Medicinal silica gel desiccant with high adsorption speed and preparation method thereof

Abstract

The invention discloses a medicinal silica gel desiccant with high adsorption speed and a preparation method thereof, and belongs to the technical field of desiccant preparation. The medicinal silica gel desiccant with high adsorption speed is prepared from the following components in parts by weight: 50-65 parts of silica gel, 4-8 parts of calcium chloride, 3-6 parts of magnesium sulfate, 3-7 parts of ferric oxide, 1-4 parts of an antibacterial compound, 5-10 parts of a modified surfactant, 1-2 parts of potassium hydroxide, 10-30 parts of ice water, 2-4 parts of acrylic acid, 2-4 parts of acrylamide and 0.4-0.8 part of sodium carboxymethyl starch. 0.2 to 0.3 part of benzoin dimethyl ether, 0.005 to 0.015 part of polyethylene glycol diacrylate and 1 to 2 parts of methanol. The silica gel desiccant prepared by the method has excellent antibacterial performance, adsorption rate and adsorption capacity.

Description

Technical Field

[0001] The invention belongs to the technical field of desiccant preparation, and in particular relates to a medicinal silica gel desiccant with fast adsorption speed and a preparation method thereof. Background Art

[0002] As an indispensable part of modern drug storage and transportation, the adsorption speed and effect of medicinal silica gel desiccant are directly related to the quality and safety of drugs. In the current medical and health care field, with the increasing requirements for drug quality and safety, the research and development of medicinal silica gel desiccant is particularly important.

[0003] From the industry background, silica gel desiccant has the characteristics of being non-toxic, odorless, non-corrosive, and non-polluting, and its advantages of fast moisture absorption speed and strong moisture absorption capacity have been widely used in the pharmaceutical field. Especially in the storage and transportation of medicines, silica gel desiccant can effectively absorb moisture in the air, keep the medicines dry, and prevent them from getting damp and deteriorating.

[0004] However, with the advancement of science and technology and the continuous development of pharmaceutical production processes, the performance requirements for pharmaceutical silica gel desiccants are also increasing. Among them, adsorption speed, as one of the important indicators for measuring desiccant performance, has received widespread attention. Rapid adsorption can quickly reduce the humidity of the drug storage environment and effectively prevent various problems caused by moisture in drugs, such as reduced efficacy and drug deterioration.

[0005] Patent CN 113426424 B discloses a temperature-sensitive composite silica gel desiccant and a preparation method thereof. Silica sol, N-isopropylacrylamide and azobisisobutyronitrile are dissolved in a dispersion and reacted under nitrogen protection, magnetic stirring and a constant temperature water bath; the reaction liquid is filtered, and then the solid reactant obtained by filtration is placed in a vacuum oven for drying; the dried reactant is immersed in a lithium chloride solution; after filtering and washing, the final product is placed in an oven for drying to obtain the final desiccant. The desiccant prepared by the invention has excellent hygroscopic properties and good regeneration properties. However, when the prepared desiccant is used in medicines, its antibacterial properties, adsorption speed and adsorption capacity still have room for improvement. Summary of the invention

[0006] The object of the present invention is to provide a medicinal silica gel desiccant with fast adsorption speed and a preparation method thereof, so as to solve the technical problems of poor antibacterial property, adsorption speed and adsorption capacity of the desiccant in the prior art.

[0007] In order to achieve the above object, the present invention adopts the following technical solutions:

[0008] The invention provides a medicinal silica gel desiccant with fast adsorption speed. The desiccant is composed of the following components in parts by weight: 50-65 parts of silica gel, 4-8 parts of calcium chloride, 3-6 parts of magnesium sulfate, 3-7 parts of ferric oxide, 1-4 parts of antibacterial compounds, 5-10 parts of modified surfactants, 1-2 parts of potassium hydroxide, 10-30 parts of ice water, 2-4 parts of acrylic acid, 2-4 parts of acrylamide, 0.4-0.8 parts of sodium carboxymethyl starch, 0.2-0.3 parts of benzoin dimethyl ether, 0.005-0.015 parts of polyethylene glycol diacrylate, and 1-2 parts of methanol, wherein the antibacterial compound is prepared from dipropylenetriamine, methyl acrylate, acrylic acid and N,N-methylenebisacrylamide, and the modified surfactant is prepared from didodecylmethyl tertiary amine, chloroacetic acid, corn starch, urea and sodium silicate.

[0009] Preferably, the method for preparing the antibacterial compound comprises the following steps:

[0010] Q1: Dissolve dipropylene triamine in a container containing methanol, then drop methyl acrylate into the container, and perform an ice bath reaction under a nitrogen atmosphere. After the reaction is completed, continue to add methyl acrylate, and then continue to perform an ice bath reaction under a nitrogen atmosphere, and then perform a heating treatment to obtain a crude product;

[0011] Q2: The crude product is placed in a rotary evaporator for vacuum drying, the sticky product is collected and washed, and dried to obtain an intermediate product;

[0012] Q3: Acrylic acid is dissolved in deionized water at room temperature, and then N,N-methylenebisacrylamide is added to react to obtain a gel, which is then mixed with the intermediate product and fully stirred and dissolved to obtain an antibacterial compound.

[0013] In the above process, dipropylene triamine and methyl acrylate are reacted by Michael addition reaction and amidation reaction to prepare an intermediate product, and then acrylic acid reacts with N, N-methylene bis acrylamide to obtain a gel with a loading function, which is then combined with the intermediate product to obtain an antibacterial compound. The synthetic reaction formula of the intermediate product is as follows:

[0014]

[0015] Preferably, in Q1, the dosage ratio of dipropylenetriamine, methanol, methyl acrylate added for the first time and methyl acrylate added for the second time is (4-4.24) g: (6-6.5) mL: (0.18-0.26) mL: (0.02-0.08) mL, the ice bath reaction temperature is 0-1°C, the reaction time is 2-4h, the ice bath reaction temperature is continued to be 0-1°C, the reaction time is 30-40min, the heating treatment temperature is 25-30°C, and the reaction time is 48-50min.

[0016] Preferably, in Q2, the vacuum drying temperature is 40-50°C, the mixture is washed with ether 3-5 times, the drying temperature is 30-40°C, and the drying time is 12-14h; in Q3, the dosage ratio of acrylic acid, deionized water, N,N-methylenebisacrylamide and the intermediate product is (200-300) mg: (1-1.5) mL: (5-7.5) mg: (50-75) mg, and the stirring time is 45-60 min.

[0017] Preferably, the preparation method of the modified surfactant comprises the following steps:

[0018] S1: Add didodecylmethyl tertiary amine to a three-necked flask, then mix chloroacetic acid and deionized water and stir, after stirring completely, add the chloroacetic acid solution to the three-necked flask, continue to stir and mix to form an emulsion, heat the emulsion in an oil bath to raise the temperature to the reflux temperature, then dropwise add sodium hydroxide solution, continue the reflux reaction, after the reaction is completed, pour the reaction product into a separatory funnel, cool and stand, and then separate the layers into a water layer and a product layer;

[0019] S2: Add corn starch to deionized water, stir and mix to obtain corn starch emulsion, add corn starch emulsion into a three-necked flask, add urea and sodium silicate at the same time, stir and dissolve evenly, treat in a water bath, then add the product layer, continue to heat up after stirring, and after treatment, cool to room temperature to obtain a modified surfactant.

[0020] In the above process, didodecylmethyl tertiary amine reacts with chloroacetic acid to undergo quaternization reaction, the chlorine atom in chloroacetic acid replaces the nitrogen atom of the tertiary amine, and the added sodium hydroxide solution can neutralize the hydrochloric acid produced during the reaction, thereby causing the reaction to proceed in the direction of generating a quaternary ammonium salt; subsequently, under alkaline conditions, the carboxyl groups in the product layer react with the hydroxyl groups in the corn starch molecules to undergo esterification reaction to generate a modified surfactant.

[0021] Preferably, in S1, the dosage ratio of didodecylmethyl tertiary amine, chloroacetic acid, deionized water and sodium hydroxide solution is (20-25) g: (5.66-8.49) g: (10-15) mL: (10-15) mL, the mixing and stirring speed is 2000-3000 rpm, the stirring time is 20-30 min, the continued stirring time is 30-45 min, the oil bath heating temperature is 90-100 ° C, the dropping time is 30-40 min, and the reflux reaction time is 2-8 h.

[0022] Preferably, in S2, the dosage ratio of corn starch, deionized water, urea, sodium silicate and product layer is (20-30) g: (100-120) mL: (0.6-0.9) g: (0.1-0.15) g: (0.8-1.2) mL, the water bath treatment temperature is 70-80°C, the time is 30-50 min, the heating treatment temperature is 90-100°C, and the treatment time is 30-40 min.

[0023] Preferably, the method for preparing the medicinal silica gel desiccant with fast adsorption speed comprises the following steps:

[0024] Step (1): adding potassium hydroxide to a beaker containing ice water, adding acrylic acid during stirring to obtain an acrylic acid solution, placing the acrylic acid solution in a beaker, adding acrylamide, sodium carboxymethyl starch, benzoin dimethyl ether and polyethylene glycol diacrylate, stirring evenly, placing the mixture in an ultraviolet radiation box, irradiating, soaking the product in a methanol solution, vacuum drying, and crushing to obtain a composite water-absorbing resin;

[0025] Step (2): After uniformly mixing silica gel, composite water-absorbing resin, calcium chloride, magnesium sulfate, ferric oxide, antibacterial compound and surfactant, the mixture is pressed into granules by an extruder, and dried to obtain a medicinal silica gel desiccant with a fast adsorption speed.

[0026] Preferably, in step (1), the irradiation time is 15-20 min, the soaking time is 6-8 h, the vacuum drying temperature is 70-80° C., and the time is 4-6 h.

[0027] Preferably, in step (2), the mixing time is 2-3 hours, the drying temperature is 110-120° C., and the drying time is 3-5 hours.

[0028] In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are:

[0029] 1. The present invention first uses dipropylenetriamine, methyl acrylate, acrylic acid and N,N-methylenebisacrylamide as raw materials to prepare an antibacterial compound, then uses didodecylmethyl tertiary amine, chloroacetic acid and corn starch as raw materials to prepare a modified surfactant, and then prepares a composite water-absorbent resin. The antibacterial compound, the modified surfactant and the composite water-absorbent resin are added to silica gel to prepare a silica gel desiccant, which can effectively improve its antibacterial performance, adsorption speed and adsorption capacity.

[0030] 2. In the present invention, dipropylenetriamine reacts with methyl acrylate to obtain an intermediate product, and then acrylic acid reacts with N,N-methylenebisacrylamide to obtain a gel that can load the intermediate product, thereby obtaining an antibacterial compound. The obtained antibacterial compound is added to a medicinal silica gel desiccant, which can effectively improve the antibacterial performance of the desiccant. The antibacterial compound can attract the negative charge on the surface of the bacteria through electrostatic action, and the cations interact with the phospholipid molecules in the cell membrane, resulting in cell membrane rupture, leakage of intracellular substances and bacterial death; and the antibacterial compound can also penetrate the cell membrane into the bacteria, interact with the DNA and RNA of the bacteria, affect the replication and transcription process of the bacterial genetic material, and inhibit the growth of the bacteria; and the antibacterial compound contains multiple active sites, which can act simultaneously with multiple sites on the surface of the bacteria to form multivalent chelation, thereby enhancing the affinity between the antibacterial compound and the bacteria and improving the antibacterial effect; the antibacterial compound is added to the silica gel desiccant and can be gradually released as the desiccant absorbs water, so that the antibacterial compound can provide lasting antibacterial protection in the entire drug packaging environment.

[0031] 3. The present invention uses didodecylmethyl tertiary amine, chloroacetic acid and corn starch as raw materials to prepare a modified surfactant, which is added to a silica gel desiccant to effectively improve its adsorption capacity and adsorption rate. The long-chain alkyl and polar groups in the modified surfactant work together to make the surface of the silica gel desiccant have more active sites, which can adsorb more water molecules. The introduction of the modified surfactant can also change the microstructure of the surface of the silica gel desiccant, increase its specific surface area, and further improve the adsorption capacity; the modified surfactant improves the wettability and permeability of the surface of the silica gel desiccant, making it easier for water molecules to contact and adsorb on the surface of the silica gel desiccant, and the modified surfactant can also affect the diffusion and migration of water molecules on the surface of the silica gel desiccant, thereby accelerating the adsorption rate; at the same time, corn starch is used as a raw material in the modified surfactant, which has good biocompatibility and environmental friendliness, and reduces the pollution caused by the silica gel desiccant to the environment. DETAILED DESCRIPTION

[0032] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0033] Example 1

[0034] This embodiment discloses a method for preparing an antibacterial compound, comprising the following steps:

[0035] Q1: 4.12 g of dipropylene triamine was dissolved in a container containing 6.25 mL of methanol, and then 0.22 mL of methyl acrylate was dropped into the container, and an ice bath reaction was carried out under a nitrogen atmosphere at 0°C for 4 hours. After the reaction was completed, 0.05 mL of methyl acrylate was added, and then an ice bath reaction was continued under a nitrogen atmosphere at 0°C for 40 minutes, and then a heating treatment was carried out at 30°C for 50 minutes to obtain a crude product;

[0036] Q2: The crude product was placed in a rotary evaporator at 50°C for vacuum drying, the viscous product was collected and washed with ether 5 times, and dried at 40°C for 14 h to obtain the intermediate product;

[0037] Q3: Under room temperature conditions, 250 mg of acrylic acid was dissolved in 1.25 mL of deionized water, and then 6.25 mg of N,N-methylenebisacrylamide was added to react to obtain a gel, which was then mixed with 62.5 mg of the intermediate product and stirred for 60 minutes to dissolve to obtain an antibacterial compound.

[0038] This embodiment discloses a method for preparing a modified surfactant, comprising the following steps:

[0039] S1: 22.5g of didodecylmethyl tertiary amine was added to a three-necked flask, and then 7.08g of chloroacetic acid and 12.5mL of deionized water were mixed and stirred at 2000rpm for 30min. After stirring was complete, the chloroacetic acid solution was added to the three-necked flask, and the stirring and mixing were continued for 30min to form an emulsion. The temperature of the emulsion was raised to the reflux temperature by heating in an oil bath at 100°C, and then 12.5mL of sodium hydroxide solution was added dropwise for 30min. The reflux reaction was continued for 6h. After the reaction was completed, the reaction product was poured into a separatory funnel, cooled and allowed to stand, and then separated into a water layer and a product layer;

[0040] S2: Add 25g corn starch to 110mL deionized water, stir and mix to obtain corn starch emulsion, add the corn starch emulsion into a three-necked flask, add 0.75g urea and 0.125g sodium silicate at the same time, stir and dissolve evenly, treat in a water bath at 80℃ for 40min, then add 1mL product layer, continue to heat up after stirring, treat at 100℃ for 40min, and after treatment, cool to room temperature to obtain a modified surfactant.

[0041] The present embodiment discloses a medicinal silica gel desiccant with fast adsorption speed, which is composed of the following components in parts by weight: 57.5 parts of silica gel, 6 parts of calcium chloride, 4.5 parts of magnesium sulfate, 5 parts of ferric oxide, 2.5 parts of antibacterial compounds, 7.5 parts of modified surfactants, 1.5 parts of potassium hydroxide, 20 parts of ice water, 3 parts of acrylic acid, 3 parts of acrylamide, 0.6 parts of sodium carboxymethyl starch, 0.25 parts of benzoin dimethyl ether, 0.005 parts of polyethylene glycol diacrylate, and 1.5 parts of methanol.

[0042] This embodiment discloses a method for preparing a medicinal silica gel desiccant with fast adsorption speed, comprising the following steps:

[0043] Step (1): adding potassium hydroxide to a beaker containing ice water, adding acrylic acid during stirring to obtain an acrylic acid solution, placing the acrylic acid solution in a beaker, adding acrylamide, sodium carboxymethyl starch, benzoin dimethyl ether and polyethylene glycol diacrylate, stirring evenly, placing the mixture in an ultraviolet radiation box, irradiating for 20 minutes, soaking the product in a methanol solution for 8 hours, vacuum drying at 70° C. for 6 hours, and crushing to obtain a composite water-absorbing resin;

[0044] Step (2): After mixing silica gel, composite water-absorbing resin, calcium chloride, magnesium sulfate, ferric oxide, antibacterial compound and surfactant for 3 hours, the mixture is pressed into granules by an extruder, and dried at 120° C. for 4 hours to obtain a medicinal silica gel desiccant with a fast adsorption rate.

[0045] Example 2

[0046] This embodiment discloses a method for preparing an antibacterial compound, comprising the following steps:

[0047] Q1: 4 g of dipropylene triamine was dissolved in a container containing 6 mL of methanol, and then 0.18 mL of methyl acrylate was dropped into the container, and an ice bath reaction was carried out under a nitrogen atmosphere at 0°C for 4 hours. After the reaction was completed, 0.02 mL of methyl acrylate was added, and then an ice bath reaction was continued under a nitrogen atmosphere at 0°C for 40 minutes, and then a heating treatment was carried out at 30°C for 50 minutes to obtain a crude product;

[0048] Q2: The crude product was placed in a rotary evaporator at 50°C for vacuum drying, the viscous product was collected and washed with ether 5 times, and dried at 40°C for 14 h to obtain the intermediate product;

[0049] Q3: 200 mg of acrylic acid was dissolved in 1 mL of deionized water at room temperature, and then 5 mg of N,N-methylenebisacrylamide was added to react to obtain a gel, which was then mixed with 50 mg of the intermediate product and stirred for 60 minutes to dissolve to obtain an antibacterial compound.

[0050] This embodiment discloses a method for preparing a modified surfactant, comprising the following steps:

[0051] S1: 20g of didodecylmethyl tertiary amine was added to a three-necked flask, and then 5.66g of chloroacetic acid and 10mL of deionized water were mixed and stirred at 2000rpm for 30min. After stirring was complete, the chloroacetic acid solution was added to the three-necked flask, and the stirring and mixing were continued for 30min to form an emulsion. The temperature of the emulsion was raised to the reflux temperature by heating in an oil bath at 100°C, and then 15mL of sodium hydroxide solution was added dropwise for 30min. The reflux reaction was continued for 6h. After the reaction was completed, the reaction product was poured into a separatory funnel, cooled and allowed to stand, and then separated into a water layer and a product layer;

[0052] S2: Add 20g corn starch into 100mL deionized water, stir and mix to obtain corn starch emulsion, add the corn starch emulsion into a three-necked flask, add 0.6g urea and 0.1g sodium silicate at the same time, stir and dissolve evenly, treat in a water bath at 80℃ for 40min, then add 0.8mL product layer, continue to heat up after stirring, treat at 100℃ for 40min, and after treatment, cool to room temperature to obtain a modified surfactant.

[0053] The present embodiment discloses a medicinal silica gel desiccant with fast adsorption speed, which is composed of the following components in parts by weight: 50 parts of silica gel, 4 parts of calcium chloride, 3 parts of magnesium sulfate, 3 parts of ferric oxide, 1 part of an antibacterial compound, 5 parts of a modified surfactant, 1 part of potassium hydroxide, 10 parts of ice water, 2 parts of acrylic acid, 2 parts of acrylamide, 0.4 parts of sodium carboxymethyl starch, 0.2 parts of benzoin dimethyl ether, 0.01 parts of polyethylene glycol diacrylate, and 1 part of methanol.

[0054] This embodiment discloses a method for preparing a medicinal silica gel desiccant with fast adsorption speed, comprising the following steps:

[0055] Step (1): adding potassium hydroxide to a beaker containing ice water, adding acrylic acid during stirring to obtain an acrylic acid solution, placing the acrylic acid solution in a beaker, adding acrylamide, sodium carboxymethyl starch, benzoin dimethyl ether and polyethylene glycol diacrylate, stirring evenly, placing the mixture in an ultraviolet radiation box, irradiating for 20 minutes, soaking the product in a methanol solution for 8 hours, vacuum drying at 70° C. for 6 hours, and crushing to obtain a composite water-absorbing resin;

[0056] Step (2): After mixing silica gel, composite water-absorbing resin, calcium chloride, magnesium sulfate, ferric oxide, antibacterial compound and surfactant for 3 hours, the mixture is pressed into granules by an extruder, and dried at 120° C. for 4 hours to obtain a medicinal silica gel desiccant with a fast adsorption rate.

[0057] Example 3

[0058] This embodiment discloses a method for preparing an antibacterial compound, comprising the following steps:

[0059] Q1: 4.24 g of dipropylene triamine was dissolved in a container containing 6.5 mL of methanol, and then 0.26 mL of methyl acrylate was dropped into the container, and an ice bath reaction was carried out under a nitrogen atmosphere at 0°C for 4 hours. After the reaction was completed, 0.08 mL of methyl acrylate was added, and then an ice bath reaction was continued under a nitrogen atmosphere at 0°C for 40 minutes, and then a heating treatment was carried out at 30°C for 50 minutes to obtain a crude product;

[0060] Q2: The crude product was placed in a rotary evaporator at 50°C for vacuum drying, the viscous product was collected and washed with ether 5 times, and dried at 40°C for 14 h to obtain the intermediate product;

[0061] Q3: 300 mg of acrylic acid was dissolved in 1.5 mL of deionized water at room temperature, and then 7.5 mg of N,N-methylenebisacrylamide was added to react to obtain a gel, which was then mixed with 75 mg of the intermediate product and stirred for 60 minutes to dissolve to obtain an antibacterial compound.

[0062] This embodiment discloses a method for preparing a modified surfactant, comprising the following steps:

[0063] S1: 25g of didodecylmethyl tertiary amine was added to a three-necked flask, and then 8.49g of chloroacetic acid and 15mL of deionized water were mixed and stirred at 2000rpm for 30min. After stirring was complete, the chloroacetic acid solution was added to the three-necked flask, and the stirring and mixing were continued for 30min to form an emulsion. The temperature of the emulsion was raised to the reflux temperature by heating in an oil bath at 100°C, and then 10mL of sodium hydroxide solution was added dropwise for 30min. The reflux reaction was continued for 6h. After the reaction was completed, the reaction product was poured into a separatory funnel, cooled and allowed to stand, and then separated into a water layer and a product layer;

[0064] S2: Add 30g corn starch into 120mL deionized water, stir and mix to obtain corn starch emulsion, add the corn starch emulsion into a three-necked flask, add 0.9g urea and 0.15g sodium silicate at the same time, stir and dissolve evenly, treat in a water bath at 80℃ for 40min, then add 1.2mL product layer, continue to heat up after stirring, treat at 100℃ for 40min, and after treatment, cool to room temperature to obtain a modified surfactant.

[0065] The present embodiment discloses a medicinal silica gel desiccant with fast adsorption speed, which is composed of the following components in parts by weight: 65 parts of silica gel, 8 parts of calcium chloride, 6 parts of magnesium sulfate, 7 parts of ferric oxide, 4 parts of antibacterial compounds, 10 parts of modified surfactants, 2 parts of potassium hydroxide, 30 parts of ice water, 4 parts of acrylic acid, 4 parts of acrylamide, 0.8 parts of sodium carboxymethyl starch, 0.3 parts of benzoin dimethyl ether, 0.015 parts of polyethylene glycol diacrylate, and 2 parts of methanol.

[0066] This embodiment discloses a method for preparing a medicinal silica gel desiccant with fast adsorption speed, comprising the following steps:

[0067] Step (1): adding potassium hydroxide to a beaker containing ice water, adding acrylic acid during stirring to obtain an acrylic acid solution, placing the acrylic acid solution in a beaker, adding acrylamide, sodium carboxymethyl starch, benzoin dimethyl ether and polyethylene glycol diacrylate, stirring evenly, placing the mixture in an ultraviolet radiation box, irradiating for 20 minutes, soaking the product in a methanol solution for 8 hours, vacuum drying at 70° C. for 6 hours, and crushing to obtain a composite water-absorbing resin;

[0068] Step (2): After mixing silica gel, composite water-absorbing resin, calcium chloride, magnesium sulfate, ferric oxide, antibacterial compound and surfactant for 3 hours, the mixture is pressed into granules by an extruder, and dried at 120° C. for 4 hours to obtain a medicinal silica gel desiccant with a fast adsorption rate.

[0069] Example 4

[0070] This embodiment discloses a method for preparing an antibacterial compound, comprising the following steps:

[0071] Q1: 4.07 g of dipropylene triamine was dissolved in a container containing 6.1 mL of methanol, and then 0.20 mL of methyl acrylate was dropped into the container, and an ice bath reaction was carried out under a nitrogen atmosphere at 0°C for 4 hours. After the reaction was completed, 0.04 mL of methyl acrylate was added, and then an ice bath reaction was continued under a nitrogen atmosphere at 0°C for 40 minutes, and then a heating treatment was carried out at 30°C for 50 minutes to obtain a crude product;

[0072] Q2: The crude product was placed in a rotary evaporator at 50°C for vacuum drying, the viscous product was collected and washed with ether 5 times, and dried at 40°C for 14 h to obtain the intermediate product;

[0073] Q3: Under room temperature conditions, 220 mg of acrylic acid was dissolved in 1.1 mL of deionized water, and then 6 mg of N,N-methylenebisacrylamide was added to react to obtain a gel, which was then mixed with 65 mg of the intermediate product and stirred for 60 minutes to dissolve to obtain an antibacterial compound.

[0074] This embodiment discloses a method for preparing a modified surfactant, comprising the following steps:

[0075] S1: 22g of didodecylmethyl tertiary amine was added to a three-necked flask, and then 6.13g of chloroacetic acid and 11mL of deionized water were mixed and stirred at 2000rpm for 30min. After stirring was complete, the chloroacetic acid solution was added to the three-necked flask, and the stirring and mixing were continued for 30min to form an emulsion. The temperature of the emulsion was raised to the reflux temperature by heating in an oil bath at 100°C, and then 13mL of sodium hydroxide solution was added dropwise for 30min. The reflux reaction was continued for 6h. After the reaction was completed, the reaction product was poured into a separatory funnel, cooled and allowed to stand, and then separated into a water layer and a product layer;

[0076] S2: Add 22g corn starch to 105mL deionized water, stir and mix to obtain corn starch emulsion, add the corn starch emulsion into a three-necked flask, add 0.8g urea and 0.2g sodium silicate at the same time, stir and dissolve evenly, treat in a water bath at 80℃ for 40min, then add 0.9mL product layer, continue to heat up after stirring, treat at 100℃ for 40min, and after treatment, cool to room temperature to obtain a modified surfactant.

[0077] The present embodiment discloses a medicinal silica gel desiccant with fast adsorption speed, which is composed of the following components in parts by weight: 54 parts of silica gel, 5 parts of calcium chloride, 4 parts of magnesium sulfate, 4 parts of ferric oxide, 2 parts of antibacterial compounds, 6 parts of modified surfactants, 1.2 parts of potassium hydroxide, 15 parts of ice water, 2.5 parts of acrylic acid, 3.5 parts of acrylamide, 0.5 parts of sodium carboxymethyl starch, 0.22 parts of benzoin dimethyl ether, 0.005 parts of polyethylene glycol diacrylate, and 1.2 parts of methanol.

[0078] This embodiment discloses a method for preparing a medicinal silica gel desiccant with fast adsorption speed, comprising the following steps:

[0079] Step (1): adding potassium hydroxide to a beaker containing ice water, adding acrylic acid during stirring to obtain an acrylic acid solution, placing the acrylic acid solution in a beaker, adding acrylamide, sodium carboxymethyl starch, benzoin dimethyl ether and polyethylene glycol diacrylate, stirring evenly, placing the mixture in an ultraviolet radiation box, irradiating for 20 minutes, soaking the product in a methanol solution for 8 hours, vacuum drying at 70° C. for 6 hours, and crushing to obtain a composite water-absorbing resin;

[0080] Step (2): After mixing silica gel, composite water-absorbing resin, calcium chloride, magnesium sulfate, ferric oxide, antibacterial compound and surfactant for 3 hours, the mixture is pressed into granules by an extruder, and dried at 120° C. for 4 hours to obtain a medicinal silica gel desiccant with a fast adsorption rate.

[0081] Example 5

[0082] This embodiment discloses a method for preparing an antibacterial compound, comprising the following steps:

[0083] Q1: 4.21 g of dipropylene triamine was dissolved in a container containing 6.4 mL of methanol, and then 0.24 mL of methyl acrylate was dropped into the container, and an ice bath reaction was carried out under a nitrogen atmosphere at 0°C for 4 hours. After the reaction was completed, 0.06 mL of methyl acrylate was added, and then an ice bath reaction was continued under a nitrogen atmosphere at 0°C for 40 minutes, and then a heating treatment was carried out at 30°C for 50 minutes to obtain a crude product;

[0084] Q2: The crude product was placed in a rotary evaporator at 50°C for vacuum drying, the viscous product was collected and washed with ether 5 times, and dried at 40°C for 14 h to obtain an intermediate product;

[0085] Q3: Under room temperature conditions, 270 mg of acrylic acid was dissolved in 1.4 mL of deionized water, and then 7 mg of N,N-methylenebisacrylamide was added to react to obtain a gel, which was then mixed with 70 mg of the intermediate product and stirred for 60 minutes to dissolve to obtain an antibacterial compound.

[0086] This embodiment discloses a method for preparing a modified surfactant, comprising the following steps:

[0087] S1: 24g of didodecylmethyl tertiary amine was added to a three-necked flask, and then 7.28g of chloroacetic acid and 13mL of deionized water were mixed and stirred at 2000rpm for 30min. After stirring was complete, the chloroacetic acid solution was added to the three-necked flask, and the stirring and mixing were continued for 30min to form an emulsion. The temperature of the emulsion was raised to the reflux temperature by heating in an oil bath at 100°C, and then 11mL of sodium hydroxide solution was added dropwise for 30min. The reflux reaction was continued for 6h. After the reaction was completed, the reaction product was poured into a separatory funnel, cooled and allowed to stand, and then separated into a water layer and a product layer;

[0088] S2: Add 27g corn starch to 115mL deionized water, stir and mix to obtain corn starch emulsion, add the corn starch emulsion into a three-necked flask, add 0.7g urea and 0.3g sodium silicate at the same time, stir and dissolve evenly, treat in a water bath at 80℃ for 40min, then add 1.1mL product layer, continue to heat up after stirring, treat at 100℃ for 40min, and after treatment, cool to room temperature to obtain a modified surfactant.

[0089] The present embodiment discloses a medicinal silica gel desiccant with fast adsorption speed, which is composed of the following components in parts by weight: 61 parts of silica gel, 7 parts of calcium chloride, 5 parts of magnesium sulfate, 6 parts of ferric oxide, 3 parts of antibacterial compounds, 7 parts of modified surfactants, 1.7 parts of potassium hydroxide, 25 parts of ice water, 3.5 parts of acrylic acid, 2.5 parts of acrylamide, 0.7 parts of sodium carboxymethyl starch, 0.28 parts of benzoin dimethyl ether, 0.005 parts of polyethylene glycol diacrylate, and 1.4 parts of methanol.

[0090] This embodiment discloses a method for preparing a medicinal silica gel desiccant with fast adsorption speed, comprising the following steps:

[0091] Step (1): adding potassium hydroxide to a beaker containing ice water, adding acrylic acid during stirring to obtain an acrylic acid solution, placing the acrylic acid solution in a beaker, adding acrylamide, sodium carboxymethyl starch, benzoin dimethyl ether and polyethylene glycol diacrylate, stirring evenly, placing the mixture in an ultraviolet radiation box, irradiating for 20 minutes, soaking the product in a methanol solution for 8 hours, vacuum drying at 70° C. for 6 hours, and crushing to obtain a composite water-absorbing resin;

[0092] Step (2): After mixing silica gel, composite water-absorbing resin, calcium chloride, magnesium sulfate, ferric oxide, antibacterial compound and surfactant for 3 hours, the mixture is pressed into granules by an extruder, and dried at 120° C. for 4 hours to obtain a medicinal silica gel desiccant with a fast adsorption rate.

[0093] Comparative Example 1

[0094] Comparative Example 1 Compared with Example 1, in the process of preparing the antibacterial compound in Comparative Example 1, no dipropylenetriamine was added, and other conditions remained unchanged.

[0095] Comparative Example 2

[0096] Comparative Example 2 Compared with Example 1, in the process of preparing the antibacterial compound in Comparative Example 2, methyl acrylate was not added, and other conditions remained unchanged.

[0097] Comparative Example 3

[0098] Comparative Example 3 Compared with Example 1, in the process of preparing the antibacterial compound in Comparative Example 3, no acrylic acid was added, and other conditions remained unchanged.

[0099] Comparative Example 4

[0100] Comparative Example 4 Compared with Example 1, in the process of preparing the modified surfactant in Comparative Example 4, did not add didodecylmethyl tertiary amine, and other conditions remained unchanged.

[0101] Comparative Example 5

[0102] Comparative Example 5 Compared with Example 1, in the process of preparing the modified surfactant in Comparative Example 5, no chloroacetic acid was added, and other conditions remained unchanged.

[0103] Comparative Example 6

[0104] Comparative Example 6 Compared with Example 1, in the process of preparing the modified surfactant in Comparative Example 6, no corn starch was added, and other conditions remained unchanged.

[0105] Comparative Example 7

[0106] Comparative Example 7 Compared with Example 1, in the process of preparing the medicinal silica gel desiccant in Comparative Example 7, no antibacterial compound was added, and other conditions remained unchanged.

[0107] Comparative Example 8

[0108] Comparative Example 8 Compared with Example 1, in the process of preparing the medicinal silica gel desiccant in Comparative Example 8, no modified surfactant was added, and other conditions remained unchanged.

[0109] Comparative Example 9

[0110] Comparative Example 9 Compared with Example 1, in the process of preparing the medicinal silica gel desiccant in Comparative Example 9, no sodium carboxymethyl starch was added, and other conditions remained unchanged.

[0111] The performance of the medicinal silica gel desiccant prepared in Examples 1-5 and Comparative Examples 1-9 was tested. The adsorption capacity of the samples was tested according to GB / T41897-2022, and the antibacterial performance of the samples was tested according to WS / T 650-2019. The obtained samples were dried and placed in an environment with a certain temperature and humidity (20°C, humidity 65%). The humidity in the environment was measured at 5min, 10min, 15min, 20min, 40min, and 1h, respectively, to obtain the adsorption rate. The test results are shown in Table 1:

[0112] Table 1

[0113]

[0114]

[0115] It can be seen from the test results in Table 1 that the medicinal silica gel desiccant prepared in Examples 1-5 of the present invention has excellent adsorption capacity, adsorption speed and antibacterial performance. Comparison between Comparative Example 1 and Examples 1-5 shows that the addition of dipropylenetriamine can improve the antibacterial performance of the medicinal silica gel desiccant; comparison between Comparative Example 2 and Examples 1-5 shows that the addition of methyl acrylate can improve the antibacterial performance of the medicinal silica gel desiccant; comparison between Comparative Example 3 and Examples 1-5 shows that the addition of acrylic acid can improve the antibacterial performance of the medicinal silica gel desiccant; comparison between Comparative Example 4 and Examples 1-5 shows that the addition of didodecylmethyl tertiary amine can improve the adsorption capacity and adsorption speed of the medicinal silica gel desiccant; comparison between Comparative Example 5 and Examples 1-5 shows that the addition of chloroacetic acid can improve the antibacterial performance of the medicinal silica gel desiccant. The adsorption capacity and adsorption rate of the medicinal silica gel desiccant are improved by comparing Comparative Example 6 with Examples 1-5; the addition of corn starch can improve the adsorption capacity and adsorption rate of the medicinal silica gel desiccant; the comparison between Comparative Example 7 and Examples 1-5 shows that the addition of antibacterial compounds can improve the antibacterial properties of the medicinal silica gel desiccant; the comparison between Comparative Example 8 and Examples 1-5 shows that the addition of modified surfactants can improve the adsorption capacity and adsorption rate of the medicinal silica gel desiccant; the comparison between Comparative Example 9 and Examples 1-5 shows that the addition of sodium carboxymethyl starch can improve the adsorption capacity and adsorption rate of the medicinal silica gel desiccant.

[0116] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

[0117] The preferred embodiments of the present invention disclosed above are only used to help explain the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to only specific implementation methods. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A medicinal silica gel desiccant with fast adsorption speed, characterized in that: The invention is composed of the following components in parts by weight: 50-65 parts of silica gel, 4-8 parts of calcium chloride, 3-6 parts of magnesium sulfate, 3-7 parts of ferric oxide, 1-4 parts of antibacterial compounds, 5-10 parts of modified surfactants, 1-2 parts of potassium hydroxide, 10-30 parts of ice water, 2-4 parts of acrylic acid, 2-4 parts of acrylamide, 0.4-0.8 parts of sodium carboxymethyl starch, 0.2-0.3 parts of benzoin dimethyl ether, 0.005-0.015 parts of polyethylene glycol diacrylate, and 1-2 parts of methanol, wherein the antibacterial compound is prepared from dipropylenetriamine, methyl acrylate, acrylic acid and N,N-methylenebisacrylamide, and the modified surfactant is prepared from didodecylmethyl tertiary amine, chloroacetic acid, corn starch, urea and sodium silicate.

2. The medicinal silica gel desiccant with fast adsorption speed according to claim 1, characterized in that: The method for preparing the antibacterial compound comprises the following steps: Q1: Dissolve dipropylene triamine in a container containing methanol, then drop methyl acrylate into the container, and perform an ice bath reaction under a nitrogen atmosphere. After the reaction is completed, continue to add methyl acrylate, and then continue to perform an ice bath reaction under a nitrogen atmosphere, and then perform a heating treatment to obtain a crude product; Q2: The crude product is placed in a rotary evaporator for vacuum drying, the sticky product is collected and washed, and dried to obtain an intermediate product; Q3: Acrylic acid is dissolved in deionized water at room temperature, and then N,N-methylenebisacrylamide is added to react to obtain a gel, which is then mixed with the intermediate product and fully stirred and dissolved to obtain an antibacterial compound.

3. The medicinal silica gel desiccant with fast adsorption speed according to claim 2, characterized in that: In the Q1, the dosage ratio of dipropylenetriamine, methanol, methyl acrylate added for the first time and methyl acrylate added for the second time is (4-4.24) g: (6-6.5) mL: (0.18-0.26) mL: (0.02-0.08) mL, the ice bath reaction temperature is 0-1°C, the reaction time is 2-4h, the ice bath reaction temperature is continued to be 0-1°C, the reaction time is 30-40min, the heating treatment temperature is 25-30°C, and the reaction time is 48-50min.

4. The medicinal silica gel desiccant with fast adsorption speed according to claim 2, characterized in that: In the Q2, the vacuum drying temperature is 40-50°C, and the mixture is washed with ether 3-5 times. The drying temperature is 30-40°C, and the drying time is 12-14 hours. In the Q3, the usage ratio of acrylic acid, deionized water, N,N-methylenebisacrylamide and the intermediate product is (200-300) mg: (1-1.5) mL: (5-7.5) mg: (50-75) mg, and the stirring time is 45-60 minutes.

5. The medicinal silica gel desiccant with fast adsorption speed according to claim 1, characterized in that: The preparation method of the modified surfactant comprises the following steps: S1: Add didodecylmethyl tertiary amine to a three-necked flask, then mix chloroacetic acid and deionized water and stir, after stirring completely, add the chloroacetic acid solution to the three-necked flask, continue to stir and mix to form an emulsion, heat the emulsion in an oil bath to raise the temperature to the reflux temperature, then dropwise add sodium hydroxide solution, continue the reflux reaction, after the reaction is completed, pour the reaction product into a separatory funnel, cool and stand, and then separate the layers into a water layer and a product layer; S2: Add corn starch to deionized water, stir and mix to obtain corn starch emulsion, add corn starch emulsion into a three-necked flask, add urea and sodium silicate at the same time, stir and dissolve evenly, treat in a water bath, then add the product layer, continue to heat up after stirring, and after treatment, cool to room temperature to obtain a modified surfactant.

6. The medicinal silica gel desiccant with fast adsorption speed according to claim 5, characterized in that: In the S1, the dosage ratio of didodecylmethyl tertiary amine, chloroacetic acid, deionized water and sodium hydroxide solution is (20-25) g: (5.66-8.49) g: (10-15) mL: (10-15) mL, the mixing and stirring speed is 2000-3000 rpm, the stirring time is 20-30 min, the continued stirring time is 30-45 min, the oil bath heating temperature is 90-100° C., the dropping time is 30-40 min, and the reflux reaction time is 2-8 h.

7. The medicinal silica gel desiccant with fast adsorption speed according to claim 5, characterized in that: In S2, the usage ratio of corn starch, deionized water, urea, sodium silicate and product layer is (20-30) g: (100-120) mL: (0.6-0.9) g: (0.1-0.15) g: (0.8-1.2) mL, the water bath treatment temperature is 70-80°C, the time is 30-50 min, the heating treatment temperature is 90-100°C, and the treatment time is 30-40 min.

8. The method for preparing the medicinal silica gel desiccant with fast adsorption speed according to any one of claims 1 to 7, characterized in that: The following steps are involved: Step (1): adding potassium hydroxide to a beaker containing ice water, adding acrylic acid during stirring to obtain an acrylic acid solution, placing the acrylic acid solution in a beaker, adding acrylamide, sodium carboxymethyl starch, benzoin dimethyl ether and polyethylene glycol diacrylate, stirring evenly, placing the mixture in an ultraviolet radiation box, irradiating, soaking the product in a methanol solution, vacuum drying, and crushing to obtain a composite water-absorbing resin; Step (2): After uniformly mixing silica gel, composite water-absorbing resin, calcium chloride, magnesium sulfate, ferric oxide, antibacterial compound and surfactant, the mixture is pressed into granules by an extruder, and dried to obtain a medicinal silica gel desiccant with a fast adsorption speed.

9. The method for preparing the medicinal silica gel desiccant with fast adsorption speed according to claim 8, characterized in that: In the step (1), the irradiation time is 15-20 minutes, the soaking time is 6-8 hours, and the vacuum drying temperature is 70-80° C. for 4-6 hours.

10. The method for preparing the medicinal silica gel desiccant with fast adsorption speed according to claim 8, characterized in that: In the step (2), the mixing time is 2-3 hours, the drying temperature is 110-120° C., and the drying time is 3-5 hours.

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