Oxygen uptake composition as well as preparation method and application thereof

Abstract

The invention discloses an oxygen uptake composition as well as a preparation method and application thereof, and relates to the technical field of deoxidizing agents. The oxygen uptake composition comprises an oxygen uptake component, a carrier and an auxiliary agent. The oxygen uptake component comprises a derivative of ascorbic acid; the carrier comprises a porous material; the auxiliaries comprise a catalyst, a water absorbent, a flow aid and a silane coupling agent. The oxygen uptake composition does not start oxygen uptake in the early stage, oxygen uptake performance loss is avoided, meanwhile, humidity rising can be effectively avoided, food is prevented from being affected by humidity, and the oxygen uptake efficiency is high. The oxygen uptake composition is used for preparing a food deoxidizer, and the food deoxidizer is formed by mixing and curing the oxygen uptake composition and epoxy resin. The oxygen-absorbing composition and the epoxy resin are mixed more uniformly due to hydrogen bonds and curing reaction, and are combined more firmly. Therefore, the prepared food deoxidizer can absorb oxygen more uniformly and stably, and the oxygen absorption efficiency of the prepared food deoxidizer is fully improved.

Description

Technical Field

[0001] The present application relates to the technical field of deoxidizers, and specifically to an oxygen absorbing composition and a preparation method and application thereof. Background Art

[0002] The presence of oxygen is one of the main causes of food spoilage. For foods that are sensitive to oxygen, it is very important to prevent or reduce the contact between oxygen and themselves. Therefore, with the advancement of science and technology and the improvement of consumers' requirements for food safety and quality, the research and application of deoxidizers have gradually gained attention.

[0003] There are many types of deoxidizers, and iron-based deoxidizers are an important type and are widely used in the food industry. They mainly use reduced iron powder to undergo a redox reaction with oxygen to reduce the oxygen concentration in food packaging. However, the reaction of iron-based deoxidizers requires the participation of water, so their deoxidation effect will be affected in a low humidity environment. But if it is in a high humidity environment, it will also cause the food to become damp, affecting the taste and quality. Therefore, it is necessary to develop more non-iron-based food deoxidizers.

[0004] The Chinese patent application with publication number CN 106666323A discloses a method for preparing a composite food deoxidizer. The method uses montmorillonite as a filler, provides platinum ions through a chloroplatinic acid solution, loads platinum ions on the montmorillonite, and melts and wraps the platinum ions at high temperature to increase the catalytic efficiency, generates magnesium nitride by burning magnesium powder in nitrogen, and melts on the surface of the filler, oxidizes humic acid with hydrogen peroxide, sulfonates the oxidized humic acid with sulfur trioxide, increases the absorption of sulfur dioxide and ammonia, and finally mixes with iron powder and sodium dithionite to prepare a method for preparing a composite food deoxidizer. The composite food deoxidizer prepared by the invention has an oxygen absorption rate that is 18~22% higher than that of traditional deoxidizers; and the moisture regain after use is 26~35% lower than that of traditional deoxidizers.

[0005] Although the performance of the composite food deoxidizer in the above scheme has been improved, iron powder is still used and the process conditions are relatively complicated. Summary of the invention

[0006] In view of the deficiencies of the prior art, the present application provides an oxygen absorbing composition and a preparation method and application thereof. The oxygen absorbing composition is a non-ferrous material and has a simple preparation process. The carrier and the oxygen absorbing component are fully mixed in a solution under the action of a catalyst, and then evaporated and dried to obtain a residual solid; the residual solid is then mixed and ground with other additives to obtain the oxygen absorbing composition.

[0007] In order to achieve the above objectives, this application adopts the following technical solutions: In a first aspect, the present application provides an oxygen absorbing composition, comprising an oxygen absorbing component, a carrier and an auxiliary agent; the oxygen absorbing component comprises ascorbic acid or a derivative of ascorbic acid, and any one of p-aminophenol and sodium dithionite; the auxiliary agent comprises a catalyst, a water absorbent, a flow aid and a silane coupling agent.

[0008] In a second aspect, the present application provides a method for preparing an oxygen absorbing composition, the preparation method comprising: Under nitrogen protection, the oxygen absorbing component is added to ethanol and stirred for 20 to 40 minutes to obtain an oxygen absorbing component solution; Then, under nitrogen protection, the carrier is added to the oxygen absorbing component solution and stirred for 5 to 15 minutes; Then, half of the catalyst was added to the solution under nitrogen protection, and stirring was continued for 20 to 40 minutes; then the other half of the catalyst was added, and stirring was continued for 10 to 30 minutes to obtain a mixed solution I; Then, the water absorbent, the flow aid and the silane coupling agent are added to the mixed solution I, and stirred for 10 to 30 minutes to obtain a mixed solution II; Finally, the mixed solution II is evaporated, dried and ground at 90-120° C. to obtain the oxygen absorbing composition.

[0009] In a third aspect, the present application provides an application of an oxygen absorbing composition, wherein the oxygen absorbing composition is used to prepare a food deoxidizer, and the preparation method of the food deoxidizer comprises: Adding the oxygen absorbing composition to the epoxy resin, and then stirring at room temperature for a first set time under nitrogen protection to obtain a mixture I; Then, a curing agent is added to the mixture I, and the mixture is stirred for a second set time under nitrogen protection to obtain a mixture II; Finally, the mixture II is cured under the conditions of nitrogen protection and the first set temperature, and the food deoxidizer is obtained after curing.

[0010] Beneficial technical effects: In the oxygen absorption composition provided by the present application, the oxygen absorption component is mainly ascorbic acid or a derivative of ascorbic acid, which has hydrophobic properties and is relatively stable, not easily affected by environmental factors such as temperature and light, and the micropore air permeability of the surface of the oxygen absorption composition particles prepared with porous materials as carriers is small. When placed in the air, oxygen gradually penetrates from the external micropores into the interior of the particles, and oxygen absorption is started. Therefore, oxygen absorption can be not started in the early stage, and oxygen absorption can be started rapidly when the amount of oxygen is large, avoiding the loss of oxygen absorption performance. Moreover, more hydroxyl groups are still retained in the derivatives of ascorbic acid. Under the action of silane coupling agents, they can be better combined with carriers, water absorbents and flow aids, making the oxygen absorption composition more durable and effective; at the same time, the carrier has a larger specific surface area, and the derivatives of ascorbic acid are more attached to its surface, which can fully improve the oxygen absorption efficiency. Moreover, a certain amount of p-aminophenol or sodium dithionite is added, both of which have certain reducibility and can undergo redox reactions with oxygen. Sodium dithionite can react quickly in the presence of water, and p-aminophenol is relatively stable and can work in a wide temperature range. The addition of the two cooperates with the derivatives of ascorbic acid to improve the applicability of food deoxidizers. In addition, the water absorbent further absorbs the water produced by the oxygen absorption reaction, promotes the reaction equilibrium to move toward the oxygen absorption direction, and increases the total oxygen absorption; at the same time, the absorption of water can effectively prevent the humidity from rising and prevent the food from being affected by humidity. BRIEF DESCRIPTION OF THE DRAWINGS

[0011] Figure 1 Schematic diagram of the components of the oxygen absorbing composition.

[0012] Figure 2 is a flow chart for preparing an oxygen absorbing composition.

[0013] Figure 3 The present invention is a flow chart of preparing food oxygen absorber by using oxygen absorbing composition.

[0014] Figure 4 It is a schematic diagram of the principle of forming hydrogen bonds in the process of preparing food oxygen absorbers using oxygen absorbing compositions. DETAILED DESCRIPTION

[0015] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present application clearer, the present application is further described in detail below in conjunction with the embodiments. However, this should not be understood as the scope of the present application being limited to the following examples. Without departing from the above-mentioned method ideas of the present application, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of this application.

[0016] In this application, the terms used in this application are for the purpose of describing specific embodiments only and are not intended to limit the application.

[0017] The terms “first”, “second” and “third” appearing in the present application are used for descriptive purposes only and should not be understood as indicating or implying relative importance.

[0018] In addition, as used in this application, the singular forms "for", "or", "an", "any", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.

[0019] In a first aspect, the present application provides an oxygen absorbing composition, the composition of the oxygen absorbing composition is as follows Figure 1 As shown, it includes an oxygen absorbing component, a carrier and an auxiliary agent; the oxygen absorbing component includes ascorbic acid or a derivative of ascorbic acid, and any one of p-aminophenol and sodium dithionite; the auxiliary agent includes a catalyst, a water absorbent, a flow aid and a silane coupling agent.

[0020] In a possible implementation, in the oxygen absorbing composition, the mass ratio of the oxygen absorbing component, the carrier, the catalyst, the water absorbent, the flow aid, and the silane coupling agent is (60-70): (20-40): (2-10): (2-10): (0.2-2): (0.5-2).

[0021] In a possible implementation, in the oxygen absorbing component, the mass ratio of p-aminophenol or sodium dithionite to ascorbic acid or an ascorbic acid derivative is (10-20): (80-90).

[0022] In a possible implementation, in the oxygen absorbing component, the derivative of ascorbic acid includes one or more of ascorbic acid glucoside, 3-O-ethyl ascorbic acid ether, ascorbic acid palmitate, and ascorbic acid stearate.

[0023] In a possible implementation, the carrier includes a porous material; the porous material includes one or more of mesoporous silica, diatomaceous earth, and zeolite; and the specific surface area of ​​the carrier is 200~500m² / g.

[0024] In a possible implementation, the catalyst includes one or more of calcium hydroxide, sodium hydroxide, and sodium carbonate.

[0025] In a possible implementation, the water absorbing agent includes one or both of calcium chloride and a water absorbing resin.

[0026] In a possible implementation, the glidant includes one or more of micro-powdered silica gel, magnesium stearate, and talc.

[0027] In a possible implementation, the silane coupling agent includes one or more of γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and N-(β-aminoethyl)-γ-aminopropyltriethoxysilane.

[0028] In a second aspect, the present application provides a method for preparing an oxygen absorbing composition, such as Figure 2 As shown, the preparation method comprises: Under nitrogen protection, the oxygen absorbing component is added to ethanol and stirred for 20 to 40 minutes to obtain an oxygen absorbing component solution; Then, under nitrogen protection, the carrier is added to the oxygen absorbing component solution and stirred for 5 to 15 minutes; Then, half of the catalyst was added to the solution under nitrogen protection, and stirring was continued for 20 to 40 minutes; then the other half of the catalyst was added, and stirring was continued for 10 to 30 minutes to obtain a mixed solution I; Then, the water absorbent, the flow aid and the silane coupling agent are added to the mixed solution I, and stirred for 10 to 30 minutes to obtain a mixed solution II; Finally, the mixed solution II is evaporated, dried and ground at 90-120° C. to obtain the oxygen absorbing composition.

[0029] In a third aspect, the present application provides an application of an oxygen absorbing composition, wherein the oxygen absorbing composition is used to prepare a food deoxidizer, and the preparation method of the food deoxidizer is as follows: Figure 3 As shown, including: The oxygen absorbing composition is added to the epoxy resin, and then stirred at room temperature for a first set time under nitrogen protection to obtain a mixture I; Then, a curing agent is added to the mixture I, and the mixture is stirred for a second set time under nitrogen protection to obtain a mixture II; Finally, the mixture II is cured under the conditions of nitrogen protection and the first set temperature, and the food deoxidizer is obtained after curing.

[0030] The food deoxidizer is formed by mixing and curing the oxygen absorbing composition and epoxy resin. The oxygen absorbing component that is the main component in the oxygen absorbing composition is a derivative of ascorbic acid, which has a large number of oxygen-containing functional groups (such as hydroxyl groups, ester groups, and ether bonds) in its structure, and generates a large number of hydrogen bonds (such as hydroxyl groups and epoxy groups) with the oxygen-containing groups (such as hydroxyl groups and epoxy groups) in the epoxy resin. Figure 4 As shown in the figure, the attraction between them can be enhanced. This attraction helps to overcome the repulsive force between molecules, making it easier for the two to mix with each other and improving the uniformity of the mixture; after adding the curing agent, the oxygen-containing groups in the epoxy resin react with the curing agent to solidify the entire system, and the oxygen-absorbing composition and the epoxy resin are more firmly combined. The above two points enable the prepared food deoxidizer to absorb oxygen more evenly and stably, fully improving the oxygen absorption efficiency of the prepared food deoxidizer.

[0031] In a possible implementation, the mass ratio of the oxygen absorbing composition to the epoxy resin is (30-50): (50-70).

[0032] In a possible implementation, the curing agent is one or more of an amine curing agent and a phenol curing agent.

[0033] In a possible implementation, the first set time is 1 to 2 hours.

[0034] In a possible implementation, the second set time is 5 to 10 minutes.

[0035] In a possible implementation, the first set temperature is 20-60°C.

[0036] The experimental raw materials used in this application come from the following sources: Vector: Shanghai MacLean Biochemical Technology Co., Ltd.; Ascorbic acid derivatives: Bashifu (Shanghai) Biopharmaceutical Technology Co., Ltd.; p-Aminophenol: Jiangsu Bosite Chemical Technology Co., Ltd.; Sodium dithionite: Bashifu (Shanghai) Biopharmaceutical Technology Co., Ltd.; Catalyst: Shanghai MacLean Biochemical Technology Co., Ltd.; Water absorbent: Jiangsu Runfeng Synthetic Technology Co., Ltd.; Flow aid: Jiangsu Runfeng Synthetic Technology Co., Ltd.; Silane coupling agent: Jiangsu Runfeng Synthetic Technology Co., Ltd.; Curing agent: Shanghai MacLean Biochemical Technology Co., Ltd.; Epoxy resin: Jiangsu Bosite Chemical Technology Co., Ltd.; Polystyrene resin: Jiangsu Bosite Chemical Technology Co., Ltd.

[0037] The following will specifically describe an oxygen absorbing composition provided by the present application and its preparation method and application in combination with different examples.

[0038] Embodiment 1: A method for preparing a food deoxidizer, the preparation method comprising: 1. Under nitrogen protection, add ascorbyl glucoside and p-aminophenol to ethanol and stir for 30 minutes to obtain an oxygen absorbing component solution; 2. Then, under nitrogen protection, add mesoporous silica to the oxygen absorbing component solution and stir for 10 minutes; 3. Then, under nitrogen protection, half of the calcium hydroxide was added to the solution, and stirring was continued for 30 min; then, the other half of the calcium hydroxide was added, and stirring was continued for 20 min to obtain a mixed solution I; 4. Then, calcium chloride, micropowder silica gel and γ-aminopropyltrimethoxysilane were added to the mixed solution I and stirred for 15 minutes to obtain a mixed solution II; 5. Finally, the mixed solution II is evaporated, dried and ground at 100° C. to obtain the oxygen absorbing composition.

[0039] In the above steps 1 to 5, the mass ratio of ascorbyl glucoside to p-aminophenol, mesoporous silica, calcium hydroxide, calcium chloride, micropowder silica gel, and γ-aminopropyltrimethoxysilane is 65:20:6:8:0.5:0.5.

[0040] In the oxygen absorbing component, the mass ratio of p-aminophenol to ascorbic acid glucoside is 10:90.

[0041] 6. Add the oxygen absorbing composition to the epoxy resin, and then stir at room temperature for 1 hour under nitrogen protection to obtain a mixture I; the mass ratio of the oxygen absorbing composition to the epoxy resin is 50:50; 7. Then, an amine curing agent was added to the mixture I, and the mixture was stirred for 5 minutes under nitrogen protection to obtain a mixture II; 8. Finally, the mixture II is cured under nitrogen protection at 40°C to obtain the food deoxidizer.

[0042] Embodiment 2: A method for preparing a food deoxidizer, the preparation method comprising: 1. Under nitrogen protection, add 3-O-ethyl ascorbic acid ether and sodium dithionite to ethanol and stir for 25 minutes to obtain an oxygen absorbing component solution; 2. Then, under nitrogen protection, add diatomaceous earth to the oxygen absorbing component solution and stir for 8 minutes; 3. Then, under nitrogen protection, half of the sodium carbonate was added to the solution and stirring continued for 25 min; then, the other half of the sodium carbonate was added and stirring continued for 15 min to obtain a mixed solution I; 4. Then add the water-absorbing resin, magnesium stearate and N-(β-aminoethyl)-γ-aminopropyltriethoxysilane to the mixed solution I and stir for 10 minutes to obtain a mixed solution II; 5. Finally, the mixed solution II is evaporated, dried and ground at 110° C. to obtain the oxygen absorbing composition.

[0043] In the above steps 1 to 5, the mass ratio of 3-O-ethyl ascorbic acid ether to sodium dithionite, diatomaceous earth, sodium carbonate, water-absorbing resin, magnesium stearate, and N-(β-aminoethyl)-γ-aminopropyltriethoxysilane is 60:25:4:10:0.2:0.8.

[0044] In the oxygen absorbing component, the mass ratio of sodium dithionite to 3-O-ethyl ascorbic acid ether is 20:80.

[0045] 6. Add the oxygen absorbing composition to the epoxy resin, and then stir at room temperature for 1.5 hours under nitrogen protection to obtain a mixture I; the mass ratio of the oxygen absorbing composition to the epoxy resin is 60:40; 7. Then, a phenolic curing agent was added to the mixture I, and the mixture was stirred for 8 minutes under nitrogen protection to obtain a mixture II; 8. Finally, the mixture II is cured under nitrogen protection at 50°C to obtain the food deoxidizer.

[0046] Embodiment 3: A method for preparing a food deoxidizer, the preparation method comprising: 1. Under nitrogen protection, add ascorbyl palmitate and p-aminophenol to ethanol and stir for 35 minutes to obtain an oxygen absorbing component solution; 2. Then, under nitrogen protection, add zeolite to the oxygen absorbing component solution and stir for 7 minutes; 3. Then, under nitrogen protection, half of the sodium hydroxide was added to the solution and stirring continued for 20 minutes; then, the other half of the sodium hydroxide was added and stirring continued for 25 minutes to obtain a mixed solution; 4. Then, calcium chloride, talc and γ-aminopropyltriethoxysilane were added to the mixed solution I and stirred for 20 minutes to obtain a mixed solution II; 5. Finally, the mixed solution is evaporated, dried and ground at 105° C. to obtain the oxygen absorbing composition.

[0047] In the above steps 1 to 5, the mass ratio of ascorbyl palmitate to p-aminophenol, zeolite, sodium hydroxide, calcium chloride, talc, and γ-aminopropyltriethoxysilane is 70:20:2:6:1:1.

[0048] In the oxygen absorbing component, the mass ratio of p-aminophenol to ascorbyl palmitate is 15:85.

[0049] 6. Add the oxygen absorbing composition to the epoxy resin, and then stir at room temperature for 2 hours under nitrogen protection to obtain a mixture I; the mass ratio of the oxygen absorbing composition to the epoxy resin is 40:60; 7. Then, an amine curing agent was added to the mixture I, and the mixture was stirred for 10 minutes under nitrogen protection to obtain a mixture II; 8. Finally, the mixture II is cured under nitrogen protection at 60°C to obtain the food deoxidizer.

[0050] Embodiment 4: A method for preparing a food deoxidizer, the preparation method comprising: 1. Under nitrogen protection, add ascorbyl glucoside and sodium dithionite to ethanol and stir for 20 minutes to obtain an oxygen absorbing component solution; 2. Then, under nitrogen protection, add mesoporous silica to the oxygen absorbing component solution and stir for 5 minutes; 3. Then, under nitrogen protection, add half of the calcium hydroxide to the solution and continue stirring for 40 minutes; then add the other half of the calcium hydroxide and continue stirring for 30 minutes to obtain a mixed solution; 4. Then add the water-absorbing resin, micro-powder silica gel and γ-aminopropyltrimethoxysilane to the mixed solution I and stir for 30 minutes to obtain a mixed solution II; 5. Finally, the mixed solution is evaporated, dried and ground at 95° C. to obtain the oxygen absorbing composition.

[0051] In the above steps 1 to 5, the mass ratio of ascorbyl glucoside to sodium dithionite, mesoporous silica, calcium hydroxide, water-absorbing resin, micropowder silica gel, and γ-aminopropyltrimethoxysilane is 64:24:3:5:2:2.

[0052] In the oxygen absorbing component, the mass ratio of sodium dithionite to ascorbyl glucoside is 16:84.

[0053] 6. Add the oxygen absorbing composition to the epoxy resin, and then stir at room temperature for 1.5 hours under nitrogen protection to obtain a mixture I; the mass ratio of the oxygen absorbing composition to the epoxy resin is 45:55; 7. Then, an amine curing agent was added to the mixture I, and the mixture was stirred for 7 minutes under nitrogen protection to obtain a mixture II; 8. Finally, the mixture II is cured under nitrogen protection at 45°C to obtain the food deoxidizer.

[0054] Embodiment 5: A method for preparing a food deoxidizer, the preparation method comprising: 1. Under nitrogen protection, add 3-O-ethyl ascorbic acid ether and p-aminophenol to ethanol and stir for 30 minutes to obtain an oxygen absorbing component solution; 2. Then, under nitrogen protection, add diatomaceous earth to the oxygen absorbing component solution and stir for 10 minutes; 3. Then, under nitrogen protection, half of the sodium hydroxide was added to the solution and stirring continued for 35 minutes; then, the other half of the sodium hydroxide was added and stirring continued for 25 minutes to obtain a mixed solution; 4. Then, calcium chloride, magnesium stearate and N-(β-aminoethyl)-γ-aminopropyltriethoxysilane were added to the mixed solution I and stirred for 25 minutes to obtain a mixed solution II; 5. Finally, the mixed solution is evaporated, dried and ground at 120° C. to obtain the oxygen absorbing composition.

[0055] In the above steps 1 to 5, the mass ratio of 3-O-ethyl ascorbic acid ether to p-aminophenol, diatomaceous earth, sodium hydroxide, calcium chloride, magnesium stearate, and N-(β-aminoethyl)-γ-aminopropyltriethoxysilane is 60:22:8:8:0.5:1.5.

[0056] In the oxygen absorbing component, the mass ratio of p-aminophenol to 3-O-ethyl ascorbic acid ether is 18:82.

[0057] 6. Add the oxygen absorbing composition to the epoxy resin, and then stir at room temperature for 1 hour under nitrogen protection to obtain a mixture I; the mass ratio of the oxygen absorbing composition to the epoxy resin is 35:65; 7. Then, an amine curing agent was added to the mixture I, and the mixture was stirred for 6 minutes under nitrogen protection to obtain a mixture II; 8. Finally, the mixture II is cured under nitrogen protection at 35°C to obtain the food deoxidizer.

[0058] Embodiment 6: A method for preparing a food deoxidizer, the preparation method comprising: 1. Under nitrogen protection, add ascorbyl stearate and sodium dithionite to ethanol and stir for 20 minutes to obtain an oxygen absorbing component solution; 2. Then, under nitrogen protection, add zeolite to the oxygen absorbing component solution and stir for 15 minutes; 3. Then, under nitrogen protection, add half of the sodium carbonate to the solution and continue stirring for 40 minutes; then add the other half of the sodium carbonate and continue stirring for 10 minutes to obtain a mixed solution; 4. Then add the water-absorbing resin, talcum powder and γ-aminopropyltriethoxysilane to the mixed solution I and stir for 20 minutes to obtain a mixed solution II; 5. Finally, the mixed solution is evaporated, dried and ground at 115° C. to obtain the oxygen absorbing composition.

[0059] In the above steps 1 to 5, the mass ratio of ascorbic stearate to sodium dithionite, zeolite, sodium carbonate, water-absorbing resin, talc and γ-aminopropyltriethoxysilane is 60:28:5:5:1.5:0.5.

[0060] In the oxygen absorbing component, the mass ratio of sodium dithionite to ascorbic stearate is 12:88.

[0061] 6. Add the oxygen absorbing composition to the epoxy resin, and then stir at room temperature for 2 hours under nitrogen protection to obtain a mixture I; the mass ratio of the oxygen absorbing composition to the epoxy resin is 30:70; 7. Then, an amine curing agent was added to the mixture I, and the mixture was stirred for 9 minutes under nitrogen protection to obtain a mixture II; 8. Finally, the mixture II is cured under nitrogen protection at 50°C to obtain the food deoxidizer.

[0062] Comparative Example 1: A method for preparing a food deoxidizer, the preparation method comprising: 1. Under nitrogen protection, add ascorbic acid and p-aminophenol to ethanol and stir for 30 minutes to obtain an oxygen absorbing component solution; 2. Then, under nitrogen protection, add mesoporous silica to the oxygen absorbing component solution and stir for 10 minutes; 3. Then, under nitrogen protection, half of the calcium hydroxide was added to the solution, and stirring was continued for 30 min; then, the other half of the calcium hydroxide was added, and stirring was continued for 20 min to obtain a mixed solution I; 4. Then, calcium chloride, micropowder silica gel and γ-aminopropyltrimethoxysilane were added to the mixed solution I and stirred for 15 minutes to obtain a mixed solution II; 5. Finally, the mixed solution II is evaporated, dried and ground at 100° C. to obtain the oxygen absorbing composition.

[0063] In the above steps 1 to 5, the mass ratio of ascorbic acid to p-aminophenol, mesoporous silica, calcium hydroxide, calcium chloride, micropowder silica gel, and γ-aminopropyltrimethoxysilane is 65:20:6:8:0.5:0.5.

[0064] In the oxygen absorbing component, the mass ratio of p-aminophenol to ascorbic acid is 10:90.

[0065] 6. Add the oxygen absorbing composition to the polystyrene resin, and then stir at room temperature for 1 hour under nitrogen protection to obtain a mixture I; the mass ratio of the oxygen absorbing composition to the polystyrene resin is 50:50; 7. Then, an amine curing agent was added to the mixture I, and the mixture was stirred for 5 minutes under nitrogen protection to obtain a mixture II; 8. Finally, the mixture II is cured under nitrogen protection at 40°C to obtain the food deoxidizer.

[0066] Comparative Example 2: A method for preparing a food deoxidizer, the preparation method comprising: 1. Under nitrogen protection, add ascorbyl palmitate and p-aminophenol to ethanol and stir for 35 minutes to obtain an oxygen absorbing component solution; 2. Then, under nitrogen protection, add zeolite to the oxygen absorbing component solution and stir for 7 minutes; 3. Then, under nitrogen protection, half of the sodium hydroxide was added to the solution and stirring continued for 20 minutes; then, the other half of the sodium hydroxide was added and stirring continued for 25 minutes to obtain a mixed solution; 4. Then add calcium chloride and talcum powder to the mixed solution I and stir for 20 minutes to obtain a mixed solution II; 5. Finally, the mixed solution is evaporated, dried and ground at 105° C. to obtain the oxygen absorbing composition.

[0067] In the above steps 1 to 5, the mass ratio of ascorbyl palmitate, p-aminophenol, zeolite, sodium hydroxide, calcium chloride and talc is 71:20:2:6:1.

[0068] In the oxygen absorbing component, the mass ratio of p-aminophenol to ascorbyl palmitate is 15:85.

[0069] 6. Add the oxygen absorbing composition to the polystyrene resin, and then stir at room temperature for 2 hours under nitrogen protection to obtain a mixture I; the mass ratio of the oxygen absorbing composition to the polystyrene resin is 40:60; 7. Then, an amine curing agent was added to the mixture I, and the mixture was stirred for 10 minutes under nitrogen protection to obtain a mixture II; 8. Finally, the mixture II is cured under nitrogen protection at 60°C to obtain the food deoxidizer.

[0070] Comparative Example 3: A method for preparing a food deoxidizer, the preparation method comprising: 1. Under nitrogen protection, add ascorbic acid and p-aminophenol to ethanol and stir for 30 minutes to obtain an oxygen absorbing component solution; 2. Then, under nitrogen protection, add diatomaceous earth to the oxygen absorbing component solution and stir for 10 minutes; 3. Then, under nitrogen protection, half of the sodium hydroxide was added to the solution and stirring continued for 35 minutes; then, the other half of the sodium hydroxide was added and stirring continued for 25 minutes to obtain a mixed solution; 4. Then add calcium chloride and magnesium stearate to the mixed solution I and stir for 25 minutes to obtain a mixed solution II; 5. Finally, the mixed solution is evaporated, dried and ground at 120° C. to obtain the oxygen absorbing composition.

[0071] In the above steps 1 to 5, the mass ratio of ascorbic acid to p-aminophenol, diatomaceous earth, sodium hydroxide, calcium chloride and magnesium stearate is 61.5:22:8:8:0.5.

[0072] In the oxygen absorbing component, the mass ratio of p-aminophenol to ascorbic acid is 18:82.

[0073] 6. Add the oxygen absorbing composition to the polystyrene resin, and then stir at room temperature for 1 hour under nitrogen protection to obtain a mixture I; the mass ratio of the oxygen absorbing composition to the polystyrene resin is 35:65; 7. Then, an amine curing agent was added to the mixture I, and the mixture was stirred for 6 minutes under nitrogen protection to obtain a mixture II; 8. Finally, the mixture II is cured under nitrogen protection at 35°C to obtain the food deoxidizer.

[0074] Referring to GB / T 41896-2022, the normal pressure water (oil) displacement method is used to test the total oxygen absorption of the food deoxidizer per unit mass (5g), as well as the time consumed to reach the total oxygen absorption, so as to comprehensively reflect the oxygen absorption performance and oxygen absorption efficiency of each group of food deoxidizers.

[0075] Table 1 Performance test results of food deoxidizers prepared in Examples 1 to 6 and Comparative Examples 1 to 3

[0076] As can be seen from Table 1, the total oxygen absorption of 5g of the food deoxidizer prepared in Examples 1 to 6 is higher than that in Comparative Examples 1 to 3, and the time consumed to reach a higher total oxygen absorption is lower than that in Comparative Examples 1 to 3 as a whole. This is because in Examples 1 to 6, the derivatives of ascorbic acid in the oxygen absorption composition still retain more hydroxyl groups, and under the action of the silane coupling agent, they can be better combined with the carrier, the water absorbent and the flow aid, making the oxygen absorption composition more durable and effective; at the same time, the carrier has a larger specific surface area, and the derivatives of ascorbic acid are more attached to its surface, which can fully improve the oxygen absorption efficiency. In addition, the water absorbent further absorbs the moisture produced by the oxygen absorption reaction, promotes the reaction equilibrium to move in the direction of oxygen absorption, and increases the total oxygen absorption.

[0077] Moreover, in the food deoxidizers prepared in Examples 1 to 6, the oxygen-absorbing component that is the main component in the oxygen-absorbing composition is a derivative of ascorbic acid, which has more oxygen-containing functional groups (such as hydroxyl groups, ester groups, and ether bonds), and produces more hydrogen bonds with the oxygen-containing groups (such as hydroxyl groups and epoxy groups) in the epoxy resin, making the two mixed more evenly; and after adding the curing agent, the oxygen-containing groups in the epoxy resin react with the curing agent to cure the entire system, and the oxygen-absorbing composition and the epoxy resin are more firmly combined. The above two points enable the prepared food deoxidizer to absorb oxygen more evenly and stably, and fully improve the oxygen absorption efficiency of the prepared food deoxidizer.

[0078] The food deoxidizer prepared in Comparative Example 1 does not use a derivative of ascorbic acid with hydrophobic properties and relatively stable, but directly uses ascorbic acid; the food deoxidizer prepared in Comparative Example 2 does not use a silane coupling agent, and the derivative of ascorbic acid cannot be better combined with the carrier, the water absorbent and the flow aid; the food deoxidizer prepared in Comparative Example 3 does not use a derivative of ascorbic acid with hydrophobic properties and relatively stable, nor does it use a silane coupling agent. In addition, epoxy resin is not used in the food deoxidizers prepared in Comparative Examples 1 to 3, so the oxygen absorption composition is not mixed evenly in the resin, and the combination of the two is not strong enough. In summary, the total oxygen absorption amount and oxygen absorption efficiency of the oxygen absorption composition prepared in Comparative Examples 1 to 3 are inferior to those of Examples 1 to 6.

[0079] In addition, it should be noted that: in the food deoxidizers prepared in Examples 1 to 6, the derivatives of ascorbic acid have hydrophobic properties and are relatively stable, and are not easily affected by environmental factors such as temperature and light. Moreover, the micropore air permeability of the surface of the oxygen-absorbing composition particles prepared with porous materials as carriers is small. When placed in the air, oxygen gradually penetrates from the external micropores into the interior of the particles, and oxygen absorption is started. Therefore, oxygen absorption can be not started in the early stage, and oxygen absorption can be started rapidly when the amount of oxygen is large, thereby avoiding the loss of oxygen absorption performance. At the same time, the water absorbing agent absorbs water to effectively avoid humidity rising and avoid the food being affected by humidity.

[0080] The above results show and describe the basic principles and main features of the present application as well as the advantages of the present application.

[0081] Those skilled in the art should understand that the present application is not limited by the above embodiments, and the above embodiments and descriptions are only for explaining the principles of the present application. Without departing from the spirit and scope of the present application, the present application may have various changes and improvements, and these changes and improvements fall within the scope of the present application for which protection is sought. The scope of protection sought in the present application is defined by the equivalents of the attached claims.

Claims

1. An oxygen absorbing composition, characterized in that The oxygen absorbing composition comprises an oxygen absorbing component, a carrier and an auxiliary agent; the oxygen absorbing component comprises ascorbic acid or an ascorbic acid derivative, and any one of p-aminophenol and sodium dithionite; the auxiliary agent comprises a catalyst, a water absorbent, a flow aid and a silane coupling agent.

2. An oxygen absorbing composition according to claim 1, characterized in that: In the oxygen absorbing composition, the mass ratio of the oxygen absorbing component, the carrier, the catalyst, the water absorbent, the flow aid, and the silane coupling agent is (60-70): (20-40): (2-10): (2-10): (0.2-2): (0.5-2).

3. An oxygen absorbing composition according to claim 1, characterized in that: In the oxygen absorbing component, the mass ratio of p-aminophenol or sodium dithionite to ascorbic acid or an ascorbic acid derivative is (10-20): (80-90).

4. An oxygen absorbing composition according to claim 1, characterized in that: In the oxygen absorbing component, the derivatives of ascorbic acid include one or more of ascorbyl glucoside, 3-O-ethyl ascorbic acid ether, ascorbyl palmitate, and ascorbyl stearate.

5. An oxygen absorbing composition according to claim 1, characterized in that: The carrier comprises a porous material; the porous material comprises one or more of mesoporous silica, diatomaceous earth, and zeolite; the specific surface area of ​​the carrier is 200-500 m² / g.

6. An oxygen absorbing composition according to claim 1, characterized in that: The catalyst includes one or more of calcium hydroxide, sodium hydroxide, and sodium carbonate; the water absorbent includes one or two of calcium chloride and water-absorbing resin; and the glidant includes one or more of micro-powder silica gel, magnesium stearate, and talc.

7. An oxygen absorbing composition according to claim 1, characterized in that: The silane coupling agent includes one or more of γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and N-(β-aminoethyl)-γ-aminopropyltriethoxysilane.

8. The method for preparing an oxygen absorbing composition according to any one of claims 1 to 7, characterized in that: The preparation method comprises: Under nitrogen protection, the oxygen absorbing component is added to ethanol and stirred for 20 to 40 minutes to obtain an oxygen absorbing component solution; Then, under nitrogen protection, the carrier is added to the oxygen absorbing component solution and stirred for 5 to 15 minutes; Then, half of the catalyst was added to the solution under nitrogen protection, and stirring was continued for 20 to 40 minutes; then the other half of the catalyst was added, and stirring was continued for 10 to 30 minutes to obtain a mixed solution I; Then, the water absorbent, the flow aid and the silane coupling agent are added to the mixed solution I and stirred for 10 to 30 minutes to obtain a mixed solution II; Finally, the mixed solution II is evaporated, dried and ground at 90-120° C. to obtain the oxygen absorbing composition.

9. The use of an oxygen absorbing composition according to any one of claims 1 to 7, characterized in that: Used for preparing food deoxidizer; the food deoxidizer comprises epoxy resin and the oxygen absorbing composition according to any one of claims 1 to 7; the mass ratio of the oxygen absorbing composition to the epoxy resin is (30 to 50): (50 to 70).

10. The use of an oxygen absorbing composition according to claim 9, characterized in that: The preparation method of the food deoxidizer comprises: The oxygen absorbing composition is added to the epoxy resin, and then stirred at room temperature for a first set time under nitrogen protection to obtain a mixture I; Then, a curing agent is added to the mixture I, and the mixture is stirred for a second set time under nitrogen protection to obtain a mixture II; Finally, the mixture II is cured under the conditions of nitrogen protection and the first set temperature, and the food deoxidizer is obtained after curing; The curing agent is one or more of an amine curing agent and a phenolic curing agent; the first setting time is 1 to 2 hours, the second setting time is 5 to 10 minutes, and the first setting temperature is 20 to 60°C.

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