LU502660B1 - Antibacterial synergistic bacterially-anti-adhesive material, preparation method and application thereof - Google Patents

Antibacterial synergistic bacterially-anti-adhesive material, preparation method and application thereof Download PDF

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LU502660B1
LU502660B1 LU502660A LU502660A LU502660B1 LU 502660 B1 LU502660 B1 LU 502660B1 LU 502660 A LU502660 A LU 502660A LU 502660 A LU502660 A LU 502660A LU 502660 B1 LU502660 B1 LU 502660B1
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bacterially
adhesive material
polymer microspheres
antibacterial
modified polymer
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LU502660A
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German (de)
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Zili Liu
Jianliang Zuo
Jing Lin
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Univ Guangzhou
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06Polymers provided for in subclass C08G
    • C08F290/062Polyethers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/66Additives characterised by particle size
    • C09D7/69Particle size larger than 1000 nm
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/16Solid spheres

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  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polymers & Plastics (AREA)
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Abstract

Disclosed are an antibacterial synergistic bacterially-anti-adhesive material, a preparation method and an application thereof, where the antibacterial synergistic bacterially-anti-adhesive material includes modified polymer microspheres, epoxy resin, diethylenetriamine, and absolute ethanol as solvent; the modified polymer microsphere is prepared by the following steps: (1) uniformly mixing carboxyl-containing vinyl monomer, polyethylene glycol methacrylate, styrene monomer and initiator, followed by reacting under microwave conditions; (2) after the reaction, washing a reaction product with an organic solvent to remove unreacted monomers to obtain micron-sized polymer microspheres; (3) adding a dispersion stabilizer and the micron-sized polymer microspheres obtained in step (2) into Tollens' reagent for uniformly dispersing, followed by reacting under ultrasonic conditions. The antibacterial synergistic bacterially-anti-adhesive material can be solidified and sprayed onto the surface of any object to improve the antibacterial performance and anti-bacterial adhesion performance of the object.

Description

DESCRIPTION LU502660
ANTIBACTERIAL SYNERGISTIC BACTERIALLY-ANTI-ADHESIVE
MATERIAL, PREPARATION METHOD AND APPLICATION THEREOF
TECHNICAL FIELD
The present disclosure belongs to the field of coating chemical industry, and particularly relates to an antibacterial synergistic bacterially-anti-adhesive material, a preparation method and application thereof.
BACKGROUND
Microorganisms have existed on Earth for billions of years, and have evolved to adapt to any environment with continuous evolutionary reproduction. A great number of microorganisms can be found in environments where humans live, such as daily fiber garments, sanitary ceramics, steel for construction, marine vessels, medical supplies, and disinfection of drinking water, etc.
Microorganisms multiply rapidly under suitable temperature and nutrients, leading to deterioration and mold, as well as septic infection of wounds and other phenomena, posing a serious threat to human health. Moreover, microorganisms often adhere to the surface of various materials under interface effects and form adhesive biofilms as a result of growth and reproduction, causing pathogenic bacteria transmission, microbial contamination and corrosion that seriously endanger human health and national economic development. Yet, existing antimicrobial materials are vulnerable to corrosion, mechanical impact and mechanical friction that affect the antimicrobial performance of antimicrobial materials.
SUMMARY
In view of the shortcomings of the prior art, the present disclosure provides an antibacterial synergistic bacterially-anti-adhesive material, its preparation method and application.
In order to achieve the above objectives, the present disclosure adopts technical scheme as follows: an antibacterial synergistic bacterially-anti-adhesive material, including modified polymer microspheres, epoxy resin, diethylenetriamine (DETA), and absolute ethanol as solvent.
The modified polymer microspheres account for 5 percent (%) - 20% by weight of the antibacterial synergistic bacterially-anti-adhesive material; the epoxy resin accounts for 0.5% - 2% by weight of the antibacterial synergistic bacterially-anti-adhesive material; and the DETA accounts for 0.1% - 5% of the weight of the antibacterial synergisti€502660 bacterially-anti-adhesive material.
The modified polymer microspheres are prepared according to the following steps: (1) uniformly mixing 5% - 10% by mass of carboxyl-containing vinyl monomer, 5% - 10% by mass of polyethylene glycol methacrylate (PEGMA), 80% - 90% by mass of styrene monomer, and initiator to obtain a reaction system A, and reacting the reaction system A at 60 - 80 degree
Celsius (°C) for 4 - 5 hours (h) under microwave condition, where the reaction system A is protected by an inert gas atmosphere and stirred at a constant temperature while reacting; (2) washing a reaction product after the reaction with an organic solvent to remove unreacted monomers to obtain micron-sized polymer microspheres; (3) adding a dispersion stabilizer and the micron-sized polymer microspheres obtained in the step (2) into a Tollens' reagent for uniformly dispersing, followed by ultrasonically reacting at 58 - 62°C for 2.5 - 3.5 h; washing the microspheres-added reagent with deionized water to remove unreacted substances after the reaction, and obtaining solid precipitate, namely the modified polymer microspheres.
The antibacterial synergistic bacterially-anti-adhesive material can be solidified and sprayed onto the surface of any object, after that, the property of inorganic nano-silver rapid releasing and sterilization of the material enables the surface of the object a good antibacterial effect and while effectively preventing the adhesion of bacteria such as Escherichia coli (E. coli) and
Staphylococcus; such efficient and durable functions of anti bacteria and anti cohesion are highly resistant to corrosion and mechanical wearing, and remain effective as being exposed to corrosion of acid, alkali, salt and mechanical shock as well as mechanical friction.
Preferably, the carboxyl-containing vinyl monomer in step (1) of preparing the modified polymer microsphere is one or two selected form a group of methacrylic acid an acrylic acid; the initiator is azodiisobutyronitrile with an amount of 0.5% - 5% of a total weight of the carboxyl-containing vinyl monomer, polyethylene glycol methacrylate and styrene monomer.
Preferably, the Tollens' reagent in the step (3) of preparing modified polymer microspheres is in a concentration of 0.01 - 0.3 mole per liter (mol/L).
Preferably, the Tollens' reagent in the step (3) of preparing modified polymer microspheres is in a concentration of 0.05 - 0.3 mol/L.
The antibacterial synergistic bacterially-anti-adhesive material achieves a rather better performance in anti-bacteria and anti-adhesion when the concentration of Tollens' reagent in step (3) is in a range of 0.05 - 0.3 mol/L.
Preferably, the Tollens' reagent in the step (3) of preparing modified polymer microspheres is in 4)502660 concentration of 0.01 - 0.3 mol/L.
The antibacterial synergistic bacterially-anti-adhesive material achieves a rather better performance in anti-bacteria and anti-adhesion when the concentration of Tollens' reagent in step (3) is in a range of 0.05 - 0.3 mol/L.
Preferably, the microwave condition in step (1) of preparing the modified polymer microspheres refers to power of 500 - 1,000 Watts (W), and the inert gas is nitrogen.
Preferably, the dispersion stabilizer in step (3) of preparing the modified polymer microspheres is polyvinylpyrrolidone with an amount of 0.5% - 5% of the total weight of the carboxyl-containing vinyl monomer, polyethylene glycol methacrylate and styrene monomer.
Preferably, the reaction system A in step (1) of preparing the modified polymer microspheres is reacted at 70°C for 4 - 5 h under the microwave condition.
Preferably, the ultrasonically reacting in step (3) of preparing the modified polymer microspheres is ultrasonically reacting at 60°C for 3 h.
The disclosure also provides a preparation method of the antibacterial synergistic bacterially-anti-adhesive material according to any one of the above, including: (1) uniformly mixing 5% - 10% by mass of carboxyl-containing vinyl monomer, 5% - 10% by mass of PEGMA, 80% - 90% by mass of styrene monomer, and initiator to obtain a reaction system A, and reacting the reaction system A at 60 - 80°C for 4 - 5 h under microwave conditions, where the reaction system A is protected by an inert gas atmosphere and stirred at a constant temperature while reacting; (2) washing a reaction product after the reaction with an organic solvent to remove unreacted monomers to obtain micron-sized polymer microspheres; (3) adding a dispersion stabilizer and the micron-sized polymer microspheres obtained in the step (2) into a Tollens' reagent for uniformly dispersing, followed by ultrasonically reacting at 58 - 62°C for 2.5 - 3.5 h; washing the microspheres-added reagent with deionized water to remove unreacted substances after the reaction, and obtaining solid precipitate, namely the modified polymer microspheres; and (4) uniformly mixing the modified polymer microspheres accounting for 5 - 20% of a weight of the antibacterial synergistic bacterially-anti-adhesive material, epoxy resin accounting for 0.5 - 2% of the weight of the antibacterial synergistic bacterially-anti-adhesive material, DETA accounting for 0.1 - 5% of the weight of the antibacterial synergistic bacterially-anti-adhesive material and the balance of ethanol to obtain the antibacterial synergistic bacterially-anti-adhesive material.
The method above is simple with less requirements on cost and preparing conditions.
The disclosure also provides an application of the antibacterial synergisti¢;502660 bacterially-anti-adhesive material of being solidified and sprayed onto the surface of an object.
The present disclosure has the advantages that: an antibacterial synergistic bacterially-anti-adhesive material, its preparation method and application are provided by the present disclosure, where the antibacterial synergistic bacterially-anti-adhesive material can be solidified and sprayed onto the surface of any object; after that, the property of inorganic nano-silver rapid releasing and sterilization of the material enables the surface of the object a good antibacterial effect and while effectively preventing the adhesion of bacteria such as Æ. coli and Staphylococcus; such efficient and durable functions of anti bacteria and anti cohesion are highly resistant to corrosion and mechanical wearing, and remains effective as being exposed to acid, alkali, salt corrosion and mechanical shock and mechanical friction. The preparation method of the antibacterial synergistic bacterially-anti-adhesive material is simple with less requirements on cost and preparing conditions.
BRIEF DESCRIPTION OF THE FIGURES
FIG. 1 shows a phenogram of antibacterial synergistic bacterially-anti-adhesive material according to the embodiment of the present disclosure, in which a: scanning electron microscope (SEM) diagram, b: contact angle diagram.
FIG. 2 illustrates a physical diagram of the application performance of the antibacterial synergistic bacterially-anti-adhesive material according to the embodiment of the present disclosure, in which a: Staphylococcus aureus (S. aureus) of blank group, and b: S. aureus of experimental group.
FIG. 3 shows a physical picture of the application performance of the antibacterial synergistic bacterially-anti-adhesive material according to the embodiment of the present disclosure, in which a: S. aureus of blank group, and b: S. aureus of experimental group.
FIG. 4 shows a physical diagram of the application performance of antibacterial synergistic bacterially-anti-adhesive material according to the embodiment of the present disclosure, in which a: Escherichia coli (E. coli) of blank group, B: Æ. coli of experimental group.
FIG. 5 shows a physical diagram of the application performance of antibacterial synergistic bacterially-anti-adhesive material according to the embodiment of the present disclosure, in which a: E. coli of blank group, b: E. coli of experimental group.
FIG. 6 shows a physical diagram of the application performance of antibacterial synergistic bacterially-anti-adhesive material according to the embodiment of the present disclosure, in which a: S. aureus of blank group, b: S. aureus of experimental group.
FIG. 7 shows a physical diagram of the application performance of antibacterial synergisti€592660 bacterially-anti-adhesive material according to the embodiment of the present disclosure, in which a: S. aureus of blank group, and b: S. aureus of experimental group.
DESCRIPTION OF THE INVENTION
The objectives, technical scheme and advantages of the present disclosure will be better explained in the following in conjunction with specific embodiments.
Embodiment 1
An antibacterial synergistic bacterially-anti-adhesive material provided by the embodiment of the present disclosure, comprising modified polymer microspheres, epoxy resin, diethylenetriamine (DETA), and absolute ethanol as solvent; the modified polymer microspheres account for 20 percent (%) of a weight of the antibacterial synergistic bacterially-anti-adhesive material; the epoxy resin accounts for 0.5% of the weight of the antibacterial synergistic bacterially-anti-adhesive material; and the DETA accounts for 0.1% of the weight of the antibacterial synergistic bacterially-anti-adhesive material.
The modified polymer microspheres are prepared as follows: (1) uniformly mixing 5% by mass of methacrylic acid, 5% by mass of polyethylene glycol methacrylate (PEGMA), 90% by mass of styrene monomer, and azodiisobutyronitrile as an initiator to obtain a reaction system A, where the initiator is in an amount of 0.5% of a total weight of the methacrylic acid, polyethylene glycol methacrylate and styrene monomer; then reacting the reaction system A at 70 degree Celsius (°C) for 5 hours (h) under microwave conditions. (2) washing a reaction product with an organic solvent after reacting the reaction system A to remove unreacted monomers to obtain micron-sized polymer microspheres; (3) adding a dispersion stabilizer and the micron-sized polymer microspheres obtained in step (2) into a Tollens' reagent, followed by ultrasonically reacting at 60°C for 3 h, where the dispersion stabilizer is polyvinylpyrrolidone with an amount of 0.5% of the total weight of methacrylic acid, polyethylene glycol methacrylate and styrene monomer, the Tollens' reagent is in a concentration of 0.05 mole per liter (mol/L) and is uniformly dispersed; after the reaction is finished, washing the ultrasonically reacted reagent with deionized water to remove unreacted materials and obtaining a solid precipitate, 1. e., the modified polymer microspheres.
A preparation method of the antibacterial synergistic bacterially-anti-adhesive material as provided in this embodiment, where the method includes the following steps:
(1) uniformly mixing methacrylic acid, PEGMA, styrene monomer, and initiator according to, 4502660 weight ratio to obtain the reaction system A, and reacting the reaction system A at 70°C for 5 h under the microwave condition, where the reaction system A is protected in an inert gas atmosphere and stirred under constant temperature while reacting; (2) washing the reaction product with an organic solvent to remove unreacted monomers after the reaction to obtain micron-sized polymer microspheres; (3) adding the dispersion stabilizer and the micron-sized polymer microspheres obtained in step (2) into Tollens' reagent for uniformly dispersing, followed by ultrasonically reacting at 60°C for 3 h; after the reaction is finished, washing the ultrasonically reacted reagent with deionized water to remove unreacted materials and obtaining a solid precipitate, i. e., the modified polymer microspheres; (4) uniformly mixing the modified polymer microspheres, epoxy resin, DETA and ethanol according to the weight ratio to obtain the antibacterial synergistic bacterially-anti-adhesive material.
Embodiment 2
An antibacterial synergistic bacterially-anti-adhesive material prepared by the presnet embodiment of the present disclosure, where the present embodiment differs from Embodiment 1 only in that the concentration of Tollens' reagent in step (3) of preparing the modified polymer microspheres is 0.1 mol/L.
Embodiment 3
An antibacterial synergistic bacterially-anti-adhesive material prepared by the presnet embodiment of the present disclosure, where the present embodiment differs from Embodiment 1 only in that the concentration of Tollens' reagent in step (3) of preparing the modified polymer microspheres is 0.3 mol/L.
Efficacy embodiment 1
Hereby, Staphylococcus is Staphylococcus aureus (S. aureus) ATCC29213, and Escherichia coli (Æ. coli) 1s ATCC25922. 1. Method for calculating antibacterial rate: (1) respectively soaking stainless steel plates in sterile water, absolute ethanol and acetone for 15 minutes (min), cleaning the soaked-plates with an ultrasonic cleaner for 10 min so as to remove oil stains on them, vacuum drying the plates at 80°C overnight to remove the residual water and solvent on the stainless steel plates, cutting the stainless steel plates into samples of 1.5 centimeters (cm) x1.5 cm, and sterilizing them under an ultraviolet lamp for 30 min;
(2) setting the samples treated in step (1) as blank groups, and taking the antibacterial synergisti¢;502660 bacterially-anti-adhesive materials of Embodiments 1 - 3 as samples of experimental groups; (3) preparing conical flasks with 36 milliliters (mL) of 0.03 mol/L phosphate buffer solution (PBS), and adding 4 mL of bacterial suspension with a bacterial concentration of about (1x10°) - (5x10°) colony-forming unit (CFU)/mL into the above conical flasks after the conical flask are sterilized, where the conical flasks are all in an overall concentration of (1x10°) - (5x10°)
CFU/mL; (4) respectively adding the samples of blank groups and the experimental groups into the conical flasks, mark them respectively, followed by shaking culture of 1 min at 25°C with rotating speed of 200 revolutions per minute (rpm), and sampling at "0" contact time; (5) counting numbers of colonies by two times of 10-fold dilution method after the shaking culture of 1 min, where 100 microliters (ul) of a solution with proper dilution ratio is taken by a pipette for plate coating, and the numbers of colonies are recorded after culturing in a biochemical incubator at a constant temperature of 37°C for 36 h; (6) culturing the samples of blank groups and experimental groups after "0" contact time in a shaking table at constant temperature of 25°C for 6 h under a rotating speed of 200 rpm; (7) diluting each conical flask to an appropriate dilution ratio by 10-fold dilution method after 6 h, coating 100 pL of the solution with the appropriate dilution ratio with a pipette, followed by culture in the biochemical incubator at constant temperature of 37°C for 36 h, recording the numbers of colonies and taking photos; and (8) comparing flasks of blank groups and experimental groups in terms of concentration of viable bacteria, where the antibacterial rate is calculated as follows:
Y = me x 100%; where Y is antibacterial rate of sample,
Wr; is an average value of the concentration of viable bacteria in the flasks of three blank groups after shaking contact for 6 h, and
Or: is an average value of the concentration of viable bacteria in flasks of three experimental groups after 6 h of shaking contact. 2. Method for testing and calculating bacterially-anti-adhesion rate: samples of experimental groups, namely stainless steel plates whose surfaces respectively coated with the antibacterial synergistic bacterially-anti-adhesive materials of Embodiments 1 - 3, and samples (1.5 cm * 1.5 cm) of blank groups, namely cleaned and sterilized stainless steel plates, are vertically put into 10’ CFU/mL bacterial solution and cultured at 37°C for 4 h; vertically pulling the samples out of the bacterial solution and suspending the samples for 3 min to remove residual bacterial droplets; transferring the treated sample to 25 mL of MH broth solution,502660 followed by further culture in an incubator at 37°C for 24 h; rinsing off unadhered bacteria from the samples with sterile water; putting the samples into 5 mL of PBS and placing the solutions in an ultrasonic instrument for 2 min so as to ultrasonically remove the bacteria strongly adhered to the surface of the samples; then coating 100 uL of solution by the plate coating, followed by incubation in a incubator at 37°C for 24 h, and counting bacteria after incubation to extrapolate the number of bacteria that were adhered; the bacterially-anti-adhesion rate is calculated as follows: bacterially-anti-adhesion rate (%) = (CFUplnemL! - CFUsampiemL”")/CFUplanemL"!, where the
CFUblank represents the number of tested bacteria in sample of blank group, and the CFUsample represents the number of tested bacteria in sample of experimental group. 3. Method for testing mechanical performance: placing the stainless steel plates respectively sprayed with antibacterial synergistic bacterially-anti-adhesive materials of Embodiments 1 - 3 on a steel wool friction tester, carrying out friction tests on the plates with contact pressure setting at 25 kilopascals (KPa) and friction times of 60 times; then placing the stainless steel plates treated by the friction test on an impact tester, where a 1 kilogram (kg) hammer falls freely at an altitude of 1 meter (m) to impact a coated surface of the stainless steel plates, followed by testing of antibacterial rate of the samples. 4. Method for testing chemical corrosion performance: soaking the stainless steel plates coated with the antibacterial synergistic bacterially-anti-adhesive materials of Embodiments 1 - 3 in HCI with pH = 1 for 3 days, taking out the soaked plates and soaking in NaOH with pH = 14 for another 3 days, then testing the samples for antibacterial rate after chemical corrosion.
Experimental results
FIG. 1 shows a scanning electron microscope (SEM) image of the apparent morphology of the antibacterial synergistic bacterially-anti-adhesive material of Embodiment 1, where the synthesized modified polymer microspheres have a particle size of about 2 micrometers (um), and the nano-silver has a particle size of about 40 nano-meters (nm).
FIG. 2 shows the antibacterial performance of the stainless steel plate coated with the antibacterial synergistic bacterially-anti-adhesive material of Embodiment 1 on S. aureus, and the performance is significant. The results of antibacterial rate and bacterially-anti-adhesion rate obtained by antibacterial experiment are shown in Table 1; object sprayed with antibacterial synergistic bacterially-anti-adhesive material of Embodiment 1 on the surface presents good antibacterial performance and anti-bacterial adhesion performance, and the performance remain,5p2660 unaffected after exposure to mechanical friction, mechanical impact and chemical corrosion.
FIG. 3 shows a SEM image of S. aureus adhered to the surface of the stainless steel plate coated with the antibacterial synergistic bacterially-anti-adhesive material of Embodiment 1; it can be seen from FIG. 3 that there is very small amount of S. aureus adhered to the stainless steel plate coated with the antibacterial synergistic bacterially-anti-adhesive material of Embodiment 1, indicating that the material is effective in reducing the adhesion of bacteria on the surface of objects and provides good anti-bacterial adhesion performance.
Table 1 Antibacterial rate and bacterially-anti-adhesion rate of antibacterial synergistic bacterially-anti-adhesive material of Embodiment 1 . . . . Antibacterial Tate | Antibacterial rate
Antibacteri | Bacterially-anti after mechanical ; . after chemical al rate -adhesion rate performance . . . corrosion testing testing 92.12% 93.12% 91.09% 90.19% 93.09% 94.31% 92.35% 91.32%
FIG. 4 shows the antibacterial performance of the stainless steel plate coated with the antibacterial synergistic bacterially-anti-adhesive material of Embodiment 2 on E. coli, and the performance is excellent, Table 2 illustrates the antibacterial rate results obtained from the antibacterial experiment, where material of Embodiment 2 enables object with good antibacterial performance after being sprayed onto the surface of the object, and the antibacterial performance of the surface of the object is not affected after being exposed to mechanical friction, mechanical impact and chemical corrosion.
FIG. 5 shows a SEM image of Æ. coli adhered to the stainless steel plate coated with the antibacterial synergistic bacterially-anti-adhesive material of Embodiment 2 after the anti-bacterial adhesion experiment, where the number of Æ. coli adhered to the stainless steel plate of Embodiment 2 is very small, which proves that the antibacterial synergistic bacterially-anti-adhesive material of Embodiment 2 is effective in improving the ability of anti-bacterial adhesion on the surface of the object after being sprayed onto the surface of the object, therefore achieving a good anti-bacterial adhesion performance by greatly reducing the bacterial adhesion on the surface of the object.
Table 2 Antibacterial rate and bacterially-anti-adhesion rate of antibacterial synergistic bacterially-anti-adhesive material in Embodiment 2
Antibacteri | Bacterially-anti Antibacterial rate Antibacterial rate ; after mechanical after chemical al rate -adhesion rate . . performance corrosion testing
As shown in FIG. 6, the stainless steel plate coated with the antibacterial synergistic bacterially-anti-adhesive material of Embodiment 3 has excellent bactericidal effect against S. aureus; Table 3 shows results of antibacterial rate obtained from the antibacterial experiment, and it can be seen form Table 3 that the material of Embodiment 3 endows object with good antibacterial performance after being sprayed onto the surface of the object, and the antibacterial performance of the surface of the object is not affected after being exposed to mechanical friction, mechanical impact and chemical corrosion.
After the anti-bacterial adhesion experiment, the SEM image of S. aureus adhered to the surface of the stainless steel plate coated with the antibacterial synergistic bacterially-anti-adhesive material of Embodiment 3 is shown in FIG. 7, where the number of S. aureus is very small, and the material improves the ability of the object surface of anti-bacterial adhesion after being sprayed onto the surface of the subject, and achieves excellent anti-bacterial adhesion performance by greatly reducing the adhesion of bacteria on the object surface.
It is found by comparing the results of Table 1, Table 2 and Table 3 that the antibacterial and anti-bacterial adhesion properties of the antibacterial synergistic bacterially-anti-adhesive material of Embodiment 3 are superior than those of Embodiment 2, and that of Embodiment 2 is superior to that of Embodiment 1.
In conclusion, it should be explained that the above embodiments are only used to illustrate the technical scheme of the present disclosure, but not to limit the scope of protection of the present disclosure. Although the present disclosure has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical scheme of the present disclosure can be modified or equivalently replaced without departing from the essence and scope of the technical scheme of the present disclosure.

Claims (10)

CLAIMS LU502660
1. An antibacterial synergistic bacterially-anti-adhesive material, characterized in that the antibacterial synergistic bacterially-anti-adhesive material comprises modified polymer microspheres, epoxy resin, diethylenetriamine (DETA), and absolute ethanol as solvent; where the modified polymer microspheres account for 5 percent (%) - 20% of a weight of the antibacterial synergistic bacterially-anti-adhesive material; the epoxy resin accounts for 0.5% - 2% of the weight of the antibacterial synergistic bacterially-anti-adhesive material; the DETA accounts for 0.1% - 5% of the weight of the antibacterial synergistic bacterially-anti-adhesive material; the modified polymer microspheres is prepared by the following steps: (1) uniformly mixing 5% - 10% by mass of carboxyl-containing vinyl monomer, 5% - 10% by mass of polyethylene glycol methacrylate (PEGMA), 80% - 90% by mass of styrene monomer, and initiator to obtain a reaction system A, and reacting the reaction system A at 60 - 80 degree Celsius (°C) for 4 - 5 hours (h) under a microwave condition, where the reaction system A is protected by an inert gas atmosphere and stirred at a constant temperature while reacting; (2) washing a reaction product after the reaction with an organic solvent to remove unreacted monomers to obtain micron-sized polymer microspheres; (3) adding a dispersion stabilizer and the micron-sized polymer microspheres obtained in the step (2) into a Tollens' reagent for uniformly dispersing, followed by ultrasonically reacting at 58 - 62°C for 2.5 - 3.5 h; washing the microspheres-added reagent with deionized water to remove unreacted substances after the reaction, and obtaining solid precipitate, namely the modified polymer microspheres.
2. The material according to claim 1, characterized in that the carboxyl-containing vinyl monomer in step (1) of preparing the modified polymer microsphere is one or two selected from a group of methacrylic acid and acrylic acid; the initiator is azodiisobutyronitrile with an amount of 0.5% - 5% of a total weight of the carboxyl-containing vinyl monomer, PEGMA and styrene monomer.
3. The material according to claim 1, characterized in that the Tollens' reagent in the step (3) of preparing modified polymer microspheres is in a concentration of 0.01 - 0.3 mole per liter (mol/L).
4. The material according to claim 3, characterized in that in the Tollens' reagent in the step (3) of preparing modified polymer microspheres is in a concentration of 0.05 - 0.3 mol/L.
5. The material according to claim 1, characterized in that the microwave condition in st¢p;502660 (1) of preparing the modified polymer microspheres comprises power of 500 - 1,000 Watts (W), and the inert gas is nitrogen.
6. The material according to claim 1, characterized in that the dispersion stabilizer in step (3) of preparing the modified polymer microspheres is polyvinylpyrrolidone with an amount of 0.5% - 5% of the total weight of the carboxyl-containing vinyl monomer, PEGMA and styrene monomer.
7. The material according to claim 1, characterized in that the reaction system A in step (1) of preparing the modified polymer microspheres is reacted at 70°C for 4 - 5 h under the microwave condition.
8. The material according to claim 1, characterized in that the ultrasonically reacting in step (3) of preparing the modified polymer microspheres is ultrasonically reacting at 60°C for 3 h.
9. A preparation method of the antibacterial synergistic bacterially-anti-adhesive material according to any one of claims 1 to 8, characterized in that the method comprises the following steps: (1) uniformly mixing 5% - 10% by mass of carboxyl-containing vinyl monomer, 5% - 10% by mass of PEGMA, 80% - 90% by mass of styrene monomer, and initiator to obtain a reaction system A, and reacting the reaction system A at 60 - 80°C for 4 - 5 h under microwave conditions, where the reaction system A is protected by an inert gas atmosphere and stirred at a constant temperature while reacting; (2) washing a reaction product after the reaction with an organic solvent to remove unreacted monomers to obtain micron-sized polymer microspheres; (3) adding a dispersion stabilizer and the micron-sized polymer microspheres obtained in the step (2) into a Tollens' reagent for uniformly dispersing, followed by ultrasonically reacting at 58 - 62°C for 2.5 - 3.5 h; washing the microspheres-added reagent with deionized water to remove unreacted substances after the reaction, and obtaining solid precipitate, namely the modified polymer microspheres; and (4) uniformly mixing the modified polymer microspheres accounting for 5 - 20% of a weight of the antibacterial synergistic bacterially-anti-adhesive material, epoxy resin accounting for 05 - 2% of the weight of the antibacterial synergistic bacterially-anti-adhesive material, DETA accounting for 0.1 - 5% of the weight of the antibacterial synergistic bacterially-anti-adhesive material and the balance of ethanol to obtain the antibacterial synergistic bacterially-anti-adhesive material.
10. An application method of the antibacterial synergistic bacterially-anti-adhesive material 592660 according to any one of claims 1 - 8, characterized in that the application method comprises solidifying and spraying the antibacterial synergistic bacterially-anti-adhesive material according to any one of claims 1 - 8 on a surface of an object.
LU502660A 2022-08-11 2022-08-11 Antibacterial synergistic bacterially-anti-adhesive material, preparation method and application thereof LU502660B1 (en)

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