CN116376250A - Antibacterial biodegradable composite material and preparation method thereof - Google Patents
Antibacterial biodegradable composite material and preparation method thereof Download PDFInfo
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- CN116376250A CN116376250A CN202310523290.7A CN202310523290A CN116376250A CN 116376250 A CN116376250 A CN 116376250A CN 202310523290 A CN202310523290 A CN 202310523290A CN 116376250 A CN116376250 A CN 116376250A
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 115
- 239000002131 composite material Substances 0.000 title claims abstract description 101
- 238000002360 preparation method Methods 0.000 title abstract description 23
- 239000000945 filler Substances 0.000 claims abstract description 52
- 239000011347 resin Substances 0.000 claims abstract description 51
- 229920005989 resin Polymers 0.000 claims abstract description 51
- 239000004014 plasticizer Substances 0.000 claims abstract description 32
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 31
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 31
- 239000000314 lubricant Substances 0.000 claims abstract description 31
- 229920001610 polycaprolactone Polymers 0.000 claims abstract description 27
- 239000004632 polycaprolactone Substances 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 66
- 238000003756 stirring Methods 0.000 claims description 48
- 239000011787 zinc oxide Substances 0.000 claims description 33
- 238000001035 drying Methods 0.000 claims description 22
- 229920000642 polymer Polymers 0.000 claims description 21
- 238000001125 extrusion Methods 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 17
- 239000002243 precursor Substances 0.000 claims description 16
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 13
- 230000000845 anti-microbial effect Effects 0.000 claims description 13
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 13
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 11
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 11
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 11
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 claims description 10
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 claims description 10
- ULBTUVJTXULMLP-UHFFFAOYSA-N butyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCCC ULBTUVJTXULMLP-UHFFFAOYSA-N 0.000 claims description 10
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 10
- 238000005469 granulation Methods 0.000 claims description 9
- 230000003179 granulation Effects 0.000 claims description 9
- 238000001746 injection moulding Methods 0.000 claims description 9
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims description 9
- 229940074439 potassium sodium tartrate Drugs 0.000 claims description 9
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims description 9
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims description 8
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000004246 zinc acetate Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 229920002521 macromolecule Polymers 0.000 claims description 5
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 4
- 239000004599 antimicrobial Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 claims description 4
- GBRSPKXOFRTAHS-UHFFFAOYSA-N 5-(4-nitrophenyl)-1,2-oxazole-3-carboxylic acid Chemical compound O1N=C(C(=O)O)C=C1C1=CC=C([N+]([O-])=O)C=C1 GBRSPKXOFRTAHS-UHFFFAOYSA-N 0.000 claims description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 2
- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 claims description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- YQEMORVAKMFKLG-UHFFFAOYSA-N glycerine monostearate Natural products CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 claims description 2
- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 0.000 claims description 2
- 239000001069 triethyl citrate Substances 0.000 claims description 2
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 claims description 2
- 235000013769 triethyl citrate Nutrition 0.000 claims description 2
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 claims 1
- VSVVZZQIUJXYQA-UHFFFAOYSA-N [3-(3-dodecylsulfanylpropanoyloxy)-2,2-bis(3-dodecylsulfanylpropanoyloxymethyl)propyl] 3-dodecylsulfanylpropanoate Chemical compound CCCCCCCCCCCCSCCC(=O)OCC(COC(=O)CCSCCCCCCCCCCCC)(COC(=O)CCSCCCCCCCCCCCC)COC(=O)CCSCCCCCCCCCCCC VSVVZZQIUJXYQA-UHFFFAOYSA-N 0.000 claims 1
- 239000012530 fluid Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 24
- 229920000747 poly(lactic acid) Polymers 0.000 description 23
- 239000004626 polylactic acid Substances 0.000 description 23
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 22
- 238000007747 plating Methods 0.000 description 11
- 229910052709 silver Inorganic materials 0.000 description 11
- 239000004332 silver Substances 0.000 description 11
- XKIVKIIBCJIWNU-UHFFFAOYSA-N o-[3-pentadecanethioyloxy-2,2-bis(pentadecanethioyloxymethyl)propyl] pentadecanethioate Chemical compound CCCCCCCCCCCCCCC(=S)OCC(COC(=S)CCCCCCCCCCCCCC)(COC(=S)CCCCCCCCCCCCCC)COC(=S)CCCCCCCCCCCCCC XKIVKIIBCJIWNU-UHFFFAOYSA-N 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000004821 distillation Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 4
- 239000003242 anti bacterial agent Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- 230000002411 adverse Effects 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000003223 protective agent Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- AXKZIDYFAMKWSA-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione Chemical compound O=C1CCCCC(=O)OCCCCO1 AXKZIDYFAMKWSA-UHFFFAOYSA-N 0.000 description 1
- ZMKVBUOZONDYBW-UHFFFAOYSA-N 1,6-dioxecane-2,5-dione Chemical compound O=C1CCC(=O)OCCCCO1 ZMKVBUOZONDYBW-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003000 extruded plastic Substances 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- 229940127554 medical product Drugs 0.000 description 1
- 239000002991 molded plastic Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920005586 poly(adipic acid) Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
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- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- 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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses an antibacterial biodegradable composite material and a preparation method thereof, and belongs to the technical field of biodegradable materials. The antibacterial biodegradable composite material comprises the following raw materials: PLA resin, PBS resin, polycaprolactone, antibacterial filler, lubricant, plasticizer and antioxidant. The antibacterial biodegradable composite material prepared by the invention is environment-friendly, has excellent biodegradability, and has good antibacterial property and mechanical property.
Description
Technical Field
The invention belongs to the technical field of biodegradable materials, and particularly relates to an antibacterial biodegradable composite material and a preparation method thereof.
Background
The biodegradable material is a polymer material which can be finally converted into carbon circulation by decomposing microorganisms such as bacteria, fungi and the like and algae existing in natural environment. The biodegradable materials which have been widely used at present mainly include polylactic acid, poly (adipic acid)/poly (butylene terephthalate), poly (butylene succinate), poly (vinyl alcohol) and the like. Compared with the traditional petrochemical plastics, the biodegradable material is more environment-friendly and is a good renewable substitute material. The biodegradable material can be used as food packaging material, medical packaging material, daily sanitary material and the like, and has the characteristics of environmental protection, safety and good biocompatibility. Meanwhile, materials having good antibacterial and antiviral properties are sometimes required in applications in these fields. The materials are generally made to have antibacterial property by adding inorganic and organic antibacterial agents, but the addition of the auxiliary agents often leads to the deterioration of the mechanical property, biocompatibility and other properties of the materials.
Chinese patent CN112442261a discloses an antibacterial biodegradable composite material, and preparation method and application thereof, comprising the following raw materials: polylactic acid, polycaprolactone, poly (butylene adipate/terephthalate), compatilizer, plasticizer, tackifier, nano plant fiber powder and organic antibacterial agent. The invention adopts the synergistic effect of the degradable plastic, the nano plant fiber powder and the organic antibacterial agent to carry out antibacterial modification on the biodegradable plastic, endows the material with a certain antibacterial effect, can be used for packaging medical products, expands the application range of the degradable material, and ensures that the mechanical property, the biocompatibility and the like of the composite material are adversely affected by the addition of the organic antibacterial agent. Therefore, it is desirable to provide an antimicrobial material and an antimicrobial biodegradable composite that do not affect the properties of the biodegradable material itself.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides an antibacterial biodegradable composite material and a preparation method thereof, which are mainly prepared from PLA resin, PBS resin, polycaprolactone, antibacterial filler and other raw materials, and have good antibacterial performance and mechanical property.
The technical scheme adopted by the invention is as follows:
an antibacterial biodegradable composite material comprises the following raw materials: PLA resin, PBS resin, polycaprolactone, antibacterial filler, lubricant, plasticizer and antioxidant.
The invention prepares the antibacterial biodegradable composite material by taking PBS resin, polycaprolactone and PLA resin as basic raw materials and then matching with self-made antibacterial filler. The PLA resin can be obtained by processing regenerated plant resources such as starch, is a recognized environment-friendly biodegradable material, and has good biocompatibility, glossiness, tensile strength and extensibility. The PBS resin is synthesized by polycondensation of succinic acid and butanediol, has good biocompatibility, mechanical property and processability, and can be completely degraded by microorganisms under natural conditions. The polycaprolactone has good compatibility with other resins, is a good biodegradable material, and can play a role in plasticizing and toughening. The basic raw materials ensure that the composite material has excellent comprehensive properties such as mechanics, processing and the like while meeting biodegradability.
Preferably, an antimicrobial biodegradable composite material is made from the following raw materials: 60-70 parts by weight of PLA resin, 20-40 parts by weight of PBS resin, 10-20 parts by weight of polycaprolactone, 2-4 parts by weight of antibacterial filler, 1-2 parts by weight of lubricant, 2-3 parts by weight of plasticizer and 1-3 parts by weight of antioxidant.
The preparation method of the antibacterial filler comprises the following steps:
(1) Adding zinc acetate and polyphenyl ether into absolute ethyl alcohol, fully stirring, decompressing and distilling to recover a solvent after the completion of the stirring, and drying to obtain a precursor; calcining the precursor to obtain a nano zinc oxide/polymer composite;
(2) Adding ammonia water and silver nitrate into water, fully stirring, adding the nano zinc oxide/polymer composite obtained in the step (1), uniformly stirring, adding a reducing solution, stirring for reaction, filtering, washing and drying to obtain a silver-plated composite;
(3) Adding the silver-plated compound obtained in the step (2) into absolute ethyl alcohol, uniformly mixing, adding a polyvinyl alcohol aqueous solution, stirring for reaction, filtering, washing and drying to obtain the antibacterial filler.
The antibacterial filler is prepared by taking a nano zinc oxide/polymer complex as a core, performing silver plating treatment to obtain a silver-plated complex, and finally performing cladding reaction with polyvinyl alcohol. The nano zinc oxide in the nano zinc oxide/polymer composite is adsorbed and loaded on the surface of a gap of the polymer carrier, so that the nano zinc oxide can be uniformly dispersed in the composite as an antibacterial component, and meanwhile, the polymer composite has better compatibility with a composite matrix, so that the antibacterial effect and the utilization rate of the nano zinc oxide in the composite are improved. In addition, the nano zinc oxide/polymer composite has higher specific surface activity, can improve the crosslinking degree of the nano zinc oxide/polymer composite with PLA and PBS in a composite material matrix, and is beneficial to improving the mechanical property of the composite material. Furthermore, the silver plating compound realizes the synergistic effect of nano zinc oxide and nano silver on the antibacterial effect, and increases the antibacterial effect, so that the composite material has better antibacterial performance, and meanwhile, the silver plating can improve the interface performance, thereby being beneficial to uniformly dispersing two nano antibacterial components in the composite material. The coating treatment introduces a high molecular polyvinyl alcohol branched chain structure into the antibacterial filler, so that adverse effects on the mechanical properties of the composite material caused by the addition of additives can be offset to a certain extent.
The polyvinylpyrrolidone is added into the reducing solution and can be used as a stabilizing and protecting agent to assist the reduction of potassium sodium tartrate on the surface of the compound body to generate a compact and uniform silver plating layer. The method is characterized in that the surface energy of the nano silver particles generated in the silver plating process is larger, agglomeration is easy to occur along with the reaction, and long chains of polyvinylpyrrolidone can be adsorbed on the surfaces of the nano silver particles, so that a space effect is generated among the nano silver particles, uneven aggregation of the nano silver particles is avoided, and the finally obtained antibacterial filler has better antibacterial performance.
Preferably, the preparation method of the antibacterial filler comprises the following steps:
(1) Adding 6-10 parts by weight of zinc acetate and 40-50 parts by weight of polyphenyl ether into 300-400 parts by weight of absolute ethyl alcohol, stirring for 70-100min at 300-350rpm, and recovering solvent by reduced pressure distillation after the completion of the stirring, and drying to obtain a precursor; calcining the precursor at 280-290 ℃ for 5-7h to obtain a nano zinc oxide/macromolecule complex;
(2) Adding 0.5-0.8 weight part of ammonia water and 1-2 weight parts of silver nitrate into 40-60 weight parts of water, stirring for 20-30min at 150-200rpm, then adding 5-7 weight parts of the nano zinc oxide/polymer composite obtained in the step (1), continuously stirring for 30-40min, adding 3-5 weight parts of reducing solution, stirring and reacting for 2-4h, filtering, washing and drying after finishing to obtain a silver-plated composite;
(3) Adding 4-5 parts by weight of the silver-plated composite obtained in the step (2) into 15-20 parts by weight of absolute ethyl alcohol, uniformly mixing, then adding 30-50 parts by weight of polyvinyl alcohol aqueous solution, stirring for 3-5 hours at 150-200rpm, filtering, washing and drying after the completion of the stirring, and obtaining the antibacterial filler.
Preferably, the reducing solution consists of polyvinylpyrrolidone, potassium sodium tartrate and water; the mass ratio of polyvinylpyrrolidone, potassium sodium tartrate and water is 1:10-30:20-40.
Preferably, the concentration of the ammonia water is 25-30wt%.
Preferably, the concentration of the aqueous polyvinyl alcohol solution is 8-12wt%.
The lubricant is at least one of n-butyl stearate, zinc stearate, glycerol tristearate, glycerol monostearate and calcium stearate.
Preferably, the lubricant is a mixture of n-butyl stearate and zinc stearate according to a mass ratio of 1-2:1.
The plasticizer is any one of acetyl tributyl citrate, dioctyl phthalate and triethyl citrate.
Preferably, the plasticizer is acetyl tributyl citrate.
The antioxidant is at least one of 2,2' -methylenebis (6-tertiary butyl-4-methylphenol), pentaerythritol tetra (3-lauryl thiopropionate), diisooctyl phenyl phosphite and didodecyl thiopropionate.
Preferably, the antioxidant is a mixture of 2,2' -methylenebis (6-tertiary butyl-4-methylphenol) and pentaerythritol tetra (3-laurylthiopropionate) according to a mass ratio of 1-3:1.
The invention also provides a preparation method of the antibacterial biodegradable composite material.
Preferably, the preparation method of the antibacterial biodegradable composite material comprises the following steps:
putting PLA resin, PBS resin, polycaprolactone, antibacterial filler, lubricant, plasticizer and antioxidant into a mixer, mixing for 10-30min, wherein the rotation speed of the mixer is 400-600rpm; putting the mixture into an extruder for extrusion and granulation, wherein the rotating speed of a screw is 100-200rpm, and the extrusion temperature is 160-170 ℃; injection molding to obtain the antibacterial biodegradable composite material.
The invention has the beneficial effects that: the preparation method of the antibacterial biodegradable composite material is simple and convenient and is easy to operate, and the obtained composite material has excellent antibacterial property and mechanical property, excellent biodegradability and environmental friendliness. In addition, the antibacterial filler takes the nano zinc oxide/polymer complex as a core, realizes the synergistic effect of the nano zinc oxide and the nano silver on the antibacterial effect through silver plating treatment, ensures that the composite material has better antibacterial performance, and can avoid adverse effects on the mechanical properties of the composite material.
Detailed Description
Part of the raw materials in this application are described as follows:
PLA resin, brand: REVODE 210, purchased from Zhejiang Seisakusho Biomaterial Co., ltd.
PBS resin, brand: TUNHE PBS TH803, available from Xinjiang blue mountain Tun river technologies Co.
Polycaprolactone, brand:
PCL purchased from Shandong Xin Fu Utility Co.
Polyvinylpyrrolidone, viscosity grade: k-30, purchased from Beijing Micida technologies Co.
Polyvinyl alcohol, degree of alcoholysis: 87.0 to 89.0mol%, viscosity: 40.0-48.0mpa.s, purchased from guangdong Weng Jiang chemical company, inc.
Nano zinc oxide, particle size: 100nm purchased from Shanghai, new Material technologies Co., ltd.
Example 1
An antibacterial biodegradable composite material is prepared from the following raw materials: 65 parts by weight of PLA resin, 30 parts by weight of PBS resin, 15 parts by weight of polycaprolactone, 3 parts by weight of antibacterial filler, 1.5 parts by weight of lubricant, 2.5 parts by weight of plasticizer and 2 parts by weight of antioxidant.
The lubricant is a mixture of n-butyl stearate and zinc stearate according to a mass ratio of 1.5:1.
The plasticizer is acetyl tributyl citrate.
The antioxidant is a mixture of 2,2' -methylenebis (6-tertiary butyl-4-methylphenol) and pentaerythritol tetra (3-laurylthiopropionate) according to a mass ratio of 2:1.
The preparation method of the antibacterial filler comprises the following steps:
(1) Adding 8 parts by weight of zinc acetate and 45 parts by weight of polyphenyl ether into 350 parts by weight of absolute ethyl alcohol, stirring for 90min at 320rpm, recovering the solvent by reduced pressure distillation after the completion of the stirring, and drying to obtain a precursor; calcining the precursor at 285 ℃ for 6 hours to obtain a nano zinc oxide/macromolecule complex;
(2) Adding 0.7 weight part of ammonia water and 1.5 weight part of silver nitrate into 50 weight parts of water, stirring for 25min at 180rpm, then adding 6 weight parts of the nano zinc oxide/polymer composite obtained in the step (1), continuously stirring for 35min, adding 4 weight parts of reducing solution, stirring and reacting for 3.5h, filtering, washing and drying after the completion of the reaction to obtain a silver-plated composite; the reducing solution consists of polyvinylpyrrolidone, potassium sodium tartrate and water according to a mass ratio of 1:20:30; the concentration of the ammonia water is 28wt%;
(3) Adding 4.5 parts by weight of the silver-plated composite obtained in the step (2) into 16 parts by weight of absolute ethyl alcohol, uniformly mixing, then adding 40 parts by weight of 10wt% polyvinyl alcohol aqueous solution, stirring for 4.5 hours at 180rpm, filtering, washing and drying after the completion of the stirring, and obtaining the antibacterial filler.
The preparation method of the antibacterial biodegradable composite material comprises the following steps:
putting PLA resin, PBS resin, polycaprolactone, an antibacterial filler, a lubricant, a plasticizer and an antioxidant into a mixer, and mixing for 25min, wherein the rotating speed of the mixer is 450rpm; putting the mixture into an extruder for extrusion and granulation, wherein the rotating speed of a screw is 180rpm, and the extrusion temperature is 165 ℃; injection molding to obtain the antibacterial biodegradable composite material.
Example 2
An antibacterial biodegradable composite material is prepared from the following raw materials: 60 parts by weight of PLA resin, 20 parts by weight of PBS resin, 10 parts by weight of polycaprolactone, 2 parts by weight of antibacterial filler, 1 part by weight of lubricant, 2 parts by weight of plasticizer and 1 part by weight of antioxidant.
The lubricant is a mixture of n-butyl stearate and zinc stearate according to a mass ratio of 1:1.
The plasticizer is acetyl tributyl citrate.
The antioxidant is a mixture of 2,2' -methylenebis (6-tertiary butyl-4-methylphenol) and pentaerythritol tetra (3-laurylthiopropionate) according to a mass ratio of 1:1.
The antibacterial filler was prepared in the same manner as in example 1.
The preparation method of the antibacterial biodegradable composite material comprises the following steps:
putting PLA resin, PBS resin, polycaprolactone, an antibacterial filler, a lubricant, a plasticizer and an antioxidant into a mixer, and mixing for 10min, wherein the rotating speed of the mixer is 600rpm; putting the mixture into an extruder for extrusion and granulation, wherein the rotating speed of a screw is 200rpm, and the extrusion temperature is 170 ℃; injection molding to obtain the antibacterial biodegradable composite material.
Example 3
An antibacterial biodegradable composite material is prepared from the following raw materials: 70 parts by weight of PLA resin, 40 parts by weight of PBS resin, 20 parts by weight of polycaprolactone, 4 parts by weight of antibacterial filler, 2 parts by weight of lubricant, 3 parts by weight of plasticizer and 3 parts by weight of antioxidant.
The lubricant is a mixture of n-butyl stearate and zinc stearate according to a mass ratio of 2:1.
The plasticizer is acetyl tributyl citrate.
The antioxidant is a mixture of 2,2' -methylenebis (6-tertiary butyl-4-methylphenol) and pentaerythritol tetra (3-laurylthiopropionate) according to a mass ratio of 3:1.
The antibacterial filler was prepared in the same manner as in example 1.
The preparation method of the antibacterial biodegradable composite material comprises the following steps:
putting PLA resin, PBS resin, polycaprolactone, an antibacterial filler, a lubricant, a plasticizer and an antioxidant into a mixer, and mixing for 30min, wherein the rotating speed of the mixer is 400rpm; putting the mixture into an extruder for extrusion and granulation, wherein the rotating speed of a screw is 100rpm, and the extrusion temperature is 160 ℃; injection molding to obtain the antibacterial biodegradable composite material.
Example 4
An antibacterial biodegradable composite material is prepared from the following raw materials: 65 parts by weight of PLA resin, 30 parts by weight of PBS resin, 15 parts by weight of polycaprolactone, 3 parts by weight of antibacterial filler, 1.5 parts by weight of lubricant, 2.5 parts by weight of plasticizer and 2 parts by weight of antioxidant.
The lubricant is a mixture of n-butyl stearate and zinc stearate according to a mass ratio of 1.5:1.
The plasticizer is acetyl tributyl citrate.
The antioxidant is a mixture of 2,2' -methylenebis (6-tertiary butyl-4-methylphenol) and pentaerythritol tetra (3-laurylthiopropionate) according to a mass ratio of 2:1.
The preparation method of the antibacterial filler comprises the following steps:
(1) Adding 8 parts by weight of zinc acetate and 45 parts by weight of polyphenyl ether into 350 parts by weight of absolute ethyl alcohol, stirring for 90min at 320rpm, recovering the solvent by reduced pressure distillation after the completion of the stirring, and drying to obtain a precursor; calcining the precursor at 285 ℃ for 6 hours to obtain a nano zinc oxide/macromolecule complex;
(2) Adding 0.7 weight part of ammonia water and 1.5 weight part of silver nitrate into 50 weight parts of water, stirring for 25min at 180rpm, adding 6 weight parts of the nano zinc oxide/polymer composite obtained in the step (1), continuously stirring for 35min, adding 4 weight parts of reducing solution, stirring for reaction for 3.5h, filtering, washing and drying after the completion of the reaction, and obtaining the antibacterial filler. The reducing solution consists of polyvinylpyrrolidone, potassium sodium tartrate and water according to a mass ratio of 1:20:30; the concentration of the aqueous ammonia was 28wt%.
The preparation method of the antibacterial biodegradable composite material comprises the following steps:
putting PLA resin, PBS resin, polycaprolactone, an antibacterial filler, a lubricant, a plasticizer and an antioxidant into a mixer, and mixing for 25min, wherein the rotating speed of the mixer is 450rpm; putting the mixture into an extruder for extrusion and granulation, wherein the rotating speed of a screw is 180rpm, and the extrusion temperature is 165 ℃; injection molding to obtain the antibacterial biodegradable composite material.
Example 5
An antibacterial biodegradable composite material is prepared from the following raw materials: 65 parts by weight of PLA resin, 30 parts by weight of PBS resin, 15 parts by weight of polycaprolactone, 3 parts by weight of antibacterial filler, 1.5 parts by weight of lubricant, 2.5 parts by weight of plasticizer and 2 parts by weight of antioxidant.
The lubricant is a mixture of n-butyl stearate and zinc stearate according to a mass ratio of 1.5:1.
The plasticizer is acetyl tributyl citrate.
The antioxidant is a mixture of 2,2' -methylenebis (6-tertiary butyl-4-methylphenol) and pentaerythritol tetra (3-laurylthiopropionate) according to a mass ratio of 2:1.
The preparation method of the antibacterial filler comprises the following steps:
adding 8 parts by weight of zinc acetate and 45 parts by weight of polyphenyl ether into 350 parts by weight of absolute ethyl alcohol, stirring for 90min at 320rpm, recovering the solvent by reduced pressure distillation after the completion of the stirring, and drying to obtain a precursor; and calcining the precursor at 285 ℃ for 6 hours to obtain the antibacterial filler.
The preparation method of the antibacterial biodegradable composite material comprises the following steps:
putting PLA resin, PBS resin, polycaprolactone, an antibacterial filler, a lubricant, a plasticizer and an antioxidant into a mixer, and mixing for 25min, wherein the rotating speed of the mixer is 450rpm; putting the mixture into an extruder for extrusion and granulation, wherein the rotating speed of a screw is 180rpm, and the extrusion temperature is 165 ℃; injection molding to obtain the antibacterial biodegradable composite material.
Example 6
An antibacterial biodegradable composite material is prepared from the following raw materials: 65 parts by weight of PLA resin, 30 parts by weight of PBS resin, 15 parts by weight of polycaprolactone, 3 parts by weight of antibacterial filler, 1.5 parts by weight of lubricant, 2.5 parts by weight of plasticizer and 2 parts by weight of antioxidant.
The lubricant is a mixture of n-butyl stearate and zinc stearate according to a mass ratio of 1.5:1.
The plasticizer is acetyl tributyl citrate.
The antioxidant is a mixture of 2,2' -methylenebis (6-tertiary butyl-4-methylphenol) and pentaerythritol tetra (3-laurylthiopropionate) according to a mass ratio of 2:1.
The preparation method of the antibacterial filler comprises the following steps:
(1) Adding 8 parts by weight of zinc acetate and 45 parts by weight of polyphenyl ether into 350 parts by weight of absolute ethyl alcohol, stirring for 90min at 320rpm, recovering the solvent by reduced pressure distillation after the completion of the stirring, and drying to obtain a precursor; calcining the precursor at 285 ℃ for 6 hours to obtain a nano zinc oxide/macromolecule complex;
(2) Adding 0.7 weight part of ammonia water and 1.5 weight part of silver nitrate into 50 weight parts of water, stirring for 25min at 180rpm, then adding 6 weight parts of the nano zinc oxide/polymer composite obtained in the step (1), continuously stirring for 35min, adding 4 weight parts of reducing solution, stirring and reacting for 3.5h, filtering, washing and drying after the completion of the reaction to obtain a silver-plated composite; the reducing solution consists of potassium sodium tartrate and water according to the mass ratio of 20:30; the concentration of the ammonia water is 28wt%;
(3) Adding 4.5 parts by weight of the silver-plated composite obtained in the step (2) into 16 parts by weight of absolute ethyl alcohol, uniformly mixing, then adding 40 parts by weight of 10wt% polyvinyl alcohol aqueous solution, stirring for 4.5 hours at 180rpm, filtering, washing and drying after the completion of the stirring, and obtaining the antibacterial filler.
The preparation method of the antibacterial biodegradable composite material comprises the following steps:
putting PLA resin, PBS resin, polycaprolactone, an antibacterial filler, a lubricant, a plasticizer and an antioxidant into a mixer, and mixing for 25min, wherein the rotating speed of the mixer is 450rpm; putting the mixture into an extruder for extrusion and granulation, wherein the rotating speed of a screw is 180rpm, and the extrusion temperature is 165 ℃; injection molding to obtain the antibacterial biodegradable composite material.
Example 7
An antibacterial biodegradable composite material is prepared from the following raw materials: 65 parts by weight of PLA resin, 30 parts by weight of PBS resin, 15 parts by weight of polycaprolactone, 3 parts by weight of antibacterial filler, 1.5 parts by weight of lubricant, 2.5 parts by weight of plasticizer and 2 parts by weight of antioxidant.
The lubricant is a mixture of n-butyl stearate and zinc stearate according to a mass ratio of 1.5:1.
The plasticizer is acetyl tributyl citrate.
The antioxidant is a mixture of 2,2' -methylenebis (6-tertiary butyl-4-methylphenol) and pentaerythritol tetra (3-laurylthiopropionate) according to a mass ratio of 2:1.
The preparation method of the antibacterial filler comprises the following steps:
adding 0.7 weight part of ammonia water and 1.5 weight part of silver nitrate into 50 weight parts of water, stirring for 25min at 180rpm, adding 6 weight parts of nano zinc oxide, continuously stirring for 35min, adding 4 weight parts of reducing solution, stirring and reacting for 3.5h, filtering, washing and drying after the completion of the reaction, and obtaining the antibacterial filler. The reducing solution consists of polyvinylpyrrolidone, potassium sodium tartrate and water according to a mass ratio of 1:20:30; the concentration of the aqueous ammonia was 28wt%.
The preparation method of the antibacterial biodegradable composite material comprises the following steps:
putting PLA resin, PBS resin, polycaprolactone, an antibacterial filler, a lubricant, a plasticizer and an antioxidant into a mixer, and mixing for 25min, wherein the rotating speed of the mixer is 450rpm; putting the mixture into an extruder for extrusion and granulation, wherein the rotating speed of a screw is 180rpm, and the extrusion temperature is 165 ℃; injection molding to obtain the antibacterial biodegradable composite material.
Test example 1
Tensile properties:
determination of tensile Properties of Plastic according to national Standard GB/T1040.2-2022 part 2: test conditions for molded and extruded plastics the antibacterial biodegradable composite material prepared in the above examples was tested. The sample size was: 170mm by 20mm by 4mm, type 1A. The average was calculated in 10 groups in parallel.
TABLE 1 tensile Property test results
| Tensile strength, MPa | |
| Example 1 | 55.62 |
| Example 4 | 51.21 |
| Example 7 | 43.97 |
Test example 2
Antibacterial properties:
the antibacterial biodegradable composite material prepared in the above embodiment is tested according to national standard GB/T31402-2015 "test method for antibacterial Property of Plastic surface". Testing strains: coli (ATCC 8739), staphylococcus aureus (ATCC 6538P), in parallel 10 groups, the average value was calculated.
TABLE 2 antibacterial Property test results
From the above table, it can be seen that the antibacterial biodegradable composite material prepared in example 1 has better antibacterial performance and mechanical strength. Compared with the embodiment 7, the antibacterial filler adopted in the embodiment 1 takes the nano zinc oxide/polymer composite as a core, silver plating treatment is carried out to obtain the silver plating composite, and finally the silver plating composite is prepared by cladding reaction with polyvinyl alcohol, wherein the nano zinc oxide in the nano zinc oxide/polymer composite is adsorbed and loaded on the gap surface of the polymer carrier, so that the nano zinc oxide can be uniformly dispersed in the composite as an antibacterial component, meanwhile, the polymer composite has better compatibility with a composite matrix, the antibacterial effect and the utilization rate of the nano zinc oxide in the composite are improved, and the nano zinc oxide/polymer composite has higher specific surface activity, can improve the crosslinking degree of PLA and PBS in the composite matrix, and is beneficial to improving the mechanical property of the composite. Compared with example 5, the antibacterial filler of example 1 is silver-plated, and the silver-plated composite realizes the synergistic effect of nano zinc oxide and nano silver on antibacterial effect, so that the composite material has better antibacterial performance. Compared with example 6, the antibacterial filler of example 1 is added with polyvinylpyrrolidone in the reducing solution, and can be used as a stabilizing and protecting agent to assist the reduction of potassium sodium tartrate on the surface of the composite body to generate a compact and uniform silver plating layer. The method is characterized in that the surface energy of the nano silver particles generated in the silver plating process is larger, agglomeration is easy to occur along with the reaction, and long chains of polyvinylpyrrolidone can be adsorbed on the surfaces of the nano silver particles, so that a space effect is generated among the nano silver particles, uneven aggregation of the nano silver particles is avoided, and the finally obtained antibacterial filler has better antibacterial performance.
The foregoing describes in detail preferred embodiments of the present invention. It should be understood that numerous modifications and variations can be made in accordance with the concepts of the invention by one of ordinary skill in the art without undue burden. Therefore, all technical solutions which can be obtained by logic analysis, reasoning or limited experiments based on the prior art by the person skilled in the art according to the inventive concept shall be within the scope of protection defined by the claims.
Claims (9)
1. An antibacterial biodegradable composite material is characterized by comprising the following raw materials: PLA resin, PBS resin, polycaprolactone, antibacterial filler, lubricant, plasticizer and antioxidant; the antibacterial filler is prepared from silver-plated composite and polyvinyl alcohol.
2. The antimicrobial biodegradable composite of claim 1, wherein the antimicrobial filler is prepared by a process comprising:
(1) Adding zinc acetate and polyphenyl ether into absolute ethyl alcohol, fully stirring, decompressing and distilling to recover a solvent after the completion of the stirring, and drying to obtain a precursor; calcining the precursor to obtain a nano zinc oxide/polymer composite;
(2) Adding ammonia water and silver nitrate into water, fully stirring, adding the nano zinc oxide/polymer composite obtained in the step (1), uniformly stirring, adding a reducing solution, stirring for reaction, filtering, washing and drying to obtain a silver-plated composite;
(3) Adding the silver-plated compound obtained in the step (2) into absolute ethyl alcohol, uniformly mixing, adding a polyvinyl alcohol aqueous solution, stirring for reaction, filtering, washing and drying to obtain the antibacterial filler.
3. The antimicrobial biodegradable composite of claim 2 wherein the reducing fluid is comprised of polyvinylpyrrolidone, potassium sodium tartrate, and water.
4. The antimicrobial biodegradable composite of claim 2, wherein the antimicrobial filler is prepared by the process of:
(1) Adding 6-10 parts by weight of zinc acetate and 40-50 parts by weight of polyphenyl ether into 300-400 parts by weight of absolute ethyl alcohol, stirring for 70-100min, and after the completion, distilling under reduced pressure to recover a solvent, and drying to obtain a precursor; calcining the precursor at 280-290 ℃ for 5-7h to obtain a nano zinc oxide/macromolecule complex;
(2) Adding 0.5-0.8 weight part of ammonia water and 1-2 weight parts of silver nitrate into 40-60 weight parts of water, stirring for 20-30min, adding 5-7 weight parts of the nano zinc oxide/polymer composite obtained in the step (1), continuously stirring for 30-40min, adding 3-5 weight parts of reducing solution, stirring and reacting for 2-4h, filtering, washing and drying after the reaction is finished, thus obtaining a silver-plated composite;
(3) Adding 4-5 parts by weight of the silver-plated composite obtained in the step (2) into 15-20 parts by weight of absolute ethyl alcohol, uniformly mixing, then adding 30-50 parts by weight of polyvinyl alcohol aqueous solution, stirring for 3-5 hours, filtering, washing and drying after the end, and obtaining the antibacterial filler.
5. The antimicrobial biodegradable composite of claim 1, made from the following materials: 60-70 parts by weight of PLA resin, 20-40 parts by weight of PBS resin, 10-20 parts by weight of polycaprolactone, 2-4 parts by weight of antibacterial filler, 1-2 parts by weight of lubricant, 2-3 parts by weight of plasticizer and 1-3 parts by weight of antioxidant.
6. The antimicrobial biodegradable composite of claim 1, wherein the lubricant is at least one of n-butyl stearate, zinc stearate, glycerol tristearate, glycerol monostearate, and calcium stearate.
7. The antimicrobial biodegradable composite of claim 1, wherein the plasticizer is any one of acetyl tributyl citrate, dioctyl phthalate, and triethyl citrate.
8. The antimicrobial biodegradable composite of claim 1, wherein the antioxidant is at least one of 2,2' -methylenebis (6-t-butyl-4-methylphenol), pentaerythritol tetrakis (3-laurylthiopropionate), diisooctylphenyl phosphite, and didodecyl thiodipropionate.
9. A method of preparing an antimicrobial biodegradable composite according to any one of claims 1-8, comprising the steps of:
and (3) putting PLA resin, PBS resin, polycaprolactone, an antibacterial filler, a lubricant, a plasticizer and an antioxidant into a mixer for mixing, putting into an extruder for extrusion granulation, and performing injection molding to obtain the antibacterial biodegradable composite material.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103980686A (en) * | 2014-06-10 | 2014-08-13 | 上海诚壹塑胶制品有限公司 | Antimicrobial biodegradable packaging hose material and method for preparing hose using same |
| US20140322286A1 (en) * | 2011-11-17 | 2014-10-30 | Sakai Chemical Industry Co., Ltd. | Surface treated zinc oxide powder, antibacterial agent, and antibacterial composition |
| CN104927200A (en) * | 2015-07-09 | 2015-09-23 | 邬际杰 | Polypropylene composite material for antibiosis anti-flaming automotive upholsteries and preparation method thereof |
| KR20170044336A (en) * | 2015-10-15 | 2017-04-25 | 연세대학교 원주산학협력단 | High-heat resistant and high-gas barrier composite resin and preparation method thereof |
| CN115365492A (en) * | 2022-09-14 | 2022-11-22 | 安徽元梦生物基材料科技有限公司 | Preparation of antibacterial and antistatic nano particles and antibacterial and antistatic polylactic acid material |
-
2023
- 2023-05-10 CN CN202310523290.7A patent/CN116376250A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140322286A1 (en) * | 2011-11-17 | 2014-10-30 | Sakai Chemical Industry Co., Ltd. | Surface treated zinc oxide powder, antibacterial agent, and antibacterial composition |
| CN103980686A (en) * | 2014-06-10 | 2014-08-13 | 上海诚壹塑胶制品有限公司 | Antimicrobial biodegradable packaging hose material and method for preparing hose using same |
| CN104927200A (en) * | 2015-07-09 | 2015-09-23 | 邬际杰 | Polypropylene composite material for antibiosis anti-flaming automotive upholsteries and preparation method thereof |
| KR20170044336A (en) * | 2015-10-15 | 2017-04-25 | 연세대학교 원주산학협력단 | High-heat resistant and high-gas barrier composite resin and preparation method thereof |
| CN115365492A (en) * | 2022-09-14 | 2022-11-22 | 安徽元梦生物基材料科技有限公司 | Preparation of antibacterial and antistatic nano particles and antibacterial and antistatic polylactic acid material |
Non-Patent Citations (2)
| Title |
|---|
| 王宝川，等: "不同粒径氧化锌以及改性纳米氧化锌对多功能PBAT复合膜的影响", 中国塑料, vol. 37, no. 4, 30 April 2023 (2023-04-30), pages 11 - 16 * |
| 钱凤珍: "1997～1998年我国塑料工业进展", 塑料工业, vol. 27, no. 02, 28 March 1999 (1999-03-28), pages 1 - 22 * |
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