CN110894311A - Preparation method and application of oxygen-releasing antibacterial material - Google Patents
Preparation method and application of oxygen-releasing antibacterial material Download PDFInfo
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Abstract
The invention discloses a preparation method and application of an oxygen-releasing antibacterial material, wherein a mesoporous silica tube is prepared by adopting a soft membrane method, calcium peroxide is used as an oxygen releasing agent and attached to the cavity of the mesoporous silica tube, meanwhile, cage-type polysilsesquioxane is used for modifying the mesoporous silica tube, the mesoporous silica tube is subjected to end capping to form a capsule-shaped structure, finally, silver-carrying treatment is carried out on the outer wall of the mesoporous silica tube, and the antibacterial property of silver ions is utilized to prepare the material with double performances of antibacterial property and oxygen releasing.
Description
Technical Field
The invention relates to an oxygen-releasing antibacterial material, in particular to a preparation method and application of the oxygen-releasing antibacterial material.
Background
With the increasing living standard and the increasing environmental awareness of people, the storage and fresh-keeping packaging of fresh fruits, vegetables and seafood becomes more and more important, and the demand for fresh-keeping packaging materials for prolonging the storage period and shelf life of the fruits, vegetables and seafood is more and more increased.
The harvesting of fruits, vegetables and seafood has obvious seasonality and regionality, needs better storage conditions and longer storage and transportation period in transportation, and regardless of fruits, vegetables and seafood, the transportation and the storage process are accompanied by respiration which is accompanied by metabolism, water evaporation and oxygen consumption, so that bacteria are bred, finally, the seafood is anoxic and dead, the fruits and the vegetables are rotten, and huge economic loss is caused.
Therefore, based on the above consideration, the invention provides a preparation method of the oxygen-release antibacterial material, and the oxygen-release antibacterial material is applied to the plastic film, and has the advantages of small addition amount, easy industrial production, obvious oxygen-release antibacterial effect and the like.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method and application of an oxygen-release antibacterial material.
The invention is realized by the following technical scheme:
a preparation method of an oxygen release antibacterial material comprises the following steps:
dissolving a surfactant in deionized water, adding hydrochloric acid, sequentially adding tetraethoxysilane and N-trimethoxypropylsilane-N, N, N-trimethyl ammonium chloride, reacting at normal temperature, standing for 2-3 days at 30-50 ℃, and performing centrifugal separation, washing, drying and roasting to obtain a mesoporous silica tube;
uniformly mixing calcium peroxide and acetone, adding a silane coupling agent, and reacting at 70-90 ℃ to obtain a surface active calcium peroxide mixed solution;
mixing the mesoporous silica tube with acetone, adding a silane coupling agent, and reacting at 75-85 ℃ to obtain a surface active mesoporous silica tube mixed solution;
adding the mixed solution of surface-active calcium peroxide into the mixed solution of the surface-active mesoporous silica tube, reacting at 70-90 ℃, and filtering, washing and drying to obtain mesoporous silica tube loaded calcium peroxide;
dissolving cage-type polysilsesquioxane in acetone, adding the mesoporous silica tube loaded with calcium peroxide, uniformly dispersing, reacting at 70-90 ℃, drying, crushing and grinding to obtain cage-type polysilsesquioxane end-capped mesoporous silica tube loaded with calcium peroxide;
adding calcium peroxide loaded on the cage-type polysilsesquioxane end-capped mesoporous silica tube into a silver nitrate solution, adjusting the pH value to 6-8, reacting for 3-5 h at a constant temperature of 70-90 ℃, then performing centrifugal separation, washing with deionized water until no silver ions exist in washing liquor, and drying to obtain the surface-loaded silver oxygen release antibacterial material.
Preferably, the surfactant is an anionic surfactant, preferably a composition of N-tetradecyl- β -sodium alanine and N-lauroylsarcosine sodium, and the concentration of the hydrochloric acid is 1.0-2.0 mol/L.
Preferably, the average particle size of the calcium peroxide is 10-30 nm, and the purity is not lower than 80%; the silane coupling agent is one or two of gamma-glycidoxypropyltrimethoxysilane and 3-aminopropyltriethoxysilane.
Preferably, the cage-type polysilsesquioxane is an octaepoxy cage-type silsesquioxane.
Preferably, the concentration of the silver nitrate solution is 0.35-0.5 mol/L.
An application of the oxygen-release antibacterial material obtained by the preparation method in plastic films.
A plastic film composition containing the oxygen-release antibacterial material comprises the following components in parts by weight:
preferably, the resin is prepared by mixing EVA and EAA according to the ratio of 1:2, preferably, the melt flow rate of the EVA resin is more than or equal to 33g/min, the content of the vinyl acetate is more than or equal to 33%, the melt flow rate of the EAA resin is more than or equal to 14g/min, and the monomer content is more than or equal to 20.5%; the compatilizer is at least one of POE-g-MAH and EVA-g-MAH, and the grafting rate is more than or equal to 2.5%; the lubricant is vinyl bis stearamide; the antioxidants are 1010 and 168 according to a 2:1 in a mass ratio; the opening agent is oleamide.
A method for preparing the plastic film composition comprises the following steps:
uniformly mixing the oxygen-releasing antibacterial material with resin, a compatilizer, a lubricant, an antioxidant and an opening agent, and discharging to obtain an oxygen-releasing antibacterial film premix;
adding the oxygen-releasing antibacterial film premix into a double-screw extruder for melt extrusion to obtain an oxygen-releasing antibacterial film modified material;
and adding the modified material of the oxygen-release antibacterial film into a film blowing machine for film making to obtain the oxygen-release antibacterial film.
Preferably, the working parameters of the double-screw extruder are as follows: the temperature of the first zone is 50-80 ℃, the temperature of the second zone is 60-90 ℃, the temperature of the third zone is 100-110 ℃, the temperature of the fourth zone is 100-120 ℃, the temperature of the fifth zone is 80-110 ℃, the temperature of the die head is 70-90 ℃, the feeding speed is 100-130 rpm, and the rotating speed of the screw is 80-120 rpm;
the working parameters of the film blowing machine are as follows: 60-80 ℃ of feeding section, 110-130 ℃ of middle section, 120-150 ℃ of front section, head temperature: the screw rotation speed is 40-70 rpm at 100-140 ℃.
The method comprises the steps of firstly preparing a mesoporous silica tube by adopting a soft membrane method, adopting calcium peroxide as an oxygen release agent to be attached to the cavity of the mesoporous silica tube, simultaneously adopting cage-type polysilsesquioxane to modify the mesoporous silica tube, carrying out end capping on the mesoporous silica tube to form a capsule-shaped structure, and preparing a material with dual performances of antibiosis and oxygen release by utilizing the antibacterial property of silver ions, wherein the diameter of a water drop in nature is 100-3000 mu m due to the surface tension effect and cannot react with peroxide through a mesoporous pore channel because the diameter of the carbon dioxide molecule is 0.337nm, and finally carrying out silver-carrying treatment on the outer wall of the mesoporous silica tube.
Compared with the prior art, the invention has the following beneficial effects:
1. by utilizing the special crystal structure of the mesoporous silica tube, the inner wall and the outer wall of the mesoporous silica tube are respectively loaded with peroxide and an antibacterial material through reaction, so that the antibacterial material with dual effects of oxygen release and antibiosis is prepared;
2. from the structural design, the oxygen-releasing antibacterial material is prepared and applied to plastic film products, and has the advantages of small addition amount, easy industrial production, obvious oxygen-releasing antibacterial effect and the like;
3. the raw materials adopted are wide in source, non-toxic, simple in processing method, low in cost and wide in market prospect.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
In the present invention, the cage-type polysilsesquioxane is an octaepoxy group cage-type silsesquioxane, which is available from hybrid plastics, USA;
example 1
The preparation method of the oxygen-release antibacterial material related to the embodiment is as follows:
(1) preparation of mesoporous silica tube
Weighing 0.5g N-tetradecyl- β -sodium alanine and N-sodium lauroyl sarcosinate composition (mass ratio is 1:1), dissolving in 20ml deionized water, adding 0.5g hydrochloric acid solution with concentration of 1.4mol/L to be uniform while stirring at normal temperature, sequentially adding 1.6g tetraethoxysilane and 0.2g N-trimethoxypropylsilane-N, N, N-trimethyl ammonium chloride, fully reacting for 0.5h at normal temperature, standing for 2 days at constant temperature of 40 ℃, performing centrifugal separation, washing, drying and roasting to obtain the mesoporous silica tube with uniform diameter.
(2) Preparation of mesoporous silica tube loaded calcium peroxide
Mixing 10g of calcium peroxide with 40ml of acetone, fully stirring, adding a gamma-glycidoxypropyltrimethoxysilane coupling agent, reacting for 2 hours at 80 ℃ to obtain a mixed solution of surface active calcium peroxide, and recording the mixed solution as a mixed solution A;
mixing 10g of the mesoporous silica tube prepared in the step (1) with 30ml of acetone, fully stirring, adding a gamma-glycidyl ether oxypropyl trimethoxy silane coupling agent, reacting at 80 ℃ for 1h to obtain a surface active mesoporous silica tube mixed solution, and recording the surface active mesoporous silica tube mixed solution as a mixed solution B;
adding the mixed solution A into a three-neck flask filled with the mixed solution B, reacting for 2 hours at the constant temperature of 80 ℃ while stirring, and filtering, washing and drying to obtain mesoporous silica tube loaded calcium peroxide;
(3) preparation method of cage-type polysilsesquioxane end-capped mesoporous silica tube loaded with calcium peroxide
Weighing 10g of cage-type polysilsesquioxane, dissolving in 60ml of acetone, adding 5g of mesoporous silica tube loaded calcium peroxide prepared in the step (2) while stirring, fully stirring and uniformly dispersing, heating to 80 ℃, reacting for 4 hours, placing in an oven, drying for 2 hours at 80 ℃, crushing, and grinding to obtain cage-type polysilsesquioxane end-capped mesoporous silica tube loaded calcium peroxide.
(4) Preparation of surface-loaded silver oxygen-releasing antibacterial material
And (3) adding 10g of cage-type polysilsesquioxane end-capped mesoporous silica tube loaded with calcium peroxide prepared in the step (3) into 100ml of silver nitrate solution with the concentration of 0.5mol/L, keeping the pH value of the solution between 6 and 8, reacting for 4 hours at the constant temperature of 80 ℃, then performing centrifugal separation, washing with deionized water until silver ions are not contained in washing liquor, and drying at the temperature of 85 ℃ to obtain the surface-loaded silver oxygen release antibacterial material.
Example 2
The preparation method of the oxygen-release antibacterial material related to the embodiment is as follows:
(1) preparation of mesoporous silica tube
Weighing 0.8g N-tetradecyl- β -sodium alanine and N-sodium lauroyl sarcosinate composition (mass ratio is 1:2), dissolving in 30ml deionized water, adding 0.5g hydrochloric acid solution with concentration of 1.4mol/L to be uniform while stirring at normal temperature, sequentially adding 2.0g tetraethoxysilane and 0.25g N-trimethoxypropylsilane-N, N, N-trimethyl ammonium chloride, fully reacting for 0.5h at normal temperature, standing for 2 days at constant temperature of 40 ℃, performing centrifugal separation, washing, drying and roasting to obtain the mesoporous silica tube with uniform diameter.
(2) Preparation of mesoporous silica tube loaded calcium peroxide
Mixing 15g of calcium peroxide with 50ml of acetone, fully stirring, adding a 3-aminopropyl triethoxysilane coupling agent, reacting at 80 ℃ for 2 hours to obtain a surface active calcium peroxide mixed solution, and recording the surface active calcium peroxide mixed solution as a mixed solution A;
mixing 10g of the mesoporous silica tube prepared in the step (1) with 30ml of acetone, fully stirring, adding a 3-aminopropyltriethoxysilane coupling agent, reacting at 80 ℃ for 1h to obtain a surface active mesoporous silica tube mixed solution, and recording the surface active mesoporous silica tube mixed solution as a mixed solution B;
adding the mixed solution A into a three-neck flask filled with the mixed solution B, reacting for 2 hours at the constant temperature of 80 ℃ while stirring, and filtering, washing and drying to obtain mesoporous silica tube loaded calcium peroxide;
(3) preparation method of cage-type polysilsesquioxane end-capped mesoporous silica tube loaded with calcium peroxide
Weighing 15g of cage-type polysilsesquioxane and dissolving in 100ml of acetone, adding 5g of mesoporous silica tube loaded calcium peroxide prepared in the step (2) while stirring, fully stirring and uniformly dispersing, heating to 80 ℃, reacting for 4 hours, placing in an oven, drying for 2 hours at 80 ℃, crushing, and grinding to obtain cage-type polysilsesquioxane end-capped mesoporous silica tube loaded calcium peroxide.
(4) Preparation of surface-loaded silver oxygen-releasing antibacterial material
And (3) adding 10g of cage-type polysilsesquioxane end-capped mesoporous silica tube loaded with calcium peroxide prepared in the step (3) into 100ml of silver nitrate solution with the concentration of 0.40mol/L, keeping the pH value of the solution between 6 and 8, reacting for 4 hours at the constant temperature of 80 ℃, then performing centrifugal separation, washing with deionized water until no silver ions exist in washing liquor, and drying at the temperature of 85 ℃ to obtain the surface-loaded silver oxygen release antibacterial material.
Example 3
The preparation method of the oxygen-release antibacterial material related to the embodiment is as follows:
(1) preparation of mesoporous silica tube
Weighing 0.9g N-tetradecyl- β -sodium alanine and N-sodium lauroyl sarcosinate composition (mass ratio is 2:1) and dissolving in 35ml deionized water, adding 0.5g hydrochloric acid solution with concentration of 1.4mol/L to be uniform while stirring at normal temperature, sequentially adding 2.5g tetraethoxysilane and 0.3g N-trimethoxypropylsilane-N, N, N-trimethyl ammonium chloride, fully reacting for 0.5h at normal temperature, standing for 2 days at constant temperature of 40 ℃, and obtaining the mesoporous silica tube with uniform diameter through centrifugal separation, washing, drying and roasting.
(2) Preparation of mesoporous silica tube loaded calcium peroxide
Mixing 18g of calcium peroxide with 70ml of acetone, fully stirring, adding a gamma-glycidoxypropyltrimethoxysilane coupling agent, reacting for 2 hours at 80 ℃ to obtain a mixed solution of surface active calcium peroxide, and recording the mixed solution as a mixed solution A;
mixing 10g of the mesoporous silica tube prepared in the step (1) with 30ml of acetone, fully stirring, adding a gamma-glycidyl ether oxypropyl trimethoxy silane coupling agent, reacting at 80 ℃ for 1h to obtain a surface active mesoporous silica tube mixed solution, and recording the surface active mesoporous silica tube mixed solution as a mixed solution B;
adding the mixed solution A into a three-neck flask filled with the mixed solution B, reacting for 2 hours at the constant temperature of 80 ℃ while stirring, and filtering, washing and drying to obtain mesoporous silica tube loaded calcium peroxide;
(3) preparation method of cage-type polysilsesquioxane end-capped mesoporous silica tube loaded with calcium peroxide
Weighing 18g of cage-type polysilsesquioxane and dissolving in 120ml of acetone, adding 5g of mesoporous silica tube loaded calcium peroxide prepared in the step (2) while stirring, fully stirring and uniformly dispersing, heating to 80 ℃, reacting for 4 hours, placing in an oven, drying for 2 hours at 80 ℃, crushing, and grinding to obtain cage-type polysilsesquioxane end-capped mesoporous silica tube loaded calcium peroxide.
(4) Preparation of surface-loaded silver oxygen-releasing antibacterial material
And (3) adding 10g of cage-type polysilsesquioxane end-capped mesoporous silica tube loaded with calcium peroxide prepared in the step (3) into 100ml of silver nitrate solution with the concentration of 0.45mol/L, keeping the pH value of the solution between 6 and 8, reacting for 4 hours at the constant temperature of 80 ℃, then performing centrifugal separation, washing with deionized water until silver ions are not contained in washing liquor, and drying at the temperature of 90 ℃ to obtain the surface-loaded silver oxygen release antibacterial material.
Example 4
The preparation method of the oxygen-release antibacterial material related to the embodiment is as follows:
(1) preparation of mesoporous silica tube
Weighing 1g N-tetradecyl- β -sodium alanine and N-lauroyl sarcosine composition (mass ratio is 1:1), dissolving in 40ml deionized water, adding 0.5g hydrochloric acid solution with concentration of 1.4mol/L to be uniform while stirring at normal temperature, sequentially adding 3.0g tetraethoxysilane and 0.4g N-trimethoxypropylsilane-N, N, N-trimethyl ammonium chloride, stirring at normal temperature for sufficient reaction for 0.5h, standing at constant temperature of 40 ℃ for 2 days, centrifugally separating, washing, drying and roasting to obtain the mesoporous silica tube with uniform diameter.
(2) Preparation of mesoporous silica tube loaded calcium peroxide
Mixing 20g of calcium peroxide with 100ml of acetone, fully stirring, adding a 3-aminopropyl triethoxysilane coupling agent, reacting at 80 ℃ for 2 hours to obtain a surface active calcium peroxide mixed solution, and recording the surface active calcium peroxide mixed solution as a mixed solution A;
mixing 10g of the mesoporous silica tube prepared in the step (1) with 30ml of acetone, fully stirring, adding a 3-aminopropyltriethoxysilane coupling agent, reacting at 80 ℃ for 1h to obtain a surface active mesoporous silica tube mixed solution, and recording the surface active mesoporous silica tube mixed solution as a mixed solution B;
adding the mixed solution A into a three-neck flask filled with the mixed solution B, reacting for 2 hours at the constant temperature of 80 ℃ while stirring, and filtering, washing and drying to obtain mesoporous silica tube loaded calcium peroxide;
(3) preparation method of cage-type polysilsesquioxane end-capped mesoporous silica tube loaded with calcium peroxide
Weighing 20g of cage-type polysilsesquioxane, dissolving in 150ml of acetone, adding 5g of mesoporous silica tube loaded calcium peroxide prepared in the step (2) while stirring, fully stirring and uniformly dispersing, heating to 80 ℃, reacting for 4 hours, placing in an oven, drying for 2 hours at 80 ℃, crushing, and grinding to obtain cage-type polysilsesquioxane end-capped mesoporous silica tube loaded calcium peroxide.
(4) Preparation of surface-loaded silver oxygen-releasing antibacterial material
And (3) adding 10g of cage-type polysilsesquioxane end-capped mesoporous silica tube loaded with calcium peroxide prepared in the step (3) into 100ml of silver nitrate solution with the concentration of 0.35mol/L, keeping the pH value of the solution between 6 and 8, reacting for 4 hours at the constant temperature of 80 ℃, then performing centrifugal separation, washing with deionized water until no silver ions exist in washing liquor, and drying at the temperature of 80-100 ℃ to obtain the surface-loaded silver oxygen-releasing antibacterial material.
Comparative example 1
The preparation method of the oxygen release material related to the embodiment comprises the following steps:
(1) preparation of mesoporous silica tube
Weighing 0.9g N-tetradecyl- β -sodium alanine and N-sodium lauroyl sarcosinate composition (mass ratio is 2:1) and dissolving in 35ml deionized water, adding 0.5g hydrochloric acid solution with concentration of 1.4mol/L to be uniform while stirring at normal temperature, sequentially adding 2.5g tetraethoxysilane and 0.3g N-trimethoxypropylsilane-N, N, N-trimethyl ammonium chloride, fully reacting for 0.5h at normal temperature, standing for 2 days at constant temperature of 40 ℃, and obtaining the mesoporous silica tube with uniform diameter through centrifugal separation, washing, drying and roasting.
(2) Preparation of mesoporous silica tube loaded calcium peroxide
Mixing 18g of calcium peroxide with 70ml of acetone, fully stirring, adding a gamma-glycidoxypropyltrimethoxysilane coupling agent, reacting for 2 hours at 80 ℃ to obtain a mixed solution of surface active calcium peroxide, and recording the mixed solution as a mixed solution A;
mixing 10g of the mesoporous silica tube prepared in the step (1) with 30ml of acetone, fully stirring, adding a gamma-glycidyl ether oxypropyl trimethoxy silane coupling agent, reacting at 80 ℃ for 1h to obtain a surface active mesoporous silica tube mixed solution, and recording the surface active mesoporous silica tube mixed solution as a mixed solution B;
adding the mixed solution A into a three-neck flask filled with the mixed solution B, reacting for 2 hours at the constant temperature of 80 ℃ while stirring, and filtering, washing and drying to obtain mesoporous silica tube loaded calcium peroxide;
(3) preparation method of cage-type polysilsesquioxane end-capped mesoporous silica tube loaded with calcium peroxide
Weighing 18g of cage-type polysilsesquioxane and dissolving in 120ml of acetone, adding 5g of mesoporous silica tube loaded calcium peroxide prepared in the step (2) while stirring, fully stirring and uniformly dispersing, heating to 80 ℃, reacting for 4 hours, placing in an oven, drying for 2 hours at 80 ℃, crushing, and grinding to obtain cage-type polysilsesquioxane end-capped mesoporous silica tube loaded calcium peroxide.
Comparative example 2
The preparation method of the antibacterial material related to the embodiment comprises the following steps:
(1) preparation of mesoporous silica tube
Weighing 0.9g N-tetradecyl- β -sodium alanine and N-sodium lauroyl sarcosinate composition (mass ratio is 2:1) and dissolving in 35ml deionized water, adding 0.5g hydrochloric acid solution with concentration of 1.4mol/L to be uniform while stirring at normal temperature, sequentially adding 2.5g tetraethoxysilane and 0.3g N-trimethoxypropylsilane-N, N, N-trimethyl ammonium chloride, fully reacting for 0.5h at normal temperature, standing for 2 days at constant temperature of 40 ℃, and obtaining the mesoporous silica tube with uniform diameter through centrifugal separation, washing, drying and roasting.
(3) Preparation by adopting cage type polysilsesquioxane end-capped mesoporous silica tube
Weighing 18g of cage-type polysilsesquioxane and dissolving in 120ml of acetone, adding 5g of the mesoporous silica tube prepared in the step (2) while stirring, fully stirring and uniformly dispersing, heating to 80 ℃, reacting for 4 hours, placing in an oven, drying for 2 hours at 80 ℃, crushing, and grinding to obtain the cage-type polysilsesquioxane end-capped mesoporous silica tube.
(4) Preparation of bacteriostatic material with silver loaded on surface
And (3) adding 10g of the cage-type polysilsesquioxane end-capped mesoporous silica tube prepared in the step (3) into 100ml of silver nitrate solution with the concentration of 0.45mol/L, keeping the pH value of the solution between 6 and 8, reacting for 4 hours at the constant temperature of 80 ℃, then performing centrifugal separation, washing with deionized water until no silver ions exist in washing liquor, and drying at the temperature of 90 ℃ to obtain the surface-loaded silver antibacterial material.
Example 5
The oxygen release antibacterial materials of the above examples 1-4 and comparative examples 1-2 are applied to a plastic film, and comprise the following components in parts by weight:
the application steps are as follows:
step A: weighing the oxygen-releasing antibacterial material according to the proportion, uniformly mixing the oxygen-releasing antibacterial material with resin, a compatilizer, a lubricant, an antioxidant and an opening agent, and discharging to obtain an oxygen-releasing antibacterial film premix;
and B: adding the oxygen-releasing antibacterial film premix into a double-screw extruder for melt extrusion to obtain an oxygen-releasing antibacterial film modified material;
and C: and adding the modified material of the oxygen-release antibacterial film into a film blowing machine for film making to obtain the oxygen-release antibacterial film.
The oxygen release amount and the antibacterial performance of the oxygen release antibacterial film are tested, and the test method and the result are as follows:
test 1:
and (3) antibacterial property test: 1g of the antibacterial oxygen release film is accurately weighed and added into a triangular flask filled with 99mL of sterile water, and the ultrasonic wave is used for 20 min. 1mL of a 1X 10-concentrated solution was added7CFU/mL bacterial suspension. Another flask containing 99mL of sterile water was used as a blank and only 1mL of the bacterial suspension was added. Placing the triangular flask in a shaking incubator, and performing shaking culture at 37 deg.C and 200r/min for 30 min. 0.2mL of each mixed solution was taken from each flask, diluted appropriately, spread on a petri dish, incubated at 37 ℃ for 24 hours, and the colonies were counted. The two groups of samples are respectively subjected to 3 parallel experiments, and the antibacterial rate is calculated according to the following formula: r ═ [ (A-B)/A ═]*100％，
R is the antibacterial rate of the bacteria,
a-average colony count for the blank control group,
b-average colony number of the added antibacterial sample to be tested.
The strains are selected from Salmonella aurantiaca and Escherichia coli.
And (3) testing 2: oxygen evolution test
The experimental device is a closed container, an injector is connected on the container, and a push handle of the injector can move, so that whether the volume of gas in the container changes or not and the change amount can be displayed;
table 1: antibacterial property test
| Salmonella enterica (%) | Escherichia coli (%) | |
| Example 1 | 99 | 98 |
| Example 2 | 97 | 97 |
| Example 3 | 99 | 99 |
| Example 4 | 96 | 95 |
| Comparative example 1 | 10 | 12 |
| Comparative example 2 | 99 | 99 |
Table 2: oxygen release test
| Day 1 (ml) | 2 days (ml) | 3 days (ml) | |
| Example 1 | 0.22 | 0.26 | 0.38 |
| Example 2 | 0.19 | 0.23 | 0.33 |
| Example 3 | 0.28 | 0.32 | 0.41 |
| Example 4 | 0.25 | 0.30 | 0.37 |
| Comparative example 1 | 0.29 | 0.34 | 0.45 |
| Comparative example 2 | 0 | 0 | 0 |
As can be seen from the test results in tables 1-2, the oxygen-releasing antibacterial plastic film prepared by adding the oxygen-releasing antibacterial material can effectively improve the antibacterial and oxygen-releasing performance of the plastic film, and the differences between comparative examples 1 and 2 and examples 1-4 are that no silver-loading step is prepared in the formula of comparative example 1, and no calcium peroxide-loading step is prepared in the formula of comparative example 2, and it can be seen from the test results that the oxygen-releasing antibacterial effect of comparative examples 1 and 2 is obviously inferior to that of examples 1-4, because the examples 1-4 utilize the special crystal structure of the mesoporous silica tube, and the inner wall and the outer wall of the mesoporous silica tube are respectively loaded with peroxide and the antibacterial material through reaction to prepare the material with dual effects of oxygen-releasing and antibacterial, and the oxygen-releasing antibacterial effect of example 3 is more obvious than that of examples 1, 2 and 4. Thus, with the most preferred formulation of example 3, the oxygen release and antimicrobial properties of the material are most balanced.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (10)
1. The preparation method of the oxygen release antibacterial material is characterized by comprising the following steps:
dissolving a surfactant in deionized water, adding hydrochloric acid, sequentially adding tetraethoxysilane and N-trimethoxypropylsilane-N, N, N-trimethyl ammonium chloride, reacting at normal temperature, standing for 2-3 days at 30-50 ℃, and performing centrifugal separation, washing, drying and roasting to obtain a mesoporous silica tube;
uniformly mixing calcium peroxide and acetone, adding a silane coupling agent, and reacting at 70-90 ℃ to obtain a surface active calcium peroxide mixed solution;
mixing the mesoporous silica tube with acetone, adding a silane coupling agent, and reacting at 75-85 ℃ to obtain a surface active mesoporous silica tube mixed solution;
adding the mixed solution of surface-active calcium peroxide into the mixed solution of the surface-active mesoporous silica tube, reacting at 70-90 ℃, and filtering, washing and drying to obtain mesoporous silica tube loaded calcium peroxide;
dissolving cage-type polysilsesquioxane in acetone, adding the mesoporous silica tube loaded with calcium peroxide, uniformly dispersing, reacting at 70-90 ℃, drying, crushing and grinding to obtain cage-type polysilsesquioxane end-capped mesoporous silica tube loaded with calcium peroxide;
adding calcium peroxide loaded on the cage-type polysilsesquioxane end-capped mesoporous silica tube into a silver nitrate solution, adjusting the pH value to 6-8, reacting for 3-5 h at a constant temperature of 70-90 ℃, then performing centrifugal separation, washing with deionized water until no silver ions exist in washing liquor, and drying to obtain the surface-loaded silver oxygen release antibacterial material.
2. The method for preparing the oxygen release antibacterial material according to claim 1, wherein the surfactant is an anionic surfactant, preferably a composition of N-tetradecyl- β -sodium alanine and N-lauroylsarcosine sodium, and the concentration of the hydrochloric acid is 1.0-2.0 mol/L.
3. The method for preparing the oxygen-release antibacterial material according to claim 1, wherein the calcium peroxide has an average particle size of 10-30 nm and a purity of not less than 80%; the silane coupling agent is one or two of gamma-glycidoxypropyltrimethoxysilane and 3-aminopropyltriethoxysilane.
4. The method for preparing the oxygen-release antibacterial material according to claim 1, wherein the cage-type polysilsesquioxane is an octaepoxy-based cage-type silsesquioxane.
5. The method for preparing the oxygen-release antibacterial material according to claim 1, wherein the concentration of the silver nitrate solution is 0.35-0.5 mol/L.
6. Use of the oxygen-releasing antibacterial material obtained by the preparation method of any one of claim 1 in a plastic film.
7. A plastic film composition containing the oxygen-releasing antibacterial material of claim 1, which comprises the following components in parts by weight:
8. the plastic film composition of claim 7, wherein the resin is EVA and EAA in a ratio of 1:2, preferably, the melt flow rate of the EVA resin is more than or equal to 33g/min, the content of the vinyl acetate is more than or equal to 33%, the melt flow rate of the EAA resin is more than or equal to 14g/min, and the monomer content is more than or equal to 20.5%; the compatilizer is at least one of POE-g-MAH and EVA-g-MAH, and the grafting rate is more than or equal to 2.5%; the lubricant is vinyl bis stearamide; the antioxidants are 1010 and 168 according to a 2:1 in a mass ratio; the opening agent is oleamide.
9. A method of making the plastic film composition of claim 7, comprising the steps of:
uniformly mixing the oxygen-releasing antibacterial material with resin, a compatilizer, a lubricant, an antioxidant and an opening agent, and discharging to obtain an oxygen-releasing antibacterial film premix;
adding the oxygen-releasing antibacterial film premix into a double-screw extruder for melt extrusion to obtain an oxygen-releasing antibacterial film modified material;
and adding the modified material of the oxygen-release antibacterial film into a film blowing machine for film making to obtain the oxygen-release antibacterial film.
10. The method of claim 9, wherein the twin screw extruder has the following operating parameters: the temperature of the first zone is 50-80 ℃, the temperature of the second zone is 60-90 ℃, the temperature of the third zone is 100-110 ℃, the temperature of the fourth zone is 100-120 ℃, the temperature of the fifth zone is 80-110 ℃, the temperature of the die head is 70-90 ℃, the feeding speed is 100-130 rpm, and the rotating speed of the screw is 80-120 rpm;
the working parameters of the film blowing machine are as follows: 60-80 ℃ of feeding section, 110-130 ℃ of middle section, 120-150 ℃ of front section, head temperature: the screw rotation speed is 40-70 rpm at 100-140 ℃.
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|---|---|---|---|---|
| US6372632B1 (en) * | 2000-01-24 | 2002-04-16 | Taiwan Semiconductor Manufacturing Company | Method to eliminate dishing of copper interconnects by the use of a sacrificial oxide layer |
| CN101734669A (en) * | 2010-02-02 | 2010-06-16 | 上海交通大学 | Method for preparing amino group or quaternary ammonium salt functional silicon dioxide mesoporous spherical material |
| CN105237794A (en) * | 2015-11-04 | 2016-01-13 | 北京化工大学 | Preparation method of super-hydrophobic elastomer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6372632B1 (en) * | 2000-01-24 | 2002-04-16 | Taiwan Semiconductor Manufacturing Company | Method to eliminate dishing of copper interconnects by the use of a sacrificial oxide layer |
| CN101734669A (en) * | 2010-02-02 | 2010-06-16 | 上海交通大学 | Method for preparing amino group or quaternary ammonium salt functional silicon dioxide mesoporous spherical material |
| CN105237794A (en) * | 2015-11-04 | 2016-01-13 | 北京化工大学 | Preparation method of super-hydrophobic elastomer |
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