CN116693993B - Preparation process of halogen-containing amine carbon nano tube modified polystyrene antibacterial material - Google Patents
Preparation process of halogen-containing amine carbon nano tube modified polystyrene antibacterial material Download PDFInfo
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- CN116693993B CN116693993B CN202310824811.2A CN202310824811A CN116693993B CN 116693993 B CN116693993 B CN 116693993B CN 202310824811 A CN202310824811 A CN 202310824811A CN 116693993 B CN116693993 B CN 116693993B
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- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 79
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 79
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000004793 Polystyrene Substances 0.000 title claims abstract description 49
- 229920002223 polystyrene Polymers 0.000 title claims abstract description 49
- 239000000463 material Substances 0.000 title claims abstract description 41
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 35
- 229910052736 halogen Inorganic materials 0.000 title claims abstract description 34
- 150000001412 amines Chemical class 0.000 title claims abstract description 32
- 150000002367 halogens Chemical class 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 19
- YAXWOADCWUUUNX-UHFFFAOYSA-N 1,2,2,3-tetramethylpiperidine Chemical compound CC1CCCN(C)C1(C)C YAXWOADCWUUUNX-UHFFFAOYSA-N 0.000 claims description 39
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 33
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 21
- 125000005504 styryl group Chemical group 0.000 claims description 21
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- -1 vinyl carbon nano-tubes Chemical compound 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 229920002554 vinyl polymer Polymers 0.000 claims description 11
- 239000003999 initiator Substances 0.000 claims description 10
- 229920005990 polystyrene resin Polymers 0.000 claims description 10
- 238000000465 moulding Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- RTJGBIGSNVJSDM-UHFFFAOYSA-N 1-(2-isocyanatopropan-2-yl)-3-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC(C(C)(C)N=C=O)=C1 RTJGBIGSNVJSDM-UHFFFAOYSA-N 0.000 claims description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 7
- 239000008187 granular material Substances 0.000 claims description 7
- UFCONGYNRWGVGH-UHFFFAOYSA-N 1-hydroxy-2,2,3,3-tetramethylpiperidine Chemical compound CC1(C)CCCN(O)C1(C)C UFCONGYNRWGVGH-UHFFFAOYSA-N 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000003995 emulsifying agent Substances 0.000 claims description 6
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 5
- 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 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 4
- 238000004440 column chromatography Methods 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 2
- 238000004132 cross linking Methods 0.000 abstract description 2
- 238000011161 development Methods 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract description 2
- 230000001954 sterilising effect Effects 0.000 abstract description 2
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 2
- 238000004220 aggregation Methods 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 238000012360 testing method Methods 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 6
- 239000003480 eluent Substances 0.000 description 5
- 239000002048 multi walled nanotube Substances 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 238000002390 rotary evaporation Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 238000010898 silica gel chromatography Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 230000001580 bacterial effect Effects 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000000845 anti-microbial effect Effects 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000012258 culturing Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920001817 Agar Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
-
- 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 carbon nanotubes, and discloses a preparation process of a halogen-containing amine carbon nanotube modified polystyrene antibacterial material, wherein the halogen-containing amine carbon nanotube antibacterial agent is blended and modified in polystyrene, and a polystyrene copolymer is grafted on the surface of the carbon nanotube, so that the interfacial compatibility of the carbon nanotube and the polystyrene material is improved, the aggregation and the dispersibility of the carbon nanotube are improved, a crosslinking site is formed in a polystyrene matrix, and the performances of the material such as impact resistance, tensile strength and the like are remarkably improved. The copolymer grafted by the carbon nano tube contains a haloamine antibacterial structure, has high-efficiency, broad-spectrum and long-acting sterilization performance, and obviously improves the antibacterial performance of the polystyrene material. Expanding the development and application of polystyrene in the fields of antibacterial materials and the like.
Description
Technical Field
The invention relates to the technical field of carbon nanotubes, in particular to a preparation process of a halogen-containing amine carbon nanotube modified polystyrene antibacterial material.
Background
The carbon nano tube has a plurality of abnormal mechanical, electrical and chemical properties, is widely applied to high polymer materials such as polystyrene, polyvinylidene fluoride and the like, has important significance for surface modification of the carbon nano tube, can be used as a carrier of an antibacterial agent, enhances the antibacterial property and other comprehensive properties of the high polymer materials, and reports that the antibacterial property, the pollution resistance and the self-cleaning property of the polyvinylidene fluoride membrane material are remarkably improved by carrying out acid treatment on the original carbon nano tube to obtain an oxidized multi-wall carbon nano tube, then grafting N-haloamine and siloxane on the oxidized multi-wall carbon nano tube as an additive and adding the additive into a casting membrane liquid through a non-solvent induced phase separation method.
The polystyrene material has good electrical insulation, high heat resistance and low price, is one of four general plastics, is widely applied to the fields of household building materials, plastic containers, foam materials and the like, improves the comprehensive performance of the polystyrene, and endows the polystyrene with unique performance, which is a research hot spot, for example, paper on research on preparation and application of halamine polymer nano-micron antibacterial materials, reports that the halamine/quaternary ammonium salt polymer antibacterial nano-micron particles with a strong bactericidal effect and containing a silica-polystyrene core-shell structure are prepared by taking silica as a core and polystyrene as a shell in an emulsion polymerization manner, and has excellent bactericidal performance and good storage stability. According to the invention, the polystyrene copolymer containing the halamine is grafted on the surface of the carbon nano tube, and then the copolymer is blended and modified with polystyrene, so that the antibacterial property, impact resistance and other properties of the material are improved.
Disclosure of Invention
(one) solving the technical problems
The invention provides a preparation process of a halogen amine-containing carbon nano tube modified polystyrene antibacterial material, which utilizes a carbon nano tube loaded halogen amine antibacterial agent to improve the antibacterial property and the impact resistance of polystyrene.
(II) technical scheme
A preparation process of a halogen-containing amine carbon nano tube modified polystyrene antibacterial material comprises the following steps:
s1: adding emulsifier sodium dodecyl sulfate and vinyl carbon nanotube into deionized water, dispersing uniformly, adding styrene and methyl styryl tetramethylpiperidine, stirring uniformly, adding initiator dropwise in nitrogen atmosphere, heating to 70-85 ℃ for reaction for 3-6h, filtering solvent after reaction, washing with deionized water and ethanol in sequence, and drying to obtain the tetramethylpiperidine-containing carbon nanotube.
S2: adding the carbon nano tube containing tetramethyl piperidine into acetone, stirring uniformly, adding sodium hypochlorite aqueous solution with the concentration of 2-8%, stirring at room temperature for reaction for 3-8 hours, filtering the solvent after the reaction, washing with deionized water, and drying to obtain the halogen-containing amine carbon nano tube antibacterial agent.
S3: extruding and granulating polystyrene resin and the halogen-containing amine carbon nano tube antibacterial agent in a double-screw extruder, and then moulding and forming the granules in a flat vulcanizing machine to obtain the halogen-containing amine carbon nano tube modified polystyrene antibacterial material.
Preferably, the preparation process of the methyl styryl tetramethylpiperidine in the S1 comprises the following steps: adding tetramethyl piperidinol, 3-isopropyl-dimethylbenzyl isocyanate and a catalyst triethylamine in a molar ratio of 1:1-1.4:0.01-0.015 into toluene, heating to 60-75 ℃ in a nitrogen atmosphere for reaction for 2-5h, removing a solvent by rotary evaporation after the reaction, and performing silica gel column chromatography separation and purification, wherein an eluent is petroleum ether and ethyl acetate solution in a volume ratio of 10:1 to obtain methyl styryl tetramethyl piperidine.
Preferably, the weight ratio of the vinyl carbon nanotube, the styrene, the methyl styryl tetramethylpiperidine and the initiator in the S2 is 100:200-800:120-600:3-12.
Preferably, the initiator in S2 includes azobisisobutyronitrile or dibenzoyl peroxide.
Preferably, the weight ratio of the polystyrene resin to the halogen-containing amine carbon nano tube antibacterial agent in the step S3 is 100:1-8.
Preferably, in the step S3, extruding and granulating are carried out in a double-screw extruder at 175-185 ℃; and (3) molding in a press vulcanizer at a pressure of 8-12MPa and a temperature of 170-185 ℃.
(III) beneficial technical effects
Synthesizing novel methyl styryl tetramethyl piperidine monomer from tetramethyl piperidine alcohol and 3-isopropyl-dimethylbenzyl isocyanate under the catalysis of triethylamine, performing in-situ graft polymerization with styrene monomer on the surface of carbon nano tube under the initiation of azodiisobutyronitrile or dibenzoyl peroxide to obtain carbon nano tube containing tetramethyl piperidine, and finally performing sodium hypochloriteHalogenating to obtain the halogen-containing amine carbon nano tube antibacterial agent, so that the polystyrene copolymer containing the halogen-containing amine antibacterial structure is grafted on the surface of the carbon nano tube. In an infrared spectrogram containing a tetramethyl piperidine carbon nanotube, 3048cm < -1 > is an expansion vibration peak of C-H on a benzene ring in a polystyrene copolymer, and 1694cm < -1 > is a characteristic peak of a benzene ring framework C-C; 3006cm-1 is the shrinkage vibration peak of-NH in the tetramethylpiperidine ring; 2914cm-1 is-CH in tetramethyl piperidine ring 3 Is characterized by an absorption peak; 1742cm-1 is methyl styryl tetramethylpiperidineThe stretching vibration peak of C=O, 1520cm-1 is the bending vibration peak of-NH. In an infrared spectrogram of the halogen-containing amine carbon nano tube antibacterial agent, 3011cm < -1 > is a telescopic vibration peak of C-H on a benzene ring in a polystyrene copolymer, 1685cm < -1 > is a characteristic peak of a benzene ring framework C-C, and the obvious disappearance of a shrinkage vibration peak of-NH in a tetramethyl piperidine ring is caused by the haloamination reaction to generate an-N-Cl bond; 2910cm-1 is-CH in tetramethyl piperidine ring 3 Is characterized by an absorption peak; 1740cm-1 is the radical of methyl styryl tetramethylpiperidine +.>The stretching vibration peak of C=O, 1501cm-1 is the bending vibration peak of-NH.
The halogen-containing amine carbon nano tube antibacterial agent is blended and modified in polystyrene, and a polystyrene copolymer is grafted on the surface of the carbon nano tube, so that the interfacial compatibility of the carbon nano tube and a polystyrene material is improved, the agglomeration and the dispersibility of the carbon nano tube are improved, a crosslinking site is formed in a polystyrene matrix, and the performances of the material such as impact resistance, tensile strength and the like are obviously improved. The copolymer grafted by the carbon nano tube contains a haloamine antibacterial structure, has high-efficiency, broad-spectrum and long-acting sterilization performance, and obviously improves the antibacterial performance of the polystyrene material. Expanding the development and application of polystyrene in the fields of antibacterial materials and the like.
Drawings
FIG. 1 is a reaction scheme for the preparation of methyl styryl tetramethylpiperidine.
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of methyl styryl tetramethylpiperidine.
FIG. 3 is a route for preparing the haloamine carbon nanotube antimicrobial.
FIG. 4 is an infrared spectrum of a haloamine carbon nanotube antimicrobial.
Fig. 5 is a mechanical property and antibacterial property test of polystyrene material.
Detailed Description
Multiwall carbon nanotubes: model: product number: TNSM0; OD value of 4-6nm, length of 0.5-2um, SSA specific surface area of 380-550m 2 And/g. All organic chemical Co.Ltd.
Polystyrene resin: brand GPS-525N; shanghai purple plastics materials Co.Ltd.
The preparation process of the vinyl carbon nanotube refers to journal "materials science and engineering plastics" 23, 4 th period, surface vinyl functionalization of multiwall carbon nanotubes:
adding 0.3g of multiwall carbon nanotube into 30mL of 98% concentrated sulfuric acid and 10mL of 70% concentrated nitric acid, refluxing for 1h at 140 ℃, filtering, weighing 0.1g of the washed acidified carbon nanotube, dispersing into 15mL of acetone and 15mL of chloroform, adding 2mL of triethylamine and 5mL of acryloyl chloride, reacting for 24h at 40 ℃, adding 10mL of ethanol, stirring for 2h, filtering, and washing to obtain the vinyl carbon nanotube.
Example 1
(1) 20mmol of tetramethyl piperidinol, 25mmol of 3-isopropyl-dimethylbenzyl isocyanate and 0.26mmol of catalyst triethylamine are added into toluene, the mixture is heated to 75 ℃ in a nitrogen atmosphere for reaction for 3 hours, the solvent is removed by rotary evaporation after the reaction, and silica gel column chromatography separation and purification are carried out, wherein the eluent is petroleum ether and ethyl acetate solution with the volume ratio of 10:1, so that the methyl styryl tetramethyl piperidine is obtained.
(2) Adding 0.05g of emulsifier sodium dodecyl sulfate and 0.2g of vinyl carbon nanotube into deionized water, uniformly dispersing, adding 0.4g of styrene and 0.24g of methyl styryl tetramethylpiperidine, uniformly stirring, dropwise adding 6mg of initiator azodiisobutyronitrile in a nitrogen atmosphere, heating to 85 ℃ for reaction for 4 hours, filtering a solvent after the reaction, washing with deionized water and ethanol in sequence, and drying to obtain the tetramethylpiperidine-containing carbon nanotube.
(3) Adding the carbon nano tube containing tetramethyl piperidine into acetone, stirring uniformly, adding sodium hypochlorite aqueous solution with the concentration of 2%, stirring at room temperature for reaction for 4 hours, filtering the solvent after the reaction, washing with deionized water, and drying to obtain the halogen-containing amine carbon nano tube antibacterial agent.
(4) Extruding and granulating 50g of polystyrene resin and 0.5g of halogen-containing amine carbon nano tube antibacterial agent in a double screw extruder at 175 ℃, and then molding the granules in a flat vulcanizing machine under the pressure of 10MPa at 175 ℃ to obtain the halogen-containing amine carbon nano tube modified polystyrene antibacterial material.
Example 2
(1) 20mmol of tetramethyl piperidinol, 20mmol of 3-isopropyl-dimethylbenzyl isocyanate and 0.2mmol of catalyst triethylamine are added into toluene, the mixture is heated to 70 ℃ in a nitrogen atmosphere for reaction for 2 hours, the solvent is removed by rotary evaporation after the reaction, silica gel column chromatography separation and purification are carried out, and the eluent is petroleum ether and ethyl acetate solution with the volume ratio of 10:1, so that the methyl styryl tetramethyl piperidine is obtained.
(2) Adding 0.12g of emulsifier sodium dodecyl sulfate and 0.2g of vinyl carbon nanotube into deionized water, uniformly dispersing, adding 1g of styrene and 0.7g of methyl styryl tetramethylpiperidine, uniformly stirring, dropwise adding 18mg of initiator azodiisobutyronitrile in a nitrogen atmosphere, heating to 70 ℃ for reaction for 6 hours, filtering the solvent after reaction, washing with deionized water and ethanol in sequence, and drying to obtain the tetramethylpiperidine-containing carbon nanotube.
(3) Adding the carbon nano tube containing tetramethyl piperidine into acetone, stirring uniformly, adding sodium hypochlorite aqueous solution with the concentration of 5%, stirring at room temperature for reaction for 3 hours, filtering the solvent after the reaction, washing with deionized water, and drying to obtain the halogen-containing amine carbon nano tube antibacterial agent.
(4) Extruding and granulating 50g of polystyrene resin and 2g of halogen-containing amine carbon nano tube antibacterial agent in a double screw extruder at 185 ℃, and then molding the granules in a flat vulcanizing machine at 185 ℃ under 8MPa pressure to obtain the halogen-containing amine carbon nano tube modified polystyrene antibacterial material.
Example 3
(1) 20mmol of tetramethyl piperidinol, 28mmol of 3-isopropyl-dimethylbenzyl isocyanate and 0.3mmol of catalyst triethylamine are added into toluene, the mixture is heated to 60 ℃ in a nitrogen atmosphere for reaction for 5 hours, the solvent is removed by rotary evaporation after the reaction, silica gel column chromatography separation and purification are carried out, and the eluent is petroleum ether and ethyl acetate solution with the volume ratio of 10:1, so that the methyl styryl tetramethyl piperidine is obtained.
(2) Adding 0.2g of emulsifier sodium dodecyl sulfate and 0.2g of vinyl carbon nanotube into deionized water, uniformly dispersing, adding 1.6g of styrene and 1.2g of methyl styryl tetramethylpiperidine, uniformly stirring, dropwise adding 24mg of initiator dibenzoyl peroxide into the nitrogen atmosphere, heating to 80 ℃ for reaction for 3 hours, filtering the solvent after reaction, washing with deionized water and ethanol in sequence, and drying to obtain the tetramethylpiperidine-containing carbon nanotube.
(3) Adding the carbon nano tube containing tetramethyl piperidine into acetone, stirring uniformly, adding sodium hypochlorite aqueous solution with the concentration of 8%, stirring at room temperature for reaction for 8 hours, filtering the solvent after the reaction, washing with deionized water, and drying to obtain the halogen-containing amine carbon nano tube antibacterial agent.
(4) Extruding and granulating 50g of polystyrene resin and 4g of halogen-containing amine carbon nano tube antibacterial agent in a double screw extruder at 180 ℃, and then molding the granules in a flat vulcanizing machine at 170 ℃ under the pressure of 12MPa to obtain the halogen-containing amine carbon nano tube modified polystyrene antibacterial material.
Comparative example 1
(1) Extruding and granulating 50g of polystyrene resin and 0.5g of carbon nano tube antibacterial agent in a double-screw extruder at 175 ℃, and then molding the granules in a flat vulcanizing machine under the pressure of 10MPa at 175 ℃ to obtain the carbon nano tube modified polystyrene antibacterial material.
Comparative example 2
(1) 20mmol of tetramethyl piperidinol, 25mmol of 3-isopropyl-dimethylbenzyl isocyanate and 0.26mmol of catalyst triethylamine are added into toluene, the mixture is heated to 75 ℃ in a nitrogen atmosphere for reaction for 3 hours, the solvent is removed by rotary evaporation after the reaction, and silica gel column chromatography separation and purification are carried out, wherein the eluent is petroleum ether and ethyl acetate solution with the volume ratio of 10:1, so that the methyl styryl tetramethyl piperidine is obtained.
(2) Adding 0.05g of emulsifier sodium dodecyl sulfate and 0.2g of vinyl carbon nanotube into deionized water, uniformly dispersing, adding 0.4g of styrene and 0.24g of methyl styryl tetramethylpiperidine, uniformly stirring, dropwise adding 6mg of initiator azodiisobutyronitrile in a nitrogen atmosphere, heating to 85 ℃ for reaction for 4 hours, filtering a solvent after the reaction, washing with deionized water and ethanol in sequence, and drying to obtain the tetramethylpiperidine-containing carbon nanotube.
(3) Extruding and granulating 50g of polystyrene resin and 0.5g of carbon nano tube containing tetramethyl piperidine in a double screw extruder at 175 ℃, and then molding the granules in a flat vulcanizing machine under the pressure of 10MPa at 175 ℃ to obtain the modified polystyrene material containing tetramethyl piperidine carbon nano tube.
Referring to the test method of GB/T1043.2-2018, a simply supported beam impact strength tester is adopted to test the impact resistance of a polystyrene material sample, an energy carrier is placed at a starting position, and the polystyrene material sample is placed on a sample support, so that an impact blade strikes the center of the sample. When placing the notch specimen, the center of the notch should be located exactly on the impact plane. The energy carrier is then released and the force change over time during the impact is recorded. The polystyrene material samples were 10 cm. Times.4 cm. Times.0.5 cm.
According to the testing method of GB/T1040.1-2018, a universal material testing machine is adopted to test the tensile property of a polystyrene material sample, the sample is connected with the testing machine through a clamp, and the central axis of the sample is kept consistent with the central axis of the testing machine. And (3) carrying out constant-speed stretching on the testing machine along the main axis direction of the test sample at the stretching speed of 50mm/min until the stress of the test sample reaches a preset value, and then measuring the load and the elongation born by the test sample in the testing process. Samples of polystyrene material were 12cm by 4cm by 0.4cm.
1mL of the solution was removed to give a concentration of 10 8 CFU/mL of streptococcus aureus bacterial liquid is added into PBS buffer solution, and diluted to 10 times sequentially after shaking evenly 5 CFU/mL, adding polystyreneAlkene material sample (1 cm×1cm×0.2 cm), shake culturing in a constant temperature incubator at 37deg.C for 24 hr, adding PBS buffer solution, sequentially diluting with 10 times of the bacterial liquid, transferring 0.5mL of bacterial liquid, inoculating into agar culture medium, shake culturing at 37deg.C for 24 hr, counting colony, and counting antibacterial rate.
Antibacterial ratio = (X-Y)/x×100%. X is the colony count after culture without polystyrene sample alkene material. Y is the number of colonies after incubation of the sample of the addition polymerization styrene material.
Claims (5)
1. A preparation process of a halogen-containing amine carbon nano tube modified polystyrene antibacterial material is characterized by comprising the following steps of: the preparation process comprises the following steps:
s1: adding emulsifier sodium dodecyl sulfate and vinyl carbon nano-tubes into deionized water, dispersing uniformly, adding styrene and methyl styryl tetramethylpiperidine, stirring uniformly, dripping an initiator into nitrogen atmosphere, heating to 70-85 ℃ for reaction for 3-6h, filtering the solvent, washing with deionized water and ethanol in sequence, and drying to obtain the tetramethylpiperidine-containing carbon nano-tubes;
s2: adding a tetramethylpiperidine-containing carbon nano tube into acetone, uniformly stirring, adding a sodium hypochlorite aqueous solution with the concentration of 2-8%, stirring at room temperature for reaction for 3-8 hours, filtering, washing and drying to obtain a halogen-containing amine carbon nano tube antibacterial agent;
s3: extruding and granulating polystyrene resin and a halogen-containing amine carbon nano tube antibacterial agent in a double-screw extruder, and then moulding and forming the granules in a flat vulcanizing machine to obtain a halogen-containing amine carbon nano tube modified polystyrene antibacterial material;
the preparation process of the methyl styryl tetramethyl piperidine in the S1 comprises the following steps: adding tetramethyl piperidinol, 3-isopropyl-dimethylbenzyl isocyanate and triethylamine as catalyst in the molar ratio of 1:1-1.4:0.01-0.015 into toluene, heating to 60-75 ℃ in nitrogen atmosphere for reaction for 2-5h, and separating and purifying by column chromatography to obtain the methyl styryl tetramethyl piperidine.
2. The process for preparing the halogen-containing amine carbon nano tube modified polystyrene antibacterial material according to claim 1, which is characterized in that: the weight ratio of the vinyl carbon nano tube, the styrene, the methyl styryl tetramethyl piperidine and the initiator in the S1 is 100:200-800:120-600:3-12.
3. The process for preparing the halogen-containing amine carbon nano tube modified polystyrene antibacterial material according to claim 1, which is characterized in that: the initiator in the S1 comprises azodiisobutyronitrile or dibenzoyl peroxide.
4. The process for preparing the halogen-containing amine carbon nano tube modified polystyrene antibacterial material according to claim 1, which is characterized in that: and in the step S3, the weight ratio of the polystyrene resin to the halogen-containing amine carbon nano tube antibacterial agent is 100:1-8.
5. The process for preparing the halogen-containing amine carbon nano tube modified polystyrene antibacterial material according to claim 1, which is characterized in that: extruding and granulating in the step S3 in a double-screw extruder at 175-185 ℃; and (3) molding in a press vulcanizer at a pressure of 8-12MPa and a temperature of 170-185 ℃.
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