CN110698727A - Antibacterial agent, preparation method thereof and polyolefin composite material - Google Patents
Antibacterial agent, preparation method thereof and polyolefin composite material Download PDFInfo
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Abstract
The invention discloses an antibacterial agent, a preparation method thereof and a polyolefin composite material. The preparation method of the antibacterial agent comprises the following steps: mixing polyvinylpyrrolidone, octadecyl trimethyl ammonium bromide, n-butyl titanate, ethanol and deionized water, and stirring and reacting at 60-80 ℃ for 6-8 hours to obtain a solution A; carrying out suction filtration, washing and drying on the solution A to obtain a sample B; calcining the sample B at 360-400 ℃ for 10-14 h to obtain mesoporous titanium dioxide; mixing the mesoporous titanium dioxide, 5-diphenylhydantoin, glycidyl methacrylate, sodium persulfate and deionized water, reacting at 70-90 ℃ for 18-24 hours, centrifuging, filtering, washing and drying to obtain a sample C; and mixing the sample C, sodium hypobromite and deionized water, reacting for 8-10 h at 25-30 ℃, centrifuging, filtering, washing and drying to obtain the antibacterial agent. The antibacterial agent prepared by the invention is applied to the polyolefin composite material, and the antibacterial performance of the polyolefin is improved.
Description
Technical Field
The invention relates to the technical field of high polymer materials, and particularly relates to an antibacterial agent, a preparation method thereof and a polyolefin composite material.
Background
"antibacterial" means to inhibit the growth, reproduction and survival of microorganisms such as bacteria and fungi for a certain period of time, "antibacterial agent" generally means a substance that can be added to a material to impart antibacterial properties to the material, "antibacterial material" is usually prepared by directly adding an antibacterial agent to a material. Polyolefin materials are known to have poor antimicrobial properties. In order to improve the antibacterial property of polyolefin materials, it is necessary to add antibacterial agents to polyolefin materials.
Disclosure of Invention
The invention mainly aims to provide an antibacterial agent, a preparation method thereof and a polyolefin composite material, and aims to solve the problem of poor antibacterial performance of polyolefin.
In order to achieve the above object, the present invention provides a method for preparing an antibacterial agent, comprising the steps of:
mixing polyvinylpyrrolidone, octadecyl trimethyl ammonium bromide, n-butyl titanate, ethanol and deionized water, and stirring and reacting at 60-80 ℃ for 6-8 hours to obtain a solution A;
carrying out suction filtration, washing and drying on the solution A to obtain a sample B;
calcining the sample B at 360-400 ℃ for 10-14 h to obtain mesoporous titanium dioxide;
mixing the mesoporous titanium dioxide, 5-diphenylhydantoin, glycidyl methacrylate, sodium persulfate and deionized water, reacting at 70-90 ℃ for 18-24 hours, centrifuging, filtering, washing and drying to obtain a sample C;
and mixing the sample C, sodium hypobromite and deionized water, reacting for 8-10 h at 25-30 ℃, centrifuging, filtering, washing and drying to obtain the antibacterial agent.
Optionally, the mass ratio of the polyvinylpyrrolidone, the octadecyl trimethyl ammonium bromide, the n-butyl titanate, the ethanol and the deionized water is (10-16): (18-24): (60-80): (30-40): (200-280).
Optionally, the mass ratio of the mesoporous titanium dioxide, the 5, 5-diphenylhydantoin, the glycidyl methacrylate, the sodium persulfate and the deionized water is (30-40): (20-24): (16-20): (0.6-1): (180-240).
Optionally, the mass ratio of the sample C, the sodium hypobromite and the deionized water is (20-30): (28-32): (160-200).
Optionally, mixing the mesoporous titanium dioxide, 5-diphenylhydantoin, glycidyl methacrylate, sodium persulfate and deionized water, reacting at 70-90 ℃ for 18-24 h, centrifuging, filtering, washing and drying to obtain a sample C, wherein the step of:
the centrifugation speed of the centrifugation is 3000-4000 r/min, and the centrifugation time is 20-60 min.
Optionally, mixing the sample C, sodium hypobromite and deionized water, reacting at 25-30 ℃ for 8-10 h, centrifuging, filtering, washing and drying to obtain the antibacterial agent, wherein the antibacterial agent comprises the following steps:
the centrifugation speed of the centrifugation is 3000-4000 r/min, and the centrifugation time is 20-60 min.
In addition, the invention also provides an antibacterial agent prepared by the preparation method of the antibacterial agent.
In addition, the invention also provides a polyolefin composite material, which comprises polyolefin and an antibacterial agent, wherein the antibacterial agent is the antibacterial agent.
Optionally, the polyolefin comprises any one of polypropylene, polyethylene, polybutylene terephthalate, polystyrene, and polyamide 6.
In the preparation method of the antibacterial agent, firstly, polyvinylpyrrolidone and octadecyl trimethyl ammonium bromide are used as composite template agents, and n-butyl titanate is used as a titanium source to synthesize mesoporous titanium dioxide; then taking mesoporous titanium dioxide as a carrier, carrying out copolymerization reaction with 5, 5-diphenylhydantoin and glycidyl methacrylate, and coating the surface of the mesoporous titanium dioxide; finally, carrying out bromination treatment to obtain the antibacterial agent of the mesoporous titanium dioxide coated by the N-halamine substance. The antimicrobial agent inhibits or inactivates microbial cells by releasing the oxidized form of the halogen in the structure and contacting the cells. Therefore, the antibacterial agent prepared by the preparation method of the antibacterial agent provided by the invention is applied to the polyolefin composite material, and the antibacterial performance of polyolefin can be improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other related drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a schematic flow chart of an embodiment of the method for producing an antibacterial agent according to the present invention.
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. It is to be understood that the described embodiments are merely a few embodiments of the invention, and not all embodiments.
It should be noted that those whose specific conditions are not specified in the examples were performed according to the conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially. In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In view of poor antibacterial property of polyolefin materials, the invention provides a preparation method of an antibacterial agent, and the prepared antibacterial agent is applied to polyolefin composite materials and can improve the antibacterial property of the polyolefin materials. With reference to the schematic flow diagram of an embodiment of the method for preparing an antimicrobial agent provided in fig. 1, the method for preparing an antimicrobial agent comprises the steps of:
s10, mixing polyvinylpyrrolidone, octadecyl trimethyl ammonium bromide, n-butyl titanate, ethanol and deionized water, and stirring and reacting at 60-80 ℃ for 6-8 hours to obtain a solution A.
Wherein the mass ratio of the polyvinylpyrrolidone, the octadecyl trimethyl ammonium bromide, the n-butyl titanate, the ethanol and the deionized water is (10-16): (18-24): (60-80): (30-40): (200-280).
And S20, carrying out suction filtration, washing and drying on the solution A to obtain a sample B.
The drying temperature is 60-80 ℃, and the drying time is 10-12 h.
S30, calcining the sample B at 360-400 ℃ for 10-14 h to obtain the mesoporous titanium dioxide.
Specifically, the sample B is placed in a muffle furnace to be calcined for 10-14 h at 360-400 ℃ to obtain the mesoporous titanium dioxide.
S40, mixing the mesoporous titanium dioxide, 5-diphenylhydantoin, glycidyl methacrylate, sodium persulfate and deionized water, reacting at 70-90 ℃ for 18-24 h, centrifuging, filtering, washing and drying to obtain a sample C.
Wherein the mass ratio of the polyvinylpyrrolidone, the octadecyl trimethyl ammonium bromide, the n-butyl titanate, the ethanol and the deionized water is (10-16): (18-24): (60-80): (30-40): (200-280). In order to ensure good centrifugal effect, the centrifugal speed of the centrifugation is 3000-4000 r/min, and the centrifugation time is 20-60 min. In addition, the drying temperature is 60-80 ℃, and the drying time is 10-12 h. When the reaction is carried out at 70 to 90 ℃ for 18 to 24 hours, it is preferable to stir the mixture to allow the reaction to proceed sufficiently.
S50, mixing the sample C, sodium hypobromite and deionized water, reacting for 8-10 hours at 25-30 ℃, centrifuging, filtering, washing and drying to obtain the antibacterial agent.
Specifically, the mass ratio of the sample C to the sodium hypobromite to the deionized water is (20-30): (28-32): (160-200). In order to ensure good centrifugal effect, the centrifugal speed of the centrifugation is 3000-4000 r/min, and the centrifugation time is 20-60 min. In addition, the drying temperature is 60-80 ℃, and the drying time is 10-12 h.
In the preparation method of the antibacterial agent, firstly, polyvinylpyrrolidone and octadecyl trimethyl ammonium bromide are used as composite template agents, and n-butyl titanate is used as a titanium source to synthesize mesoporous titanium dioxide; then taking mesoporous titanium dioxide as a carrier, carrying out copolymerization reaction with 5, 5-diphenylhydantoin and glycidyl methacrylate, and coating the surface of the mesoporous titanium dioxide; finally, carrying out bromination treatment to obtain the antibacterial agent of the mesoporous titanium dioxide coated by the N-halamine substance. The antimicrobial agent inhibits or inactivates microbial cells by releasing the oxidized form of the halogen in the structure and contacting the cells. Therefore, the antibacterial agent prepared by the preparation method of the antibacterial agent provided by the invention is applied to the polyolefin composite material, and the antibacterial performance of polyolefin can be improved.
In addition, the invention also provides an antibacterial agent prepared by the preparation method of the antibacterial agent.
The invention further provides a polyolefin composite material, which comprises polyolefin and an antibacterial agent, wherein the antibacterial agent is the antibacterial agent, and when the antibacterial agent is applied to the polyolefin composite material, the antibacterial property of the polyolefin can be effectively improved.
There are many kinds of polyolefins, such as polyethylene, polypropylene, ethylene-vinyl acetate copolymer, etc., which can improve the antibacterial performance after the antibacterial agent is added, in an embodiment of the polyolefin composite material provided by the present invention, the polyolefin includes any one of polypropylene (PP), Polyethylene (PE), polybutylene terephthalate (PBT), Polystyrene (PS), and polyamide 6(PA6), and when the antibacterial agent provided by the present invention is applied to the above five kinds of polyolefin materials, the antibacterial performance improvement effect of the prepared polyolefin composite material is more significant.
The technical solutions of the present invention are further described in detail below with reference to specific examples and drawings, it should be understood that the following examples are merely illustrative of the present invention and are not intended to limit the present invention.
In the following examples, the source information of the raw materials used is as follows: polyvinylpyrrolidone, Hubei Jusheng science and technology Co., Ltd; octadecyl trimethyl ammonium bromide, Yixing Kalima chemical Co., Ltd; n-butyl titanate, shanghai notai chemical ltd; ethanol, zhengzhou yaobang chemical ltd; 5, 5-diphenylhydantoin, Guangzhou Suoquinol chemical Co., Ltd; glycidyl methacrylate, chemical Limited Hengjing Hubei; sodium persulfate, Tianjin Zhentai chemical; sodium hypobromite, Hubei Ferry chemical Co., Ltd; deionized water, xianmen australian spring environmental protection technology ltd; PBT (model 2002U), Japan treaty; PP (model Z30S), mazineb petrochemical; PE (model 5070), brocade ethylene; PA6 (model CM1017), eastern japan; PS (model 350), taiwan george.
The following examples used the following test instrument types: model ZSK30 twin-screw extruder, W & P, Germany; JL-1000 type tensile testing machine, produced by Guangzhou Youcai laboratory instruments; HTL900-T-5B injection molding machine, manufactured by Haita plastics machinery, Inc.; XCJ-500 impact tester, manufactured by Chengde tester; QT-1196 tensile tester, Gaotai detection instruments, Inc. of Dongguan; QD-GJS-B12K model high-speed mixer, HengOde instruments, Beijing.
Example 1
(1) 100g of polyvinylpyrrolidone, 180g of octadecyl trimethyl ammonium bromide, 600g of n-butyl titanate, 300g of ethanol and 2.0kg of deionized water are weighed, added into a reaction vessel and stirred for reaction for 6 hours at the temperature of 60 ℃ to obtain a solution A.
(2) And carrying out suction filtration, washing and drying on the solution A to obtain a sample B.
(3) And placing the sample B in a muffle furnace, and calcining for 10h at 360 ℃ to obtain the mesoporous titanium dioxide.
(4) Weighing 300g of mesoporous titanium dioxide, 200g of 5, 5-diphenylhydantoin, 160g of glycidyl methacrylate, 6g of sodium persulfate and 1.8kg of deionized water, adding the materials into a reaction vessel, mixing, reacting at 70 ℃ for 18h, centrifuging (the centrifugation rate is 4000r/min, the centrifugation time is 20min), filtering, washing and drying (the drying temperature is 80 ℃, the drying time is 10h), thus obtaining a sample C.
(5) 200g of sample C, 280g of sodium hypobromite and 1.6kg of deionized water are weighed, added into a reaction vessel, mixed, reacted for 8 hours at 30 ℃, centrifuged (the centrifugation speed is 4000r/min and the centrifugation time is 20min), filtered, washed and dried (the drying temperature is 80 ℃ and the drying time is 10 hours), and the antibacterial agent P1 is obtained.
Application example 1
4 parts of the antibacterial agent P1 prepared in example 1 was added to 96 parts of PP, stirred in a high-speed mixer for 10min, and then added to a twin-screw extruder (the twin-screw extruder includes six temperature zones arranged in sequence, the temperature of the first temperature zone is 200 ℃, the temperature of the second temperature zone is 230 ℃, the temperature of the third temperature zone is 230 ℃, the temperature of the fourth temperature zone is 230 ℃, the temperature of the fifth temperature zone is 230 ℃, the temperature of the sixth temperature zone is 230 ℃, the head temperature of the twin-screw extruder is 230 ℃, and the screw rotation speed is 200r/min) to carry out blending extrusion, so as to obtain a PP composite material X1.
Comparative example 1
The procedure was the same as in application example 1, except that: no antibacterial agent P1 was added, and only 100 parts of PP was added to obtain PP material D1.
The PP composite material X1 prepared by the application comparative example 1 and the PP material D1 prepared by the comparative example 1 are made into sample bars by an injection molding machine, and the antibacterial performance data are shown in Table 1:
TABLE 1 comparison of antimicrobial Performance data for X1 and D1
As can be seen from Table 1, both Staphylococcus aureus and Escherichia coli in X1 are less than those in D1, i.e., the PP composite material prepared by using comparative example 1 has better antibacterial performance than the PP material prepared by using comparative example 1, i.e., the antibacterial agent P1 is applied to the PP composite material, so that the antibacterial performance of the PP material can be improved.
Example 2
(1) 160g of polyvinylpyrrolidone, 240g of octadecyl trimethyl ammonium bromide, 800g of n-butyl titanate, 400g of ethanol and 2.8kg of deionized water are weighed, added into a reaction vessel, and stirred and reacted for 8 hours at the temperature of 80 ℃ to obtain a solution A.
(2) And carrying out suction filtration, washing and drying on the solution A to obtain a sample B.
(3) And placing the sample B in a muffle furnace, and calcining for 14h at 400 ℃ to obtain the mesoporous titanium dioxide.
(4) Weighing 400g of mesoporous titanium dioxide, 240g of 5, 5-diphenylhydantoin, 200g of glycidyl methacrylate, 10g of sodium persulfate and 2.4kg of deionized water, adding the materials into a reaction vessel, mixing, reacting at 90 ℃ for 24h, centrifuging (the centrifugation rate is 3000r/min, the centrifugation time is 60min), filtering, washing and drying (the drying temperature is 70 ℃, the drying time is 11h) to obtain a sample C.
(5) Weighing 300g of sample C, 320g of sodium hypobromite and 2.0kg of deionized water, adding the sample C, the sodium hypobromite and the deionized water into a reaction vessel, mixing, reacting for 10 hours at 25 ℃, centrifuging (the centrifugation speed is 3000r/min, the centrifugation time is 60 minutes), filtering, washing and drying (the drying temperature is 70 ℃, the drying time is 11 hours), thus obtaining the antibacterial agent P2.
Comparative application example 2
4 parts of the antibacterial agent P2 prepared in example 2 is added into 96 parts of PBT, stirred for 10min by a high-speed mixer, and then added into a double-screw extruder (the double-screw extruder comprises six temperature zones which are sequentially arranged, the temperature of the first temperature zone is 200 ℃, the temperature of the second temperature zone is 260 ℃, the temperature of the third temperature zone is 260 ℃, the temperature of the fourth temperature zone is 260 ℃, the temperature of the fifth temperature zone is 260 ℃, the temperature of the sixth temperature zone is 260 ℃, the head temperature of the double-screw extruder is 260 ℃, and the screw rotating speed is 300r/min) for blending and extrusion, so that the PBT composite material X2 is obtained.
Comparative example 2
The procedure was the same as in application example 2, except that: the antibacterial agent P2 was not added, and only 100 parts of PBT was added to obtain a PBT material D2.
The PBT composite material X2 prepared by the application comparative example 2 and the PBT material D2 prepared by the comparative example 2 are made into sample strips by an injection molding machine, and the antibacterial performance data are shown in Table 2:
comparison of antimicrobial Performance data of tables 2X 2 and D2
As can be seen from Table 2, both Staphylococcus aureus and Escherichia coli in X2 are less than D2, i.e., the antibacterial property of the PBT composite material prepared by using comparative example 2 is better than that of the PBT material prepared by using comparative example 2, i.e., the antibacterial agent P2 is applied to the PBT composite material, so that the antibacterial property of the PBT material can be improved.
Example 3
(1) 130g of polyvinylpyrrolidone, 210g of octadecyl trimethyl ammonium bromide, 700g of n-butyl titanate, 350g of ethanol and 2.4kg of deionized water are weighed, added into a reaction vessel and stirred for reaction for 7 hours at 70 ℃ to obtain a solution A.
(2) And carrying out suction filtration, washing and drying on the solution A to obtain a sample B.
(3) And placing the sample B in a muffle furnace, and calcining for 12h at 380 ℃ to obtain the mesoporous titanium dioxide.
(4) 350g of mesoporous titanium dioxide, 220g of 5, 5-diphenylhydantoin, 180g of glycidyl methacrylate, 8g of sodium persulfate and 2.1kg of deionized water are weighed, added into a reaction vessel, mixed, reacted at 80 ℃ for 21h, centrifuged (the centrifugation rate is 3500r/min, the centrifugation time is 40min), filtered, washed and dried (the drying temperature is 60 ℃ and the drying time is 12h) to obtain a sample C.
(5) Weighing 250g of sample C, 300g of sodium hypobromite and 1.8kg of deionized water, adding the sample C, the sodium hypobromite and the deionized water into a reaction vessel, mixing, reacting for 9h at 27 ℃, centrifuging (the centrifugation rate is 3500r/min, the centrifugation time is 40min), filtering, washing and drying (the drying temperature is 60 ℃, the drying time is 12h), thus obtaining the antibacterial agent P3.
Application example 3
4 parts of the antibacterial agent P3 prepared in example 3 was added to 96 parts of PE, stirred in a high-speed mixer for 10min, and then added to a twin-screw extruder (the twin-screw extruder includes six temperature zones arranged in sequence, the temperature of the first temperature zone is 120 ℃, the temperature of the second temperature zone is 180 ℃, the temperature of the third temperature zone is 180 ℃, the temperature of the fourth temperature zone is 180 ℃, the temperature of the fifth temperature zone is 180 ℃, the temperature of the sixth temperature zone is 180 ℃, the head temperature of the twin-screw extruder is 180 ℃, and the screw rotation speed is 300r/min) to carry out blending extrusion, so as to obtain a PE composite material X3.
Comparative example 3
The procedure was the same as in application example 3, except that: the antibacterial agent P3 was not added, and only 100 parts of PE was added to obtain a PE material D3.
The PE composite material X3 prepared by the application comparative example 3 and the PE material D3 prepared by the comparative example 3 are made into sample bars by an injection molding machine, and the antibacterial performance data are shown in Table 3:
comparison of antimicrobial Performance data of tables 3X 3 and D3
As can be seen from table 3, both staphylococcus aureus and escherichia coli in X3 were less than D3, i.e., the PE composite material prepared using comparative example 3 had better antibacterial performance than the PE material prepared using comparative example 3, i.e., the antibacterial agent P3 was applied to the PE composite material, and the antibacterial performance of the PE material was improved.
Example 4
(1) 140g of polyvinylpyrrolidone, 220g of octadecyl trimethyl ammonium bromide, 650g of n-butyl titanate, 380g of ethanol and 2.2kg of deionized water are weighed, added into a reaction vessel and stirred for reaction for 6 hours at 65 ℃ to obtain a solution A.
(2) And carrying out suction filtration, washing and drying on the solution A to obtain a sample B.
(3) And placing the sample B in a muffle furnace, and calcining for 14h at 390 ℃ to obtain the mesoporous titanium dioxide.
(4) 380g of mesoporous titanium dioxide, 210g of 5, 5-diphenylhydantoin, 170g of glycidyl methacrylate, 9g of sodium persulfate and 2.3kg of deionized water are weighed, added into a reaction vessel, mixed, reacted at 75 ℃ for 19 hours, centrifuged (the centrifugation speed is 3000r/min and the centrifugation time is 60min), filtered, washed and dried (the drying temperature is 60 ℃ and the drying time is 12 hours), and the sample C is obtained.
(5) Weighing 280g of sample C, 290g of sodium hypobromite and 1.8kg of deionized water, adding the sample C, the sodium hypobromite and the deionized water into a reaction vessel, mixing, reacting for 9 hours at 28 ℃, centrifuging (the centrifugation speed is 3000r/min, the centrifugation time is 60 minutes), filtering, washing and drying (the drying temperature is 60 ℃, the drying time is 12 hours), thus obtaining the antibacterial agent P4.
Application example 4
4 parts of the antibacterial agent P4 prepared in example 4 are added into 96 parts of PA6, stirred for 10min by a high-speed mixer, and then added into a double-screw extruder (the double-screw extruder comprises six temperature zones which are sequentially arranged, the temperature of the first temperature zone is 230 ℃, the temperature of the second temperature zone is 260 ℃, the temperature of the third temperature zone is 260 ℃, the temperature of the fourth temperature zone is 260 ℃, the temperature of the fifth temperature zone is 260 ℃, the temperature of the sixth temperature zone is 260 ℃, the head temperature of the double-screw extruder is 260 ℃, and the screw rotating speed is 320r/min) for blending and extrusion, so that the PA6 composite material X4 is obtained.
Comparative example 4
The procedure was the same as in application example 4, except that: the antibacterial agent P4 was not added, and only 100 parts of PA6 was added to obtain PA6 material D4.
The PA6 composite material X4 prepared by using the comparative example 4 and the PA6 material D4 prepared by using the comparative example 4 are prepared into sample bars by using an injection molding machine, and the antibacterial performance data are shown in Table 4:
comparison of antimicrobial Performance data of tables 4X 4 and D4
As can be seen from table 4, staphylococcus aureus and escherichia coli in X4 are less than those in D4, i.e., the antibacterial performance of the PE composite material prepared by applying comparative example 4 is better than that of the PA6 material prepared by applying comparative example 4, i.e., the antibacterial agent P4 applied to the PA6 composite material can improve the antibacterial performance of the PA6 material.
Example 5
(1) 110g of polyvinylpyrrolidone, 190g of octadecyl trimethyl ammonium bromide, 750g of n-butyl titanate, 350g of ethanol and 2.5kg of deionized water are weighed, added into a reaction vessel and stirred for reaction for 6 hours at 75 ℃ to obtain a solution A.
(2) And carrying out suction filtration, washing and drying on the solution A to obtain a sample B.
(3) And placing the sample B in a muffle furnace, and calcining for 12h at 380 ℃ to obtain the mesoporous titanium dioxide.
(4) 370g of mesoporous titanium dioxide, 230g of 5, 5-diphenylhydantoin, 170g of glycidyl methacrylate, 9g of sodium persulfate and 1.9kg of deionized water are weighed, added into a reaction vessel, mixed, reacted at 75 ℃ for 19 hours, centrifuged (the centrifugation speed is 3700r/min, the centrifugation time is 40min), filtered, washed and dried (the drying temperature is 80 ℃ and the drying time is 10 hours), and the sample C is obtained.
(5) Weighing 220g of sample C, 310g of sodium hypobromite and 1.9kg of deionized water, adding the sample C, the sodium hypobromite and the deionized water into a reaction vessel, mixing, reacting for 9 hours at 25 ℃, centrifuging (the centrifugation speed is 3700r/min, the centrifugation time is 40min), filtering, washing and drying (the drying temperature is 80 ℃, the drying time is 10 hours), thus obtaining the antibacterial agent P5.
Application example 5
4 parts of the antibacterial agent P5 prepared in example 5 was added to 96 parts of PS, stirred in a high-speed mixer for 10min, and then added to a twin-screw extruder (the twin-screw extruder includes six temperature zones arranged in sequence, the temperature of the first temperature zone is 160 ℃, the temperature of the second temperature zone is 200 ℃, the temperature of the third temperature zone is 200 ℃, the temperature of the fourth temperature zone is 200 ℃, the temperature of the fifth temperature zone is 200 ℃, the temperature of the sixth temperature zone is 200 ℃, the head temperature of the twin-screw extruder is 200 ℃, and the screw rotation speed is 280r/min) to carry out blending extrusion, so as to obtain a PS composite material X5.
Comparative example 5
The procedure was the same as in application example 5, except that: the antibacterial agent P5 was not added, and only 100 parts of PS was added to obtain PS material D5.
The PS composite material X5 prepared by the application comparative example 5 and the PS material D5 prepared by the comparative example 5 are made into sample bars by an injection molding machine, and the antibacterial performance data are shown in Table 5:
comparison of antimicrobial Performance data of tables 5X 5 and D3
As can be seen from table 5, both staphylococcus aureus and escherichia coli in X5 were less than D3, i.e., the antibacterial performance of the PS composite material prepared using comparative example 5 was better than that of the PS material prepared using comparative example 5, i.e., the antibacterial agent P5 was applied to the PS composite material, and the antibacterial performance of the PS material was improved.
In conclusion, the antibacterial agent prepared by the preparation method of the antibacterial agent provided by the invention is applied to the polyolefin composite material, and the antibacterial performance of polyolefin can be improved.
The above is only a preferred embodiment of the present invention, and it is not intended to limit the scope of the invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall be included in the scope of the present invention.
Claims (9)
1. A method for preparing an antibacterial agent, comprising the steps of:
mixing polyvinylpyrrolidone, octadecyl trimethyl ammonium bromide, n-butyl titanate, ethanol and deionized water, and stirring and reacting at 60-80 ℃ for 6-8 hours to obtain a solution A;
carrying out suction filtration, washing and drying on the solution A to obtain a sample B;
calcining the sample B at 360-400 ℃ for 10-14 h to obtain mesoporous titanium dioxide;
mixing the mesoporous titanium dioxide, 5-diphenylhydantoin, glycidyl methacrylate, sodium persulfate and deionized water, reacting at 70-90 ℃ for 18-24 hours, centrifuging, filtering, washing and drying to obtain a sample C;
and mixing the sample C, sodium hypobromite and deionized water, reacting for 8-10 h at 25-30 ℃, centrifuging, filtering, washing and drying to obtain the antibacterial agent.
2. The preparation method of the antibacterial agent according to claim 1, wherein the mass ratio of the polyvinylpyrrolidone, the octadecyl trimethyl ammonium bromide, the n-butyl titanate, the ethanol and the deionized water is (10-16): (18-24): (60-80): (30-40): (200-280).
3. The method for preparing the antibacterial agent according to claim 1, wherein the mass ratio of the mesoporous titanium dioxide, the 5, 5-diphenylhydantoin, the glycidyl methacrylate, the sodium persulfate and the deionized water is (30-40): (20-24): (16-20): (0.6-1): (180-240).
4. The method for preparing the antibacterial agent according to claim 1, wherein the mass ratio of the sample C, the sodium hypobromite and the deionized water is (20-30): (28-32): (160-200).
5. The method for preparing the antibacterial agent according to claim 1, wherein the step of mixing the mesoporous titanium dioxide, the 5, 5-diphenylhydantoin, the glycidyl methacrylate, the sodium persulfate and the deionized water, reacting at 70-90 ℃ for 18-24 h, centrifuging, filtering, washing and drying to obtain a sample C is as follows:
the centrifugation speed of the centrifugation is 3000-4000 r/min, and the centrifugation time is 20-60 min.
6. The preparation method of the antibacterial agent according to claim 1, wherein the antibacterial agent is obtained by mixing the sample C, sodium hypobromite and deionized water, reacting at 25-30 ℃ for 8-10 h, centrifuging, filtering, washing and drying:
the centrifugation speed of the centrifugation is 3000-4000 r/min, and the centrifugation time is 20-60 min.
7. An antibacterial agent characterized by being produced by the method for producing an antibacterial agent according to any one of claims 1 to 6.
8. A polyolefin composite material comprising a polyolefin and an antibacterial agent, wherein the antibacterial agent is the antibacterial agent according to claim 7.
9. The polyolefin composite of claim 8, wherein the polyolefin comprises any one of polypropylene, polyethylene, polybutylene terephthalate, polystyrene, and polyamide 6.
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