CN114271291B - Carboxymethyl chitosan coated nano zinc oxide material, preparation method and application thereof, plastic master batch and application thereof - Google Patents
Carboxymethyl chitosan coated nano zinc oxide material, preparation method and application thereof, plastic master batch and application thereof Download PDFInfo
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Abstract
The invention provides a preparation method of a carboxymethyl chitosan coated nano zinc oxide material, which comprises the following steps: mixing nano zinc oxide, carboxymethyl chitosan and a dispersion medium, and ball milling; wherein, the ball milling conditions comprise: the rotating speed is 200 r/min-800 r/min; the duration is 1 h-8 h; the temperature is 20-40 ℃. The preparation method is simple, safe and environment-friendly, and the obtained carboxymethyl chitosan coated nano zinc oxide material has good dispersion property and good antibacterial effect.
Description
Technical Field
The invention relates to the field of nano materials, in particular to a carboxymethyl chitosan coated nano zinc oxide material, a preparation method and application thereof, a plastic master batch and application thereof.
Background
As natural high molecular polysaccharide, chitosan is one of edible packaging materials with more researches and wider application. Chitosan is a hydrophilic polysaccharide, is easily hygroscopic, and has poor mechanical strength in a wet state, limiting its application. Therefore, chemical modification of chitosan is started, and carboxymethyl chitosan is one of them. Some properties of the carboxymethyl chitosan are better than those of chitosan, such as solubility, film forming property, moisture absorption and retention property and the like, and meanwhile, the carboxymethyl chitosan also has a certain antibacterial effect.
The nano zinc oxide has the common characteristics of nano materials, such as the peculiar properties of small-size effect, surface effect, macroscopic quantum tunneling effect and the like, and can show more and more excellent performances compared with the common zinc oxide due to the characteristics, such as deodorization, antibiosis, photocatalysis, formaldehyde removal, photoluminescence, electric conduction, energy conservation, wavelength absorption and the like. However, because the specific surface area of the nano zinc oxide is large, the surface energy is high, and the nano zinc oxide particles are in a thermodynamically unstable state, the nano zinc oxide particles are extremely easy to agglomerate to form secondary particles, and the dispersibility is poor, so that normal cells can be damaged, physical properties and functions of the particles can be lost in final application, and the antibacterial effect of the nano zinc oxide particles is reduced. In order to prevent agglomeration among the nano zinc oxide particles, the nano zinc oxide can be modified.
The traditional technology discloses a method for modifying and dispersing a nano zinc oxide material, which comprises the following two steps: firstly, carboxymethyl chitosan coating modification is carried out on nano zinc oxide, and then mechanical dispersion is carried out on the nano zinc oxide. However, the process is complicated, and meanwhile, after mechanical dispersion, the deagglomerated nano particles are difficult to disperse again after hard agglomeration precipitation is easily formed due to incomplete coating of the surface carboxymethyl chitosan. Even though the carboxymethyl chitosan has certain antibacterial property, the result shows that the antibacterial effect of the nano zinc oxide material modified by the carboxymethyl chitosan is not obviously improved.
In the application field of medical instruments, the medical instruments inevitably contact various germs due to the natural environment of hospitals, and patients are usually in a poor-constitution and weak-constitution state, and under the condition of contacting the medical instruments for a long time, the risk of reinfection occurs easily when the medical instruments are used for assisting the functions of human bodies, so the development of medical instrument materials with antibacterial performance is an important research content of the current medical health development.
Disclosure of Invention
Based on the method, the invention provides a preparation method of the carboxymethyl chitosan coated nano zinc oxide material, which is simple, safe and environment-friendly, and the obtained carboxymethyl chitosan coated nano zinc oxide material has good antibacterial effect.
The invention is realized by the following technical scheme.
A preparation method of a carboxymethyl chitosan coated nano zinc oxide material comprises the following steps:
mixing nano zinc oxide, carboxymethyl chitosan and a dispersion medium, and ball milling;
wherein, the ball milling conditions comprise: the rotating speed is 200 r/min-800 r/min; the duration is 1 h-8 h; the temperature is 20-40 ℃.
In one embodiment, the mass ratio of the nano zinc oxide to the carboxymethyl chitosan is (1-10): 1.
In one embodiment, the mass ratio of the nano zinc oxide to the dispersion medium is 1 (100-10000).
In one embodiment, the ball milling media used in the ball milling is zirconia balls.
In one embodiment, the zirconia beads have a particle size of 0.1mm to 0.5mm.
In one embodiment, the ball milling temperature is 20℃to 30 ℃.
In one embodiment, the particle size of the nano zinc oxide is 60 nm-100 nm.
In one embodiment, the dispersion medium is water.
In one embodiment, the carboxymethyl chitosan coated nano zinc oxide material is in a colloidal state.
The invention also provides the carboxymethyl chitosan coated nano zinc oxide material prepared by the preparation method of the carboxymethyl chitosan coated nano zinc oxide material.
The invention also provides application of the carboxymethyl chitosan coated nano zinc oxide material in plastics.
The invention also provides a plastic master batch, and the raw materials of the plastic master batch comprise resin and the carboxymethyl chitosan coated nano zinc oxide material.
The invention also provides application of the plastic master batch in medical equipment.
Compared with the prior art, the preparation method of the carboxymethyl chitosan coated nano zinc oxide material has the following beneficial effects:
according to the invention, the rotational speed and the duration of the ball milling are limited, carboxymethyl chitosan is introduced to carry out coating modification on the nano zinc oxide, the ball milling treatment can simultaneously promote the modification and dispersion of the nano zinc oxide, and the nano zinc oxide can be further improved in dispersion performance, especially in water, on the premise that the surface of the nano zinc oxide is completely coated with carboxymethyl chitosan by carrying out a certain degree of refinement on the nano zinc oxide, so that the effect of obviously enhancing the antibacterial effect is finally achieved.
Furthermore, the preparation method of the carboxymethyl chitosan coated nano zinc oxide material is simple, efficient, safe and environment-friendly, has low cost and can be used for large-scale production.
Drawings
FIG. 1 is a diagram of a nanomaterial product provided by the present invention; wherein, (a) represents nano zinc oxide, and (b) represents carboxymethyl chitosan coated nano zinc oxide;
FIG. 2 is a Fourier infrared spectrum provided by the invention;
FIG. 3 is a transmission electron microscope image provided by the invention;
FIG. 4 is a diagram of a plastic master batch product provided by the invention; wherein, (a) represents a polyethylene plastic master batch, and (b) represents a modified polyethylene plastic master batch;
FIG. 5 is a graph showing the anti-Staphylococcus aureus characteristics of the plastic plate provided by the invention;
FIG. 6 is a graph showing the characterization of the plastic plate against Escherichia coli.
Detailed Description
In order that the invention may be readily understood, a more complete description of the invention will be rendered by reference to the appended drawings. The drawings illustrate preferred embodiments of the invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In the description of the invention, the meaning of "plurality" means at least two, for example, two, three, etc., unless specifically defined otherwise. In the description of the present invention, the meaning of "several" means at least one, such as one, two, etc., unless specifically defined otherwise.
The words "preferably," "more preferably," and the like in the present invention refer to embodiments of the invention that may provide certain benefits in some instances. However, other embodiments may be preferred under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
When a range of values is disclosed herein, the range is considered to be continuous and includes both the minimum and maximum values for the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range description features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to include any and all subranges subsumed therein.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The invention provides a preparation method of a carboxymethyl chitosan coated nano zinc oxide material, which comprises the following steps:
mixing nano zinc oxide, carboxymethyl chitosan and a dispersion medium, and ball milling;
wherein, the ball milling conditions comprise: the rotating speed is 200 r/min-800 r/min; the duration is 1 h-8 h; the temperature is 20-40 ℃.
The preparation method provided by the invention has the advantages of simple process, low reagent price, high yield of more than 90%, capability of well dispersing nano zinc oxide coated by carboxymethyl chitosan in a water phase, further widening the application field of the nano zinc oxide, facilitating research, no influence on environment, recovery of the produced solution and excellent antibacterial property. In addition, deionized water can be used as a reagent of the antibacterial colloid in the antibacterial performance detection, and compared with the existing reagent of the antibacterial colloid which uses an organic solvent such as dimethyl sulfoxide, N-dimethylformamide, ethanol or acetone, and the like, the detection process is safer, more environment-friendly and simpler.
In a specific example, the ball milling is performed in a planetary ball mill, after the ball milling is finished, the ball milling is kept stand for 10 to 30 minutes, and then the ball milling tank is taken out to remove the ball milling medium.
It is understood that in the present invention, the rotational speed of the ball mill includes, but is not limited to, 200r/min, 220r/min, 240r/min, 260r/min, 280r/min, 300r/min, 320r/min, 340r/min, 360r/min, 380r/min, 400r/min, 420r/min, 440r/min, 460r/min, 480r/min, 500r/min, 520r/min, 540r/min, 560r/min, 580r/min, 600r/min, 620r/min, 640r/min, 645r/min, 646r/min, 647r/min, 648r/min, 649r/min, 650r/min, 651r/min, 652r/min, 653r/min, 654r/min, 655r/min, 660r/min, 680r/min, 700r/min, 720r/min, 740r/min, 760r/min, 780r/min, 800r/min. Preferably, the rotational speed of the ball mill is 650r/min.
It is understood that in the present invention, the duration of the ball milling includes, but is not limited to, 1.0h, 1.5h, 2h, 2.5h, 3.0h, 3.5h, 4.0h, 4.5h, 5.0h, 5.5h, 6.0h, 6.5h, 7.0h, 7.5h, 8.0h. Preferably, the ball milling time is 3-4 hours. The length of the ball milling time can influence the dispersion form of the nano zinc oxide in water, and the ball milling time is controlled, so that more uniform and transparent colloid can be obtained, and a better antibacterial effect can be obtained. And (3) removing the ball milling medium after ball milling to obtain the carboxymethyl chitosan coated nano zinc oxide antibacterial colloid.
In a specific example, the mass ratio of the nano zinc oxide to the carboxymethyl chitosan is (1-10): 1. It is understood that in the present invention, the mass ratio of nano zinc oxide to carboxymethyl chitosan includes, but is not limited to, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1. Preferably, the mass ratio of the nano zinc oxide to the carboxymethyl chitosan is (1-4): 1.
In a specific example, the mass ratio of the nano zinc oxide to the dispersion medium is 1 (100-10000). It is understood that in the present invention, the mass ratio of the dispersion medium to the nano zinc oxide includes, but is not limited to, 100:1, 200:1, 210:1, 220:1, 230:1, 240:1, 250:1, 260:1, 270:1, 280:1, 290:1, 300:1, 400:1, 500:1, 600:1, 700:1, 800:1, 900:1, 1000:1, 2000:1, 3000:1, 4000:1, 5000:1, 6000:1, 7000:1, 8000:1, 9000:1, 10000:1. Preferably, the mass ratio of the nano zinc oxide to the dispersion medium is 1 (250-10000).
In one specific example, the ball milling media used in the ball milling is zirconia balls.
In a specific example, the zirconia beads have a particle size of 0.1mm to 0.5mm. It is understood that in the present invention, the particle size of the zirconia beads includes, but is not limited to, 0.1mm, 0.12mm, 0.14mm, 0.16mm, 0.18mm, 0.2mm, 0.3mm, 0.4mm, 0.5mm. Preferably, the zirconia beads have a particle size of 0.1mm to 0.2mm. The particle size of the ball milling medium can influence the dispersion form of the nano zinc oxide in water, and the particle size of the ball milling medium is controlled, so that more uniform and transparent colloid can be obtained, and a better antibacterial effect is obtained.
It will be appreciated that in the present invention, the temperature of the ball milling includes, but is not limited to, 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃, 30 ℃, 31 ℃, 32 ℃, 33 ℃,34 ℃, 35 ℃, 36 ℃, 37 ℃, 38 ℃, 39 ℃, 40 ℃. The experimental result is not affected by the climate change in four seasons in the experimental process. Preferably, the temperature of the ball milling is 20-30 ℃.
In a specific example, the mass ratio of the ball milling medium to the nano zinc oxide is (100-10000): 1. It is understood that in the present invention, the mass ratio of ball milling medium to nano zinc oxide includes, but is not limited to, 100:1, 200:1, 300:1, 400:1, 500:1, 600:1, 700:1, 800:1, 900:1, 1000:1, 2000:1, 3000:1, 4000:1, 5000:1, 6000:1, 7000:1, 8000:1, 9000:1, 10000:1, 11000:1, 12000:1, 13000:1, 14000:1, 15000:1, 16000:1, 17000:1, 18000:1, 19000:1, 20000:1.
In a specific example, the nano zinc oxide has a purity of 99.99% and is in the form of agglomerates.
In a specific example, the particle size of the nano zinc oxide is 60nm to 100nm. It is understood that in the present invention, the particle size of the nano zinc oxide includes, but is not limited to, 60nm, 62nm, 64nm, 66nm, 68nm, 70nm, 72nm, 74nm, 76nm, 78nm, 80nm, 82nm, 84nm, 86nm, 88nm, 90nm, 92nm, 94nm, 96nm, 98nm, 100nm.
In a specific example, the carboxymethyl chitosan has a purity of BR grade. The carboxymethyl chitosan coated nano zinc oxide solutions with different purities have different antibacterial properties.
In a specific example, the dispersion medium is water. Preferably, the water is deionized water. More specifically, the pH of the water is 6.5 to 6.8.
In one specific example, ball milling is performed at atmospheric pressure. During ball milling, the pH value of the liquid is kept between 6.5 and 6.8, and the experiment is not seriously influenced basically due to the change of external conditions.
In a specific example, the carboxymethyl chitosan coated nano zinc oxide material is in a colloidal state.
The invention also provides the carboxymethyl chitosan coated nano zinc oxide material prepared by the preparation method of the carboxymethyl chitosan coated nano zinc oxide material.
In a specific example, the particle size of the carboxymethyl chitosan coated nano zinc oxide material is 15 nm-25 nm.
The invention also provides application of the carboxymethyl chitosan coated nano zinc oxide material in plastics.
The invention also provides a plastic master batch, wherein the raw materials of the plastic master batch comprise resin and the carboxymethyl chitosan coated nano zinc oxide material.
In a specific example, the resin is selected from polyethylene.
Polyethylene is a thermoplastic polymer material polymerized by ethylene monomers, and has the advantages of easily available raw materials, no toxicity, light weight, excellent chemical corrosion resistance and low temperature resistance, the current use amount in the plastic industry is the first global one, the polyethylene material has the advantages of regular and simple structure, strong crystallization capability, good small molecular chain flexibility and the like, and is widely applied to the fields of agriculture, water pipelines, containers, medical appliances and the like.
The invention also provides a preparation method of the plastic master batch, which comprises the following steps:
mixing the resin with the carboxymethyl chitosan coated nano zinc oxide material, extruding and granulating.
The plastic master batch provided by the invention is not obvious different from the commercial common plastic master batch in appearance analysis, and has wide application field. Meanwhile, the plastic master batch can be prepared by adopting a simple extrusion granulation method, the yield can reach more than 95%, adverse effects on the environment are avoided, and the plastic master batch has the advantages of simple processing technology, environmental protection, low cost, easiness in realization of mass production and the like.
In a specific example, the extrusion temperature is 190 ℃ to 200 ℃. It is understood that in the present invention, the temperature of extrusion includes, but is not limited to, 190 ℃, 191 ℃, 192 ℃, 193 ℃, 194 ℃, 195 ℃, 196 ℃, 197 ℃, 198 ℃, 199 ℃, 200 ℃.
In a specific example, the mass ratio of the resin to the carboxymethyl chitosan coated nano zinc oxide material is (100-1000): 1. It is understood that in the present invention, the mass ratio of resin to carboxymethyl chitosan coated nano zinc oxide material includes, but is not limited to, 100:1, 200:1, 300:1, 400:1, 500:1, 600:1, 700:1, 800:1, 900:1, 1000:1.
In one specific example, the extruder feed rate was 10r/min and the pelletizer speed was 12r/min.
The invention also provides an antibacterial medical material, which comprises the plastic master batch.
The invention also provides a preparation method of the antibacterial medical material, which comprises the following steps:
and (3) injection molding the plastic master batch.
In one specific example, the injection molding temperature is 180 ℃ to 220 ℃. More specifically, the temperature of injection molding was 200 ℃.
In a specific example, the injection molding uses a mold size of 50mm by 2mm.
The invention also provides application of the plastic master batch in medical appliances.
More specifically, the medical device is a breathing tube. Because the breathing tube has long residence time inside and outside the body, bacteria are easy to grow under the conditions of body temperature and high humidity, and thus the respiratory tract infection of patients is caused.
The carboxymethyl chitosan coated nano zinc oxide material and the preparation method thereof are described in further detail below with reference to specific examples. The raw materials used in the following examples are all commercially available products unless otherwise specified.
Example 1
The embodiment provides a preparation method of a carboxymethyl chitosan coated nano zinc oxide material, which comprises the following steps:
putting a ball milling medium (50 g of zirconia beads with the size of 0.1 mm) into a ball milling tank with the volume of 100ml, adding 0.5g of commercial nano zinc oxide powder, 0.05g of BR-grade small molecular reagent carboxymethyl chitosan and 50g of deionized water, setting the rotating speed of a ball mill (model: UBE-V2L, hunan De-Kogyo Co., ltd.) to be 800r/min, ball milling for 1h, closing the ball milling at the temperature of 20 ℃, taking down the ball milling tank after 10min separation, and removing the ball milling medium to obtain the carboxymethyl chitosan (CMCS) coated nano zinc oxide antibacterial colloid, as shown in the figure 1 (b).
Taking a part of the carboxymethyl chitosan coated nano zinc oxide antibacterial colloid, drying to obtain powder, and carrying out Fourier infrared spectroscopy (FTIR) characterization on the powder, wherein the spectrogram is shown in figure 2 (ZnO-CMCS).
And taking a part of the carboxymethyl chitosan coated nano zinc oxide antibacterial colloid, directly dripping the nano zinc oxide antibacterial colloid into a copper mesh sample, and carrying out transmission scanning electron microscope (TEM) characterization, wherein the spectrogram is shown in figure 3 (ZnO-CMCS).
And taking a part of the carboxymethyl chitosan coated nano zinc oxide antibacterial colloid, and carrying out a minimum inhibitory concentration measurement test according to 2002 edition 2.1.8.4 of disinfection technical Specification. Testing strains: coli ATCC25922, staphylococcus aureus ATCC 29213.
Example 2
The embodiment provides a preparation method of a carboxymethyl chitosan coated nano zinc oxide material, which comprises the following steps:
putting a ball milling medium (50 g of zirconia beads with the size of 0.1 mm) into a ball milling tank with the volume of 100ml, adding 0.2g of commercial nano zinc oxide powder, 0.1g of BR-grade small molecular reagent carboxymethyl chitosan and 50g of deionized water, setting the rotating speed of a ball mill (model: UBE-V2L, hunan De-Kogyo Co., ltd.) to be 200r/min, ball milling for 4h, closing the ball milling at the temperature of 20 ℃, taking down the ball milling tank after 20min separation, and removing the ball milling medium to obtain the carboxymethyl chitosan coated nano zinc oxide antibacterial colloid.
Through observation, compared with the carboxymethyl chitosan coated nano zinc oxide antibacterial colloid prepared in example 1, the carboxymethyl chitosan coated nano zinc oxide antibacterial colloid prepared in the example is more transparent and uniform.
And taking a part of the carboxymethyl chitosan coated nano zinc oxide antibacterial colloid, and carrying out a minimum inhibitory concentration measurement test according to 2002 edition 2.1.8.4 of disinfection technical Specification. Testing strains: coli ATCC25922, staphylococcus aureus ATCC 29213.
Example 3
The embodiment provides a preparation method of a carboxymethyl chitosan coated nano zinc oxide material, which comprises the following steps:
putting a ball milling medium (50 g of zirconia beads with the size of 0.1 mm) into a ball milling tank with the volume of 100ml, adding 0.005g of commercial nano zinc oxide powder, 0.005g of BR-grade small molecular reagent carboxymethyl chitosan and 50g of deionized water, setting the rotating speed of a ball mill (model: UBE-V2L, hunan De-Kogyo Co., ltd.) to be 500r/min, ball milling for 3h, the ball milling temperature to be 20 ℃, closing the ball milling machine, taking down the ball milling tank after 30min separation, and removing the ball milling medium to obtain the carboxymethyl chitosan coated nano zinc oxide antibacterial colloid.
Through observation, compared with the carboxymethyl chitosan coated nano zinc oxide antibacterial colloid prepared in example 1, the carboxymethyl chitosan coated nano zinc oxide antibacterial colloid prepared in the example is more transparent and uniform.
And taking a part of the carboxymethyl chitosan coated nano zinc oxide antibacterial colloid, and carrying out a minimum inhibitory concentration measurement test according to 2002 edition 2.1.8.4 of disinfection technical Specification. Testing strains: coli ATCC25922, staphylococcus aureus ATCC 29213.
Example 4
The embodiment provides a preparation method of a carboxymethyl chitosan coated nano zinc oxide material, which comprises the following steps:
putting a ball milling medium (50 g of zirconia beads with the size of 0.3 mm) into a ball milling tank with the volume of 100ml, adding 0.5g of commercial nano zinc oxide powder, 0.05g of BR-grade small molecular reagent carboxymethyl chitosan and 50g of deionized water, setting the rotating speed of a ball mill (model: UBE-V2L, hunan De-Kogyo Co., ltd.) to be 800r/min, ball milling for 1h, closing the ball milling at the temperature of 20 ℃, taking down the ball milling tank after 30min separation, and removing the ball milling medium to obtain the carboxymethyl chitosan coated nano zinc oxide antibacterial colloid.
The carboxymethyl chitosan coated nano zinc oxide antibacterial colloid prepared in this example has a morphology similar to that of the carboxymethyl chitosan coated nano zinc oxide antibacterial colloid prepared in example 1.
And taking a part of the carboxymethyl chitosan coated nano zinc oxide antibacterial colloid, and carrying out a minimum inhibitory concentration measurement test according to 2002 edition 2.1.8.4 of disinfection technical Specification. Testing strains: coli ATCC25922, staphylococcus aureus ATCC 29213.
Example 5
The embodiment provides a preparation method of a carboxymethyl chitosan coated nano zinc oxide material, which comprises the following steps:
putting a ball milling medium (50 g of zirconia with the size of 0.1 mm) into a ball milling tank with the volume of 100ml, adding 0.5g of commercial nano zinc oxide powder, 0.05g of BR-grade small molecular reagent carboxymethyl chitosan and 50g of deionized water, setting the rotating speed of a ball mill (model: UBE-V2L, hunan De-Kogyo Co., ltd.) to be 800r/min, ball milling for 8h, the ball milling temperature to be 20 ℃, closing the ball milling tank, taking down the ball milling tank after 30min separation, and removing the ball milling medium to obtain the carboxymethyl chitosan coated nano zinc oxide antibacterial colloid.
Through observation, compared with the carboxymethyl chitosan coated nano zinc oxide antibacterial colloid prepared in example 1, the carboxymethyl chitosan coated nano zinc oxide antibacterial colloid prepared in the example is more transparent and uniform.
And taking a part of the carboxymethyl chitosan coated nano zinc oxide antibacterial colloid, and carrying out a minimum inhibitory concentration measurement test according to 2002 edition 2.1.8.4 of disinfection technical Specification. Testing strains: coli ATCC25922, staphylococcus aureus ATCC 29213.
Example 6
The embodiment provides a preparation method of a plastic plate, which specifically comprises the following steps:
1999g of medical polyethylene resin (PE) is weighed, 1g of carboxymethyl chitosan coated nano zinc oxide material prepared in example 1 is weighed, uniformly stirred and then placed in a granulator hopper, the twin-screw extrusion temperature is set at 190 ℃, 195 ℃ and 200 ℃, the feeding speed of an extruder is set at 10r/min, and the rate of a granulator is set: and (3) placing the prepared master batch in a hopper of an injection molding machine at 12r/min, setting the injection molding temperature to 200 ℃, and performing injection molding by using a standard mold with the mold size of 50 x 2mm to obtain the plastic plate.
Example 7
The embodiment provides a preparation method of a plastic plate, which specifically comprises the following steps:
weighing 1990g of medical polyethylene resin (PE), weighing 10g of carboxymethyl chitosan coated nano zinc oxide material prepared in example 1, uniformly stirring, placing into a granulator hopper, setting the twin-screw extrusion temperature at 190 ℃, 195 ℃ and 200 ℃, the feeding speed of an extruder at 10r/min, and setting the rate of the granulator: and (3) placing the prepared master batch in a hopper of an injection molding machine at 12r/min, setting the injection molding temperature to 200 ℃, and performing injection molding by using a standard mold with the mold size of 50 x 2mm to obtain the plastic plate.
Example 8
The embodiment provides a preparation method of a plastic plate, which specifically comprises the following steps:
weighing 1980g of medical polyethylene resin (PE), weighing 20g of carboxymethyl chitosan coated nano zinc oxide material prepared in example 1, uniformly stirring, placing into a granulator hopper, setting the twin-screw extrusion temperature at 190 ℃, 195 ℃ and 200 ℃, the feeding speed of an extruder at 10r/min, and setting the rate of the granulator: 12r/min, and preparing modified polyethylene plastic master batch, as shown in fig. 4 (b); and placing the prepared master batch into a hopper of an injection molding machine, setting the injection molding temperature to 200 ℃, and performing injection molding on a standard mold with the mold size of 50 x 2mm to obtain the plastic plate.
Comparative example 1
The comparative example provides a nano zinc oxide antibacterial colloid, a preparation method and a detection method thereof, which are basically the same as those of example 1, and are mainly different in that carboxymethyl chitosan is not added and no ball milling step is performed. The method comprises the following specific steps:
accurately weighing 0.5g of commercial nano zinc oxide powder, mixing the nano zinc oxide powder with 50g of deionized water, placing the mixture in a 50ml sample bottle, performing ultrasonic treatment for 10min to obtain nano zinc oxide aqueous antibacterial colloid, and standing for 30min, as shown in fig. 1 (a).
Taking a part of nano zinc oxide aqueous antibacterial colloid, drying to obtain powder, and carrying out Fourier infrared spectroscopy (FTIR) characterization on the powder, wherein the spectrogram is shown in figure 2 (ZnO).
And taking a part of the nano zinc oxide aqueous antibacterial colloid, and carrying out transmission scanning electron microscope (TEM) characterization, wherein a spectrogram is shown in figure 3 (ZnO).
Taking a part of the nano zinc oxide aqueous antibacterial colloid, and carrying out a minimum antibacterial concentration measurement test according to 2002 edition 2.1.8.4 of disinfection technical Specification. Testing strains: coli ATCC25922, staphylococcus aureus ATCC 29213.
Comparative example 2
The comparative example provides a carboxymethyl chitosan coated nano zinc oxide antibacterial colloid, a preparation method and a detection method thereof, which are basically the same as those of the example 1, and the main difference is that an ultrasonic dispersion method is adopted to replace the ball milling step. The method comprises the following specific steps:
mixing 0.5g of commercial nano zinc oxide powder, 0.05g of BR-grade micromolecule reagent carboxymethyl chitosan and 50g of deionized water, placing into a 50ml sample bottle, performing ultrasonic dispersion for 1h to obtain nano zinc oxide aqueous antibacterial colloid, and standing for 30min.
The nano zinc oxide aqueous antibacterial colloid prepared in the comparative example is more turbid than the carboxymethyl chitosan coated nano zinc oxide antibacterial colloid prepared in the example 1.
And taking a part of the carboxymethyl chitosan coated nano zinc oxide antibacterial colloid, and carrying out a minimum inhibitory concentration measurement test according to 2002 edition 2.1.8.4 of disinfection technical Specification. Testing strains: coli ATCC25922, staphylococcus aureus ATCC 29213.
Comparative example 3
The comparative example provides a carboxymethyl chitosan coated nano zinc oxide antibacterial colloid, a preparation method and a detection method thereof, which are basically the same as those of the example 1, and the main difference is that a mechanical stirring method is adopted to replace the ball milling step. The method comprises the following specific steps:
mixing 0.5g of commercial nano zinc oxide powder, 0.05g of BR-grade micromolecule reagent carboxymethyl chitosan and 50g of deionized water, placing into a 50ml sample bottle, mechanically stirring at a high speed for 1h, wherein the stirring speed is 1000r/min, thus obtaining nano zinc oxide aqueous antibacterial colloid, and standing for 30min.
The nano zinc oxide aqueous antibacterial colloid prepared in the comparative example is more turbid than the carboxymethyl chitosan coated nano zinc oxide antibacterial colloid prepared in the example 1.
And taking a part of the carboxymethyl chitosan coated nano zinc oxide antibacterial colloid, and carrying out a minimum inhibitory concentration measurement test according to 2002 edition 2.1.8.4 of disinfection technical Specification. Testing strains: coli ATCC25922, staphylococcus aureus ATCC 29213.
Comparative example 4
The comparative example provides a method for preparing a plastic plate, which comprises the following steps:
2000g of medical polyethylene resin (PE) is weighed and placed in a hopper of a granulator, the twin-screw extrusion temperature is set at 190 ℃, 195 ℃ and 200 ℃, the feeding speed of the extruder is 10r/min, and the rate of the granulator is set: 12r/min, the master batch is prepared, as shown in fig. 4 (a); and placing the prepared master batch into a hopper of an injection molding machine, setting the injection molding temperature to 200 ℃, and performing injection molding on a standard mold with the mold size of 50 x 2mm to obtain the plastic plate.
The results of the antibacterial experiments of examples 1 to 5 and comparative examples 1 to 3 are shown in tables 1 and 2. MIC values were measured as gradient decrements, given values based on the clarity of the two tubes, with a final result being a range of gradients.
TABLE 1
TABLE 2
As is clear from tables 1 and 2, in comparative example 1, the commercial nano zinc oxide (particle size: 60 to 100nm, purity: 99.99%) itself was not strong in antibacterial performance, and the Minimum Inhibitory Concentration (MIC) against Escherichia coli was 2500 to 5000ppm, and the Minimum Inhibitory Concentration (MIC) against Staphylococcus aureus was 5000ppm or more. The nano zinc oxide colloid obtained by ball milling and chemical modification of carboxymethyl chitosan in examples 1-5 has excellent antibacterial performance, and especially the Minimum Inhibitory Concentration (MIC) of the nano zinc oxide colloid obtained by ball milling and chemical modification of carboxymethyl chitosan in examples 2 and 3 on staphylococcus aureus is 16-32ppm, and the minimum inhibitory concentration on escherichia coli is 32-64ppm, which indicates that the particle diameter of the nano zinc oxide particle is reduced after ball milling and chemical modification of carboxymethyl chitosan, and meanwhile, the synergistic antibacterial effect of carboxymethyl chitosan and nano zinc oxide enables the nano zinc oxide colloid with better dispersion to have more excellent antibacterial effect which is about 100 times that of commercially available nano zinc oxide. The results of example 4 show that the particle size of the ball milling medium may affect the dispersion state of nano zinc oxide in the aqueous phase, thereby affecting the antibacterial effect. The grafting effect of carboxymethyl chitosan on nano zinc oxide is not obvious, the dispersing effect of nano zinc oxide in water phase is not obviously improved, and the antibacterial performance is not obviously improved by adopting the methods of ultrasonic dispersion and mechanical stirring in comparative example 2 and comparative example 3 respectively.
As can be obtained from fig. 1, the nano zinc oxide without modification treatment has poor dispersion effect in water, and the nano zinc oxide after ball milling-chemical modification with carboxymethyl chitosan can be well dispersed in an aqueous reagent to form uniform and transparent colloid.
As can be seen from FIG. 2, the surface of the nano zinc oxide without modification is inert and basically does not contain any groups, but after ball milling-chemical modification, the nano zinc oxide is subjected to surface grafting with carboxymethyl chitosan at the surface generation sites under the action of high-energy ball milling, and as can be seen from an infrared spectrogram, 3453cm -1 Is an amino telescopic vibration peak of 1632cm -1 The amino bending vibration peak shows that after ball milling-chemical modification, carboxymethyl chitosan is successfully grafted to the surface of nano zinc oxide.
As can be seen from FIG. 3, the particle size of the unmodified nano zinc oxide is about 100nm, and obvious agglomeration occurs, while the particle size of the nano zinc oxide is about 20nm after being modified by carboxymethyl chitosan, and the nano zinc oxide is relatively uniform in dispersion, and has no obvious large particle agglomeration.
The plastic sheets prepared in examples 6 to 8 and comparative example 4 were tested for gloss and antibacterial properties;
the glossiness detection uses a glossiness meter, and the model is YS3060; and (3) taking the prepared base material as a detection object, and performing an antibacterial measurement test according to national standard WAT 650-2019. Testing strains: coli ATCC25922, staphylococcus aureus ATCC 29213.
The anti-staphylococcus aureus characterization graph of the plastic plate prepared in the example 8 is shown in fig. 5 (PE-ZnO-CMCS), and the anti-staphylococcus aureus characterization graph of the plastic plate prepared in the comparative example 4 is shown in fig. 5 (PE); the graph of the anti-E.coli characterization of the plastic plate prepared in example 8 is shown in FIG. 6 (PE-ZnO-CMCS), and the graph of the anti-E.coli characterization of the plastic plate prepared in comparative example 4 is shown in FIG. 6 (PE).
The effect verification results are shown in table 3.
TABLE 3 Table 3
| Sample name | Antibacterial property | Gloss level |
| Example 6 | >2.0 | 92.7 |
| Example 7 | >2.0 | 90.5 |
| Example 8 | >2.0 | 89.8 |
| Comparative example 4 | <1.0 | 93.2 |
As can be seen from fig. 4, the appearance of the polyethylene master batch prepared by adding 1% of nano antibacterial material and the appearance of the polyethylene master batch without adding nano antibacterial material are not obvious, the influence of the sample plate after injection molding processing is not obvious, the gloss of the polyethylene plastic plate is detected to be 93.2, and the gloss of the polyethylene plastic plate prepared by adding 1% of nano antibacterial material is 89.8, which indicates that the gloss is reduced after adding 1% of nano antibacterial material, but the value is acceptable. In summary, the appearance of the polyethylene plastic plate added with the nano antibacterial material is not obviously changed.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples merely represent a few embodiments of the present invention, which facilitate a specific and detailed understanding of the technical solutions of the present invention, but are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. It should be understood that, based on the technical solutions provided by the present invention, those skilled in the art may obtain technical solutions through logical analysis, reasoning or limited experiments, which are all within the scope of protection of the appended claims. The scope of the patent is therefore intended to be covered by the appended claims, and the description and drawings may be interpreted as illustrative of the contents of the claims.
Claims (10)
1. The application of the carboxymethyl chitosan coated nano zinc oxide material in plastics is characterized in that the preparation of the carboxymethyl chitosan coated nano zinc oxide material comprises the following steps:
mixing nano zinc oxide, carboxymethyl chitosan and a dispersion medium, and ball milling;
wherein, the ball milling conditions comprise: the rotating speed is 200 r/min-800 r/min; the duration is 1 h-8 h; the temperature is 20-40 ℃;
the mass ratio of the nano zinc oxide to the carboxymethyl chitosan is (1-10) 1;
the ball milling medium adopted by ball milling is zirconia beads; the particle size of the zirconia beads is 0.1 mm-0.5 mm;
the dispersion medium is water;
the particle size of the nano zinc oxide is 60 nm-100 nm;
the mass ratio of the nano zinc oxide to the dispersion medium is 1 (100-10000).
2. The application of the carboxymethyl chitosan coated nano zinc oxide material in plastics according to claim 1, wherein the mass ratio of the nano zinc oxide to the carboxymethyl chitosan is (1-4): 1.
3. The application of the carboxymethyl chitosan coated nano zinc oxide material in plastics according to claim 1, wherein the mass ratio of the nano zinc oxide to the dispersion medium is 1 (250-10000).
4. The application of the carboxymethyl chitosan coated nano zinc oxide material in plastics according to claim 1, wherein the particle size of the zirconia beads is 0.1 mm-0.2 mm.
5. The application of the carboxymethyl chitosan coated nano zinc oxide material in plastics according to any one of claims 1-4, wherein the ball milling temperature is 20-30 ℃.
6. The application of carboxymethyl chitosan coated nano zinc oxide material according to any one of claims 1-4 in plastics, wherein the pH of the water is 6.5-6.8.
7. The application of the carboxymethyl chitosan coated nano zinc oxide material in plastics according to any one of claims 1 to 4, wherein the carboxymethyl chitosan coated nano zinc oxide material is in a colloid state.
8. A plastic master batch, which is characterized in that the raw materials of the plastic master batch comprise resin and the carboxymethyl chitosan coated nano zinc oxide material according to any one of claims 1-7.
9. The plastic masterbatch of claim 8, wherein the resin is polyethylene.
10. Use of the plastic master batch according to any one of claims 8 to 9 in medical devices.
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