foamability equation: (V1-50)/50 x 100%, the foaming was calculated and the foam volume height was measured every 10min for the measuring cylinder tested above under standing conditions.

The results of the figures are shown in figure 1, the foamability of example 2 is 415%, the foamability of comparative example 1 is 279%, and the foamability of the comparative example is 388%, and the specific experiment is shown in figure 2, wherein the shampoo of example 2 has more excellent foamability and fine foam, the effect of comparative example 2 is obviously better than that of comparative example 1, namely the key component of the shampoo is the anionic surfactant, the other components are auxiliary and improving effects, and the stability is shown in figure 3.

Comparative example 3

A preparation method of a shampoo composition comprises the following steps:

Wherein the experiment was performed with the ZPT synthesis method disclosed in CN 102702903A-ZPT obtained as prepared in example 14.

The purity of the ZPT test is 97.2% (not reaching 98.7% stated in most documents), and the heavy metal is tested: wherein, the contents of impurities of lead and chromium are obviously out of standard, wherein, the contents of iron are 9ppm, lead are 9ppm, chromium are 12 ppm, copper are 2ppm and nickel is 3 ppm.

The shampoo prepared in the example 2 and the shampoo prepared in the comparative example 3 are subjected to the scurf-removing and itching-relieving test, as is apparent from the accompanying drawings of fig. 4 and fig. 5, and it is clear from the test results of 7 days that the scurf-removing effect of the shampoo of the present invention is more excellent, stable scurf-removing can be realized within weeks, and the scurf-removing effect of the shampoo of the comparative example 3 is general, but the cleaning effect is not obviously different from that of the shampoo of the example 2.

Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. The preparation method of the shampoo composition is characterized by comprising the following steps:

(A) dispersing ammonium lauryl sulfate, ammonium laureth sulfate, cocamidopropyl hydroxysultaine, C8-C14 alkyl polyglycoside and ethylene glycol monostearate in deionized water according to the mass ratio, heating and stirring uniformly, keeping the constant temperature at 70-75 ℃,

(D) adding sodium chloride into the solution obtained in the step (C) to adjust the viscosity, adding citric acid to adjust the pH to 6-7, adding the rest of deionized water, and cooling to 25 DEG^oC, stirring for 30-40min,

the preparation method of the zinc pyrithione comprises the following steps:

(1) preparing 2-chloro-N-oxypyridine by electrocatalytic oxidation;

(2) sodium sulfydryl of 2-chloro-N-oxypyridine;

(3) complexing and synthesizing zinc pyrithione.

2. A process for the preparation of a shampoo composition according to claim 1, characterised in that the shampoo composition comprises the following components: 5-7wt.% of ammonium lauryl sulfate, 13-16wt.% of ammonium laureth sulfate, 5-6wt.% of cocamidopropyl hydroxysultaine, 1-1.5wt.% of alkylpolyglycoside having a carbon chain number of C8-C14, 100.75-1.5 wt.% of polyquaternium, 0.4-0.5 wt.% of polydimethylsiloxane, 2-4 wt.% of zinc pyrithione, 1-1.2wt.% of ethylene glycol monostearate, 0.05-0.1 wt.% of carson, 0.4-0.6 wt.% of sodium chloride, 1-1.5wt.% of amino acid; proper amount of citric acid and 1-1.2wt.% of essence.

3. A process for the preparation of a shampoo composition as claimed in claim 1 characterised in that the electrocatalytic oxidation to 2-chloro-N-oxopyridine step:

4. A process for the preparation of a shampoo composition as claimed in claim 3 characterised in that the gas diffusion electrode is prepared by:

5. The method for preparing a shampoo composition as defined in claim 1, wherein the step (2) comprises the step of sodium-sulfoniumthioate salt of 2-chloro-N-oxypyridine: preparing a mixed solution of a sodium hydrosulfide solution and a sodium hydroxide solution with the pH =8.5-9.5, wherein the molar ratio of the sodium hydrosulfide to the sodium hydroxide is 1 (0.85-1), dropwise adding the oxidized 2-chloropyridine catholyte prepared in the step (1) into the mixed solution, reacting at the temperature of 50-60 ℃ for 1-2h, naturally cooling, adjusting the pH to 2-3 by using hydrochloric acid, reacting at normal temperature and pressure for 0.5-1h, adding the sodium hydroxide to adjust the pH =9-10, and reacting at normal temperature and pressure for 0.5-1h to obtain the pyrithione sodium salt solution.

6. The method of preparing a shampoo composition according to claim 1, wherein the step (3) complex-synthesizes zinc pyrithione: adjusting pH of pyrithione sodium salt solution to 8-8.5, adding appropriate amount of ethanol, and adding water to obtain solution at 60-65%^oAdding ZnSO4 solution at 70-90 deg.C, reacting, maintaining for 1-1.5h, filtering, washing with hot water, 110-120-^oAnd C, drying for 1-1.5h, and crushing to obtain zinc pyrithione, wherein the molar ratio of the zinc sulfate to the sodium pyrithione is 1: 1.5-2.

7. The method of claim 1, wherein the zinc pyrithione produced by electrocatalysis has a purity of 97.5 to 99.3%, and wherein the zinc pyrithione has a purity of greater than 99% and has heavy metal impurities of less than 3.5ppm is selected.

8. The method of claim 1, wherein the oxidation of the 2-chloropyridine results in a conversion of 2-chloro-N-oxopyridine of greater than or equal to 98 wt.%.

9. The method for preparing a shampoo composition according to claim 1, wherein the amino acid is selected from one or more of glycine, glutamic acid, and lysine.

10. The method for preparing a shampoo composition as claimed in claim 1, wherein the viscosity of the shampoo is 2500-3500 cP.