CN111217956B - Preparation method of cationic custard apple-shaped acrylate copolymer antibacterial microspheres - Google Patents
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Abstract
The invention relates to a preparation method of cationic custard apple-shaped acrylate copolymer antibacterial microspheres, which comprises the following steps: the preparation method comprises the steps of uniformly mixing a comonomer, a quaternary ammonium salt type cationic acrylic monomer and a crosslinking monomer, and then adding an initiator and fully mixing to obtain a mixed solution; slowly dripping the mixed solution into deionized water under uniform stirring, and continuously stirring and polymerizing for 2-6 h after dripping is finished to obtain a reactant; cooling the reactant to room temperature, filtering, and removing the condensate to obtain an emulsion; and fourthly, centrifugally separating and washing the emulsion to obtain the emulsion. The invention has simple and safe process, and the obtained cationic custard fruit-shaped acrylate copolymer antibacterial microspheres can make up for the market vacancy, and can be popularized to be used as the antibacterial of fabrics, the antibacterial of automobile coatings, plastic decorative materials, floors, ceramic products and household appliances, the antibacterial and the anticorrosion of products such as water-based coatings, printing inks, dyes, adhesives and the like.
Description
Technical Field
The invention relates to the technical field of high-molecular antibacterial agents, in particular to a preparation method of cationic custard apple-shaped acrylate copolymer antibacterial microspheres.
Background
Bacteria are a typical harmful microorganism, and clinical cases of infection caused by pathogenic bacteria are increasing, becoming a public health problem of global concern. The occurrence of fungal and bacterial infections can have extremely serious consequences, including fatal diseases, increased patient mortality, and costly medical costs. The antibacterial material is a novel functional material with the function of killing or inhibiting microorganisms, has extremely wide application prospect in the fields of medical treatment, household articles, household appliances, food packaging and the like, and is widely concerned in research and application of the antibacterial material at present when the requirement of people on environmental sanitation is increasingly improved.
The traditional antibacterial agents mainly comprise four major classes of natural antibacterial agents, inorganic antibacterial agents, organic antibacterial agents and polymer antibacterial agents. Comparing and analyzing all types of antimicrobial agents, it is known that, although each type of antimicrobial agent has its advantages, it also has some disadvantages. For example: inorganic antibacterial agents such as: the invention patent CN 101883489A discloses a silver-containing inorganic antibacterial agent which has high price and certain antibacterial effectiveness delay, although the silver-containing inorganic antibacterial agent has good heat resistance, durability and safety, no secondary pollution, good stability and no drug resistance. Organic antibacterial agents, such as: the invention patent CN 107343506A discloses an organic zirconium phosphate antibacterial agent which has strong bactericidal power, relatively fast bactericidal speed and low price, but has poor heat resistance, toxicity and drug resistance to bacteria. Natural antibacterial agents, such as: the invention patent CN 108142463A discloses a natural plant antibacterial agent which has rich source, low toxicity, safe use and good biocompatibility, but has poor broad spectrum and is unstable to light, heat and chemicals when being used alone.
The macromolecular antibacterial agent is a novel antibacterial material, and is mainly characterized in that an antibacterial group is grafted on a macromolecular chain in a coordination or covalent bonding mode, and the antibacterial group is not easy to dissolve out and migrate, so that the antibacterial material has good antibacterial durability and low toxicity. The antibacterial polymer can realize the controllable change and quantity of antibacterial groups, and the introduction of antibacterial structural units is an important method for improving the antibacterial performance of the polymer, such as: rongronmin et al (patent CN 103524656A) disclose an epoxy group-containing styrene acrylate copolymer pickering emulsion with antibacterial property, and preparation and application thereof, wherein nano titanium dioxide is introduced into the epoxy group-containing styrene acrylate copolymer pickering emulsion, and can show antibacterial effect under natural light, daylight lamp and even dark dim light conditions, but the antibacterial material shows antibacterial activity to mold, and is applied to paint research. JingJingjing et al (invention patent CN 106565912A) discloses a polyquaternary ammonium salt polymer emulsion antibacterial agent, a preparation method and application thereof, and the antibacterial agent has the characteristics of strong antibacterial property, no dissolution, good durability and the like, but the monomer involved in the synthesis process is too much, and the consumption cost is relatively high. Doudasheer et al (patent CN 110437374A) disclose a quaternary ammonium salt amphiphilic cationic polymer and application thereof, which have high antibacterial property, but the antibacterial effect of the quaternary ammonium salt amphiphilic cationic polymer can be achieved only by being mixed into other materials through solution, coating, gel or blending. Zheng He et al (patent CN 110325606A) discloses a photosensitizer-doped antibacterial polymer coating composition and an antibacterial polymer film, but the antibacterial material can maintain high antibacterial activity for a long time only in the visible light region.
Although the currently disclosed polymeric antibacterial agents have the characteristics of low toxicity, environmental friendliness and the like, the effective antibacterial performance is not high due to the dispersion of antibacterial active centers. Therefore, there is a need to develop a high-efficiency, durable, environmentally friendly polymeric antimicrobial agent having broad-spectrum antimicrobial activity.
Disclosure of Invention
The invention aims to solve the technical problem of providing a simple and safe preparation method of cationic custard apple-shaped acrylate copolymer antibacterial microspheres.
In order to solve the problems, the preparation method of the cationic custard apple-shaped acrylate copolymer antibacterial microspheres comprises the following steps:
uniformly mixing 1.75-7.00 parts of comonomer, 0.38-1.50 parts of quaternary ammonium salt type cationic acrylic monomer and a crosslinking monomer in parts by mass, then adding an initiator and fully mixing to obtain a mixed solution; the dosage of the crosslinking monomer is 1-10% of the sum of the mass of the comonomer and the mass of the quaternary ammonium salt type cationic acrylic monomer; the using amount of the initiator is 0.5-3% of the sum of the mass of the comonomer and the mass of the quaternary ammonium salt type cationic acrylic monomer;
slowly dripping the mixed solution into deionized water with the mass being 10-20 times of that of the mixed solution and the temperature being 60-90 ℃ under uniform stirring, and continuously stirring and polymerizing for 2-6 hours at the temperature of 60-90 ℃ after dripping is finished to obtain a reactant;
cooling the reactant to room temperature, filtering, and removing the condensate to obtain an emulsion;
and fourthly, washing the emulsion for 5 times respectively through centrifugal separation, distilled water and absolute ethyl alcohol to obtain the cationic custard apple-shaped acrylate copolymer antibacterial microspheres.
The copolymerization monomer in the step is methyl methacrylate and N-vinyl pyrrolidone according to the ratio of 1: 0.35-1: 0.75 mass ratio of the mixture.
The quaternary ammonium salt type cationic acrylic monomer in the step is one of acrylamide propyl trimethyl ammonium chloride, methacrylamide propyl trimethyl ammonium chloride, acrylamide propyl trimethyl ammonium bromide and methacrylamide propyl trimethyl ammonium bromide.
The cross-linking monomer in the step is methacryloxypropyl trimethoxy silane.
The initiator in the step I is potassium persulfate or ammonium persulfate.
The step two is characterized in that uniform stirring is mechanical stirring, and the stirring speed is 200-450 r/min.
The step two, the slow dripping is slowly dripping by using a peristaltic pump, the dripping speed is 0.3-1.0 mL/min, and the dripping time is 0.5-2.5 h.
Compared with the prior art, the invention has the following advantages:
1. the invention takes cationic quaternary ammonium salt as an antibacterial unit, acrylic ester and N-vinyl pyrrolidone as comonomers and acryloxysilane coupling agent as a crosslinking monomer, and prepares the cationic custard fruit-shaped acrylic ester copolymer antibacterial microspheres by one-pot soap-free emulsion polymerization, and the antibacterial microspheres have electropositivity.
2. The cationic custard apple-shaped acrylate copolymer antibacterial microspheres prepared by the method are subjected to structural analysis, and the antibacterial groups of the antibacterial microspheres are polymerized together in a covalent bond mode, so that the antibacterial performance of the custard apple-shaped acrylate copolymer antibacterial microspheres is longer-acting and lasting.
The method comprises the following steps of infrared spectrum analysis:
cationic custard apple shapeThe infrared spectrum of the acrylate copolymer antibacterial microspheres is shown in figure 1, and can be seen to be 1658 cm-1Has a C = C stretching vibration absorption peak of 3444 cm-1The strong broad peak can be attributed to-OH stretching vibration absorption peak on the carboxyl hydroxyl; 2992 cm-1And 2951 cm-1In the form of-CH in acrylate3and-CH2-medium C-H stretching vibration absorption peak; 1730 cm-1At (C = O) is a telescopic absorption peak of ester carbonyl group (1441 cm)-1Is represented by-CH2-N+(CH3)3Flexural vibration absorption peak of methylene group. 1151 cm-1Is the stretching vibration absorption peak of C-O-C on the ester group, 755 cm-1And 1243 cm-1Is C-N+(CH3)3The stretching vibration absorption peak of (1). At 1192 cm-1And 844 cm-1Characteristic absorption peaks of Si-O-Si and Si-C were also observed. It can thus be shown that all the monomers participate in the polymerization.
Analysis of a scanning electron microscope:
FIG. 2 is the scanning electron microscope image of cationic custard apple-shaped acrylate copolymer antibacterial microspheres. As can be seen from the figure, the emulsion particles are spherical particles with the shape of multi-protrusion custard apple, the size is uniform, the particle size distribution is uniform, the average diameter of the emulsion particles is about 200 nm, and the particle size distribution is wide and relatively uniform, which is consistent with the dynamic light scattering test result.
Analyzing the particle size:
the particle size of the cationic custard apple-shaped acrylate copolymer antibacterial microspheres was measured using a particle size meter, and the results are shown in fig. 3. It can be seen that the custard apple-shaped acrylate copolymer microspheres have a uniform particle size distribution with an average particle size of about 200 nm.
3. The antibacterial property test is carried out on the cationic custard-apple-shaped acrylate copolymer antibacterial microspheres prepared by the invention, and the result shows that the antibacterial activity center of the antibacterial microspheres is mainly concentrated on the surfaces of the microspheres, the antibacterial sites of the antibacterial microspheres just have the bacterial action with negative charges on the surfaces, the remarkable antibacterial effect of the cationic antibacterial polymer is highlighted in the aspect of antibacterial property, the antibacterial microspheres have antibacterial properties on gram-positive bacteria (staphylococcus aureus) and gram-negative bacteria (escherichia coli), and have broad-spectrum antibacterial effect, and the defects of the traditional antibacterial agent are fundamentally overcome.
The antibacterial performance test process comprises the following steps: the method is characterized in that a nutrient agar culture medium is used as an antibacterial base material, escherichia coli and staphylococcus aureus are used as test strains, and antibacterial activity test is carried out in an incubator with proper humidity. Briefly, activated Staphylococcus aureus and Escherichia coli were inoculated into liquid media, respectively, and then each liquid medium was cultured at 37 ℃ for 12 hours on a rotary shaker at 220 rpm to give bacterial suspensions. Then, 0.1 mL of bacterial suspension was serially diluted to 10 with sterile water5 CFU mL-1. By mixing equal amounts of 1 mg mL–1Cationic custard apple-shaped acrylate antibacterial emulsion and bacterial suspension (concentration is 10)5 CFU mL-1) Mix and let stand at room temperature for 30 min. Then, 200. mu.L of the mixture solution was spread on nutrient agar medium, and the medium was incubated at 37 ℃ for 24 hours. The number of viable cells (colonies) was counted manually. The control group was prepared without adding cationic custard apple-like acrylate antibacterial emulsion. The antibacterial effect of the cationic custard apple-shaped acrylate copolymer microspheres on escherichia coli and staphylococcus aureus was evaluated by a plate counting method, and the results are shown in fig. 4. It can be seen that the presence of viable bacterial colonies is clearly evident from the antimicrobial photographs of the plates, where the long small white dots on the plates represent the survival of the surviving bacterial colonies. On the control plates, all two bacteria, e.coli (a 0), staphylococcus aureus (B0), showed relatively dense colonies, indicating unrestricted growth of e.coli and staphylococcus aureus without the addition of the antimicrobial cationic custard-like acrylate copolymer microspheres. After the bacterial suspension of the bacteria is contacted with the antibacterial agent cationic custard-shaped acrylate copolymer microspheres for a period of time, the colony growth of escherichia coli (A1) and staphylococcus aureus (B1) on the culture plate is obviously limited, which shows that the cationic custard-shaped acrylate copolymer microspheres have antibacterial activity on the selected bacteria. In addition, cationic custard apple-like acrylate copolymer microsphere pairThe antibacterial activity of escherichia coli is greater than the effect on the antibacterial activity of staphylococcus aureus. The antibacterial microspheres have the antibacterial rate of over 99 percent on escherichia coli and the antibacterial rate of over 90 percent on staphylococcus aureus. Gram-negative bacteria are more sensitive to cationic custard apple-like acrylate copolymer microspheres than gram-positive bacteria.
4. The invention has simple process, no organic solvent is involved in the whole preparation process, no toxicity, no odor, safety and reliability are realized, the obtained cationic custard-like acrylate copolymer antibacterial microspheres can make up for the market vacancy, and can be popularized and used as the antibacterial of fabrics, automobile coatings, plastic decorative materials, floors, ceramic products and household appliances, the antibacterial and the anticorrosion of products such as water-based coatings, printing ink, dyes, adhesives and the like.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 is an infrared spectrum of the cationic custard apple-shaped acrylate copolymer antibacterial microspheres of the present invention.
FIG. 2 is a scanning electron microscope image of the cationic custard apple-shaped acrylate copolymer antibacterial microspheres of the present invention.
FIG. 3 is a particle size distribution diagram of the cationic custard apple-shaped acrylate copolymer antibacterial microspheres of the present invention.
FIG. 4 is a comparative illustration of the antibacterial property of the cationic custard apple-shaped acrylate copolymer antibacterial microspheres of the present invention.
Detailed Description
Example 1 a method for preparing cationic custard apple-like acrylate copolymer antibacterial microspheres, comprising the steps of:
first, 1.75 parts of a comonomer, 0.38 parts of acrylamidopropyl trimethyl ammonium chloride, and 0.02 parts of methacryloxypropyl trimethoxy silane were uniformly mixed in parts by mass (g), and then 0.01 parts of potassium persulfate was added and sufficiently mixed to obtain a mixed solution.
Wherein: the comonomer is a mixture of 1.00 part of methyl methacrylate and 0.35 part of N-vinylpyrrolidone.
Slowly dripping the mixed solution into deionized water with the mass being 10 times that of the mixed solution and the temperature being 60 ℃ by using a peristaltic pump at the speed of 0.3 mL/min under the uniform speed mechanical stirring of 200 r/min, and continuously stirring and polymerizing for 6 hours at 60 ℃ after dripping for 2.5 hours to obtain a reactant.
And thirdly, cooling the reactant to room temperature, filtering, and removing the condensate to obtain the emulsion.
And (4) after the emulsion is centrifugally separated for 15min at the speed of 10000 r/min, washing the emulsion for 5 times respectively by using distilled water and absolute ethyl alcohol to obtain the cationic custard apple-shaped acrylate copolymer antibacterial microspheres.
Example 2 a method for preparing cationic custard apple-like acrylate copolymer antibacterial microspheres, comprising the steps of:
the method comprises the steps of uniformly mixing 7.00 parts of comonomer, 1.50 parts of methacrylamide propyl trimethyl ammonium chloride and 0.85 part of methacryloxypropyl trimethoxy silane in parts by weight, adding 0.23 part of ammonium persulfate, and fully mixing to obtain a mixed liquid.
Wherein: the comonomer is a mixture of 1.00 part of methyl methacrylate and 0.75 part of N-vinylpyrrolidone.
Slowly dripping the mixed solution into deionized water with the mass being 12 times that of the mixed solution and the temperature being 90 ℃ by adopting a peristaltic pump at the speed of 1.0 mL/min under the uniform speed mechanical stirring of 450 r/min, and continuously stirring and polymerizing for 2 h at 90 ℃ after 0.5 h of dripping is finished to obtain a reactant.
And thirdly, cooling the reactant to room temperature, filtering, and removing the condensate to obtain the emulsion.
And (4) after centrifugal separation is carried out on the emulsion for 10min at the speed of 12000 r/min, washing the emulsion for 5 times respectively by using distilled water and absolute ethyl alcohol to obtain the cationic custard apple-shaped acrylate copolymer antibacterial microspheres.
Example 3 a method for preparing cationic custard apple-like acrylate copolymer antimicrobial microspheres, comprising the steps of:
the method comprises the steps of uniformly mixing 3.00 parts of comonomer, 0.80 part of acrylamide propyl trimethyl ammonium bromide and 0.15 part of methacryloxypropyl trimethoxy silane in parts by weight, adding 0.06 part of potassium persulfate, and fully mixing to obtain a mixed liquid.
Wherein: the comonomer is a mixture of 1.00 part of methyl methacrylate and 0.45 part of N-vinylpyrrolidone.
Slowly dripping the mixed solution into deionized water with 17 times of mass and 70 ℃ at the speed of 0.5 mL/min by using a peristaltic pump under the uniform mechanical stirring of 300 r/min, and continuously stirring and polymerizing for 5 hours at 70 ℃ after dripping for 2 hours to obtain a reactant.
And thirdly, cooling the reactant to room temperature, filtering, and removing the condensate to obtain the emulsion.
And after the emulsion is centrifugally separated for 8min at the speed of 12500 r/min, washing the emulsion for 5 times respectively by using distilled water and absolute ethyl alcohol to obtain the cationic custard apple-shaped acrylate copolymer antibacterial microspheres.
Example 4 a method for preparing cationic custard apple-like acrylate copolymer antimicrobial microspheres, comprising the steps of:
first, in parts by mass, 5.25 parts of a comonomer, 1.25 parts of methacrylamidopropyl trimethyl ammonium bromide and 0.52 part of methacryloxypropyl trimethoxy silane were uniformly mixed, and then 0.16 part of ammonium persulfate was added and sufficiently mixed to obtain a mixed liquid.
Wherein: the comonomer is a mixture of 1.00 part of methyl methacrylate and 0.65 part of N-vinylpyrrolidone.
Slowly dripping the mixed solution into deionized water with the mass being 20 times that of the mixed solution and the temperature being 80 ℃ by adopting a peristaltic pump at the speed of 0.8 mL/min under the uniform speed mechanical stirring of 400 r/min, and continuously stirring and polymerizing for 4 hours at 80 ℃ after 1.5 hours of dripping is finished to obtain a reactant.
And thirdly, cooling the reactant to room temperature, filtering, and removing the condensate to obtain the emulsion.
And fourthly, after the emulsion is centrifugally separated for 5min at the speed of 14000 r/min, washing the emulsion for 5 times respectively by using distilled water and absolute ethyl alcohol to obtain the cationic custard apple-shaped acrylate copolymer antibacterial microspheres.
Claims (3)
1. The preparation method of the cationic custard apple-shaped acrylate copolymer antibacterial microspheres comprises the following steps:
uniformly mixing 1.75-7.00 parts of comonomer, 0.38-1.50 parts of quaternary ammonium salt type cationic acrylic monomer and a crosslinking monomer in parts by mass, then adding an initiator and fully mixing to obtain a mixed solution; the dosage of the crosslinking monomer is 1-10% of the sum of the mass of the comonomer and the mass of the quaternary ammonium salt type cationic acrylic monomer; the using amount of the initiator is 0.5-3% of the sum of the mass of the comonomer and the mass of the quaternary ammonium salt type cationic acrylic monomer; the comonomer is methyl methacrylate and N-vinyl pyrrolidone, and the weight ratio of the methyl methacrylate to the N-vinyl pyrrolidone is 1: 0.35-1: 0.75 mass ratio; the quaternary ammonium salt type cationic acrylic monomer is one of acrylamide propyl trimethyl ammonium chloride, methacrylamide propyl trimethyl ammonium chloride, acrylamide propyl trimethyl ammonium bromide and methacrylamide propyl trimethyl ammonium bromide; the crosslinking monomer is methacryloxypropyltrimethoxysilane; the initiator is potassium persulfate or ammonium persulfate;
slowly dripping the mixed solution into deionized water with the mass being 10-20 times of that of the mixed solution and the temperature being 60-90 ℃ under uniform stirring, and continuously stirring and polymerizing for 2-6 hours at the temperature of 60-90 ℃ after dripping is finished to obtain a reactant;
cooling the reactant to room temperature, filtering, and removing the condensate to obtain an emulsion;
and fourthly, washing the emulsion for 5 times respectively through centrifugal separation, distilled water and absolute ethyl alcohol to obtain the cationic custard apple-shaped acrylate copolymer antibacterial microspheres.
2. The method for preparing the cationic custard apple-like acrylate copolymer antibacterial microspheres of claim 1, wherein the method comprises the following steps: the step two is characterized in that uniform stirring is mechanical stirring, and the stirring speed is 200-450 r/min.
3. The method for preparing the cationic custard apple-like acrylate copolymer antibacterial microspheres of claim 1, wherein the method comprises the following steps: the step two, the slow dripping is slowly dripping by using a peristaltic pump, the dripping speed is 0.3-1.0 mL/min, and the dripping time is 0.5-2.5 h.
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