VE microemulsion as well as preparation method and application thereof

Abstract

The invention discloses a VE microemulsion as well as a preparation method and application thereof, and the VE microemulsion comprises the following components in percentage by mass: 10%-20% of VE acetate, 10%-20% of an emulsifier with a low HLB (Hydrophile-Lipophile Balance) value, 20%-30% of an emulsifier with a high HLB value, 5%-10% of a co-emulsifier and the balance of water, the HLB value of the emulsifier with high HLB value is greater than 12, and the HLB value of the emulsifier with low HLB value is 1-5. The VE microemulsion can keep stable and transparent in a wide temperature range and a wide pH value range, and is suitable for preparing transparent beverages or oral liquid.

Description

Technical Field

[0001] The invention belongs to the field of vitamins, and specifically relates to a VE microemulsion and a preparation method and application thereof. Background Art

[0002] Vitamin E (VE) has the effect of delaying aging, mainly based on its antioxidant capacity. Vitamin E is one of the most important biological free radical scavengers and antioxidants in the body. As a fat-soluble vitamin, vitamin E is a chain-breaking antioxidant. Its main function is to block the reaction chain of fat oxidation and is the first line of defense against oxidation in the body. The antioxidant effect of vitamin E is located in the cell membrane, which can block the formation of peroxides in the cell membrane, protect the cell membrane from damage by oxygen free radicals, and thus delay the process of cell aging.

[0003] General vitamin E is a viscous liquid, insoluble in water, soluble in fat and organic solvents such as ethanol, stable to heat and weak acid, unstable to strong acid and alkali, and sensitive to oxygen. Since vitamin E is sensitive to oxygen and easily oxidized, it will slowly decompose in an oxygen-containing environment and lose its function.

[0004] And currently in many patent documents related to microemulsion, most of them are only dedicated to a specific oil-soluble product, and the oil loading has different ranges, and the preparation method of some microemulsion products is complicated, and it is necessary to obtain them by certain mechanical means, such as Chinese patent CN101259101B, the microemulsion prepared for DHA / ARA products, and it is also necessary to obtain it by high-pressure homogenization, the preparation method is complicated, and the final emulsion oil droplet size is in the micron level. And in the preparation of vitamin microemulsion, such as Chinese patent 200410006272.9, vitamins are emulsified by high-pressure homogenizer, which increases energy consumption and improves cost. Chinese patent 200910018210.2 uses a large amount of emulsifiers and co-emulsifiers in the preparation of vitamin self-microemulsion, and the final emulsion does not exceed 250,000 IU / g for the vitamin A loading of easy crystallization precipitation, indicating that this formula has limited loading for this easy crystallization oil-soluble product, and the patent is vague about transparency and the maximum temperature used.

[0005] The coenzyme Q10 nano-microcapsule emulsion disclosed in Chinese Patent No. 200710304523.5 also adopts a high-pressure homogenization method, and there is no clear description of the temperature stability range of the final product. In Chinese Patent No. 20091009001.9 on the coenzyme Q10 self-emulsifying composition, there is no specific mention of the appearance and stable temperature range of the emulsion.

[0006] The existing VE microemulsions are basically stable under specific conditions, and are mostly used in cosmetics and medicines, with their applications being greatly limited. Summary of the invention

[0007] The object of the present invention is to provide a VE microemulsion and a preparation method and application thereof. The VE microemulsion can remain stable and transparent in a wide temperature range and pH range and has a wide application range. The preparation method thereof is simple to operate and is energy-saving and environmentally friendly.

[0008] The technical solution of the present invention is as follows:

[0009] A VE microemulsion, measured by mass percentage, comprises the following components:

[0010]

[0011] The HLB value of the high HLB emulsifier is greater than 12, preferably 13-17; the HLB value of the low HLB emulsifier is 1-5.

[0012] The present invention improves the emulsification ability through the emulsifier compounding technology of low and high HLB values. On the one hand, when emulsifiers with different HLB values ​​are mixed and used, the emulsifier system will be adsorbed on the oil-water interface to form an emulsifier complex. The complex is tightly arranged in an orderly structure and has high strength, which can well prevent the oil phase from agglomerating.

[0013] Preferably, the low HLB emulsifier is selected from one or more of triglycerol polyricinoleate (HLB=2), triglycerol polyricinoleate (HLB=4), decaglycerol decaoleate (HLB=5), diglycerol dioleate (HLB=4.5), monoricinoleic acid glyceride (HLB=3), interesterified polyglycerol ricinoleate (HLB=2), oleic acid polyethylene glycol glyceride (HLB=2), triglycerol monooleate (HLB=5), triglycerol monoricinoleate (HLB=5), glyceryl monostearate (HLB=4), and glyceryl dioleate (HLB=2).

[0014] Preferably, the high HLB value emulsifier is selected from one or more of polyglycerol ester emulsifiers, fatty alcohol polyoxyethylene ether emulsifiers or sucrose ester emulsifiers. Further preferably, the polyglycerol ester emulsifier is selected from one or more of decaglycerol monooleate (HLB=13), decaglycerol monoricinoleate (HLB=13), polyglycerol-10-decanoate (HLB=16), decaglycerol monoricinoleate (HLB=13), polyglycerol-10-octanoate (HLB=17), decaglycerol monolaurate (HLB=15), decaglycerol monostearate (HLB=13), decaglycerol caprylic decanoate (HLB=16), decaglycerol oleate (HLB=16), polyglycerol caprylic decanoate (HLB=17);

[0015] The fatty alcohol polyoxyethylene ether emulsifier is selected from one or more of polyethylene glycol (PEG)-12-glyceryl laurate (HLB=14), caprylic acid capric acid polyethylene glycol glyceride (HLB=14), lauric acid polyethylene glycol glyceride (HLB=14), polyoxyethylene hydrogenated castor oil (HLB=16), Tween 80 (HLB=15), and Tween 60 (HLB=15);

[0016] The sucrose ester emulsifier is selected from one or more of sucrose fatty acid ester LWA-1570 (HLB=15) and sucrose fatty acid ester SE-15 (HLB=15).

[0017] Preferably, the co-emulsifier is selected from one or more of glycerol, sorbitol, ethanol, povidone K30, povidone K12, and polyethylene glycol PEG-400.

[0018] Preferably, the high HLB value emulsifier is selected from two or more of polyglycerol ester emulsifiers, fatty alcohol polyoxyethylene ether emulsifiers or sucrose ester emulsifiers; the low HLB value emulsifier is selected from two or more of triglycerol polyricinoleate, triglycerol polyricinoleate, decaglycerol decaoleate, diglycerol dioleate, monoricinoleic acid glyceride, transesterified polyglycerol ricinoleate, oleic acid polyethylene glycol glyceride, triglycerol monooleate, triglycerol monoricinoleate, monostearic acid glyceryl, and glyceryl dioleate.

[0019] As a further preference, the VE microemulsion comprises the following components by mass percentage:

[0020]

[0021] The present invention also provides a method for preparing the VE microemulsion, comprising the following steps:

[0022] (1) heating and stirring VE acetate to form an oil phase;

[0023] (2) adding the preheated low HLB value emulsifier and high HLB value emulsifier to the oil phase in step (1) in sequence;

[0024] (3) adding the preheated co-emulsifier to the emulsion in step (2) and stirring thoroughly;

[0025] (4) Under stirring conditions, water is added to the emulsion of step (3), first stirred at 20-30° C. for 5-10 min, and then kept at 90-120° C. for 20-60 min to obtain the VE microemulsion.

[0026] Preferably, in step (1), the temperature for heating and stirring to dissolve is 50 to 70° C., more preferably 60 to 70° C., and the time for heating and stirring is 5 to 10 min.

[0027] Preferably, in step (2), the preheating temperature of the low HLB value emulsifier and the high HLB value emulsifier is 50 to 70° C., more preferably 60 to 70° C.;

[0028] After adding one emulsifier each time, stir for 4 to 6 minutes before adding another emulsifier;

[0029] In step (3), the preheating temperature of the emulsifier is 50 to 70° C., more preferably 60 to 70° C., and the stirring time after the emulsifier is added is 10 to 15 minutes.

[0030] The present invention also provides an application of the VE microemulsion, wherein the VE microemulsion is used for preparing food, medicine or health care product.

[0031] Preferably, the VE microemulsion is used to prepare a transparent beverage or oral liquid.

[0032] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0033] (1) The raw and auxiliary materials used in the formula of the present invention meet the requirements of health food regulations, the preparation process is simple, and the required equipment is simple.

[0034] (2) The present invention adopts a compound of high HLB value and low HLB value polyglycerol ester emulsifiers to emulsify the oil-water system to form a VE microemulsion of a thermodynamically stable system. The microemulsion has a large microemulsion range and can remain in the form of a microemulsion after being diluted 1000 times in an aqueous solution. The VE microemulsion is clear and transparent in high and low temperatures, wide pH values, and high salt environments. It can remain clear and transparent without breaking after high-temperature sterilization, so it can be used in transparent beverages and oral liquids. The optimal VE particle size DV (90) can be detected to be between 20 and 60 nm, thereby improving bioavailability and greatly increasing the application range of VE in food and oral liquids.

[0035] (3) The preparation method of the VE microemulsion of the present invention is simple and does not require the use of special high-pressure homogenization equipment. DETAILED DESCRIPTION

[0036] The ratios or percentages mentioned in the following examples are all based on mass unless otherwise specified.

[0037] Example 1

[0038] Preheat 12 kg of VE oil in a 50°C water bath with magnetic stirring for 10 min;

[0039] Add 10 kg of diglycerol dioleate preheated to 50°C into the preheated VE oil and stir evenly in a 65°C water bath to form an oil phase;

[0040] Add 22 kg of polyglycerol monolaurate preheated to 50°C into the oil phase and stir in a 65°C water bath for 5 minutes until the mixture is uniform.

[0041] After the oil phase is evenly mixed, 8 kg of ethanol is added, and after magnetic stirring is used to evenly mix, 48 kg of water is added, and the mixture is stirred while adding water dropwise. After the addition is completed, the mixture is stirred at room temperature for 30 minutes, and finally, the mixture is kept warm at 100° C. for 30 minutes to obtain a uniform and transparent microemulsion.

[0042] Example 2

[0043] In substantially the same manner as in Example 1, a VE microemulsion was prepared according to the recipe shown in Table 1. The contents (mass %) of the components were based on the total amount of the VE microemulsion. The insulation temperature was varied within the range of 90°C to 120°C and the insulation time was varied within the range of 30 min to 60 min. The preparation conditions and the particle size DV(90) of the obtained microemulsion are shown in Table 1.

[0044] Table 1

[0045]

[0046] It can be seen from the data in the table that according to the formulations of Examples 1 and 2, a VE microemulsion can be obtained, and its particle size DV(90) is between 100 nm and 120 nm.

[0047] Example 3

[0048] Preheat 12 kg of VE oil in a 50°C water bath with magnetic stirring for 10 min;

[0049] 5 kg of glycerol dioleate and 5 kg of diglycerol dioleate preheated to 50°C were added to the preheated VE oil in sequence. Each time an emulsifier was added, it was stirred for 5 minutes before adding another emulsifier. The mixture was stirred evenly in a 65°C water bath to form an oil phase.

[0050] Add 10 kg of Tween 80 and 12.5 kg of polyglycerol monolaurate preheated to 50°C to the oil phase. Stir for 5 minutes before adding another emulsifier each time, and stir for 5 minutes in a 65°C water bath until the mixture is uniform.

[0051] After the oil phase is evenly mixed, 7.5 kg of glycerin is added, and after magnetic stirring is used to evenly mix, 48 kg of water is added, and the mixture is stirred while adding water dropwise. After the addition is completed, the mixture is stirred at room temperature for 30 minutes, and finally, the mixture is kept warm at 100° C. for 30 minutes to obtain a uniform and transparent microemulsion.

[0052] Embodiment 4-5

[0053] In substantially the same manner as in Example 3, a VE microemulsion was prepared according to the recipe shown in Table 2. The contents (mass %) of the components were based on the total amount of the VE microemulsion. The insulation temperature was varied within the range of 90°C to 120°C and the insulation time was varied within the range of 30 min to 60 min. The preparation conditions and the particle size DV(90) of the obtained microemulsion are shown in Table 2.

[0054] Table 2

[0055]

[0056] It can be seen from the data in the table that VE microemulsions can be obtained according to the formulations of Examples 3 to 5, and the particle size DV(90) thereof is between 20 nm and 60 nm.

[0057] Comparative Examples 1-2

[0058] In the same manner as Example 1, the VE microemulsions of Comparative Examples 1 and 2 were prepared according to the formulations and heat preservation conditions shown in Table 3 below.

[0059] Table 3

[0060]

[0061]

[0062] From the data in Table 3, it can be seen that although the other components, insulation temperature and insulation time of Comparative Examples 1 to 2 are similar to those of Example 1, a clear and transparent VE microemulsion cannot be prepared due to the addition of only one lipophilic emulsifier or one hydrophilic emulsifier. The experimental results show that only when high and low specific emulsifiers are used in combination in a specific ratio can a clear and transparent VE microemulsion be prepared.

[0063] Test Example 1: Stability Test

[0064] This test example conducted performance tests on the VE microemulsions of Examples 1 to 5 under low temperature (5°C) and high temperature (100°C) conditions to detect changes in the labeled content and appearance of the VE microemulsions. The experimental results at low temperature (5°C) are shown in Table 3, and the experimental results at high temperature (100°C) are shown in Table 4.

[0065] Table 3 Appearance properties and VE acetate content of microemulsion under low temperature environment

[0066]

[0067] Table 4 Appearance properties and VE acetate content of microemulsion under high temperature environment

[0068]

[0069]

[0070] Tables 3 and 4 show that the VE microemulsions of Examples 3 to 5 have no significant changes in the labeled content and appearance properties of the VE microemulsions under low temperature (5°C) and high temperature (100°C), wherein the appearance of the microemulsions is clear and transparent, without turbidity or demulsification. However, the VE microemulsions of Examples 1 and 2 are unstable under low temperature conditions, resulting in demulsification of the microemulsion system in a short period of time. In addition, the appearance of Examples 1 and 2 is also unstable at high temperatures, and as the storage time increases, the microemulsions become completely turbid, and the microemulsion system is destroyed. The data in the table show that the microemulsions of Examples 3 to 5 have excellent stability in extreme temperature environments, and can meet the needs of the microemulsions in subsequent applications.

[0071] Application Example 1

[0072] In order to investigate the application of VE microemulsion in transparent beverages, this application example conducted experiments in this regard on the VE microemulsions of Examples 3 to 5. The results are shown in Tables 5 and 6.

[0073] Table 5 Turbidity of transparent beverages during processing and VE acetate content in beverages (α-TE / 100mL)

[0074]

[0075] Table 6 Turbidity and VE acetate content of transparent beverages at 55°C (α-TE / 100mL)

[0076]

[0077]

[0078] Tables 5 and 6 show that the VE microemulsions of Examples 3 to 5 do not break after high temperature sterilization and remain clear and transparent. They are clear and transparent in a wide pH value and high ion (pH 6.4) environment without breaking, so they can be used in transparent beverages and oral liquids.

[0079] The transparent beverage preparation process is as follows:

[0080] 1) Ingredients: Add erythritol and appropriate amount of ultrapure water to a sugar dissolving pot, heat at 40°C to fully dissolve, then add all remaining components, heat and stir to dissolve evenly, and then make up the remaining water;

[0081] 2) Filtration: Filter the prepared liquid through a 150-mesh sieve;

[0082] 3) Sterilization: Pour the filtered beverage into a kettle and heat it to boil;

[0083] 4) Filling: After sterilization, the liquid is filled in PET sterile bottles;

[0084] 5) Cooling: The canned beverage is quickly cooled in ice water.

[0085] The component contents of the transparent beverage are shown in Table 7 and Table 8:

[0086] Table 7 Transparent beverage formula (pH 3.4)

[0087] Raw material name Transparent beverage / (g / kg) Erythritol 216.67 Calcium lactate 4.16 Sucralose 2.13 Citric Acid 50.67 Sodium Citrate 7.48 Potassium chloride 0.76 Zinc sulfate monohydrate 0.11 Vitamin B6 0.01 VE microemulsion 2.09 Pure water Make up total 10000

[0088] Table 8 Transparent beverage formula (pH 6.4)

[0089]

[0090]

[0091] Content detection method: Content: refer to the first method of GB 5009.82-2016 "National Food Safety Standard Determination of Vitamin A, D and E in Food".

[0092] Turbidity: 2100N Hach turbidity meter.

Claims

1. A VE microemulsion, characterized in that: In terms of mass percentage, it includes the following components: The HLB value of the high HLB emulsifier is greater than 12, and the HLB value of the low HLB emulsifier is 1-5.

2. The VE microemulsion according to claim 1, characterized in that The low HLB value emulsifier is selected from one or more of triglycerol polyricinoleate, triglycerol polyricinoleate, decaglycerol decaoleate, diglycerol dioleate, monoricinoleic acid glyceride, transesterified polyglycerol ricinoleate, oleic acid polyethylene glycol glyceride, triglycerol monooleate, triglycerol monoricinoleate, monostearic acid glyceryl, and glyceryl dioleate.

3. The VE microemulsion according to claim 1, characterized in that The high HLB value emulsifier is selected from one or more of polyglycerol ester emulsifiers, fatty alcohol polyoxyethylene ether emulsifiers or sucrose ester emulsifiers.

4. The VE microemulsion according to claim 3, characterized in that The polyglycerol ester emulsifier is selected from one or more of polyglycerol monooleate, polyglycerol-10-decanoate, polyglycerol monoricinoleate, polyglycerol monoricinoleate, polyglycerol-10-octanoate, polyglycerol monolaurate, polyglycerol monostearate, polyglycerol caprylic caprate, polyglycerol oleate, and polyglycerol caprylic caprate; The fatty alcohol polyoxyethylene ether emulsifier is selected from one or more of polyethylene glycol-12-glycerol laurate, caprylic acid capric acid polyethylene glycol glyceride, lauric acid polyethylene glycol glyceride, polyoxyethylene hydrogenated castor oil, Tween 80, and Tween 60; The sucrose ester emulsifier is selected from one or more of sucrose fatty acid ester LWA-1570 and sucrose fatty acid ester SE-15.

5. The VE microemulsion according to claim 1, characterized in that The auxiliary emulsifier is selected from one or more of glycerol, sorbitol, ethanol, povidone K30, povidone K12, and polyethylene glycol PEG-400.

6. The VE microemulsion according to claim 1, characterized in that In terms of mass percentage, it includes the following components:

7. A method for preparing a VE microemulsion according to any one of claims 1 to 6, characterized in that: The following steps are involved: (1) heating and stirring VE acetate to form an oil phase; (2) adding the preheated low HLB value emulsifier and high HLB value emulsifier to the oil phase in step (1) in sequence; (3) adding the preheated co-emulsifier to the emulsion in step (2) and stirring thoroughly; (4) Under stirring conditions, water is added to the emulsion of step (3), first stirred at 20-30° C. for 5-10 min, and then kept at 90-120° C. for 20-60 min to obtain the VE microemulsion.

8. The method for preparing the VE microemulsion according to claim 7, characterized in that: In step (1), the temperature of heating and stirring is 60 to 70° C., and the time of heating and stirring is 5 to 10 minutes.

9. The method for preparing the VE microemulsion according to claim 7, characterized in that: In step (2), the preheating temperature of the low HLB value emulsifier and the high HLB value emulsifier is 50 to 70° C.; After adding one emulsifier each time, stir for 4 to 6 minutes before adding another emulsifier; In step (3), the preheating temperature of the emulsifier is 50-70° C., and the stirring time after the emulsifier is added is 10-15 minutes.

10. Use of the VE microemulsion according to any one of claims 1 to 6 or the VE microemulsion obtained by the preparation method according to any one of claims 7 to 9, characterized in that: The VE microemulsion is used for preparing food, medicine or health care products; preferably for preparing transparent beverages or oral liquids.

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