阅读说明：本技术 一种化妆品用尿囊素的制备方法 (Preparation method of allantoin for cosmetics ) 是由 黄惠民 马柏跃 徐跃邦 于 2020-12-30 设计创作，主要内容包括：本发明公开了一种化妆品用尿囊素的制备方法,通过将锰盐、铋盐、钴盐、钨酸钠和磷钨酸溶液进行混合得到反应产物,将反应产物进行煅烧得到二氧化锰基复合物,将二氧化锰基复合物与硫酸溶液进行接触反应,制得二氧化锰基复合物/硫酸组合物,接着将乙醛酸和尿素混合,加入所述二氧化锰基复合物/硫酸组合物作为催化剂进行缩合反应,制得尿囊素。该制备方法可以提高尿囊素的产率。(The invention discloses a preparation method of allantoin for cosmetics, which comprises the steps of mixing manganese salt, bismuth salt, cobalt salt, sodium tungstate and phosphotungstic acid solution to obtain a reaction product, calcining the reaction product to obtain a manganese dioxide-based compound, carrying out contact reaction on the manganese dioxide-based compound and sulfuric acid solution to obtain a manganese dioxide-based compound/sulfuric acid composition, mixing glyoxylic acid and urea, adding the manganese dioxide-based compound/sulfuric acid composition as a catalyst to carry out condensation reaction, and obtaining the allantoin. The preparation method can improve allantoin yield.)

1. A preparation method of allantoin for cosmetics is characterized in that: the preparation method comprises the following preparation steps:

1) mixing manganese salt, bismuth salt, cobalt salt, sodium tungstate and phosphotungstic acid solution, adding alkali into the system, carrying out ultrasonic oscillation, filtering after the reaction is finished, taking a filter cake, and finally drying to obtain a reaction product;

2) calcining the reaction product obtained in the step 1) to obtain a manganese dioxide-based compound;

3) carrying out contact reaction on the manganese dioxide-based compound in the step 2) and a sulfuric acid solution, wherein the weight ratio of the manganese dioxide-based compound to the sulfuric acid solution is 12:30-45, the pH value of the sulfuric acid solution is 3-5, and filtering to obtain a filter cake after the reaction is finished so as to obtain a manganese dioxide-based compound/sulfuric acid composition;

4) the method comprises the steps of carrying out oxidation reaction on glyoxal and nitric acid to obtain glyoxylic acid, mixing the glyoxylic acid and urea, adding the manganese dioxide-based compound/sulfuric acid composition as a catalyst to carry out condensation reaction to obtain allantoin, wherein the molar ratio of the glyoxylic acid to the urea to the manganese dioxide-based compound/sulfuric acid composition is 1:4-7:0.008-0.012, the condensation reaction temperature is 68-80 ℃, and the reaction time is 4-6 hours.

2. A process for producing allantoin for cosmetics according to claim 1, wherein: the weight ratio of the manganese salt, the bismuth salt, the cobalt salt, the sodium tungstate, the phosphotungstic acid and the alkali is 10: 0.2-0.5:1-1.5: 6-15: 3-6:18-28.

3. A process for producing allantoin for cosmetics according to claim 1, wherein: in the step 1), the mixing temperature is 18-30 ℃, and the mixing time is 25-45 min.

4. A process for producing allantoin for cosmetics according to claim 1, wherein: in the step 1), the oscillation temperature is 20-30 ℃, the oscillation time is 3-7h, and the ultrasonic frequency is 30-40 kHz.

5. A process for producing allantoin for cosmetics according to claim 1, wherein: in the step 1), the drying temperature is 110-125 ℃, and the drying time is 30-40 h.

6. A process for producing allantoin for cosmetics according to claim 1, wherein: in the step 1), the manganese salt is at least one of manganese chloride, manganese sulfate, manganese acetate and manganese nitrate, the bismuth salt is at least one of bismuth laurate, bismuth isooctanoate and bismuth naphthenate, and the cobalt salt is at least one of cobalt naphthenate, cobalt stearate, cobalt neodecanoate and cobalt boroacylate.

7. A process for producing allantoin for cosmetics according to claim 1, wherein: in the step 2), the calcination process is to heat up from 18 ℃ to 30 ℃ at 1.2-1.6 ℃/min to 250 ℃ at 180 ℃ and preserve heat for 25-35min, and then heat up from 0.5-1.4 ℃/min to 400 ℃ at 350 ℃ and preserve heat for 1.5-3 h.

Technical Field

The invention relates to the field of allantoin synthesis, in particular to a preparation method of allantoin for cosmetics.

Background

Allantoin, also known as ureido-acetic lactam, ureido-hydantoin, uretidiodione and glyoxylurea, is an organic fine chemical and one of important deep-processing products of urea, and is widely applied to the aspects of medicines, cosmetics and agriculture. Allantoin can be directly used as cosmetic raw material, and skin care product containing 0.5% allantoin can significantly improve water loss of skin and reduce red swelling. Allantoin is an amphoteric compound, and can be mixed with alcohol-soluble aluminum chlorohydroxyacetin, allantoin polygalacturonic acid, allantoin protein, allantoin racemic panol, etc. to form metal salt or addition product. They not only retain the properties of allantoin itself, but also do not lose the original properties of the adduct, and are therefore widely used as additives for cosmetics, such as beauty creams, freckle creams, shampoos, soaps, toothpaste, lipsticks, and the like. They have effects of softening keratin, preventing hair from splitting, preventing hair from breaking, lubricating, protecting tissue, repairing, hydrophilizing, absorbing water, and preventing water loss, and have good skin caring and repairing effects.

Disclosure of Invention

The invention provides a preparation method of allantoin for cosmetics, aiming at solving the problems.

The invention adopts the following technical scheme:

a preparation method of allantoin for cosmetics comprises the following preparation steps:

1) mixing manganese salt, bismuth salt, cobalt salt, sodium tungstate and phosphotungstic acid solution, adding alkali into the system, carrying out ultrasonic oscillation, filtering after the reaction is finished, taking a filter cake, and finally drying to obtain a reaction product;

2) calcining the reaction product obtained in the step 1) to obtain a manganese dioxide-based compound;

3) carrying out contact reaction on the manganese dioxide-based compound in the step 2) and a sulfuric acid solution, wherein the weight ratio of the manganese dioxide-based compound to the sulfuric acid solution is 12:30-45, the pH value of the sulfuric acid solution is 3-5, and filtering to obtain a filter cake after the reaction is finished so as to obtain a manganese dioxide-based compound/sulfuric acid composition;

4) the method comprises the steps of carrying out oxidation reaction on glyoxal and nitric acid to obtain glyoxylic acid, mixing the glyoxylic acid and urea, adding the manganese dioxide-based compound/sulfuric acid composition as a catalyst to carry out condensation reaction to obtain allantoin, wherein the molar ratio of the glyoxylic acid to the urea to the manganese dioxide-based compound/sulfuric acid composition is 1:4-7:0.008-0.012, the condensation reaction temperature is 68-80 ℃, and the reaction time is 4-6 hours.

As a preferable aspect of the present invention, the present invention is characterized in that: the weight ratio of the manganese salt, the bismuth salt, the cobalt salt, the sodium tungstate, the phosphotungstic acid and the alkali is 10: 0.2-0.5:1-1.5: 6-15: 3-6:18-28.

As a preferred technical scheme of the invention, in the step 1), the mixing temperature is 18-30 ℃, and the mixing time is 25-45 min.

As a preferred technical scheme of the invention, in the step 1), the oscillation temperature is 20-30 ℃, the oscillation time is 3-7h, and the ultrasonic frequency is 30-40 kHz.

As a preferred technical scheme of the invention, in the step 1), the drying temperature is 110-125 ℃, and the drying time is 30-40 h.

As a preferable technical solution of the present invention, in step 1), the manganese salt is at least one of manganese chloride, manganese sulfate, manganese acetate and manganese nitrate, the bismuth salt is at least one of bismuth laurate, bismuth isooctanoate and bismuth naphthenate, and the cobalt salt is at least one of cobalt naphthenate, cobalt stearate, cobalt neodecanoate and cobalt boroacylate.

As a preferred technical scheme of the invention, in the step 2), the calcination process is to heat up from 18 ℃ to 30 ℃ to 250 ℃ at 1.2-1.6 ℃/min and preserve heat for 25-35min, then to heat up to 400 ℃ at 0.5-1.4 ℃/min and preserve heat for 1.5-3 h.

The invention has the beneficial effects that:

according to the invention, sodium tungstate is used as a template, manganese salt, bismuth salt, cobalt salt and alkali are subjected to contact reaction to generate precipitates, then the template is removed by calcination to obtain a manganese dioxide-based compound, and finally the manganese dioxide-based compound and sulfuric acid are combined to obtain a composition, wherein the composition has excellent catalytic efficiency on allantoin, so that the yield of the allantoin is improved.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

A preparation method of allantoin for cosmetics comprises the following preparation steps:

1) mixing manganese salt, bismuth salt, cobalt salt, sodium tungstate and phosphotungstic acid solution, adding alkali into the system, carrying out ultrasonic oscillation, filtering after the reaction is finished, taking a filter cake, and finally drying to obtain a reaction product;

2) calcining the reaction product obtained in the step 1) to obtain a manganese dioxide-based compound;

3) carrying out contact reaction on the manganese dioxide-based compound in the step 2) and a sulfuric acid solution, wherein the weight ratio of the manganese dioxide-based compound to the sulfuric acid solution is 12:30, the pH value of the sulfuric acid solution is 3, and filtering to obtain a filter cake after the reaction is finished so as to obtain a manganese dioxide-based compound/sulfuric acid composition;

4) the method comprises the steps of carrying out oxidation reaction on glyoxal and nitric acid to obtain glyoxylic acid, then mixing the glyoxylic acid and urea, adding the manganese dioxide-based compound/sulfuric acid composition as a catalyst to carry out condensation reaction to obtain the allantoin, wherein the molar ratio of the glyoxylic acid to the urea to the manganese dioxide-based compound/sulfuric acid composition is 1:4:0.008, the condensation reaction temperature is 68 ℃, and the reaction time is 4 hours.

Further, the weight ratio of the manganese salt, the bismuth salt, the cobalt salt, the sodium tungstate, the phosphotungstic acid and the alkali is 10: 0.2:1: 6: 3:18.

Further, in step 1), the temperature of the mixing is 18 ℃ and the mixing time is 25 min.

Further, in the step 1), the oscillation temperature is 20 ℃, the oscillation time is 3h, and the ultrasonic frequency is 30-40 kHz.

Further, in the step 1), the drying temperature is 110 ℃, and the drying time is 30 h.

Further, in the step 1), the manganese salt is at least one of manganese chloride, manganese sulfate, manganese acetate and manganese nitrate, the bismuth salt is at least one of bismuth laurate, bismuth isooctanoate and bismuth naphthenate, and the cobalt salt is at least one of cobalt naphthenate, cobalt stearate, cobalt neodecanoate and cobalt boroacylate.

Further, in the step 2), the calcination process is to heat up to 180-DEG C from 18-30 ℃ at 1.2-1.6 ℃/min and preserve heat for 25min, and then heat up to 350 ℃ at 0.5-1.4 ℃/min and preserve heat for 1.5 h.

Example 2

A preparation method of allantoin for cosmetics comprises the following preparation steps:

1) mixing manganese salt, bismuth salt, cobalt salt, sodium tungstate and phosphotungstic acid solution, adding alkali into the system, carrying out ultrasonic oscillation, filtering after the reaction is finished, taking a filter cake, and finally drying to obtain a reaction product;

2) calcining the reaction product obtained in the step 1) to obtain a manganese dioxide-based compound;

3) carrying out contact reaction on the manganese dioxide-based compound in the step 2) and a sulfuric acid solution, wherein the weight ratio of the manganese dioxide-based compound to the sulfuric acid solution is 12:40, the pH value of the sulfuric acid solution is 4, and filtering to obtain a filter cake after the reaction is finished so as to obtain a manganese dioxide-based compound/sulfuric acid composition;

4) the method comprises the steps of carrying out oxidation reaction on glyoxal and nitric acid to obtain glyoxylic acid, then mixing the glyoxylic acid and urea, adding the manganese dioxide-based compound/sulfuric acid composition as a catalyst to carry out condensation reaction to obtain the allantoin, wherein the molar ratio of the glyoxylic acid to the urea to the manganese dioxide-based compound/sulfuric acid composition is 1:5.5:0.01, the condensation reaction temperature is 75 ℃, and the reaction time is 5 hours.

Further, the weight ratio of the manganese salt, the bismuth salt, the cobalt salt, the sodium tungstate, the phosphotungstic acid and the alkali is 10: 0.4:1.3: 10: 4.5:25.

Further, in step 1), the mixing temperature is 25 ℃ and the mixing time is 35 min.

Further, in the step 1), the oscillation temperature is 25 ℃, the oscillation time is 5h, and the ultrasonic frequency is 30-40 kHz.

Further, in the step 1), the drying temperature is 120 ℃ and the drying time is 35 h.

Further, in the step 1), the manganese salt is at least one of manganese chloride, manganese sulfate, manganese acetate and manganese nitrate, the bismuth salt is at least one of bismuth laurate, bismuth isooctanoate and bismuth naphthenate, and the cobalt salt is at least one of cobalt naphthenate, cobalt stearate, cobalt neodecanoate and cobalt boroacylate.

Further, in the step 2), the calcining process is to heat up to 220 ℃ from 18 ℃ to 30 ℃ at a speed of 1.2-1.6 ℃/min and preserve heat for 30min, and then heat up to 380 ℃ at a speed of 0.5-1.4 ℃/min and preserve heat for 2 h.

Example 3

A preparation method of allantoin for cosmetics comprises the following preparation steps:

1) mixing manganese salt, bismuth salt, cobalt salt, sodium tungstate and phosphotungstic acid solution, adding alkali into the system, carrying out ultrasonic oscillation, filtering after the reaction is finished, taking a filter cake, and finally drying to obtain a reaction product;

2) calcining the reaction product obtained in the step 1) to obtain a manganese dioxide-based compound;

3) carrying out contact reaction on the manganese dioxide-based compound in the step 2) and a sulfuric acid solution, wherein the weight ratio of the manganese dioxide-based compound to the sulfuric acid solution is 12:45, the pH value of the sulfuric acid solution is 5, and filtering to obtain a filter cake after the reaction is finished so as to obtain a manganese dioxide-based compound/sulfuric acid composition;

4) the method comprises the steps of carrying out oxidation reaction on glyoxal and nitric acid to obtain glyoxylic acid, mixing the glyoxylic acid and urea, adding the manganese dioxide-based compound/sulfuric acid composition as a catalyst to carry out condensation reaction to obtain the allantoin, wherein the molar ratio of the glyoxylic acid to the urea to the manganese dioxide-based compound/sulfuric acid composition is 1:7:0.012, the condensation reaction temperature is 80 ℃, and the reaction time is 6 hours.

Further, the weight ratio of the manganese salt, the bismuth salt, the cobalt salt, the sodium tungstate, the phosphotungstic acid and the alkali is 10: 0.5:1.5: 15: 6:28.

Further, in step 1), the mixing temperature is 30 ℃ and the mixing time is 45 min.

Further, in the step 1), the oscillation temperature is 30 ℃, the oscillation time is 7h, and the ultrasonic frequency is 30-40 kHz.

Further, in the step 1), the drying temperature is 125 ℃ and the drying time is 40 h.

Further, in the step 1), the manganese salt is at least one of manganese chloride, manganese sulfate, manganese acetate and manganese nitrate, the bismuth salt is at least one of bismuth laurate, bismuth isooctanoate and bismuth naphthenate, and the cobalt salt is at least one of cobalt naphthenate, cobalt stearate, cobalt neodecanoate and cobalt boroacylate.

Further, in the step 2), the calcining process is to heat up to 250 ℃ from 18 ℃ to 30 ℃ at a speed of 1.2-1.6 ℃/min and preserve heat for 35min, and then heat up to 400 ℃ at a speed of 0.5-1.4 ℃/min and preserve heat for 3 h.

Finally, it should be noted that: these embodiments are merely illustrative of the present invention and do not limit the scope of the present invention. In addition, other variations and modifications will be apparent to persons skilled in the art based on the foregoing description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the scope of the invention.