CN114431339B - Low-additive stability-increasing microencapsulated potassium diformate feed additive and preparation method thereof - Google Patents
Low-additive stability-increasing microencapsulated potassium diformate feed additive and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a low-addition stability-increasing microencapsulated potassium diformate feed additive, and also discloses a preparation method of the low-addition stability-increasing microencapsulated potassium diformate feed additive, which comprises the following steps: preparing a potassium diformate core material, adding the core material into an oily solvent, and uniformly stirring to obtain a suspension; preparing a monomer solution; and (3) regulating the temperature of the suspension to 45-55 ℃ under the protection of nitrogen, continuously stirring, dropwise adding a monomer solution into the suspension in the stirring process, stirring, cooling, washing, filtering, and drying at low temperature to obtain the low-addition stability-increasing microencapsulated potassium diformate feed additive. According to the invention, the hydrophobic separation wall material is formed in the potassium diformate core material, the process is controlled to be free of water, the influence of water on the potassium diformate is reduced in the coating process, and the obtained wall material has good hydrophobicity after microencapsulation is finished, so that the influence of subsequent transportation and storage processes on the potassium diformate is effectively avoided, the adverse effect of the external environment on the potassium diformate is reduced, and the product has good moisture resistance and high stability.
Description
Technical Field
The invention relates to the technical field of potassium diformate, in particular to a low-additive stability-enhancing microencapsulated potassium diformate feed additive and a preparation method thereof.
Background
Intestinal problems often occur in piglets after weaning, particularly in wasting, diarrhea, stunted development and even death. Antibiotics are often added to weaned piglet diets in order to relieve and prevent growth arrest and disease caused by weaning stress in piglets. After the antibiotics are approved as feed additives in the last 50 th century, the antibiotics play an important role in preventing and treating animal diseases, improving animal productivity and breeding benefits and the like, and promote the development of animal husbandry. However, with the long-term use and intensive research of feed antibiotics, side effects thereof are also gradually prominent, mainly including:
1. the microecological balance of the gastrointestinal tract of the livestock is destroyed, the immune system of the livestock is disturbed, the resistance of the livestock to diseases is reduced, and the sustainable development of the livestock industry is seriously threatened;
2. generating a drug-resistant strain, and causing interactive genetics and cross-propagation of antibiotic resistance;
3. residue is caused in animal products and environment, which affects animal food safety and threatens human health.
Based on the negative effects of feed antibiotics, the European Union has completely banned the application of antibiotics in livestock and poultry production in 2006, and in recent years, organic acid feed additives have been developed to a great extent because they can maintain the acidic environment of intestinal tracts, inhibit the growth of harmful bacteria such as escherichia coli, salmonella and the like, and have no adverse effects on animals. Formic acid is the organic acid with the strongest acidity under the same unit weight, and can inhibit the growth of intestinal harmful bacteria and promote the growth of animals when being added into feed, but the formic acid has the problems of pungent smell, strong corrosiveness, poor palatability and the like, so that the use of the formic acid in the feed is limited. However, the organic acid additive has the problems of unstable application effect, larger addition amount, higher cost and the like at present, and the wide application of the organic acid additive in the feed industry is limited.
The potassium diformate is a dimer formed by associating formic acid and potassium formate through hydrogen bonds, the molecular formula is HCOOH & HCOOK, the formic acid and the potassium formate can be dissociated in weak acid and weak base environments, and the formic acid can enter intestinal tracts to play a role in inhibiting bacteria and promoting growth.
At present, the potassium diformate still has the advantages of high component release speed, unstable application effect, large effective use dosage, easy moisture absorption, easy influence of environmental factors in the processing and storage processes, and the problem of the practical application of the potassium diformate is solved by improving the rear-end processing technology of the potassium diformate, thereby being beneficial to promoting the large-scale application and popularization of the potassium diformate in the feed industry.
Disclosure of Invention
The invention aims to solve the defects in the prior art, and provides a low-addition stability-increasing microencapsulated potassium diformate feed additive and a preparation method thereof.
A preparation method of a low-addition stability-enhancing microencapsulated potassium diformate feed additive comprises the following steps:
s1, grinding potassium diformate, porous silicon dioxide, a dispersing agent and a surfactant for 2-6 hours, maintaining the system temperature to be less than or equal to 50 ℃ in the grinding process, adding N, N' -methylene bisacrylamide and an initiator, and continuously grinding for 1-2 hours to obtain a potassium diformate core material; adding into oily solvent, and stirring at 30-40deg.C to obtain suspension;
s2, adding N-vinyl caprolactam and N-tertiary butyl acrylamide into ethanol, and uniformly stirring to obtain a monomer solution;
s3, regulating the temperature of the suspension to 45-55 ℃ under the protection of nitrogen, continuously stirring, dropwise adding a monomer solution into the suspension in the stirring process, continuously stirring for 3-6 hours, cooling, washing, filtering, and drying at low temperature to obtain the low-addition stability-increasing microencapsulated potassium diformate feed additive.
The initiator is firstly dispersed in the potassium diformate core material, so that the monomer solution can be promoted to polymerize on the surface of the core material to form a microcapsule wall material, the encapsulation efficiency is effectively prevented from being reduced by the self-polymerization of the monomer, and the encapsulation efficiency is high and can reach more than 85%.
Preferably, in S1, the mass ratio of the potassium diformate, the porous silica, the dispersing agent, the surfactant, the N, N' -methylene bisacrylamide and the initiator is 1-5:4-10:0.1-1:0.1-1:0.1-0.2: 0.01-0.05.
Preferably, in S1, the oily solvent is xylene.
Preferably, in S1, the initiator is ammonium persulfate.
Preferably, in S1, the surfactant is at least one of octylphenol polyoxyethylene ether, sodium dodecyl sulfate, and sodium dodecyl benzene sulfonate.
Preferably, in S1, the porous silica has a diameter of 612-945nm.
Preferably, in S1, the porous silica is prepared by the steps of: and (3) aging the cotton fiber, washing, drying, crushing, dripping tetraethyl silicate, cleaning, drying and sintering.
Specifically, the porous silica is prepared by the following steps: immersing cotton fibers in a sodium hydroxide solution, aging at room temperature for 10-20h, filtering, washing, drying, crushing, adding into an ethanol solution, stirring, adding ammonia water, stirring uniformly, dropwise adding tetraethyl silicate in a stirring state, stirring at room temperature, filtering, ultrasonic cleaning, freeze-drying, sintering, heating to 700-760 ℃ at a speed of 10-20 ℃/min from room temperature, preserving heat for 1-3h, air-cooling to room temperature, and crushing to obtain porous silicon dioxide.
Further, the mass ratio of the cotton fiber, the ammonia water and the tetraethyl silicate is 5-10:1-3: 1-5, wherein the mass fraction of the ammonia water is 10-20%.
Further, the concentration of the sodium hydroxide solution is 0.2 to 1mol/L.
Further, after the room temperature aging, water is used for washing 2 to 4 times.
Further, the mass fraction of the ethanol solution is 60-80%.
Further, ethanol and water are adopted to carry out ultrasonic cleaning in sequence before freeze drying.
In porous silica, cotton fiber is aged by sodium hydroxide, a defect structure is formed on the surface of the fiber, tetraethyl silicate is hydrolyzed to form silica nanoparticles, the silica nanoparticles are deposited and distributed on the surface of the fiber with the defect structure, the porous silica still keeps the tubular structure of the fiber after sintering, meanwhile, the tube body is porous, the diameter of the porous silica is 612-945nm, the particle size of the nanoparticles is 80-125nm, and the pore diameter is 150-300nm.
Preferably, in S2, the mass ratio of the N-vinyl caprolactam to the N-tertiary butyl acrylamide is 1-5:5-15.
Preferably, in S3, the mass ratio of the potassium diformate core material to the N-vinyl caprolactam is 6-16:1-5.
The low-addition stability-increasing microencapsulated potassium diformate feed additive is prepared by adopting the preparation method of the low-addition stability-increasing microencapsulated potassium diformate feed additive.
The technical effects of the invention are as follows:
the invention disperses potassium diformate, initiator and N, N' -methylene bisacrylamide in oily solvent to form potassium diformate core material, wherein N-vinyl caprolactam is adopted as microencapsulation skeleton, hydrophobic N-tertiary butyl acrylamide is adopted as monomer, and the two are matched on the surface of the core material to carry out interfacial free radical polymerization reaction and wrap the core material, thus not only reducing the self-polymerization phenomenon of hydrophobic monomer, having high coating efficiency, but also the microcapsule has core-shell structure, good hydrophobic effect, stable existence in certain temperature and pH value environment and good slow release and isolation effects.
And through the compound grinding of potassium diformate and porous silica, potassium diformate has good affinity with porous silica, and potassium diformate enters into the hollow structure of porous silica, so that potassium diformate is fixed on porous silica through hydrogen bond combination, and then microencapsulation is carried out, so that potassium diformate enteric-coated can be realized, the product can be dissolved in intestinal tracts, and dissolved potassium diformate has hydrogen bond action with porous silica, so that the residence time of potassium diformate in intestinal tracts can be prolonged, and the antibacterial effect is obvious.
According to the invention, the hydrophobic separation wall material is formed in the potassium diformate core material, the process is controlled to be free of water, the influence of water on the potassium diformate is reduced in the coating process, and the obtained wall material has good hydrophobicity after microencapsulation is finished, so that the influence of subsequent transportation and storage processes on the potassium diformate is effectively avoided, the adverse effect of the external environment on the potassium diformate is reduced, and the product has good moisture resistance and high stability.
The invention can regulate the release speed of the potassium diformate, realize the prolongation of the action time, realize the enteric solubility of the potassium diformate, ensure that the effective component potassium diformate can reach the end section of the intestinal tract, has good absorption effect of the potassium diformate, improves the bioavailability, has excellent antibacterial property, effectively reduces the dosage used at present and reduces the cost.
Drawings
FIG. 1 is a graph showing the pH change of potassium diformate microcapsules obtained in example 5 and comparative examples 1-2 at various times when immersed in simulated gastric fluid and simulated intestinal fluid.
FIG. 2 is a graph showing the time-dependent inhibition of the potassium diformate microcapsules obtained in example 5 and comparative examples 1 to 2.
Detailed Description
The invention is further illustrated below in connection with specific embodiments.
Example 1
A preparation method of a low-addition stability-enhancing microencapsulated potassium diformate feed additive comprises the following steps:
I. immersing 5g of cotton fiber into 30g of 0.2mol/L sodium hydroxide solution, aging at room temperature for 10h, filtering, washing with water for 2 times, drying, crushing, adding into 60% ethanol solution, stirring for 2h, adding 1g of 10% ammonia water, stirring uniformly, dropwise adding 1g of tetraethyl silicate in the stirring state, stirring at room temperature for 5h, stirring at a stirring speed of 1000r/min, filtering, sequentially ultrasonically cleaning with ethanol and water, freeze-drying, adding into a sintering furnace, heating to 700 ℃ at a speed of 10 ℃/min from room temperature, preserving heat for 1h, cooling to room temperature by air, and crushing to obtain porous silica;
II. Grinding 1g of potassium diformate, 4g of porous silica, 0.1g of dispersing agent and 0.1g of sodium dodecyl sulfate for 2h, maintaining the system temperature to be less than or equal to 50 ℃ in the grinding process, adding 0.1g of N, N' -methylene bisacrylamide and 0.01g of ammonium persulfate, and continuously grinding for 1h to obtain a potassium diformate core material; adding the mixture into 60g of dimethylbenzene, and uniformly stirring at 30 ℃ at a stirring speed of 1000r/min to obtain a suspension;
III, adding 1g N-vinyl caprolactam and 5g N-tertiary butyl acrylamide into 20g of ethanol, and uniformly stirring to obtain a monomer solution;
IV, regulating the temperature of the suspension to 45 ℃ under the protection of nitrogen, and continuously stirring, wherein a monomer solution is dropwise added in the stirring process, and the mass ratio of the potassium diformate core material to the N-vinyl caprolactam is 6:1, a step of; stirring for 3h, cooling, washing with deionized water for 2 times, filtering, sending into an oven, and drying at 40 ℃ for 20h to obtain the low-addition stability-increasing microencapsulated potassium diformate feed additive.
Example 2
A preparation method of a low-addition stability-enhancing microencapsulated potassium diformate feed additive comprises the following steps:
I. immersing 10g of cotton fibers into 60g of 1mol/L sodium hydroxide solution, aging for 20 hours at room temperature, filtering, washing for 4 times with water, drying, crushing, adding into 80% ethanol solution with mass fraction, stirring for 4 hours, adding 3g of 20% ammonia water with mass fraction, stirring uniformly, dropwise adding 5g of tetraethyl silicate in a stirring state, stirring for 10 hours at room temperature, stirring at a stirring speed of 2000r/min, filtering, sequentially ultrasonically cleaning with ethanol and water, freeze-drying, adding into a sintering furnace, heating to 760 ℃ from room temperature at a speed of 20 ℃/min, preserving heat for 3 hours, cooling to room temperature by air, and crushing to obtain porous silica;
II. Grinding 5g of potassium diformate, 10g of porous silica, 1g of dispersing agent and 1g of sodium dodecyl benzene sulfonate for 6h, maintaining the system temperature to be less than or equal to 50 ℃ in the grinding process, adding 0.2g of N, N' -methylene bisacrylamide and 0.05g of ammonium persulfate, and continuously grinding for 2h to obtain a potassium diformate core material; adding into 100g of dimethylbenzene, and uniformly stirring at 40 ℃ at a stirring speed of 2000r/min to obtain a suspension;
III, adding 5g N-vinyl caprolactam and 15g N-tertiary butyl acrylamide into 30g of ethanol, and uniformly stirring to obtain a monomer solution;
IV, regulating the temperature of the suspension to 55 ℃ under the protection of nitrogen, and continuously stirring, wherein a monomer solution is dropwise added in the stirring process, and the mass ratio of the potassium diformate core material to the N-vinyl caprolactam is 16:5, a step of; stirring for 6h, cooling, washing with deionized water for 6 times, filtering, sending into an oven, and drying at 50 ℃ for 30h to obtain the low-addition stability-increasing microencapsulated potassium diformate feed additive.
Example 3
A preparation method of a low-addition stability-enhancing microencapsulated potassium diformate feed additive comprises the following steps:
I. immersing 6g of cotton fibers into 50g of 0.4mol/L sodium hydroxide solution, aging for 18h at room temperature, filtering, washing for 3 times with water, drying, crushing, adding into 65% ethanol solution, stirring for 3.5h, adding 1.5g of 18% ammonia water, stirring uniformly, dropwise adding 2g of tetraethyl silicate in a stirring state, stirring for 8h at room temperature, stirring at 1200r/min, filtering, sequentially ultrasonically cleaning with ethanol and water, freeze-drying, adding into a sintering furnace, heating to 720 ℃ from room temperature at a speed of 17 ℃/min, preserving heat for 2.5h, air-cooling to room temperature, and crushing to obtain porous silica;
II. Grinding 2g of potassium diformate, 8g of porous silica, 0.2g of dispersing agent and 0.8g of sodium dodecyl sulfate for 3 hours, maintaining the system temperature to be less than or equal to 50 ℃ in the grinding process, adding 0.17g of N, N' -methylene bisacrylamide and 0.02g of ammonium persulfate, and continuously grinding for 1.8 hours to obtain a potassium diformate core material; adding the mixture into 70g of dimethylbenzene, and uniformly stirring at 37 ℃ at a stirring speed of 1200r/min to obtain a suspension;
III, adding 4g N-vinyl caprolactam and 8g N-tertiary butyl acrylamide into 28g of ethanol, and uniformly stirring to obtain a monomer solution;
IV, regulating the temperature of the suspension to 48 ℃ under the protection of nitrogen, and continuously stirring, wherein a monomer solution is dropwise added in the stirring process, and the mass ratio of the potassium diformate core material to the N-vinyl caprolactam is 14:2; stirring for 5h, cooling, washing with deionized water for 3 times, filtering, and drying at 48 ℃ for 23h in an oven to obtain the low-addition stability-increasing microencapsulated potassium diformate feed additive.
Example 4
A preparation method of a low-addition stability-enhancing microencapsulated potassium diformate feed additive comprises the following steps:
I. immersing 8g of cotton fiber into 40g of 0.8mol/L sodium hydroxide solution, aging for 12 hours at room temperature, filtering, washing for 3 times with water, drying, crushing, adding into 75% ethanol solution with mass fraction, stirring for 2.5 hours, adding 2.5g of 12% ammonia water into the mixture, stirring uniformly, dropwise adding 4g of tetraethyl silicate into the mixture under stirring, stirring for 6 hours at room temperature, stirring at 1800r/min, filtering, sequentially ultrasonically cleaning with ethanol and water, freeze-drying, adding into a sintering furnace, heating to 740 ℃ from room temperature at a speed of 13 ℃/min, preserving heat for 1.5 hours, air-cooling to room temperature, and crushing to obtain porous silica;
II. Grinding 4g of potassium diformate, 6g of porous silica, 0.6g of dispersing agent and 0.2g of sodium dodecyl benzene sulfonate for 5 hours, maintaining the system temperature to be less than or equal to 50 ℃ in the grinding process, adding 0.13g of N, N' -methylene bisacrylamide and 0.04g of ammonium persulfate, and continuously grinding for 1.2 hours to obtain a potassium diformate core material; adding the mixture into 90g of dimethylbenzene, and uniformly stirring at 33 ℃ at 1800r/min to obtain a suspension;
III, adding 2g N-vinyl caprolactam and 12g N-tertiary butyl acrylamide into 22g of ethanol, and uniformly stirring to obtain a monomer solution;
IV, regulating the temperature of the suspension to 52 ℃ under the protection of nitrogen, and continuously stirring, wherein monomer solution is dropwise added into the suspension in the stirring process, and the mass ratio of the potassium diformate core material to the N-vinyl caprolactam is 8:4, a step of; stirring for 4 hours, cooling, washing for 5 times by adopting deionized water, filtering, sending into an oven, and drying at 42 ℃ for 27 hours to obtain the low-addition stability-increasing microencapsulated potassium diformate feed additive.
Example 5
A preparation method of a low-addition stability-enhancing microencapsulated potassium diformate feed additive comprises the following steps:
I. immersing 7g of cotton fibers into 45g of 0.6mol/L sodium hydroxide solution, aging for 15h at room temperature, filtering, washing for 3 times with water, drying, crushing, adding into 70% ethanol solution with mass fraction, stirring for 3h, adding 2g of 15% ammonia water with mass fraction, stirring uniformly, dropwise adding 3g of tetraethyl silicate in the stirring state, stirring for 7h at room temperature, stirring at 1500r/min, filtering, sequentially ultrasonically cleaning with ethanol and water, freeze-drying, adding into a sintering furnace, heating to 730 ℃ from room temperature at a speed of 15 ℃/min, preserving heat for 2h, cooling to room temperature by air, and crushing to obtain porous silica;
II. Grinding 3g of potassium diformate, 7g of porous silica, 0.4g of dispersing agent and 0.5g of octyl phenol polyoxyethylene ether for 4 hours, maintaining the system temperature to be less than or equal to 50 ℃ in the grinding process, adding 0.15g of N, N' -methylene bisacrylamide and 0.03g of ammonium persulfate, and continuously grinding for 1.5 hours to obtain a potassium diformate core material; adding into 80g of dimethylbenzene, and uniformly stirring at 35 ℃ at a stirring speed of 1500r/min to obtain a suspension;
III, adding 3g N-vinyl caprolactam and 10g N-tertiary butyl acrylamide into 25g of ethanol, and uniformly stirring to obtain a monomer solution;
IV, regulating the temperature of the suspension to 50 ℃ under the protection of nitrogen, continuously stirring, and dropwise adding a monomer solution into the suspension in the stirring process, wherein the mass ratio of the potassium diformate core material to the N-vinyl caprolactam is 11:3, a step of; stirring for 4.5h, cooling, washing with deionized water for 4 times, filtering, sending into an oven, and drying at 45 ℃ for 25h to obtain the low-addition stability-enhancing microencapsulated potassium diformate feed additive.
Comparative example 1
A method for preparing microencapsulated potassium diformate feed additive, comprising the following steps:
I. grinding 3g of potassium diformate, 0.15g of N, N' -methylene bisacrylamide, 0.03g of ammonium persulfate and 0.5g of octyl phenol polyoxyethylene ether for 5.5h, and maintaining the system temperature to be less than or equal to 50 ℃ in the grinding process to obtain a potassium diformate core material; adding into 80g of dimethylbenzene, and uniformly stirring at 35 ℃ at a stirring speed of 1500r/min to obtain a suspension;
II. Adding 3g N-vinyl caprolactam and 10g N-tertiary butyl acrylamide into 25g of ethanol, and uniformly stirring to obtain a monomer solution;
III, regulating the temperature of the suspension to 50 ℃ under the protection of nitrogen, and continuously stirring, wherein a monomer solution is dropwise added in the stirring process, and the mass ratio of the potassium diformate core material to the N-vinyl caprolactam is 11:3, a step of; stirring for 4.5h, cooling, washing with deionized water for 4 times, filtering, sending into an oven, and drying at 45 ℃ for 25h to obtain the microencapsulated potassium diformate feed additive.
Comparative example 2
The conventional preparation method of the potassium diformate microcapsule feed comprises the following steps:
(1) Preparing a core material: 1g of mesoporous silica is taken and placed in 20mL of potassium diformate solution with mass fraction of 3%, and the microcapsule core material is prepared by mechanically stirring for 3 hours at 40 ℃, centrifuging and drying for 12 hours at 50 ℃.
(2) Preparation of core material/sodium alginate solution: 1g of core material is weighed and added into 200mL of sodium alginate solution with mass fraction of 2%, and the mixture is stirred at 40 ℃ until the mixture is uniformly mixed, so as to obtain solution I.
(3) Preparation of chitosan-calcium chloride solution: 1.5g of chitosan is weighed and added into 150mL bodyStirring acetic acid solution with integration number of 2% at 40deg.C until uniform solution is formed, and adding CaCl with mass fraction of 20mL and 15% 2 The solution is stirred uniformly to obtain a solution II.
(4) Preparation of slow-release microcapsules: sucking the solution I by a needle tube with the inner diameter of 0.5mm, slowly dripping the solution I into 170mL of solution II, solidifying for 30min until a microcapsule is formed, washing the microcapsule by distilled water until no chloride ions exist, and drying the microcapsule in a drying oven at 50 ℃ for 12h to obtain the microcapsule with the particle diameter of 2.0-2.5 mm.
The potassium diformate microcapsules obtained in example 5 and comparative examples 1-2 were used for the test.
Test example 1
The products of example 5 and comparative example 2 were subjected to a moisture absorption test, test method: at 60% humidity and room temperature, 1g of each sample was placed on an electronic balance, and the weight was recorded at regular time to measure the degree of moisture absorption, and the test results are shown in the following table:
| Time | example 5 | Comparative example 2 |
| 0h | 1.00g | 1.00g |
| 2h | 1.00g | 1.02g |
| 4h | 1.00g | 1.05g |
| 8h | 1.00g | 1.06g |
| 16h | 1.01g | 1.07g |
As can be seen from the above table, compared with the prior art of microencapsulated potassium diformate, the microencapsulated potassium diformate product of the present invention has significantly improved hygroscopicity, no moisture absorption phenomenon before 8 hours, and particularly, the moisture absorption rate at 16 hours is only 1%, and the moisture resistance is good.
Test example 2
1.2g of each group of samples were placed in 200mL of hydrochloric acid solution (simulated gastric fluid system) with pH=2.0 and 200mL of PBS buffer solution (simulated intestinal system) with pH=7.2, respectively, and stirred at a constant temperature of 37 ℃ at a speed of 80r/min, and the pH value of the solution was detected at regular time.
The results are shown in FIG. 1. As can be seen from fig. 1:
1. the potassium diformate microcapsules obtained in example 5 and comparative example 1 were immersed in simulated gastric fluid for a long period of time, and the pH of the solution was hardly changed, indicating that the microcapsule wall material was not broken and the potassium diformate was not released in this environment. Whereas the potassium diformate microcapsule obtained in comparative example 2 was immersed in simulated gastric fluid, but brought to pH 3, the applicant believes that this is due to the fact that comparative example 2 uses sodium alginate and chitosan as wall materials, and the wall materials (particularly chitosan) react under acidic conditions, thereby raising the pH.
2. Each group of potassium diformate microcapsules is soaked in simulated intestinal juice, and the microcapsule wall material breaks in alkaline environment, so that the potassium diformate is effectively released, but the wall materials of the potassium diformate microcapsules obtained in the example 5 and the comparative example 1 are more resistant to alkaline environment relative to the wall materials of the potassium diformate microcapsules obtained in the comparative example 2, so that the effective component potassium diformate can reach the tail section of the intestinal tract along with intestinal peristalsis.
Test example 3
1.2g of each group of samples was placed in PBS buffer solution with pH=7.2, and the samples were placed in a constant temperature water bath at 37℃and stirred with a magnetic stirrer with a rotation speed of 80r/min, so that the potassium diformate in the microcapsules was fully released. Sucking 5mL of slow release liquid in a centrifuge tube with a mark at intervals of 0.5h by using a pipetting gun, centrifuging for 30min in a centrifuge with a speed of 5000r/min, diluting for 30 times by using distilled water, performing absorbance test on each diluted slow release liquid by using an atomic absorption spectrophotometer, and converting into the content of potassium diformate in each slow release liquid, thereby calculating the encapsulation rate.
Encapsulation efficiency = content of potassium diformate in microspheres/initial potassium diformate dose x 100%
The results are as follows:
| test item | Encapsulation efficiency% |
| Example 5 | 85.4 |
| Comparative example 1 | 74.6 |
| Comparative example 2 | 61.2 |
As can be seen from the table above: the encapsulation efficiency of the potassium diformate microcapsule obtained in example 5 was the highest, and comparative example 1 was slightly inferior to example 5, and the applicant believes that this is due to the limited adsorption capacity of mesoporous silica to potassium diformate, whereas in example 5, potassium diformate was adsorbed by using a tubular structure of porous silica, the loading of porous silica was large, and the stability was high, so that the encapsulation efficiency was 85% or more.
Test example 4
Each group of potassium diformate microcapsule samples was added to a PBS buffer solution of ph=7.2 used in test example 2 at an addition amount of 4% (based on the actual content of potassium diformate), 2mL was added to a test tube containing 8mL of the medium, 100 μl of the bacterial suspension of escherichia coli which had been cultured to the logarithmic growth phase was further added, and the mixture was treated at 37 ℃ in a water bath at a stirring speed of 220r/min, and absorbance at a wavelength of 630nm was measured with a visible spectrophotometer at 1h, 2h, 3h, 4h, 6h, 8h, 10h, 12h, 15h, 18h, respectively, and the antibacterial ratio was calculated as shown in fig. 2.
Antibacterial ratio= (OD 1 -OD)/OD×100％
OD is absorbance of the sample; OD (optical density) 1 Is absorbance of the microcapsule-free bacteria-containing culture solution.
As can be seen from fig. 2: in the embodiment 5, porous silica is adopted to adsorb potassium diformate, so that the potassium diformate is slowly released in intestinal tracts, and the long-acting sterilization and bacteriostasis are realized, and the antibacterial rate is steadily increased within 16 hours and can reach more than 90 percent at most; in comparative example 2, mesoporous silica is adopted to adsorb potassium diformate, but the antibacterial time is short, the antibacterial rate is only stable, and the highest antibacterial rate can reach 82%, but the antibacterial rate is continuously reduced after 6 hours, so that the continuous antibacterial in the intestinal tract is difficult to maintain; in comparative example 1, the potassium diformate was not protected by the adsorption structure, so that the potassium diformate was released after entering the intestinal tract, and the antibacterial rate initially reached a peak and was then continuously decreased.
Test example 5
The potassium diformate microcapsules obtained in example 5 and comparative examples 1-2 were added to pig feed for group feeding in an amount of 4% (added according to the actual content of potassium diformate). Each group of healthy piglets with the feeding objects of 10 healthy piglets of 28 days old are respectively weighed after being fed for 14 days, the average weight gain of each group of piglets is calculated, diarrhea or death phenomenon of the piglets is recorded in the feeding process, the diarrhea rate and the death rate are calculated, and the test results are shown in the following table:
| example 5 | Comparative example 1 | Comparative example 2 | |
| Average weight gain, kg | 5.4 | 4.8 | 4.3 |
| Daily average feed intake, kg | 0.38 | 0.31 | 0.22 |
| Diarrhea rate, |
0 | 0 | 30 |
| |
0 | 0 | 10 |
From the table, the diarrhea and death phenomena do not occur in both the example 5 and the comparative example 1, the growth performance of the example 5 is better, and the immunity and the growth performance of the piglets can be obviously improved after the piglet feed is used for feeding the piglets.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (6)
1. The preparation method of the low-addition stability-enhancing microencapsulated potassium diformate feed additive is characterized by comprising the following steps of:
s1, grinding potassium diformate, porous silicon dioxide, a dispersing agent and a surfactant for 2-6 hours, maintaining the system temperature to be less than or equal to 50 ℃ in the grinding process, adding N, N' -methylene bisacrylamide and an initiator, and continuously grinding for 1-2 hours to obtain a potassium diformate core material; adding into oily solvent, and stirring at 30-40deg.C to obtain suspension;
s2, adding N-vinyl caprolactam and N-tertiary butyl acrylamide into ethanol, and uniformly stirring to obtain a monomer solution;
s3, regulating the temperature of the suspension to 45-55 ℃ under the protection of nitrogen, continuously stirring, dropwise adding a monomer solution into the suspension in the stirring process, continuously stirring for 3-6 hours, cooling, washing, filtering, and drying at low temperature to obtain the low-addition stability-increasing microencapsulated potassium diformate feed additive; in S1, the mass ratio of potassium diformate, porous silicon dioxide, dispersant, surfactant, N' -methylene bisacrylamide and initiator is 1-5:4-10:0.1-1:0.1-1:0.1-0.2:0.01-0.05; in S1, an initiator is ammonium persulfate; in S2, the mass ratio of the N-vinyl caprolactam to the N-tertiary butyl acrylamide is 1-5:5-15; in S3, the mass ratio of the potassium diformate core material to the N-vinyl caprolactam is 6-16:1-5.
2. The method for preparing a low-additive stability-enhancing microencapsulated potassium diformate feed additive according to claim 1, wherein in S1, the oily solvent is xylene.
3. The method for preparing the low-additive stability-increasing microencapsulated potassium diformate feed additive according to claim 1, wherein in S1, the surfactant is at least one of octylphenol polyoxyethylene ether, sodium dodecyl sulfate and sodium dodecyl benzene sulfonate.
4. The method for preparing the low-addition stability-enhancing microencapsulated potassium diformate feed additive according to claim 1, wherein in S1, the porous silica has a diameter of 612-945nm.
5. The method for preparing the low-addition stability-enhancing microencapsulated potassium diformate feed additive according to claim 1, wherein in S1, the porous silica is prepared by the following steps: and (3) aging the cotton fiber, washing, drying, crushing, dripping tetraethyl silicate, cleaning, drying and sintering.
6. A low-additive stability-enhancing microencapsulated potassium diformate feed additive, characterized in that the low-additive stability-enhancing microencapsulated potassium diformate feed additive is prepared by the preparation method of any one of claims 1-5.
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