CN115058107A - Antibacterial mildew-proof biodegradable polylactic acid plastic and preparation method thereof - Google Patents
Antibacterial mildew-proof biodegradable polylactic acid plastic and preparation method thereof Download PDFInfo
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- CN115058107A CN115058107A CN202210727283.4A CN202210727283A CN115058107A CN 115058107 A CN115058107 A CN 115058107A CN 202210727283 A CN202210727283 A CN 202210727283A CN 115058107 A CN115058107 A CN 115058107A
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- 239000004626 polylactic acid Substances 0.000 title claims abstract description 42
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 41
- 229920003023 plastic Polymers 0.000 title claims abstract description 34
- 239000004033 plastic Substances 0.000 title claims abstract description 34
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 26
- 239000010881 fly ash Substances 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 17
- 239000004014 plasticizer Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims abstract description 14
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 229940068041 phytic acid Drugs 0.000 claims abstract description 14
- 235000002949 phytic acid Nutrition 0.000 claims abstract description 14
- 239000000467 phytic acid Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 239000011347 resin Substances 0.000 claims abstract description 11
- 229920005989 resin Polymers 0.000 claims abstract description 11
- 229920001661 Chitosan Polymers 0.000 claims abstract description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 10
- 230000003449 preventive effect Effects 0.000 claims abstract description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- 239000006185 dispersion Substances 0.000 claims abstract description 9
- 229910052709 silver Inorganic materials 0.000 claims abstract description 8
- 239000004332 silver Substances 0.000 claims abstract description 8
- 238000005119 centrifugation Methods 0.000 claims abstract description 7
- 239000002131 composite material Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000002105 nanoparticle Substances 0.000 claims description 16
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 15
- 229910052725 zinc Inorganic materials 0.000 claims description 12
- 239000011701 zinc Substances 0.000 claims description 12
- 239000011246 composite particle Substances 0.000 claims description 10
- 238000004806 packaging method and process Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 claims description 7
- 101710134784 Agnoprotein Proteins 0.000 claims description 6
- 238000000071 blow moulding Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 4
- TWFZGCMQGLPBSX-UHFFFAOYSA-N Carbendazim Natural products C1=CC=C2NC(NC(=O)OC)=NC2=C1 TWFZGCMQGLPBSX-UHFFFAOYSA-N 0.000 claims description 3
- 239000005747 Chlorothalonil Substances 0.000 claims description 3
- 239000006013 carbendazim Substances 0.000 claims description 3
- JNPZQRQPIHJYNM-UHFFFAOYSA-N carbendazim Chemical compound C1=C[CH]C2=NC(NC(=O)OC)=NC2=C1 JNPZQRQPIHJYNM-UHFFFAOYSA-N 0.000 claims description 3
- CRQQGFGUEAVUIL-UHFFFAOYSA-N chlorothalonil Chemical compound ClC1=C(Cl)C(C#N)=C(Cl)C(C#N)=C1Cl CRQQGFGUEAVUIL-UHFFFAOYSA-N 0.000 claims description 3
- 239000004308 thiabendazole Substances 0.000 claims description 3
- 235000010296 thiabendazole Nutrition 0.000 claims description 3
- WJCNZQLZVWNLKY-UHFFFAOYSA-N thiabendazole Chemical compound S1C=NC(C=2NC3=CC=CC=C3N=2)=C1 WJCNZQLZVWNLKY-UHFFFAOYSA-N 0.000 claims description 3
- 229960004546 thiabendazole Drugs 0.000 claims description 3
- 230000000052 comparative effect Effects 0.000 abstract description 10
- 230000004888 barrier function Effects 0.000 abstract description 7
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 abstract description 4
- -1 silver ions Chemical class 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract description 3
- 230000000536 complexating effect Effects 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract description 2
- 238000009456 active packaging Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 235000013305 food Nutrition 0.000 description 5
- 230000000845 anti-microbial effect Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000005022 packaging material Substances 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- 241000228197 Aspergillus flavus Species 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
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- 238000011161 development Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
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- 239000002253 acid Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
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- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- HPXRVTGHNJAIIH-PTQBSOBMSA-N cyclohexanol Chemical group O[13CH]1CCCCC1 HPXRVTGHNJAIIH-PTQBSOBMSA-N 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
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- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000009920 food preservation Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
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- 150000007523 nucleic acids Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000012536 packaging technology Methods 0.000 description 1
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- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
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- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/14—Gas barrier composition
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention relates to an antibacterial mildew-proof biodegradable polylactic acid plastic and a preparation method thereof, belonging to the technical field, and comprising the following raw materials: polylactic resin, an antibacterial agent, a mildew preventive and a plasticizer; the antibacterial agent is prepared by the following steps: dispersing the fly ash-zinc-silver nano particles in deionized water under ultrasonic, adding phytic acid aqueous solution after uniform dispersion, stirring for 15min, and obtaining the antibacterial agent through centrifugation, washing and drying. According to the technical scheme, the phytic acid is used for complexing silver ions and zinc ions and then coated on the fly ash, the functional coordination compound can promote the uniform dispersion of the fly ash in a PLA matrix, the better interface compatibility and interaction between the fly ash and PLA are facilitated, the polyethylene glycol and the chitosan are used as the composite plasticizer, the plasticity of the plastic is increased, the thermal property of the plastic is also increased, and the prepared plastic has better mechanical, antibacterial and gas barrier properties compared with a comparative example.
Description
Technical Field
The invention belongs to the technical field of plastics, and particularly relates to an antibacterial mildew-proof biodegradable polylactic acid plastic and a preparation method thereof.
Background
Food safety issues have led to the development and related applications of active packaging materials. Active packaging can extend the shelf life of food products by increasing the gas barrier, antimicrobial, and antioxidant properties of the packaging material. Meanwhile, as a promising form of active packaging, antibacterial packaging is advantageous for food preservation because active packaging can retard food spoilage by inactivating or inhibiting the growth of various microorganisms. Therefore, while the gas barrier property of the packaging material is reduced, the adoption of a proper antibacterial packaging technology is an effective way for prolonging the shelf life of the food, the living standard of people is gradually improved along with the development of the country, the health consciousness of people and the consciousness of environmental protection are increasingly strengthened, and the establishment of comfortable, clean, antibacterial and mildewproof living, learning and working environments for preventing the spread of diseases is an enthusiastic pursuit of people. The product waste can be automatically biodegraded, and the environmental pollution is not a pressing requirement of the international environmental protection business at present. Unfortunately, people are creating favorable conditions for the propagation and growth of microorganisms and bacteria while improving their living environment. The increasing white pollution also puts a great strain on the environment on which we live.
Polylactic acid (PLA) is obtained by polycondensation of lactic acid obtained after fermentation of starch. The polylactic acid has good biodegradation performance, and degradation products are carbon dioxide and water, so that no adverse effect is generated on the environment. The polylactic acid has wide application prospect in the fields of food packaging, fiber textile, daily plastic and the like. PLA is considered a valuable candidate for replacing petroleum-based polymers in many fields (packaging, medicine, agriculture, etc.) because of its good optical, thermo-mechanical properties and processability. However, both the gas barrier properties and the antimicrobial properties of pure PLA are difficult to meet with active packaging requirements in view of various packaging conditions.
Disclosure of Invention
The invention aims to provide an antibacterial mildew-proof biodegradable polylactic acid plastic and a preparation method thereof.
The technical problems to be solved by the invention are as follows: both the gas barrier and the antimicrobial properties of pure PLA are difficult to meet with the requirements for active packaging.
The purpose of the invention can be realized by the following technical scheme:
an antibacterial mildew-proof biodegradable polylactic acid plastic comprises the following raw materials in parts by mass: 60-90 parts of polylactic resin, 3-5 parts of an antibacterial agent, 1-2 parts of a mildew preventive and 1-3 parts of a plasticizer;
the antibacterial agent is prepared by the following steps:
dispersing the fly ash-zinc-silver nano particles in deionized water under ultrasonic, adding phytic acid aqueous solution after uniform dispersion, stirring for 15min, and obtaining the antibacterial agent through centrifugation, washing and drying.
Further, the using amount ratio of the fly ash-zinc-silver nano particles to the deionized water to the phytic acid aqueous solution is 0.05-0.1 g: 80-120 mL: 0.1-0.2 g.
Further, the fly ash-zinc-silver nano particles are prepared by the following steps:
s1, dispersing the fly ash and zinc acetate dihydrate in deionized water, continuously stirring at 500rpm for 20min, dropwise adding a NaOH solution with the mass fraction of 12%, adjusting the pH to 12, heating at 160 ℃ for 6h, filtering, washing and drying at 80 ℃ to obtain fly ash-zinc nanoparticles;
s2, putting the fly ash-zinc nano particles into a nitric acid solution with the volume fraction of 5-10% under the stirring state, transferring the mixed solution into a polytetrafluoroethylene-lined autoclave, filtering, and dropwise adding AgNO into the solid 3 ·6H 2 O and stirring for 2 hours, filtering, washing and drying,obtaining the fly ash-zinc-silver nano particles.
Further, in step S1, the usage ratio of the fly ash, zinc acetate dihydrate and NaOH solution is 2-4 g: 3-15 g: 40-60 mL.
Further, in step S2, the ratio of the used amounts of the fly ash-zinc nanoparticles, the nitric acid solution and the AgNO 3.6H 2O is 0.05-0.1 g: 40-60 mL: 0.01-0.02 g.
Further, the mildew preventive is one of thiabendazole, chlorothalonil and carbendazim.
Further, the plasticizer is a mixture of polyethylene glycol and a chitosan solution, wherein the mass ratio of the polyethylene glycol to the chitosan solution is 5: 1-3.
A preparation method of antibacterial mildew-proof biodegradable polylactic acid plastic comprises the following steps:
a1, weighing the raw materials according to the mass parts of the formula, uniformly mixing the polylactic resin, the antibacterial agent and the mildew preventive, extruding the mixture by an extruder to prepare a master batch, and cooling and granulating the master batch;
a2, adding the master batch into an extruder, and then adding a plasticizer, wherein the temperature of the extruder is controlled to be between 140 ℃ and 240 ℃ to obtain composite particles;
and A3, blow molding and packaging the composite particles to prepare the antibacterial mildew-proof biodegradable polylactic acid plastic.
The invention has the beneficial effects that:
(1) in the technical scheme of the invention, in the fly ash-zinc-silver nano particles, a compact protective film on the surface of the fly ash is damaged and SiO is dissociated in the fly ash under an alkaline environment 2 The activity of the fly ash is improved, so that part of surface particles are negatively charged, the adsorption of zinc ions in a system is realized, the porosity and the specific surface area of the fly ash are increased after the fly ash is treated by an acid solution, the deposition of silver ions on the fly ash is realized, and the zinc ions after the hydrothermal treatment are converted into ZnO, however, the Ag is introduced + On one hand, the sterilization effect is achieved (the sterilization effect is that the sterilization effect is achieved, the electrostatic adsorption is generated with the cell wall, the cell wall is deformed, the reaction is generated with protein and nucleic acid in the cell, and the growth and the propagation of the aspergillus flavus are damaged); on the other hand, Ag + Can enhance the photocatalytic antibacterial activity of ZnOThe cell composition of the mould is destroyed, and the synergistic bacteriostasis effect is achieved.
(2) In the technical scheme of the invention, the phytic acid is symmetrically connected to the cyclohexanol ring through six phosphate groups and can interact with positively charged metal ions and biomolecules, so that the phytic acid is chelated with silver ions in the fly ash-zinc-silver nano particles and is coated on the surface of the fly ash, and the fly ash-zinc-silver nano particles coated with the phytic acid can be better dispersed in PLA (polylactic acid), so that the mechanical and gas barrier properties of the PLA (polylactic acid) are remarkably improved.
(3) In the technical scheme of the invention, the terminal hydroxyl and carboxyl in the PLA chain can reduce the thermal stability of the polymer, and the addition of PEG into the PLA matrix can play a role in plasticization, but the hydroxyl is introduced into the composite material and can also reduce the thermal stability, and the chitosan is introduced, so that the terminal hydroxyl and carboxyl in the PLA chain can be neutralized, and the antibacterial purpose can be achieved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The fly ash-zinc-silver nano particle is prepared by the following steps:
s1, dispersing 2g of fly ash and 3g of zinc acetate dihydrate in deionized water, continuously stirring at 500rpm for 20min, dropwise adding 40mL of 12% NaOH solution by mass fraction, adjusting the pH to 12, filtering, washing and drying at 80 ℃ to obtain fly ash-zinc nanoparticles;
s2, putting 0.05g of fly ash-zinc nano particles into 40mL of nitric acid solution with volume fraction of 5% under the stirring state, transferring the mixed solution into a polytetrafluoroethylene-lined autoclave, heating for 6h at 160 ℃, filtering, and then dropwise adding 0.01g of A into the solidgNO 3 ·6H 2 And O, stirring for 2 hours, filtering, washing and drying to obtain the fly ash-zinc-silver nano particles.
Example 2
The fly ash-zinc-silver nano particle is prepared by the following steps:
s1, dispersing 3g of fly ash and 8g of zinc acetate dihydrate in deionized water, continuously stirring at 500rpm for 20min, dropwise adding 50mL of 12% NaOH solution by mass fraction, adjusting the pH to 12, filtering, washing and drying at 80 ℃ to obtain fly ash-zinc nanoparticles;
s2, placing 0.08g of fly ash-zinc nano particles into 50mL of nitric acid solution with volume fraction of 8% under the stirring state, transferring the mixed solution into a polytetrafluoroethylene-lined autoclave, heating for 6h at 160 ℃, filtering, and dropwise adding 0.015g of AgNO into the solid 3 ·6H 2 And O, stirring for 2 hours, filtering, washing and drying to obtain the fly ash-zinc-silver nano particles.
Example 3
The fly ash-zinc-silver nano particle is prepared by the following steps:
s1, dispersing 4g of fly ash and 15g of zinc acetate dihydrate in deionized water, continuously stirring at 500rpm for 20min, dropwise adding 60mL of 12% NaOH solution by mass fraction, adjusting the pH to 12, filtering, washing and drying at 80 ℃ to obtain fly ash-zinc nanoparticles;
s2, putting 0.1g of fly ash-zinc nano particles into 60mL of nitric acid solution with volume fraction of 10% under the stirring state, transferring the mixed solution into a polytetrafluoroethylene-lined autoclave, heating at 160 ℃ for 6h, filtering, and then dropwise adding 0.02g of AgNO into the solid 3 ·6H 2 And O, stirring for 2 hours, filtering, washing and drying to obtain the fly ash-zinc-silver nano particles.
Comparative example 1
This comparative example is the material prepared in step S1 of example 2.
Example 4
The antibacterial agent is prepared by the following steps:
0.05g of fly ash-zinc-silver nano particles prepared in the example 1 are dispersed in 80mL of deionized water under ultrasonic wave, after uniform dispersion, 0.1g of phytic acid aqueous solution is added, stirred for 15min, and the antibacterial agent is obtained through centrifugation, washing and drying.
Example 5
The antibacterial agent is prepared by the following steps:
0.08g of fly ash-zinc-silver nano particles prepared in the example 2 are dispersed in 100mL of deionized water under ultrasonic wave, after uniform dispersion, 0.15g of phytic acid aqueous solution is added, stirred for 15min, and the antibacterial agent is obtained through centrifugation, washing and drying.
Example 6
The antibacterial agent is prepared by the following steps:
0.1g of fly ash-zinc-silver nano particles prepared in the embodiment 3 are dispersed in 120mL of deionized water under ultrasonic wave, after uniform dispersion, 0.2g of phytic acid aqueous solution is added, stirred for 15min, and the antibacterial agent is obtained through centrifugation, washing and drying.
Comparative example 2
The antibacterial agent is prepared by the following steps:
0.1g of fly ash-zinc-silver nano particles prepared in the comparative example 1 are dispersed in 120mL of deionized water under ultrasonic wave, 0.2g of phytic acid aqueous solution is added after uniform dispersion, stirring is carried out for 15min, and the antibacterial agent is obtained through centrifugation, washing and drying.
Example 7
An antibacterial mildew-proof biodegradable polylactic acid plastic comprises the following raw materials in parts by mass: 60 parts of polylactic resin, 3 parts of the antibacterial agent prepared in example 4, 1 part of thiabendazole and 1 part of plasticizer (the mass ratio of polyethylene glycol to chitosan solution is 5: 1);
the method comprises the following steps:
a1, weighing the raw materials according to the mass parts of the formula, uniformly mixing the polylactic resin, the antibacterial agent and the mildew preventive, extruding the mixture by an extruder to prepare a master batch, and cooling and granulating the master batch;
a2, adding the master batch into an extruder, and then adding a plasticizer, wherein the temperature of the extruder is controlled to be 140 ℃ to obtain composite particles;
and A3, blow molding and packaging the composite particles to prepare the antibacterial mildew-proof biodegradable polylactic acid plastic.
Example 8
An antibacterial mildew-proof biodegradable polylactic acid plastic comprises the following raw materials in parts by mass: 75 parts of polylactic resin, 4 parts of the antibacterial agent prepared in example 5, 1.5 parts of chlorothalonil and 2 parts of plasticizer (the mass ratio of polyethylene glycol to chitosan solution is 5: 2);
the method comprises the following steps:
a1, weighing the raw materials according to the mass parts of the formula, uniformly mixing the polylactic resin, the antibacterial agent and the mildew preventive, extruding the mixture by an extruder to prepare a master batch, and cooling and granulating the master batch;
a2, adding the master batch into an extruder, and then adding a plasticizer, wherein the temperature of the extruder is controlled to be 200 ℃ to obtain composite particles;
and A3, blow molding and packaging the composite particles to prepare the antibacterial mildew-proof biodegradable polylactic acid plastic.
Example 9
An antibacterial mildew-proof biodegradable polylactic acid plastic comprises the following raw materials in parts by mass: 90 parts of polylactic resin, 5 parts of the antibacterial agent prepared in example 6, 2 parts of carbendazim and 3 parts of plasticizer (the mass ratio of polyethylene glycol to chitosan solution is 5: 3);
the method comprises the following steps:
a1, weighing the raw materials according to the mass parts of the formula, uniformly mixing the polylactic resin, the antibacterial agent and the mildew preventive, extruding the mixture by an extruder to prepare a master batch, and cooling and granulating the master batch;
a2, adding the master batch into an extruder, and then adding a plasticizer, wherein the temperature of the extruder is controlled to be 240 ℃ to obtain composite particles;
and A3, blow molding and packaging the composite particles to prepare the antibacterial mildew-proof biodegradable polylactic acid plastic.
Comparative example 3
This comparative example is different from example 9 in that the antibacterial agent prepared in example 6 was replaced with the substance prepared in comparative example 2, and the rest of the procedure and the raw materials were synchronized in example 9.
The polylactic acid plastics prepared in examples 7 to 9 and comparative example 3 were subjected to a performance test, the polylactic acid plastics were prepared into sample bars, and tensile properties were tested, and the antibacterial properties of the treated leathers were tested against Candida albicans and Aspergillus flavus of fungi and molds according to GB/T1040-1992 test method for tensile properties of plastics, which was in accordance with QB/T4199 and 2011, and the test results are shown in Table 1 below.
TABLE 1
As shown in the above table 1, the functional coordination compound can promote the uniform dispersion of the fly ash in the PLA matrix by complexing the silver ions and the zinc ions with the phytic acid and then coating the complex on the fly ash, which is beneficial to the better interface compatibility and interaction between the fly ash and the PLA, and the polyethylene glycol and the chitosan are used as the composite plasticizer, so that the plasticity of the plastic is increased, the thermal property of the plastic is also increased, and the prepared plastic has better mechanical, antibacterial and gas barrier properties compared with a comparative example.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (8)
1. An antibacterial mildew-proof biodegradable polylactic acid plastic is characterized in that: the composite material comprises the following raw materials in parts by mass: 60-90 parts of polylactic resin, 3-5 parts of an antibacterial agent, 1-2 parts of a mildew preventive and 1-3 parts of a plasticizer;
the antibacterial agent is prepared by the following steps:
dispersing the fly ash-zinc-silver nano particles in deionized water under ultrasonic, adding phytic acid aqueous solution after uniform dispersion, stirring for 15min, and obtaining the antibacterial agent through centrifugation, washing and drying.
2. The antibacterial and mildewproof biodegradable polylactic acid plastic as claimed in claim 1, wherein: the dosage ratio of the fly ash-zinc-silver nano particles, the deionized water and the phytic acid aqueous solution is 0.05-0.1 g: 80-120 mL: 0.1-0.2 g.
3. The antibacterial and mildewproof biodegradable polylactic acid plastic as claimed in claim 1, wherein: the fly ash-zinc-silver nano particle is prepared by the following steps:
s1, dispersing the fly ash and zinc acetate dihydrate in deionized water, continuously stirring at 500rpm for 20min, dropwise adding a NaOH solution with the mass fraction of 12%, adjusting the pH to 12, filtering, washing and drying at 80 ℃ to obtain fly ash-zinc nanoparticles;
s2, putting the fly ash-zinc nano particles into a nitric acid solution with the volume fraction of 5-10% under the stirring state, transferring the mixed solution into a polytetrafluoroethylene-lined autoclave, heating for 6 hours at 160 ℃, filtering, and then dropwise adding AgNO into the solid 3 ·6H 2 And O, stirring for 2 hours, filtering, washing and drying to obtain the fly ash-zinc-silver nano particles.
4. The antibacterial and mildewproof biodegradable polylactic acid plastic as claimed in claim 3, wherein: in step S1, the usage ratio of the fly ash, the zinc acetate dihydrate and the NaOH solution is 2-4 g: 3-15 g: 40-60 mL.
5. The antibacterial and mildewproof biodegradable polylactic acid plastic as claimed in claim 3The method is characterized in that: in step S2, fly ash-zinc nanoparticles, nitric acid solution and AgNO 3 ·6H 2 The dosage ratio of O is 0.05-0.1 g: 40-60 mL: 0.01-0.02 g.
6. The antibacterial and mildewproof biodegradable polylactic acid plastic as claimed in claim 1, wherein: the mildew preventive is one of thiabendazole, chlorothalonil and carbendazim.
7. The antibacterial and mildewproof biodegradable polylactic acid plastic and the preparation method thereof according to claim 1 are characterized in that: the plasticizer is a mixture of polyethylene glycol and a chitosan solution, wherein the mass ratio of the polyethylene glycol to the chitosan solution is 5: 1-3.
8. A method for preparing the antibacterial and mildewproof biodegradable polylactic acid plastic as claimed in any one of claims 1 to 7, which is characterized in that: the method comprises the following steps:
a1, weighing the raw materials according to the mass parts of the formula, uniformly mixing the polylactic resin, the antibacterial agent and the mildew preventive, extruding the mixture by an extruder to prepare a master batch, and cooling and granulating the master batch;
a2, adding the master batch into an extruder, and then adding a plasticizer, wherein the temperature of the extruder is controlled to be between 140 ℃ and 240 ℃ to obtain composite particles;
and A3, blow molding and packaging the composite particles to prepare the antibacterial mildew-proof biodegradable polylactic acid plastic.
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| CN1923891A (en) * | 2006-09-21 | 2007-03-07 | 同济大学 | Anti-bacterium mildew-proof biodegradable polylactic acid foam plastic and preparation method thereof |
| JP2015063645A (en) * | 2013-09-26 | 2015-04-09 | 日本電気株式会社 | Polylactic acid-based resin composition and molded article prepared using the same |
| CN114573962A (en) * | 2022-04-01 | 2022-06-03 | 安徽海铭塑业有限公司 | Degradable food packaging material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1923891A (en) * | 2006-09-21 | 2007-03-07 | 同济大学 | Anti-bacterium mildew-proof biodegradable polylactic acid foam plastic and preparation method thereof |
| JP2015063645A (en) * | 2013-09-26 | 2015-04-09 | 日本電気株式会社 | Polylactic acid-based resin composition and molded article prepared using the same |
| CN114573962A (en) * | 2022-04-01 | 2022-06-03 | 安徽海铭塑业有限公司 | Degradable food packaging material |
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