CN117700793A - Nano silver suicide resin material and preparation method thereof - Google Patents
Nano silver suicide resin material and preparation method thereof Download PDFInfo
- Publication number
- CN117700793A CN117700793A CN202311787110.2A CN202311787110A CN117700793A CN 117700793 A CN117700793 A CN 117700793A CN 202311787110 A CN202311787110 A CN 202311787110A CN 117700793 A CN117700793 A CN 117700793A
- Authority
- CN
- China
- Prior art keywords
- silver
- resin material
- suicide
- solution
- nano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000011347 resin Substances 0.000 title claims abstract description 66
- 229920005989 resin Polymers 0.000 title claims abstract description 66
- 239000000463 material Substances 0.000 title claims abstract description 59
- 206010010144 Completed suicide Diseases 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- -1 polyethylene Polymers 0.000 claims abstract description 121
- 239000004698 Polyethylene Substances 0.000 claims abstract description 72
- 229920000573 polyethylene Polymers 0.000 claims abstract description 72
- 239000000243 solution Substances 0.000 claims abstract description 71
- 229910052709 silver Inorganic materials 0.000 claims abstract description 45
- 239000004332 silver Substances 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- 238000001035 drying Methods 0.000 claims abstract description 16
- 239000003446 ligand Substances 0.000 claims abstract description 12
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920003023 plastic Polymers 0.000 claims abstract description 10
- 239000004033 plastic Substances 0.000 claims abstract description 10
- 239000003999 initiator Substances 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 230000000844 anti-bacterial effect Effects 0.000 claims description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 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
- 238000003756 stirring Methods 0.000 claims description 15
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 11
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 11
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 10
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 229940100890 silver compound Drugs 0.000 claims description 6
- 150000003379 silver compounds Chemical class 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 5
- 239000008055 phosphate buffer solution Substances 0.000 claims description 5
- 229910001923 silver oxide Inorganic materials 0.000 claims description 5
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims description 5
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 2
- 230000001954 sterilising effect Effects 0.000 abstract description 7
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 7
- 230000004048 modification Effects 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 5
- 238000005054 agglomeration Methods 0.000 abstract description 4
- 230000002776 aggregation Effects 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 3
- 230000008961 swelling Effects 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 2
- 230000001550 time effect Effects 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 239000003242 anti bacterial agent Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000004793 Polystyrene Substances 0.000 description 11
- 241000894006 Bacteria Species 0.000 description 10
- 239000000843 powder Substances 0.000 description 9
- 244000005700 microbiome Species 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000011081 inoculation Methods 0.000 description 6
- 229940072049 amyl acetate Drugs 0.000 description 5
- PGMYKACGEOXYJE-UHFFFAOYSA-N anhydrous amyl acetate Natural products CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 4
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 4
- 102000004169 proteins and genes Human genes 0.000 description 4
- 108090000623 proteins and genes Proteins 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 230000006820 DNA synthesis Effects 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 102000003960 Ligases Human genes 0.000 description 1
- 108090000364 Ligases Proteins 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000012039 electrophile Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/02—Chemical treatment or coating of shaped articles made of macromolecular substances with solvents, e.g. swelling agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a nano silver suicide resin material and a preparation method thereof, belonging to the field of plastic modification processing. The preparation method comprises the following steps: mixing low molecular weight polyethylene with solvent and heating to 90-110 deg.c to dissolve and form mixed solution; the mixed solution, the initiator and the maleic anhydride are mixed for reaction, and the modified low molecular weight polyethylene solution is obtained through filtration; reacting the modified low molecular weight polyethylene solution with a silver-containing modifying compound to form a silver-polyethylene ligand solution; and (3) immersing the resin material in the silver-polyethylene coordination compound solution, and then washing and drying sequentially to obtain the nano silver suicide resin material. According to the invention, silver ions are bridged through double coordination to form a stable ligand structure, and then are introduced into the resin material in a swelling and impregnating physical mode, so that the technical problems of particle agglomeration and short sterilization time effect are effectively solved.
Description
Technical Field
The invention belongs to the field of plastic modification processing, and particularly relates to a nano silver suicide resin material and a preparation method thereof.
Background
The antibacterial material is a novel functional material with the function of killing or inhibiting the growth and reproduction activities of microorganisms, and is prepared by adding an inorganic antibacterial agent, an organic antibacterial agent, a natural antibacterial agent or a high molecular antibacterial agent with the function of killing or inhibiting the bacteria into a matrix material and mixing the inorganic antibacterial agent, the organic antibacterial agent, the natural antibacterial agent or the high molecular antibacterial agent. The inorganic antibacterial agent mainly comprises silver, copper, zinc and other metal antibacterial agents with bactericidal or bacteriostatic ability, the metal ions are tiny in size and contact with the cell wall of the microorganism or enter the interior of the cell, are combined with sulfhydryl groups on internal proteins to coagulate the cell proteins and destroy the activity of synthetase in the microorganism, meanwhile, the DNA synthesis of the microorganism is interfered, the metabolism of the bacteria and the synthesis of the protein are hindered, the cell permeability is increased, the death of the microorganism is finally caused, and the combination of the metal ions and the protein also destroys the respiratory system, the electron transmission system and the substance transmission system of the microorganism, so that the microorganism is killed. In the inorganic antibacterial agent materials, the silver simple substance is widely applied to the preparation of plastic products with antibacterial performance due to the excellent characteristics of broad-spectrum efficient sterilization capability, durability and no decomposition.
In the prior art, a mode of constructing an antibacterial function by utilizing metallic silver is mainly realized by directly adding silver ions or nano silver powder as a bactericide, and the mode can realize the antibacterial performance of a material, but has the following problems: silver ions are fixed on a specific carrier in a loading mode such as impregnation, the release speed of the silver ions is too high, and the long-acting antibacterial property of the antibacterial material is difficult to maintain; compared with silver ions, the silver simple substance serving as the nano silver powder has the advantages of slow release speed, long sterilization time and wider application range, but the nano silver powder is directly added as an additive in the preparation process of products such as plastics and the like, so that the nano silver is easy to agglomerate, and the antibacterial effect of the nano silver is reduced. The patent CN106496774A discloses a preparation method of nano silver antibacterial plastic, wherein antibacterial silver ions or metal oxides thereof are fixedly supported in nano zeolite by an ion substitution method, and then a matrix material, an auxiliary agent and a dispersing agent are added for mixing and injection molding to form the nano silver antibacterial plastic; patent CN111234434B discloses an antibacterial plastic and a door cabinet using the antibacterial plastic, the invention directly loads nano silver antibacterial agent on the surface of graphene oxide, and then adds additives such as dispersing agent and the like to modify and disperse the nano silver antibacterial agent through post-treatment, but because the modifying and dispersing operation is carried out after loading, the agglomeration phenomenon of the nano silver antibacterial agent loaded before modifying and dispersing is not obviously improved, and the obtained antibacterial performance is excessively different.
Therefore, the design of the silver powder has important significance in avoiding the reduction of antibacterial performance caused by the agglomeration phenomenon caused by directly applying the nano silver powder and simultaneously avoiding the short sterilization time effect caused by the excessively high release speed of silver ions.
Disclosure of Invention
According to the defects of the prior art, the modified low-molecular-weight polyethylene with multiple electron bodies is obtained by modifying and grafting polyethylene with specific molecular weight, then metal silver ions are used as electrophiles to coordinate and crosslink with electron sites on the modified low-molecular-weight polyethylene, a stable ligand structure is generated in situ, and then the ligand is soaked in a resin material through swelling, so that the nano silver suicide resin material is obtained, and the problems in the background art are solved. Specifically, the technical scheme of the invention comprises the following contents:
a preparation method of a nano silver suicide resin material, which comprises the following steps:
mixing low molecular weight polyethylene with solvent and heating to 90-110 deg.c to dissolve and form mixed solution;
the mixed solution, the initiator and the maleic anhydride are mixed for reaction, and the modified low molecular weight polyethylene solution is obtained through filtration;
the modified low molecular weight polyethylene solution reacts with a silver-containing modified compound under acidic conditions to form a silver-polyethylene coordination compound solution;
and (3) immersing the resin material in the silver-polyethylene coordination compound solution, and then washing and drying sequentially to obtain the nano silver suicide resin material.
Further, the molecular weight of the low molecular weight polyethylene is 1000 to 5000.
Further, the solvent includes toluene or amyl acetate.
Further, the initiator comprises benzoyl peroxide or dilauroyl peroxide.
Further, the low molecular weight polyethylene: and (3) an initiator: the mass ratio of the maleic anhydride comprises: 100:1-5:4-8.
Further, the reaction conditions of the mixed solution, the initiator and the grafting monomer are reaction temperature 120-160 ℃ and reaction time 5-7 h.
Further, the preparation method of the silver-containing modified compound comprises the following steps:
dissolving a phenyl compound in acetone, adding a phosphate buffer solution to adjust the pH value of the solution dissolved with the phenyl compound to be 4.5-6.5, adding an inorganic silver compound into the solution dissolved with the phenyl compound, continuously stirring for 1-2 h, and removing the acetone by reduced pressure evaporation to obtain the silver-containing modified compound.
Further, the phenyl compound includes terephthalcrylic acid or terephthalaldehyde, the inorganic silver compound includes silver nitrate or silver oxide, and the phenyl compound: the mass ratio of the inorganic silver compound is 1-2:1, silver ions in silver nitrate or silver oxide are modified to coordinate and bridge two oxygen atoms in the phenyl compound, and the phenyl compound has low water solubility, so that the loss of silver ions during the modification coordination and bridge is avoided.
Further, the modified low molecular weight polyethylene solution: the mass ratio of the silver-containing modified compound comprises 10: 1-5, wherein the reaction conditions of the modified low molecular weight polyethylene solution and the silver-containing modified compound comprise a reaction temperature of 30-50 ℃, a stirring rotation speed of 100-300 r/min and a reaction time of 2-4 h, silver ions in the silver-containing modified compound are further coordinated and bridged with oxygen atoms of the modified low molecular weight polyethylene and are combined into the modified low molecular weight polyethylene, and the modified low molecular weight polyethylene and the phenyl compound are coordinated and bridged in a synergistic way, so that the silver ions form a stable ligand structure, slow release of the silver ions is realized, and further long-acting sterilization is realized.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, silver ions with sterilization effect are innovatively loaded in the modified low-molecular-weight polyethylene material through cooperative double coordination bridging, a stable ligand structure is formed in situ, and then the silver ions are indirectly introduced into the resin material through the modified low-molecular-weight polyethylene material in a swelling and impregnation physical mode, so that the agglomeration phenomenon caused by directly adopting nano silver powder or particles is avoided, and the direct addition of silver ions is avoided, so that the sterilization aging caused by the excessively high silver ion release speed is short, and the chemical structure of the resin molecules is not damaged.
Drawings
Fig. 1 is a schematic view of the effect of the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below by means of embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Unless otherwise indicated, the starting materials and reagents used in the present invention are commercially available or may be prepared by known methods.
The relevant reagent and raw material information are as follows:
polyethylene, toluene, amyl acetate, benzoyl peroxide, dilauryl peroxide, maleic anhydride, terephthaloyl acid, terephthalaldehyde, silver oxide, silver nitrate, phosphate buffer, PP resin (polypropylene), ABS resin (acrylonitrile-butadiene-styrene terpolymer), and PS resin (polystyrene) were all purchased from shanghai alaa Ding Shiji limited.
The nano silver powder is purchased from Zhongkeruping science and technology Co.
Preparation example 1:
the preparation of the silver-containing modified compound specifically comprises the following steps:
1g of terephthaloyl acid is weighed and placed in a beaker, 20ml of acetone is added into the beaker to be uniformly mixed and stirred, at the moment, the pH of the dissolved terephthaloyl acid solution is regulated to 4.5 by using phosphate buffer solution, 1g of silver nitrate is added to be mixed and stirred for 1h, and then acetone is removed by decompression evaporation through a rotary evaporator to obtain silver-containing modified compound solution.
Preparation example 2:
the preparation of the silver-containing modified compound specifically comprises the following steps:
weighing 2g of terephthalaldehyde, placing in a beaker, adding 30ml of methanol into the beaker, mixing and stirring uniformly, adjusting the pH of the dissolved terephthalaldehyde solution to 5.5 by using phosphate buffer solution, adding 1g of silver nitrate, mixing and stirring for 2 hours, and removing the methanol by decompression evaporation through a rotary evaporator to obtain the silver-containing modified compound solution.
Preparation example 3:
the preparation of the silver-containing modified compound specifically comprises the following steps:
2g of terephthaloyl acid is weighed and placed in a beaker, 30ml of acetone is added into the beaker to be uniformly mixed and stirred, at the moment, the pH of the dissolved terephthaloyl acid solution is regulated to 6.5 by using phosphate buffer solution, 1g of silver oxide is added to be mixed and stirred for 2 hours, and then acetone is removed by decompression evaporation through a rotary evaporator to obtain silver-containing modified compound solution.
Example 1:
the preparation method of the nano silver suicide resin material specifically comprises the following steps:
200g of polyethylene with the molecular weight of 1000 is weighed and added into a flask, 600ml of toluene is weighed and added into the flask to be mixed with the polyethylene, the flask containing the polyethylene is heated to 90 ℃, after the polyethylene is completely dissolved, 8g of maleic anhydride and 2g of benzoyl peroxide are respectively weighed and added into the dissolved polyethylene to be uniformly mixed, after the reaction system is heated to 120 ℃, the reaction is carried out for 7 hours, and the reaction solution is filtered to obtain the modified low molecular weight polyethylene solution. 500g of modified low molecular weight polyethylene solution is weighed and placed in a flask, 50g of silver-containing modified compound solution of preparation example 1 and the modified low molecular weight polyethylene solution are weighed, uniformly mixed and placed in a water bath kettle, the water bath temperature is controlled to be 30 ℃, a stirring rod is placed, the stirring speed is controlled to be 100r/min, and after 2 hours of reaction, the silver-polyethylene ligand solution is obtained. And (3) immersing the PP resin in the silver-polyethylene coordination compound solution for 30s, taking out, washing the surface with ethanol, and placing in a drying oven and drying at 60 ℃ for 6h to obtain the nano silver suicide resin material.
Example 2:
the preparation method of the nano silver suicide resin material specifically comprises the following steps:
200g of polyethylene with the molecular weight of 2000 is weighed and added into a flask, 600ml of amyl acetate is weighed and added into the flask to be mixed with the polyethylene, the flask containing the polyethylene is heated to 100 ℃, after the polyethylene is completely dissolved, 10g of maleic anhydride and 4g of benzoyl peroxide are respectively weighed and added into the dissolved polyethylene to be uniformly mixed, after the reaction system is heated to 120 ℃, the reaction is carried out for 7 hours, and the reaction solution is filtered to obtain the modified low molecular weight polyethylene solution. 500g of modified low molecular weight polyethylene solution is weighed and placed in a flask, 100g of silver-containing modified compound solution of preparation example 1 and the modified low molecular weight polyethylene solution are weighed, uniformly mixed and placed in a water bath kettle, the water bath temperature is controlled to be 40 ℃, a stirring rod is placed, the stirring speed is controlled to be 200r/min, and the silver-polyethylene ligand solution is obtained after 3h of reaction. And (3) immersing the ABS resin in the silver-polyethylene coordination compound solution for 30s, taking out, washing the surface with ethanol, and placing in a drying oven and drying at 60 ℃ for 6h to obtain the nano silver suicide resin material.
Example 3:
the preparation method of the nano silver suicide resin material specifically comprises the following steps:
200g of polyethylene with the molecular weight of 3000 is weighed and added into a flask, 600ml of toluene is weighed and added into the flask to be mixed with the polyethylene, the flask containing the polyethylene is heated to 110 ℃, after the polyethylene is completely dissolved, 12g of maleic anhydride and 6g of benzoyl peroxide are respectively weighed and added into the dissolved polyethylene to be uniformly mixed, after the reaction system is heated to 130 ℃, the reaction is carried out for 6 hours, and the reaction solution is filtered to obtain the modified low molecular weight polyethylene solution. 500g of modified low molecular weight polyethylene solution is weighed and placed in a flask, 150g of silver-containing modified compound solution of preparation example 2 and the modified low molecular weight polyethylene solution are weighed, uniformly mixed and placed in a water bath kettle, the water bath temperature is controlled to be 50 ℃, a stirring rod is placed, the stirring speed is controlled to be 300r/min, and after 4 hours of reaction, the silver-polyethylene ligand solution is obtained. And (3) immersing the PP resin in the silver-polyethylene coordination compound solution for 30s, taking out, washing the surface with ethanol, and placing in a drying oven and drying at 60 ℃ for 6h to obtain the nano silver suicide resin material.
Example 4:
the preparation method of the nano silver suicide resin material specifically comprises the following steps:
200g of polyethylene with the molecular weight of 4000 is weighed and added into a flask, 600ml of amyl acetate is weighed and added into the flask to be mixed with the polyethylene, the flask containing the polyethylene is heated to 110 ℃, 14g of maleic anhydride and 8g of benzoyl peroxide are respectively weighed and added into the dissolved polyethylene together to be uniformly mixed after the polyethylene is completely dissolved, the reaction system is heated to 140 ℃, after the reaction is carried out for 6 hours, the reaction solution is filtered to obtain the modified low molecular weight polyethylene solution. 500g of modified low molecular weight polyethylene solution is weighed and placed in a flask, 200g of silver-containing modified compound solution of preparation example 2 and the modified low molecular weight polyethylene solution are weighed, uniformly mixed and placed in a water bath kettle, the water bath temperature is controlled to be 50 ℃, a stirring rod is placed, the stirring speed is controlled to be 300r/min, and the silver-polyethylene ligand solution is obtained after 4h of reaction. And (3) immersing the PS resin in the silver-polyethylene coordination compound solution for 30s, taking out, washing the surface with ethanol, and placing in a drying oven and drying at 60 ℃ for 6h to obtain the nano silver suicide resin material.
Example 5:
the preparation method of the nano silver suicide resin material specifically comprises the following steps:
200g of polyethylene with molecular weight of 5000 is weighed and added into a flask, 600ml of toluene is weighed and added into the flask to be mixed with the polyethylene, the flask containing the polyethylene is heated to 110 ℃, 16g of maleic anhydride and 10g of benzoyl peroxide are respectively weighed and added into the dissolved polyethylene together after the polyethylene is completely dissolved and are uniformly mixed, the reaction system is heated to 160 ℃, after reaction is carried out for 5 hours, the reaction solution is filtered to obtain the modified low molecular weight polyethylene solution. 500g of modified low molecular weight polyethylene solution is weighed and placed in a flask, 250g of silver-containing modified compound solution of preparation example 2 and the modified low molecular weight polyethylene solution are uniformly mixed and placed in a water bath kettle, the water bath temperature is controlled to be 50 ℃, a stirring rod is placed, the stirring speed is controlled to be 300r/min, and the silver-polyethylene ligand solution is obtained after 4h of reaction. And (3) immersing the ABS resin in the silver-polyethylene coordination compound solution for 30s, taking out, washing the surface with ethanol, and placing in a drying oven and drying at 60 ℃ for 6h to obtain the nano silver suicide resin material.
Example 6:
the preparation method of the nano silver suicide resin material specifically comprises the following steps:
the benzoyl peroxide in example 4 is replaced by dilauroyl peroxide, and the rest conditions are unchanged, so that the nano silver suicide resin material is prepared.
Example 7:
the preparation method of the nano silver suicide resin material specifically comprises the following steps:
the benzoyl peroxide in example 4 was changed to dilauroyl peroxide, and the silver-containing modified compound solution was changed to the silver-containing modified compound of preparation example 3, and the remaining conditions were unchanged, to prepare the nano silver suicide resin material.
Example 8:
the preparation method of the nano silver suicide resin material specifically comprises the following steps:
the PS resin of example 4 was immersed in the silver-polyethylene complex solution for 30s to 60s, and the remaining conditions were unchanged, to prepare a nano silver suicide resin material.
Example 9:
the preparation method of the nano silver suicide resin material specifically comprises the following steps:
the PS resin of example 4 was immersed in the silver-polyethylene complex solution for 30s to 120s, and the remaining conditions were unchanged, to prepare a nano silver suicide resin material.
Example 10:
the preparation method of the nano silver suicide resin material specifically comprises the following steps:
the PS resin of example 4 was immersed in the silver-polyethylene complex solution for 30s instead of 180s, and the remaining conditions were unchanged, to prepare a nano silver suicide resin material.
Comparative example 1:
the preparation method of the nano silver suicide resin material specifically comprises the following steps:
200g of silver nitrate is weighed and completely dissolved by deionized water, PS resin is immersed in the silver nitrate solution for 120s, then the PS resin is taken out, the surface is washed by ethanol, and the PS resin is placed in a drying oven and dried for 6h at 60 ℃ to obtain the nano silver self-sterilizing resin material.
Comparative example 2:
the preparation method of the nano silver suicide resin material specifically comprises the following steps:
10g of nano silver powder is weighed and dissolved in toluene, the nano silver powder is uniformly dispersed under the action of ultrasound, then PS resin is soaked in toluene solution in which the nano silver powder is dispersed for 120s, the surface is washed by ethanol after being taken out, and the nano silver self-sterilizing resin material is obtained after being placed in a drying oven and dried for 6h at 60 ℃.
The nano silver suicide resin materials of examples 1 to 10 and comparative examples 1 to 2 were tested according to the test method of the antibacterial properties of plastics and non-porous surfaces of ISO 22196-2011, and the test results are shown in the following tables 1 and 2:
blank control: (free of silver ions and nanosilver particles)
200g of polyethylene with molecular weight 4000 is weighed and added into a flask, 600ml of amyl acetate is weighed and added into the flask to be mixed with the polyethylene, the flask containing the polyethylene is heated to 110 ℃, 14g of maleic anhydride and 8g of benzoyl peroxide are respectively weighed and added into the dissolved polyethylene to be uniformly mixed after the polyethylene is completely dissolved, the reaction system is heated to 140 ℃, after the reaction is carried out for 6 hours, the reaction solution is filtered to obtain a modified low molecular weight polyethylene solution, PS resin is immersed into the modified low molecular weight polyethylene solution for 30 seconds, the surface is washed by ethanol, and the mixture is placed into a drying box and dried for 6 hours at 60 ℃ to obtain the nano silver suicide resin material.
TABLE 1 detection results of E.coli
Wherein, antibacterial = log mean of residual viable bacteria 24h after inoculation of untreated plaques-log mean of residual viable bacteria 24h after inoculation of antibacterial plaques, by way of example: antibacterial property of example 1 = log mean of residual live bacteria 24h after blank inoculation-log mean of residual live bacteria 24h after example 1 inoculation = 6.25-1.59 = 4.66 ≡4.7, one position is reserved after decimal point.
TABLE 2 Staphylococcus aureus assay results
Wherein, antibacterial = log mean of residual viable bacteria 24h after inoculation of untreated plaques-log mean of residual viable bacteria 24h after inoculation of antibacterial plaques, by way of example: antibacterial activity=log mean of residual viable bacteria 24h after blank inoculation-log mean of residual viable bacteria 24h after example 1 inoculation=5.87-1.69=4.18≡4.2, one position is reserved after decimal point.
The foregoing embodiments have described the technical solutions and advantageous effects of the present invention in detail, and it should be understood that the foregoing embodiments are merely specific examples of the present invention, and are not intended to limit the present invention. The present invention is subject to various changes and modifications without departing from the spirit and scope thereof, and such changes and modifications fall within the scope of the invention as hereinafter claimed.
Claims (10)
1. The preparation method of the nano silver suicide resin material is characterized by comprising the following steps of:
mixing low molecular weight polyethylene with solvent and heating to 90-110 deg.c to dissolve and form mixed solution;
the mixed solution, the initiator and the maleic anhydride are mixed for reaction, and the modified low molecular weight polyethylene solution is obtained through filtration;
reacting the modified low molecular weight polyethylene solution with a silver-containing modifying compound to form a silver-polyethylene ligand solution;
and (3) immersing the resin material in the silver-polyethylene coordination compound solution, and then washing and drying sequentially to obtain the nano silver suicide resin material.
2. The method for preparing a nano-silver suicide resin material according to claim 1, wherein the molecular weight of the low molecular weight polyethylene is 1000-5000.
3. The method for preparing a nano-silver suicide resin material according to claim 1, wherein the initiator comprises benzoyl peroxide or dilauroyl peroxide.
4. The method for preparing a nano-silver suicide resin material according to claim 1, wherein the low molecular weight polyethylene: and (3) an initiator: the mass ratio of the maleic anhydride comprises: 100:1-5:4-8.
5. The method for preparing the nano-silver suicide resin material according to claim 1, wherein the reaction conditions of the mixed reaction of the mixed solution, the initiator and the grafting monomer comprise a reaction temperature of 120-160 ℃ and a reaction time of 5-7 h.
6. The method for preparing the nano-silver suicide resin material according to claim 1, wherein the method for preparing the silver-containing modified compound comprises the following steps:
dissolving a phenyl compound in acetone, adding a phosphate buffer solution to adjust the pH value of the solution dissolved with the phenyl compound to be 4.5-6.5, adding an inorganic silver compound into the solution dissolved with the phenyl compound, continuously stirring for 1-2 h, and removing the acetone by reduced pressure evaporation to obtain the silver-containing modified compound.
7. The method for preparing a nano-silver suicide resin material according to claim 6, wherein the phenyl compound comprises terephthalcrylic acid or terephthalaldehyde, the inorganic silver compound comprises silver nitrate or silver oxide, and the phenyl compound: the mass ratio of the inorganic silver compound is 1-2:1.
8. The method for preparing a nano-silver suicide resin material according to claim 1, wherein the modified low molecular weight polyethylene solution: the mass ratio of the silver-containing modified compound comprises 10:1 to 5.
9. A nano silver suicide resin material prepared by the method for preparing a nano silver suicide resin material according to any one of claims 1 to 8.
10. Use of the nano-silver suicide resin material of claim 9 in the field of antibacterial plastic products.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311787110.2A CN117700793A (en) | 2023-12-25 | 2023-12-25 | Nano silver suicide resin material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311787110.2A CN117700793A (en) | 2023-12-25 | 2023-12-25 | Nano silver suicide resin material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117700793A true CN117700793A (en) | 2024-03-15 |
Family
ID=90158699
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311787110.2A Pending CN117700793A (en) | 2023-12-25 | 2023-12-25 | Nano silver suicide resin material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117700793A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000204182A (en) * | 1999-08-16 | 2000-07-25 | Natl Inst Of Sericultural & Entomological Science | Antibacterial polymer raw material and its production |
| US20030190370A1 (en) * | 2000-10-09 | 2003-10-09 | Kim Sung Soo | Antibacterial agents, and antibacterial and deodorizing solution comprising the same |
| CN101926363A (en) * | 2009-06-23 | 2010-12-29 | 上海六立纳米材料科技有限公司 | Method for preparing liquid antibacterial agent containing complex silver |
| CN112900092A (en) * | 2021-03-04 | 2021-06-04 | 阳东 | Antibacterial soil-release fabric and preparation method thereof |
| CN116218041A (en) * | 2023-01-06 | 2023-06-06 | 山东东宏管业股份有限公司 | Long-acting antibacterial agent for polyolefin matrix, and preparation method and application thereof |
-
2023
- 2023-12-25 CN CN202311787110.2A patent/CN117700793A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000204182A (en) * | 1999-08-16 | 2000-07-25 | Natl Inst Of Sericultural & Entomological Science | Antibacterial polymer raw material and its production |
| US20030190370A1 (en) * | 2000-10-09 | 2003-10-09 | Kim Sung Soo | Antibacterial agents, and antibacterial and deodorizing solution comprising the same |
| CN101926363A (en) * | 2009-06-23 | 2010-12-29 | 上海六立纳米材料科技有限公司 | Method for preparing liquid antibacterial agent containing complex silver |
| CN112900092A (en) * | 2021-03-04 | 2021-06-04 | 阳东 | Antibacterial soil-release fabric and preparation method thereof |
| CN116218041A (en) * | 2023-01-06 | 2023-06-06 | 山东东宏管业股份有限公司 | Long-acting antibacterial agent for polyolefin matrix, and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 卡特迈尔等: "原子价与分子结构", 30 June 1981, 人民教育出版社, pages: 252 - 254 * |
| 朱鹏飞;吴明华;鲍进跃;: "马来酸酐改性甲基丙烯酰胺接枝棉织物的纳米银整理", 印染助剂, no. 01, 20 January 2016 (2016-01-20), pages 45 - 49 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Janardhanan et al. | Synthesis and surface chemistry of nano silver particles | |
| DE69509464T2 (en) | Antimicrobial | |
| EP2224054B1 (en) | Method for antimicrobial treatment of fiber, process for production of antimicrobial fiber, and antimicrobial fiber | |
| CN108589266A (en) | The method of nano-metal particle/metal organic frame composite antibacterial fibre cellulose fiber | |
| CN109232953B (en) | Polyvinimidyl chloramine type antibacterial cellulose membrane, preparation method and application | |
| US6294183B1 (en) | Antimicrobial resin composition and antimicrobial resin molded article comprising same | |
| US20240199826A1 (en) | Sustained-release antibacterial film and preparation method thereof | |
| CN102037988B (en) | Composite antibacterial agent and preparation method thereof | |
| CN107022241A (en) | A kind of Nano Silver and gelatin modified antibacterial prepared Chinese ink and preparation method thereof | |
| CN114541033B (en) | Monoatomic antibacterial antiviral mildew-proof aldehyde-removing non-woven fabric and preparation method thereof | |
| CN117700793A (en) | Nano silver suicide resin material and preparation method thereof | |
| Xu et al. | Synthesis and properties of the metallo-supramolecular polymer hydrogel poly [methyl vinyl ether-alt-mono-sodium maleate]· AgNO 3: Ag+/Cu 2+ ion exchange and effective antibacterial activity | |
| CN111676695A (en) | Dual-antibacterial non-woven fabric and preparation method thereof | |
| CN110527756A (en) | A kind of environment-friendly highly efficient leather nano antibacterial agent and its preparation method and application | |
| CN113354898A (en) | Antibacterial master batch and antibacterial plastic | |
| JPH07252378A (en) | Antibacterial mildewproof thermoplastic composition | |
| CN116732783A (en) | Metal organic framework composite antibacterial film and preparation method thereof | |
| CN111096393A (en) | Composite metal cysteamine chelate as well as preparation method and application thereof | |
| CN112831068B (en) | Preparation method of novel antibacterial composite material | |
| JP3650979B2 (en) | Antibacterial / antifungal polymer particles | |
| CN106689201B (en) | Nano silver antibacterial agent and preparation method thereof | |
| CN111296480B (en) | Iron-based metal-organic framework material loaded with silver nanoparticles and preparation method and application thereof | |
| CN114747668A (en) | Organic composite trace element and preparation method thereof | |
| JP2019048275A (en) | Method for manufacturing membrane filter for suppression of microorganism | |
| CN113402964A (en) | Antibacterial coating material, preparation method thereof, antibacterial coating and product |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |