Preparation method and application of modified nano silicon dioxide monoglyceride acid regurgitation inhibitor
By modifying nano-silica multiple times and introducing amino and guanidine groups, the problem of acid reflux during the storage of monoglyceride was solved, and an efficient and stable acid reflux inhibition effect was achieved, which is suitable for food, cosmetics and pharmaceutical fields.
Patent Information
- Application Number
- CN202510784358.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-12
- Publication Date
- 2025-09-19
AI Technical Summary
Monoglycerides are prone to acid reflux during storage, resulting in decreased emulsification properties and unpleasant odor, affecting product stability, sensory quality and stability. Existing antioxidants and stabilizers have the disadvantages of short-lasting effects, easy inactivation, difficulty in separation and potential health risks.
By modifying nanosilica multiple times, the surface of nanosilica was modified with silane coupling agents such as 4-amino-3,3-dimethylbutyltrimethoxysilane, (N,N-dimethyl-3-aminopropyl)trimethoxysilane and 2-(3-trimethoxysilylpropyl)guanidine, amino and guanidine groups were introduced to enhance its interaction ability with acidic substances in monoglycerides, thereby inhibiting acid reflux.
Significantly reduces the monoglyceride acid reflux rate by 75%-90%. The inhibitor is simple to operate, easy to separate, pollution-free, has a long service life, and is not easily inactivated. It is suitable for food, cosmetics, and pharmaceutical fields.
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of food additives, and in particular to a preparation method and application of a modified nano-silicon dioxide monoglyceride acid reflux inhibitor. Background Art
[0002] Monoglycerides (monoglycerides of fatty acids) are important nonionic surfactants widely used in food, cosmetics, pharmaceuticals, and industrial sectors due to their excellent emulsifying, stabilizing, and thickening properties. In the food industry, monoglycerides are commonly used in baked goods, dairy products, ice cream, margarine, and other products to improve texture and stability. In cosmetics, monoglycerides act as emulsifiers and emollients, enhancing product texture and moisturizing properties. In the pharmaceutical field, monoglycerides are also used as drug carriers to improve drug solubility and bioavailability.
[0003] However, monoglycerides are prone to acid reversion during storage. This occurs when the ester bonds of monoglycerides hydrolyze under the influence of moisture, temperature, or microorganisms, generating free acids and glycerol. This acid reversion not only reduces the emulsifying properties of monoglycerides but can also produce an unpleasant odor, affecting the sensory quality and stability of the product. Furthermore, the accumulation of free fatty acids can trigger further oxidation reactions, leading to further deterioration of product quality.
[0004] To address the acid reflux associated with monoglycerides, traditional methods typically involve adding antioxidants (such as BHA, BHT, and vitamin E) or stabilizers (such as citric acid and phosphates). While these methods can somewhat slow the onset of monoglyceride acid reflux, they suffer from short-term effects, are prone to inactivation, are difficult to separate, and pose potential health risks.
[0005] Therefore, developing an efficient, stable, and easily separable inhibitor to address the acid reflux problem of monoglycerides during storage is of great practical significance and application value. In recent years, nanomaterials have demonstrated tremendous potential in the field of food additives due to their unique surface and small size effects. Nanosilica, a non-toxic, harmless nanomaterial with a high specific surface area, has been widely used in food packaging, drug carriers, and functional additives. By modifying its surface, its functionality and stability can be further improved, making it an ideal monoglyceride acid reflux inhibitor. Summary of the Invention
[0006] The present invention aims to provide a method for preparing and applying a modified nano-silica monoglyceride acid reflux inhibitor. The inhibitor, which is prepared by multiple modification of nano-silica with a composite silane coupling agent, has the advantages of simple operation, easy separation, no pollution, long service life, and resistance to inactivation.
[0007] The present invention first provides a method for preparing a modified nano-silica monoglyceride acid reflux inhibitor, comprising the following preparation steps: (1) Adding silica to an organic solvent to form a nano-silica suspension; (2) 4-amino-3,3-dimethylbutyltrimethoxysilane is added to the above suspension, and its methoxy group reacts with the hydroxyl group on the surface of the nano-silica to form a stable Si-O-Si bond. At the same time, amino groups are introduced to enhance the surface activity of the nano-silica, thereby obtaining the first grafted modified nano-silica; (3) Adding (N,N-dimethyl-3-aminopropyl)trimethoxysilane to the first modified nanosilica suspension further modifies the surface of the nanosilica, introduces more amino groups, and enhances its ability to interact with the acidic substances in monoglyceride, thereby obtaining the second modified nanosilica; (4) Adding 2-(3-trimethoxysilylpropyl)guanidine to the nano-silica suspension that has been modified twice not only increases the basic groups on the surface of the nano-silica, but also neutralizes the acidic substances in the monoglyceride through the strong alkalinity of the guanidine group, thereby effectively inhibiting the acid reflux phenomenon, and obtaining the third modified nano-silica; (5) The nano-silica suspension that has been modified three times is separated, washed, and dried to obtain a modified nano-silica inhibitor.
[0008] Wherein, the structural formulas of 4-amino-3,3-dimethylbutyltrimethoxysilane, (N,N-dimethyl-3-aminopropyl)trimethoxysilane and 2-(3-trimethoxysilylpropyl)guanidine are as follows: ; ; ; Preferably, the mass ratio of the 4-amino-3,3-dimethylbutyltrimethoxysilane to the nano-silicon dioxide is 1-3:10, preferably 2-2.5:10.
[0009] Preferably, the mass ratio of the (N,N-dimethyl-3-aminopropyl)trimethoxysilane to the first modified nano-silica is 0.5-2.5:10, preferably 1.5-2:10.
[0010] Preferably, the mass ratio of the 2-(3-trimethoxysilylpropyl)guanidine to the second modified nano-silica is 0.5-1.5:10, preferably 1-1.2:10.
[0011] Preferably, the organic solvent comprises one or more of ethanol, methanol, isopropanol or tetrahydrofuran.
[0012] Preferably, the average particle size of the nano-silicon dioxide is 10-100 nm; preferably, the average particle size is 20-50 nm, and more preferably, the average particle size is 20-30 nm.
[0013] Preferably, the reaction temperature of the graft modification is 50-100°C, and the reaction time is 2-6h; further, the reaction temperature of the first graft modification is 60-70°C, and the reaction time is 4-6h; the reaction temperature of the second graft modification is 70-80°C, and the reaction time is 3-5h; the reaction temperature of the third graft modification is 80-90°C, and the reaction time is 2-4h.
[0014] The present invention also provides a modified nano-silicon dioxide material prepared by the above preparation method.
[0015] The modified nano silicon dioxide prepared by the present invention is used to reduce acid reflux during the storage of monoglyceride.
[0016] Specifically, the modified nano-silica inhibitor is added to the monoglyceride at a rate of 0.1%-5% of the mass of the monoglyceride, stirred evenly, and then stored.
[0017] The modified nano-silica monoglyceride acid reflux inhibitor prepared by the present invention can reduce the monoglyceride acid reflux rate by 75%-90% under high temperature environment.
[0018] The technical principles and beneficial effects of the present invention are as follows: The methoxy group of the silane coupling agent in the present invention undergoes a condensation reaction with the hydroxyl group on the surface of the nano-silica to form a stable Si-O-Si bond, while simultaneously introducing amino and guanidine groups to neutralize fatty acids, thereby reducing fatty acid stimulation and jointly inhibiting monoglyceride-related acid reflux.
[0019] The present invention uses a composite silane coupling agent to modify nano-silica multiple times, significantly improving its ability to inhibit monoglyceride acid reflux. The inhibitor is also simple to operate, easy to separate, pollution-free, has a long service life, and is not easily inactivated. It has promising application prospects and can be widely used in the fields of food, cosmetics, and medicine, with significant economic and social benefits. DETAILED DESCRIPTION
[0020] The present invention will be further described below with reference to the examples, but the scope of the present invention is not limited thereto. The raw materials and reagents used in the examples are all commercially available products, and the experimental conditions can be adjusted according to actual conditions. However, it should be understood that the following examples are merely illustrative of the embodiments of the present invention and are not intended to limit the scope of the present invention.
[0021] Monoglyceride acid regurgitation rate test method: Weigh 10g of each monoglyceride blank sample and experimental sample, dissolve them in 100ml of hot ethanol, and titrate with a known concentration of KOH (or NaOH) standard solution using phenolphthalein as the indicator. The solution will turn slightly red at the end point. Calculate the acid value and acid regurgitation rate according to the following formula.
[0022] Acid value (mgKOH / g) =
[0023] V : KOH titration volume (mL), C: KOH standard solution concentration (mol / L), m: sample mass (g), 56.1: molar mass of KOH (g / mol) Acid reflux rate = Example 1
[0024] A modified nano-silica monoglyceride acid reflux inhibitor, the preparation method of which is as follows: (1) Add 10 g of nano-silica (particle size 20-30 nm) to 100 mL of anhydrous ethanol and disperse it using an ultrasonic disperser at a power of 300 W for 30 min to form a uniform nano-silica suspension.
[0025] (2) Add 2 g of 4-amino-3,3-dimethylbutyltrimethoxysilane to the above suspension and stir at 60°C for 4 h. After the reaction, centrifuge and wash with anhydrous ethanol three times to remove unreacted silane coupling agent.
[0026] (3) The modified nano-silica was redispersed in 100 mL of anhydrous ethanol, 1.5 g of (N,N-dimethyl-3-aminopropyl)trimethoxysilane was added, and stirred at 70 °C for 3 h. After the reaction was completed, the mixture was centrifuged and washed three times with anhydrous ethanol.
[0027] (4) The nano-silica modified twice was redispersed in 100 mL of anhydrous ethanol, and 1 g of 2-(3-trimethoxysilylpropyl)guanidine was added. The mixture was stirred and reacted at 80°C for 2 h. After the reaction, the mixture was centrifuged and washed with anhydrous ethanol three times. Finally, it was vacuum-dried at 60°C for 12 h to obtain the modified nano-silica inhibitor.
[0028] The prepared modified nano-silica inhibitor was added to monoglyceride at a rate of 1% by mass based on the monoglyceride, stirred evenly, and stored at 30°C. After six months of storage, the monoglyceride's acid regurgitation rate was 20%. After another month of storage, the acid regurgitation rate of the monoglyceride remained unchanged, and the modified nano-silica showed no signs of deactivation. Example 2
[0029] A modified nano-silica monoglyceride acid reflux inhibitor, the preparation method of which is as follows: (1) Add 10 g of nano-silica (particle size (30-40 nm)) into 150 mL of methanol and use an ultrasonic disperser at a power of 350 W for 40 min to form a uniform nano-silica suspension.
[0030] (2) Add 2 g of 4-amino-3,3-dimethylbutyltrimethoxysilane to the above suspension and stir at 65°C for 5 h. After the reaction, centrifuge and wash with methanol three times to remove unreacted silane coupling agent.
[0031] (3) The modified nano-silica was redispersed in 150 mL of methanol, 1.5 g of (N,N-dimethyl-3-aminopropyl)trimethoxysilane was added, and stirred at 75 °C for 4 h. After the reaction was completed, the mixture was centrifuged and washed with methanol three times.
[0032] (4) The nano-silica modified twice was redispersed in 150 mL of anhydrous ethanol, and 1 g of 2-(3-trimethoxysilylpropyl)guanidine was added. The mixture was stirred and reacted at 85°C for 3 h. After the reaction, the mixture was centrifuged and washed with anhydrous ethanol three times. Finally, it was vacuum-dried at 70°C for 10 h to obtain the modified nano-silica inhibitor.
[0033] The prepared modified nano-silica inhibitor was added to monoglyceride at 1% of its mass, stirred evenly, and stored at 30°C. After six months of storage, the acid regurgitation rate of the monoglyceride was 30%. After another month of storage, the acid regurgitation rate of the monoglyceride did not change significantly, indicating that the modified nano-silica maintained good stability. Example 3
[0034] A modified nano-silica monoglyceride acid reflux inhibitor, the preparation method of which is as follows: (1) Add 10 g of nano-silica (particle size (40-50 nm)) to 200 mL of isopropanol and disperse it using an ultrasonic disperser at a power of 400 W for 50 min to form a uniform nano-silica suspension.
[0035] (2) Add 2 g of 4-amino-3,3-dimethylbutyltrimethoxysilane to the above suspension and stir at 70°C for 6 h. After the reaction, centrifuge and wash with isopropanol three times to remove unreacted silane coupling agent.
[0036] (3) The modified nano-silica was redispersed in 200 mL of isopropanol, 1.5 g of (N,N-dimethyl-3-aminopropyl)trimethoxysilane was added, and the mixture was stirred at 80 °C for 5 h. After the reaction was completed, the mixture was centrifuged and washed three times with isopropanol.
[0037] (4) The nano-silica modified twice was redispersed in 200 mL of isopropanol, 1 g of 2-(3-trimethoxysilylpropyl)guanidine was added, and the mixture was stirred at 90°C for 4 h. After the reaction, the mixture was centrifuged and washed three times with anhydrous ethanol. Finally, the mixture was vacuum-dried at 80°C for 8 h to obtain the modified nano-silica inhibitor.
[0038] The prepared modified nano-silica inhibitor was added to monoglyceride at a rate of 1% by mass based on the monoglyceride, stirred evenly, and stored at 30°C. After six months of storage, the monoglyceride's acid regurgitation rate was 25%. After another month of storage, the acid regurgitation rate of the monoglyceride remained unchanged, indicating that the modified nano-silica maintained good stability. Example 4
[0039] 10 g of nano-silica was added to 100 mL of anhydrous ethanol and dispersed using an ultrasonic disperser at a power of 300 W for 30 min to form a uniform nano-silica suspension.
[0040] Unmodified nanosilica was added to monoglyceride at 1% of its mass, stirred evenly, and stored at 30°C. After six months of storage, the monoglyceride's acid regurgitation rate was 90%. After another month of storage, the acid regurgitation rate rose to 95%, indicating that the unmodified nanosilica gradually lost its activity during storage. Example 5
[0041] A modified nano-silica monoglyceride acid reflux inhibitor, the preparation method of which is as follows: (1) Add 10 g of nano-silica (particle size 20-30 nm) to 100 mL of anhydrous ethanol and disperse it using an ultrasonic disperser at a power of 300 W for 30 min to form a uniform nano-silica suspension.
[0042] (2) Add 2.5 g of 4-amino-3,3-dimethylbutyltrimethoxysilane to the above suspension and stir at 65°C for 5 h. After the reaction, centrifuge and wash with anhydrous ethanol three times to remove unreacted silane coupling agent.
[0043] (3) The modified nano-silica was redispersed in 100 mL of anhydrous ethanol, 2 g of (N,N-dimethyl-3-aminopropyl)trimethoxysilane was added, and stirred at 75 °C for 4 h. After the reaction was completed, the mixture was centrifuged and washed three times with anhydrous ethanol.
[0044] (4) The nano-silica modified twice was redispersed in 100 mL of anhydrous ethanol, and 1.2 g of 2-(3-trimethoxysilylpropyl)guanidine was added. The mixture was stirred and reacted at 85°C for 3 h. After the reaction, the mixture was centrifuged and washed with anhydrous ethanol three times. Finally, it was vacuum-dried at 70°C for 10 h to obtain the modified nano-silica inhibitor.
[0045] The prepared modified nano-silica inhibitor was added to monoglyceride at a rate of 1% by mass based on the monoglyceride, stirred evenly, and stored at 30°C. After six months of storage, the monoglyceride's acid regurgitation rate was 10%. After another month of storage, the acid regurgitation rate of the monoglyceride remained unchanged, and the modified nano-silica showed no signs of deactivation. Example 6
[0046] A modified nano-silica monoglyceride acid reflux inhibitor, the preparation method of which is as follows: (1) Add 10 g of nano-silica (particle size 20-30 nm) to 100 mL of anhydrous ethanol and disperse it using an ultrasonic disperser at a power of 300 W for 30 min to form a uniform nano-silica suspension.
[0047] (2) Add 2.5 g of 4-amino-3,3-dimethylbutyltrimethoxysilane to the above suspension and stir at 65°C for 5 h. After the reaction, centrifuge and wash with anhydrous ethanol three times to remove unreacted silane coupling agent.
[0048] (3) The modified nano-silica was redispersed in 100 mL of anhydrous ethanol, 1.2 g of 2-(3-trimethoxysilylpropyl)guanidine was added, and the mixture was stirred at 75 °C for 4 h. After the reaction was completed, the mixture was centrifuged and washed three times with anhydrous ethanol.
[0049] (4) The nano-silica modified twice was redispersed in 100 mL of anhydrous ethanol, and 2 g of (N,N-dimethyl-3-aminopropyl)trimethoxysilane was added. The mixture was stirred and reacted at 85°C for 3 h. After the reaction, the mixture was centrifuged and washed with anhydrous ethanol three times. Finally, the mixture was vacuum-dried at 70°C for 10 h to obtain the modified nano-silica inhibitor.
[0050] The prepared modified nano-silica inhibitor was added to monoglyceride at a rate of 1% by mass based on the monoglyceride, stirred evenly, and stored at 30°C. After six months of storage, the monoglyceride's acid regurgitation rate was 12%. After another month of storage, the acid regurgitation rate remained unchanged, and the modified nano-silica showed no signs of deactivation. Example 7
[0051] A modified nano-silica monoglyceride acid reflux inhibitor, the preparation method of which is as follows: (1) Add 10 g of nano-silica (particle size 20-30 nm) to 100 mL of anhydrous ethanol and disperse it using an ultrasonic disperser at a power of 300 W for 30 min to form a uniform nano-silica suspension.
[0052] (2) Add 2.5 g of 4-amino-3,3-dimethylbutyltrimethoxysilane to the above suspension and stir at 65°C for 5 h. After the reaction, centrifuge and wash with anhydrous ethanol three times to remove unreacted silane coupling agent.
[0053] (3) The modified nano-silica was redispersed in 100 mL of anhydrous ethanol, 2 g of (N,N-dimethyl-3-aminopropyl)trimethoxysilane was added, and the mixture was stirred at 75°C for 4 h. After the reaction was completed, the mixture was centrifuged and washed three times with anhydrous ethanol to obtain the modified nano-silica inhibitor.
[0054] The prepared modified nano-silica inhibitor was added to monoglyceride at a rate of 1% by mass based on the monoglyceride, stirred evenly, and stored at 30°C. After six months of storage, the monoglyceride's acid regurgitation rate was 40%. After another month of storage, the acid regurgitation rate of the monoglyceride remained unchanged, and the modified nano-silica showed no signs of deactivation. Example 8
[0055] A modified nano-silica monoglyceride acid reflux inhibitor, the preparation method of which is as follows: (1) Add 10 g of nano-silica (particle size 20-30 nm) to 100 mL of anhydrous ethanol and disperse it using an ultrasonic disperser at a power of 300 W for 30 min to form a uniform nano-silica suspension.
[0056] (2) Add 2.5 g of 4-amino-3,3-dimethylbutyltrimethoxysilane to the above suspension and stir at 65°C for 5 h. After the reaction, centrifuge and wash three times with anhydrous ethanol to remove unreacted silane coupling agent. This yields a modified nano-silica inhibitor.
[0057] The prepared modified nano-silica inhibitor was added to monoglyceride at a rate of 1% by mass, stirred evenly, and stored at 30°C. After six months of storage, the monoglyceride's acid regurgitation rate was 50%. After another month of storage, the acid regurgitation rate of the monoglyceride rose to 70%, indicating that the modified nano-silica had become inactivated.
[0058] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.
Claims
1. A method for preparing a modified nano-silica monoglyceride acid reflux inhibitor, characterized in that: The steps include: (1) Uniformly dispersing nano-silica in an organic solvent to obtain a silica suspension; (2) Adding 4-amino-3,3-dimethylbutyltrimethoxysilane to the silica suspension, stirring to react I, and centrifuging and washing to obtain the first modified silica; (3) The first modified silica is uniformly dispersed in an organic solvent, (N,N-dimethyl-3-aminopropyl)trimethoxysilane is added, stirred to react II, and centrifuged and washed to obtain the second modified silica; (4) uniformly dispersing the second modified silica in an organic solvent, adding 2-(3-trimethoxysilylpropyl)guanidine, stirring to react III, centrifuging, washing, and drying to obtain the modified nano-silica monoglyceride acid reflux inhibitor; The modification order of step (3) and step (4) can be interchanged.
2. The method for preparing the modified nano-silica monoglyceride acid reflux inhibitor according to claim 1, wherein: The mass ratio of the 4-amino-3,3-dimethylbutyltrimethoxysilane to the nano-silicon dioxide is 1-3:
10.
3. The method for preparing the modified nano-silica monoglyceride acid reflux inhibitor according to claim 1, wherein: The mass ratio of the (N,N-dimethyl-3-aminopropyl)trimethoxysilane to the nano-silicon dioxide is 0.5-2.5:
10.
4. The method for preparing the modified nano-silica monoglyceride acid reflux inhibitor according to claim 1, wherein: The mass ratio of the 2-(3-trimethoxysilylpropyl)guanidine to the nano-silicon dioxide is 0.5-1.5:
10.
5. The method for preparing the modified nano-silica monoglyceride acid reflux inhibitor according to claim 1, wherein: The average particle size of the nano-silicon dioxide is 10-100 nm.
6. The method for preparing the modified nano-silica monoglyceride acid reflux inhibitor according to claim 1, wherein: The organic solvent includes one or more of ethanol, methanol, isopropanol or tetrahydrofuran.
7. The method for preparing the modified nano-silica monoglyceride acid reflux inhibitor according to claim 1, wherein: The reaction temperature of the stirring reaction I is 60-70°C, and the reaction time is 4-6 hours; the reaction temperature of the stirring reaction II is 70-80°C, and the reaction time is 3-5 hours; the reaction temperature of the stirring reaction III is 80-90°C, and the reaction time is 2-4 hours.
8. A modified nano-silica prepared according to the method according to any one of claims 1 to 7.
9. Use of the modified nano-silica according to claim 8 in inhibiting monoglyceride acid reflux.
10. The use according to claim 9, characterized in that The application method is: the modified nano-silicon dioxide and monoglyceride are evenly stirred and then stored; the addition amount of the modified nano-silicon dioxide is 0.1%-5% of the mass of the monoglyceride.