CN114015120B - Antibacterial agent for plastic modification based on black phosphazene and preparation method thereof - Google Patents
Antibacterial agent for plastic modification based on black phosphazene and preparation method thereof Download PDFInfo
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- CN114015120B CN114015120B CN202111466772.0A CN202111466772A CN114015120B CN 114015120 B CN114015120 B CN 114015120B CN 202111466772 A CN202111466772 A CN 202111466772A CN 114015120 B CN114015120 B CN 114015120B
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- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000003242 anti bacterial agent Substances 0.000 title claims abstract description 57
- 229920003023 plastic Polymers 0.000 title claims abstract description 45
- 239000004033 plastic Substances 0.000 title claims abstract description 45
- 238000012986 modification Methods 0.000 title claims abstract description 25
- 230000004048 modification Effects 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910052709 silver Inorganic materials 0.000 claims abstract description 44
- 239000004332 silver Substances 0.000 claims abstract description 44
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000000463 material Substances 0.000 claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 23
- 238000005516 engineering process Methods 0.000 claims abstract description 11
- 239000011248 coating agent Substances 0.000 claims abstract description 10
- 238000000576 coating method Methods 0.000 claims abstract description 10
- 239000005922 Phosphane Substances 0.000 claims abstract description 9
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910000064 phosphane Inorganic materials 0.000 claims abstract description 9
- 238000011068 loading method Methods 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 3
- -1 dimethyl octadecyl Chemical group 0.000 claims description 61
- 239000002135 nanosheet Substances 0.000 claims description 60
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 56
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 48
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 238000001035 drying Methods 0.000 claims description 31
- 239000008367 deionised water Substances 0.000 claims description 30
- 229910021641 deionized water Inorganic materials 0.000 claims description 30
- 235000019270 ammonium chloride Nutrition 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 25
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 23
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical group CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 23
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 23
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 23
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 21
- RZXLPPRPEOUENN-UHFFFAOYSA-N Chlorfenson Chemical compound C1=CC(Cl)=CC=C1OS(=O)(=O)C1=CC=C(Cl)C=C1 RZXLPPRPEOUENN-UHFFFAOYSA-N 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 20
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 19
- 238000001914 filtration Methods 0.000 claims description 18
- 239000006185 dispersion Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical class [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000013078 crystal Substances 0.000 claims description 13
- 101710134784 Agnoprotein Proteins 0.000 claims description 11
- JHYNEQNPKGIOQF-UHFFFAOYSA-N 3,4-dihydro-2h-phosphole Chemical compound C1CC=PC1 JHYNEQNPKGIOQF-UHFFFAOYSA-N 0.000 claims description 10
- 239000007791 liquid phase Substances 0.000 claims description 10
- 238000001179 sorption measurement Methods 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- UDEGSYXELBQAAG-UHFFFAOYSA-N azanium;methanol;chloride Chemical compound [NH4+].[Cl-].OC UDEGSYXELBQAAG-UHFFFAOYSA-N 0.000 claims description 9
- 238000005342 ion exchange Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 229920001296 polysiloxane Polymers 0.000 claims description 7
- 239000011541 reaction mixture Substances 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 4
- RECVMTHOQWMYFX-UHFFFAOYSA-N oxygen(1+) dihydride Chemical compound [OH2+] RECVMTHOQWMYFX-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- 238000000498 ball milling Methods 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 40
- 239000012752 auxiliary agent Substances 0.000 abstract description 16
- 238000012545 processing Methods 0.000 abstract description 9
- 238000001125 extrusion Methods 0.000 abstract description 6
- 229920001169 thermoplastic Polymers 0.000 abstract description 6
- 239000011159 matrix material Substances 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 229920005992 thermoplastic resin Polymers 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000005728 strengthening Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 2
- 239000010410 layer Substances 0.000 description 17
- 239000002064 nanoplatelet Substances 0.000 description 15
- BSWGGJHLVUUXTL-UHFFFAOYSA-N silver zinc Chemical compound [Zn].[Ag] BSWGGJHLVUUXTL-UHFFFAOYSA-N 0.000 description 15
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 150000005215 alkyl ethers Chemical class 0.000 description 5
- 230000002431 foraging effect Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 5
- 241000894006 Bacteria Species 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910021389 graphene Inorganic materials 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- 241000588724 Escherichia coli Species 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 241000222120 Candida <Saccharomycetales> Species 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 241000192125 Firmicutes Species 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- RJQXTJLFIWVMTO-TYNCELHUSA-N Methicillin Chemical compound COC1=CC=CC(OC)=C1C(=O)N[C@@H]1C(=O)N2[C@@H](C(O)=O)C(C)(C)S[C@@H]21 RJQXTJLFIWVMTO-TYNCELHUSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000002730 additional effect Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000002538 fungal effect Effects 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229960003085 meticillin Drugs 0.000 description 1
- 244000000010 microbial pathogen Species 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 239000003642 reactive oxygen metabolite Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
Classifications
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
-
- 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
-
- 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
- C08K3/16—Halogen-containing compounds
-
- 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
- C08K3/28—Nitrogen-containing compounds
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- 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
- C08K2003/026—Phosphorus
-
- 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
- C08K3/16—Halogen-containing compounds
- C08K2003/168—Zinc halides
-
- 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
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Abstract
The invention relates to the technical field of high polymer material processing, in particular to a black phosphazene-based antibacterial agent for plastic modification and a preparation method thereof; the antibacterial agent is prepared by loading silver and zinc ions on a carrier of sulfonated graphene oxide doped with black phosphazene, and coating a double-layer oligomer of the carrier by using a fluid-like technology, wherein the formed solid powder has a viscous fluid-like characteristic under the condition of no solvent; the antibacterial agent is a two-nanometer material based on the black phosphane, and can play a role in strengthening and toughening in a matrix, so that the mechanical property of plastics is slightly improved, which is not possessed by the traditional solid powder antibacterial auxiliary agent; the antibacterial agent and other modification auxiliary agents can be simply mixed with various thermoplastic plastic base materials in proportion, and the mixture is melted, extruded and granulated by a double-screw extrusion granulator set to prepare the required plastic compound, and the combination mode of the antibacterial agent and other modification auxiliary agents and the mixture ratio of the antibacterial agent and the thermoplastic resin base materials can be flexibly prepared according to different performance requirements of customers so as to adjust the performance and the cost of the antibacterial agent and other modification auxiliary agents.
Description
Technical Field
The invention relates to the technical field of polymer material processing, in particular to a black phosphazene-based antibacterial agent for plastic modification and a preparation method thereof.
Technical Field
The mildew of daily plastic products (especially kitchen and bathroom plastic products) is the most common problem in the field of plastic processing application, and the health hazard of the daily plastic products caused by pathogenic microorganisms is always one of the main threats faced by people in life. The antibacterial agent is used for modifying the plastic, so that the color change of the product and the degradation of the product caused by bacterial growth, mildew and fermentation can be prevented, and the color retention of the plastic in the internal and external environments is optimized. In the process of developing the antibacterial plastic technology, inorganic antibacterial auxiliary agents loaded by silver, copper, zinc ions and the like are the main technology for preparing the antibacterial plastic at present. For example, chinese patent CA1344494A discloses an antibacterial agent which is prepared by loading silver ions on nano silicon oxide and is coated by insoluble aluminum salt, and the antibacterial auxiliary agent can be applied to processing and application of various thermoplastics. Chinese patent CN1817138A discloses a silver-loaded antimicrobial agent using mesoporous silica, which kills most gram-negative and positive bacteria including escherichia coli. Chinese patent CN1919000a discloses a silver-loaded antibiotic auxiliary agent using zeolite as carrier, which can provide good antibacterial effect for various plastic product surfaces.
Most of antibacterial plastic products sold in the market at present take inorganic powder materials loaded with nontoxic heavy metal ions such as silver, zinc, copper and the like as the antibacterial auxiliary agents for plastic antibacterial modification. In the processing process, the antibacterial auxiliary agents and plastics are firstly subjected to high-temperature mechanical blending extrusion above the melting temperature of the antibacterial auxiliary agents and plastics to prepare the required antibacterial plastics, and then various products required by daily life are prepared through extrusion or injection molding. Therefore, the high dispersibility of the antibacterial auxiliary agent in the processing process and the long-acting stable release of silver ions in the use process of the product are key factors for influencing the antibacterial effect of the antibacterial auxiliary agent in the plastic product. At present, most of antibacterial auxiliary agents based on inorganic carriers for loading silver, zinc and copper ions have certain problems in the two key technologies, the traditional inorganic materials are difficult to obtain ultrafine uniform dispersion of single particles in plastics, and under the condition that the inorganic carriers loaded with the silver, zinc and copper ions are not protected, the release of the metal ions is in a trend of more before less, faster before slow, so that the antibacterial performance of the inorganic materials cannot be stably and long-term exerted. Therefore, development of an efficient long-life antibacterial agent special for plastic modification is needed to meet the requirements of efficient and long-period antibacterial application of antibacterial plastics and products thereof.
Disclosure of Invention
The purpose of the invention is that: overcomes the defects in the prior art and provides an efficient long-life antibacterial agent for plastic modification, which takes sulfonated graphene oxide doped with black phosphazene as a carrier to load silver and zinc ions.
In order to solve the technical problems, the invention adopts the following technical scheme:
the antibacterial agent is prepared by loading silver and zinc ions on a carrier of sulfonated graphene oxide doped with black phosphazene, and coating a double-layer oligomer of the antibacterial agent by using a fluid-like technology, wherein the formed solid powder antibacterial agent has a viscous fluid-like characteristic under the condition of no solvent.
Further, the inner oligomer in the double-layer oligomer is dimethyl octadecyl [ 3-trimethoxy silicon propyl ] ammonium chloride, and the outer oligomer is nonylphenol polyoxyethylene ether potassium sulfonate.
Another object of the invention is: overcomes the defects in the prior art and provides a preparation method of a black phosphazene-based antibacterial agent for plastic modification.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of a black phosphazene-based antibacterial agent for plastic modification comprises the following steps:
1) Adding black phosphorus and methyl pyrrolidone into a ball mill according to a certain proportion, grinding, filtering, vacuum drying, dispersing the obtained black phosphorus crystal powder in a saturated NaOH/NMP solution, performing ultrasonic vibration dispersion, and then performing centrifugal separation and vacuum drying to obtain liquid-phase stripped black phosphane nano-sheets for later use;
2) Dispersing the black phosphazene nano-sheets obtained in the step 1) in deionized water, and then proportionally mixing AgNO 3 、ZnCl 2 Adding sulfonated graphene oxide into the dispersion system to adsorb silver and zinc ions, continuously stirring and mixing for a period of time, and then filtering and vacuum drying;
3) Putting the silver and zinc ion-loaded and sulfonated graphene oxide doped black phosphorus nano-sheet obtained in the step 2) into deionized water together with dimethyl octadecyl [ 3-trimethoxy silicon propyl ] ammonium chloride methanol solution according to a material putting proportion, and stirring for a period of time at normal temperature to enable the dimethyl octadecyl [ 3-trimethoxy silicon propyl ] ammonium chloride to be coated on the surface of the silver and zinc ion-loaded and sulfonated graphene oxide doped black phosphorus nano-sheet through physical adsorption; then standing and aging the reaction mixture to enable the black phosphazene nano-sheet to be subjected to dimethyl octadecyl [ 3-trimethoxy silicon propyl ] ammonium chloride; washing the obtained product with deionized water, filtering and drying;
4) Mixing the product obtained in the step 3) with a nonylphenol polyoxyethylene ether sulfonate potassium salt aqueous solution according to a material throwing proportion, stirring at 70 ℃ to enable chlorine ions in dimethyl octadecyl [ 3-trimethoxy silicone propyl ] ammonium chloride coated on black phospholene nano-sheets loaded with silver and zinc ions and doped with sulfonated graphene oxide to carry out ion exchange reaction with sulfonate ions in nonylphenol polyoxyethylene ether sulfonate potassium salt, washing the product with deionized water, filtering and drying in an oven after the reaction is completed, and obtaining the black phospholene nano-sheets coated on the inner layer and the outer layer of the silver and zinc ions and doped with sulfonated graphene oxide.
Further, the material ratio of black phosphorus to methyl pyrrolidone in the step 1) is as follows: 200.0mL of methylpyrrolidone was added per 100.0g of black phosphorus; ball milling time is 24 hours, ultrasonic vibration is carried out for 24 hours, drying temperature of vacuum drying is 95 ℃, and drying time is 12 hours;
the material ratio of the black phosphorus crystal powder to the saturated NaOH/NMP solution is as follows: every 100g of black phosphorus crystal powder, 1500.0-2000.0 mL of NaOH/NMP solution is put in.
Further, the black phosphazene nanosheets in the step 1) are stored for standby under nitrogen atmosphere.
Further, in the step 2), the black phosphazene nano-sheet and AgNO 3 、ZnCl 2 And the mass percentages of the sulfonated graphene oxide are respectively as follows: 93.0 to 98.0wt percent of black phosphane nano-sheet and AgNO 3 2.0～6.0wt.％，ZnCl 2 0.5 to 1.0wt.% of sulfonated graphene oxide, 0.5 to 1.0wt.%.
Further, in the step 2), the mixing and stirring time is 8-10 hours, the vacuum drying temperature is 95 ℃, the drying time is 12 hours, and the adding amount of deionized water is as follows: 300.0-400.0 mL of water ion water is put in every 100g of black phosphazene nano-sheets.
Further, the material feeding ratio in the step 3) is as follows: 30.0-50.0 mL of dimethyl octadecyl [ 3-trimethoxy silicon propyl ] ammonium chloride methanol solution with the mass percentage concentration of 40.0wt.% and 250.0-400.0 mL of water ion water are added into each 100g of black phosphazene nano-sheet which is loaded with silver ions and zinc ions and doped with sulfonated graphene oxide and is obtained in the step 2).
Further, the material feeding ratio in the step 4) is as follows: the material throwing proportion is as follows: 180.0-200.0 mL of nonylphenol polyoxyethylene ether potassium sulfonate aqueous solution with the mass percentage concentration of 10.0wt.% is added into 100.0g of the product obtained in the step (3).
Further, in the step 3), the stirring time at normal temperature is 3-5 h, the standing aging time is 20h, the drying temperature of the product is 105 ℃, and the drying time is 24h;
the reaction time in the step 4) is 24 hours, the drying temperature is 105 ℃, and the drying time is 24 hours.
The technical scheme of the invention has the beneficial effects that:
(1) The black phosphane nanometer sheet is used as an emerging two-dimensional nanometer material, has an ultrathin layer structure and a huge specific surface area, has extremely high molecular adsorption energy and extremely high adsorption effect on metal ions, adopts the black phosphane nanometer sheet as a carrier, introduces a small amount of sulfonated graphite oxide, obviously improves the ion exchange adsorption performance, can adsorb a large amount of silver and zinc ions on the surface of the black phosphane nanometer sheet, and obviously improves the loading capacity of the silver and zinc ions as antibacterial active ingredients; the high loading of silver and zinc ions is more helpful to promote the antibacterial efficacy and longer service life of the modified plastic.
(2) The tendency of the black phosphazenes to decompose generates reactive oxygen species, thereby destroying the bacterial and fungal outer membranes and causing them to die. A great deal of researches show that the black phosphazene has extremely strong resistance to various bacteria including escherichia coli, methicillin-resistant staphylococcus aureus, candida otorhinoceros and the like, 99 percent of the bacteria are killed within 2 hours, and the black phosphazene has the advantages of broad antibacterial spectrum, high sterilization efficiency and difficult generation of drug resistance. Therefore, when the black phosphazene not only plays the function of an efficient carrier, but also can be organically combined with silver and zinc ions to generate antibacterial effect superposition, so that the antibacterial capability of the black phosphazene is more remarkable than that of the traditional inorganic carrier loaded with silver and zinc ion antibacterial auxiliary agents.
(3) The polysiloxane quaternary ammonium salt is used as an inner crown, the long-chain alkyl ether potassium salt is used as an outer crown, and the silver and zinc ion loaded black phosphazene nano-sheet is coated by a surface self-assembly technology and an ion exchange technology, so that a compound with fluid-like characteristics is formed. The double coating can effectively protect silver and zinc ions loaded on the black phosphazene nano-sheet, so that the obtained antibacterial agent is not easy to leak and run off in the storage, transportation and processing processes, has good storage and processing stability, prolongs the time of the silver and zinc ions in a plastic matrix, and further improves the action period of the antibacterial agent.
(4) The characteristic of macroscopic fluid is obtained by applying the special internal and external crown oligomer composite coating mode of the fluid-like technology and using the internal and external crown oligomer composite coating mode as powder. This particular morphology is extremely advantageous for the uniform dispersion of silver, zinc ion loaded black phosphazene nanoplatelets in plastic resin matrices, even in monodisperse form. Compared with the traditional inorganic powder material, the inorganic powder material has better dispersion performance, thereby being beneficial to the uniform release of the solid powder antibacterial agent in the resin matrix and playing better antibacterial effect.
(5) The antibacterial agent is a two-nanometer material based on the black phosphane, and can play a role in strengthening and toughening in a matrix, so that the mechanical property of plastics is slightly improved, and the additional effect is not possessed by the traditional solid powder antibacterial auxiliary agent.
(6) The high-efficiency long-life antibacterial agent prepared by the invention can be prepared into a plastic compound with high-efficiency long-life antibacterial function by simply mixing the high-efficiency long-life antibacterial agent with various thermoplastic plastic base materials according to a certain proportion, and then carrying out melt extrusion granulation by a double-screw extrusion granulator set, and can flexibly prepare the combination mode of the high-efficiency long-life antibacterial agent and other modification auxiliary agents and the proportion of the high-efficiency long-life antibacterial agent and thermoplastic resin raw materials according to different performance requirements of customers so as to adjust the performance and cost of the high-efficiency long-life antibacterial agent and the thermoplastic resin raw materials, thereby rapidly and simply achieving the target requirements of product design, and practicing the optimal design concept of plastic modification formula and processing technology.
Drawings
FIG. 1 is a scanning electron micrograph of liquid phase exfoliated black phospholene nanoplatelets prepared in step 1) of example 1.
Fig. 2 is a transmission electron micrograph of the liquid phase exfoliated black phosphane nanoplatelets prepared in step 1) of example 1.
Fig. 3 is a transmission electron micrograph of the product obtained by coating the silver-zinc ion-loaded and sulfonated graphite oxide-doped black phosphazene nanoplatelets described above with a polysiloxane quaternary ammonium salt and a long-chain alkyl ether potassium salt in steps 2) to 4) of example 1.
Fig. 4 is a photograph showing the appearance of silver-zinc ion-loaded sulfonated graphite oxide doped black phosphazene nanoplatelets prepared in steps 2) to 4) of example 1 after being coated with a polysiloxane quaternary ammonium salt and a long-chain alkyl ether potassium salt.
Detailed Description
The following examples will provide those skilled in the art with a more complete understanding of the present invention, and are intended to be illustrative of some, but not all, of the examples. These examples are not intended to limit the scope of the invention. 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 fall within the scope of the invention. Reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic may be included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
It should be noted that the experimental methods used in the following examples are conventional methods unless otherwise specified. Materials, reagents, etc. used in the examples were commercially available with negligible effect on product performance from different product models unless specifically stated.
Example 1
A preparation method of a high-efficiency long-life antibacterial agent based on black phosphazene comprises the following steps:
1) 100.0g of bulk black phosphorus and 200.0mL of NMP are put into a ball mill for grinding for 24 hours, then filtered and dried in a vacuum oven at 95 ℃ for 12 hours; dispersing the obtained black phosphorus crystal powder in 1600.0mL of saturated NaOH/NMP solution, placing the dispersion liquid into an ultrasonic vibrator for vibrating for 24 hours, then centrifugally separating, drying in a vacuum oven at 95 ℃ for 12 hours, and preserving the obtained liquid-phase stripped black phosphorus alkene nano-sheet in a nitrogen atmosphere for later use.
2) 93.0g of the black phosphazene nanosheets obtained in step 1) were dispersed in 350.0mL of deionized water, and then 5.5g of AgNO was added 3 、1.0g ZnCl 2 And 0.5g of sulfonated graphene oxide are added into the water dispersion system to adsorb silver and zinc ions, stirring and mixing are continued for 9 hours, then filtration is carried out, and drying is carried out in a vacuum oven at 95 ℃ for 12 hours.
3) Taking 100.0g of silver-zinc ion-loaded and sulfonated graphene oxide-doped black phosphorus nano-sheet obtained in the step 2), adding the silver-zinc ion-loaded and sulfonated graphene oxide-doped black phosphorus nano-sheet into 300mL of deionized water together with 40.0mL of dimethyl octadecyl [ 3-trimethoxy silicon propyl ] ammonium chloride methanol solution (with the mass percentage concentration of 40.0 wt.%), stirring for 3.5h at normal temperature, and coating the silver-zinc ion-loaded and sulfonated graphene oxide-doped black phosphorus nano-sheet surface by physical adsorption of dimethyl octadecyl [ 3-trimethoxy silicon propyl ] ammonium chloride; however, the reaction mixture is kept stand for 20 hours for aging, so that the black phosphazene nano-sheet is subjected to dimethyl octadecyl [ 3-trimethoxy silicon propyl ] ammonium chloride; the resulting product was washed with deionized water, filtered, and dried in an oven at 105 ℃ for 24h.
4) Mixing 100.0g of the product obtained in the step 3) with 190.0mL of nonylphenol polyoxyethylene ether sulfonate aqueous solution (the mass percentage concentration is 10 wt.%), and stirring at 70 ℃ to enable chloride ions in dimethyl octadecyl [ 3-trimethoxy silicon propyl ] ammonium chloride coated on the surface of a black phosphazene nano-sheet loaded with silver and zinc ions and doped with sulfonated graphene oxide to carry out ion exchange reaction with sulfonate ions in nonylphenol polyoxyethylene ether sulfonate potassium salt; after 24 hours of reaction, washing the product with deionized water, filtering, and drying in an oven at 105 ℃ for 24 hours to obtain a silver-and zinc-ion-loaded and sulfonated graphene oxide doped black phosphazene nano-sheet coated by taking dimethyl octadecyl [ 3-trimethoxy silicon propyl ] ammonium chloride as an inner layer and nonylphenol polyoxyethylene ether sulfonate potassium salt as an outer layer, thereby preparing the efficient long-life antibacterial agent based on black phosphazene.
Example 2
A preparation method of a high-efficiency long-life antibacterial agent based on black phosphazene comprises the following steps:
1) 100.0g of bulk black phosphorus and 200.0mL of NMP are put into a ball mill for grinding for 24 hours, then filtered and dried in a vacuum oven at 95 ℃ for 12 hours; the obtained black phosphorus crystal powder is dispersed in 1500.0mL of saturated NaOH/NMP solution, the dispersion is placed into an ultrasonic vibrator to vibrate for 24h, then centrifugal separation is carried out, and the obtained black phosphorus crystal powder is dried in a vacuum oven at 95 ℃ for 12h, and the obtained liquid-phase stripped black phosphorus alkene nano-sheet is preserved for standby under nitrogen atmosphere.
2) 94.0g of the black phosphazene nanoplatelets obtained in step 1) are dispersed in 400.0mL of deionized water, and then 4.0g of AgNO is added 3 、1.0g ZnCl 2 And 1.0g of sulfonated graphene oxide are added into the water dispersion system to adsorb silver and zinc ions, stirring and mixing are continued for 9 hours, then filtration is carried out, and drying is carried out in a vacuum oven at 95 ℃ for 12 hours.
3) Taking 100.0g of silver-zinc ion-loaded and sulfonated graphene oxide-doped black phosphorus nano-sheet obtained in the step 2), putting into 350mL of deionized water together with 50m.0L of dimethyl octadecyl [ 3-trimethoxy silicon propyl ] ammonium chloride methanol solution (with the mass percentage concentration of 40.0 wt.%), stirring for 3.5h at normal temperature, and coating the silver-zinc ion-loaded and sulfonated graphene oxide-doped black phosphorus nano-sheet surface with dimethyl octadecyl [ 3-trimethoxy silicon propyl ] ammonium chloride by physical adsorption; however, the reaction mixture is kept stand for 20 hours for aging, so that the black phosphazene nano-sheet is subjected to dimethyl octadecyl [ 3-trimethoxy silicon propyl ] ammonium chloride; the resulting product was washed with deionized water, filtered, and dried in an oven at 105 ℃ for 24h.
4) Mixing 100.0g of the product obtained in the step 3) with 200.0mL of nonylphenol polyoxyethylene ether sulfonate aqueous solution (the mass percentage concentration is 10.0 wt.%), and stirring at 70 ℃ to enable chloride ions in dimethyl octadecyl [ 3-trimethoxy silicon propyl ] ammonium chloride coated on the surfaces of the graphene nano-sheets loaded with silver and zinc ions and doped with sulfonated graphene oxide to carry out ion exchange reaction with sulfonate ions in nonylphenol polyoxyethylene ether sulfonate potassium salt; after 24 hours of reaction, washing the product with deionized water, filtering, and drying in an oven at 105 ℃ for 24 hours to obtain a silver-and zinc-ion-loaded and sulfonated graphene oxide doped black phosphazene nano-sheet coated by taking dimethyl octadecyl [ 3-trimethoxy silicon propyl ] ammonium chloride as an inner layer and nonylphenol polyoxyethylene ether sulfonate potassium salt as an outer layer, thereby preparing the efficient long-life antibacterial agent based on black phosphazene.
Example 3
A preparation method of a high-efficiency long-life antibacterial agent based on black phosphazene comprises the following steps:
1) 100.0g of bulk black phosphorus and 200.0mL of NMP are put into a ball mill for grinding for 24 hours, then filtered and dried in a vacuum oven at 95 ℃ for 12 hours; the obtained black phosphorus crystal powder is dispersed in 1800.0mL of saturated NaOH/NMP solution, the dispersion liquid is placed into an ultrasonic vibrator to vibrate for 24h, and then centrifugal separation and drying are carried out in a vacuum oven at 95 ℃ for 12h, and the obtained liquid-phase stripped black phosphorus alkene nano-sheet is preserved for standby under nitrogen atmosphere.
2) 96.0g of the black phosphazene nanoplatelets obtained in the step 1) are dispersed in 390.0mL of deionized water, and then 2.5g of AgNO is added 3 、0.5g ZnCl 2 And 1.0g of sulfonated graphene oxide are added into the water dispersion system to adsorb silver and zinc ions, stirring and mixing are continued for 8 hours, then filtration is carried out, and drying is carried out in a vacuum oven at 95 ℃ for 12 hours.
3) Taking 100.0g of the silver-zinc ion-loaded and sulfonated graphene oxide-doped black phosphorus nano sheet obtained in the step 2), putting into 370mL of deionized water together with 45.0mL of dimethyl octadecyl [ 3-trimethoxy silicon propyl ] ammonium chloride methanol solution (with the mass percentage concentration of 40.0 wt.%), and stirring for 5 hours at normal temperature, so that the dimethyl octadecyl [ 3-trimethoxy silicon propyl ] ammonium chloride coats the silver-zinc ion-loaded and sulfonated graphene oxide-doped black phosphorus nano sheet surface through physical adsorption; however, the reaction mixture is kept stand for 20 hours for aging, so that the black phosphazene nano-sheet is subjected to dimethyl octadecyl [ 3-trimethoxy silicon propyl ] ammonium chloride; the resulting product was washed with deionized water, filtered, and dried in an oven at 105 ℃ for 24h.
4) Mixing 100.0g of the product obtained in the step 3) with 185.0mL of nonylphenol polyoxyethylene ether sulfonate aqueous solution (the mass percentage concentration is 10 wt.%), and stirring at 70 ℃ to enable chloride ions in dimethyl octadecyl [ 3-trimethoxy silicon propyl ] ammonium chloride coated on the surface of a graphene nano-sheet loaded with silver and zinc ions and doped with sulfonated graphene oxide to carry out ion exchange reaction with sulfonate ions in nonylphenol polyoxyethylene ether sulfonate potassium salt; after 24 hours of reaction, washing the product with deionized water, filtering, and drying in an oven at 105 ℃ for 24 hours to obtain a silver-and zinc-ion-loaded and sulfonated graphene oxide doped black phosphazene nano-sheet coated by taking dimethyl octadecyl [ 3-trimethoxy silicon propyl ] ammonium chloride as an inner layer and nonylphenol polyoxyethylene ether sulfonate potassium salt as an outer layer, thereby preparing the efficient long-life antibacterial agent based on black phosphazene.
Example 4
A preparation method of a high-efficiency long-life antibacterial agent based on black phosphazene comprises the following steps:
1) 100.0g of bulk black phosphorus and 200.0mL of NMP are put into a ball mill for grinding for 24 hours, then filtered and dried in a vacuum oven at 95 ℃ for 12 hours; the obtained black phosphorus crystal powder is dispersed in 1650mL of saturated NaOH/NMP solution, the dispersion is placed into an ultrasonic vibrator to vibrate for 24h, then centrifugal separation is carried out, and the obtained black phosphorus crystal powder is dried in a vacuum oven at 95 ℃ for 12h, and the obtained liquid-phase stripped black phosphorus alkene nano-sheet is preserved for standby under nitrogen atmosphere.
2) Taking 95.0g of the black phosphazene nanoplatelets obtained in the step 1) and dispersing in 390mL of deionized water, and then dispersing 3.4g of AgNO 3 、0.8g ZnCl 2 And 0.8g of sulfonated graphene oxide are added into the water dispersion system to adsorb silver and zinc ions, stirring and mixing are continued for 10 hours, then filtration is carried out, and drying is carried out in a vacuum oven at 95 ℃ for 12 hours.
3) Taking 100.0g of the silver-zinc ion-loaded and sulfonated graphene oxide-doped black phosphorus nano sheet obtained in the step 2), putting into 280.0mL of deionized water together with 35mL of dimethyl octadecyl [ 3-trimethoxy silicon propyl ] ammonium chloride methanol solution (the mass percentage concentration is 40.0 wt.%), and stirring for 4 hours at normal temperature, so that the dimethyl octadecyl [ 3-trimethoxy silicon propyl ] ammonium chloride coats the silver-zinc ion-loaded and sulfonated graphene oxide-doped black phosphorus nano sheet surface through physical adsorption; however, the reaction mixture is kept stand for 20 hours for aging, so that the black phosphazene nano-sheet is subjected to dimethyl octadecyl [ 3-trimethoxy silicon propyl ] ammonium chloride; the resulting product was washed with deionized water, filtered, and dried in an oven at 105 ℃ for 24h.
4) Mixing 100.0g of the product obtained in the step 3) with 195.0mL of nonylphenol polyoxyethylene ether sulfonate aqueous solution (the mass percentage concentration is 10 wt.%), and stirring at 70 ℃ to enable chloride ions in dimethyl octadecyl [ 3-trimethoxy silicon propyl ] ammonium chloride coated on the surface of the graphene nano-sheet loaded with silver and zinc ions and doped with sulfonated graphene oxide to carry out ion exchange reaction with sulfonate ions in nonylphenol polyoxyethylene ether sulfonate potassium salt; after 24 hours of reaction, washing the product with deionized water, filtering, and drying in an oven at 105 ℃ for 24 hours to obtain a silver-and zinc-ion-loaded and sulfonated graphene oxide doped black phosphazene nano-sheet coated by taking dimethyl octadecyl [ 3-trimethoxy silicon propyl ] ammonium chloride as an inner layer and nonylphenol polyoxyethylene ether sulfonate potassium salt as an outer layer, thereby preparing the efficient long-life antibacterial agent based on black phosphazene.
Example 5
A preparation method of a high-efficiency long-life antibacterial agent based on black phosphazene comprises the following steps:
1) 100.0g of bulk black phosphorus and 200.0mL of NMP are put into a ball mill for grinding for 24 hours, then filtered and dried in a vacuum oven at 95 ℃ for 12 hours; dispersing the obtained black phosphorus crystal powder in 2000.0mL of saturated NaOH/NMP solution, placing the dispersion liquid into an ultrasonic vibrator for vibrating for 24 hours, then centrifugally separating, drying in a vacuum oven at 95 ℃ for 12 hours, and preserving the obtained liquid-phase stripped black phosphorus alkene nano-sheet under nitrogen atmosphere for later use.
2) 93.0g of the black phosphazene nanoplatelets obtained in step 1) were dispersed in 390.0mL of deionized water, and then 5.0g of AgNO was added 3 、1.4g ZnCl 2 And 0.6g of sulfonated graphene oxide are added into the water dispersion system to adsorb silver and zinc ions, stirring and mixing are continued for 8 hours, then filtration is carried out, and drying is carried out in a vacuum oven at 95 ℃ for 12 hours.
3) Taking 100.0g of silver-zinc ion-loaded and sulfonated graphene oxide-doped black phosphorus nano-sheet obtained in the step 2), putting the silver-zinc ion-loaded and sulfonated graphene oxide-doped black phosphorus nano-sheet into 300.0mL of deionized water together with 30mL of dimethyl octadecyl [ 3-trimethoxy silicon propyl ] ammonium chloride methanol solution (the mass percentage concentration is 40.0 wt.%), stirring for 4.5h at normal temperature, and coating the silver-zinc ion-loaded and sulfonated graphene oxide-doped black phosphorus nano-sheet surface by physical adsorption of dimethyl octadecyl [ 3-trimethoxy silicon propyl ] ammonium chloride; however, the reaction mixture is kept stand for 20 hours for aging, so that the black phosphazene nano-sheet is subjected to dimethyl octadecyl [ 3-trimethoxy silicon propyl ] ammonium chloride; the resulting product was washed with deionized water, filtered, and dried in an oven at 105 ℃ for 24h.
4) Mixing 100.0g of the product obtained in the step 3) with 200.0mL of nonylphenol polyoxyethylene ether sulfonate aqueous solution (the mass percentage concentration is 10.0 wt.%), and stirring at 70 ℃ to enable chloride ions in dimethyl octadecyl [ 3-trimethoxy silicon propyl ] ammonium chloride coated on the surfaces of the graphene nano-sheets loaded with silver and zinc ions and doped with sulfonated graphene oxide to carry out ion exchange reaction with sulfonate ions in nonylphenol polyoxyethylene ether sulfonate potassium salt; after 24 hours of reaction, washing the product with deionized water, filtering, and drying in an oven at 105 ℃ for 24 hours to obtain a silver-and zinc-ion-loaded and sulfonated graphene oxide doped black phosphazene nano-sheet coated by taking dimethyl octadecyl [ 3-trimethoxy silicon propyl ] ammonium chloride as an inner layer and nonylphenol polyoxyethylene ether sulfonate potassium salt as an outer layer, thereby preparing the efficient long-life antibacterial agent based on black phosphazene.
The liquid phase exfoliated black phospholene nanoplatelets prepared according to step 1) of the method described in example 1 were shown in fig. 1 and the transmission electron microscopy was shown in fig. 2, and the black phospholene nanoplatelets were found to have multi-wrinkled thin-layer nanostructures. After the silver and zinc ion-loaded and sulfonated graphite oxide doped black phospholene nanoplatelets are coated by using polysiloxane quaternary ammonium salt and long-chain alkyl ether potassium salt according to the steps 2) to 4) in the method described in the example 1, the external color deepening of the surface of the black phospholene nanoplatelets with a thin layer nano structure can be clearly observed, and obvious edges exist at the periphery of the black phospholene nanoplatelets, so that the existence of an oligomer coating layer is indicated. Fig. 4 shows a photograph of the appearance of silver-zinc ion-loaded sulfonated graphite oxide doped black phosphazene nanoplatelets coated with a polysiloxane quaternary ammonium salt and a long-chain alkyl ether potassium salt, which can be clearly found to exhibit macroscopic fluid-like characteristics.
In order to verify the antibacterial modification effect of the high-efficiency long-life antibacterial agent prepared by the invention on thermoplastic plastics, the invention takes ABS resin as an example, the high-efficiency long-life antibacterial agent prepared by the above example and the ABS resin are subjected to melt blending extrusion granulation by a double screw extruder according to the mass percent, test bars are prepared for carrying out various performance detection, and the same mass percent of commercial glass zeolite is added to load the antibacterial modified ABS resin of the silver ion antibacterial agent for comparison example. The antibacterial performance test method comprises the following steps: the plastic specimen containing the antibacterial master batch was smeared on a plate, and staphylococcus aureus representing gram-positive bacteria and escherichia coli representing gram-negative bacteria were cultured at 35 ℃ for 24 hours, and the sterilization rate was measured after exposure to sunlight for 2 hours. All performance test results are shown in table 1.
Table 1 comparison of the properties of the antibacterial modified ABS resin compositions prepared in examples 1 to 5 and the modified ABS resin with the same amount of commercially available antibacterial agent
The data in table 1 show that the high-efficiency long-life antibacterial agent prepared by the embodiment of the invention is applied to antibacterial functional modification of ABS resin and other thermoplastics, so that the modified plastic compound has excellent antibacterial performance, and the instant antibacterial effect is obviously better than that of the glass zeolite loaded silver ion antibacterial agent currently marketed. Particularly, after the plastic product is placed for 12 months, the antibacterial efficacy of the commercial glass zeolite loaded silver ion antibacterial agent is obviously reduced, and the long-life high-efficiency antibacterial agent of the invention has high retention rate of antibacterial efficacy on modified plastics. In addition, the mechanical property test result also shows that the black phosphazene nano-sheet can generate nano-reinforcing and toughening effects on the ABS resin matrix, thereby effectively improving the strength and toughness of the prepared antibacterial modified ABS compound. Therefore, the technology of the invention has the dual effects of improving the antibacterial capability and mechanical property of the thermoplastic plastics, which are not available in the prior art.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative examples and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description.
Furthermore, it should be understood that while the present description describes embodiments, not every embodiment is presented by way of example only, and that this description is provided for clarity only, and that the present disclosure is not limited to the embodiments described in the figures, as such, and that the embodiments described in the examples may be combined in any suitable manner to form other embodiments that will be apparent to those of skill in the art.
Claims (9)
1. An antibacterial agent for plastic modification based on black phosphazene, which is characterized in that: the antibacterial agent is prepared by loading silver and zinc ions on a carrier of sulfonated graphene oxide doped with black phosphazene, and coating a double-layer oligomer of the carrier by using a fluid-like technology, wherein the formed solid powder antibacterial agent has a viscous fluid-like characteristic under the condition of no solvent;
the inner layer oligomer in the double-layer oligomer is dimethyl octadecyl [ 3-trimethoxy silicon propyl ] ammonium chloride, and the outer layer oligomer is nonylphenol polyoxyethylene ether potassium sulfonate.
2. The method for preparing the black-phosphorus-based antibacterial agent for plastic modification according to claim 1, wherein the method comprises the following steps: the preparation method comprises the following steps:
1) Adding black phosphorus and methyl pyrrolidone into a ball mill according to a certain proportion, grinding, filtering, vacuum drying, dispersing the obtained black phosphorus crystal powder in a saturated NaOH/NMP solution, performing ultrasonic vibration dispersion, and then performing centrifugal separation and vacuum drying to obtain liquid-phase stripped black phosphane nano-sheets for later use;
2) Dispersing the black phosphazene nano-sheets obtained in the step 1) in deionized water, and then proportionally mixing AgNO 3 、ZnCl 2 Adding sulfonated graphene oxide into the dispersion system to adsorb silver and zinc ions, continuously stirring and mixing for a period of time, and then filtering and vacuum drying;
3) Putting the silver and zinc ion-loaded and sulfonated graphene oxide doped black phosphorus nano-sheet obtained in the step 2) into deionized water together with dimethyl octadecyl [ 3-trimethoxy silicon propyl ] ammonium chloride methanol solution according to a material putting proportion, and stirring for a period of time at normal temperature to enable the dimethyl octadecyl [ 3-trimethoxy silicon propyl ] ammonium chloride to be coated on the surface of the silver and zinc ion-loaded and sulfonated graphene oxide doped black phosphorus nano-sheet through physical adsorption; then standing and aging the reaction mixture to enable the black phosphazene nano-sheet to be subjected to dimethyl octadecyl [ 3-trimethoxy silicon propyl ] ammonium chloride; washing the obtained product with deionized water, filtering and drying;
4) Mixing the product obtained in the step 3) with a nonylphenol polyoxyethylene ether sulfonate potassium salt aqueous solution according to a material throwing proportion, stirring at 70 ℃ to enable chlorine ions in dimethyl octadecyl [ 3-trimethoxy silicone propyl ] ammonium chloride coated on black phospholene nano-sheets loaded with silver and zinc ions and doped with sulfonated graphene oxide to carry out ion exchange reaction with sulfonate ions in nonylphenol polyoxyethylene ether sulfonate potassium salt, washing the product with deionized water, filtering and drying in an oven after the reaction is completed, and obtaining the black phospholene nano-sheets coated on the inner layer and the outer layer of the silver and zinc ions and doped with sulfonated graphene oxide.
3. The method for preparing the black-phosphorus-based antibacterial agent for plastic modification according to claim 2, characterized in that: the material ratio of the black phosphorus to the methyl pyrrolidone in the step 1) is as follows: 200.0mL of methylpyrrolidone was added per 100.0g of black phosphorus; the ball milling time is 24 hours, the ultrasonic vibration is 24 hours, the drying temperature of vacuum drying is 95 ℃, and the drying time is 12 hours;
the material ratio of the black phosphorus crystal powder to the saturated NaOH/NMP solution is as follows: every 100g of black phosphorus crystal powder, 1500.0-2000.0 mL of NaOH/NMP solution is put in.
4. The method for preparing the black-phosphorus-based antibacterial agent for plastic modification according to claim 2, characterized in that: and (3) the black phosphazene nano-sheets in the step 1) are stored for standby under nitrogen atmosphere.
5. The method for preparing the black-phosphorus-based antibacterial agent for plastic modification according to claim 2, characterized in that: the black phosphazene nano-sheet and AgNO in the step 2) 3 、ZnCl 2 And the mass percentages of the sulfonated graphene oxide are respectively as follows: 93.0-98.0wt.% of black phosphazene nano-sheet and AgNO 3 2.0~6.0wt.%，ZnCl 2 0.5-1.0 wt.% of sulfonated graphene oxide, 0.5-1.0 wt.%.
6. The method for preparing the black-phosphorus-based antibacterial agent for plastic modification according to claim 2, characterized in that: the mixing and stirring time in the step 2) is 8-10 h, the vacuum drying temperature is 95 ℃, the drying time is 12h, and the adding amount of deionized water is as follows: 300.0-400.0 mL of water ion water is put into every 100g of black phosphazene nano-sheets.
7. The method for preparing the black-phosphorus-based antibacterial agent for plastic modification according to claim 2, characterized in that: the material throwing proportion in the step 3) is as follows: 30.0-50.0 mL of dimethyl octadecyl [ 3-trimethoxy silicon propyl ] ammonium chloride methanol solution with the mass percentage concentration of 40.0wt.% and 250.0-400.0 mL of water ion water are added into each 100g of black phosphazene nano-sheet which is loaded with silver ions and zinc ions and doped with sulfonated graphene oxide and is obtained in the step 2).
8. The method for preparing the black-phosphorus-based antibacterial agent for plastic modification according to claim 2, characterized in that: the material throwing proportion in the step 4) is as follows: the material throwing proportion is as follows: 180.0-200.0 mL of a nonylphenol polyoxyethylene ether sulfonate aqueous solution with the mass percentage concentration of 10.0wt.% is added into 100.0g of the product obtained in the step (3).
9. The method for preparing the black-phosphorus-based antibacterial agent for plastic modification according to claim 2, characterized in that:
the stirring time at normal temperature in the step 3) is 3-5 h, the standing aging time is 20h, the drying temperature of the product is 105 ℃, and the drying time is 24h;
the reaction time in the step 4) is 24 hours, the drying temperature is 105 ℃, and the drying time is 24 hours.
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