CN117210031B - Modified nano zinc oxide powder and preparation method and application thereof - Google Patents
Modified nano zinc oxide powder and preparation method and application thereof Download PDFInfo
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- CN117210031B CN117210031B CN202311164837.5A CN202311164837A CN117210031B CN 117210031 B CN117210031 B CN 117210031B CN 202311164837 A CN202311164837 A CN 202311164837A CN 117210031 B CN117210031 B CN 117210031B
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 327
- 238000002360 preparation method Methods 0.000 title claims abstract description 45
- 239000011787 zinc oxide Substances 0.000 claims abstract description 131
- 239000003607 modifier Substances 0.000 claims abstract description 46
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- 238000000034 method Methods 0.000 claims abstract description 33
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- 238000000227 grinding Methods 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 14
- 235000013305 food Nutrition 0.000 claims abstract description 14
- 238000010902 jet-milling Methods 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000004806 packaging method and process Methods 0.000 claims abstract description 13
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- 239000002131 composite material Substances 0.000 claims description 29
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 22
- 229920001285 xanthan gum Polymers 0.000 claims description 22
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
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- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 7
- 229960003237 betaine Drugs 0.000 claims description 7
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 7
- 229960004889 salicylic acid Drugs 0.000 claims description 7
- 239000011975 tartaric acid Substances 0.000 claims description 7
- 235000002906 tartaric acid Nutrition 0.000 claims description 7
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 claims description 5
- 238000005516 engineering process Methods 0.000 claims description 5
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- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
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- 230000001580 bacterial effect Effects 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
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- 241000344726 Iris spuria Species 0.000 description 1
- RJQXTJLFIWVMTO-TYNCELHUSA-N Methicillin Chemical compound COC1=CC=CC(OC)=C1C(=O)N[C@@H]1C(=O)N2[C@@H](C(O)=O)C(C)(C)S[C@@H]21 RJQXTJLFIWVMTO-TYNCELHUSA-N 0.000 description 1
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
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Abstract
The application relates to a modified nano zinc oxide powder and a preparation method and application thereof. The method comprises the following steps: 1) Immersing zinc oxide in the first active liquid, filtering and drying to obtain active zinc oxide; 2) Jet milling the active zinc oxide to obtain milled zinc oxide; 3) Immersing the crushed zinc oxide in a second active liquid, filtering, drying and grinding to obtain active nano zinc oxide; 4) Uniformly mixing the active nano zinc oxide and the surface modifier in a weight ratio of 1 (0.8-1.5), drying and grinding to obtain the modified nano zinc oxide powder with the particle size of 10-90nm. The zinc oxide is used as a base material, and the modified nano zinc oxide powder obtained by the treatment of the first active liquid, the air current crushing, the second active liquid treatment, the surface modifier and the like sequentially has good compatibility with polymers, and has good ultraviolet resistance, antibacterial property and physical property when being applied to packaging materials in the food packaging field.
Description
Technical Field
The application relates to the field of environment-friendly materials, in particular to a modified nano zinc oxide powder and a preparation method and application thereof.
Background
Zinc oxide is an oxide of zinc, has larger energy band gap and exciton binding energy, high transparency and excellent normal-temperature luminous performance, and has application in products such as liquid crystal displays, thin film transistors, light-emitting diodes and the like in the semiconductor field. However, zinc oxide with larger particles has poor dispersibility and is limited in application, so that researches are mainly conducted on zinc oxide with nano-sized particles at present.
The nano zinc oxide has extremely high chemical activity, excellent catalytic activity and photocatalytic activity, and has the functions of resisting infrared radiation and ultraviolet radiation and sterilizing. Therefore, the coating is used in chemical coating, ceramic, electronic and food packaging the method is widely applied in various fields such as optics, biological medicine and the like.
When the nano zinc oxide is used for producing food packages, such as packaging films or packaging bottles which are filled in Polyhydroxyalkanoates (PHA), polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polycarbonate (PC) and other materials, the packaging materials have better antibacterial property due to the addition of the nano zinc oxide.
However, the specific surface area and specific surface energy of the nano zinc oxide are larger, so that the nano zinc oxide is easy to agglomerate in the filling process, and is easy to disperse unevenly in a polymeric material, thereby affecting the physical properties of the food packaging film; moreover, the nano zinc oxide has stronger surface polarity, so the nano zinc oxide has poor compatibility with polymers, thereby the physical properties of the food packaging film are limited, and the application of the nano zinc oxide is restricted.
In order to improve the compatibility of the nano zinc oxide, a surface modifier is generally adopted to carry out surface modification on the nano zinc oxide. The common surface modifier comprises a silane coupling agent, a titanate coupling agent, an acrylic ester polymer and epoxy resin, and after the surface treatment of the nano zinc oxide, the compatibility of the nano zinc oxide can be improved, but the nano zinc oxide has low toxicity or is not environment-friendly.
In addition, in the production process of nano zinc oxide, the nano zinc oxide is usually required to be produced by a precipitation method, a sol-gel method, a microemulsion method, a hydrothermal method and the like, and is directly mixed with the surface modifier, or is mixed with a diluted solution of the surface modifier, and the nano zinc oxide production method has the advantages of complex process, difficult purity control and the like, and the nano zinc oxide itself is aggregated in the mixing process with the surface modifier, so that further research on the modification of the nano zinc oxide is required.
Disclosure of Invention
In order to solve the technical problems, the application provides a modified nano zinc oxide powder and a preparation method and application thereof.
In a first aspect, the present application provides a method for preparing a modified nano zinc oxide powder, comprising the steps of:
1) Weighing 15-30 parts of absolute ethyl alcohol, 0.5-3 parts of betaine and 20-30 parts of water according to parts by weight, and uniformly mixing to obtain a first active liquid; immersing zinc oxide in the first active liquid, filtering and drying to obtain active zinc oxide;
2) Jet milling the active zinc oxide to obtain zinc oxide with the particle size of 1-10 mu m;
3) According to the weight portions, 10 to 20 portions of absolute ethyl alcohol, 0.01 to 0.05 portion of dodecylphenol polyoxyethylene ether and 10 to 30 portions of water are weighed and evenly mixed, and 2-hydroxysuccinic acid is added to adjust the PH to 5 to 6, so as to obtain a second active liquid; immersing the crushed zinc oxide in a second active liquid, filtering, drying and grinding to obtain active nano zinc oxide;
4) Uniformly mixing the active nano zinc oxide and the surface modifier in a weight ratio of 1 (0.8-1.5), drying and grinding to obtain the modified nano zinc oxide powder with the particle size of 10-90nm.
The preparation method is simple to operate, and can process zinc oxide in a low-temperature environment, so that the processing efficiency is improved; in the step 1), the substances such as adherents, impurities and the like on the surface of the zinc oxide are removed completely through the soaking treatment of the first active liquid, so that the purity of the zinc oxide is improved, and meanwhile, the agglomeration of the zinc oxide into blocks during jet milling is reduced, so that the jet milling is more convenient.
Step 2) crushing active zinc oxide particles by air current to obtain crushed zinc oxide; in the step 3), the second active liquid is used for treatment, so that the agglomeration of crushed zinc oxide is reduced, and meanwhile, the impurity is further removed, and the purity is improved; in the step 4), the active nano zinc oxide is subjected to surface modification and cladding by a surface modifier, so that the specific surface energy and polarity of the nano zinc oxide are reduced, and the obtained modified nano zinc oxide powder is easy to be compatible with a polymer.
In summary, this application is through adopting zinc oxide as the substrate, through first active liquid treatment, jet milling, second active liquid treatment and surface modifier in proper order for the modified nanometer zinc oxide powder that obtains has the compatibility good, and be difficult for taking place from the coalescence piece, and then be compatible with the polymer easily, when being used for packaging material, can play better filling effect, compatibility to the ultraviolet resistance, antibacterial property and the mechanical properties of reinforcing product.
The absolute ethyl alcohol has sterilization and disinfection effects, and can also be used as a cleaning agent for cleaning impurities on the surfaces of articles, and as zinc oxide is generally prepared by a high-temperature calcination or precipitation method of zinc carbonate, the prepared zinc oxide can entrain some impurities or dust in the transportation, packaging or processing process, so that the purity of the zinc oxide is affected; the betaine is tetradecyl dimethyl betaine, is an amphoteric surfactant and has the effects of sterilization, cleaning and the like, so that the first active liquid obtained by compounding absolute ethyl alcohol, water and tetradecyl dimethyl betaine is subjected to the effects of active treatment, impurity removal and the like, and after the first active liquid is soaked, ethanol on the surface of dried zinc oxide is volatilized completely, a small amount of tetradecyl dimethyl betaine is attached to the surface of zinc oxide, the surface activity of zinc oxide is improved, the occurrence of drastic masses is reduced, the jet milling efficiency is improved, and the processing efficiency is further improved.
The dodecylphenol polyoxyethylene ether is a surfactant, has an HLB value of 14.5, and has a good dispersing effect. The second active liquid obtained by mixing absolute ethyl alcohol, water, dodecylphenol polyoxyethylene ether and 2-hydroxysuccinic acid can improve the activity, reduce self-agglomeration, further improve the dispersibility of active nano zinc oxide and a surfactant, ensure that the obtained modified nano zinc oxide powder is more easily compatible with a polymer and is not easy to self-agglomerate, and can further improve the uniformity resistance, the ultraviolet resistance and the physical property when used in food packaging materials.
Preferably, the particle size of the crushed zinc oxide is 1-10 mu m; the particle size of the active nano zinc oxide is 5-50nm; the particle size of the zinc oxide is 0.1-1mm. The above particle size is a preferred choice for the present application.
The method for testing the nanoscale particle size in the application is as follows; and (3) when the materials are ground in a grinder, taking out a little zinc oxide from the grinder when the grinding is carried out for a certain time, observing the particle size of the zinc oxide by adopting an electron microscope, and stopping grinding when the observed particle size is in the range of 10-90nm to obtain the modified nano zinc oxide powder.
Similarly, when the active nano zinc oxide with the particle size of 5-50nm is obtained, a small amount of active nano zinc oxide is taken out in the grinding process, and is observed by an electron microscope, and when the particle size of 5-50nm is observed, grinding is stopped, so that the active nano zinc oxide is obtained.
Preferably, the specific process in 2) is as follows: sequentially feeding and extruding active zinc oxide, pressurizing, introducing air flow, carrying out air flow crushing and deagglomeration, sieving formed powder, collecting qualified products, and carrying out air flow crushing on unqualified products again to obtain crushed zinc oxide; wherein the working pressure of the jet milling is 0.98-1.02MPa, and the air demand is 2-4m 3 And/or min.
According to the technical scheme, zinc oxide is fed and extruded, and meanwhile, the extruded zinc oxide is driven to flow rapidly through air flow during extrusion, in the flowing process, certain pressure is applied to enable granular zinc oxide to collide with each other, cracking is generated, the formed finer powder zinc oxide is subjected to multiple collisions and cracking, screening is further carried out, zinc oxide powder with a proper particle size range is selected for collection, crushed zinc oxide is obtained, and unqualified powder is subjected to air flow crushing again. According to the process, zinc oxide is cracked by collision under the combined action of air flow and air pressure, the formed powder is further screened to obtain zinc oxide powder with uniform particle size, and then the zinc oxide powder is collected, wherein a cloth bag is adopted in the collection process, so that dust flying can be reduced, and the possibility of pollution to workshop environment is reduced.
According to the scheme, the zinc oxide is crushed at a low temperature to form crushed zinc oxide. The crushed zinc oxide which is crushed to form a polyhedron has better ultraviolet absorption effect, antibacterial property and the like; the active nano zinc oxide obtained after the treatment of the second active liquid is easy to carry out surface modification and cladding with a surface modifier, so that the compatibility of the modified nano zinc oxide powder is further improved, the modified nano zinc oxide powder is convenient to be compatible with a polymer, and the practicability of the modified nano zinc oxide powder is improved; and has better filling effect in food packaging materials, so that the product has better antibacterial property, ultraviolet resistance and mechanical property.
Preferably, the air flow crushing equipment is adopted in the step 2), and the air flow crushing equipment is sequentially provided with a feeding system, an air flow crushing classifier and a cloth bag collector according to the processing technology; the jet mill also comprises a material controller, and the feeding system, the jet mill classifier and the cloth bag collector are electrically connected with the material controller.
Preferably, the filtering area of the cloth bag collector is 8-12m 2 The filter bag in the cloth bag collector is a polyester fiber filter cylinder; the jet mill classifier consists of a jet mill mechanism and a classifying mechanism, and the jet mill comprises an induced draft fan, and the power of the induced draft fan is preferably 1.8-2.4KW; the classifier power is preferably 0.98-1.3KW.
The jet mill classifier is of a structure integrating crushing and classifying, and crushing and classifying in the processing process are completed at one time, so that the production efficiency is improved. The principle of the jet milling process is that compressed air is utilized to be cooled, filtered and dried, and then supersonic air flow is formed by a Laval nozzle in a jet milling classifier and is injected into a milling chamber, so that zinc oxide is in a flowing state, zinc oxide subjected to acceleration force is converged at a nozzle intersection point, and intense collision, friction and shearing are generated in the converging process to form superfine milling of particles.
The jet milling mode is non-medium milling, so that the obtained nano zinc oxide has higher purity. And the process does not need heating or solvent matching processing, so that the zinc oxide can be carried out at normal temperature, and the micron-sized zinc oxide is obtained.
The particle size of the crushed zinc oxide can be screened through a grading mechanism in the jet mill grader, so that zinc oxide with different particle sizes can be conveniently selected; the specific principle of the grading mechanism is as follows: the crushed zinc oxide rises to a turbine classification area in the classification mechanism under the action of air flow, and under the rotation of a classification turbine of the classification mechanism, the crushed zinc oxide is subjected to the action of centrifugal force and air flow viscosity at the same time, so that centripetal force is generated, when the crushed zinc oxide is subjected to the action that the centrifugal force is larger than the centripetal force, coarse particles above the classification diameter fall down to the crushing area of the air flow crushing mechanism along the wall of a cylinder of the classification mechanism to be continuously crushed, and zinc oxide with qualified particle size enters a cloth bag collector along with the air flow through the turbine to be collected. Through the screening effect, the uniformity of the particles of the crushed zinc oxide is further improved, the subsequent treatment is convenient, and the crushed zinc oxide is also convenient to treat with the surface modifier.
In addition, the adoption of cloth bag collection can reduce the flying of nano zinc oxide dust, thereby influencing the workshop environment and improving the environmental protection of production.
Preferably, the surface modifier is prepared from the following raw materials in parts by weight:
0.1-0.3 part of polylysine-PEG copolymer
10-20 parts of polyethylene glycol solution
10-22 parts of organic acid solution
1-3 parts of embryo Bei Nian protein solution
1-3 parts of xanthan gum solution
Ammonium persulfate 0.01-0.05 parts
2-5 parts of chitosan.
Preferably, the preparation of the surface modifier comprises the following steps:
(1) According to the weight portions, chitosan is weighed and dissolved in an organic acid solution, heated to 65-85 ℃, and stirred for 1-3 hours to obtain a composite material A;
(2) Weighing ammonium persulfate according to parts by weight, adding the ammonium persulfate into the composite material A obtained in the step 1), uniformly stirring, adding a polyethylene glycol solution, and stirring for 1-3 hours to obtain a composite material B;
(3) Weighing xanthan gum solution, embryo Bei Nian protein solution and polylysine-PEG copolymer according to parts by weight, adding the xanthan gum solution, the embryo Bei Nian protein solution and the polylysine-PEG copolymer into the composite material B obtained in the step 2), stirring for 0.5-1h, and regulating the PH value to 5.0-6.0 to obtain the surface modifier.
The composition of the raw materials and the dosage of the raw materials are all in the preferred range of the application, wherein the chitosan has antibacterial property and ultraviolet resistance, contains amino and carboxyl, and the organic acid solution contains hydroxyl, carboxyl and the like, so that the chitosan is easy to dissolve in the organic acid solution and is compounded with the organic acid to obtain the composite material A.
The mass fraction of the polyethylene glycol solution is 5-10%. The polyethylene glycol contains hydroxyl and further carries out a compounding reaction with the composite material A, so that the composite material B is obtained, and the polyethylene glycol has better adhesiveness, so that the obtained composite material B also has better adhesiveness after compounding.
The xanthan gum solution is prepared by dissolving 5-10 parts by weight of xanthan gum in 50 parts by weight of deionized water, and has good adhesiveness and film forming property, and the film forming property and adhesiveness of the treating agent are further improved.
The tenascin solution is prepared by dissolving 10-20 parts by weight of tenascin in 50 parts by weight of water, and the tenascin Bei Nian is extracted from the podophylloid gland of marine mussels, has the function of extremely strong adhesion matrix, and when the tenascin solution is further compounded with the composite material B, the prepared surface modifier has excellent adhesion, antibacterial property, ultraviolet resistance and the like, so that the surface modifier has extremely strong adhesion effect on the surface of nano zinc oxide.
The polylysine-PEG copolymer has better film forming property and adhesiveness, and the polylysine-PEG copolymer and the embryo Bei Nian protein solution, the xanthan gum solution and the composite material B cooperate to further enhance the adhesion of the surface modifier to the surface of the nano zinc oxide to form a coating film with stable adhesion.
In conclusion, after the organic acid, chitosan and polyethylene glycol are compounded, the prepared composite material A has antibacterial property, oxidation resistance, adhesiveness and film forming property, and further is compounded with a tire Bei Nian protein solution, a polylysine-PEG copolymer and a xanthan gum solution to play a role in synergistic film forming and adhesion, so that the better modification effect of the formed surface modifier on nano zinc oxide is further improved, a coating film is formed on the surface of the surface modifier, the compatibility of modified nano zinc oxide powder and a polymer is improved, and meanwhile, the modified nano zinc oxide powder has better antibacterial property and ultraviolet resistance when being used in a base material.
According to the preparation method, the organic acid, the chitosan, the polyethylene glycol, the tire Bei Nian protein solution, the polylysine-PEG copolymer and the xanthan gum solution are compounded, so that the obtained modifier has good environmental protection, and also has good modification and coating effects, so that the compatibility of the modified nano zinc oxide powder and the polymer is better, and meanwhile, the coating film formed by the surface modifier can also have synergistic effect with the nano zinc oxide, so that the antibacterial property, the ultraviolet resistance and the like of the modified nano zinc oxide powder are further enhanced. When the obtained modified nano zinc oxide powder is used in food packaging materials, the modified nano zinc oxide powder has better uniformity resistance, ultraviolet resistance and physical properties.
Preferably, the organic acid solution consists of citric acid, tartaric acid, salicylic acid and water.
Preferably, the weight ratio of the citric acid to the tartaric acid to the salicylic acid to the water is (0.5-0.8): (0.2-0.5): (0.1-0.3):10.
The citric acid, the tartaric acid and the salicylic acid all contain hydroxyl and carboxyl, so that the citric acid, the tartaric acid and the salicylic acid can be compounded with chitosan, the composite material A containing the organic acid-chitosan composite is further compounded with polyethylene glycol solution, the obtained composite material B has better adhesiveness and the like, and is further mixed with xanthan gum solution, a fetal Bei Nian protein solution and a polylysine-PEG copolymer, so that the surface modifier has better film forming property, adhesiveness, antibacterial property, ultraviolet resistance and the like. When the modified nano zinc oxide powder is mixed with a surface modifier, a coating film can be formed on the surface of the surface modifier, so that the prepared modified nano zinc oxide powder has better compatibility, antibacterial property, ultraviolet resistance and the like. When used in food packaging, the antibacterial property and the ultraviolet resistance of the packaging bag are further improved.
In a second aspect, the present application provides a modified nano zinc oxide powder having a particle size of 10-90nm, prepared by a method of preparing a modified nano zinc oxide powder.
The modified nano zinc oxide powder with the particle size of 10-90nm is easy to be compatible with the polymer, and the obtained product has better antibacterial property and ultraviolet resistance.
In a third aspect, the application provides an application of modified nano zinc oxide powder, wherein the modified nano zinc oxide powder is used in food packaging, and the ratio of the modified nano zinc oxide powder in the food packaging is 1-20%.
The dosage range is fully and uniformly mixed with the raw material system of the food packaging product, and the oxidation resistance and the antibacterial property of the product are further improved.
In summary, the present application has the following beneficial effects:
1. according to the modified nano zinc oxide powder packaging material, zinc oxide is used as a base material, and the zinc oxide powder is sequentially subjected to first active liquid treatment, jet milling, second active liquid treatment and surface modifier, so that the obtained modified nano zinc oxide powder has good compatibility, is not easy to self-agglomerate, is easily compatible with polymers, and has high practicability, so that the modified nano zinc oxide powder packaging material plays a good filling role, and the ultraviolet resistance, the antibacterial property and the physical property of the product are enhanced.
2. Through feeding extrusion, pressurization, ventilation flow crushing and deagglomeration, the powder that forms gets into the screening machine and sieves, collects the conforming product, and the disconforming product carries out the reposition of redundant personnel crushing again, a series of operations realize producing crushing zinc oxide under normal atmospheric temperature to improve machining efficiency and product purity.
3. After being compounded by organic acid, chitosan and polyethylene glycol, the prepared composite material A has antibacterial property, oxidation resistance, adhesiveness and film forming property, and further is compounded with a tire Bei Nian protein solution, a polylysine-PEG copolymer and a xanthan gum solution to play a role in synergistic film forming and adhesion, so that the better modification effect of the formed surface modifier on nano zinc oxide is further improved, a coating film is formed on the surface of the surface modifier, the compatibility of the modified nano zinc oxide and a polymer is improved, and meanwhile, the modified nano zinc oxide powder is used in food packaging materials to play a role in better antibacterial property and ultraviolet resistance and has better mechanical property.
Drawings
Fig. 1 is a schematic front view of a jet mill according to the present application.
Fig. 2 is a schematic top view of the jet milling apparatus described herein.
Reference numerals: 1. a feeding system; 2. a jet mill classifier; 3. a cloth bag collector.
Detailed Description
The present application is described in further detail below in conjunction with figures 1-2 and examples.
Partial sources of raw materials:
polylysine-PEG copolymer with average molecular weight of 3400-10000, preparation example preferably 5000, substitution rate of end group not less than 95%, and example 97.5%;
the model of the biological technology limited company of Shanxi blue iris of the manufacturing company of the tyre mucin is YDBF, and the content is not less than 90 percent;
the average molecular weight of chitosan is 10000-30000, the preparation example is preferably 20000, and the deacetylation is 88%;
the model of the biological technology Co.Ltd of Shandong Xiyue of xanthan gum manufacturer is SEFGTGHB, food grade;
the average molecular weight of polyethylene glycol is 200-400, and the preparation example is preferably 200;
the average molecular weight of PP is 3-8 ten thousand, and the application example is preferably 5 ten thousand; the melt index was 16.0.+ -. 3.0g/10min.
Preparation example of surface modifier
Preparation example 1
A method of preparing a surface modifying agent comprising the steps of:
(1) Weighing 0.2kg of chitosan, dissolving in 1kg of organic acid solution, heating to 75 ℃, and stirring for 2 hours to obtain a composite material A;
(2) Weighing 0.001kg of ammonium persulfate, adding the ammonium persulfate into the composite material A obtained in the step 1), uniformly stirring, adding 1kg of polyethylene glycol solution with the mass fraction of 8%, and stirring for 2 hours at the rotating speed of 100r/min to obtain a composite material B;
(3) Weighing 0.1kg of a tire Bei Nian protein solution, 0.1kg of a xanthan gum solution and 0.01kg of a polylysine-PEG copolymer, adding the mixture into the composite material B obtained in the step 2), stirring the mixture for 0.8h at the rotating speed of 100r/min, and adding sodium hydroxide to adjust the pH value to 5.5 to obtain the surface modifier.
The xanthan gum solution is prepared by dissolving 0.08kg of xanthan gum in 0.5kg of deionized water;
the embryo Bei Nian protein solution is prepared by dissolving 0.1kg of embryo mucin in 0.5kg of water;
the organic acid solution is prepared from citric acid, tartaric acid, salicylic acid and water in a weight (kg) ratio of 0.5:0.2: and (3) uniformly compounding and dissolving the mixture to obtain the product.
PREPARATION EXAMPLES 2-3
Preparation examples 2 to 3 differ from preparation example 1 in that: the amounts of the raw materials used are different, and are shown in Table 1;
TABLE 1 raw materials consumption (kg) for preparation examples 1-3
Preparation of comparative example
Preparation of comparative example 1
The preparation comparative example 1 is different from the preparation example 1 in that: the xanthan gum solution and polylysine-PEG copolymer were equally replaced with the fetal Bei Nian protein solution.
Preparation of comparative example 2
The preparation comparative example 2 is different from the preparation example 1 in that: the feta Bei Nian protein solution was replaced with a xanthan solution.
Preparation of comparative example 3
The preparation comparative example 3 is different from the preparation example 1 in that the step (2) is not provided, and the specific process is as follows:
(1) Weighing 0.2kg of chitosan, dissolving in 1kg of organic acid solution, heating to 75 ℃, and stirring for 2 hours to obtain a composite material A;
(2) Weighing 0.1kg of a tire Bei Nian protein solution, 0.1kg of a xanthan gum solution and 0.01kg of a polylysine-PEG copolymer, adding the mixture into the composite material A obtained in the step 1), stirring the mixture for 0.8h at the rotating speed of 100r/min, and adding sodium hydroxide to adjust the pH value to 5.5 to obtain the surface modifier.
Preparation of comparative example 4
The preparation comparative example 4 differs from the preparation example 1 in that there is no step (3), and the specific process is:
(1) Weighing 0.2kg of chitosan, dissolving in 1kg of organic acid solution, heating to 75 ℃, and stirring for 2 hours to obtain a composite material A;
(2) Weighing 0.001kg of ammonium persulfate, adding the ammonium persulfate into the composite material A obtained in the step 1), uniformly stirring, adding 1kg of polyethylene glycol solution with the mass fraction of 8%, stirring for 2 hours at the rotating speed of 100r/min, and adding sodium hydroxide to adjust the pH value to 5.5 to obtain the surface modifier.
Preparation of comparative example 5
The preparation comparative example 5 is different from the preparation example 1 in that: no organic acid solution. The method comprises the following specific steps:
(1) Weighing 1kg of polyethylene glycol solution with mass fraction of 8%, 0.2kg of chitosan and 0.001kg of ammonium persulfate, heating to 75 ℃, and stirring for 2 hours at the rotating speed of 100r/min to obtain a composite material B;
(2) Weighing 0.1kg of a tire Bei Nian protein solution, 0.1kg of a xanthan gum solution and 0.01kg of a polylysine-PEG copolymer, adding the mixture into the composite material B obtained in the step 1), stirring the mixture for 0.8h at the rotating speed of 100r/min, and adding sodium hydroxide to adjust the pH value to 5.5 to obtain the surface modifier.
Examples
Example 1
A modified nano zinc oxide powder, the particle size of the modified nano zinc oxide powder is 10-90nm.
The modified nano zinc oxide powder is prepared by the following method:
1) 1.5kg of absolute ethyl alcohol, 0.5kg of betaine and 2.5kg of water are weighed and uniformly mixed to obtain a first active liquid; completely immersing 2kg of zinc oxide with the particle size of 0.1mm in the first active liquid, stirring for 10min at the rotating speed of 100r/min, filtering, spreading filter residues in a culture dish, and then putting in a 50 ℃ oven for drying for 5h to obtain active zinc oxide;
2) Placing active zinc oxide into jet mill, feeding and extruding the active zinc oxide in turn, pressurizing, pulverizing and deagglomerating by ventilation flow, sieving the formed powder in a sieving machine, collecting qualified products, and pulverizing unqualified products again by flow division, wherein the working pressure of jet mill is 1.0MPa, and the air requirement is 3m 3 Collecting zinc oxide with particle size of 1-10 μm to obtain pulverized zinc oxide;
3) Weighing 1.5kg of absolute ethyl alcohol, 0.02kg of dodecylphenol polyoxyethylene ether and 2kg of water, uniformly mixing, adding 2-hydroxysuccinic acid to adjust the pH to 5-6 to obtain a second active liquid, immersing the crushed zinc oxide obtained in the step 2) into the second active liquid, stirring for 10min at the rotating speed of 100r/min, filtering, spreading filter residues in a culture dish, drying in a baking oven at 50 ℃ for 5h, and transferring to a grinding machine for grinding to obtain active nano zinc oxide with the particle size of 20-50 nm;
4) Uniformly mixing active nano zinc oxide and a surface modifier according to the weight (kg) ratio of 1:0.8, putting the mixture into a baking oven at 50 ℃ for drying for 6 hours, and transferring the dried mixture into a grinding machine for grinding to obtain modified nano zinc oxide powder with the particle size of 10-90nm.
2) The air flow crushing equipment is provided with a feeding system 1, an air flow crushing classifier 2 and a cloth bag collector 3 in sequence according to the processing technology; the jet mill also comprises a material controller, the feeding system 1, the jet mill classifier 2 and the cloth bag collector 3 are electrically connected with the material controller, and under the control of the material controller, active zinc oxide is sequentially fed, extruded, pressurized, flowed, collided, crushed, screened, collected and the like, so that the active zinc oxide can be crushed at a lower temperature, and the crushed zinc oxide has the advantages of uniform particle size and high purity.
Examples 2 to 8
Examples 2-8 differ from example 1 in that: the sources of the surface modifying agents are different, and are shown in table 2;
TABLE 2 Source of surface modifying Agents for examples 1-8
| Examples | Source of surface modifier |
| Example 1 | Preparation example 1 |
| Example 2 | Preparation example 2 |
| Example 3 | Preparation example 3 |
| Example 4 | Preparation of comparative example 1 |
| Example 5 | Preparation of comparative example 2 |
| Example 6 | Preparation of comparative example 3 |
| Example 7 | Preparation of comparative example 4 |
| Example 8 | Preparation of comparative example 5 |
Comparative example
Comparative example 1
Comparative example 1 differs from example 1 in that: step 1) of example 1 is not present; step 1) of comparative example 1 is as follows: putting zinc oxide into jet mill, feeding and extruding the zinc oxide in turn, pressurizing, pulverizing by ventilation flow, deagglomerating, sieving the formed powder in a sieving machine, collecting qualified products, and pulverizing unqualified products again by split flow, wherein the working pressure of jet mill is 1.0MPa, and the air requirement is 3m 3 The zinc oxide having a particle diameter of 1 to 10 μm was collected and pulverized zinc oxide was obtained (the remaining procedure was the same as in example 1).
Comparative example 2
Comparative example 2 is different from example 1 in that: step 3) of example 1 is not present; step 3) in comparative example 2 is: uniformly mixing crushed zinc oxide and a surface modifier in a weight (kg) ratio of 1:0.8, drying in a 50 ℃ oven for 6 hours, transferring to a grinder for grinding to obtain modified nano zinc oxide powder with the particle size of 10-90nm (the rest steps are the same as those of the example 1)
Comparative example 3
Comparative example 3 is different from example 1 in that: step 1) and step 3) in example 1 were not present; comparative example 3 the specific process is as follows:
1) Sequentially feeding and extruding zinc oxide, pressurizing, crushing and deagglomerating by an aeration flow, sieving the formed powder by a sieving machine, collecting qualified products, and carrying out split-flow crushing on unqualified products again, wherein the working pressure of the air flow crushing is 1.0MPa, and the air demand is 3m 3 And (3) collecting zinc oxide with the particle size of 1-10 mu m to obtain crushed zinc oxide.
2) Uniformly mixing the crushed zinc oxide and the surface modifier according to the weight (kg) ratio of 1:0.8, putting the mixture into a baking oven at 50 ℃ for drying for 6 hours, and transferring the dried mixture into a grinder for grinding to obtain the modified nano zinc oxide powder with the particle size of 10-90nm.
Comparative example 4
Comparative example 4 differs from example 1 in that: and (3) exchanging the first active liquid in the step (1) with the second active liquid in the step (3).
Comparative example 5
Comparative example 5 is different from example 1 in that: the surface modifier is replaced by the surface modifier containing the silane coupling agent in equal quantity (the surface modifier is obtained by uniformly mixing KH550 and water in a weight ratio of 1:40).
Application example
Application example 1
Weighing 0.5kg of the modified nano zinc oxide powder obtained in the example 1, uniformly mixing the powder with 10kg of PP, putting the mixture into an extruder for extrusion and granulation, and putting the obtained granules into an injection molding machine for injection molding to obtain a test sample.
Application examples 2 to 13
Application examples 2 to 13 differ from application example 1 in that: the sources of the modified nano zinc oxide powder are different, and are shown in the table 3;
TABLE 3 Source of modified nano Zinc oxide powder Using examples 1-13
Performance test
The test samples obtained in application examples 1 to 13 were subjected to the following performance tests, as shown in Table 4.
Detection method/test method
1. Antibacterial property
Referring to ASTME2149-2013a for detection, performing an antibacterial effect experiment with the test sample oscillating contact time of 24 hours, wherein the experimental strain is methicillin-resistant staphylococcus aureus ATCC33591; the number of bacteria (CFU/mL) obtained after elution at different contact times, wherein the control group is a test sample to which the modified nano zinc oxide powder of the present application was not added.
2. Anti-ultraviolet aging
The test samples obtained in application examples 1 to 13 were tested using an ultraviolet aging test box and referring to astm g154-00A, specifically: the test sample fixing device is arranged on the test frame, and when the sample is not filled in the test frame, the test frame is required to be filled in by the blackboard to keep the inner wall of the test box closed.
The illumination temperature can be 60 ℃; the condensing section temperature was 50 ℃. The period of each condensation of illumination can be selected from 4H illumination and 4H condensation, the two types of circulation are carried out, after the two types of circulation are placed for 80 hours, the two types of circulation are taken out and placed for 2 hours, and then the tensile strength is detected, and the tensile strength data is recorded as L1.
The test sample obtained in application examples 1-13 which is not subjected to ultraviolet aging is placed for 80 hours at normal temperature and normal pressure under the humidity of 50%, and then the tensile strength is detected, wherein the tensile strength is detected by using GB/T1040.1-2018, and the data is recorded as L2; the ultraviolet aging rate is = [ (L2-L1)/L2 ]. 100%, the larger the ultraviolet aging rate is, the poorer the ultraviolet aging resistance effect is, otherwise, the ultraviolet aging resistance effect is better, and the specific is shown in a table 4;
table 4 Experimental data for application examples 1-13
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As can be seen from application examples 9-11 of application example 1 and Table 4, the bacteria count and ultraviolet aging rate of application examples 9-11 are higher than those of application example 1, and the tensile strength of application examples 9-11 is lower than that of application example 1, which means that the obtained modified nano zinc oxide powder has higher purity, antibacterial property, compatibility, ultraviolet resistance and the like through treatment of the first active liquid and the second active liquid, is used in food packaging materials, has better antibacterial effect and ultraviolet resistance, and has better tensile strength.
As can be seen from the comparison of application examples 1 and 12 and the combination of Table 4, the number of bacteria and the ultraviolet aging rate of application example 12 were both higher than those of application example 1, and the tensile strength of application example 12 was lower than that of application example 1, indicating that the activity against zinc oxide was not good after the first active liquid and the second active liquid were exchanged.
As can be seen from the comparison of application examples 1 and 13 and the combination of Table 4, the bacteria count and ultraviolet aging rate of application example 13 are higher than those of application example 1, but the tensile strength of application example 13 is close to that of application example 1, which shows that the silane coupling agent can improve the compatibility of nano zinc oxide, but the antibacterial property and the ultraviolet resistance are not good.
Comparing application example 1 with application examples 4-5, it can be seen that the bacterial count and ultraviolet aging rate of application example 1 are higher than those of application example 1, and the tensile strength of application examples 4-5 is lower than that of application example 1, which indicates that the xanthan gum solution, polylysine-PEG copolymer and embryo Bei Nian protein solution are compounded to play a better role, and further, the compatibility of the modified nano zinc oxide powder and the polymer is enhanced, so that the antibacterial property, ultraviolet resistance and physical property of the modified nano zinc oxide powder after being applied to food packaging are further improved.
For application example 1 and application examples 6-8, it can be seen that the bacterial count and ultraviolet aging rate of application example 1 are higher than those of application example 1, and the tensile strength of application examples 6-8 is lower than that of application example 1, which indicates that the surface modifier obtained by the preparation process of the application has better modification effect, better coating effect on nano zinc oxide, improved compatibility of modified nano zinc oxide powder and polymer, and better antibacterial property, ultraviolet resistance and physical property when the surface modifier is used in food packaging.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.
Claims (8)
1. The preparation method of the modified nano zinc oxide powder is characterized by comprising the following steps: 1) Weighing 15-30 parts of absolute ethyl alcohol, 0.5-3 parts of betaine and 20-30 parts of water according to parts by weight, and uniformly mixing to obtain a first active liquid; immersing zinc oxide in the first active liquid, filtering and drying to obtain active zinc oxide; 2) Jet milling the active zinc oxide to obtain milled zinc oxide; 3) According to the weight portions, 10 to 20 portions of absolute ethyl alcohol, 0.01 to 0.05 portion of dodecylphenol polyoxyethylene ether and 10 to 30 portions of water are weighed and evenly mixed, and 2-hydroxysuccinic acid is added to adjust the PH to 5 to 6, so as to obtain a second active liquid; immersing the crushed zinc oxide in a second active liquid, filtering, drying and grinding to obtain active nano zinc oxide; 4) Uniformly mixing active nano zinc oxide and a surface modifier in a weight ratio of 1 (0.8-1.5), drying, and grinding to obtain modified nano zinc oxide powder with a particle size of 10-90 nm;
the surface modifier is prepared from the following raw materials in parts by weight: 0.1-0.3 part of polylysine-PEG copolymer, 10-20 parts of polyethylene glycol solution, 10-22 parts of organic acid solution, 1-3 parts of embryo Bei Nian protein solution, 1-3 parts of xanthan gum solution, 0.01-0.05 part of ammonium persulfate and 2-5 parts of chitosan;
the preparation of the surface modifier comprises the following steps: (1) According to the weight portions, chitosan is weighed and dissolved in an organic acid solution, heated to 65-85 ℃, and stirred for 1-3 hours to obtain a composite material A; (2) Weighing ammonium persulfate according to parts by weight, adding the ammonium persulfate into the composite material A obtained in the step (1), uniformly stirring, adding a polyethylene glycol solution, and stirring for 1-3 hours to obtain a composite material B; (3) Weighing xanthan gum solution, embryo Bei Nian protein solution and polylysine-PEG copolymer according to parts by weight, adding the xanthan gum solution, the embryo Bei Nian protein solution and the polylysine-PEG copolymer into the composite material B obtained in the step (2), stirring for 0.5-1h, and regulating the pH value to 4.5-5.5 to obtain the surface modifier.
2. The method for preparing the modified nano zinc oxide powder according to claim 1, which is characterized in that: the particle size of the crushed zinc oxide is 1-10 mu m; the particle size of the active nano zinc oxide is 5-50nm; the particle size of the zinc oxide is 0.1-1mm.
3. The method for preparing the modified nano zinc oxide powder according to claim 1, wherein the specific process in 2) is as follows: sequentially feeding and extruding active zinc oxide, pressurizing, introducing air flow, carrying out air flow crushing and deagglomeration, sieving formed powder, collecting qualified products, and carrying out air flow crushing on unqualified products again to obtain crushed zinc oxide; wherein the working pressure of the jet milling is 0.98-1.02MPa, and the air demand is 2-4m 3 And/or min.
4. A method for preparing a modified nano zinc oxide powder according to claim 3, characterized in that: the air flow crushing equipment is adopted in the step 2), and the air flow crushing equipment is sequentially provided with a feeding system, an air flow crushing classifier and a cloth bag collector according to the processing technology; the jet mill also comprises a material controller, and the feeding system, the jet mill classifier and the cloth bag collector are electrically connected with the material controller.
5. The method for preparing the modified nano zinc oxide powder according to claim 1, which is characterized in that: the organic acid solution is composed of citric acid, tartaric acid, salicylic acid and water.
6. The method for preparing the modified nano zinc oxide powder according to claim 5, which is characterized in that: the weight ratio of the citric acid to the tartaric acid to the salicylic acid to the water is (0.5-0.8): (0.2-0.5): (0.1-0.3):10.
7. A modified nano zinc oxide powder, characterized in that the particle size of the modified nano zinc oxide powder is 10-90nm, and the modified nano zinc oxide powder is prepared by the preparation method of the modified nano zinc oxide powder of any one of claims 1-6.
8. The application of the modified nano zinc oxide powder is characterized in that: use of a modified nano zinc oxide powder according to claim 7 in food packaging, said modified nano zinc oxide powder having a proportion of 1-20% in the food packaging.
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| KR100740275B1 (en) * | 2006-02-24 | 2007-07-18 | 주식회사 선진화학 | Method for preparing of zinc oxide powder with nano size |
| CN111924872A (en) * | 2020-08-10 | 2020-11-13 | 东莞世皓新材料生物科技有限公司 | Method for preparing modified nano zinc oxide by sol-gel process |
| CN113549343A (en) * | 2021-06-30 | 2021-10-26 | 科迈特新材料有限公司 | Modified nano zinc oxide compound for plastics and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100740275B1 (en) * | 2006-02-24 | 2007-07-18 | 주식회사 선진화학 | Method for preparing of zinc oxide powder with nano size |
| CN111924872A (en) * | 2020-08-10 | 2020-11-13 | 东莞世皓新材料生物科技有限公司 | Method for preparing modified nano zinc oxide by sol-gel process |
| CN113549343A (en) * | 2021-06-30 | 2021-10-26 | 科迈特新材料有限公司 | Modified nano zinc oxide compound for plastics and preparation method thereof |
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