Organic deoxidizer and preparation method thereof
Through the specific ratio of adsorption main agent, catalyst and acid-base regulator, combined with the preparation method of modified mesoporous silica, the problem of releasing carbon dioxide after oxygen absorption by organic deoxidizer is solved, and the oxygen adsorption effect without CO2 is achieved, avoiding packaging bulges and product corrosion, and reducing production costs.
Patent Information
- Application Number
- CN202510427086.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-07
- Publication Date
- 2025-07-01
AI Technical Summary
Existing organic deoxidants easily release carbon dioxide after oxygen absorption, resulting in packaging bulge and corrosive problems to the product.
The adsorption agent, catalyst and acid-base regulator of a specific ratio are used to react polysaccharides with oxygen to form aldehydes or carboxylic acids and water, and carbon dioxide is not produced during the process. The organic deoxidant consists of polysaccharide alcohols, metal ion compounds and modified mesoporous silica. The modified mesoporous silica is prepared by a four-step modification method, which increases the oxygen adsorption amount and oxygen absorption rate.
It solves the problem of organic deoxidants releasing carbon dioxide after oxygen absorption, avoids packaging bulges and product corrosion, and reduces production costs and saves more than 50%.
Smart Images
Figure BDA0005347034490000071
Abstract
Description
Technical Field
[0001] This application relates to the technical field of deoxidizers, and particularly to an organic deoxidizer and a preparation method thereof. Background Art
[0002] A deoxidizer, also known as an oxygen absorber or oxygen scavenger, is an additive that can absorb oxygen. Deoxidizers are widely used in the food industry, as well as in industries such as display panels, metal aluminum foils, and electronic appliances. In the food industry, they are mainly applied to high-fat cooked food products such as mooncakes, pastries, baked goods, roasted nuts, and meats, as well as fresh foods such as fruits and vegetables. The deoxidizer is placed together in a packaging container, and it absorbs the oxygen in the packaging container to delay food spoilage and extend the food shelf life. In the electronics industry, they are mainly applied to scenarios such as high-precision electronic components, oxygen-sensitive metal parts, and precision instruments. By placing a deoxidizer, it absorbs the oxygen in a closed environment to slow down the oxidation rate of electronic components, display panel circuits, and aluminum foils, thereby extending the service life of electronic components.
[0003] Currently, existing deoxidizers are generally divided into inorganic deoxidizers and organic deoxidizers. Inorganic deoxidizers are a type of deoxidizer mainly composed of reduced iron powder, added with adsorbents such as activated carbon and auxiliaries. Organic deoxidizers generally use antioxidant organic substances such as vitamins as the main body and some metal ion compounds as catalysts. Since iron-based deoxidizers cannot pass through metal detectors and contain some corrosive elements, they cannot meet the requirements of electronic products. In the electronics industry, people usually use organic deoxidizers represented by vitamin substances. However, vitamin-based organic deoxidizers usually release carbon dioxide after absorbing oxygen, causing the packaging to bulge. At the same time, the released carbon dioxide forms carbonic acid with water vapor in the air, and this acidic substance is also corrosive to the product.
[0004] To inhibit the problem of carbon dioxide release after vitamin substances absorb oxygen, people have adopted adding calcium hydroxide particles as an adsorbent. However, due to the influence of the external temperature, and the calcium hydroxide particles will be wrapped by the main agent powder, affecting the adsorption efficiency. Moreover, adding calcium hydroxide particles, the combination of particles and powder is also not conducive to production. Summary of the Invention
[0005] In order to improve the problem that existing organic deoxidizers are prone to release carbon dioxide after absorbing oxygen, this application provides an organic deoxidizer and a preparation method thereof. This organic deoxidizer will not release carbon dioxide after absorbing oxygen, and can improve the packaging bulging and corrosiveness problems brought about by existing organic deoxidizers after absorbing oxygen.
[0006] In the first aspect, an organic deoxidizer provided by this application adopts the following technical solution: An organic deoxidizer, comprising an adsorption main agent, a catalyst, and an acid-base regulator in a weight ratio of (10 - 20):(1 - 5):(4 - 5). The adsorption main agent is obtained by mixing a polyol substance, a solvent, and a porous carrier in a weight ratio of (20 - 100):(30 - 50):(15 - 35). The catalyst is obtained by mixing a metal ion compound, a solvent, and a porous carrier in a weight ratio of (5 - 25):15:15.
[0007] The organic deoxidizer of the present application is obtained by mixing an adsorption main agent, a catalyst, and an acid-base regulator in specific ratios. Among them, the adsorption main agent is obtained by dissolving a polyol substance in a solvent and then adsorbing it with a porous carrier, and it is a solid powder. The catalyst is obtained by dissolving a metal ion compound in a solvent and then adsorbing it with a porous carrier, and it is also a solid powder. Loading the polyol substance and the metal ion compound on the porous carrier respectively can increase the oxygen adsorption amount of the organic deoxidizer. Then, under suitable pH conditions, through the catalytic action of metal ions, the polyol substance reacts with oxygen to generate the corresponding aldehyde or carboxylic acid and water. This process produces no CO2 and can solve the problem that the existing organic deoxidizer is prone to releasing CO2 after absorbing oxygen, causing the package to bulge or being corrosive to the product. At the same time, compared with vitamin-based organic deoxidizers, the cost can be saved by more than 50%.
[0008] In some specific embodiments, the porous carrier uses modified mesoporous silica, and the preparation method of the modified mesoporous silica includes the following steps: S1. Graft a mercapto silane coupling agent on the surface of mesoporous silica to obtain a first product; S2. Graft a copolymer of 4-carboxyphenylboronic acid and dopamine on the surface of the first product to obtain a second product; S3. Control the biomimetic mineralization growth of a Ce-doped calcium silicate / calcium carbonate composite on the surface of the second product to form a third product with a multi-level ordered structure; S4. Crosslink and strengthen the third product to form a modified mesoporous silica with a three-dimensional interpenetrating network structure.
[0009] The present application modifies mesoporous silica through the above four-step method. The adsorption of the modified mesoporous silica with water is more than 1:2, which is beneficial to obtaining a dry adsorption main agent and catalyst, facilitating the production of a dry powder organic deoxidizer. Moreover, the specific surface area of the modified mesoporous silica is 800 - 1200m 2 , the pore volume is 2.8 - 4.5cm 3 / g, the maximum oxygen absorption per gram > 100mL, and the oxygen absorption rate is 50 - 60mL / 24h, which can improve the oxygen adsorption effect of the organic deoxidizer and enhance the deoxidation efficiency.
[0010] In some specific embodiments, in step S1, the weight ratio of the mercapto silane coupling agent to the mesoporous silica is (4 - 6):100.
[0011] In some specific embodiments, in step S1, the mesoporous silica is dispersed in an 80% ethanol aqueous solution at a ratio of (1 - 2):200, and then the mercapto silane coupling agent is added. The reaction is refluxed at 55 - 65°C under nitrogen protection. After completion, the solid is collected by filtration and dried to obtain the first product.
[0012] In this application, the silanol groups generated by the hydrolysis of the mercapto silane coupling agent react with the hydroxyl groups on the surface of the mesoporous silica, realizing the grafting of the mercapto silane coupling agent on the surface of the mesoporous silica.
[0013] In some specific embodiments, in step S2, the weight ratio of the first product, 4-carboxyphenylboronic acid, and dopamine hydrochloride is 1:(0.2 - 0.3):(0.3 - 0.4).
[0014] In some specific embodiments, in step S2, the first product is added to the monomer mixture, and ozone is introduced for reaction. Then, the filter residue is collected by filtration to obtain the second product; wherein, in the monomer mixture, the molar concentration ratio of 4-carboxyphenylboronic acid to dopamine hydrochloride is 2:(1 - 1.5), and the pH is 8 - 9.
[0015] In this step, 4-carboxyphenylboronic acid contains a phenylboronic acid group, which has pH and glucose responsiveness and can form dynamic covalent bonds. Dopamine hydrochloride contains a catechol structure and has strong adhesion. Introducing ozone to initiate the copolymerization of these two monomers can combine the characteristics of both to form a copolymer layer with dynamic responsiveness and strong adhesion. Then, the copolymer layer combines with the mercapto silane coupling agent grafted on the surface of the mesoporous silica, thereby fixing the copolymer layer formed by carboxyphenylboronic acid and dopamine hydrochloride on the surface of the mesoporous silica.
[0016] In some specific embodiments, in step S3, the biomimetic mineralization growth treatment includes the following steps: The second product is added to the mineralization kettle. A 0.05 - 0.1 mol / L Na2SiO3 solution and a 0.025 - 0.05 mol / L CaCl2 solution are pumped in from channel A, and a 0.15 - 0.2 mol / L NaHCO3 solution and a 0.75 - 0.1 mg / mL SIT-PEP solution are pumped in from channel B. The flow rate ratio of channel A to channel B is controlled to be 1:2. Then, a Ce(NO3)3 solution is added stepwise, and the pH value is adjusted in real time to be between 8 - 9 for mineralization reaction for 5 h. Then, the solid is collected by freeze centrifugation, washed and dried to obtain the third product.
[0017] This step is to perform biomimetic mineralization growth treatment on the second product, and regulate the formation structure of Ce-doped calcium silicate / calcium carbonate composite on the surface of mesoporous silica through SIT-PEP solution to form a composite material with a multi-level ordered structure.
[0018] The SIT-PEP solution is a silicon transporter mimetic peptide, which can be customized from GL Biochem (Shanghai) Ltd.
[0019] Among them, the step of adding Ce(NO3)3 solution step by step is as follows: in the first 1 h of the reaction, a 0.01 - 0.02 mol / L Ce(NO3)3 solution is introduced at a rate of 0.01 L / min, in the middle 2 - 3 h, a 0.03 - 0.05 mol / L Ce(NO3)3 solution is introduced at a rate of 0.01 L / min, and in the last 1 h, a 0.08 - 0.1 mol / L Ce(NO3)3 solution is introduced at a rate of 0.01 L / min.
[0020] In some specific embodiments, in step S4, the step of crosslinking and strengthening the third product is as follows: 1 part by weight of the third product is added to 8 - 12 parts by weight of the crosslinking solution, and the reaction is irradiated with ultraviolet light of 365 nm in a nitrogen atmosphere, then collected by filtration, and the solid is taken and dried to obtain modified mesoporous silica; the crosslinking solution is a mixed solution of pentaerythritol tetra(3-mercaptopropionate), diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide, ethylene glycol diacrylate and tetrahydrofuran, the mass concentration of pentaerythritol tetra(3-mercaptopropionate) is 15 - 20%, the mass concentration of diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide is 1 - 2%, and the mass concentration of ethylene glycol diacrylate is 15 - 20%.
[0021] In this step, after diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide absorbs ultraviolet light of 365 nm, it undergoes homolytic cleavage to generate benzoyl radicals and phosphoryl radicals. The radicals attack the thiol groups of pentaerythritol tetra(3-mercaptopropionate) to generate active sulfur radicals, and then a chain reaction occurs with the olefins in ethylene glycol diacrylate. The alternating addition of thiol and olefin forms a three-dimensional interpenetrating network, wrapping the mesoporous silica in the crosslinked matrix, strengthening the structure of the modified mesoporous silica and having a higher adsorption rate.
[0022] In the present application, the specific surface area of the modified mesoporous silica is 800 - 1200 m 2 / g, the pore volume is 2.8 - 4.5 cm 3 / g, the maximum oxygen absorption per gram > 100 mL, and the oxygen absorption rate is 50 - 60 mL / 24 h.
[0023] In this application, the polyol substances include, but are not limited to, one or more of xylitol, mannitol, erythritol, maltitol, and sorbitol.
[0024] In this application, the metal ion compounds include, but are not limited to, one or more of copper sulfate, ferrous sulfate, manganese sulfate, and zinc sulfate.
[0025] In this application, the acid-base regulators include, but are not limited to, one or more of quicklime, slaked lime, baking soda, soda ash, and sodium phosphate.
[0026] In a second aspect, the preparation method of an organic deoxidizer provided by this application adopts the following technical solution: A preparation method of an organic deoxidizer includes the following steps: After grinding the polyol substances into powder, add them to a solvent. After fully dissolving and stirring evenly, add a porous carrier and stir evenly to obtain the main adsorbent. Add the metal ion compound to a solvent. After fully stirring and dissolving completely, add a porous carrier and stir evenly to obtain the catalyst. Mix the main adsorbent, the catalyst, and the acid-base regulator evenly according to the ratio to obtain the organic deoxidizer.
[0027] In this application, after dissolving the polyol substances in a solvent, then adsorb them with a porous carrier to obtain a solid powder-like main adsorbent, and dissolve the metal ion compound in a solvent, then add a porous carrier for adsorption to obtain a solid powder-like catalyst. Finally, evenly mix the main adsorbent, the catalyst, and the acid-base regulator to obtain the organic deoxidizer. Among them, using this method to prepare the organic deoxidizer is beneficial to the uniform mixing of the polyol substances, the metal ion compounds, and the acid-base regulator, facilitating the production of the organic deoxidizer. However, it should be noted that the three need to be mixed before use and should not be mixed in advance, as mixing in advance is likely to reduce the use effect.
[0028] In summary, this application at least includes the following beneficial technical effects: (1) The organic deoxidizer of the present application is obtained by mixing an adsorption main agent, a catalyst and an acid-base regulator in a specific ratio, wherein the adsorption main agent is obtained by dissolving a polyol substance in a solvent and then adsorbing it on a porous carrier, and is a solid powdery substance, and the catalyst is obtained by dissolving a metal ion compound in a solvent and then adsorbing it on a porous carrier, and is also a solid powdery substance. The polyol substance and the metal ion compound are respectively loaded on a porous carrier, which can increase the oxygen adsorption capacity of the organic deoxidizer, and then under appropriate pH conditions, through the catalytic effect of metal ions, the polyol substance reacts with oxygen to generate corresponding aldehydes or carboxylic acids and water. This process does not produce CO2, which can solve the problem that the existing organic deoxidizer easily releases CO2 after absorbing oxygen, causing packaging bulging or corrosiveness to the product. At the same time, compared with vitamin-based organic deoxidizers, more than 50% of the cost can be saved.
[0029] (2) The present application uses a four-step method to modify mesoporous silica. The adsorption ratio of the modified mesoporous silica to water is above 1:2, which is conducive to obtaining a dry adsorption main agent and catalyst, and is convenient for the production of dry powdered organic deoxidizer. The specific surface area of the modified mesoporous silica is 800-1200m 2 , pore volume is 2.8-4.5cm 3 / gThe maximum oxygen absorption capacity of a single gram is >100mL, and the oxygen absorption rate is 50-60mL / 24h, which can improve the adsorption effect of organic deoxidizer on oxygen and enhance the deoxygenation efficiency. DETAILED DESCRIPTION
[0030] The following is a further explanation in conjunction with specific experiments. Among them, mesoporous silica can be commercially available with a specific surface area of >600m 2 / g of mesoporous silica, or homemade mesoporous silica can be used. The mesoporous silica used in the following examples of the present application is prepared by the following method: A method for preparing mesoporous silica comprises the following steps: The first step is to add hexadecyltrimethylammonium bromide to deionized water, stir thoroughly to dissolve, and then add anhydrous ethanol and mix well to obtain a mixed solution, wherein the weight ratio of hexadecyltrimethylammonium bromide, deionized water and anhydrous ethanol is 0.1:40:20; The second step is to add methyl orthosilicate dropwise into the mixed solution while maintaining magnetic stirring at a stirring speed of 500 rpm; wherein the weight ratio of methyl orthosilicate to the mixed solution is 1:60; The third step is to slowly drip ammonia water into the product of the second step, adjust the pH to 10-11, and react at room temperature for 7 hours to form a white sol; the fourth step is to let the white sol stand for 24 hours, collect the precipitate by centrifuge, and dry it to obtain mesoporous silica.
[0031] Preparation Example
Preparation Example 1
[0032]
Preparation Example 2
Preparation Example 1
[0033]
Preparation Example 3
Preparation Example 1
[0034]
Preparation Example 4
Preparation Example 1
[0035]
Example 1
[0036] In this example, the preparation method of the organic deoxidizer includes the following steps: After grinding mannitol into powder according to the ratio of each raw material in the adsorption main agent, add it to deionized water. After fully dissolving and stirring evenly, add mesoporous silica and stir evenly to obtain the adsorption main agent; Add copper sulfate to deionized water according to the ratio of each raw material in the catalyst. After fully stirring and dissolving completely, add mesoporous silica and stir evenly to obtain the catalyst; Mix the adsorption main agent, catalyst, and acid-base regulator evenly according to the ratio to obtain the organic deoxidizer.
[0037]
Example 2
[0038] In this example, the preparation method of the organic deoxidizer includes the following steps: After grinding erythritol into powder according to the ratio of each raw material in the adsorption main agent, add it to deionized water. After fully dissolving and stirring evenly, add mesoporous silica and stir evenly to obtain the adsorption main agent; Add manganese sulfate to deionized water according to the ratio of each raw material in the catalyst. After fully stirring and dissolving completely, add mesoporous silica and stir evenly to obtain the catalyst; Mix the adsorption main agent, catalyst, and acid-base regulator evenly according to the ratio to obtain the organic deoxidizer.
[0039]
Example 3
Example 2
Preparation Example 1
[0040]
Example 4
Example 1
Preparation Example 2
[0041]
Example 5
Example
Preparation Example 3
[0042]
Example 6
Example 2
Preparation Example 4
[0043] Performance detection test 1. Deoxidation rate: In a closed environment, the removal rate of oxygen per unit time, with the unit of mL / 24h.
[0044] 2. Unit maximum oxygen removal amount: Pack 5g of the deoxidizer in a packaging bag. In a closed environment, test the total amount of oxygen that can be removed by the deoxidizer per unit mass, with the unit of mL / g, and check whether the packaging bag bulges after the deoxidizer absorbs oxygen and the carbon dioxide release amount.
[0045] Table 1 Combined with the above Examples 1-6 and the detection results in Table 1, it can be seen that: Using the organic deoxidizer prepared with the adsorption main agent, catalyst and acid-base regulator of the present application for deoxidation will not release carbon dioxide, and can prevent problems such as packaging bulging or corrosion from occurring.
[0046] Combined with the above Examples 1-6 and the detection results in Table 1, it can be seen that: Using the modified mesoporous silica obtained by the four-step modification method of the present application as the porous carrier can effectively improve the deoxidation rate and the unit maximum oxygen removal amount of the organic deoxidizer.
[0047] This specific implementation manner is only an interpretation of the present application, and it is not a limitation to the present application. Those skilled in the art can make modifications without creative contributions to this specific implementation manner according to needs after reading this specification, but as long as it is within the scope of the claims of the present application, it is protected by the patent law.
Claims
1. An organic deoxidizer, characterized in that: The invention comprises an adsorption main agent, a catalyst and an acid-base regulator in a weight ratio of (10-20): (1-5): (4-5), wherein the adsorption main agent is obtained by mixing a polyol substance, a solvent and a porous carrier in a weight ratio of (20-100): (30-50): (15-35), and the catalyst is obtained by mixing a metal ion compound, a solvent and a porous carrier in a weight ratio of (5-25): 15:
15.
2. An organic deoxidizer according to claim 1, characterized in that: The porous carrier adopts modified mesoporous silica, and the preparation method of the modified mesoporous silica comprises the following steps: S1, grafting a mercaptosilane coupling agent onto the surface of mesoporous silica to obtain a first product; S2, grafting a copolymer of 4-carboxyphenylboronic acid and dopamine hydrochloride onto the surface of the first product to obtain a second product; S3, controlling the bionic mineralization growth of Ce-doped calcium silicate / sodium carbonate complex on the surface of the second product to form a third product with a multi-level ordered structure; S4. The third product is cross-linked and strengthened to form a modified mesoporous silica with a three-dimensional interpenetrating network structure.
3. An organic deoxidizer according to claim 2, characterized in that: In step S1, the weight ratio of the mercaptosilane coupling agent to the mesoporous silica is (4-6):
100.
4. An organic deoxidizer according to claim 2, characterized in that: In step S1, mesoporous silica is dispersed in an ethanol aqueous solution, and then a mercaptosilane coupling agent is added, and the mixture is heated under reflux under nitrogen protection to react. After the reaction is completed, the solid is collected by filtration and dried to obtain a first product.
5. An organic deoxidizer according to claim 2, characterized in that: In step S2, the weight ratio of the first product, 4-carboxyphenylboronic acid and dopamine hydrochloride is 1:(0.2-0.3):(0.3-0.4).
6. An organic deoxidizer according to claim 2, characterized in that: In step S2, the first product is added to a monomer mixture, ozone is introduced to react, and then the residue is filtered and collected to obtain a second product; wherein, in the monomer mixture, the molar concentration ratio of 4-carboxyphenylboronic acid to dopamine hydrochloride is 2:(1-1.5), and the pH is 8-9.
7. An organic deoxidizer according to claim 2, characterized in that: In step S3, the biomimetic mineralization growth process includes the following steps: The second product is added into the mineralization kettle, 0.05-0.1mol / L Na2SiO3 solution and 0.025-0.05mol / L CaCl2 solution are pumped into channel A, 0.15-0.2mol / L NaHCO3 solution and 0.75-0.1mg / mL SIT-PEP solution are pumped into channel B, the flow rate ratio of channel A to channel B is controlled to be 1:2, Ce(NO3)3 solution is added in a stepwise manner, the pH value is adjusted to between 8 and 9 in real time for mineralization reaction, and then the solid is collected by frozen centrifugation, and the third product is obtained after washing and drying.
8. An organic deoxidizer according to claim 2, characterized in that: In step S4, the steps of cross-linking and strengthening the third product are as follows: 1 part by weight of the third product is added to 8-12 parts by weight of a cross-linking liquid, and the mixture is irradiated with 365 nm ultraviolet light under a nitrogen atmosphere for reaction, and then the mixture is collected and filtered, and the solid is dried to obtain modified mesoporous silica; the cross-linking liquid is a mixed solution of pentaerythritol tetrakis(3-mercaptopropionate), diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide, ethylene glycol diacrylate and tetrahydrofuran, wherein the mass concentration of pentaerythritol tetrakis(3-mercaptopropionate) is 15-20%, the mass concentration of diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide is 1-2%, and the mass concentration of ethylene glycol diacrylate is 15-20%.
9. An organic deoxidizer according to claim 2, characterized in that: The specific surface area of the modified mesoporous silica is 800-1200 m 2 / g, pore volume is 2.8-4.5cm 3 / g, the maximum oxygen absorption capacity of a single gram is >100mL, and the oxygen absorption rate is 50-60mL / 24h.
10. A method for preparing an organic deoxidizer according to any one of claims 1 to 9, characterized in that: The following steps are involved: Grind the polyol substance into powder, add it into the solvent, fully dissolve it and stir it evenly, then add it into the porous carrier, stir it evenly, and obtain the adsorption main agent; Add the metal ion compound to the solvent, stir thoroughly to dissolve it completely, then add the porous carrier and stir evenly to obtain a catalyst; The adsorption main agent, the catalyst and the acid-base regulator are uniformly mixed according to a proportion to obtain an organic deoxidizer.