Preparation method and application of polyglycerol methyl glucose fatty acid ester

Abstract

The invention discloses a preparation method and application of polyglycerol methyl glucose fatty acid ester, and belongs to the technical field of preparation of emulsifiers, polyglycerol, methyl glucose and fatty acid are added into a reaction kettle with a partition plate, a catalyst and an emulsifying aid are added into the reaction kettle, nitrogen replacement is performed for 3-5 times, vacuumizing is performed to-0.08 MPa, the temperature of a system is increased to 150-190 DEG C, stirring is performed for 3-5 times, and the polyglycerol methyl glucose fatty acid ester is obtained. The method comprises the following steps: adding polyglycerol methyl glucose fatty acid ester into a reaction kettle, keeping the pressure at-0.08 MPa, reacting for 3-6 hours, cooling to 90 DEG C or below when the acid value of a reaction system is tested to be less than or equal to 6.0 mgKOH / g, and filtering the obtained reaction liquid through a 500-mesh filter screen to obtain polyglycerol methyl glucose fatty acid ester; the reaction process for preparing the polyglycerol methyl glucose fatty acid ester does not need to use a solvent, the reaction control is simple and convenient, the expanded production is easy, and the polyglycerol methyl glucose fatty acid ester can be applied to daily chemical products such as cream and emulsion.

Description

Technical Field

[0001] The invention belongs to the technical field of emulsifier preparation, and specifically relates to a preparation method and application of polyglycerol methyl glucose fatty acid ester. Background Art

[0002] Emulsifier is a key component for mixing two immiscible liquids (such as oil and water) to form a uniform emulsion, and is widely used in food, cosmetics, pharmaceuticals and industrial fields. Polyglycerol-3 methyl glucose distearate is a good O / W emulsifier, which is widely used in daily chemicals (such as creams, lotions, etc.) because it does not contain PEG (polyethylene glycol) ingredients. However, its composition and preparation method have not been publicly reported at home and abroad. Therefore, the preparation method of polyglycerol methyl glucose fatty acid ester has become a current research focus. Summary of the invention

[0003] To solve the above problems, the purpose of the present invention is to provide a preparation method and application of polyglycerol methyl glucose fatty acid ester.

[0004] In order to achieve the above object, the present invention is implemented through the following technical solutions:

[0005] A method for preparing polyglycerol methyl glucose fatty acid ester comprises the following steps: adding polyglycerol, methyl glucose and fatty acid into a reaction kettle with a partition, adding a catalyst and an emulsifying aid thereto, replacing the reaction kettle with nitrogen for 3 to 5 times, evacuating the reaction kettle to -0.08 MPa, heating the system to 150 to 190° C., maintaining the pressure at -0.08 MPa for reaction for 3 to 6 hours, cooling the reaction system to below 90° C. when the acid value is ≤6.0 mgKOH / g, filtering the reaction solution through a 500-mesh filter to obtain polyglycerol methyl glucose fatty acid ester;

[0006] The catalyst is p-toluenesulfonic acid, sulfuric acid, potassium hydroxide, potassium carbonate or an activated clay-supported catalyst.

[0007] The activated clay-supported catalyst is prepared according to the following method:

[0008] In parts by weight, 1 part of alkaline inorganic matter is added to 20-30 parts of water, stirred and dispersed evenly, and then 4-6 parts of activated clay are added thereto, stirred and mixed for 3-5 hours, and then allowed to stand for 6-8 hours, and the supernatant is removed. The residue is dried at 110-120°C for 3-5 hours, ground into powder, sieved with a 100-mesh filter, and then heated to 800°C at 2°C / min in a muffle furnace, and maintained for 4-6 hours for calcination to obtain an activated clay-supported catalyst.

[0009] The alkaline inorganic substance is calcium oxide, sodium carbonate or potassium carbonate.

[0010] The mass ratio of the polyglycerol to methyl glucose is 100:5-30.

[0011] The added amount of the fatty acid is 1.7 to 2.5 times the total mass of the polyglycerol and the methyl glucose.

[0012] The fatty acid is a saturated fatty acid of C12 to C18.

[0013] When the catalyst is p-toluenesulfonic acid, sulfuric acid, potassium hydroxide or potassium carbonate, the amount of catalyst added is 0.3-1.5% of the total mass of polyglycerol, methyl glucose and fatty acids; when the catalyst is an activated clay-supported catalyst, the amount of catalyst added is 2-4% of the total mass of polyglycerol, methyl glucose and fatty acids.

[0014] The emulsifying aid is polyglyceryl-3 distearate.

[0015] The added amount of the emulsifying aid is 1-2% of the total mass of polyglycerol, methyl glucose and fatty acid.

[0016] Preferably, the mass ratio of the polyglycerol to methyl glucose is 100:5-15; the added amount of the fatty acid is 2.1-2.4 times the total mass of the polyglycerol and methyl glucose; and the fatty acid is stearic acid with a C16 / C18 mass ratio of 60 / 40 or 35 / 65.

[0017] Preferably, when the catalyst is p-toluenesulfonic acid, sulfuric acid, potassium hydroxide or potassium carbonate, the amount of catalyst added is 0.5-0.7% of the total mass of polyglycerol, methyl glucose and fatty acids; when the catalyst is an activated clay-supported catalyst, the amount of catalyst added is 3% of the total mass of polyglycerol, methyl glucose and fatty acids.

[0018] The invention also includes the application of polyglycerol methyl glucose fatty acid ester in cream and emulsion daily chemical products.

[0019] Compared with the prior art, the present invention has the following advantages:

[0020] The polyglycerol methyl glucose fatty acid ester of the present invention is reacted in a reactor with a partition, and the partition helps to break the phase separation and promote the full mixing of the reactants, thereby ensuring uniform mixing and facilitating the smooth progress of the reaction.

[0021] The polyglycerol methyl glucose fatty acid ester of the present invention adds polyglycerol-3 distearate as an emulsifying aid, thereby improving the problem of poor miscibility between reaction materials and improving compatibility, so that the reaction can be started at a relatively low temperature, and after the reaction is completed, there is no need to remove the catalyst, and the product quality is not affected. The activated clay-supported catalyst is used, which can not only exert its excellent catalytic performance, but also utilize the good decolorization function of the activated clay to make the color of the final product light. In this way, the dual effects of catalysis and decolorization can be achieved, and the purpose of one dose with two uses is achieved. In addition, the supported catalyst can be recycled after filtering, thereby reducing the production cost.

[0022] The invention does not require the use of solvents in the reaction process for preparing polyglycerol methyl glucose fatty acid esters, has simple reaction control, is easy to expand production, and can be applied to daily chemical products such as creams and lotions. DETAILED DESCRIPTION

[0023] In order to better understand the technical solution of the present invention, the above content of the present invention is further described in detail below through specific implementation methods in the form of embodiments, but this should not be understood as the scope of the above subject matter of the present invention being limited to the following examples. All technologies realized based on the above content of the present invention belong to the scope of the present invention.

[0024] The polyglycerol described in the present application meets the following requirements: chromaticity (APHA) ≤ 100, moisture (%) ≤ 2.0, conductivity (10% aqueous solution) ≤ 200 us / cm, hydroxyl value (mg KOH / g) 850-1300;

[0025] Polyglycerol-3 distearate meets the following requirements: acid value (mgKOH / g) ≤ 6.0, iodine value (gI 2 / 100g)≤3.0, saponification value (mgKOH / g)120~140.

[0026] Example 1

[0027] Add 0.1 kg of calcium oxide to 2 kg of water, stir and disperse evenly, then add 0.4 kg of activated clay, stir and mix for 3 hours, let stand for 6 hours, remove the supernatant, dry the residue at 110°C for 3 hours, grind it into powder, sieve it with a 100-mesh filter, and then heat it to 800°C in a muffle furnace at 2°C / min, keep it for 4 hours for calcination, and obtain an activated clay-supported catalyst.

[0028] Example 2

[0029] Add 0.1 kg of sodium carbonate to 2.5 kg of water, stir and disperse evenly, then add 0.5 kg of activated clay, stir and mix for 4 hours, let stand for 7 hours, remove the supernatant, dry the residue at 115°C for 4 hours, grind it into powder, sieve it with a 100-mesh filter, and then heat it to 800°C in a muffle furnace at 2°C / min, keep it for 5 hours for calcination, and obtain an activated clay-supported catalyst.

[0030] Example 3

[0031] Add 0.1 kg of potassium carbonate to 3 kg of water, stir and disperse evenly, then add 0.6 kg of activated clay, stir and mix for 5 hours, let stand for 8 hours, remove the supernatant, dry the residue at 120°C for 5 hours, grind it into powder, sieve it with a 100-mesh filter, and then heat it to 800°C at 2°C / min in a muffle furnace, keep it for 6 hours for calcination, and obtain an activated clay-supported catalyst.

[0032] Example 4

[0033] 100g polyglycerol, 10g methyl glucose and 230g stearic acid (C16 / C18 mass ratio is 60 / 40) are added to a reactor with a baffle, and then 10g active clay solid catalyst and 5g polyglycerol-3 distearate are added thereto. After nitrogen replacement 4 times, vacuum is evacuated to -0.08MPa, the system is heated to 165°C, and the pressure is kept at -0.08MPa for 4h. The acid value of the test reaction system is 2.0mgKOH / g, and the temperature is lowered to below 90°C. The obtained reaction solution is filtered through a 500-mesh filter, and after cooling, a white block of polyglycerol methyl glucose fatty acid ester is obtained. After testing, the product acid value is 2.0mgKOH / g, the saponification value is 123mgKOH / g, and the iodine value is 0.8g I 2 / 100g.

[0034] Example 5

[0035] 100g polyglycerol, 15g methyl glucose and 210g stearic acid (C16 / C18 mass ratio is 35 / 65) are added to a reactor with a baffle, and 13g active clay solid catalyst and 3.6g polyglycerol-3 distearate are added thereto. After nitrogen replacement 5 times, vacuum is evacuated to -0.08MPa, the system is heated to 175°C, and the pressure is kept at -0.08MPa for 5h. The acid value of the test reaction system is 3.5mgKOH / g, and the temperature is lowered to below 90°C. The obtained reaction solution is filtered through a 500-mesh filter, and after cooling, a white block of polyglycerol methyl glucose fatty acid ester is obtained. After testing, the product acid value is 3.5mgKOH / g, the saponification value is 125mgKOH / g, and the iodine value is 1.1g I 2 / 100g.

[0036] Example 6

[0037] 100g polyglycerol, 7g methyl glucose and 230g stearic acid (C16 / C18 mass ratio is 60 / 40) are added to a reactor with a baffle, and then 4.6g potassium carbonate and 4.5g polyglycerol-3 distearate are added thereto. After nitrogen replacement 3 times, vacuum is evacuated to -0.08MPa, the system is heated to 160°C, and the pressure is kept at -0.08MPa for 6h. The acid value of the test reaction system is 2.5mgKOH / g, and the temperature is lowered to below 90°C. The obtained reaction solution is filtered through a 500-mesh filter, and after cooling, a light yellow solid polyglycerol methyl glucose fatty acid ester is obtained. After testing, the product acid value is 2.5mgKOH / g, the saponification value is 132mgKOH / g, and the iodine value is 0.9g I 2 / 100g.

[0038] Example 7

[0039] 100g polyglycerol, 12g methyl glucose and 240g stearic acid (C16 / C18 mass ratio is 35 / 65) are added to a reactor with a baffle, and 5g sulfuric acid and 3.6g polyglycerol-3 distearate are added thereto. After nitrogen replacement 4 times, vacuum is evacuated to -0.08MPa, the system is heated to 185°C, and the pressure is kept at -0.08MPa for 5h. The acid value of the test reaction system is 3.0mgKOH / g, and the temperature is lowered to below 90°C. The obtained reaction solution is filtered through a 500-mesh filter, and after cooling, a light yellow solid polyglycerol methyl glucose fatty acid ester is obtained. After testing, the product acid value is 3.0mgKOH / g, the saponification value is 127mgKOH / g, and the iodine value is 0.9g I 2 / 100g.

[0040] Example 8

[0041] 100g polyglycerol, 8g methyl glucose and 225g stearic acid (C16 / C18 mass ratio is 60 / 40) are added to a reactor with a baffle, and then 4.5g potassium carbonate and 4g polyglycerol-3 distearate are added thereto. After nitrogen replacement 5 times, vacuum is evacuated to -0.08MPa, the system is heated to 170°C, and the pressure is kept at -0.08MPa for 4.5h. The acid value of the test reaction system is 2.0mgKOH / g, and the temperature is lowered to below 90°C. The obtained reaction solution is filtered through a 500-mesh filter, and after cooling, a light yellow solid polyglycerol methyl glucose fatty acid ester is obtained. After testing, the product acid value is 2.0mgKOH / g, the saponification value is 135mgKOH / g, and the iodine value is 0.8g I 2 / 100g.

[0042] Example 9

[0043] 100g polyglycerol, 10g methyl glucose and 220g stearic acid (C16 / C18 mass ratio is 60 / 40) are added to a reactor with a baffle, and then 5g p-toluenesulfonic acid and 4.5g polyglycerol-3 distearate are added thereto. After nitrogen replacement 4 times, vacuum is evacuated to -0.08MPa, the system is heated to 150°C, and the pressure is kept at -0.08MPa for 4h. The acid value of the test reaction system is 2.1mgKOH / g, and the temperature is lowered to below 90°C. The obtained reaction solution is filtered through a 500-mesh filter, and after cooling, a light yellow solid polyglycerol methyl glucose fatty acid ester is obtained. After testing, the product acid value is 2.1mgKOH / g, the saponification value is 122mgKOH / g, and the iodine value is 1.2g I 2 / 100g.

[0044] Example 10

[0045] 100g polyglycerol, 30g methyl glucose and 325g stearic acid (C16 / C18 mass ratio is 60 / 40) are added to a reactor with a baffle, and then 1.4g potassium hydroxide and 4.6g polyglycerol-3 distearate are added thereto. After nitrogen replacement 3 times, vacuum is evacuated to -0.08MPa, the system is heated to 190°C, and the pressure is kept at -0.08MPa for 6h. The acid value of the test reaction system is 2.8mgKOH / g, and the temperature is lowered to below 90°C. The obtained reaction solution is filtered through a 500-mesh filter, and after cooling, a light yellow solid polyglycerol methyl glucose fatty acid ester is obtained. After testing, the product acid value is 2.8mgKOH / g, the saponification value is 135mgKOH / g, and the iodine value is 1.3g I 2 / 100g.

[0046] Embodiment 11

[0047] 100g polyglycerol, 11g methyl glucose and 230g stearic acid (C16 / C18 mass ratio is 35 / 65) are added to a reactor with a baffle, and then 4g potassium carbonate and 3.5g polyglycerol-3 distearate are added thereto. After nitrogen replacement 4 times, vacuum is evacuated to -0.08MPa, the system is heated to 160°C, and the pressure is kept at -0.08MPa for 6h. The acid value of the test reaction system is 2.6mgKOH / g, and the temperature is lowered to below 90°C. The obtained reaction solution is filtered through a 500-mesh filter, and after cooling, a light yellow solid polyglycerol methyl glucose fatty acid ester is obtained. After testing, the product acid value is 2.6mgKOH / g, the saponification value is 132mgKOH / g, and the iodine value is 1.1g I 2 / 100g.

[0048] Example 12

[0049] The activated clay-supported catalyst recovered in Example 4 was used as a new catalyst, and the experiment was carried out according to the experimental conditions in Example 4 to obtain a white block of polyglycerol methyl glucose fatty acid ester; after the recovered activated clay-supported catalyst was repeatedly used for 3 times, the efficiency of the activated clay-supported catalyst was still good, and under the same experimental conditions, a qualified product could still be obtained. After testing, the product acid value was 2.9 mgKOH / g, the saponification value was 122 mgKOH / g, and the iodine value was 1.1 g I 2 / 100g. This indicates that the activated clay-supported catalyst has good recycling performance.

[0050] Comparative Example 1

[0051] 100g polyglycerol, 5g methyl glucose and 180g stearic acid (C16 / C18 mass ratio is 60 / 40) were added to a reactor with a baffle. After nitrogen replacement 4 times, the system was evacuated to -0.08MPa, the temperature was raised to 180°C, and the pressure was kept at -0.08MPa for 6h. Since no catalyst and emulsifier were added, the acid value of the reaction system was 17mgKOH / g. After testing, the acid value of the product was 17mgKOH / g, the saponification value was 137mgKOH / g, and the iodine value was 1.1g I 2 / 100g.

[0052] Comparative Example 2

[0053] 100g polyglycerol, 35g methyl glucose and 250g stearic acid (C16 / C18 mass ratio is 60 / 40) were added to a reactor with a baffle, and then 4g potassium carbonate was added thereto. After nitrogen replacement 4 times, the system was evacuated to -0.08MPa, and the system was heated to 180°C and the pressure was kept at -0.08MPa for 6h. Due to the excessive addition of methyl glucose, the acid value of the reaction system was 19mgKOH / g. After testing, the acid value of the product was 19mgKOH / g, the saponification value was 140mgKOH / g, and the iodine value was 1.1g I 2 / 100g.

[0054] Comparative Example 3

[0055] 100g polyglycerol, 20g methyl glucose and 210g stearic acid (C16 / C18 mass ratio is 35 / 65) are added to a reactor with a baffle, and then 3g sulfuric acid is added thereto. After nitrogen replacement 4 times, the system is evacuated to -0.08MPa, the system is heated to 170°C, and the pressure is maintained at -0.08MPa for 6h. Since no emulsifier is added, the acid value of the reaction system is 13mgKOH / g. After testing, the acid value of the product is 13mgKOH / g, the saponification value is 138mgKOH / g, and the iodine value is 0.9g I 2 / 100g.

[0056] It can be seen from the above results that the acid values ​​of the products prepared in Comparative Examples 1 to 3 all exceed 12 mgKOH / g, indicating that a lot of fatty acids in the products do not participate in the esterification reaction and a lot of them remain, thus affecting the performance of the products.

[0057] Performance Testing

[0058] The polyglycerol methyl glucose fatty acid esters obtained in Examples 4 to 11 and Comparative Examples 1 to 3 were respectively used as emulsifiers to prepare creams according to the formula in Table 1, and the specific steps were as follows:

[0059] 1) Water phase: Mix the water phase and water-soluble ingredients (such as glycerin), heat to 65°C while stirring, and ensure that all ingredients are completely dissolved; Oil phase: Mix the oil phase ingredients (such as fatty acids, emulsifiers, etc.), heat to 65°C while stirring, and ensure that all oils are completely melted;

[0060] 2) adding the oil phase heated to 65° C. to the water phase at 65° C. and stirring to obtain a crude emulsion; homogenizing the crude emulsion with a homogenizer at 10,000 r / min for 5 minutes to obtain a uniform emulsion;

[0061] 3) heating the emulsion to 60° C., adding 0.15% of Carbopol 940 thickener thereto to increase the viscosity of the emulsion and stabilize the emulsion system; during the cooling process, the emulsion is kept uniformly stirred to avoid emulsion stratification or particle aggregation. The viscosity of the emulsion will gradually increase as the temperature decreases, and finally a cream with a paste-like texture is formed;

[0062] 4) When the emulsion cools to 35-40°C, add flavors, pigments, etc. Adding them at this time can avoid the impact of high temperature on these ingredients. Finally, add the neutralizer and adjust the pH of the cream to 6.5.

[0063] Table 1 Formula of the prepared cream

[0064]

[0065]

[0066] The creams prepared in Examples 4 to 11 and Comparative Examples 1 to 3 were subjected to performance tests respectively, so as to evaluate the performance of emulsifiers prepared by different methods.

[0067] Stability test method: store the cream at 45°C for 1 month and observe whether it has stratification, precipitation or other physical changes; Texture: tested by manual application and subjective feelings of users;

[0068] Moisturizing effect test method: Apply the sample on the skin of volunteers and use a corneometer to measure the change in moisturizing after 8 hours;

[0069] Thermal stability test method: the sample is cycled between -25℃ and 50℃ for multiple times to observe whether stratification, precipitation or other changes occur; Usage test method: the finished product is applied to the skin of volunteers and evaluated through subjective surveys of volunteers and objective measurements of skin conditions;

[0070] Skin irritation test method: Apply the finished product on the skin of volunteers to observe whether there are adverse skin reactions such as erythema and scaling. The test results are shown in Table 2.

[0071] Table 2 Cream performance test results

[0072]

[0073]

[0074] It can be seen from the results in Table 2 that the cream prepared by using the polyglycerol methyl glucose fatty acid ester prepared by the present invention is excellent in moisturizing, skin absorbability and skin irritation compared with the comparative example. At the same time, these formulas show good adaptability in different usage scenarios, especially the stability under high temperature and freezing conditions is more outstanding, indicating that the polyglycerol methyl glucose fatty acid ester prepared by the present invention has a good application in daily chemical products such as creams and lotions.

[0075] Although the above describes the specific implementation methods of the present invention, it does not limit the scope of protection of the present invention. Based on the technical solution of the present invention, various modifications or variations that can be made by those skilled in the art without creative work are still within the scope of protection of the present invention.

Claims

1. A method for preparing polyglycerol methyl glucose fatty acid ester, characterized in that: Add polyglycerol, methyl glucose and fatty acid into a reaction kettle with a baffle, then add a catalyst and an emulsifying agent thereto, replace with nitrogen 3 to 5 times, evacuate to -0.08 MPa, heat the system to 150 to 190° C., keep the pressure at -0.08 MPa for 3 to 6 hours, test the acid value of the reaction system and find that it is ≤6.0 mgKOH / g, cool the temperature to below 90° C., filter the reaction solution through a 500-mesh filter to obtain polyglycerol methyl glucose fatty acid ester; The catalyst is p-toluenesulfonic acid, sulfuric acid, potassium hydroxide, potassium carbonate or an activated clay-supported catalyst.

2. The method for preparing polyglycerol methyl glucose fatty acid ester according to claim 1, wherein: The activated clay-supported catalyst is prepared according to the following method: In parts by weight, 1 part of alkaline inorganic matter is added to 20-30 parts of water, stirred and dispersed evenly, and then 4-6 parts of activated clay are added thereto, stirred and mixed for 3-5 hours, and then allowed to stand for 6-8 hours, and the supernatant is removed. The residue is dried at 110-120°C for 3-5 hours, ground into powder, sieved with a 100-mesh filter, and then heated to 800°C at 2°C / min in a muffle furnace, and maintained for 4-6 hours for calcination to obtain an activated clay-supported catalyst.

3. The method for preparing polyglycerol methyl glucose fatty acid ester according to claim 2, wherein: The alkaline inorganic substance is calcium oxide, sodium carbonate or potassium carbonate.

4. The method for preparing polyglycerol methyl glucose fatty acid ester according to claim 1, wherein: The mass ratio of the polyglycerol to methyl glucose is 100:5-30; the added amount of the fatty acid is 1.7-2.5 times the total mass of the polyglycerol and methyl glucose; and the fatty acid is a saturated fatty acid of C12-C18.

5. The method for preparing polyglycerol methyl glucose fatty acid ester according to claim 1, characterized in that: When the catalyst is p-toluenesulfonic acid, sulfuric acid, potassium hydroxide or potassium carbonate, the amount of catalyst added is 0.3-1.5% of the total mass of polyglycerol, methyl glucose and fatty acids; when the catalyst is an activated clay-supported catalyst, the amount of catalyst added is 2-4% of the total mass of polyglycerol, methyl glucose and fatty acids.

6. The method for preparing polyglycerol methyl glucose fatty acid ester according to claim 1, characterized in that: The emulsifying aid is polyglyceryl-3 distearate.

7. The method for preparing polyglycerol methyl glucose fatty acid ester according to claim 1, characterized in that: The added amount of the emulsifying aid is 1-2% of the total mass of polyglycerol, methyl glucose and fatty acid.

8. The method for preparing polyglycerol methyl glucose fatty acid ester according to claim 1, characterized in that: The mass ratio of the polyglycerol to methyl glucose is 100:5-15; the added amount of the fatty acid is 2.1-2.4 times the total mass of the polyglycerol and methyl glucose; the fatty acid is stearic acid with a C16 / C18 mass ratio of 60 / 40 or 35 / 65.

9. The method for preparing polyglycerol methyl glucose fatty acid ester according to claim 1, characterized in that: When the catalyst is p-toluenesulfonic acid, sulfuric acid, potassium hydroxide or potassium carbonate, the amount of catalyst added is 0.5-0.7% of the total mass of polyglycerol, methyl glucose and fatty acids; when the catalyst is an activated clay-supported catalyst, the amount of catalyst added is 3% of the total mass of polyglycerol, methyl glucose and fatty acids.

10. Use of the polyglycerol methyl glucose fatty acid ester according to claim 1 in creams and emulsions for daily use.

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