CN111607207B - Expandable biodegradable particles and biodegradable foaming beads with antibacterial function - Google Patents
Expandable biodegradable particles and biodegradable foaming beads with antibacterial function Download PDFInfo
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- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
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- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/18—Binary blends of expanding agents
- C08J2203/184—Binary blends of expanding agents of chemical foaming agent and physical blowing agent, e.g. azodicarbonamide and fluorocarbon
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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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Abstract
The invention provides an expandable biodegradable particle, which is a multilayer core-shell structure at least comprising a hydrolysis sacrificial outer layer, an antibacterial intermediate layer and a biodegradable core layer, wherein the hydrolysis sacrificial outer layer contains a biodegradable material and a hydrolysis resistance agent, the antibacterial intermediate layer contains a biodegradable material and an antibacterial agent, and the biodegradable core layer contains a biodegradable material and a nucleating agent. This expandable biodegradable particle can be foamed in the aqueous phase disperse system, and in the foaming process, the sacrificial skin of hydrolysising dissolves gradually, and when the foaming of biodegradable sandwich layer was accomplished and breaks away from the aqueous phase disperse system, the sacrificial skin of hydrolysising just dissolved completely. Because the outer layer is sacrificed by hydrolysis, the expandable biodegradable particles can be prepared from common biodegradable materials by foaming in an aqueous phase system by using an intermittent high-pressure foaming kettle, and can maintain a stable cellular structure. Meanwhile, the antibacterial agent is only added in the antibacterial layer, so that the addition amount of the antibacterial agent can be reduced, and the cost is reduced.
Description
Technical Field
The invention relates to an expandable biodegradable particle, biodegradable expanded beads with an antibacterial function and a preparation method thereof, belonging to the field of biodegradable materials.
Background
The foaming material has light weight, good heat insulation, buffering and sound insulation effects, high strength and low production energy consumption, and is widely applied to many fields. The foamed materials in the market comprise foamed polyethylene, foamed polypropylene, foamed polystyrene and other blended or copolymerized foamed resins. However, most of them are non-biodegradable materials, and the use of a large amount of them causes serious environmental pollution. Since 2018, developed countries such as europe and the united states have begun to popularize foaming materials with less pollution and environmental protection, so as to reduce the burden of the environment. Therefore, the development of biodegradable foamed materials is urgently needed.
At present, the biodegradable materials which can be industrially and stably produced mainly comprise: polylactic acid, poly adipic acid-butylene terephthalate copolymer, poly butylene succinate and the like, and the foaming material prepared from the materials can effectively solve the problems of environmental pollution and the like. However, when the biodegradable materials such as polylactic acid are applied to non-disposable packages contacting with food or in the field needing no bacteria or less bacteria, the biodegradable materials are easy to be infected with and breed various microorganisms due to the lack of antibacterial property, so that pathogenic bacteria and the like cause potential harm to the health of people. In recent years, with the improvement of living standard and the enhancement of health consciousness of people, the demand of antibacterial material products is increasing, so that the development of biodegradable foam materials with antibacterial function is important.
The patent application CN110615975A of China petrochemical company Limited discloses an antibacterial and mildewproof polylactic acid composition, foamed beads, a preparation method thereof and a molded body, wherein the preparation method of the foamed beads is to uniformly disperse an antibacterial and mildewproof auxiliary agent in a polylactic acid biodegradable composition for granulation and foaming. In order to achieve a certain antibacterial effect, the content of the antibacterial agent in the polylactic acid biodegradable bead is high. The high content of the antibacterial agent can inhibit the microbial activity of the polylactic acid foaming product in the later-stage composting treatment, seriously influences the degradation rate and cannot achieve the aim of biodegradation in a short time.
Disclosure of Invention
The invention aims to overcome the problem of slow degradation of antibacterial biodegradable materials, simultaneously adopts a method of a hydrolysis protective layer to break through the limitation of easy hydrolysis of biodegradable materials such as polylactic acid and the like, and adopts a traditional intermittent high-pressure foaming kettle to prepare biodegradable beads and foaming products which have antibacterial function, high foaming ratio, light weight and good buffering performance in a water-phase dispersion system.
The invention provides an expandable biodegradable particle, which is a multilayer core-shell structure at least comprising a hydrolysis sacrificial outer layer, an antibacterial intermediate layer and a biodegradable core layer, wherein the hydrolysis sacrificial outer layer contains a biodegradable material and a hydrolysis resistant agent, the antibacterial intermediate layer contains a biodegradable material and an antibacterial agent, the biodegradable core layer contains a biodegradable material and a nucleating agent, the expandable biodegradable particle can be foamed in an aqueous dispersion system, the hydrolysis sacrificial outer layer is gradually dissolved in the foaming process, and when the foaming of the biodegradable core layer is finished and the biodegradable core layer is separated from the aqueous dispersion system, the hydrolysis sacrificial outer layer is just completely dissolved.
The sacrificial layer of hydrolysising provides the guard action for the biodegradable particle of can expanding in aqueous phase disperse system foaming, can protect antibiotic intermediate level and biodegradable sandwich layer not by hydrolysising, and when the particle was dispersed in aqueous phase, the sacrificial layer of hydrolysising dissolved gradually with certain speed, when treating that the particle foaming is accomplished and break away from aqueous phase system, the sacrificial layer of hydrolysising just in time was dissolved totally. The thickness of the hydrolyzed sacrificial layer needs to be precisely controlled: if the thickness is too thin, not only the hydrolysis sacrificial layer on the outer layer but also the antibacterial layer on the middle layer can be hydrolyzed in the foaming process, and the material can lose the antibacterial function; if the thickness is too thick, the hydrolysis sacrificial layer still remains after the foaming process is finished, the antibacterial layer cannot be exposed outside the foaming beads, and the antibacterial function of the material is also limited.
In the expandable biodegradable microparticle, the hydrolysis sacrificial outer layer contains 80-99.9 wt% of biodegradable material and 0.1-20 wt% of hydrolysis resistance agent, and more preferably contains 90-99 wt% of biodegradable material and 1-10 wt% of hydrolysis resistance agent. The antibacterial intermediate layer contains 70-99.9 wt% of biodegradable material and 0.1-30 wt% of antibacterial agent, and more preferably contains 80-99 wt% of biodegradable material and 1-20 wt% of antibacterial agent. The biodegradable core layer contains 50-99.9 wt% of biodegradable material and 0.01-5 wt% of nucleating agent, and more preferably contains 70-99 wt% of biodegradable material and 0.01-3 wt% of nucleating agent.
In the expandable biodegradable microparticles, the hydrolysis sacrificial outer layer accounts for 1-10 wt%, the antibacterial intermediate layer accounts for 1-10 wt%, and the biodegradable core layer accounts for 80-98 wt%, based on the total mass of the expandable biodegradable microparticles. More preferably, the hydrolysis sacrificial outer layer accounts for 1-5 wt%, the antibacterial middle layer accounts for 1-5 wt%, and the biodegradable core layer accounts for 90-98 wt%.
In the expandable biodegradable microparticle, the biodegradable core layer further contains an auxiliary agent, and the auxiliary agent comprises at least one of a lubricant, a chain extender and an antioxidant.
In the expandable biodegradable microparticles, the biodegradable material comprises at least one of polylactic acid, poly (butylene adipate-terephthalate) copolymer and poly (butylene succinate).
In the expandable biodegradable microparticles, the contents of the components are as follows: 50-100 parts of polylactic acid, 0-40 parts of poly (butylene adipate-terephthalate) copolymer, 0-40 parts of poly (butylene succinate), 0.01-5 parts of nucleating agent, 0.01-10 parts of lubricant, 0.01-10 parts of chain extender, 0.01-10 parts of antioxidant, 0.01-5 parts of antibacterial agent and 0.01-5 parts of hydrolysis resistant agent.
In the expandable biodegradable microparticle, the polylactic acid is one or more of L-lactic acid homopolymer, D-lactic acid homopolymer and copolymer of L-lactic acid and D-lactic acid. The weight of the polylactic acid accounts for 50-99.8 wt% of the total weight of the expandable biodegradable particles, and more preferably accounts for 80-95 wt%.
In the expandable biodegradable microparticles, the melt flow rate of the polybutylene adipate-terephthalate copolymer is 1 to 10g/10min, preferably 1 to 5g/10min, and more preferably 2 to 5g/10 min. The polybutylene adipate-terephthalate copolymer constitutes 0-40 wt%, more preferably 0-20 wt% of the total weight of the expandable biodegradable microparticles.
In the expandable biodegradable particles, the nucleating agent is one or a mixture of more of talcum powder, montmorillonite, azodicarbonamide, ethylene bis stearamide, barium azodicarboxylate, diisopropyl azodicarboxylate, N-dinitrosopentamethylene tetramine and 4, 4' -oxydiphenylsulfonylhydrazide in any proportion. The nucleating agent mainly plays a role in promoting foaming, and the proper selection of the nucleating agent can adjust the cell size of the expanded beads and improve the uniformity of cell density. The nucleating agent is preferably azodicarbonamide and is present in an amount of 0.01 to 5 wt%, more preferably 0.01 to 3 wt%, based on the total weight of the expandable biodegradable microparticles.
In the expandable biodegradable particles, the antibacterial agent comprises ammonium dihydrogen phosphate, lithium carbonate, silver salt containing nano-silver or silver ions, copper salt, zinc salt, vanillin or ethyl vanillin compounds, acylanilines, quaternary ammonium salts, biguanidine, phenols, chitin and derivatives thereof and the like. The antibacterial agent is preferably chitin and its derivatives, more preferably chitosan, and is 0.01-5 wt%, more preferably 0.01-3 wt% of the total weight of the expandable biodegradable microparticles.
In the expandable biodegradable particles, the antioxidant is one or a mixture of hindered phenols, hindered amines, phosphites and the like according to any proportion. The antioxidant is preferably 1, 3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, and is 0-10 wt%, more preferably 0.01-5 wt%, of the total weight of the expandable biodegradable microparticles.
In the expandable biodegradable particles, the hydrolysis resistance agent is one or a mixture of more of carbonized diamine, glycidyl ether, triglycidyl isocyanate and the like according to any proportion. The hydrolysis resistant agent is preferably a carbonized diamine, and accounts for 0.01-5 wt%, more preferably 0.01-3 wt% of the total weight of the expandable biodegradable particles.
In the expandable biodegradable particles, the chain extender is one or a mixture of more of oxazoline, isocyanate, maleic anhydride and the like according to any proportion. The chain extender is preferably styrene-methyl methacrylate-glycidyl methacrylate copolymer, and accounts for 0-10 wt%, more preferably 0.01-5 wt% of the total weight of the expandable biodegradable microparticles.
In the expandable biodegradable particles, the foaming agent is one or a mixture of more of air, carbon dioxide, butane, pentane, heptane and the like according to any proportion. The blowing agent is preferably carbon dioxide.
The invention also provides a method for preparing the expandable biodegradable particles, which comprises the steps of mixing and co-extruding the raw materials of the hydrolysis sacrificial outer layer, the antibacterial middle layer and the biodegradable core layer by a core-shell multilayer co-extrusion process, and then granulating by a granulator to obtain the expandable biodegradable particles, wherein the weight of each single expandable biodegradable particle is 0.1-5 mg. Because the hydrolysis sacrificial layer, the antibacterial layer and the biodegradable layer are made of the same biodegradable material as the base material, different layers are tightly welded, the compatibility is good, and the structural integrity of the multilayer particles cannot be damaged in the granulating process. And the cross section area of the particles before foaming is very small, and the exposed biodegradable core layer at the section cannot be influenced by hydrolysis.
In the method for the expandable biodegradable particles, the three-layer extrusion rate ratio is 1:1: 98-10: 10:80, preferably 1:1: 98-5: 5: 90. The extrusion temperature was 100-200 ℃. The thicknesses of the hydrolysis sacrificial outer layer, the antibacterial middle layer and the biodegradable core layer can be controlled by adjusting the extrusion rate ratio of the three layers, and the faster the extrusion rate is, the thicker the corresponding layer thickness is.
The invention also provides biodegradable foaming beads with an antibacterial function, which are obtained by foaming the expandable biodegradable particles in an aqueous phase dispersion system. The antibacterial layer mainly provides the required antibacterial property for the foaming product, and the biodegradable foaming core layer provides sufficient mechanical property and degradable environmental protection property.
The foaming is carried out in a high-pressure foaming kettle, the foaming multiplying power is 5-50 times, and the density of the obtained foaming beads is 25-260 g/L.
The invention also provides a method for preparing the biodegradable foam bead with the antibacterial function, which comprises the following steps: adding a gaseous physical foaming agent into a high-pressure foaming kettle, and uniformly dispersing the expandable biodegradable particles in a water-phase dispersion medium; stirring at high temperature and high pressure, wherein the gaseous physical foaming agent can permeate into the expandable biodegradable particles under the action of the high temperature and high pressure, and finally the pressure inside and outside the expandable biodegradable particles is balanced; and then releasing the expandable biodegradable particles and the dispersion medium into the atmosphere with the pressure lower than that of the foaming kettle, and instantly expanding the expandable biodegradable particles under the action of pressure difference under high pressure inside the expandable biodegradable particles, so as to prepare the biodegradable foamed beads with the antibacterial function.
In the method for preparing the biodegradable expanded beads with the antibacterial function, the foaming temperature is 120-160 ℃, and the foaming pressure is 1-5 MPa.
The invention also provides a biodegradable foamed product with the antibacterial function, which is obtained by injecting the biodegradable foamed beads with the antibacterial function into a mold, heating by water vapor, cooling and shaping.
The invention has the following technical effects:
(1) the outer layer of the expandable biodegradable particle is coated with the hydrolysis sacrificial layer, so that the antibacterial intermediate layer and the biodegradable core layer are protected from hydrolysis in the foaming of the water-phase dispersion system, and the hydrolysis sacrificial layer is just completely dissolved when the foaming of the particle is finished and the particle is separated from the water-phase system. Common biodegradable materials and a conventional intermittent high-pressure foaming kettle can be adopted to foam in a water phase system, so that biodegradable foaming beads with an antibacterial function are obtained, and a stable cell structure can be maintained. The traditional method for preventing the biological material from hydrolyzing in the foaming process is to add a hydrolysis-resistant agent into the foaming material by blending, and the addition amount is usually large. In the case of biodegradable materials, large amounts of hydrolysis resistance agents can hinder the rate of hydrolysis of biodegradable materials in industrial composting processes.
(2) The antibacterial layer of the present invention provides an antibacterial function to the biodegradable expanded beads. The antibacterial agent is only added into the antibacterial layer, and the core layer is not added, so that the total addition amount of the antibacterial agent in the particles can be reduced, the cost is reduced, the activity of microorganisms of the later-stage biodegradable material during industrial composting is not hindered, the biodegradation rate is not delayed, and the biodegradation effect is not influenced.
Drawings
Fig. 1 is a schematic cross-sectional view of the expandable biodegradable microparticles of the present invention before and after foaming.
Fig. 2 is a cross-sectional SEM image of the biodegradable bead having antibacterial function of the present invention.
Fig. 3 is an SEM image of the antibacterial layer in the biodegradable bead having antibacterial function according to the present invention.
Detailed Description
Example 1
Fig. 1 is a schematic cross-sectional view of the inventive biodegradable expandable microparticles of the present invention before and after foaming. Before foaming, the expandable biodegradable particles are of a three-layer core-shell structure comprising a hydrolysis sacrificial outer layer 1, an antibacterial middle layer 2 and a biodegradable core layer 3. After foaming, the outer layer 1 is completely dissolved by hydrolysis, and cells 4 are formed in the biodegradable core layer 3, so that the biodegradable foamed bead with the antibacterial function is obtained.
Preparing the expandable biodegradable particles with the core-shell structure: uniformly mixing 90 parts by mass of polylactic acid resin and 10 parts by mass of carbonized diamine, putting the mixture into an extruder A, mixing 97.5 parts by mass of polylactic resin and 2.5 parts by mass of nano-silver antibacterial agent uniformly, putting into an extruder B, uniformly mixing 80 parts by mass of polylactic acid resin, 17.5 parts by mass of a polybutylene adipate-terephthalate copolymer, 1 part by mass of azodicarbonamide, 1 part by mass of 1, 3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene and 0.5 part by mass of an ethylene-methyl methacrylate-glycidyl methacrylate copolymer, feeding the mixture into an extruder C, the extruder A, B, C co-extruded at an extrusion rate of 3:3:94 to obtain the expandable biodegradable particles with the core-shell structure.
Preparation of biodegradable expanded beads with antibacterial function: and adding the expandable biodegradable particles with the core-shell structure into a high-pressure foaming kettle, introducing carbon dioxide, heating and pressurizing until the foaming temperature and the foaming pressure are set. And then releasing the pressure to the atmospheric pressure instantly to obtain the biodegradable expanded beads with antibacterial function.
Preparation of biodegradable foamed products with antibacterial function: and pressurizing the biodegradable foaming beads with the antibacterial function, injecting the beads into a flat plate mold with the length of 300mm, the width of 200mm and the thickness of 50mm, and heating by steam to obtain a cuboid biodegradable foaming product.
Example 2
Expandable biodegradable microparticles having a core-shell structure, biodegradable expanded beads having an antibacterial function, and biodegradable expanded products having an antibacterial function were prepared in the same manner as in example 1, except that chitosan was used instead of the nano-silver antibacterial agent in the antibacterial intermediate layer.
Example 3
Expandable biodegradable microparticles having a core-shell structure, biodegradable expanded beads having an antibacterial function, and biodegradable expanded products having an antibacterial function were prepared in the same manner as in example 1, except that 95 parts by mass of polylactic acid resin and 5 parts by mass of chitosan were used in the antibacterial intermediate layer.
Example 4
Expandable biodegradable fine particles having a core-shell structure, biodegradable expanded beads having an antibacterial function, and biodegradable expanded products having an antibacterial function were prepared in the same manner as in example 1, except that 92.5 parts by mass of polylactic acid resin and 7.5 parts by mass of chitosan were used in the antibacterial intermediate layer.
Example 5
Expandable biodegradable microparticles having a core-shell structure, biodegradable expanded beads having an antibacterial function, and biodegradable expanded products having an antibacterial function were prepared in the same manner as in example 1, except that 90 parts by mass of polylactic acid resin and 10 parts by mass of chitosan were used in the antibacterial intermediate layer.
Comparative example 1
Expandable biodegradable microparticles having a core-shell structure, biodegradable expanded beads having an antibacterial function, and biodegradable foamed products having an antibacterial function were prepared in the same manner as in example 1, except that the expandable biodegradable microparticles having a core-shell structure were obtained by co-extrusion using the extruder A, B, C at an extrusion rate of 1:3: 96.
Comparative example 2
Expandable biodegradable microparticles having a core-shell structure, biodegradable expanded beads having an antibacterial function, and biodegradable foamed products having an antibacterial function were prepared in the same manner as in example 1, except that the expandable biodegradable microparticles having a core-shell structure were obtained by co-extrusion using the extruder A, B, C at an extrusion rate of 6:3: 91.
The biodegradable foamed products having antibacterial function of examples 1-5 and comparative examples 1-2 were tested, and the test results are shown in table 1.
The antibacterial test is carried out according to CN110615975A, namely QB/T2591-2003A < antibacterial property test method and antibacterial effect of antibacterial plastics >, and the bacteria for detection: escherichia coli ATCC 25922, Staphylococcus aureus ATCC 6538. The sample piece is soaked in hot water at 50 ℃ for 16h before the antibacterial test.
The test procedure was as follows: and (3) sterilizing a sample to be detected by using 75% ethanol, drying the sample, and diluting the strain into a bacterial suspension with a proper concentration by using sterile water for later use. 0.2mL of the bacterial suspension was dropped on the surface of the sample, and a polylactic acid film (4.0 cm. times.4.0 cm) having a thickness of 0.1mm was coated thereon to form a uniform liquid film between the sample and the film. Culturing at 37 ℃ for 18-24 hours with the relative humidity of 90%. The bacterial liquid is washed by sterile water, diluted to a proper concentration gradient, and 0.1mL of the bacterial liquid is uniformly coated on the prepared sterile agar culture medium. The culture was carried out at 37 ℃ for 18 to 24 hours, and the results were observed. The negative control was replaced with a sterile plate and the other operations were identical.
In examples 1 to 5, the extrusion rate ratio of the three layers was the same, and when the foaming of the biodegradable core layer 3 was completed, the outer layer 1 was just completely dissolved by hydrolysis, and the foamed article obtained was good in appearance and had a closed cell ratio of 80% or more. In addition, the antibacterial agents in the examples 1 and 2 are different in type, and the antibacterial properties of the foamed products are similar; in examples 2 to 5, the types of the antibacterial agents are the same, the contents of the antibacterial agents are sequentially increased, and the antibacterial properties of the foamed products are sequentially increased, which indicates that the antibacterial properties of the foamed products are more greatly influenced by the contents of the antibacterial agents.
The three-layer extrusion rate ratios of comparative examples 1, 2 and example 1 were different. The extrusion rate of the extruder a in the comparative example 1 is low, the thickness of the obtained hydrolysis sacrificial outer layer 1 is thin, the hydrolysis sacrificial outer layer 1 is completely dissolved before the foaming of the biodegradable core layer 3 is completed, so that the structures of the antibacterial intermediate layer 2 and the biodegradable core layer 3 are damaged, and the finally obtained foamed product has poor appearance, low closed cell rate and poor antibacterial property, so that the mechanical property and the antibacterial property are not ideal. The extrusion rate of the extruder a in the comparative example 2 is high, the thickness of the obtained hydrolyzed sacrificial outer layer 1 is thick, and the hydrolyzed sacrificial outer layer 1 is not completely dissolved, so that the antibacterial intermediate layer 2 cannot be completely exposed, and the antibacterial performance of the finally obtained foamed product is not ideal.
TABLE 1
Claims (10)
1. An expandable biodegradable microparticle characterized by: it is the multilayer nucleocapsid structure including hydrolysising sacrificial skin, antibiotic intermediate level and biodegradable sandwich layer at least, the sacrificial skin of hydrolysising contains biodegradable material and hydrolysis resistance agent, antibiotic intermediate level contains biodegradable material and antibacterial agent, the biodegradable sandwich layer contains biodegradable material and nucleating agent, but expandable biodegradable microparticle can be foamed in aqueous phase disperse system, the foaming in-process, the sacrificial skin of hydrolysising dissolves gradually biodegradable sandwich layer foaming is accomplished and is broken away from during the aqueous phase disperse system, the sacrificial skin of hydrolysising just dissolves almost completely.
2. The expandable biodegradable microparticle of claim 1, wherein: the hydrolysis sacrificial outer layer contains 80-99.9 wt% of biodegradable material and 0.1-20 wt% of hydrolysis resistance agent, the antibacterial middle layer contains 70-99.9 wt% of biodegradable material and 0.1-30 wt% of antibacterial agent, and the biodegradable core layer contains 50-99.9 wt% of biodegradable material and 0.01-5 wt% of nucleating agent.
3. The expandable biodegradable microparticle of claim 1, wherein: based on the total mass of the expandable biodegradable microparticles, the hydrolysis sacrificial outer layer accounts for 1-10 wt%, the antibacterial middle layer accounts for 1-10 wt%, and the biodegradable core layer accounts for 80-98 wt%.
4. The expandable biodegradable microparticle of claim 1, wherein: the biodegradable core layer also contains an auxiliary agent, and the auxiliary agent comprises at least one of a lubricant, a chain extender and an antioxidant.
5. The expandable biodegradable microparticle of any of claims 1-4, wherein: the biodegradable material comprises at least one of polylactic acid, poly adipic acid-butylene terephthalate copolymer and polybutylene succinate.
6. A method for preparing the expandable biodegradable microparticles according to any one of claims 1 to 5, characterized in that: and mixing and co-extruding the raw materials of the hydrolysis sacrificial outer layer, the antibacterial middle layer and the biodegradable core layer by a core-shell multilayer co-extrusion process, and then granulating by a granulator to obtain the expandable biodegradable particles.
7. A biodegradable expanded bead having an antibacterial function, characterized in that: is obtained by foaming in an aqueous dispersion the expandable biodegradable microparticles according to any of claims 1-5.
8. Biodegradable expanded beads having antibacterial function according to claim 7, characterized in that: the foaming is carried out in a high-pressure foaming kettle, the foaming multiplying power is 5-50 times, and the density of the obtained foaming beads is 25-260 g/L.
9. A method for preparing biodegradable expanded beads having antibacterial function according to claim 7 or 8, comprising the steps of: adding a gaseous physical foaming agent into a high-pressure foaming kettle, and uniformly dispersing the expandable biodegradable particles in a water-phase dispersion medium; stirring at high temperature and high pressure to enable the gaseous physical foaming agent to permeate into the expandable biodegradable particles until the pressure inside and outside the expandable biodegradable particles reaches balance; and then releasing the expandable biodegradable particles and the dispersion medium into the atmosphere with the pressure lower than that of the foaming kettle, and instantly expanding the expandable biodegradable particles under the action of pressure difference under high pressure inside the expandable biodegradable particles, so as to prepare the biodegradable foamed beads with the antibacterial function.
10. A biodegradable foamed product having an antibacterial function, which is obtained by injecting the biodegradable foamed beads having an antibacterial function according to claim 7 or 8 into a mold, heating with steam, and cooling to set.
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Denomination of invention: A biodegradable microparticle and a biodegradable foam bead with antibacterial function Effective date of registration: 20230901 Granted publication date: 20220419 Pledgee: Agricultural Bank of China Limited by Share Ltd. Wuxi science and Technology Branch Pledgor: WUXI HI-TEC ENVIRONMENTAL MATERIAL CO.,LTD. Registration number: Y2023980054903 |
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