阅读说明：本技术 一种过硫酸氢钾缓释剂及其制备方法与应用 (Potassium hydrogen persulfate sustained-release agent and preparation method and application thereof ) 是由 舒绪刚 吴紫倩 李侨光 林羽 于 2019-11-01 设计创作，主要内容包括：本发明提供了一种过硫酸氢钾缓释剂及其制备方法与应用,涉及水体消毒技术领域。本发明以过硫酸氢钾水溶液作为芯材,聚吡咯作为壁材,通过原位聚合法制得粒径为10～1000μm的过硫酸氢钾-聚吡咯微胶囊,不仅使得过硫酸氢钾的稳定性大大提高,储运方便,还使得释药时间明显延长,药物利用率提高；再利用羟丙甲基纤维素将过硫酸氢钾-聚吡咯微胶囊进行包被,进一步隔离空气中的水分和保证过硫酸氢钾的稳定性。本发明能通过改变过硫酸氢钾药物的浓度及包裹量,灵活地控制药效时间；再通过调节聚吡咯壁材以及羟丙甲基纤维素的厚度调控药物的释放速度,进而可以设计出具有理想的释药时间的缓释消毒剂。(The invention provides a potassium hydrogen persulfate sustained-release agent, a preparation method and an application thereof, and relates to the technical field of water body disinfection. The potassium hydrogen persulfate-polypyrrole microcapsule with the particle size of 10-1000 mu m is prepared by an in-situ polymerization method by taking a potassium hydrogen persulfate aqueous solution as a core material and polypyrrole as a wall material, so that the stability of the potassium hydrogen persulfate is greatly improved, the storage and the transportation are convenient, the drug release time is obviously prolonged, and the drug utilization rate is improved; and then the hydroxypropyl methylcellulose is utilized to coat the potassium hydrogen persulfate-polypyrrole microcapsules, so that the moisture in the air is further isolated and the stability of the potassium hydrogen persulfate is ensured. The invention can flexibly control the drug effect time by changing the concentration and the wrapping amount of the potassium hydrogen persulfate drug; the release speed of the medicament is regulated and controlled by adjusting the thickness of the polypyrrole wall material and the hydroxypropyl methylcellulose, so that the slow-release disinfectant with ideal medicament release time can be designed.)

1. The preparation method of the potassium hydrogen persulfate slow-release agent is characterized by comprising the following steps of:

(1) preparation of W/O emulsion: completely dissolving a surfactant A in toluene, adding benzoyl peroxide, and uniformly mixing to form an oil phase; completely dissolving a surfactant B and potassium hydrogen persulfate in deionized water to form a water phase; mixing the oil phase and the water phase, and uniformly dispersing to form a W/O emulsion soft membrane plate;

(2) preparation of potassium hydrogen persulfate-polypyrrole microcapsules: condensing and refluxing the W/O emulsion soft membrane under the protection of protective gas, stirring, performing ultrasonic treatment, adding oxidizing acid to adjust the pH value, dropwise adding pyrrole monomer while stirring, reducing the stirring speed after the color is changed from white to brown, and continuing to react to obtain the potassium hydrogen persulfate-polypyrrole microcapsule;

(3) coating of oxone-polypyrrole microcapsules: and taking hydroxypropyl methylcellulose dissolved in an ethanol solution as a coating solution, and coating the oxone-polypyrrole microcapsules by using a bottom spray coating technology to obtain the oxone sustained release agent.

2. The preparation method according to claim 1, wherein the hydrophilic-lipophilic balance value of the surfactant A is 4.79-6.68, and preferably the surfactant A is prepared from span 80: span 80 with tween 80 being 7-11: 2 and tween 80; the surfactant B is at least one of sodium dodecyl benzene sulfonate and p-toluenesulfonic acid.

3. The preparation method according to claim 1, wherein the mass ratio of the surfactant A to the surfactant B to the benzoyl peroxide to the potassium hydrogen persulfate is surfactant A: surfactant B: benzoyl peroxide: 2.0-4.0: 4-10: 0.8-2.2: 1.

4. The production method according to claim 1, wherein in the step (1), the mass ratio of the oxone to the deionized water is oxone: deionized water is 0.15-0.6: 1.

5. The preparation method according to claim 1, wherein in the step (2), the W/O emulsion flexible membrane is stirred at 55-75 ℃ after being condensed and refluxed, and preferably, the stirring time in the step (2) is 10min, the ultrasonic time is 10min, and the protective gas is nitrogen.

6. The method according to claim 1, wherein in the step (2), an oxidizing acid is added to a pH of 2.0 to 3.5, preferably the oxidizing acid is peroxyacetic acid.

7. The method according to claim 1, wherein the reaction is continued for 1.5 to 2 hours.

8. The preparation method according to claim 1, wherein the concentration of ethanol in the ethanol solution is 23.67-39.45 g/mL; the mass concentration of hydroxypropyl methyl cellulose in the coating liquid is 0.012-0.030 g/mL; the coating is carried out in a coating granulator with a fan, and the coating process parameters are as follows: the proportion of the adopted potassium hydrogen persulfate-polypyrrole microcapsules to the coating liquid is 1.0-1.5 g: 1mL, 35-38 Hz of fan frequency, 65-75 ℃ of inlet air temperature and 6-8 r/min of liquid supply speed.

9. The oxone sustained-release agent produced by the production method according to any one of claims 1 to 8.

10. The use of the oxone sustained release formulation of claim 9 for the disinfection of water.

Technical Field

The invention relates to the technical field of water body disinfection, and relates to a potassium hydrogen persulfate slow-release agent, and a preparation method and application thereof.

Background

Water is the root of life. With the development of industrial technology, the problem of water pollution is getting worse. The waste water mainly comprises domestic waste water and industrial waste water, the latter has stronger destructive effect, and the natural degradation means can not degrade the waste water, thereby bringing serious influence on the sustainable development of human beings. The potassium hydrogen persulfate composite salt is a novel oxidation disinfectant, and is widely applied to the fields of water treatment, livestock breeding, food medical treatment and the like due to the advantages of environmental protection, high efficiency, safety, low toxicity and the like. At present, potassium hydrogen persulfate powder is widely applied in the market, and is difficult to store and transport due to large specific surface area; secondly, the potassium hydrogen persulfate effervescent tablet is prepared, for example, the preparation method of the potassium hydrogen persulfate compound salt effervescent tablet is disclosed in the literature (preparation and quality evaluation of Queentington. potassium hydrogen persulfate compound salt effervescent tablet, Hebei science and technology university, 2018.), but the cost is higher, and the process conditions are complicated. In addition, the potassium hydrogen persulfate has active property, so that the potassium hydrogen persulfate powder and the potassium hydrogen persulfate effervescent tablets need to be stored under the condition of low-temperature drying, and the storage and the transportation are troublesome.

Disclosure of Invention

In order to overcome the above disadvantages and shortcomings of the prior art, the present invention provides a method for preparing a product with high stability and utilization rate at a low cost and with a simple process, and an application thereof.

In order to achieve the purpose, the invention adopts the technical scheme that:

in a first aspect, the invention provides a preparation method of a potassium hydrogen persulfate slow-release agent, which comprises the following steps:

(1) preparation of W/O emulsion: completely dissolving a surfactant A in toluene, adding benzoyl peroxide, and uniformly mixing to obtain an oil phase; completely dissolving a surfactant B and potassium hydrogen persulfate in deionized water to obtain a water phase; mixing the oil phase and the water phase, and uniformly dispersing to obtain a W/O emulsion soft membrane plate;

(2) preparation of potassium hydrogen persulfate-polypyrrole microcapsules: condensing and refluxing the W/O emulsion soft membrane under the protection of protective gas, stirring, performing ultrasonic treatment, adding oxidizing acid to adjust the pH value, dropwise adding pyrrole monomer while stirring, reducing the stirring speed after the color is changed from white to brown, and continuing to react to obtain the potassium hydrogen persulfate-polypyrrole microcapsule;

(3) coating of oxone-polypyrrole microcapsules: dissolving HPMC (hydroxypropyl methylcellulose) in ethanol solution to serve as coating solution, and coating the potassium hydrogen persulfate-polypyrrole microcapsules by using a bottom spray coating technology to obtain the potassium hydrogen persulfate sustained-release agent.

The preparation method takes the potassium hydrogen persulfate aqueous solution as a core material and the polypyrrole as a wall material of the microcapsule, and prepares the potassium hydrogen persulfate-polypyrrole microcapsule with the particle size of 10-1000 mu m by an in-situ polymerization method, so that the stability of the potassium hydrogen persulfate is greatly improved, the storage and the transportation are convenient, the drug release time is obviously prolonged, and the drug utilization rate is improved; utilize HPMC to carry out the coating with potassium peroxydisulfate-polypyrrole microcapsule simultaneously, wherein the trace moisture in the HPMC not only can keep apart the air, can dissolve rapidly and rupture of membranes in aqueous solution again, can guarantee potassium peroxydisulfate and release smoothly simultaneously, prevent potassium peroxydisulfate-polypyrrole microcapsule and make potassium peroxydisulfate release in the moisture absorption of storage in-process, further guaranteed the stability of potassium peroxydisulfate. In the step (2), the oxidizing acid not only has the function of adjusting pH, but also can promote the formation of microcapsule wall materials by utilizing the strong oxidizing property of the oxidizing acid; in the step (3), compared with the combination operation of only using any one or two of condensation reflux, stirring and ultrasound, the combined operation of condensation reflux, stirring and ultrasound can more effectively reduce the interfacial tension, minimize the interfacial free energy, further fully demulsify and stratify, optimize the stability of the emulsion, and further facilitate the formation of the oxone-polypyrrole microcapsules. In addition, the applicant respectively puts the oxone sustained release agent, the oxone powder and the oxone effervescent tablet prepared by the preparation method into solutions with the same strain and the same bacteria content, researches the minimum drug effect concentration required by sterilization and inactivation of different disinfectants, researches the respective longest drug effect time under the effective concentration of each disinfectant and the stability (temperature and moisture absorption condition) of different treating agents, and finds that: the stability of the potassium hydrogen persulfate powder is poor, and the potassium hydrogen persulfate powder is easy to absorb moisture, so that the potassium hydrogen persulfate slow-release agent prepared by the preparation method has the best stability and is not influenced by moisture in the air; the minimum effective concentration of each disinfectant is almost the same (the main effective component of each disinfectant is potassium hydrogen persulfate, and the main components of each disinfectant are the same, and the difference is different dosage forms); however, the effective action time of the potassium hydrogen persulfate slow-release agent prepared by the preparation method is longest, and the difference of the effective action time of the potassium hydrogen persulfate powder and the effective action time of the potassium hydrogen persulfate effervescent tablet is not obvious.

As a preferable embodiment of the preparation method, the HLB (hydrophilic-lipophilic balance) value of the surfactant A is 4.79-6.68; as a further preferable embodiment of the production method of the present invention, the surfactant dissolved in toluene is a nonionic surfactant; as a still further preferable embodiment of the preparation method of the present invention, the nonionic surfactant is prepared by mixing, by mass, span 80: span 80 with tween 80 being 7-11: 2 and tween 80; as a still further preferable embodiment of the production method of the present invention, the nonionic surfactant has an HLB value of 6.08, which is prepared from span 80: span 80 and tween 80 with tween 80 being 10: 2. Span 80 and Tween 80 are oil-soluble surfactants, have poor hygroscopicity, and are favorable for the stability of potassium hydrogen persulfate.

As a preferable embodiment of the production method of the present invention, the mass ratio of the surfactant a to the oxone is surfactant a: 2.0-4.0: 1 of potassium hydrogen persulfate.

As a preferred embodiment of the preparation method of the present invention, the mass ratio of the benzoyl peroxide to the oxone is benzoyl peroxide: 0.8-2.2: 1 of potassium hydrogen persulfate.

In a preferred embodiment of the production method of the present invention, the mass ratio of the oxone to the surfactant B is 4 to 10: 1.

As a preferable embodiment of the preparation method of the present invention, the surfactant B is at least one of sodium dodecylbenzenesulfonate and p-toluenesulfonic acid.

As a preferable embodiment of the production method of the present invention, in the step (1), the mass ratio of the oxone to the deionized water is oxone: deionized water is 0.15-0.6: 1.

As a preferred embodiment of the preparation method of the present invention, in the step (1), the oil phase and the water phase are mixed and then dispersed uniformly by centrifugation; as a more preferable embodiment of the preparation method, the rotation speed of the centrifugation is 6000r/min, and the time of the centrifugation is 10 min.

In the step (2), after the W/O emulsion flexible membrane is condensed and refluxed, the W/O emulsion flexible membrane is stirred at the temperature of 55-75 ℃; as a more preferable embodiment of the production method of the present invention, the stirring time at 55 to 75 ℃ is 10 min. As a further preferable embodiment of the preparation method of the present invention, the W/O emulsion is stirred at 60 ℃ for 10min after being condensed and refluxed.

As a preferable embodiment of the preparation method of the present invention, in the step (2), the sonication time is 10 min.

As a preferred embodiment of the preparation method of the present invention, in the step (2), the shielding gas is nitrogen.

As a preferable embodiment of the preparation method, in the step (2), an oxidizing acid is added to a pH value of 2.0-3.5; as a more preferable embodiment of the production method of the present invention, in the step (2), an oxidizing acid is added to a pH of 2.0.

As a preferred embodiment of the production method of the present invention, the oxidizing acid is peracetic acid.

As a preferred embodiment of the preparation method of the invention, the time for continuing the reaction is 1.5-2 h; as a more preferred embodiment of the preparation process according to the invention, the time for the further reaction is 2 h.

In a preferred embodiment of the preparation method of the present invention, the mass concentration of ethanol in the ethanol solution is 23.67-39.45 g/mL.

In a preferred embodiment of the preparation method of the present invention, the mass concentration of the hydroxypropyl methylcellulose in the coating solution is 0.012-0.030 g/mL.

As a preferable embodiment of the preparation method, the ratio of the potassium hydrogen persulfate-polypyrrole microcapsule used for coating to the coating liquid is 1.0-1.5 g: 1 mL.

As a preferred embodiment of the preparation method of the present invention, the coating is carried out in a coating granulator with a blower, and the coating process parameters are: the frequency of a fan is 35-38 Hz, the air inlet temperature is 65-75 ℃, and the liquid supply speed is 6-8 r/min; as a further preferred embodiment of the preparation method of the present invention, the process parameters of the coating are: the frequency of the fan is 35Hz, the air inlet temperature is 65 ℃, and the liquid supply speed is 6 r/min.

In a second aspect, the invention provides a potassium hydrogen persulfate slow-release agent prepared by the preparation method.

In a third aspect, the invention also provides the application of the potassium hydrogen persulfate slow-release agent in the aspect of water body disinfection.

As a preferable embodiment of the application of the invention, the addition amount of the potassium hydrogen persulfate slow-release agent in the water body is 0.20-5.0 wt.%.

The applicant utilizes the potassium hydrogen persulfate slow release agents (0.20-5.0 wt.%) with different concentrations to respectively contain 5 x 10 potassium hydrogen persulfate⁸The water body containing CFU/mL escherichia coli, staphylococcus aureus and salmonella is sterilized, and the addition amount of the potassium hydrogen persulfate slow-release agent in the water body is 0.20-0.33 wt%, and when the slow-release agent acts for 10min, the sterilization rate of the three bacteria reaches 100%; when the addition amount of the potassium hydrogen persulfate slow-release agent in a water body is 0.22-0.35 wt.%, the potassium hydrogen persulfate slow-release agent only acts on staphylococcus aureus for 5min, and the sterilization rate reaches 100%. The potassium hydrogen persulfate slow release agent pair respectively contains 1 × 10 of potassium hydrogen persulfate⁷And (3) sterilizing the CFU/mL water body containing escherichia coli, salmonella, staphylococcus aureus and hemolytic streptococcus, and finding that when the potassium hydrogen persulfate slow-release agent acts for 10min, the minimum effective concentration for eliminating the hemolytic streptococcus is 2.4-2.8 wt%, and the minimum effective concentration for eliminating the escherichia coli and the staphylococcus aureus is 2.4-2.9 wt%.

As a preferable embodiment of the application of the invention, the time for disinfecting the potassium hydrogen persulfate slow-release agent in the water body is within 48 h; as a more preferable embodiment of the application of the invention, the time for disinfecting the potassium hydrogen persulfate slow-release agent in the water body is 36 h. Applicant proceeds with 5X 10⁸CFU/mL E.coli as test bacterium was assayedThe sterilization effect of the potassium hydrogen persulfate slow-release agent is that after the potassium hydrogen persulfate slow-release agent (with the concentration of 0.3 wt.%) acts for a certain time, the sterilization rate is detected, and if the sterilization rate reaches 100%, an equal amount of test bacteria is added for continuing the test; if the sterilization rate is lower than 100%, stopping the test, and detecting the sterilization rate at each time point when the action time is respectively 10min, 30min, 60min, 6h, 12h, 24h, 36h and 48h, wherein the result shows that the sterilization rate reaches 100% when the action time is 10min-36h, and the sterilization rate reaches 80-87% when the action time is 48 h.

As a preferable embodiment of the application of the invention, the temperature of the potassium hydrogen persulfate slow-release agent for disinfection in water is 30-35 ℃. The applicant finds that the bactericidal effect of the potassium hydrogen persulfate slow-release agent is enhanced along with the increase of the action temperature, the difference of the bactericidal effect is not obvious at 30 ℃ and 35 ℃, and the influence of the subsequent temperature increase on the bactericidal effect is not obvious.

Compared with the prior art, the invention has the following advantages and beneficial effects:

(1) the potassium hydrogen persulfate-polypyrrole microcapsule is prepared firstly and then coated, so that the polypyrrole and HPMC are used for isolating trace moisture in air, the stability of the potassium hydrogen persulfate is ensured, the storage and the transportation are convenient, the excellent surface permeability of the HPMC is used, the potassium hydrogen persulfate is slowly released, and the utilization rate of the medicine is improved;

(2) the invention can flexibly control the drug effect time by changing the concentration and the wrapping amount of the potassium hydrogen persulfate drug; the release speed of the medicament is regulated and controlled by regulating the thickness of the polypyrrole wall material and the HPMC, so that the slow-release disinfectant with ideal medicament release time can be designed.

Detailed Description

To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.